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Sample records for base metal complexes

  1. Molecular Split-Ring Resonators Based on Metal String Complexes

    CERN Document Server

    Shen, Yao; Ai, Qing; Peng, Shie-Ming; Jin, Bih-Yaw

    2014-01-01

    Metal string complexes or extended metal atom chains (EMACs) belong to a family of molecules that consist of a linear chain of directly bonded metal atoms embraced helically by four multidentate organic ligands. These four organic ligands are usually made up of repeating pyridyl units, single-nitrogen-substituted heterocyclic annulenes, bridged by independent amido groups. Here, in this paper, we show that these heterocyclic annulenes are actually nanoscale molecular split-ring resonators (SRRs) that can exhibit simultaneous negative electric permittivity and magnetic permeability in the UV-Vis region. Moreover, a monolayer of self-assembled EMACs is a periodic array of molecular SRRs which can be considered as a negative refractive index material. In the molecular scale, where the quantum-size effect is significant, we apply the tight-binding method to obtain the frequency-dependent permittivity and permeability of these molecular SRRs with their tensorial properties carefully considered.

  2. From Metal String Complexes to Metal Wires

    Institute of Scientific and Technical Information of China (English)

    PENG; SheMing

    2001-01-01

    Our efforts to extend the metal number from dinuclear metal complexes to linear oligonuclear metal complexes with all-syn form of oligo-( α-pyridyl)amido ligands are successful. The oligonuclear complexes are divided into two systems according their MM bond strength, one is the oligonickel( Ⅱ ) complexes without M-M bond, the other is the oligochromium(Ⅱ) and cobalt(H) complexes with a strong M-M bond. Their structures and magnetic behaviors for various metal complexes with specific metal numbers are summarized. The potential application of these metal complexes as a molecular metal wire is discussed by the band structures of hypothetical onedinensional metal strings based on the polynuclear Cr, Co and Ni complexes. Moreover, self-assembled monolayers of n-alkanethiols are employed as a two-dinensional matrix to isolate the metal string complexes, which exhibit protrusions under the measurements of scanning tunneling microscopy (STM) imaging. The topographic STM images reveal that the protruding features for tricobalt and trichromium complexes are, respectively, 0.3 nm and 0.6 nm higher than that of trinickel complex. The increasing trend in conductivity is consistent with their bond orders, obtained from qualitative EHMO calculations.  ……

  3. From Metal String Complexes to Metal Wires

    Institute of Scientific and Technical Information of China (English)

    PENG SheMing

    2001-01-01

    @@ Our efforts to extend the metal number from dinuclear metal complexes to linear oligonuclear metal complexes with all-syn form of oligo-( α-pyridyl)amido ligands are successful. The oligonuclear complexes are divided into two systems according their MM bond strength, one is the oligonickel( Ⅱ ) complexes without M-M bond, the other is the oligochromium(Ⅱ) and cobalt(H) complexes with a strong M-M bond. Their structures and magnetic behaviors for various metal complexes with specific metal numbers are summarized. The potential application of these metal complexes as a molecular metal wire is discussed by the band structures of hypothetical onedinensional metal strings based on the polynuclear Cr, Co and Ni complexes. Moreover, self-assembled monolayers of n-alkanethiols are employed as a two-dinensional matrix to isolate the metal string complexes, which exhibit protrusions under the measurements of scanning tunneling microscopy (STM) imaging. The topographic STM images reveal that the protruding features for tricobalt and trichromium complexes are, respectively, 0.3 nm and 0.6 nm higher than that of trinickel complex. The increasing trend in conductivity is consistent with their bond orders, obtained from qualitative EHMO calculations.

  4. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.

    2016-09-06

    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

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

    Science.gov (United States)

    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

  6. Some Transition Metal Complexes of NO Type Schiff Base: Preparation and Characterization

    Directory of Open Access Journals (Sweden)

    Erdal CANPOLAT

    2016-04-01

    Full Text Available Metal complexes of Schiff base ligand (5-bromo-3-methoxysalicyliden-p-iminoacetophenone oxime derived from 5-bromo-3-methoxsalicylaldehyde and p-aminoacetophenoneoxime is reported. Schiff base was found to be bidentate ligand involving the imino nitrogen and carboxyl oxygen atoms in the complexes. Metal to ligand ratio were found to be 1:2 for all of the complexes. Co(II, Ni(II, and Zn(II complexes have been found tetrahedral geometry and Cu(II complex has been found four coordinated geometry. The complexes are found to have the formulae [M(L2]. The compounds obtained have been characterized by their elemental analyses, IR, 1H-NMR, 13C-NMR, UV spectra, magnetic susceptibility and thermogravimetric analyses (TGA.

  7. Synthesis and Characterization of Metal Complexes with Schiff Base Ligands

    Science.gov (United States)

    Wilkinson, Shane M.; Sheedy, Timothy M.; New, Elizabeth J.

    2016-01-01

    In order for undergraduate laboratory experiments to reflect modern research practice, it is essential that they include a range of elements, and that synthetic tasks are accompanied by characterization and analysis. This intermediate general chemistry laboratory exercise runs over 2 weeks, and involves the preparation of a Schiff base ligand and…

  8. Synthesis, spectral characterization of Schiff base transition metal complexes: DNA cleavage and antimicrobial activity studies

    Indian Academy of Sciences (India)

    N Raman; J Dhaveethu Raja; A Sakthivel

    2007-07-01

    A new series of transition metal complexes of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) have been synthesized from the Schiff base (L) derived from 4-aminoantipyrine, 3-hydroxy-4-nitrobenzaldehyde and -phenylenediamine. Structural features were obtained from their elemental analyses, magnetic susceptibility, molar conductance, mass, IR, UV-Vis, 1H NMR and ESR spectral studies. The data show that these complexes have composition of ML type. The UV-Vis, magnetic susceptibility and ESR spectral data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The redox behaviour of copper and vanadyl complexes was studied by cyclic voltammetry. Antimicrobial screening tests gave good results in the presence of metal ion in the ligand system. The nuclease activity of the above metal complexes shows that Cu, Ni and Co complexes cleave DNA through redox chemistry whereas other complexes are not effective.

  9. A review on versatile applications of transition metal complexes incorporating Schiff bases

    Directory of Open Access Journals (Sweden)

    Ahmed M. Abu-Dief

    2015-06-01

    Full Text Available Schiff bases and their complexes are versatile compounds synthesized from the condensation of an amino compound with carbonyl compounds and widely used for industrial purposes and also exhibit a broad range of biological activities including antifungal, antibacterial, antimalarial, antiproliferative, anti-inflammatory, antiviral, and antipyretic properties. Many Schiff base complexes show excellent catalytic activity in various reactions and in the presence of moisture. Over the past few years, there have been many reports on their applications in homogeneous and heterogeneous catalysis. The high thermal and moisture stabilities of many Schiff base complexes were useful attributes for their application as catalysts in reactions involving at high temperatures. The activity is usually increased by complexation therefore to understand the properties of both ligands and metal can lead to the synthesis of highly active compounds. The influence of certain metals on the biological activity of these compounds and their intrinsic chemical interest as multidentate ligands has prompted a considerable increase in the study of their coordination behaviour. Development of a new chemotherapeutic Schiff bases and their metal complexes is now attracting the attention of medicinal chemists. This review compiles examples of the most promising applied Schiff bases and their complexes in different areas.

  10. Complex-Morphology Metal-Based Nanostructures: Fabrication, Characterization, and Applications

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    Antonella Gentile

    2016-06-01

    Full Text Available Due to their peculiar qualities, metal-based nanostructures have been extensively used in applications such as catalysis, electronics, photography, and information storage, among others. New applications for metals in areas such as photonics, sensing, imaging, and medicine are also being developed. Significantly, most of these applications require the use of metals in the form of nanostructures with specific controlled properties. The properties of nanoscale metals are determined by a set of physical parameters that include size, shape, composition, and structure. In recent years, many research fields have focused on the synthesis of nanoscale-sized metallic materials with complex shape and composition in order to optimize the optical and electrical response of devices containing metallic nanostructures. The present paper aims to overview the most recent results—in terms of fabrication methodologies, characterization of the physico-chemical properties and applications—of complex-morphology metal-based nanostructures. The paper strongly focuses on the correlation between the complex morphology and the structures’ properties, showing how the morphological complexity (and its nanoscale control can often give access to a wide range of innovative properties exploitable for innovative functional device production. We begin with an overview of the basic concepts on the correlation between structural and optical parameters of nanoscale metallic materials with complex shape and composition, and the possible solutions offered by nanotechnology in a large range of applications (catalysis, electronics, photonics, sensing. The aim is to assess the state of the art, and then show the innovative contributions that can be proposed in this research field. We subsequently report on innovative, versatile and low-cost synthesis techniques, suitable for providing a good control on the size, surface density, composition and geometry of the metallic

  11. Antibacterial Evaluation of Some Schiff Bases Derived from 2-Acetylpyridine and Their Metal Complexes

    OpenAIRE

    Thong Kwai Lin; Chai Lay Ching; Cher Lin Ooi; Hadi, A. Hamid A.; Mahmood Ameen Abdulla; Nura Suleiman Gwaram; Hapipah Mohd Ali; Hamid Khaledi

    2012-01-01

    A series of Schiff bases derived from 2-acetylpyridne and their metal complexes were characterized by elemental analysis, NMR, FT-IR and UV-Vis spectral studies. The complexes were screened for anti-bacterial activity against Methicillin-resistant Staphylococcus aureus (MRSA), Acinetobacter baumanni (AC), Klebsiella pneumonie (KB) and Pseudomonas aeruginosa (PA) using the disc diffusion and micro broth dilutio...

  12. Antibacterial evaluation of some Schiff bases derived from 2-acetylpyridine and their metal complexes.

    Science.gov (United States)

    Gwaram, Nura Suleiman; Ali, Hapipah Mohd; Khaledi, Hamid; Abdulla, Mahmood Ameen; Hadi, A Hamid A; Lin, Thong Kwai; Ching, Chai Lay; Ooi, Cher Lin

    2012-01-01

    A series of Schiff bases derived from 2-acetylpyridne and their metal complexes were characterized by elemental analysis, NMR, FT-IR and UV-Vis spectral studies. The complexes were screened for anti-bacterial activity against Methicillin-resistant Staphylococcus aureus (MRSA), Acinetobacter baumanni (AC), Klebsiella pneumonie (KB) and Pseudomonas aeruginosa (PA) using the disc diffusion and micro broth dilution assays. Based on the overall results, the complexes showed the highest activities against MRSA while a weak antibacterial activity was observed against A. baumanii and P. aeruginosa. PMID:22609786

  13. Spectroscopic studies and biological activity of some transition metal complexes of unusual Schiff base

    Science.gov (United States)

    Abu Al-Nasr, Ahmad K.; Ramadan, Ramadan M.

    2013-03-01

    Unusual Schiff base ligand, 4-ethanimidoyl-6-[(1E)-N-(2-hydroxy-4-methylphenyl)ethanimidoyl]benzene-1,3-diol, L, was synthesized via catalytic process involving the interaction of some metal ions with a macrocyclic Schiff base (MSB). The transition metal derivatives [ML(H2O)4](NO3)3, M = Cr(III) and Fe(III), [NiL(H2O)4](NO3)2, [ML(H2O)2](NO3)2, M = Zn(II) and Cd(II), [Cl2Pd(μ-Cl)2PdL], [PtL(Cl)2] and [PtL(Cl)4] were also synthesized from the corresponding metal species with L. The Schiff bases and complexes were characterized by elemental analysis, mass spectrometry, IR and 1H NMR spectroscopy. The crystal structure of L was determined by X-ray analysis. The spectroscopic studies revealed a variety of structure arrangements for the complexes. The biological activities of L and metal complexes against the Escherchia coli as Gram-negative bacteria and Staphylococcus aureus as Gram-positive bacteria, and the two fungus Aspergillus flavus and Candida albicans were screened. The cytotoxicity of [PtL(Cl)2] complex, a cis-platin analogous, was checked as an antitumor agent on two breast cancer cell lines (MCF7 and T47D) and human liver carcinoma cell line (HepG2).

  14. Conducting metal dithiolate complexes

    DEFF Research Database (Denmark)

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.; Clemenson, P. I.; Carneiro, K.; Yueqiuan, S.; Mortensen, Kell

    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound......Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  15. Conducting metal dithiolate complexes

    DEFF Research Database (Denmark)

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.;

    1985-01-01

    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound......Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  16. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  17. Design, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

    Science.gov (United States)

    Hanif, Muhammad; Chohan, Zahid H.

    2013-03-01

    A new series of three biologically active triazole derived Schiff base ligands L1-L3 have been synthesized in equimolar reaction of 3-amino-1H-1,2,4-triazole with pyrrol-2-carboxaldehyde, 4-bromo-thiophene-2-carboxaldehyde, and 5-iodo-2-hydroxy benzaldehyde. The prepared Schiff bases were used for further complex formation reaction with different metal elements like Co(II), Ni(II), Cu(II) and Zn(II) as chlorides by using a molar ratio of ligand:metal as 2:1. The structure and bonding nature of all the compounds were identified by their physical, spectral and analytical data. All the metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which showed a distorted octahedral geometry. All the synthesized compounds, were studied for their in vitro antibacterial, and antifungal activities, against four Gram-negative (Escherichia coli, Shigella sonnei, Pseudomonas aeruginosa and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and against six fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) by using agar-well diffusion method. It has been shown that all the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. In vitro Brine Shrimp bioassay was also carried out to investigate the cytotoxic properties of these compounds. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

  18. Tridentate Schiff base (ONO) transition metal complexes: Synthesis, crystal structure, spectroscopic and larvicidal studies

    Indian Academy of Sciences (India)

    SUNDARAMURTHY SANTHA LAKSHMI; KANNAPPAN GEETHA; P MAHADEVI

    2016-07-01

    A series of four new Schiff base transition metal complexes [Co(II), Ni(II), Cu(II) and Zn(II)] derived from N-(salicylidene)-L-alanine and N,N,N',N'-tetramethylethylene-1,2-diamine (tmen) were designed, synthesized and tested for larvicidal activity against Culex quinquefasciatus, the southern house mosquito, which is the primary vector of St. Louis encephalitis virus and West Nile virus. All the complexes were characterized by physicochemical and spectral studies such as UV-Visible, FTIR, and EPR. The X-ray crystallographic analysis of Ni(II) complex revealed that, Ni(II) cation is surrounded by nitrogen and oxygen atoms from the Schiff base ligand, the oxygen atom of a water molecule, and two nitrogen atoms from tmen. Intermolecularhydrogen bonding stabilizes the Ni(II) complex. Results indicated that all the complexes exhibited higher mosquito larvicidal activity against C. quinquefasciatus.

  19. Synthesis and Characterization of Dinuclear Metal Complexes Stabilized by Tetradentate Schiff Base Ligands

    Directory of Open Access Journals (Sweden)

    Eid A. Abdalrazaq

    2010-01-01

    Full Text Available Problem statement: The synthesis, spectroscopic properties and theoretical calculations of acetylacetonimine and acetylacetanilidimine Schiff-base ligands, L1H and L2H, respectively and their dinuclear complexes of the type [M2LnCl2(H2O2], where n = 1 or 2, M = Co(II, Ni(II, Cu(II, Zn(II and Cd(II are described. Approach: The new tetradentate dianion Schiff base ligand which was used as stabilizers for the complexes were prepared by condensation of hydrazine with acetylacetone or acetylacetanilide. The dinuclear complexes of theses ligands were synthesized by treating an ethanolic solution of the prepared ligand with hydrated metal salts in molar ratio of 1:2 (L:M. Results: The ligand and their dinuclear metal complexes were characterized by CHN elemental analysis, FT-IR, UV-Vis, 1HNMR (for the ligands, conductivity, magnetic susceptibility and theoretical calculation by using MM2 modeling program. Conclusion: The reaction of these ligands in a 1:2 (L:M afford dinuclear M(II metal complexes with tetrahedral arrangement around Co(II, Zn(II and Cd(II and square planar around Ni(II and Cu(II.

  20. Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Morten B. Ley

    2015-09-01

    Full Text Available This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability.

  1. Modularly designed transition metal PNP and PCP pincer complexes based on aminophosphines: synthesis and catalytic applications.

    Science.gov (United States)

    Benito-Garagorri, David; Kirchner, Karl

    2008-02-01

    Transition metal complexes are indispensable tools for any synthetic chemist. Ideally, any metal-mediated process should be fast, clean, efficient, and selective and take place in a catalytic manner. These criteria are especially important considering that many of the transition metals employed in catalysis are rare and expensive. One of the ways of modifying and controlling the properties of transition metal complexes is the use of appropriate ligand systems, such as pincer ligands. Usually consisting of a central aromatic backbone tethered to two two-electron donor groups by different spacers, this class of tridentate ligands have found numerous applications in various areas of chemistry, including catalysis, due to their combination of stability, activity, and variability. As we focused on pincer ligands featuring phosphines as donor groups, the lack of a general method for the preparation of both neutral (PNP) and anionic (PCP) pincer ligands using similar precursor compounds as well as the difficulty of introducing chirality into the structure of pincer ligands prompted us to investigate the use of amines as spacers between the aromatic ring and the phosphines. By introduction of aminophosphine and phosphoramidite moieties into their structure, the synthesis of both PNP and PCP ligands can be achieved via condensation reactions between aromatic diamines and electrophilic chlorophosphines (or chlorophosphites). Moreover, chiral pincer complexes can be easily obtained by using building blocks obtained from the chiral pool. Thus, we have developed a modular synthetic strategy with which the steric, electronic, and stereochemical properties of the ligands can be varied systematically. With the ligands in hand, we studied their reactivity towards different transition metal precursors, such as molybdenum, ruthenium, iron, nickel, palladium, and platinum. This has resulted in the preparation of a range of new pincer complexes, including various iron complexes, as

  2. SYNTHESIS AND PROPERTIES OF METAL COMPLEXES OF β-DIKETONE BASED SIDE CHAIN LIQUID CRYSTAL POLYSILOXANE

    Institute of Scientific and Technical Information of China (English)

    WU Fuzhou; ZHANG Rongben; JIANG Yingyan

    1991-01-01

    A new type of metal coordinated liquid crystalline polymers has been synthesized by complexation of metal ions with β-diketone based side chain liquid crystal polysiloxane (DKLCP).The complexation of copper ions with DKLCP greatly increases the phase transition temperature Tk from crystalline state to liquid crystalline state and Tcl from LC to isotropic state and makes the range of phase transition △T(△T= Tcl- Tk ) widened. These complexes are soluble in common organic solvents. However, the incorporation of europium ions into DKLCP molecules gives rise to reduction in liquid crystallinity and crosslinking in some cases. The DKLCP coordinated with suitable amount of Eu ions can show good liquid crystallinity and fluorescent property.

  3. Antibacterial Evaluation of Some Schiff Bases Derived from 2-Acetylpyridine and Their Metal Complexes

    Directory of Open Access Journals (Sweden)

    Thong Kwai Lin

    2012-05-01

    Full Text Available A series of Schiff bases derived from 2-acetylpyridne and their metal complexes were characterized by elemental analysis, NMR, FT-IR and UV-Vis spectral studies. The complexes were screened for anti-bacterial activity against Methicillin-resistant Staphylococcus aureus (MRSA, Acinetobacter baumanni (AC, Klebsiella pneumonie (KB and Pseudomonas aeruginosa (PA using the disc diffusion and micro broth dilution assays. Based on the overall results, the complexes showed the highest activities against MRSA while a weak antibacterial activity was observed against A. baumanii and P. aeruginosa.

  4. Synthesis, Spectroscopic Characterization and Biological Activities of Transition Metal Complexes Derived from a Tridentate Schiff Base

    Directory of Open Access Journals (Sweden)

    J. Senthil Kumaran

    2013-01-01

    Full Text Available A new series of Cu (II, Ni (II, Co (II and Zn (II complexes have been synthesized from the Schiff base derived from 4-hydroxy-3-methoxybenzylidine-4-aminoantipyrine and 2-aminophenol. The structural features have been determined from their elemental analysis, magnetic susceptibility, molar conductance, Mass, IR, UV-Vis, 1H-NMR, 13C-NMR and ESR spectral studies. The redox behavior of the copper complex has been studied by cyclic voltammetry. The data confirm that the complexes have composition of ML2 type. The electronic absorption spectral data of the complexes propose an octahedral geometry around the central metal ion. All the metal complexes with DNA structure were guided by the presence of inter-molecular C–H⋯O and C–H⋯N hydrogen bonds. The biological activity of the synthesized compounds were tested against the bacterial species such as Bacillus subtilis, Staphylococcus aureus, Proteus vulgaris and fungal species such as Candida albicans by the well-diffusion method.

  5. Metal effect on the supramolecular structure, photophysics, and acid-base character of trinuclear pyrazolato coinage metal complexes.

    Science.gov (United States)

    Omary, Mohammad A; Rawashdeh-Omary, Manal A; Gonser, M W Alexander; Elbjeirami, Oussama; Grimes, Tom; Cundari, Thomas R; Diyabalanage, Himashinie V K; Gamage, Chammi S Palehepitiya; Dias, H V Rasika

    2005-11-14

    Varying the coinage metal in cyclic trinuclear pyrazolate complexes is found to significantly affect the solid-state packing, photophysics, and acid-base properties. The three isoleptic compounds used in this study are [[3,5-(CF3)2Pz]M]3 with M = Cu, Ag, and Au (i.e., Cu3, Ag3, and Au3, respectively). They form isomorphous crystals and exist as trimers featuring nine-membered M3N6 rings with linear two-coordinate metal sites. On the basis of the M-N distances, the covalent radii of two-coordinate Cu(I), Ag(I), and Au(I) were estimated as 1.11, 1.34, and 1.25 angstroms, respectively. The cyclic [[3,5-(CF3)2Pz]M]3 complexes pack as infinite chains of trimers with a greater number of pairwise intertrimer M...M interactions upon proceeding to heavier coinage metals. However, the intertrimer distances are conspicuously short in Ag3 (3.204 angstroms) versus Au3 (3.885 angstroms) or Cu3 (3.813 angstroms) despite the significantly larger covalent radius of Ag(I). Remarkable luminescence properties are found for the three M3 complexes, as manifested by the appearance of multiple unstructured phosphorescence bands whose colors and lifetimes change qualitatively upon varying the coinage metal and temperature. The multiple emissions are assigned to different phosphorescent excimeric states that exhibit enhanced M...M bonding relative to the ground state. The startling luminescence thermochromic changes in crystals of each compound are related to relaxation between the different phosphorescent excimers. The trend in the lowest energy phosphorescence band follows the relative triplet energy of the three M(I) atomic ions. DFT calculations indicate that [[3,5-(R)2Pz]M]3 trimers with R = H or Me are bases with the relative basicity order Ag < Cu < Au while fluorination (R = CF3) renders even the Au trimer acidic. These predictions were substantiated experimentally by the isolation of the first acid-base adduct, [[Au3]2:toluene]infinity, in which a trinuclear Au(I) complex acts as

  6. Derivatives of phosphate Schiff base transition metal complexes: synthesis, studies and biological activity

    Science.gov (United States)

    El-Wahab, Z. H. Abd; El-Sarrag, M. R.

    2004-01-01

    We report the synthesis and structural characterization of series of tetra- and hexacoordinate metal chelate complexes of phosphate Schiff base ligands having the general composition LMX n·H 2O and L 2MX n (L=phosphate Schiff base ligand; M=Ag +, Mn 2+, Cu 2+, Zn 2+, Cd 2+, Hg 2+, or Fe 3+ and X=NO 3-, Br - or Cl -). The structure of the prepared compounds was investigated using elemental analysis, IR, 1H and 31P NMR, UV-vis, mass spectra, solid reflectance, magnetic susceptibility and conductance measurements as well as conductometric titration. In all the complexes studied, the ligands act as a chelate ligand with coordination involving the phosphateO-atom and the azomethineN-atom. IR, solid reflectance spectra and magnetic moment measurement are used to infer the structure and to illustrate the coordination capacity of ligand. IR spectra show the presence of coordinated nitrate and water molecule, the magnetic moments of all complexes show normal magnetic behavior and the electronic spectra of the metal complexes indicate a tetra- and octahedral structure for Mn 2+, octahedral structure of Fe 3+ and both square-planar and distorted octahedral structure for Cu 2+ complexes. Antimicrobial activity of the ligands and their complexes were tested using the disc diffusion method and the chosen strains include Staphylococcus aureus, Pseudomonas aereuguinosa, Klebsiella penumoniae, Escherichia coli, Microsporum canis, Trichophyton mentagrophyte and Trichophyton rubrum. Some known antibiotics are included for the sake of comparison and the chosen antibiotic are Amikacin, Doxycllin, Augmantin, Sulperazon, Unasyn, Septrin, Cefobid, Ampicillin, Nitrofurantion, Traivid and Erythromycin.

  7. Synthesis, characterization and antibacterial studies of some metal complexes of a schiff base derived from benzaldehyde and sulfonamide

    International Nuclear Information System (INIS)

    Neutral complexes of Cu(II), Ni(II), and Co(II) with a schiff base derived from benzaldehyde and sulfonamide have been synthesized and characterized the basis of on FTIR, UV-VIS, molar conductance and atomic absorption spectroscopic data. These metal complexes were also screened for their antibacterial activity against two bacterial species E.coli and Salmonella typhae. The metal complexes showed enhanced antibacterial activity as compared to uncomplexed ligand. (author)

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

    Science.gov (United States)

    Davenport, T C; Tilley, T D

    2015-07-21

    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

  9. Synthesis and Characterization of Schiff Base Metal Complexes and Reactivity Studies with Maleimide Epoxy Resin

    International Nuclear Information System (INIS)

    A novel malemide epoxy containing Co(II), Ni(II) and Cu(II) ions have been synthesized by curing malemide epoxy resin (MIEB-13) and Co(II), Ni(II) and Cu(II) complexes of macrocyclic bis-hydrazone Schiff base. The Schiff base was synthesized by reacting 1,4-dicarbnyl phenyl dihydrazide with 2,6-diformyl-4-methyl phenol. The Schiff base and its Co(II), Ni(II) and Cu(II) complexes have been characterized by elemental analyses, spectral (IR, 1H NMR, UV-vis., FAB mass, ESR), thermal and magnetic data. The curing reaction of maleimide epoxy compound with metal complexes was studied as curing agents. The stability of cured samples was studied by thermo-gravimetric analyses and which have excellent chemical (acid/alkali/solvent) and water absorption resistance. Further, the scanning electron microscopy (SEM) and definitional scanning colorimetric (DSC) techniques were confirmed the phase homogeneity of the cured systems

  10. Co (II and Zn (II Metal Complexes of Heterocyclic Schiff Bases: A Synthesis, Spectral and Antimicrobial Study

    Directory of Open Access Journals (Sweden)

    Sachin R. Joshi

    2014-09-01

    Full Text Available The Schiff bases have been synthesised by the reaction of Benzoinoxime primary ligand with heterocyclic compounds such as 2-aminothiazole (SL1 and 8-hydroxyquinoline (SL2 to form the secondary ligand, which than react with the metal halides to form complexes of Co (II and Zn (II. The elemental analysis data shows that the metal to ligand ratio in all Co (II simple is 1:2 for simple complexes and 1:2:2 for metal complex with oxime as a primary ligand and SL1 as a secondary ligand while it is 1:2:1 for metal complex with oxime as a primary ligand and SL3 as a secondary ligand whereas Zn (II complexes of mixed ligand exhibit the stoichiometry 1:2:2. The structural features have been determined from IR, UV-Vis, and XRD data. All the complex shows a distorted octahedral geometry to mononuclear Co (II complexes of mixed ligands, while square planner geometry to mononuclear Co (II complexes of oximes. Zn (II complexes of mixed ligands shows a distorted octahedral geometry, while square planner geometry to mononuclear Zn (II complexes of oximes. All the synthesised compounds were screened for antimicrobial activity.

  11. The first example of intensive luminescence of LMCT state based on metal complexes in solution

    International Nuclear Information System (INIS)

    A bridge complex rac-C6H10(IndH4)2ZrC2, featuring a unique long-living luminescence in liquid solutions at 20 deg C, has been prepared for the first time by catalytic hydrogenation of bis-indinyl complex C6H10(Ind)2Zr2Cl2. It has been identified that quantum yields of luminescence of the complex solutions at room temperature are the greatest ones for the known compounds possessing emission states of charge transfer from ligand to metal. Linear correlations of quantum yield of metal complex luminescence in a solution with steric features of the solvent molecules have been detected for the first time

  12. Ferrocene base metal chelates

    International Nuclear Information System (INIS)

    Review of the works, devoted to different types of ferrocene metal chelates and to a possibility of ferrocene-containing ligand modification by means of complexing, is presented. Structure, properties and spectral characteristics of transitional metal, rare earth element, Cd2+, UO22+, Th4+ etc. complexes with ferrocene diketones, ferrocene acyl derivatives based on thiosemicarbazones and hydrazones and other heterometal ferrocene-containing metal chelates, are considered. 134 refs., 1 tab

  13. Synthesis, spectroscopic and biological studies of transition metal complexes of novel schiff bases derived from amoxicillin and sugars

    International Nuclear Information System (INIS)

    Fe (II), Co (II) and Ni (II) metal complexes of new Schiff bases derived from amoxicillin with sugars (D-Glucose, D-Galactose and D-Mannose) have been synthesized and characterized by elemental analysis, FTIR, electronic absorption, and atomic absorption spectroscopy, magnetic moment measurements and thermal analysis. It has been found that Schiff bases behave as bi-dentate ligands forming complexes with 1:2 (metal:ligand) stoichiometry. The complexes were neutral as confirmed by their low conductance values. The biological applications of complexes have been studied on two gram negative (Escherichia coli and Pseudomonas aeruginosa) and two gram positive (Bacillus subtilis and Staphylococcus aureus) microorganisms by Agar diffusion disc method. It has been found that all the complexes have higher biological activities than the pure amoxicillin. (author)

  14. Synthesis, spectroscopic and biological studies of transition metal complexes of novel schiff bases derived from cephradine and sugars

    International Nuclear Information System (INIS)

    Fe(II), Co(II) and Ni(II) metal complexes of novel schiff bases derived from Cephradine and sugars (D-Glucose, L. Arabinose and D-Galactose) were synthesized and characterized by elemental analysis, magnetic susceptibility, thermal analysis, electronic absorption and FT-IR spectral studies. It has been found that schiff bases behave as bi-dentate-ligands forming complexes with 1:2 (metal:ligand) stoichiometry. the neutral nature of the complexes was confirmed by their low conductance values. The biological activities of complexes have been evaluated against two gram negative (Escherichia coli and Pseudomonas aeruginosa) and two gram positive (Bacillus subtilis and staphylococcus aureus) bacteria by Agar diffusion disc method. It has been found that the complexes have higher activity as compared to the pure Cephradine against the same bacteria. (author)

  15. Chitosan-based Schiff base-metal complexes (Mn, Cu, Co) as heterogeneous, new catalysts for the -isophorone oxidation

    Indian Academy of Sciences (India)

    C S Thatte; M V Rathnam; A C Pise

    2014-05-01

    A new chitosan-based Schiff base was prepared and complexed with manganese, cobalt and copper. These Schiff base metal complexes were used as heterogeneous catalysts for the air oxidation of -isophorone to ketoisophorone. The obtained complexes were characterized by means of FT-IR, 1HNMR spectroscopy, elemental analysis, powder X-ray diffraction, field emission gun scanning electron microscopy, electron spin resonance spectroscopy, ICP-AES and solubility tests. Thermal properties were also investigated using thermal gravimetric analysis. Data obtained by thermal analysis revealed that these complexes showed good thermal stability. The conversion and selectivity of -isophorone to ketoisophorone for each prepared catalyst was studied using a batch reactor and gas chromatography for product identification and quantification. The results were compared against the homogeneous bis-salicylaldehyde ethylenedi-imine-Mn catalyst. The use of methanol, acetone, methyl isobutyl ketone and -hexane as solvent and its effect on conversion and selectivity was also investigated. Acetone was found to be a promising solvent for the -isophorone oxidation. The role of triethyl amine and acetyl acetone in the oxidation reaction has also been investigated.

  16. Synthesis, Spectral Characterization, and Biological Evaluation of Transition Metal Complexes of Bidentate N, O Donor Schiff Bases

    Directory of Open Access Journals (Sweden)

    Sajjad Hussain Sumrra

    2014-01-01

    Full Text Available New series of three bidentate N, O donor type Schiff bases (L1–(L3 were prepared by using ethylene-1,2-diamine with 5-methyl furfural, 2-anisaldehyde, and 2-hydroxybenzaldehyde in an equimolar ratio. These ligands were further complexed with Co(II, Cu(II, Ni(II, and Zn(II metals to produce their new metal complexes having an octahedral geometry. These compounds were characterized on the basis of their physical, spectral, and analytical data. Elemental analysis and spectral data of the uncomplexed ligands and their metal(II complexes were found to be in good agreement with their structures, indicating high purity of all the compounds. All ligands and their metal complexes were screened for antimicrobial activity. The results of antimicrobial activity indicated that metal complexes have significantly higher activity than corresponding ligands. This higher activity might be due to chelation process which reduces the polarity of metal ion by coordinating with ligands.

  17. Synthesis and Structural Characterization of Schiff Base Ligand and their Metal Complexes

    Directory of Open Access Journals (Sweden)

    Amit Kumar Gautam

    2016-05-01

    Full Text Available In the present work, the synthesis and structural characterization of a 2-phenyl- 3(benzamido propyl quinazoline (3H -4- one semicarbazone/ thiosemicarbazone hydrochloride and its metal complexes have been reported. All the synthesized compounds were characterized by using various physico-chemical techniques such as Infrared spectra, electronic spectra, molar conductivity and magnetic susceptibility measurements. The ligand and metal ions reacted to form in the 2:1 ratio as found from the elemental analyses and general stiochiometry was determined, [M(PBPQS2X2] and [M(PBPQT2X2]; where M = Co(II, Ni(II and Cu(II; PBPQS = 2-phenyl- 3 (benzamido propyl quinazoline (3H -4- one semicarbazone and PBPQT = 2- phenyl- 3 (benzamido propyl quinazoline (3H -4- one thiosemicarbazone. On the basis of analytical data, a proposed structure for the Cu(II complexes are distorted octahedral and those for Co(II and Ni(II complexes are octahedral. Ligands PBPQS/ PBPQT have been proposed to act in a bidentate manner co-ordinating to the metal ions though azomethine nitrogen and oxygen/ sulphur atom of either semicarbazone/ thiosemicarbazone moiety. The remaining co-ordination sites are occupied by negative ions such as Cl-, Br-, I- or NO3-. The ligands and its metal complexes were tested for their possible antimicrobial potentials.

  18. Low-polarity electrolytes on the base of crown ether complexes with alkali metal ions

    International Nuclear Information System (INIS)

    New low-polar electrolytes on the basis of 15-crown-5 complexes with alkali metal (lithium, sodium) ions in solvent characterized by low dielectrical permittivity: benzene, toluene, ethylene glycol dimethyl ether, tetrahydrofuran and methylene chloride, characterized by specific electrical permittivity equal to 10-5-10-2 Ohm-1·cm-1, are suggested and studied. 15 refs., 2 figs.,

  19. Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes

    Science.gov (United States)

    Ceyhan, Gökhan; Çelik, Cumali; Uruş, Serhan; Demirtaş, İbrahim; Elmastaş, Mahfuz; Tümer, Mehmet

    2011-10-01

    In this study, two Schiff base ligands (HL 1 and HL 2) and their Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) metal complexes were synthesized and characterized by the analytical and spectroscopic methods. Alkane oxidation activities of the metal complexes were studied on cyclohexane as substrate. The ligands and their metal complexes were evaluated for their antimicrobial activity against Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus and Enterococcus faecalis (as Gram-positive bacteria) and Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica, Klebsiella fragilis, Saccharomyces cerevisiae, and Candida albicans (as Gram-negative bacteria). The antioxidant properties of the Schiff base ligands were evaluated in a series of in vitro tests: 1,1-diphenyl-2-picrylhydrazyl (DPPH rad ) free radical scavenging and reducing power activity of superoxide anion radical generated non-enzymatic systems. Electrochemical and thermal properties of the compounds were investigated.

  20. Synthesis, Spectroscopic, and Magnetic Studies of Mono- and Polynuclear Schiff Base Metal Complexes Containing Salicylidene-Cefotaxime Ligand

    Directory of Open Access Journals (Sweden)

    J. R. Anacona

    2013-01-01

    Full Text Available Metal complexes of a Schiff base ligand derived from cefotaxime and salicylaldehyde were prepared. The salicilydene-cefotaxime ligand (H2L and mononuclear [M(L] (M(II = Co, Ni and Cu, dinuclear [Ag2(L(OAc2], and tetranuclear metal complexes [M4(L(OH6] (M(II = Ni, Cu were characterized on the basis of analytical, thermal, magnetic, and spectral studies (IR, UV-visible, 1H NMR, 13C NMR, and EPR. The electronic spectra of the complexes and their magnetic moments suggesttetrahedral geometry for the isolated complexes. The complexes are nonelectrolytes and insoluble in water and common organic solvents but soluble in DMSO.

  1. Structural and Spectroscopic Aspects of Schiff Base Metal Complexes of Cobalt(II, Nickel(II and Copper(II

    Directory of Open Access Journals (Sweden)

    B.K. Rai

    2014-09-01

    Full Text Available The complexes of Co(II, Ni(II and Cu(II with Schiff base 2-butyl thioquinazoline 4(3H thiosemicarbazone were synthesized. The general formulae of the complexes are of the type {M(L2X2], L=2 – butyl thioquinazoline 4(3H thiosemicarbazone; x = Cl-, Br-, I- and NO3-. Elemental analyses and spectral (IR, electronic studies of the synthesized complexes suggest the presence of octahedral, environment around the central metal ion. These complexes were also subjected to study their antimicrobial screening against, Gram positive bacteria Candida albicans and gram negative bacteria Escherichia coli by disc diffusion technique.

  2. Hexaniobate as nanoscale catalyst support for copper oxidase mimics based on metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Bizeto, Marcos Augusto [Universidade Federal de Sao Paulo (UNIFESP), Diadema, SP (Brazil); Alves, Wendel Andrade [Universidade Federal do ABC, SP (Brazil); Barbosa, Cesar Augusto Sales [Universidade Estadual de Campinas (UNICAMP), Campinas, SP (Brazil). Bunge Fertilizantes; Ferreira, Ana Maria da Costa; Constantino, Vera Regina Leopoldo [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica

    2006-07-01

    Inorganic materials such as nanoporous zeolitic systems and layered structures have been considered special containers for chemical reactions, in which catalytically active species can show an energetic and/or spatial configuration that favors reactions of low activation energy. In this work, hexaniobate nanoscrolls were evaluated as a support for a metal complex that mimics copper oxidase enzymes. The cationic metal complex, 2-[2-(2-pyridyl)ethylimino-1-ethyl]pyridine-imidazole copper(II), [Cu(apip)imH]{sup 2}, was immobilized into hexaniobate scrolls by an ion exchange reaction. Chemical analysis, electronic and vibrational spectroscopies, thermogravimetric analysis and electron paramagnetic resonance (EPR) techniques were used to characterize the hexaniobatecopper complex system. High-resolution transmission electron microscopy of isolated hexaniobate particles containing the cationic complex showed the presence of scrolls with a wall thickness of about 4.5-7.0 nm and an external diameter of about 25-30 nm. X ray diffraction patterns confirmed the presence of the copper complex in the interlayer spaces of hexaniobate nanoscrolls. The reactivity of the copper complex supported on hexaniobate nanoscrolls was investigated for catechol oxidation in the presence of hydrogen peroxide. The formation of hydroxyl radicals (-OH) during the reaction was suggested by EPR data, which were obtained by monitoring the kinetics of DMPO/-OH adduct formation (DMPO is 5,5' dimethyl-1-pyrroline-N-oxide, used as spin trap). (author)

  3. Synthesis and antioxidant activities of transition metal complexes based 3-hydroxysalicylaldehyde-S-methylthiosemicarbazone.

    Science.gov (United States)

    Bal-Demirci, Tülay; Şahin, Musa; Kondakçı, Esin; Özyürek, Mustafa; Ülküseven, Bahri; Apak, Reşat

    2015-03-01

    The nickel(II), iron(III), oxovanadium(IV) complexes of the 3-hydroxysalicylidene-S-methyl-thiosemicarbazone (L) were obtained from the 3-hydroxysalicyldehyde-S-methylthiosemicarbazone with the R1-substituted-salicylaldehyde (R1: H, 3-OH) in the presence of Ni(II), Fe(III), VO(IV) as template ion. The ligand and its complexes were characterized by elemental analysis, electronic, UV/Vis., (1)HNMR, EPR and IR studies. The free ligand and its metal complexes have been tested for in vitro antioxidant capacity by reduction of copper(II) neocuproine (Cu(II)-Nc) using the CUPRAC method. The ligand exhibited more potent in vitro antioxidant capacity than its complexes. The obtained trolox equivalent antioxidant capacity (TEAC) value of the iron(III) complex (TEACCUPRAC=3.27) was higher than those of other complexes. Furthermore, the antioxidant activity of the free ligand and its complexes were determined by in vitro methods measuring the scavenging activity of reactive oxygen species (ROS) including hydroxyl radical (OH), superoxide anion radical (O2(-)), and hydrogen peroxide (H2O2), showing that especially the V(IV) and Fe(III) complexes had significant scavenging activity for ROS. PMID:25467658

  4. Synthesis and antioxidant activities of transition metal complexes based 3-hydroxysalicylaldehyde-S-methylthiosemicarbazone

    Science.gov (United States)

    Bal-Demirci, Tülay; Şahin, Musa; Kondakçı, Esin; Özyürek, Mustafa; Ülküseven, Bahri; Apak, Reşat

    2015-03-01

    The nickel(II), iron(III), oxovanadium(IV) complexes of the 3-hydroxysalicylidene-S-methyl-thiosemicarbazone (L) were obtained from the 3-hydroxysalicyldehyde-S-methylthiosemicarbazone with the R1-substituted-salicylaldehyde (R1: H, 3-OH) in the presence of Ni(II), Fe(III), VO(IV) as template ion. The ligand and its complexes were characterized by elemental analysis, electronic, UV/Vis., 1H NMR, EPR and IR studies. The free ligand and its metal complexes have been tested for in vitro antioxidant capacity by reduction of copper(II) neocuproine (Cu(II)-Nc) using the CUPRAC method. The ligand exhibited more potent in vitro antioxidant capacity than its complexes. The obtained trolox equivalent antioxidant capacity (TEAC) value of the iron(III) complex (TEACCUPRAC = 3.27) was higher than those of other complexes. Furthermore, the antioxidant activity of the free ligand and its complexes were determined by in vitro methods measuring the scavenging activity of reactive oxygen species (ROS) including hydroxyl radical (radOH), superoxide anion radical (O2rad -), and hydrogen peroxide (H2O2), showing that especially the V(IV) and Fe(III) complexes had significant scavenging activity for ROS.

  5. Electrochemical analysis of metal complexes.

    OpenAIRE

    Jong, de, J.

    1987-01-01

    The present study is concerned with the electroanalytical chemistry of complexes of metals with large ligands. The main purpose was to develop quantitative descriptions of the voltammetric current-potential relation of metal complex systems with different diffusion coefficients of the species involved and of the conductometric response of metal/polyelectrolyte systems at various metal-to-ligand ratios. A further goal was to illustrate the theoretical treatments with some experiments on model ...

  6. Synthesis, characterization and thermal study of some transition metal complexes of an asymmetrical tetradentate Schiff base ligand

    Directory of Open Access Journals (Sweden)

    ACHUT S. MUNDE

    2010-03-01

    Full Text Available Complexes of Cu(II, Ni(II, Co(II, Mn(II and Fe(III with an asymmetric tetradentate Schiff base ligand derived from dehydroacetic acid, 4-methyl-o-phenylenediamine and salicylic aldehyde were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV–Vis, IR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a dibasic tetadentate ligand towards the central metal ion with an ONNO donor atoms sequence. From the microanalytical data, the stoichiometry of the complexes 1:1 (metal:ligand was found. The physico-chemical data suggested square planar geometry for the Cu(II and Ni(II complexes and octahedral geometry for the Co(II, Mn(II and Fe(III complexes. The thermal behaviour (TGA/DTA of the complexes was studied and kinetic parameters were determined by Horowitz–Metzger and Coats–Redfern methods. The powder X-ray diffraction data suggested a monoclinic crystal system for the Co(II, Mn(II and Fe(III complexes. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma viride.

  7. Control of Metal Arrays Based on Heterometallics Masquerading in Heterochiral Aggregations of Chiral Clothespin-Shaped Complexes.

    Science.gov (United States)

    Naito, Masaya; Inoue, Ryo; Iida, Masayuki; Kuwajima, Yuuki; Kawamorita, Soichiro; Komiya, Naruyoshi; Naota, Takeshi

    2015-09-01

    Heterometal arrays in molecular aggregations were obtained by the spontaneous and ultrasound-induced gelation of organic liquids containing the chiral, clothespin-shaped trans-bis(salicylaldiminato) d8 transition-metal complexes 1. Heterometallic mixtures of complexes 1 a (Pd) and 1 b (Pt) underwent strict heterochiral aggregation entirely due to the organic shell structure of the clothespin shape, with no effect of the metal cores. This phenomenon provides an unprecedented means of generating highly controlled heterometallic arrangements such as alternating sequences [(+)-Pd(-)-Pt(+)-Pd(-)-Pt⋅⋅⋅] as well as a variety of single metal-enriched arrays (e.g., [(+)-Pt(-)-Pd(+)-Pd(-)-Pd(+)-Pd(-)-Pd⋅⋅⋅] and [(+)-Pd(-)-Pt(+)-Pt(-)-Pt(+)-Pt(-)-Pt⋅⋅⋅]) upon the introduction of an optically active masquerading unit with a different metal core in the heterochiral single-metal sequence. The present method can be applied to form various new aggregates with optically active Pd and Pt units, to allow 1) tuning of the gelation ultrasound sensitivity based on the different hearing abilities of the metal units; 2) aggregation-induced chirality transfer between heterometallic species; and 3) aggregation-induced chirality enhancement. A mechanistic rationale is proposed for these molecular aggregations based on the molecular structures of the units and the morphologies of the aggregates. PMID:26212577

  8. Dioxygen Affinities and Biomimetic Catalytic Performance of Transition-metal Complexes with Crowned Bis-Schiff Bases

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The dioxygen affinities and biomimetic catalytic performance of transition-metal complexes with (15-crown-5) salophen and its substituted derivatives were examined. The oxygenation constants of Co(II) complexes with crowned bis-Schiff bases were measured and their Mn(III) complexes were employed as models to mimic monooxygenase in catalytic epoxidation of styrene. The highest conversion and selectivity were up to 57.2% and 100% respectively at ambient temperature and pressure. The effects of crown ether ring and substituents R on the dioxygen affinities and catalytic activities were also investigated through comparing with the uncrowned analogues.

  9. Two polymeric metal complexes based on polycarbazole containing complexes of 8-hydroxyquinoline with Zn(II) and Ni(II) in the backbone: Synthesis, characterization and photovoltaic applications

    International Nuclear Information System (INIS)

    Highlights: ► We have synthesized two photosensitizers of D–π–A polymeric metal complexes. ► The polymeric metal complexes possess excellent thermal stability and good open-circuit voltages. ► The application of the photosensitizers in dye-sensitized solar cells was investigated. ► The polymeric metal complex containing d10 Zn(II) exhibited better device performance than that containing low spin d8 Ni(II). - Abstract: Two novel polymeric metal complexes PZn(Q)2–C and PNi(Q)2–C based on polycarbazole containing complexes of 8-hydroxyquinoline with Zn(II) and Ni(II) were synthesized and applied in dye-sensitized solar cells (DSSCs) as photosensitizers. They possess moderate thermal stability and good open-circuit voltages, and the power conversion efficiency of them reached to 1.11% and 0.45%, respectively, under simulated AM 1.5 G solar irradiation (100 mW cm−2), which shows a new strategy to design photosensitizers for DSSCs.

  10. Two polymeric metal complexes based on polycarbazole containing complexes of 8-hydroxyquinoline with Zn(II) and Ni(II) in the backbone: Synthesis, characterization and photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Deng Jinyan; Guo Lihui; Xiu Qian; Zhang Lirong; Wen Gaojun [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, College of Chemistry, Xiangtan, Hunan 411105 (China); Zhong Chaofan, E-mail: zhongcf798@yahoo.com.cn [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, College of Chemistry, Xiangtan, Hunan 411105 (China)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer We have synthesized two photosensitizers of D-{pi}-A polymeric metal complexes. Black-Right-Pointing-Pointer The polymeric metal complexes possess excellent thermal stability and good open-circuit voltages. Black-Right-Pointing-Pointer The application of the photosensitizers in dye-sensitized solar cells was investigated. Black-Right-Pointing-Pointer The polymeric metal complex containing d{sup 10} Zn(II) exhibited better device performance than that containing low spin d{sup 8} Ni(II). - Abstract: Two novel polymeric metal complexes PZn(Q){sub 2}-C and PNi(Q){sub 2}-C based on polycarbazole containing complexes of 8-hydroxyquinoline with Zn(II) and Ni(II) were synthesized and applied in dye-sensitized solar cells (DSSCs) as photosensitizers. They possess moderate thermal stability and good open-circuit voltages, and the power conversion efficiency of them reached to 1.11% and 0.45%, respectively, under simulated AM 1.5 G solar irradiation (100 mW cm{sup -2}), which shows a new strategy to design photosensitizers for DSSCs.

  11. A fluorescent, photochromic and thermochromic trifunctional material based on a layered metal-viologen complex.

    Science.gov (United States)

    Wan, Fang; Qiu, Li-Xia; Zhou, Liang-Liang; Sun, Yan-Qiong; You, Yi

    2015-11-14

    The azide anion as an energy acceptor and an electron donor has been introduced into a metal-viologen compound to form a 2D layered viologen-based trifunctional material, which exhibits the rare discolored function of reversible photochromism and thermochromism. Interestingly, its fluorescence can be switched by visible light irradiation and heating in air. PMID:26445888

  12. Studies on some metal complexes of quinoxaline based unsymmetric ligand: Synthesis, spectral characterization, in vitro biological and molecular modeling studies.

    Science.gov (United States)

    Dhanaraj, Chellaian Justin; Johnson, Jijo

    2016-08-01

    Mononuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes of an unsymmetric Schiff base ligand, 3-(-(3-(-3,5-dichloro-2-hydroxybenzylideneamino)propylimino)methyl)quinoxalin-2(1H) -one (L) were synthesized and characterized by various analytical and spectral techniques. The molar conductance values of metal complexes indicate non-electrolytic behavior of the metal complexes. The Schiff base act as tetra dentate ONNO donor ligand in Co(II), Ni(II), Zn(II) complexes and tridentate NNO donor in Cu(II) complex. Thermal stabilities of the newly synthesized compounds were determined by thermal analysis. Crystallinity, average grain size and unit cell parameters were determined from powder X-ray diffraction study. Electrochemical behaviors of the compounds were examined by cyclic voltammetry technique. The Schiff base and its complexes have been screened for their in vitro antimicrobial activities against some bacterial and fungal strains by disc diffusion method. The interaction of the compounds with calf thymus DNA (CT DNA) has been investigated by electronic absorption spectral titration and viscosity measurement (hydrodynamic) methods. Furthermore, the pUC18 DNA cleavage activities of the complexes have been explored. The compounds were also subjected to in vitro antioxidant, anticancer activity screening, druglikeness and bioactivity predictions using Molinspiration software. Molecular docking studies of the present compounds were carried out against B-DNA dodecamer d(CGCGAATTCGCG)2 and vascular endothelial growth factor receptor (VEGFR-2) kinase. Quantum chemical calculations were done with DFT method to determine the optimum geometry of the ligand and its metal complexes. From the quantum chemical parameters, the reactivity parameters of the compounds were established. PMID:27236046

  13. Synthesis, Structure and Characterization of New Metal Complexes of Schiff Bases Derived from Isatin N-Benzylisatin and 4-Aminoantipyrine

    Directory of Open Access Journals (Sweden)

    *A. J. Abdulghani

    2011-09-01

    Full Text Available The two Schiff bases (z-3-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylimino indolin-2-one (LIH, and (z-1-benzyl-3-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-yliminoindolin-2-one (LII have been prepared by condensation reaction of isatin and 1-benzyl isatin with 4-aminoantipyrine in dioxane and their structures were characterized by CHN analysis, NMR, IR and mass spectroscopy. A new Hg-metallated biSchiff base ((E-3-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylimino-2-oxoindolin-1-yl((E-3-(2-methyl-5-oxo-1-phenyl-2,5-dihydro-1H-pyrazol-3-ylimino-2-oxoindolin-1-ylmercury (Hg(LI2 was synthesized by condensation reaction of bis(2,3-dioxoindolin-1-yl mercury(II (Hg(isatin2 with 4-aminoantipyrine(4-AAP. Reaction of LIH with Pt(II and Cu(II complexes in basic medium led to binding of the metal ions at N-1 atom of isatin ring while reaction of LIH and LII with metal salts in neutral medium resulted in the formation of metal complexes where the metal ion is coordinated to carbonyl and azomethine groups of the two ligands. The metal complexes were characterized and their structures were suggested depending on CHNM and thermal analysis, FTIR and electronic spectra, magnetic susceptibility as well as conductivity measurements. The structures of the Ni(II, Pt(II and Hg(II complexes were further supported by NMR spectroscopy.

  14. Metallic complexes with glyphosate: a review

    International Nuclear Information System (INIS)

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  15. Complex formation in the system double charged metal cation-Stenhouse base in water-alcohol solution

    International Nuclear Information System (INIS)

    Using the method of potentiometric titration complex formation reaction of the system metal(II) salt cation (Me2+ = Fe2+, Cd2+, Hg2+, Zn2+, Mn2+, Co2+, Ni2+) Stenhouse base in water-alcohol solution has been studied. Compositions of equilibrium complexes, the constants of their formation and instability have been determined. CoCl2 x 6H2O, NiCl2 x 6H2O and Mn(NO3)2 x 6H2O have been shown to have the most stabilizing effect on Stenhouse base

  16. Electrochemical analysis of metal complexes.

    NARCIS (Netherlands)

    Jong, de H.G.

    1987-01-01

    The present study is concerned with the electroanalytical chemistry of complexes of metals with large ligands. The main purpose was to develop quantitative descriptions of the voltammetric current-potential relation of metal complex systems with different diffusion coefficients of the species involv

  17. A new Mannich base and its transition metal (II) complexes - Synthesis, structural characterization and electrochemical study

    Indian Academy of Sciences (India)

    N Raman; S Esthar; C Thangaraja

    2004-06-01

    new Mannich base, N-(1-morpholinobenzyl) semicarbazide (MBS), formed by the condensation of morpholine, semicarbazide and benzaldehyde, and its Cu(II), Ni(II), Co(II) and Zn(II) complexes have been synthesized. Their structures have been elucidated on the basis of analytical, magnetic, electrical conductivity and spectral study as well as elemental analyses. The complexes exhibit square-planar geometry. The monomeric and non-electrolytic nature of the complexes is evidenced by their magnetic susceptibility and low conductance data. The electrochemical property of the ligand and its complexes in acetonitrile solution was studied by cyclic voltammetry. The X-band ESR spectra of the Cu(II) complex in DMSO at 300 and 77 K were recorded and their salient features are reported.

  18. Spectroscopic and electrochemical characterization of some Schiff base metal complexes containing benzoin moiety

    Science.gov (United States)

    El-Shahawi, M. S.; Al-Jahdali, M. S.; Bashammakh, A. S.; Al-Sibaai, A. A.; Nassef, H. M.

    2013-09-01

    The ligation behavior of bis-benzoin ethylenediamine (B2ED) and benzoin thiosemicarbazone (BTS) Schiff bases towards Ru3+, Rh3+, Pd2+, Ni2+ and Cu2+ were determined. The bond length of M-N and spectrochemical parameters (10Dq, β, B and LFSE) of the complexes were evaluated. The redox characteristics of selected complexes were explored by cyclic voltammetry (CV) at Pt working electrode in non aqueous solvents. Au mesh (100 w/in.) optically transparent thin layer electrode (OTTLE) was also used for recording thin layer CV for selected Ru complex. Oxidation of some complexes occurs in a consecutive chemical reaction of an EC type mechanism. The characteristics of electron transfer process of the couples M2+/M3+ and M3+/M4+ (M = Ru3+, Rh3+) and the stability of the complexes towards oxidation and/or reduction were assigned. The nature of the electroactive species and reduction mechanism of selected electrode couples were assigned.

  19. Mixed ligand transition metal complexes of tridentate schiff base with thiocyanate

    International Nuclear Information System (INIS)

    A tridentate Schiff base C/sub 13/H/sub 20/N/sub 2/O having ONN donor sequence has been synthesised from the condensation of 1.6-diaminohexane with salicylaldehyde. Several new thiocyanato complexes of Cu (II), Pd (II), Pd (II), Pd, (II), Ti (III) and V(IV) containing the above ligand have been synthesised and characterized by elemental analyses, conductivity, magnetic measurements, IR and NMR spectra and electronic spectroscopic studies. Magnetic and spectral data support the octahedral geometries for Ti (III) and V(IV) complexes, whereas Cu(II) and Pd(II) complexes are square-planar in nature. (author)

  20. A control on hydrophobic and hydrophilic interactions between HEWL and metal Schiff-base complexes comprising of different metal ions and ligands

    International Nuclear Information System (INIS)

    The structural effects of different copper(II) and nickel(II) Schiff base complexes on hen egg white lysozyme (HEWL) have been investigated through steady state and time resolved absorption and fluorescence, and circular dichroism spectroscopy. The Schiff base ligands with N4 donor atoms show both hydrophobic and hydrophilic interactions, however hydrophilic interaction prevails with ligands having N2O2 donor atoms. Variation of metal ions from Cu2+ to Ni2+ with each type of Schiff base ligand increases the probability of hydrophilic over hydrophobic interactions, which supports their significance in regulating the binding affinity between HEWL and metal complexes. On photo-excitation the complexes comprising of Cu2+ ion instead of Ni2+ ion and ligands with N4 donor system rather than N2O2 donor system, increases the probability of intersystem crossing to populate the corresponding triplet state as observed from laser flash photolysis study. The better binding affinity of nickel complexes with different selectivities compared to copper complexes towards HEWL emphasizes the potentiality of less explored nickel complexes in drug–protein interactions. - Highlights: • NiII and CuII -Schiff base complexes bind hen egg white lysozyme spontaneously. • Both hydrophobic and hydrophilic interactions are effective for N4 ligands. • For N2O2 ligands the hydrophilic is predominant over hydrophobic interaction. • Binding affinity and selectivity of NiII-complexes are better than CuII-complexes. • Replacement of Cu2+ by Ni2+ in a ligand enhances chance of hydrophilic interaction

  1. A control on hydrophobic and hydrophilic interactions between HEWL and metal Schiff-base complexes comprising of different metal ions and ligands

    Energy Technology Data Exchange (ETDEWEB)

    Koley Seth, Banabithi; Ray, Aurkie; Basu, Samita, E-mail: samita.basu@saha.ac.in

    2015-05-15

    The structural effects of different copper(II) and nickel(II) Schiff base complexes on hen egg white lysozyme (HEWL) have been investigated through steady state and time resolved absorption and fluorescence, and circular dichroism spectroscopy. The Schiff base ligands with N{sub 4} donor atoms show both hydrophobic and hydrophilic interactions, however hydrophilic interaction prevails with ligands having N{sub 2}O{sub 2} donor atoms. Variation of metal ions from Cu{sup 2+} to Ni{sup 2+} with each type of Schiff base ligand increases the probability of hydrophilic over hydrophobic interactions, which supports their significance in regulating the binding affinity between HEWL and metal complexes. On photo-excitation the complexes comprising of Cu{sup 2+} ion instead of Ni{sup 2+} ion and ligands with N{sub 4} donor system rather than N{sub 2}O{sub 2} donor system, increases the probability of intersystem crossing to populate the corresponding triplet state as observed from laser flash photolysis study. The better binding affinity of nickel complexes with different selectivities compared to copper complexes towards HEWL emphasizes the potentiality of less explored nickel complexes in drug–protein interactions. - Highlights: • Ni{sup II} and Cu{sup II} -Schiff base complexes bind hen egg white lysozyme spontaneously. • Both hydrophobic and hydrophilic interactions are effective for N{sub 4} ligands. • For N{sub 2}O{sub 2} ligands the hydrophilic is predominant over hydrophobic interaction. • Binding affinity and selectivity of Ni{sup II}-complexes are better than Cu{sup II}-complexes. • Replacement of Cu{sup 2+} by Ni{sup 2+} in a ligand enhances chance of hydrophilic interaction.

  2. Synthesis, physical characterization and antimicrobial activity of trivalent metal Schiff base complexes

    Directory of Open Access Journals (Sweden)

    AMIT KUMAR

    2010-05-01

    Full Text Available M(III complexes of Cr, Mn and Fe with a Schiff base derived from 2-amino-4-ethyl-5-hydroxybenzaldehyde and thiocarbohydrazide were synthesized and characterized by several techniques, including elemental analysis (C,H,N, molar conductance measurements, magnetic measurements, and electronic, mass and IR spectral studies. Based on these studies, a five-coordinated square pyramidal geometry for all the complexes was proposed. The Schiff base ligand and the complexes were also tested for their antimicrobial activity (against the bacteria Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Bacillus megaterium, and the fungi Kluyveromyces fragilis, Rhodotorula rubra, Candida albicans and Trichoderma reesei to assess their inhibiting potential. An attempt was also made to correlate the antimicrobial activity with the geometry of the complexes. All complexes were found to be less active against the pathogens E. coli, S. aureus and P. aeruginosa. The Cr(III complex showed the best antimicrobial activity, but the ligand alone was found to be active against the fungus T. reesei.

  3. Metal complexes of triazine - Schiff bases: Spectroscopic and thermodynamic studies of complexation of some divalent metal ions with 3-(a-acetylethylidenehydrazino-5,6-diphenyl-1,2,4-triazine

    Directory of Open Access Journals (Sweden)

    A. TAHA

    1999-10-01

    Full Text Available Metal complexes of some divalent metal ions (Co, Ni, Cu and Zn with 3-(a-acetylethylidenehydrazino-5,6-diphenyl-1,2,4-triazine (AHDT as a Schiff-base have been investigated potentiometrically and spectrophotometrically and found to have the stoichiometric formulae 1:1 and 1:2 (M:L. The formation constants of the proton-ligand and metal-ligand complexes have been determined potentiometrically at different temperatures (10, 20, 30, 40 and 50°C at an ionic strength of 0.1 M KNO3 in 75% (v/v dioxane-water solution. The standard thermodynamic parameters, viz. DG°, DH°, and DS°, for the proton-ligand and the stepwise metal-ligand complexes have been evaluated.

  4. Synthesis, characterization and antibacterial activity of a tridentate Schiff base derived from cephalothin and sulfadiazine, and its transition metal complexes

    Science.gov (United States)

    Anacona, J. R.; Noriega, Natiana; Camus, Juan

    2015-02-01

    Metal(II) coordination compounds of a cephalothin Schiff base (H2L) derived from the condensation of cephalothin antibiotic with sulfadiazine were synthesized. The Schiff base ligand, mononuclear [ML(H2O)3] (M(II) = Mn, Co, Ni, Zn) complexes and magnetically diluted dinuclear copper(II) complex [CuL(H2O)3]2 were characterized by several techniques, including elemental and thermal analysis, molar conductance and magnetic susceptibility measurements, electronic, FT-IR, EPR and 1H NMR spectral studies. The cephalothin Schiff base ligand H2L behaves as a dianionic tridentate NOO chelating agent. The biological applications of complexes have been studied on two bacteria strains (Escherichia coli and Staphylococcus aureus) by agar diffusion disc method.

  5. Preparation, spectral and biological investigation of formaldehyde-based ligand containing piperazine moiety and its various polymer metal complexes

    Science.gov (United States)

    Khan, Shamim Ahmad; Nishat, Nahid; Parveen, Shadma; Rasool, Raza

    2011-10-01

    A novel tetradentate salicylic acid-formaldehyde ligand containing piperazine moiety (SFP) was synthesized by condensation of salicylic acid, formaldehyde and piperazine in presence of base catalyst, which was subjected for the preparation of coordination polymers with metal ions like manganese(II), cobalt(II), copper(II), nickel(II) and zinc(II). All the synthesized polymeric compounds were characterized by elemental analysis, IR, 1H NMR and electronic spectral studies. The thermal stability was determined by thermogravimetric analysis and thermal data revealed that all the polymer metal complexes show good thermal stability than their parent ligand. Electronic spectral data and magnetic moment values revealed that polymer metal complexes of Mn(II), Co(II) and Ni(II) show an octahedral geometry while Cu(II) and Zn(II) show distorted octahedral and tetrahedral geometry respectively. The antimicrobial screening of the ligand and coordination polymers was done by using Agar well diffusion method against various bacteria and fungi. It was evident from the data that antibacterial and antifungal activity increased on chelation and all the polymer metal complexes show excellent antimicrobial activity than their parent ligand.

  6. Metal complexes of Schiff base derived from sulphametrole and o-vanilin . Synthesis, spectral, thermal characterization and biological activity

    Science.gov (United States)

    Mohamed, Gehad G.; Sharaby, Carmen M.

    2007-04-01

    Metal complexes of Schiff base derived from condensation of o-vanilin (3-methoxysalicylaldehyde) and sulfametrole [ N1-(4-methoxy-1,2,5-thiadiazole-3-yl)sulfanilamide] (H 2L) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, mass spectra, UV-vis and thermal analysis (TGA). From the elemental analyses data, the complexes were proposed to have the general formulae [M 2X 3(HL)(H 2O) 5]· yH 2O (where M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), X = Cl, y = 0-3); [Fe 2Cl 5(HL)(H 2O) 3]·2H 2O; [(FeSO 4) 2(H 2L)(H 2O) 4] and [(UO 2) 2(NO 3) 3(HL)(H 2O)]·2H 2O. The molar conductance data reveal that all the metal chelates were non-electrolytes. The IR spectra show that, H 2L is coordinated to the metal ions in a tetradentate manner with ON and NO donor sites of the azomethine-N, phenolic-OH, enolic sulphonamide-OH and thiadiazole-N. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, Δ H*, Δ S* and Δ G* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligand, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Salmonella typhi, Bacillus subtillus, Staphylococcus aureus and Fungi ( Aspergillus terreus and Aspergillus flavus). The activity data show that the metal complexes to be more potent/antimicrobial than the parent Shciff base ligand against one or more microbial species.

  7. Spectral characterization, electrochemical and anticancer studies on some metal(II) complexes containing tridentate quinoxaline Schiff base

    Science.gov (United States)

    Chellaian, Justin Dhanaraj; Johnson, Jijo

    2014-06-01

    Co(II), Ni(II), Cu(II) and Zn(II) complexes of a tridentate ONO donor Schiff base ligand derived from 3-(2-aminoethylamino)quinoxalin-2(1H)-one were synthesized. The ligand and its metal complexes were characterized using elemental analysis, molar conductance, IR, 1H NMR, mass, magnetic susceptibility, electronic spectra and ESR spectral studies. Electrochemical behavior of the synthesized compounds was studied using cyclic voltammetry. The grain size of the synthesized compounds was determined by powder XRD. The Schiff base and its complexes have been screened for their antimicrobial activities against the bacterial species E. coli, K. pneumoniae, P. aeruginosa and S. aureus; fungal species include, A. niger, and C. albicans by disc diffusion method. The results show that the complexes have higher activity than the free ligand. The interaction of the complexes with calf thymus DNA (CT DNA) has been investigated by electronic absorption method. Furthermore, the DNA cleavage activity of the complexes was studied using agarose gel electrophoresis. In vitro anticancer studies of the ligand and its complexes using MTT assay was also done.

  8. Discovery of Antischistosomal Drug Leads Based on Tetraazamacrocyclic Derivatives and Their Metal Complexes.

    Science.gov (United States)

    Khan, M O Faruk; Keiser, Jennifer; Amoyaw, P N A; Hossain, Mohammad F; Vargas, Mireille; Le, Justin G; Simpson, Natalie C; Roewe, Kimberly D; Freeman, TaRynn N Carder; Hasley, Travis R; Maples, Randall D; Archibald, Stephen J; Hubin, Timothy J

    2016-09-01

    Praziquantel (PZQ) is the only drug available for the treatment of schistosomiasis, and since its large-scale use might be associated with the onset of resistance, new antischistosomal drugs should be developed. A series of 26 synthetic tetraazamacrocyclic derivatives and their metal complexes were synthesized, characterized, and screened for antischistosomal activity by application of a phased screening program. The compounds were first screened against newly transformed schistosomula (NTS) of harvested Schistosoma mansoni cercariae, then against adult worms, and finally, in vivo using the mouse model of S. mansoni infection. At a concentration of 33 μM, incubation with a total of 12 compounds resulted in the mortality of NTS at the 62% to 100% level. Five of these showing 100% inhibition of viability of NTS at 10 μM were selected for further screening for determination of the 50 inhibitory concentrations (IC50s) against both NTS and adult worms. Against NTS, all 5 compounds showed IC50s comparable to the IC50 of the standard drug, PZQ (0.87 to 9.65 μM for the 5 compounds versus 2.20 μM for PZQ). Three of these, which are the bisquinoline derivative of cyclen and its Fe(2+) and Mn(2+) complexes, showed micromolar IC50s (1.62 μM, 1.34 μM, and 4.12 μM, respectively, versus 0.10 μM for PZQ) against adult worms. In vivo, the worm burden reductions were 12.3%, 88.4%, and 74.5%, respectively, at a single oral dose of 400 mg/kg of body weight. The Fe(2+) complex exhibited activity in vivo comparable to that of PZQ, pointing to the discovery of a novel drug lead for schistosomiasis. PMID:27324765

  9. Electro-oxidation of methanol on mixed catalysts based on platinum and organic metal complexes in acidic media

    International Nuclear Information System (INIS)

    New electro-catalysts were developed based on platinum and organic metal complexes for methanol oxidation reaction (MOR) in acidic media. As complexes nitrogen containing ligands such as N,N'-bis(salicylidene)ethylenediamine (salen), N,N'-bis(salicylidene)phenylenediamine (salophen), N,N'-mono-8-quinolyl-o-phenylenediamine (mqph) and N,N'-bis(anthranilidene)ethylenediamine (anthen), coordinated to V, Mn, Fe, Co, Ni, Cu, Mo, Pd and Sn were synthesized and tested. Mixture of platinum tetraammine complex with one of the organic metal complexes with 50/50 mixing ratio was supported on carbon powder, and heat-treated at 400-700 deg. C in argon atmosphere. Powder, thus obtained was put on a glassy carbon disk electrode, and tested for electrochemical MOR in sulfuric acid solutions. Among catalysts tested, Fe(salen), VO(salen), Ni(mqph) or Pd(mqph) turned out to be good co-catalysts mixed with Pt for MOR. Compared with platinum-ruthenium alloy catalysts, the new catalysts showed very promising catalytic ability. It is inferred that after the heat treatment, the organic complex catalyst played a role in mitigating CO poisoning on Pt surface

  10. Studies on coordination chemistry and bioactivity of complexes of a tridentate ONS Schiff base with some heavier transition metal ions

    International Nuclear Information System (INIS)

    A tridentate Schiff base, S-benzyl-β-N-(2-hydroxyphenyl)methylenedithiocarbazate, (HONSH), with a donor sequence of ONS, was synthesized from the condensation of S-benzyldithiocarbazate (SBDTC) with an equimolar amount of 2-hydroxybenzaldehyde in absolute ethanol. The reactions of HONSH with metal ions [La(III), Ce(IV) and Th(IV)] yielded complexes of compositions, [La(ONS)NO3.2H2O], [Ce(ONS)(NO3)2] and [Th(ONS)2]. The ligands and the complexes were characterized from elemental analyses and spectroscopic measurements. The metal complexes were found to be active against colon cancer cell lines with the CD50 values of 27.5, 28.4 and 19.3 μg/ml for the La(III), Ce(FV) and Th(IV) complexes, respectively. The La(IH) complex was found to be very active against leukemic cell lines with the CD50 value of 6.8 μg/ml. (author)

  11. Complex metal hydrides

    DEFF Research Database (Denmark)

    Ley, Morten Brix

    2014-01-01

    og batterier de to mest lovende energibærere til mobile applikationer. Komplekse metalhydrider er blevet undersøgt i vid udstrækning over de sidste tyve år, siden de gravimetrisk og volumetrisk kan indeholde store mængder brint. Derfor er metal borhydrider velegnet til faststofopbevaring af brint...

  12. Synthesis of fatty monoester lubricant base oil catalyzed by Fe-Zn double-metal cyanide complex

    Indian Academy of Sciences (India)

    Ravindra K Raut; Mehejabeen Shaikh; Srinivas Darbha

    2014-07-01

    Fatty monoester lubricant base oils as high as 96.7 mol% were prepared by reacting methyl oleate with long-chain alcohols viz., 2-ethyl-1-hexanol (C8−OH), 1-decanol (C10OH) and 1-dodecanol (C12OH) in the presence of a solid Fe-Zn double-metal cyanide (DMC) complex catalyst. Unlike many other acid catalysts, DMC doesn't produce undesired ether side products. The catalyst was reusable in four recycling experiments with little loss in catalytic activity and ester yield. The long-chain esters prepared in the study have the desired physical properties for their application as lubricant base oils.

  13. Synthesis, Structure and Characterization of Schiff Base Metal Complexes and Their Electrochemical Properties of Thionyl Chloride Reduction

    Institute of Scientific and Technical Information of China (English)

    CHE,Tu-Lin; GAO,Quan-Chang; ZHAO,Jian-She; ZHANG,Gai

    2008-01-01

    A symmetric tetradentate Schiff base ligand bis(3-methoxysalicylidene)-o-phenylenediamine (H2L) was prepared.A series of transition metal complexes with this Schiff base ligand have been synthesized and structurally characterized by IR and elemental analysis.The catalysis for reduction of thionyl chloride was studied by means of coristant resistance discharge.The result shows that [Mn(Ⅲ)LCI(H2O)]CH3OH and [Co(Ⅱ)HLCI(H2O)] have a good catalytic activity for the reduction of thionyl chloride,which improves the cell voltage,the rate of discharge,and the lifetime of Li/SOCl2 batteries.

  14. Model based multi-wavelength spectrophotometric method for calculation of formation constants of phenanthrenequinone thiosemicarbazone complexes with some metallic cations

    Directory of Open Access Journals (Sweden)

    Naser Samadi

    2013-04-01

    Full Text Available In traditional spectrophotometric determination of stability constants of complexation, it is necessary to find a wavelength at which only one of the components has absorbance without any spectroscopic interference of the other reaction components. In the present work, a simple multi-wavelength model-based method has been developed to determine stability constants for complexation reaction regardless of the spectra overlapping of components. Also, pure spectra and concentration profiles of all components are extracted using multi-wavelength model based method. In the present work spectrophotometric titration of several cationic metal ions with new synthetic ligand were studied in order to calculate the formation constant(s. In order to estimate the formation constants a chemometrics method, model based analysis was applied.

  15. Synthesis, spectroscopic characterization and biological evaluation studies of Schiff's base derived from naphthofuran-2-carbohydrazide with 8-formyl-7-hydroxy-4-methyl coumarin and its metal complexes

    Science.gov (United States)

    Halli, M. B.; Sumathi, R. B.; Kinni, Mallikarjun

    2012-12-01

    Metal complexes of the type ML2, where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and L = Schiff's base derived from the condensation of naphthofuran-2-carbohydrazide with 8-formyl-7-hydroxy-4-methyl coumarin have been synthesized. The chelation of the complexes have been elucidated in the light of analytical, IR, UV-vis, 1H NMR, mass, ESR spectral data, thermal and magnetic studies. The measured molar conductance values indicate that, the complexes are non-electrolytic in nature. The redox behavior of one of the synthesized metal complexes was investigated by cyclic voltammetry. The Schiff's base and its metal complexes have been screened for their in vitro antibacterial and antifungal activities by MIC method. The DNA cleavage activities of all the complexes were studied by agarose gel electrophoresis method. In addition, the free ligand along with its complexes has been studied for their antioxidant activity.

  16. Metallacarborane-Based Metal-Organic Framework with a Complex Topology

    Energy Technology Data Exchange (ETDEWEB)

    Kennedy, RD; Clingerman, DJ; Morris, W; Wilmer, CE; Sarjeant, AA; Stern, CL; O' Keeffe, M; Snurr, RQ; Hupp, JT; Farha, OK; Mirkin, CA

    2014-03-01

    The long, linear cobalt(III) bis(dicarbollide)-based bis(isophthalic acid) anion was synthesized as a tetraphenylphosphonium salt in five steps from 8-iodo-closo-1,2-C2B10H11. The solvothermal reaction between the anionic bis(isophthalic acid) linker and copper(II) nitrate in acidified DMF yielded single crystals. Despite the tendency for copper(II) and analogous linear tetraacids to form members of an isoreticular family of metal-organic frameworks (MOFs) with the fof topology, single-crystal X-ray diffraction analysis revealed the growth of three different frameworks. These MOFs, NU-150, NU-151, and NU-152, have three distinct topologies: fof, sty, and hbk, respectively. NU-152 has a novel quadrinodal topology in which cuboctahedral coordination polyhedra are each connected to 10 neighboring polyhedra via the cobalt bis(dicarbollide) portions of the linkers. The formation of these frameworks illustrates the limitations of structure prediction in MOP chemistry and the possibility of using flexible linkers to generate unexpected topologies. Furthermore, this work represents the first example of the incorporation of an anionic bis(dicarbollide) unit into a MOF.

  17. Synthesis, characterization and antimicrobial activities of mixed ligand transition metal complexes with isatin monohydrazone Schiff base ligands and heterocyclic nitrogen base

    Science.gov (United States)

    Devi, Jai; Batra, Nisha

    2015-01-01

    Mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with various uninegative tridentate ligands derived from isatin monohydrazone with 2-hydroxynapthaldehyde/substituted salicylaldehyde and heterocyclic nitrogen base 8-hydroxyquinoline have been synthesized and characterized by elemental analysis, conductometric studies, magnetic susceptibility and spectroscopic techniques (IR, UV-VIS, NMR, mass and ESR). On the basis of these characterizations, it was revealed that Schiff base ligands existed as monobasic tridentate ONO bonded to metal ion through oxygen of carbonyl group, azomethine nitrogen and deprotonated hydroxyl oxygen and heterocyclic nitrogen base 8-hydroxyquinoline existed as monobasic bidentate ON bonded through oxygen of hydroxyl group and nitrogen of quinoline ring with octahedral or distorted octahedral geometry around metal ion. All the compounds have been tested in vitro against various pathogenic Gram positive bacteria, Gram negative bacteria and fungi using different concentrations (25, 50, 100, 200 μg/mL) of ligands and their complexes. Comparative study of antimicrobial activity of ligands, and their mixed complexes indicated that complexes exhibit enhanced activity as compared to free ligands and copper(II) Cu(LIV)(Q)ṡH2O complex was found to be most potent antimicrobial agent.

  18. Inventory of metal complexes circulating in plant fluids: a reliable method based on HPLC coupled with dual elemental and high-resolution molecular mass spectrometric detection.

    Science.gov (United States)

    Flis, Paulina; Ouerdane, Laurent; Grillet, Louis; Curie, Catherine; Mari, Stéphane; Lobinski, Ryszard

    2016-08-01

    Description of metal species in plant fluids such as xylem, phloem or related saps remains a complex challenge usually addressed either by liquid chromatography-mass spectrometry, X-ray analysis or computational prediction. To date, none of these techniques has achieved a complete and true picture of metal-containing species in plant fluids, especially for the least concentrated complexes. Here, we present a generic analytical methodology for a large-scale (> 10 metals, > 50 metal complexes) detection, identification and semiquantitative determination of metal complexes in the xylem and embryo sac liquid of the green pea, Pisum sativum. The procedure is based on direct injection using hydrophilic interaction chromatography with dual detection by elemental (inductively coupled plasma mass spectrometry) and molecular (high-resolution electrospray mass spectrometry) mass spectrometric detection. Numerous and novel complexes of iron(II), iron(III), copper(II), zinc, manganese, cobalt(II), cobalt(III), magnesium, calcium, nickel and molybdenum(IV) with several ligands including nicotianamine, citrate, malate, histidine, glutamine, aspartic acid, asparagine, phenylalanine and others are observed in pea fluids and discussed. This methodology provides a large inventory of various types of metal complexes, which is a significant asset for future biochemical and genetic studies into metal transport/homeostasis. PMID:27111838

  19. Metal based biologically active compounds: design, synthesis, and antibacterial/antifungal/cytotoxic properties of triazole-derived Schiff bases and their oxovanadium(IV) complexes.

    Science.gov (United States)

    Chohan, Zahid H; Sumrra, Sajjad H; Youssoufi, Moulay H; Hadda, Taibi B

    2010-07-01

    A new series of oxovanadium(IV) complexes have been designed and synthesized with a new class of triazole Schiff bases derived from the reaction of 3,5-diamino-1,2,4-triazole with 2-hydroxy-1-naphthaldehyde, pyrrole-2-carboxaldehyde, pyridine-2-carboxaldehyde and acetyl pyridine-2-carboxaldehyde, respectively. Physical (magnetic susceptibility, molar conductance), spectral (IR, (1)H NMR, (13)C NMR, mass and electronic) and analytical data have established the structures of these synthesized Schiff bases and their oxovanadium(IV) complexes. The Schiff bases, predominantly act as bidentate and coordinate with the vanadium(IV) metal to give a stoichiometric ratio of 1:2 [M:L], forming a general formulae, [M(L-H)(2)] and [M(L)(2)]SO(4) where L = (L(1))-(L(4)) and M = VO(IV) of these complexes in a square-pyramidal geometry. In order to evaluate the biological activity of Schiff bases and to assess the role of vanadium(IV) metal on biological activity, the triazole Schiff bases and their oxovanadium(IV) complexes have been studied for in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexenari, Pseudomonas aeruginosa, Salmonella typhi) and two Gram-positive (Staphylococcus aureus, Bacillus subtilis) bacterial strains, in vitro antifungal activity against Trichophyton longifucus, Candida albican, Aspergillus flavus, Microscopum canis, Fusarium solani and Candida glaberata. The simple Schiff bases showed weaker to significant activity against one or more bacterial and fungal strains. In most of the cases higher activity was exhibited upon coordination with vanadium(IV) metal. Brine shrimp bioassay was also carried out for in vitro cytotoxic properties against Artemia salina. PMID:20338672

  20. The dynamic behavior of thin-film ionic transition metal complex-based light-emitting electrochemical cells

    International Nuclear Information System (INIS)

    Light-emitting electrochemical cells (LECs) have received increasing attention during recent years due to their simple architecture, based on solely air-stabile materials, and ease of manufacture in ambient atmosphere, using solution-based technologies. The LEC's active layer offers semiconducting, luminescent as well as ionic functionality resulting in device physical processes fundamentally different as compared with organic light-emitting diodes. During operation, electrical double layers (EDLs) form at the electrode interfaces as a consequence of ion accumulation and electrochemical doping sets in leading to the in situ development of a light-emitting p-i-n junction. In this paper, we comment on the use of impedance spectroscopy in combination with complex nonlinear squares fitting to derive key information about the latter events in thin-film ionic transition metal complex-based light-emitting electrochemical cells based on the model compound bis-2-phenylpyridine 6-phenyl-2,2′-bipyridine iridium(III) hexafluoridophosphate ([Ir(ppy)2(pbpy)][PF6]). At operating voltages below the bandgap potential of the ionic complex used, we obtain the dielectric constant of the active layer, the conductivity of mobile ions, the transference numbers of electrons and ions, and the thickness of the EDLs, whereas the transient thickness of the p-i-n junction is determined at voltages above the bandgap potential. Most importantly, we find that charge transport is dominated by the ions when carrier injection from the electrodes is prohibited, that ion movement is limited by the presence of transverse internal interfaces and that the width of the intrinsic region constitutes almost 60% of the total active layer thickness in steady state at a low operating voltage.

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

    Science.gov (United States)

    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

  2. Electron Transfer Mediators for Photoelectrochemical Cells Based on Cu(I Metal Complexes

    Directory of Open Access Journals (Sweden)

    Michele Brugnati

    2007-01-01

    Full Text Available The preparation and the photoelectrochemical characterization of a series of bipyridine and pyridyl-quinoline Cu(I complexes, used as electron transfer mediators in regenerative photoelectrochemical cells, are reported. The best performing mediators produced maximum IPCEs of the order of 35–40%. The J-V curves recorded under monochromatic light showed that the selected Cu(I/(II couples generated higher Vocs and fill factors compared to an equivalent I-/I3- cell, due to a decreased dark current.

  3. Design, spectral characterization, DFT and biological studies of transition metal complexes of Schiff base derived from 2-aminobenzamide, pyrrole and furan aldehyde

    Science.gov (United States)

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B. S.; Sharma, Deepansh

    2015-05-01

    A series of two biologically active Schiff base ligands L1, L2 have been synthesized in equimolar reaction of 2-aminobenzamide with pyrrol-2-carboxaldehyde and furan-2-carboxaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 2:1. The characterization of newly formed complexes was done by 1H NMR, UV-Vis, TGA, IR, mass spectrophotometry, EPR and molar conductivity studies. The thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II) and Ni(II) complexes and distorted octahedral geometry for Cu(II) complexes. All the synthesized compounds, were studied for their in vitro antimicrobial activities, against four bacterial strains and two fungal strains by using serial dilution method. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

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

    Science.gov (United States)

    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.

  5. Lanthanide metal complex-based membrane electrodes for sensing of biological amino alcohols

    International Nuclear Information System (INIS)

    Electrodes selective for amino alcohols were prepared by incorporating lanthanide tris(β-diketonates) in PVC membranes, which formed 1:1 highly coordinated complexes with amino alcohols. Several electrodes gave near-Nernstian slopes for 2-amino-3-methyl-1-butanol in the linear concentration range of 1.0 x 10-1 to 1.0 x 10-3 M, while the low detection limits of these electrodes were order of ∼10-4 M. Although the observed response profiles were significantly dependent on the natures of the targeted amino alcohols, the electrodes exhibited stable potentiometric signals in the pH range of 6-12 in short time period of 20 s. The related monoalcohol, diol, and zwitterionic amino acid substrates gave no response, indicating that the present type of lanthanide tris(β-diketonates) were applicable in potentiometric sensing of amino alcohols

  6. Unusual cocrystals made of a Schiff base metal complex and an organic molecule - Close-packing vs. hydrogen bond interactions

    Science.gov (United States)

    Buvaylo, Elena A.; Kokozay, Vladimir N.; Rubini, Katia; Vassilyeva, Olga Yu.; Skelton, Brian W.

    2014-08-01

    The mononuclear complexes [ML2]0 (M = Co, Ni, Zn; HL - Schiff base ligand formed in situ from 2-pyridinecarbaldehyde and anthranilic acid, AA) can efficiently interact with unreacted AA molecules to produce CoL2·AA·H2O (1), NiL2·AA·H2O (2) and ZnL2·AA·0.25CH3OH·0.5H2O (3) cocrystals. Compounds 1-3 have been obtained as single crystals and characterized by elemental analysis, IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction techniques. The compounds crystallize in the triclinic space group P1‾, with 1 and 2 being isomorphous. Neutral ML2 molecules in 1-3 show no crystallographically imposed symmetry with the metal atoms octahedrally surrounded by two anionic ligands in a mer configuration. Of the two crystallographically distinct AA molecules, one molecule only is engaged in H-bonding N/Osbnd H⋯O interactions with ML2 units. The solid-state organization of the cocrystals is described as an insertion of the organic molecules between the layers of ML2 complexes as they occur in the reported native NiL2·H2O structure.

  7. Synthesis and spectral studies on metal complexes of s-triazine based ligand and non linear optical properties

    Science.gov (United States)

    Shanmugakala, R.; Tharmaraj, P.; Sheela, C. D.

    2014-11-01

    A series of transition metal complexes of type [ML] and [ML2]Cl2 (where M = Cu(II), Ni(II), Co(II) have synthesized from 2-phenylamino-4,6-dichloro-s-triazine and 3,5-dimethyl pyrazole; their characteristics have been investigated by means of elemental analyses, magnetic susceptibility, molar conductance, IR, UV-Vis, Mass, NMR and ESR spectra. The electrochemical behavior of copper(II) complexes we have studied, by using cyclic voltammetry. The ESR spectra of copper(II) complexes are recorded at 300 K and 77 K and their salient features are appropriately reported. Spectral datas, we found, show that the ligand acts as a neutral tridentate, and coordinates through the triazine ring nitrogen and pyrazolyl ring nitrogen atoms to the metal ion. Evident from our findings, the metal(II) complexes of [ML] type exhibit square pyramidal geometry, and that of [ML2]Cl2 exhibit octahedral geometry. The in vitro antimicrobial activities of the ligand and its complexes are evaluated against Bacillus subtilis, Micrococcus luteus, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus mutans, Escherichia coli, Enterobacter aerogenes, Klebsiella pneumoniae, Proteus vulgaris, Cryptococcus neoformans, Pseudomonas aeruginosa, Salmonella typhi, Serratia marcescens, Shigella flexneri, Vibrio cholera, Vibris parahaemolyticus, Aspergillus niger, Candida albicans and Penicillium oxalicum by well-diffusion method. The second harmonic generation efficiency of the ligand and its complexes are determined and compared with urea and KDP.

  8. Synthesis and characterization of bioactive binuclear transition metal complexes of Schiff base ligand derived from 4-amino-pyrimidine-2-one, diacetyl and glycine

    Directory of Open Access Journals (Sweden)

    Srivastava Abhay Nanda

    2014-01-01

    Full Text Available A series of novel binuclear transition metal complexes was synthesized by reaction of a Schiff base ligand (1-Methyl-2-(2-oxo-1,2-dihydro-pyrimidin-4-ylimino-propylideneamino-acetic acid (LaH derived from 4-amino-pyrimidine-2-one, diacetyl, glycine and corresponding chloride salt of Cu(II, Ni(II, Co(II and Zn(II metals in 1:1 (metal : ligand molar ratio. The compounds were characterized by elemental analyses, molar conductance measurement, magnetic moment measurement and various spectral studies viz. IR, UV-visible, 1H-NMR, 13C-NMR, EPR and ESI-MS. Molar conductance measurement data revealed non-electrolytic nature of metal complexes. Electronic absorption spectral data, electronic paramagnetic resonance parameters and magnetic moment values revealed an octahedral geometry for binuclear metal complexes. Cyclic voltammetric study of Ni(II complex shows a couple of one electron anodic responses near 0.70 V and 1.10 V. In vitro biological activity of Schiff base ligand and binuclear complexes has been checked against bacteria (Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Salmonella typhi and fungi (Candida albicans and Candida parapsilosis to assess their antibacterial and antifungal properties.

  9. Synthesis, Characterization, Antimicrobial, DNA Cleavage, and Antioxidant Studies of Some Metal Complexes Derived from Schiff Base Containing Indole and Quinoline Moieties

    Directory of Open Access Journals (Sweden)

    Mahendra Raj Karekal

    2013-01-01

    Full Text Available A new Schiff base of 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide and 3-formyl-2-hydroxy-1H-quinoline (HL, and its Cu(II, Co(II, Ni(II, Zn(II, Cd(II, and Hg(II complexes have been synthesized and characterized in the light of microanalytical, IR, H1 NMR, UV-Vis, FAB-mass, ESR, XRD, and TGA spectral studies. The magnetic susceptibility measurements and low conductivity data provide evidence for monomeric and neutral nature of the complexes. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as tridentate ligand. The Cu(II, Co(II, and Ni(II complexes were octahedral, whereas Zn(II, Cd(II, and Hg(II complexes were tetrahedral in nature. The redox behavior of the Cu(II complex was investigated by electrochemical method using cyclic voltammetry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC method. The DNA cleavage experiment performed using agarose gel electrophoresis method showed the cleavage of DNA by all the metal complexes. The free radical scavenging activity of newly synthesized compounds has been determined at a different concentration range by means of their interaction with the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH.

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

    Science.gov (United States)

    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 Ω-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 β lie in the range 0.19-0.37 which indicated the covalent character in metal ligand ‘σ' 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.

  11. Some regularities in formation and solvent extraction of complexes in metal-salicylic acid or its derivative- organic base systems

    International Nuclear Information System (INIS)

    The influence of concentrations of the reagents, pH and solvent on the conditions for the formation and extraction of Sc, Ti, Zr, Hf, Th complexes has been examined in salicylic acid (H2Sal)-heterocyclic amine systems. The extraction chemism and factors, which affect the reactions between the metal ions and the ligands, are discussed. It has been shown that Zr, Hf, Ti form species of ion associate type, Sc and Th form different-ligand complexes under conditions for interphase equilibrium in a Me-H2Sal-heterocyclic amine system

  12. Potentiometric and Thermodynamic Studies of Some Schiff-Base Derivatives of 4-Aminoantipyrine and Their Metal Complexes

    Directory of Open Access Journals (Sweden)

    A. A. El-Bindary

    2013-01-01

    Full Text Available The proton-ligand dissociation constant of 4-(4-amino-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-ylideneamino-phenol ( and 4-(4-amino-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-ylideneamino-benzoic acid ( and metal-ligand stability constants of their complexes with metal ions (Mn2+, Co2+, Ni2+, and Cu2+ have been determined potentiometrically in 0.1 mol·dm−3 KCl and 10% (by volume ethanol-water mixture and at 298, 308, and 318 K. The stability constants of the formed complexes increase in the order Mn2+, Co2+, Ni2+, and Cu2+. The effect of temperature was studied, and the corresponding thermodynamic parameters (, , and were derived and discussed. The dissociation process is nonspontaneous, endothermic, and entropically unfavourable. The formation of the metal complexes has been found to be spontaneous, endothermic, and entropically favourable.

  13. Study on Syntheses and Anti-bacterial Activities of Some New Transition Metal Complexes with Schiff Base Ligand Containing Pyridine and Amide Moieties

    Institute of Scientific and Technical Information of China (English)

    LI, Mei-Ying(李美英); HU, Pei-Zhi(胡培植); ZHU, Jun-Cheng(朱军成); LIU, Yi(刘义); XU,Kuo-Xi(徐括喜)

    2004-01-01

    Several new transition metal complexes using Schiff base containing pyridine and amide moieties (N, N'-bis(β- salicylaliminoethyl)-2, 6-pyridinedicarboxylic amide, H4L) as the ligand have been prepared. Their compositions and structures are corroborated by elemental analysis, IR, UV, 1H NMR, DTA-TG and molar conductivity data. Their anti-bacterial activities have been studied by microcalorimetry. The result shows that the ligand and all complexes are potential anti-bacteria reagent and their inhibitory capacities are concentration-depended. The Mn complex has the strongest inhibitory capacity.

  14. Studies on complexation of a tridentate ONS Schiff base with lighter and heavier metals ions, and investigation into their biological properties

    International Nuclear Information System (INIS)

    Several new complexes of a tridentate ONS Schiff base derived from the condensation of S-benzyldithiocarbazate with salicylaldehyde have been characterised by elemental analyses, molar conductivity measurements, infrared, and electronic spectral studies. The tridentate Schiff base (HONSH) behaves as a dinegatively charged ligand coordinating through the thiolo sulphur, the azomethine nitrogen atom and the hydroxyl oxygen atom. It forms mono-ligand complexes of the general formula, [M(ONS)X], [M = Ni(II), Cu(II), Cr(III), Sb(III), Zn(II), Zr(IV) or U(VI) and X = H2O, Cl]. The ligand produced bis-chelated complex with Th(IV) of composition, [Th(ONS)2]. Square-planar structures were proposed for the Ni(II) and Cu(II) complexes. Antimicrobial tests indicated that the Schiff base and five of the metal complexes of Cu(II), Ni(II), U(VI), Zn(II) and Sb(III) were found to be strongly active against bacteria. Ni(II) and Sb(III) complexes were the most effective against Pseudomonas aeruginosa (gram negative) while the Cu(II) complex proved to be the best against Bacillus cereus (gram positive bacteria). Antifungal activities were also noted with the Schiff base and the U(VI) complex. These compounds have shown results against Candida albicans fungi. But none of these compounds were effective against Aspergillus ochraceous fungi. (author)

  15. Synthesis of antibacterial and antifungal activity of metal (ii) complexes with schiff base derived from 3-methoxy-5-bromosalicylaldehyde

    International Nuclear Information System (INIS)

    In this study, the complexes of co (ii), ni (ii), cu (ii) and zn (ii) with 2-((e)-((4-aminophenyl)imino)methyl)-4-bromo-6-methoxyphenol were prepared and characterized by physical, spectral and analytical data. the metal: ligand stoichiometric ratio is 1:2 in all the complexes. it was determined that the bidentate behavior of the ligand is accomplished via the phenolic oxygen and the azomethine nitrogen atoms. both the antibacterial and antifungal activities and mic values of compounds were reported. among the tested compounds, the most effective compound providing a mic value of 64 micro g/ml are zn(l)2 against c. tropicalis and b. subtilis. (author)

  16. Model based multi-wavelength spectrophotometric method for calculation of formation constants of phenanthrenequinone thiosemicarbazone complexes with some metallic cations

    OpenAIRE

    Naser Samadi; Mina Salamati; Abdolhossein Naseri

    2013-01-01

    In traditional spectrophotometric determination of stability constants of complexation, it is necessary to find a wavelength at which only one of the components has absorbance without any spectroscopic interference of the other reaction components. In the present work, a simple multi-wavelength model-based method has been developed to determine stability constants for complexation reaction regardless of the spectra overlapping of components. Also, pure spectra and concentration profiles of al...

  17. Base-Free Selective Oxidation of Glycerol over LDH Hosted Transition Metal Complexes Using 3% H2O2 as Oxidant

    Directory of Open Access Journals (Sweden)

    Xiaoli Wang

    2016-07-01

    Full Text Available A series of transition metal sulphonato-Schiff base complexes were intercalated into Mg–Al layered-double hydroxides (LDHs. The obtained catalysts were characterized by FTIR, XRD, N2 sorption, SEM and elemental analysis, and then were used in the selective oxidation of glycerol (GLY using 3% H2O2 as an oxidant. It was found that their catalytic performances were closely related to the loading of active complexes, the Schiff base ligands and the metal centers of the catalysts, as well as the reaction conditions. The optimal conversion of GLY was 85.0%, while the selectivity of 1,3-dihydroxyacetone (DHA was 56.5%. Moreover, the catalysts could be reused at least 10 times.

  18. A facile metal-free "grafting-from" route from acrylamide-based substrate toward complex macromolecular combs

    KAUST Repository

    Zhao, Junpeng

    2013-01-01

    High-molecular-weight poly(N,N-dimethylacrylamide-co-acrylamide) was used as a model functional substrate to investigate phosphazene base (t-BuP 4)-promoted metal-free anionic graft polymerization utilizing primary amide moieties as initiating sites. The (co)polymerization of epoxides was proven to be effective, leading to macromolecular combs with side chains being single- or double-graft homopolymer, block copolymer and statistical copolymer. © 2013 The Royal Society of Chemistry.

  19. Methyl Complexes of the Transition Metals.

    Science.gov (United States)

    Campos, Jesús; López-Serrano, Joaquín; Peloso, Riccardo; Carmona, Ernesto

    2016-05-01

    Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last five years. After a panoramic overview on M-CH3 compounds of Groups 3 to 11, which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity. PMID:26991740

  20. Metal Complexes of Quinolone Antibiotics and Their Applications: An Update

    Directory of Open Access Journals (Sweden)

    Valentina Uivarosi

    2013-09-01

    Full Text Available Quinolones are synthetic broad-spectrum antibiotics with good oral absorption and excellent bioavailability. Due to the chemical functions found on their nucleus (a carboxylic acid function at the 3-position, and in most cases a basic piperazinyl ring (or another N-heterocycle at the 7-position, and a carbonyl oxygen atom at the 4-position quinolones bind metal ions forming complexes in which they can act as bidentate, as unidentate and as bridging ligand, respectively. In the polymeric complexes in solid state, multiple modes of coordination are simultaneously possible. In strongly acidic conditions, quinolone molecules possessing a basic side nucleus are protonated and appear as cations in the ionic complexes. Interaction with metal ions has some important consequences for the solubility, pharmacokinetics and bioavailability of quinolones, and is also involved in the mechanism of action of these bactericidal agents. Many metal complexes with equal or enhanced antimicrobial activity compared to the parent quinolones were obtained. New strategies in the design of metal complexes of quinolones have led to compounds with anticancer activity. Analytical applications of complexation with metal ions were oriented toward two main directions: determination of quinolones based on complexation with metal ions or, reversely, determination of metal ions based on complexation with quinolones.

  1. Synthesis, characterization and biological relevance of some metal (II) complexes with oxygen, nitrogen and oxygen (ONO) donor Schiff base ligand derived from thiazole and 2-hydroxy-1-naphthaldehyde

    Science.gov (United States)

    Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2015-04-01

    The novel Schiff base ligand 2-((2-hydroxynaphthalen-1-yl)methylene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-hydroxy-1-naphthaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes have been characterized by microanalysis, molar conductance, IR, 1H NMR, ESI-mass, UV-Visible, TGA/DTA, ESR and powder X-ray diffraction data to explicate their structures. The IR results confirmed the tridentate binding of the ligand involving oxygen atom of amide carbonyl, azomethine nitrogen and naphthol oxygen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. Thermogravimetric studies for Cu(II) and Ni(II) complexes indicated the presence of coordinated water molecules and the final product is the metal oxide. In order to appraise the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antimicrobial activity by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 (Bangal re Genei, Bengaluru, Cat. No 105850) as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties against Artemia salina. Furthermore, the antioxidant activity were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH). The ligand exhibited better in vitro-antioxidant activity than its metal complexes.

  2. Synthesis, spectroscopic characterisation, DNA cleavage, superoxidase dismutase activity and antibacterial properties of some transition metal complexes of a novel bidentate Schiff base derived from isatin and 2-aminopyrimidine

    Science.gov (United States)

    Nitha, L. P.; Aswathy, R.; Mathews, Niecy Elsa; Sindhu kumari, B.; Mohanan, K.

    2014-01-01

    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a Schiff base, formed by the condensation of isatin with 2-aminopyrimidine have been synthesised and characterised through elemental analysis, molar conductance measurements, magnetic susceptibility, IR, UV-Vis, 1HNMR, FAB mass and EPR spectral studies. The spectral data revealed that the ligand acts as neutral bidentate, coordinating to the metal ion through the carbonyl oxygen and azomethine nitrogen. Molar conductance values adequately support the electrolytic nature of the complexes. On the basis of the above observations the complexes have been formulated as [M(ISAP)2]X2, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); X = Cl, OAc; ISAP = 2-[N-indole-2-one]aminopyrimidine. The ligand and copper(II) complex were subjected to X-ray diffraction studies. The DNA cleavage study was monitored by gel electrophoresis method. The superoxide dismutase (SOD) mimetic activities of the ligand and the metal complexes were checked using NBT assay. The in vitro antibacterial activity of the synthesized compounds has been tested against gram negative and gram positive bacteria.

  3. Synthesis, Physico-Chemical Characterization, Antibacterial and Antifungal Activities Studies of a New Schiff Base Ligand and its Transition Metal Complexes

    International Nuclear Information System (INIS)

    The complexes of Co(II), Cu(II) and Zn(II) with the Schiff base 2-((E)-((4-(4-aminophenoxy)phenyl)imino)methyl)-6-ethoxyphenol (LH) have been synthesized and their structure have been elucidated on the basis of elemental analyses, IR, 1H- and 13C-NMR spectra, electronic spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA). Mononuclear complexes with a metal:ligand ratio of 1:1 have been prepared with Co+2 and Zn+2 salts, whereas the copper(II) complex is dinuclear which have a metal:ligand ratio of 2:1. According to the results, it is suggested that the ligand is coordinated to each metal atom by the phenolic oxygen and the azomethine nitrogen atoms. The synthesized compounds were tested for antimicrobial activity against in vitro antibacterial (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Salmonella typhimurium) and antifungal activities (Candida globrata and Candida tropicalis) by the minimum inhibitory concentration (MIC) method. All of the selected compounds showed weak antimicrobial activity against test microorganisms (256-1024 μ g/mL). (author)

  4. Spectroscopy and interactions of metal and metal cation complexes

    OpenAIRE

    Plowright, Richard J.

    2010-01-01

    The work in this thesis looks at the spectroscopy and interactions of metals and metal cation complexes. There are two aspects of this vast subject that are considered: the electronic spectroscopy of Au-RG complexes and the ion-molecule chemistry of metals important in the mesosphere-lower thermosphere (MLT) region of the atmosphere. The spectroscopy of the molecular states in the vicinity of the strong Au 2P3/2, 1/2 ← 2S1/2 atomic transition, have been studied for the Au-RG (RG = Ne, Ar...

  5. Synthesis, spectroscopic studies, antimicrobial activities and antitumor of a new monodentate V-shaped Schiff base and its transition metal complexes

    Science.gov (United States)

    Ramadan, Ramadan M.; Abu Al-Nasr, Ahmad K.; Noureldeen, Amani F. H.

    2014-11-01

    Reaction of 4-aminoacetophenone and 4-bromobenzaldehyde in ethanol resulted in the formation of the monodentate V-shaped Schiff base (E)-1-(4-((4-bromo-benzylidene)amino)phenyl)ethanone (L). Interaction of L with different di- and trivalent metal ions revealed disubstituted derivatives. The ligand and its complexes were characterized by elemental analysis, mass, IR and NMR spectrometry. Biological activities of the ligand and complexes against the Escherchia coli and Staphylococcus aureus bacterias, and the two fungus Aspergillus flavus and Candida albicans were screened. The cytotoxicity of the compounds were checked as antitumor agents on liver carcinoma cell line (HepG2). They exhibited in vitro broad range of antitumor activities towards the cell line; the [ZnL2(H2O)2](NO3)2 complex was stronger antitumor towards HepG2 cell line as well as two breast cancer cell lines (MCF7 and T47D) relative to cis-platin.

  6. Physiochemical characterization and antimicrobial evaluation of phenylthiourea-formaldehyde polymer (PTF) based polymeric ligand and its polymer metal complexes

    Science.gov (United States)

    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.

  7. Synthesis, spectroscopic, cytotoxic aspects and computational study of N-(pyridine-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base and some of its transition metal complexes

    Science.gov (United States)

    Abd El-Aziz, Dina M.; Etaiw, Safaa Eldin H.; Ali, Elham A.

    2013-09-01

    N-(pyridine-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base (L) and its Cu(II), Fe(III), Co(II), Ni(II) and Zn(II) complexes were synthesized and characterized by a set of chemical and spectroscopic measurements using elemental analysis, electrical conductance, mass spectra, magnetic susceptibility and spectral techniques (IR, UV-Vis, 1H NMR). Elemental and mass spectrometric data are consistent with the proposed formula. IR spectra confirm the bidentate nature of the Schiff base ligand. The octahedral geometry around Cu(II), Fe(III), Ni(II) and Zn(II) as well as tetrahedral geometry around Co(II) were suggested by UV-Vis spectra and magnetic moment data. The thermal degradation behavior of the Schiff base and its complexes was investigated by thermogravimetric analysis. The structure of the Schiff base and its transition metal complexes was also theoretically studied using molecular mechanics (MM+). The obtained structures were minimized with a semi-empirical (PM3) method. The in vitro antitumor activity of the synthesized compounds was studied. The Zn-complex exhibits significant decrease in surviving fraction of breast carcinoma (MCF 7), liver carcinoma (HEPG2), colon carcinoma (HCT116) and larynx carcinoma (HEP2) cell lines human cancer.

  8. Metal complexes of Schiff’s bases derived from 3-(arylazo-2,4-pentanediones with 2-aminophenol and 2-aminothiophenol

    Directory of Open Access Journals (Sweden)

    K. KRISHNANKUTTY

    2007-11-01

    Full Text Available Phenylazo- and thiazolylazo-2,4-pentanediones on reaction with 2-aminophenol and 2-aminothiophenol yielded a new series of polydentate Schiff’s base ligands. The structure and tautomeric nature of these compounds and their metal complexes were established on the basis of their IR, 1H-NMR and mass spectral data. The spectral and analytical data revealed the condensation of both carbonyl groups of 3-(2-thiazolylazo- 2,4-pentanedione with 2-aminophenol to form an N2O2 tetradentate ligand. Details on the formation of its [ML] complexes with Ni(II, Cu(II and Zn(II and the nature of their bonding are discussed based on analytical, IR, 1H-NMR and mass spectral data.

  9. Metal complexes with paramagnetic thiosemicarbazone

    International Nuclear Information System (INIS)

    The complexes of Ni(2), Fe(2), Zn(2), Cd(2), Pd(2) and Pt(2) with the stable nitroxyl radical of thiosemicarbazone 4-formyl- 2, 2, 5, 5-tetramethyl-3-imidazoline-1-oxyl of the composition ML2 are synthesized. In the basis of the data of physical methods (IR, EPR, electron spectroscopy) a conclusion is made on the way of the ligand coordination. The study of the magnetic properties of the complexes has shown that in the compounds prepared a weak exchange interaction between unpaired electrons of paramagnetic centres takes place

  10. Synthesis, Characterization, Crystal Structure and Antibacterial Activities of Transition Metal(II Complexes of the Schiff Base 2-[(4-Methylphenyliminomethyl]-6-methoxyphenol

    Directory of Open Access Journals (Sweden)

    Guo-Liang Zhao

    2009-05-01

    Full Text Available Five transition metal(II complexes, [ML2Cl2] 1~5, were synthesized from the reaction of MCl2·nH2O (M = Mn, Co, Ni, Cu, Cd and the Schiff base ligand 2-[(4-methylphenyliminomethyl]-6-methoxyphenol (C15H15NO2, L, obtained by condensation of o-vanillin (2-hydroxy-3-methoxybenzaldehyde with p-toluidine. They were characterized by elemental analysis, molar conductance, FT-IR spectra, thermal analysis. The structure of complex 1 was determined by single-crystal X-ray diffraction. Its crystal structure is of monoclinic system, space group P21/c with a = 9.0111(18 Å, b = 11.222(2 Å, c =28.130 (6 Å, α = 90 º, β = 92.29(3 º, γ = 90 º, V = 2867.6(10 Å3, Z = 4. The Mn atom is six-coordinate and displays distorted octahedral geometry.The Schiff base ligand and its complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia coli, Staphylococcus aureus and Bacillus subtilis. It has been found that the complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.

  11. Complexation of metal ions with humic acid: metal ion charge neutralization model

    International Nuclear Information System (INIS)

    The humic acid complexation reaction presented in this work is based on the concept of metal ion charge neutralization upon complexation to humic acid functional groups. Experimental results from the complexation of UO22+, Am3+, and Cm3+ with humic acids of different origin are presented to demonstrate and validate the proposed model. By introducing the operational humic acid concentration and the loading capacity, the complexation constants are derived, which are independent of the metal ion concentration, pH, and origin of humic acid. The loading capacity is an operational term needed for the intercomparison of stability constants and is the mole fraction of the maximum available complexing sites of humic acid under a given set of experimental conditions. The metal ion charge neutralization model adequately describes the thermodynamic equilibrium reaction of metal ions with humic acid and allows a direct application of the resulting stability constants for geochemical modeling of actinide migration at an environmentally relevant pH. (orig.)

  12. Determination of complexable metals by chelometric titration

    International Nuclear Information System (INIS)

    A rapid, simple method for the determination of total complexable metal ions (Fe3+, Al3+, Mn2+, Ni2+, Co2+, Pb2+, and Rare Earths) in feed to the Hanford strontium recovery process has been developed. The method consists of complexing the metal ions with EDTA and titrating the excess with copper (II) ion. Pyrocatechol violet is used as a colorimetric end point indicator. Samples of actual process feed were analyzed and the results compared very favorably with results by atomic absorption. Use of a synthetic feed standard showed an average accuracy of 99.7% and a relative precision of +- 1.9% (95% C.L.). Interference studies run on the method show that oxalate and phosphate interfere above mole ratios of 0.1 and 0.3, respectively (anion : total complexable cations). Of the complexable metal ions commonly encountered in this feed (specifically excluding alkali and alkaline-earth metals), the only complexable ion not determinable by this method is Cr

  13. Special Issue: Practical Applications of Metal Complexes

    Directory of Open Access Journals (Sweden)

    Iztok Turel

    2015-04-01

    Full Text Available In 1913 Alfred Werner received the Nobel Prize in Chemistry for his work that was of great importance for the development of coordination chemistry. In the years that followed numerous complexes consisting of metal ions and organic ligands were isolated, thus building a strong connection between inorganic and organic chemistry. Coordination compounds have many interesting properties which find diverse applications in numerous aspects of human life. Fourteeen contributions were received for this Special Issue covering very different aspects of metal complexes and their practical applications. The highest number of manuscripts deals with the biological activity of complexes which might potentially be used in the clinical practice. Authors have tested their cytotoxicity, antibacterial activity and enzyme inhibition. Their optical properties were studied in view of their potential use in photodynamic therapy. Moreover, optical properties could also be used for bioanalysis. It is also known that metal complexes are useful catalysts and a few such examples are also described herein. Many other interesting properties and facts about the isolated and described complexes are also reported (radioactivity, design of metal-organic frameworks, etc..

  14. Synthesis, structure and superoxide dismutase activity of two self-assembly transition metal complexes containing a tridentate amino-Schiff base deviating from salicylaldehyde with glycine

    Institute of Scientific and Technical Information of China (English)

    HAN Jing; BAI FengYing; ZHAO HaiYan; XING YongHeng; ZENG XiaoQing; GE MaoFa

    2009-01-01

    Two new transition metal (Cu, Ni) complexes with amino-Schiff base ligand, (C_9H_7NO_3)Cu(C_(14)H_(12)N_2).H_2O (1) and (C_9H_7NO_3)Ni(C_3H_4N_2)_3.H_2O(2), have been designed and synthesized in ethanol solution at room temperature. Both of the complexes have been characterized by elemental analysis, IR spectra, UV-vis spectroscopy and X-ray single crystal diffraction. For complex 1, the coordination environment of the central copper atom is a distorted square pyramid, and one-dimensional chain is formed through the inter-molecular hydrogen bonds (O4-H2W…O3, O4-H2W…O3~(#1)(#1:…x+1, y,-z+3/2)) and weak interactions (π-π stacking interaction) between the phenyl rings. For complex 2, the nickel atom is 6-coordinated and in a distorted octahedral environment, and a discrete hydrogen-bond cluster (four molecules are connected by hydrogen bonds into a group) is formed via two types of intra-molecular hydrogen bonds (O-H…O, N-H…O) and inter-molecular hydrogen bonds (O-H…O, N-H…O).

  15. Four Hybrid Materials Based on Preyssler P5W30 Polyoxometalate and First-Row Transition-Metal Complex.

    Science.gov (United States)

    Hu, Tuo-Ping; Zhao, Ya-Qin; Jagličić, Zvonko; Yu, Kai; Wang, Xing-Po; Sun, Di

    2015-08-01

    Four Preyssler P5W30 based inorganic-organic hybrids, formulated as {[Cu12(pbtz)2(Hpbtz)2(OH)4(H2O)16][Na(H2O)P5W30O110]}·16H2O (1; H2pbtz = 5'-(pyridin-2-yl)-1H,2'H-3,3'-bi(1,2,4-triazole)), {[Cu10(ttbz)2(Httbz)4(OH)6(H2O)8][K(H2O)H2P5W30O110]}·30H2O (2; Httbz = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), {[Ni6(bpz)6(H2O)16][Na(H2O)H2P5W30O110]}·36H2O (3; bpz = 3,3',5,5'-tetramethyl-4,4-bipyrazole), {[Co4(bpz)6(H2O)9][K(H2O)H6P5W30O110]}·46H2O (4), have been isolated and structurally identified via microanalysis, thermogravimetry (TG), infrared (IR) spectroscopy, and X-ray single-crystal diffraction. Compound 1 exhibits a 3D binodal (3,6)-connected ant framework composed of dodeca-supported P5W30 polyoxometalate (POM) clusters and discrete [Cu6(pbtz)(Hpbtz)(OH)2(H2O)8] subunits. Compound 2 is a pillared-layer 3D network constructed from [Cu5(ttbz)(Httbz)2(OH)3(H2O)4] sheets pillared by individual P5W30 clusters. Compound 3 contains octa-supporting P5W30 POM clusters and novel [Ni6(bpz)6] crown-like metallamacrocycles, which construct a (4,4)-connected pts network. Compound 4 displays a complicated 3D (5,5)-connected {4(5)·6(4)·8}{4(5)·6(5)} network built by pentasupporting P5W30 POM clusters and discrete [Co4(bpz)6(H2O)9] subunits. In 1-4, the unified features are the Preyssler-type [P5W30O110] POM as the fundamental building block, which supports the transition-metal compounds with different modes to give the resultant diverse networks. The magnetism studies indicated antiferromagnetically coupled systems for the hexa- and pentanuclear Cu(II) units in 1 and 2, respectively. The electrochemical properties demonstrate that all compounds have electrocatalytic abilities toward the reduction of hydrogen peroxide. Furthermore, the catalytic activities of 1 in the cyanosilylation of aldehydes reaction have been investigated. PMID:26196681

  16. Hydrogen storage in complex metal hydrides

    Directory of Open Access Journals (Sweden)

    BORISLAV BOGDANOVIĆ

    2009-02-01

    Full Text Available Complex metal hydrides such as sodium aluminohydride (NaAlH4 and sodium borohydride (NaBH4 are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides. The most important point for a wide application of these materials is the reversibility under moderate technical conditions. At present, only NaAlH4 has favourable thermodynamic properties and can be employed as a thermally reversible means of hydrogen storage. By contrast, NaBH4 is a typical non- -reversible complex metal hydride; it reacts with water to produce hydrogen.

  17. 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

    Science.gov (United States)

    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.

  18. TDPAC studies on metal-complex ferrimagnets

    International Nuclear Information System (INIS)

    TDPAC spectra of 117In (left-arrow 117Cd) and 111Cd (left-arrow 111mCd) in the mixed metal complex N(C4H9)4(M(II)Fe(III)(C2O4)3)(M=Fe,Ni), the related substraces and LiNbO3 have been studied. In this paper, pure potassium iron (III) oxalate was prepared and mixed metal complexes were synthesized by changing amount of reagents and the order added, then observed by TDPAC. 2 mol%Cd was dispersed throughout potassium iron oxalate and potassium nickel oxalate, formulating M(II)0.98Cd(II)0.02C2O4·2H2O (M=Fe, Ni) with the same crystal structure. The formation reaction of mixed metal complex-Fe(II) was faster than that of iron oxalate. Its mixed metal complex-Ni(II) was slower than that of iron oxalate. The rate of quadrupole oscillation was obtained by ωQ(117In)=67.3 Mrad/s and ωQ(111Cd)=29.7 Mrad/s of which values were determined by TDPAC spectra of 117In and 111Cd in LiNbO3 at 4K. The value showed pure ion bond of oxygen coordinated with 117In and 111Cd. 0.08 η was determined by TDPAC spectrum of 111Cd(left-arrow 111mCd). The rate of ωQ of mixed metal oxalate complex was larger than 2.3, indicating 5s and 5p orbital electron took part in bond of oxygen of oxalic acid or approaching oxygen ion to In nucleus depend on the structual relaxation in decaying of 117In(left-arrow 117Cd). (S.Y.)

  19. The structure of metallic complexes of polyacetylene with alkali metals

    Science.gov (United States)

    Baughman, R. H.; Murthy, N. S.; Miller, G. G.

    1983-07-01

    The crystal structures of sodium, potassium, rubidium, and cesium doped polyacetylene have been determined using crystal packing and x-ray diffraction analyses. Each of these metallic complexes is tetragonal, with the polyacetylene chains forming a host lattice in which the alkali metal ions are present in channels. Lithium appears to be too small to stabilize the channel structure and an amorphous structure is observed. Predicted unit cell parameters and x-ray diffraction intensities are in agreement with observed values. Similarities with the alkali metal doped graphite suggest that hybridization between carbon pz orbitals and metal s orbitals occurs. Such hybridization is expected to result in a high conductivity component normal to the chain direction. On the other hand, direct overlap between polymer chains appears small, since alkali metal columns separate polymer chains. Compositions calculated for the channel structures (from meridional diffraction spacings, the intensity of equatorial diffraction lines, measured volume expansion, and distances in model complexes) all range from y=0.12 to 0.18 for (CHMy)x, where M is sodium, potassium, rubidium, or cesium.

  20. Transition metal complexes with thiosemicarbazide-based ligands. Part 58. Synthesis, spectral and structural characterization of dioxovanadium(V complexes with salicylaldehyde thiosemicarbazone

    Directory of Open Access Journals (Sweden)

    LJILJANA S. VOJINOVIĆ-JEŠIĆ

    2011-06-01

    Full Text Available The first two complexes of dioxovanadium(V with salicylaldehyde thiosemicarbazone (SALTSC, of the coordination formulas [VO2(SALTSC––H]∙H2O (1 and NH4[VO2(SALTSC–2H] (2, were synthesized and characterized by elemental analysis, conductometric measurements, IR and UV–Vis spectroscopy and X-ray analysis. The complexes were obtained in the reaction of an aqueous ammoniacal solution of NH4VO3 and SALTSC. The results of the characterization showed that SALTSC was coordinated in the usual ONS tridentate mode as monoanion in complex 1 and dianion in complex 2. In both complexes, the vanadium atom is in a deformed square-pyramidal environment and is slightly shifted towards the apical oxo-ligand (» 0.52 Å.

  1. Synthesis and biological activities of transition metal complexes based on acetylsalicylic acid as neo-anticancer agents.

    Science.gov (United States)

    Rubner, Gerhard; Bensdorf, Kerstin; Wellner, Anja; Kircher, Brigitte; Bergemann, Silke; Ott, Ingo; Gust, Ronald

    2010-10-14

    [(μ(4)-η(2))-(Prop-2-ynyl)-2-acetoxybenzoate]dicobalthexacarbonyl (Co-ASS), a derivative of aspirin (ASS), demonstrated high growth-inhibitory potential against various tumor cells with interference in the arachidonic acid cascade as probable mode of action. The significance of the kind of metal and cluster was verified in this structure-activity study: Co(2)(CO)(6) was respectively exchanged by a tetrameric cobalt-, trimeric ruthenium-, or trimeric ironcarbonyl cluster. Furthermore, the metal binding motif was changed from alkyne to 1,3-butadiene. Compounds were evaluated for growth inhibition, antiproliferative effects, and apoptosis induction in breast (MCF-7, MDA-MB 231) and colon cancer (HT-29) cell lines and for COX-1/2 inhibitory effects at isolated isoenzymes. Additionally, the major COX metabolite prostaglandin E2 (PGE(2)) was quantified in arachidonic acid-stimulated MDA-MB 231 breast tumor cells. It was demonstrated that the metal cluster was of minor importance for effects on cellular activity if an alkyne was used as ligand. Generally, no correlation existed between growth inhibition and COX activity. Cellular growth inhibition and antiproliferative activity at higher concentrations of the most active compounds Prop-ASS-Co(4) and Prop-ASS-Ru(3) correlated well with apoptosis induction. PMID:20857911

  2. Late transition metal organometallic chemistry. rhodium, iridium and gold complexes with sigma and pi hydrocarbon-based ligands.

    OpenAIRE

    Fernández-Espada Pastor, María

    2015-01-01

    Los resultados que se presentan en esta Memoria se encuadran en una de las líneas de investigación que desarrolla el grupo de Química Organometálica y Catálisis Homogénea del Instituto de Investigaciones Químicas (Centro Mixto Universidad de Sevilla−CSIC), que tiene como objetivo el estudio de las reacciones de ruptura y formación de enlaces C—H, C—O, C—C y otros similares, inducidas de manera selectiva por complejos de metales de los grupos 9 (Rh e Ir) y, por primera vez en esta Tesis Doctor...

  3. Selective detection of 2,4,6-trinitrophenol based on a fluorescent nanoscale bis(8-hydroxyquinoline) metal complex.

    Science.gov (United States)

    Lv, Xiao-Jun; Qi, Liang; Gao, Xiang-Yu; Wang, Huan; Huo, Yuan; Zhang, Zhi-Qi

    2016-04-01

    The reliable and accurate detection of explosives such as 2,4,6-trinitrophenol (TNP) and 2,4,6-trinitrotoluene (TNT) is in high demand for homeland security and public safety. Although extremely high sensitivity towards TNT has been demonstrated, detection of TNP remains a challenge. In this work, a fluorescent nanoscale complex composed of bis(8-hydroxyquinoline) and Al(3+) ions has been prepared, characterized and applied in detection of TNP. This complex exhibits the ability to sense the nitro explosive TNP via a fluorescence quenching mechanism with high selectivity. A simple paper test system for the rapid monitoring of TNP was also investigated. The results show that Bhq-Al is a quite ideal sensing material for trace-level detection of TNP. PMID:26838414

  4. Amorphous metal based nanoelectromechanical switch

    KAUST Repository

    Mayet, Abdulilah M.

    2013-04-01

    Nanoelectromechanical (NEM) switch is an interesting ultra-low power option which can operate in the harsh environment and can be a complementary element in complex digital circuitry. Although significant advancement is happening in this field, report on ultra-low voltage (pull-in) switch which offers high switching speed and area efficiency is yet to be made. One key challenge to achieve such characteristics is to fabricate nano-scale switches with amorphous metal so the shape and dimensional integrity are maintained to achieve the desired performance. Therefore, we report a tungsten alloy based amorphous metal with fabrication process development of laterally actuated dual gated NEM switches with 100 nm width and 200 nm air-gap to result in <5 volts of actuation voltage (Vpull-in). © 2013 IEEE.

  5. Antiretroviral activity of thiosemicarbazone metal complexes.

    Science.gov (United States)

    Pelosi, Giorgio; Bisceglie, Franco; Bignami, Fabio; Ronzi, Paola; Schiavone, Pasqualina; Re, Maria Carla; Casoli, Claudio; Pilotti, Elisabetta

    2010-12-23

    Thiosemicarbazones display a wide antimicrobial activity by targeting bacteria, fungi, and viruses. Here, we report our studies on the antiviral activity of two thiosemicarbazone metal complexes, [bis(citronellalthiosemicarbazonato)nickel(II)] and [aqua(pyridoxalthiosemicarbazonato)copper(II)] chloride monohydrate, against the retroviruses HIV-1 and HTLV-1/-2. Both compounds exhibit antiviral properties against HIV but not against HTLVs . In particular, the copper complex shows the most potent anti-HIV activity by acting at the post-entry steps of the viral cycle. PMID:21121632

  6. Metal-Metal Bonding in Uranium-Group 10 Complexes.

    Science.gov (United States)

    Hlina, Johann A; Pankhurst, James R; Kaltsoyannis, Nikolas; Arnold, Polly L

    2016-03-16

    Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-κ(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3M(0), M = Ni (3-Ni), Pd (3-Pd), and Pt (3-Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3-Ni with two further U-Ni complexes XU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3Ni(0), X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U-M bonds are significantly shorter than any other crystallographically characterized d-f-block bimetallic, even though the ligand flexes to allow a variable U-M separation. Excellent agreement is found between the experimental and computed structures for 3-Ni and 3-Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U-M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U-Ni bond than U-Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U-X adducts 3-Ni, 4, and 5. The data show a trend in uranium-metal bond strength that decreases from 3-Ni down to 3-Pt and suggest that exchanging the iodide for a fluoride strengthens the metal-metal bond. Despite short U-TM (transition metal) distances, four other computational approaches also suggest low U-TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3-Pd than 3-Ni, consistent with slightly larger U-TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal

  7. Structure and Reactivity of Isolated Mononuclear and Oligonuclear Metal Complexes

    OpenAIRE

    Menges, Fabian

    2013-01-01

    This thesis reports on investigations on the structure and reactivity of dipeptide-alkali metal complexes, a series of ruthenium bearing catalysts, dysprosium based single molecule magnets and organometallic di-cobalt complexes. A variety of experimental and theoretical methods was used dependent on the problem: collision induced dissociation, hydrogen/deuterium exchange reactions, gas phase reactions with \\(D_2\\), infrared multiple-photon dissociation and the determination of minimum energy...

  8. Evaluation of heavy metal complex phytotoxicity

    OpenAIRE

    Vita Vasilyevna Datsenko; Nataliya Lvovna Khimenko

    2016-01-01

    The experimental data dealing with the effect of heavy metals contained in the technogenic contaminated soils on plant objects under controlled conditions was discussed. The aim of this work is to define the quantitative indicators of copper and zinc potential phytotoxicity, namely germination energy, simultaneous germination and duration of the test plants. It was found that the activity of the test plant growth is linked with copper and zinc complex action. Joint effect of copper and zinc i...

  9. Complex Metal Oxide Chemical Gas Sensors

    OpenAIRE

    Šutka, A

    2015-01-01

    The demand for alternative gas sensor materials is increasing following the progress in the electronic industry. Complex ternary oxide materials have been emerging rapidly over 10 last years. Among ternary metal oxide compounds, the spinel ferrites are the most attractive materials due to structural and compositional versatility. This report will highlight the recent developments and will show the potential of the spinel ferrites on gas sensor technology. Sensing mechanisms for a range of gas...

  10. TDPAC studies on metal-complex ferrimagnets

    Energy Technology Data Exchange (ETDEWEB)

    Ohkubo, Yoshitaka [Kyoto Univ., Kumatori, Osaka (Japan). Research Reactor Inst.; Abe, Shizuko; Okada, Takuya [and others

    1997-03-01

    TDPAC spectra of {sup 117}In (left-arrow {sup 117}Cd) and {sup 111}Cd (left-arrow {sup 111m}Cd) in the mixed metal complex N(C{sub 4}H{sub 9}){sub 4}(M(II)Fe(III)(C{sub 2}O{sub 4}){sub 3})(M=Fe,Ni), the related substraces and LiNbO{sub 3} have been studied. In this paper, pure potassium iron (III) oxalate was prepared and mixed metal complexes were synthesized by changing amount of reagents and the order added, then observed by TDPAC. 2 mol%Cd was dispersed throughout potassium iron oxalate and potassium nickel oxalate, formulating M(II){sub 0.98}Cd(II){sub 0.02}C{sub 2}O{sub 4}{center_dot}2H{sub 2}O (M=Fe, Ni) with the same crystal structure. The formation reaction of mixed metal complex-Fe(II) was faster than that of iron oxalate. Its mixed metal complex-Ni(II) was slower than that of iron oxalate. The rate of quadrupole oscillation was obtained by {omega}{sub Q}({sup 117}In)=67.3 Mrad/s and {omega}{sub Q}({sup 111}Cd)=29.7 Mrad/s of which values were determined by TDPAC spectra of {sup 117}In and {sup 111}Cd in LiNbO{sub 3} at 4K. The value showed pure ion bond of oxygen coordinated with {sup 117}In and {sup 111}Cd. 0.08 {eta} was determined by TDPAC spectrum of {sup 111}Cd(left-arrow {sup 111m}Cd). The rate of {omega}{sub Q} of mixed metal oxalate complex was larger than 2.3, indicating 5s and 5p orbital electron took part in bond of oxygen of oxalic acid or approaching oxygen ion to In nucleus depend on the structual relaxation in decaying of {sup 117}In(left-arrow {sup 117}Cd). (S.Y.)

  11. Binding of dihydromyricetin and its metal ion complexes with bovine serum albumin

    OpenAIRE

    Guo, Qingquan; Yuan, Juan; Zeng, Jinhua

    2014-01-01

    The binding mechanisms of the interaction of three dihydromyricetin (DMY)–metal complexes (DMY–Cu (II) complex, DMY–Mn (II) complex, DMY–Zn (II) complex) and DMY with bovine serum albumin (BSA) were investigated using fluorescence and ultraviolet spectroscopy at different temperatures. The results indicated some differences in the binding process between different DMY–metal complexes and BSA compared with that of free DMY. All of the complexes and DMY quenched the fluorescence of BSA based on...

  12. Metal complexes of tetrazole-containing azomethins

    International Nuclear Information System (INIS)

    Complexes of M(L-H)2, M(L-H)2·nMX2 (n=1, 2) type were prepared in result of interaction of methanol solutions of acetates and chlorides of corresponding metals (M=Cu, Zn, Cd) and L (L-tetrazole-containing azomethins) at molar ratio of reagents, equal to 1:2. Composition of synthesized azomethins and their complexes was investigated by the methods of IR, UV spectroscopy and magnetic measurements. The most general way of coordination lies in formation of M-L σ-bond due to the presence of N-H aminogroup in ligand system. Formation of complexes of complicated composition is caused by nonplanar structure of azomethins

  13. Determination of catecholamines based on the measurement of the metal nanoparticle-enhanced fluorescence of their terbium complexes

    International Nuclear Information System (INIS)

    We have developed a method for the determination of the three catecholamines (CAs) epinephrine (EP), norepinephrine (NE), and dopamine (DA) at sub-nanomolar levels. It is found that the luminescence of the complexes formed between the CAs and Tb 3+ ion is strongly enhanced in the presence of colloidal silver nanoparticles (Ag-NPs). The Ag-NPs cause a transfer of the resonance energy to the fluorophores through the interaction of the excited-state fluorophores and surface plasmon electrons in the Ag-NPs. Under the optimized condition, the luminescence intensity of the system is linearly related to the concentration of the CAs. Linearity is observed in the concentration ranges of 2. 5-110 nM for EP, 2. 8-240 nM for NE, and 2. 4-140 nM for DA, with limits of detection as low as 0. 25 nM, 0. 64 nM and 0. 42 nM, respectively. Relative standard deviations were determined at 10 nM concentrations (for n = 10) and gave values of 0. 98%, 1. 05% and 0. 96% for EP, NE and DA, respectively. Catecholamines were successfully determined in pharmaceutical preparations, and successful recovery experiments are demonstrated for urine and serum samples. (author)

  14. Magmatogene fluids of metal-bearing reefs in the Bushveld Complex, South Africa: Based on research data on fluid inclusions in quartz

    Science.gov (United States)

    Zhitova, L. M.; Kinnaird, J. A.; Gora, M. P.; Shevko, E. P.

    2016-01-01

    Fluid inclusions in the Merensky Reef quartz and later pegmatite veins crosscutting the Platreef rocks of the Bushveld Complex are studied by a suite of advanced high-precision methods. Based on the conducted studies, we identify a few types of fluids, some having been separated during the crystallization of volatile matter-rich residual melt of original basic magma, while others are derivatives of later felsic (granite) melts that formed crosscutting veins in fully devitrified ultrabasic and basic rocks. The earliest fluid is captured by quartz in symplectitic intergrowths with intercumulus plagioclase from the Merensky Reef pyroxenite occurs as a homogenous dense dry reduced gas (CH4-N2 ± CO2) mixture separated from the aluminosilicate melt at 800-900°C and 3050 bar. The following heterophase highly concentrated fluids (60-80 wt % NaCl eq.) separated at over 550°C and below 3050 bar transport a large number of metals. Major saline components of such fluids included Na, K, Fe, Ca, and Mn chlorides, Ca and Na sulphates and carbonates. According to LA ICP-MS analysis data, inclusions of these fluids contain high concentrations of Fe, Cr, K, and Na at the level of a few wt % and also significant contents of Cu, Sn, Sb, Mo, Au, Ag, Bi, and Ni in a concentration range from a few to thousands of ppm. Relatively lower-temperature (much higher than 450°C) fluids accompanying the crystallization of crosscutting quartz-feldspar pegmatite veins at the Platreef are also highly concentrated (from 70-80% to 40-14 wt % NaCl eq.), oxidized and metal-bearing. High concentrations of metals such as Na, K, Ca, Mn, Fe, and Pb at the level of wt % and also Ni, Co, Cu, As, Mo, Sn, Sb, and Bi (1-500 ppm) in inclusions in quartz of later pegmatite veins suggest the possible participation of magmatogene fluids related to later felsic intrusions in the redistribution of primary magmatic concentrations of metals. The oxidation of reduced heterophase fluids may be the most important

  15. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Science.gov (United States)

    2010-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  16. Metal ammine complexes for hydrogen storage

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Sørensen, Rasmus Zink; Johannessen, Tue;

    2005-01-01

    The hopes of using hydrogen as an energy carrier are severely dampened by the fact that there is still no safe, high-density method available for storing hydrogen. We investigate the possibility of using metal ammine complexes as a solid form of hydrogen storage. Using Mg(NH3)(6)Cl-2 as the example......, we show that it can store 9.1% hydrogen by weight in the form of ammonia. The storage is completely reversible, and by combining it with an ammonia decomposition catalyst, hydrogen can be delivered at temperatures below 620 K....

  17. Evaluation of heavy metal complex phytotoxicity

    Directory of Open Access Journals (Sweden)

    Vita Vasilyevna Datsenko

    2016-07-01

    Full Text Available The experimental data dealing with the effect of heavy metals contained in the technogenic contaminated soils on plant objects under controlled conditions was discussed. The aim of this work is to define the quantitative indicators of copper and zinc potential phytotoxicity, namely germination energy, simultaneous germination and duration of the test plants. It was found that the activity of the test plant growth is linked with copper and zinc complex action. Joint effect of copper and zinc is manifested both in inhibition of lettuce growth and determined, above all, by the nature contamination, soil properties and biological specificity of the test plants.

  18. A Straightforward Electrochemical Approach to Imine- and Amine-bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State.

    Science.gov (United States)

    Chapman, Michael R; Henkelis, Susan E; Kapur, Nikil; Nguyen, Bao N; Willans, Charlotte E

    2016-08-01

    Synthetic methods to prepare organometallic and coordination compounds such as Schiff-base complexes are diverse, with the route chosen being dependent upon many factors such as metal-ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal-salen/salan complexes which comprise diverse metal-ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (M(II/III/IV) where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol-switch is described which allows access to analytically pure Fe(II/III)-salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers Mn(II/IV)-salen complexes in high yield. PMID:27547645

  19. Structural, photophysical and magnetic properties of transition metal complexes based on the dipicolylamino-chloro-1,2,4,5-tetrazine ligand.

    Science.gov (United States)

    Nazarenko, Iuliia; Pop, Flavia; Sun, Qinchao; Hauser, Andreas; Lloret, Francesc; Julve, Miguel; El-Ghayoury, Abdelkrim; Avarvari, Narcis

    2015-05-21

    The ligand 3-chloro-6-dipicolylamino-1,2,4,5-tetrazine (Cl-TTZ-dipica) , prepared by the direct reaction between 3,6-dichloro-1,2,4,5-tetrazine and di(2-picolyl)-amine, afforded a series of four neutral transition metal complexes formulated as [Cl-TTZ-dipica-MCl2]2, with M = Zn(II), Cd(II), Mn(II) and Co(II), when reacted with the corresponding metal chlorides. The dinuclear structure of the isostructural complexes was disclosed by single crystal X-ray analysis, clearly indicating the formation of [M(II)-(μ-Cl)2M(II)] motifs and the involvement of the amino nitrogen atom in semi-coordination with the metal centers, thus leading to distorted octahedral coordination geometries. Moreover, the chlorine atoms, either coordinated to the metal or as a substituent on the tetrazine ring, engage respectively in specific anion-π intramolecular and intermolecular interactions with the electron-poor tetrazine units in the solid state, thus controlling the supramolecular architecture. Modulation of the emission properties is observed in the case of the Zn(II) and Cd(II) complexes when compared to the free ligand. A striking difference is observed in the magnetic properties of the Mn(II) and Co(II) complexes. An antiferromagnetic coupling takes place in the dimanganese(II) compound (J = -1.25 cm(-1)) while the Co(II) centers are ferromagnetically coupled in the corresponding complex (J = +0.55 cm(-1)), the spin Hamiltonian being defined as H = -JSA·SB. PMID:25868861

  20. Mixed-metal hydroxycarboxylic acid complexes

    International Nuclear Information System (INIS)

    Formation constants for mixed-metal complexes, Kmmc, between uranium(VI), as the central metal ion, and each one of the metal ions, iron(III), aluminium(III), indium(III) and copper(II) have been determined using data from potentiometric measurements. In each case one of the hydroxycarboxylic acids, citric, tartaric or malic, was used as a ligand. At 298.15 K the values of -log Kmmc for the investigated systems are uranyl iron(II) citrate, 2.45; uranyl iron(III) malate, 7.37; uranyl aluminium(III) citrate, 8.21; uranyl aluminium(III) tartarate, >12; uranyl aluminium(III) malate, 8.06; uranyl indium(III) citrate, 11.3; uranyl indium(III) tartarate, 7.88; uranyl indium(III) malate, 7.45; uranyl copper(II) citrate -1.41; uranyl copper(II) tartarate, -1.17; and uranyl copper(II) malate, -1.11. (author)

  1. Metal plasmon enhanced europium complex luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Liu Feng [Department of Chemistry, Queen' s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6 (Canada); Aldea, Gabriela [Department of Chemistry, Queen' s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6 (Canada); Petru Poni Institute of Macromolecular Chemistry Iasi, Aleea Grigore Ghica Voda 41A, 700487 Iasi (Romania); Nunzi, Jean-Michel, E-mail: nunzijm@queensu.c [Department of Chemistry, Queen' s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6 (Canada)

    2010-01-15

    The plasmon enhanced luminescence of a rare-earth complex Tris(6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium (Eu(fod){sub 3}) was investigated. A polyvinyl alcohol (PVA) thin film was successfully adopted as a spacer to separate the Eu complex from the silver island film (SIF), and five-fold enhancement of the radiative decay rate of the Eu complex on SIF was demonstrated based on the luminescence intensity and lifetime measurement. Investigation of the distance dependent luminescence indicates that 7 nm is an optimal distance for SIF enhanced Eu luminescence. Plasmon enhanced rare-earth luminescence based on an organic film spacer would find potential applications in plasmon enhanced organic light emitting diode (OLED) devices.

  2. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  3. Surface-Induced Modification of Supported Late Transition Metal Complexes

    OpenAIRE

    Snezhkova, Olesia

    2016-01-01

    The work presented in this thesis addresses the investigation of the electronic, magnetic, and structural properties of late transition metal complexes supported on various surfaces. The research is aimed at studying the interaction between the molecules and the support, together with the intermolecular interaction. This knowledge is essential e.g. for the development of organic molecule-based devices and the creation of active and stable catalysts. In this work, the modification of th...

  4. Spectroscopic investigations of new binuclear transition metal complexes of Schiff bases derived from 4,6-diacetylresorcinol and 3-amino-1-propanol or 1,3-diamino-propane

    Science.gov (United States)

    Emara, Adel A. A.; Saleh, Akila A.; Adly, Omima M. I.

    2007-11-01

    The bifunctional carbonyl compound; 4,6-diacetylresorcinol (DAR) serves as precursor for the formation of different Schiff base ligands, which are either di- or tetra-basic with two symmetrical sets of either O 2N or N 2O tridentate chelating sites. The condensation of 4,6-diacetylresorcinol with 3-amino-1-propanol (3-AP) or 1,3-diaminopropane (DAP), yields the corresponding hexadentate Schiff base ligands, abbreviated as H 4L a and H 2L b, respectively. The structures of these ligands were elucidated by elemental analyses, IR, mass, 1H NMR and electronic spectra. Reaction of the Schiff base ligands with copper(II), nickel(II), cobalt(II), zinc(II), cadmium(II), iron(III), chromium(III), vanadyl(IV) and uranyl(VI) ions in 1:2 molar ratio afforded the corresponding transition metal complexes. A variety of binuclear complexes for the metal complexes were obtained with the ligands in its di- or tetra-deprotonated forms. The structures of the newly prepared complexes were identified by elemental analyses, infrared, electronic, mass, 1H NMR and ESR spectra as well as magnetic susceptibility measurements and thermal gravimetric analysis (TGA). The bonding sites are the azomethine and amino nitrogen atoms, and phenolic and alcoholic oxygen atoms. The metal complexes exhibit different geometrical arrangements such as square planar, tetrahedral, square pyramid and octahedral arrangement.

  5. Nitrogen vacancy complexes in nitrogen irradiated metals

    International Nuclear Information System (INIS)

    Gas desorption and positron annihilation techniques have been employed to study the evolution of nitrogen associated defects in nitrogen irradiated metals: Fe, Ni, Mo and W. Nitrogen in these metals has a rather high affinity to vacancy type defects. The results obtained for low irradiation dose show that substitutional nitrogen (NV; with V = vacancy) is formed. The nitrogen vacancy complex dissociates at temperatures ranging from 350 K for Ni to 900 K for Mo and 1,100 K for W. At high doses defects are formed which can be characterized as nitrogen saturated vacancy clusters. These defect, as observed by helium probing, disappear during annealing for nickel at 800 K, and for Mo at 1,100 K. The direct observation of the desorbing nitrogen for nickel and molybdenum reveals a very fast desorption transient at the dissociation temperature of the clusters. This is the characteristic desorption transient of a small nitride cluster, e.g., by shrinkage with constant rate. For iron the nitrogen desorption is more complicated because of a general background that continuously rises with temperature. With the positron beam technique depth information was obtained for defects in iron and the defect character could be established with the help of the information provided on annihilation with conduction and core electrons of the defect trapped positrons

  6. Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

    Science.gov (United States)

    Mahmoud, W H; Mahmoud, N F; Mohamed, G G; El-Sonbati, A Z; El-Bindary, A A

    2015-01-01

    The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity. PMID:26067934

  7. Interaction between metals and nucleic acids. Part 3. Synthesis and structural studies of copper(II) complexes with Schiff base ligands derived from barbituric acid

    Energy Technology Data Exchange (ETDEWEB)

    Sasaki, I.; Gaudemer, A.; Chiaroni, A.; Riche, C.

    1986-02-17

    Schiff bases have been prepared from 5-formylbarbituric acid and 5-formyl-1,3-dimethyl-barbituric acid and various di- or tri-amines. The structure of the corresponding copper(II) complexes have been established by elemental analysis and spectroscopic methods. The molecular structure of one of the complexes, Cu(DiMeBardpt), was determined by X-ray diffraction. Electrochemical study shows that these complexes are reduced at slightly more negative potentials than the corresponding complexes obtained from uracil, which suggests that these new ligands are better electron-donors.

  8. VCD Studies on Chiral Characters of Metal Complex Oligomers

    OpenAIRE

    Hisako Sato; Akihiko Yamagishi

    2013-01-01

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy l...

  9. 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

    Science.gov (United States)

    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.

  10. Enhanced Structural Support of Metal Sites as Nodes in Metal-Organic Frameworks Compared to Metal Complexes

    OpenAIRE

    Das, Sanjit

    2013-01-01

    Metal-organic frameworks are a new class of crystalline, porous solid-state materials with metal ions periodically linked by organic linkers. This gives rise to one-, two- or three-dimensional structures. Here, we compare the stability of similar metal sites toward external ligand (solvent) induced disruption of the coordination environment in metal complexes and in metal-organic frameworks. Our experimental results show that a metal site as node of a metal-organic framework retains much high...

  11. Unique chemical properties of metal-carbon bonds in metal-carboranyl and metal-carboryne complexes

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The metal-carbon bonds in metal-carboranyl and metal-carboryne complexes behave very differently from those in classical organometallic complexes. The unique electronic and steric properties of ico-sahedral carboranyl moiety make the M-C bond in metal-carboranyl complexes inert toward unsaturated molecules, and on the other hand, the sterically demanding carborane cage can induce unexpected C-C coupling reactions. The M-C bonds in metal-carboryne complexes are, however, active toward various kinds of unsaturated molecules and the reactivity patterns are dependent upon the electronic configurations of the metal ions. This account provides an overview of our recent work in this area.

  12. New tetradentate Schiff bases of 2-amino-3,5-dibromobenzaldehyde with aliphatic diamines and their metal complexes: Synthesis, characterization and thermal stability

    Science.gov (United States)

    Mohammadi, Khosro; Azad, Seyyedeh Sedigheh; Amoozegar, Ameneh

    2015-07-01

    The tetradentate Schiff base ligands (L1-L4), were synthesized by reaction between 2-amino-3,5-dibromobenzaldehyde and aliphatic diamines. Then, nickel and oxovanadium(IV) complexes of these ligands were synthesized and characterized by 1H NMR, Mass, IR, UV-Vis spectroscopy and thermogravimetry. The kinetic parameters of oxovanadium(IV) complexes were calculated from thermal studies. According to the results of thermogravimetric data, the thermal stability of oxovanadium(IV) complexes is as follow: VOL2(ClO4)2 >VOL4(ClO4)2 >VOL3(ClO4)2 >VOL1(ClO4)2

  13. TAXUS VI 2-year follow-up: randomized comparison of polymer-based paclitaxel-eluting with bare metal stents for treatment of long, complex lesions

    DEFF Research Database (Denmark)

    Grube, Eberhard; Dawkins, Keith D; Guagliumi, Giulio;

    2007-01-01

    ) paclitaxel-eluting TAXUS MR stent in treatment of complex lesion subsets, we evaluated the 2-year follow-up of TAXUS VI. METHOD AND RESULTS: TAXUS VI was a randomized multi-centre study enrolling 446 patients with complex lesions, including small vessels in 28% of patients and a mean lesion length of 20.6 mm...... to prevent one re-percutaneous coronary intervention at 2 years was 12.5. CONCLUSION: Treatment of complex coronary lesions with the polymer-based MR paclitaxel-eluting TAXUS MR stent is associated with a sustained clinical benefit and low rates of TVR up to 2 years after device implantation...

  14. Coupling of metal-based light-harvesting antennas and electron-donor subunits: Trinuclear Ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands

    DEFF Research Database (Denmark)

    Campagna, Sebastiano; Serroni, Scolastica; Puntoriero, Fausto; Loiseau, Frédérique; De Cola, Luisa; Kleverlaan, Cornelis J.; Becher, Jan; Sørensen, Ane Plough; Hascoat, Philippe; Thorup, Niels

    2002-01-01

    (mu-2,3-dpp)}(2)Ru(bpy-TTF1)](PF6)(6) (9; bpy=2,2'-bipyridine; 2,3-dpp = 2,3-bis(2'-pyridyl)pyrazine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy-TTF2)](PF6)(6) (10). These compounds can be viewed as coupled antennas and charge-separation systems, in which the multichromophoric trinuclear metal subunits act...... as light-harvesting antennas and the tetrathiafulvalene electron donors can induce charge separation. The absorption spectra, redox behavior, and luminescence properties (both at room temperature in acetonitrile and at 77 K in a rigid matrix of butyronitrile) of the trinuclear metal complexes have......)(4,4'-Mebpy)](2+) (4,4'-Mebpy = 4,4'-dimethyl-2,2'-bipyridine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy)](6+). The absorption spectra and redox behavior of all the new metal compounds can be interpreted by a multicomponent approach, in which specific absorption features and redox processes can be assigned to...

  15. Studies on coordination chemistry and bioactivity of metal complexes of a bidentate NN schiff base, (2-pyridyl-methylene)(phenyl) hydrazine, produced from the condensation of pyridine-2-carboxaldehyde with phenylhydrazine

    International Nuclear Information System (INIS)

    A bidentate Schiff base, (2-pyridyl-methylene)(phenyl) hydrazine, with NN donor sequence, was isolated from the condensation of pyridine-2-carboxaldehyde with phenylhydrazine in ethanol. Metal complexes of this ligand with Ni(II), Zn(It), and Cu(n) ions were synthesized and characterized by a variety of physico-chemical techniques. The structure of the Schiff base was solved by X-ray diffraction studies, which indicated that it was monoclinic with a space group of C2/c. The complexes were all four coordinated. The compounds were tested against four pathogenic bacteria and fungi. The nickel complex, [Ni(NN)2Cl2], in particular, was found to be active against all the fungi tested. The complexes were however inactive against leukemic cell lines (CEM-SS). (author)

  16. Protection of metal artefacts with the formation of metal-oxalates complexes by Beauveria bassiana.

    Directory of Open Access Journals (Sweden)

    Edith eJoseph

    2012-01-01

    Full Text Available Several fungi present high tolerance to toxic metals and some are able to transform metals into metal-oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated in vitro. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g.L-1, and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal-oxalates can be used in the restoration and conservation of archaeological and modern metal artefacts. The production of copper-oxalates was confirmed directly using metallic pieces (both archaeological and modern. The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal-oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates and probably goethite. However, the formation of a homogeneous layer on the object is not yet optimal. Silver nitrate was extracellularly reduced into nanoparticles of elemental silver by an unknown mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artefacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals.

  17. Metallic complexes with glyphosate: a review; Complexos metalicos com o herbicida glifosato: revisao

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, Claudia F.B.; Mazo, Luiz Henrique [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: claudiabreda@iqsc.usp.br

    2005-11-15

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  18. Supramolecular structures constructed from three novel rare earth metal complexes

    Indian Academy of Sciences (India)

    Huaze Dong; Xiaojun Feng; Xia Liu; BiN Zheng; Jianhong Bi; Yan Xue; Shaohua Gou; Yanping Wang

    2015-05-01

    Three rare earth metal supramolecular complexes, {[Tb(2)4](ClO4)3·2H2O(1), [Eu(2)2(H2O)5] (ClO4)3(2) and [Gd(NO3)3(2)2]·2CH3CH2OH(3) ( 2 = 3-Dimethylamino-1-pyridin-2-yl-propenone), have been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. The crystal structure analysis reveals that the coordination numbers of three complexes (1–3) are 8, 9 and 10, respectively. Three complexes assembled into 3D frameworks based on C-H⋯O, O-H⋯O hydrogen bond linkages.

  19. VCD Studies on Chiral Characters of Metal Complex Oligomers

    Directory of Open Access Journals (Sweden)

    Hisako Sato

    2013-01-01

    Full Text Available The present article reviews the results on the application of vibrational circular dichroism (VCD spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes.

  20. FEM study of extrusion complexity and dead metal zone

    OpenAIRE

    S.Z. Qamar

    2009-01-01

    Purpose: Quality of the extruded product and efficiency of the manufacturing process can be seriously affected by inconsistent metal flow through the extrusion die. Metal flow problems can also significantly reduce die life. Various researchers have investigated the effect of profile complexity on extrusion pressure, product quality, die life, etc. However, the relationship between shape complexity and metal flow through the extrusion die has not been studied in detail. Cold extrusion experim...

  1. Studies on Transition Metal-Quercetin Complexes Using Electrospray Ionization Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Yuanzhen Liu

    2015-05-01

    Full Text Available To systematically study the effects of the number of d electrons of the first transition metal ions (Fe, Co, Ni, Cu and Zn on the formation and stability of metal flavonoid complexes, we took the quercetin/M2+ complex as a model system to investigate the structures and properties of these complexes. Based on considerable structural information obtained through ESI-MSn, all of the first transition metal ions (Fe2+, Co2+, Ni2+, Cu2+ and Zn2+ were found to form different complexes with quercetin, while with the number of chelating flavonoids decreasing along with the reduction of the metal ionic radius. Quercetin forms different complexes with the above metal divalent ions through its 5-OH and 4-carbonyl groups; the complex stability is highly dependent on both the metallic ion and the flavonoid chelator itself. As for the central ion (M2+, when chelated with quercetin to form the complex, the stability of the complex decreased in the following order: Cu2+ > Ni2+ > Co2+ > Fe2+ > Zn2+. With flavonoid: metal stoichiometries at 2:1, the complexes formed between quercetin and metal ions (Fe2+, Ni2+, Co2+ and Zn2+ have the similar fragmentation mechanism, while Cu2+ displayed different fragmentation mechanism due to the concurrent oxidation.

  2. Computational chemistry and metal-based radiopharmaceuticals

    International Nuclear Information System (INIS)

    Computer-assisted techniques have found extensive use in the design of organic pharmaceuticals but have not been widely applied on metal complexes, particularly on radiopharmaceuticals. Some examples of computer generated structures of complexes of In, Ga and Tc with N, S, O and P donor ligands are referred. Besides parameters directly related with molecular geometries, molecular properties of the predicted structures, as ionic charges or dipole moments, are considered to be related with biodistribution studies. The structure of a series of oxo neutral Tc-biguanide complexes are predicted by molecular mechanics calculations, and their interactions with water molecules or peptide chains correlated with experimental data of partition coefficients and percentage of human protein binding. The results stress the interest of using molecular modelling to predict molecular properties of metal-based radiopharmaceuticals, which can be successfully correlated with results of in vitro studies. (author)

  3. 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

    Science.gov (United States)

    Karaoğlu, Kaan; Baran, Talat; Değirmencioğlu, İsmail; 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).

  4. Metal complexes for DNA-mediated charge transport

    OpenAIRE

    Barton, Jacqueline K.; Olmon, Eric D.; Sontz, Pamela A.

    2011-01-01

    In all organisms, oxidation threatens the integrity of the genome. DNA-mediated charge transport (CT) may play an important role in the generation and repair of this oxidative damage. In studies involving long-range CT from intercalating Ru and Rh complexes to 5′-GG-3′ sites, we have examined the efficiency of CT as a function of distance, temperature, and the electronic coupling of metal oxidants bound to the base stack. Most striking is the shallow distance dependence and the sensitivity of...

  5. Metal complexes of a pentadentate N2O3bis(semicarbazone) Schiff-base. A case study of structure-spectroscopy correlation.

    Science.gov (United States)

    Inoue, Mayara Hissami; Ribeiro, Ronny Rocha; Sabino, José Ricardo; Nunes, Fábio Souza

    2016-07-01

    Schiff condensation of 2,6-diformyl 4-methylphenol with semicarbazide hydrochloride in 1:2 molar ratio produces the bis(semicarbazone) ligand, herein called H3L. A comprehensive spectroscopic analysis of the compound was performed by (1)H and (13)C NMR, FTIR and electronic spectroscopies. Assignments to the UV-vis spectrum of H3L were supported by semi-empirical quantum mechanics ZINDO/S calculations. The ligand H3L forms monoclinic crystals in the space group P21/c and its structure is stabilized by classic hydrogen bonds with propanone molecules. It promptly reacts with first row metal ions to produce the following coordination compounds: [Co2(L)(μ-NO3)]·DMF, [Ni2(H2L)(μ-CH3COO)(CH3COO)2]·2H2O, [Cu2(L)(μ-NO3)(H2O)2]·H2O, [Cu2(L)(μ-CH3COO)(H2O)2]·H2O and [Cu2(H2L)(μ-Cl)Cl2]·3H2O, that have different compositions, depending on the degree of deprotonation of the ligand upon coordination. Electronic and EPR spectroscopies as well as effective magnetic moment measurements of the complexes were used in an attempt to better understand their mode of coordination, the microsymmetry around the metal ions and magnetic properties. PMID:27082654

  6. Identification of major metal complexing compounds in Blepharis aspera

    International Nuclear Information System (INIS)

    Verbascoside and isoverbascoside, present at 0.7% and 0.2% (w/w dryweight), were identified to be major compounds that could contribute to the metal complexation in Blepharis aspera collected in Botswana, Africa. The metallophyte B. aspera has high ability to cope with a high level of metal accumulation. The presence of metal complexing compounds and/or antioxidants can prevent oxidative reactions in lipids, proteins and DNA that take place due to the metal accumulation. On-line liquid chromatography-solid phase extraction-nuclear magnetic resonance (LC-SPE-NMR) was applied for the identification, while electrospray-mass spectrometry (ESI-MS) and UV-vis spectroscopy was used to assess whether these compounds can complex with metals. It was found that verbascoside and isoverbascoside may form complexes with nickel, iron (verbascoside only) and copper. Thus, the presence of verbascoside and isoverbascoside can explain the survival of B. aspera in mineral-rich areas

  7. Metal Ion Selectivity of Kojate Complexes: A Theoretical Study

    Directory of Open Access Journals (Sweden)

    Sarita Singh

    2013-01-01

    Full Text Available Density functional calculations have been performed on four-coordinate kojate complexes of selected divalent metal ions in order to determine the affinity of the metal ions for the kojate ion. The complexation reactions are characterized by high energies, showing that they are highly exothermic. It is found that Ni(II exhibits the highest affinity for the kojate ion, and this is attributed to the largest amount of charge transfer from the ligand to the metal ion. The Ni(II complex has distorted square planar structure. The HOMOs and LUMOs of the complexes are also discussed. All complexes display a strong band at ~1500 cm−1 corresponding to the stretching frequency of the weakened carbonyl bond. Comparison of the complexation energies for the two steps shows that most of the complexation energy is realized in the first step. The energy released in the second step is about one-third that of the first step.

  8. Kinetics of the reactions of hydrated electrons with metal complexes

    International Nuclear Information System (INIS)

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni2+, Co2+ and Cu2+. Rates of the reactions of the complexes with e-(aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e-(aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  9. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    OpenAIRE

    Yedil Yergozhin; B. Taussarova; R. Ashkeyeva; L. Tugelbayeva

    2013-01-01

    The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

  10. Donor Schiff Base Polymeric Complexes

    Directory of Open Access Journals (Sweden)

    Shubhangi N. Kotkar

    2013-01-01

    Full Text Available A series of new polymeric complexes of Mn(II, Co(II, Ni(II, Cu(II, and Zn(II were prepared with a Schiff base ligand derived from condensation of 2,4-dihydroxy acetophenone and p-phenylene diamine and characterized by elemental analysis and IR and NMR spectral data. The antimicrobial activity of the Schiff base and its polymeric complexes have been studied.

  11. Chemistry and Properties of Complex Intermetallics from Metallic Fluxes

    Energy Technology Data Exchange (ETDEWEB)

    Kanatzidis, Mercouri G. [Northwestern Univ., Evanston, IL (United States)

    2015-03-28

    This project investigated the reaction chemistry and synthesis of new intermetallic materials with complex compositions and structures using metallic fluxes as solvents. It was found that the metallic fluxes offer several key advantages in facilitating the formation and crystal growth of new materials. The fluxes mostly explored were liquid aluminum, gallium and indium. The main purpose of this project was to exploit the potential of metallic fluxes as high temperature solvent for materials discovery in the broad class of intermetallics. This work opened new paths to compound formation. We discovered many new Si (or Ge)-based compounds with novel structures, bonding and physicochemical properties. We created new insights about the reaction chemistry that is responsible for stabilizing the new materials. We also studied the structural and compositional relationships to understand their properties. We investigated the use of Group-13 metals Al, Ga and In as solvents and have generated a wide variety of new results including several new ternary and quaternary materials with fascinating structures and properties as well as new insights as to how these systems are stabilized in the fluxes. The project focused on reactions of metals from the rare earth element family in combination with transition metals with Si and Ge. For example molten gallium has serves both as a reactive and non-reactive solvent in the preparation and crystallization of intermetallics in the system RE/M/Ga/Ge(Si). Molten indium behaves similarly in that it too is an excellent reaction medium, but it gives compounds that are different from those obtained from gallium. Some of the new phase identified in the aluminide class are complex phases and may be present in many advanced Al-matrix alloys. Such phases play a key role in determining (either beneficially or detrimentally) the mechanical properties of advanced Al-matrix alloys. This project enhanced our basic knowledge of the solid state chemistry

  12. The mechanism of alkene addition to a nickel bis(dithiolene) complex: the role of the reduced metal complex.

    Science.gov (United States)

    Dang, Li; Shibl, Mohamed F; Yang, Xinzheng; Alak, Aiman; Harrison, Daniel J; Fekl, Ulrich; Brothers, Edward N; Hall, Michael B

    2012-03-14

    The binding of an alkene by Ni(tfd)(2) [tfd = S(2)C(2)(CF(3))(2)] is one of the most intriguing ligand-based reactions. In the presence of the anionic, reduced metal complex, the primary product is an interligand adduct, while in the absence of the anion, dihydrodithiins and metal complex decomposition products are preferred. New kinetic (global analysis) and computational (DFT) data explain the crucial role of the anion in suppressing decomposition and catalyzing the formation of the interligand product through a dimetallic complex that appears to catalyze alkene addition across the Ni-S bond, leading to a lower barrier for the interligand adduct. PMID:22364208

  13. Fixation of metallic sulfosalicylate complexes on an anionic exchange resin

    International Nuclear Information System (INIS)

    Since sulfosalicylate ions have acid-base properties, sulfosalicylate complexes have an apparent stability which varies with the ph. As a result, the fixation of sulfo-salicylates on an anionic exchange resin depends on the ph of the solution in equilibrium with the resin. This research has been aimed at studying the influence of the ph on the fixation on an anionic exchange resin (Dowex 1 x 4) of sulfosalicylate anions on the one hand, and of metallic sulfosalicylate complexes on the other hand. In the first part of this work, a determination has been made, by frontal analysis of the distribution of sulfosalicylate ions in the resin according to the total sulfosalicylate I concentration in the aqueous solution in equilibrium with the resin. The exchange constants of these ions between the resin and the solution have been calculated. In the second part, a study has been made of the fixation of anionic sulfosalicylate complexes of Fe(III), Al(III), Cr(III), Cu(II), Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Fe(II) and UO22+. By measuring the partition coefficients of these different elements between the resin and the solution it has been possible to give interpretation for the modes of fixation of the metallic ions, and to calculate their exchange constant between the resin and the solution. The relationship has been established for each metallic element studied, between its partition coefficient, the ph and the total concentration of the complexing agent in solution. Such a relationship makes it possible to predict, for given conditions, the nature of the species in solution and in the resin, as well as the partition coefficient of a metallic, element. Finally, in the third part of the work, use has been made of results obtained previously, to carry out some separations (Ni2+ - Co2+; Ni2+ - Co2+ - Cu2+; UO22+ - Fe3+; UO22+ - Cr3+; UO22+ - Cu2+; UO22+ - Ni2+; UO22+ - Co2+; UO22+ - Mn2+ and UO22+ - Cd2+), as well as the purification of a uranyl sulfosalicylate solution

  14. Cumulant Approximated Second-Order Perturbation Theory Based on the Density Matrix Renormalization Group for Transition Metal Complexes: A Benchmark Study.

    Science.gov (United States)

    Phung, Quan Manh; Wouters, Sebastian; Pierloot, Kristine

    2016-09-13

    The complete active space second order perturbation theory (CASPT2) can be extended to larger active spaces by using the density matrix renormalization group (DMRG) as solver. Two variants are commonly used: the costly DMRG-CASPT2 with exact 4-particle reduced density matrix (4-RDM) and the cheaper DMRG-cu(4)-CASPT2 in which the 4-cumulant is discarded. To assess the accuracy and limitations of the latter variant DMRG-cu(4)-CASPT2 we study the spin state energetics of iron porphyrin Fe(P) and its model compound FeL2, a model for the active center of NiFe hydrogenase, and manganese-oxo porphyrin MnO(P)(+); a series of excited states of chromium hexacarbonyl Cr(CO)6; and the interconversion of two Cu2O2(2+) isomers. Our results clearly show that PT2 on top of DMRG is essential in order to obtain quantitative results for transition metal complexes. Good results were obtained with DMRG-cu(4)-CASPT2 as compared to full CASPT2 and DMRG-CASPT2 in calculations with small- and medium-sized active spaces. In calculations with large-sized active spaces (∼30 active orbitals), the performance of DMRG-cu(4)-CASPT2 is less impressive due to the errors originating from both the finite number of renormalized states m and the 4-RDM approximation. PMID:27547847

  15. Investigation of metal-polyelectrolyte complex toxicity.

    Science.gov (United States)

    Karahan, Mesut; Mustafaeva, Zeynep; Koç, Rabia Çakır; Bağırova, Melahat; Allahverdiyev, Adil M

    2014-05-01

    Water-soluble binary and ternary copper complexes of polyelectrolytes were synthesized, and the toxicity of these complexes was tested in mouse fibroblast cell line (L929) in vitro. Both the binary and ternary complexes were prepared at the ratio of 0.4 mole copper(II) ions per monomer of acrylic acid and 0.5 mole copper(II) ions per monomer of methyl vinyl ether maleic anhydride, furthermore at the ratio of 1 and 2 mole bovine serum albumin per mole of polyacrylic acid and poly(methyl vinyl ether-co-maleic anhydride), respectively. Compared to binary copper(II)-polyelectrolyte complexes, these ternary complexes have been determined to be of least toxicity. PMID:22914259

  16. Inkjet printing of 3D metallic silver complex microstructures

    NARCIS (Netherlands)

    Wits, Wessel W.; Sridhar, Ashok

    2010-01-01

    To broaden the scope of inkjet printing, this paper focuses on printing of an organic silver complex ink on glass substrates towards the fabrication of metallic 3D microstructures. The droplet formation sequence of the inkjet printer is optimised to print continuous layers of metal. A brief discussi

  17. A Simple Method for Drawing Chiral Mononuclear Octahedral Metal Complexes

    Science.gov (United States)

    Mohamadou, Aminou; Haudrechy, Arnaud

    2008-01-01

    Octahedral transition-metal complexes are involved in a number of reactions and octahedral coordination geometry, frequently observed for metallic centers, includes important topographical stereochemistry. Depending on the number and nature of different ligands, octahedral coordination units with at least two different monodentate ligands give…

  18. Effects of Lability of Metal Complex on Free Ion Measurement Using DMT

    NARCIS (Netherlands)

    Weng, L.P.; Riemsdijk, van W.H.; Temminghoff, E.J.M.

    2010-01-01

    Very low concentrations of free metal ion in natural samples can be measured using the Donnan membrane technique (DMT) based on ion transport kinetics. In this paper, the possible effects of slow dissociation of metal complexes on the interpretation of kinetic DMT are investigated both theoretically

  19. COMPLEX EVALUATION OF WORKING CONDITIONS IN WORKSHOPS OF METAL HEAT TREATMENT

    Directory of Open Access Journals (Sweden)

    A. M. Lazarenkov

    2015-05-01

    Full Text Available The results of complex evaluation of working conditions in workshops of metal heat treatment, and based on research of industrial environmental factors jobs are given. The hygienic overview of working conditions classification in working stations of metals heat treatment shops is given.

  20. Compartmentation and complexation of metals in hyperaccumulator plants

    Science.gov (United States)

    Leitenmaier, Barbara; Küpper, Hendrik

    2013-01-01

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their “strange” behavior in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defense against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites (e.g., nicotianamine) and possibly for export of Cu in Cd/Zn hyperaccumulators [metallothioneins (MTs)]. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e., detoxified by binding to strong ligands such as MTs. PMID:24065978

  1. Compartmentation and complexation of metals in hyperaccumulator plants

    Directory of Open Access Journals (Sweden)

    Barbara eLeitenmaier

    2013-09-01

    Full Text Available Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their strange behaviour in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defence against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e. detoxified by binding to strong ligands such as metallothioneins.

  2. Heavy metal complexes with organic ligands from surface waters of the uranium mining area in Ronneburg, Thuringia

    International Nuclear Information System (INIS)

    The study focussed on nickel and uranium. A method based on size exclusion chromatography was developed to isolate heavy metals complexed with organic ligands. The compounds and complexes present in the surface waters were characterized. (P.A.)

  3. π-Conjugated bis(terpyridine)metal complex molecular wires.

    Science.gov (United States)

    Sakamoto, Ryota; Wu, Kuo-Hui; Matsuoka, Ryota; Maeda, Hiroaki; Nishihara, Hiroshi

    2015-11-01

    Bottom-up approaches have gained significant attention recently for the creation of nano-sized, ordered functional structures and materials. Stepwise coordination techniques, in which ligand molecules and metal sources are reacted alternatively, offer several advantages. Coordination bonds are stable, reversible, and self-assembling, and the resultant metal complex motifs may contain functionalities unique to their own characteristics. This review focuses on metal complex wire systems, specifically the bottom-up fabrication of linear and branched bis(terpyridine)metal complex wires on electrode surfaces. This system possesses distinct and characteristic electronic functionalities, intra-wire redox conduction and excellent long-range electron transport ability. This series of comprehensive studies exploited the customizability of bis(terpyridine)metal complex wires, including examining the influence of building blocks. In addition, simple yet effective electron transfer models were established for redox conduction and long-range electron transport. A fabrication technique for an ultra-long bis(terpyridine)metal complex wire is also described, along with its properties and functionalities. PMID:25864838

  4. New group 6 metal carbonyl complexes with 4,5-dimethyl-N,N-bis(pyridine-2-yl-methylene)benzene-1,2-diimine Schiff base: Synthesis, spectral, cyclic voltammetry and biological activity studies

    Science.gov (United States)

    Mohamed, Rania G.; Elantabli, Fatma M.; Helal, Nadia H.; El-Medani, Samir M.

    2015-04-01

    Thermal reaction of M(CO)6 (M = Cr, Mo or W) with a Schiff base (DMPA) derived from the condensation of 4,5-dimethyl-1,2-phenylenediamine and pyridine-2-carboxaldehyde in THF in absence and presence of a secondary ligand; 2-aminobenzimidazole (Abz), thiourea (Tu) or 2-(2‧-pyridyl)benzimidazole (pybz) were studied. The reaction of Cr(CO)6 gave the four complexes Cr2(CO)2(DMPA)2; 1, Cr(DMPA)2(Abz)2; 2, Cr2(CO)4(DMPA)2(Tu)2; 3 and Cr(DMPA)2(Pybz); 4, while the thermal reaction of Mo(CO)6 resulted in the formation of the two complexes Mo2(O)6(DMPA)2; 5, and Mo2(O)2(CO)2(DMPA)2(Tu)2; 6. Thermal reaction of W(CO)6 and the Schiff base DMPA gave the complex W(O)2(DMPA)2; 7. The ligand DMPA and its metal complexes have been reported and characterized based on elemental analyses, IR, 1H NMR, magnetic measurements, and thermal analysis. Cyclic voltammetry and biological activity were also investigated.

  5. Conformations and vibrational spectroscopy of metal-ion/polylalanine complexes

    NARCIS (Netherlands)

    R.C. Dunbar; J.D. Steill; J. Oomens

    2010-01-01

    The thermochemistry and structures of complexes of dialanine and trialanine with a series of singly and doubly charged metal ions have been examined by spectroscopic and computational approaches. Complexes with Li+, K+, Cs+, Ca2+, Sr2+ and Ba2+ were formed by electrospray ionization, and studied by

  6. Homochiral metal complexes for biodegradable polymer synthesis

    OpenAIRE

    Buffet, Jean-Charles

    2010-01-01

    Chapter One introduces the principle of alkoxide and phosphine oxide as ligands for lanthanides and electropositive metals, ligand self-recognition, stereoselective polymerisation of lactide, fixation of CO2 and finally copolymerisation of CO2 and epoxide. Chapter Two shows the synthesis of the proligands rac-HLR (a racemic phosphine oxide-alkoxide, A, where R = tBu, Ph or C6H3-Me-3,5) and explores the resolution into diastereomeric RRR- and SSS-M(LR)3 to afford C3–symmetric...

  7. Bioinspired catalysis metal-sulfur complexes

    CERN Document Server

    Weigand, Wolfgang

    2014-01-01

    The growing interest in green chemistry calls for new, efficient and cheap catalysts. Living organisms contain a wide range of remarkably powerful enzymes, which can be imitated by chemists in the search for new catalysts. In bioinspired catalysis, chemists use the basic principles of biological enzymes when creating new catalyst analogues. In this book, an international group of experts cover the topic from theoretical aspects to applications by including a wide variety of examples of different systems. This valuable overview of bioinspired metal-sulfur catalysis is a must-have for all sci

  8. Nonlinear d10-ML2 Transition-Metal Complexes

    OpenAIRE

    Wolters, Lando P.; Bickelhaupt, F. Matthias

    2013-01-01

    We have investigated the molecular geometries of a series of dicoordinated d10-transition-metal complexes ML2 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+; L=NH3, PH3, CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand–metal–ligand (L–M–L) angle: this angle varies from 180° to 128.6° as a function of the metal as well as the ligands. Our main objective is to present a detailed explanation why ML2 complexes can become bent...

  9. Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups

    OpenAIRE

    Alarcón-Correa, M.; Lee, T-C; Fischer, P.

    2015-01-01

    Host–guest inclusion complexes are abundant in molecular systems and of fundamental importance in living organisms. Realizing a colloidal analogue of a molecular dynamic inclusion complex is challenging because inorganic nanoparticles (NPs) with a well-defined cavity and portal are difficult to synthesize in high yield and with good structural fidelity. Herein, a generic strategy towards the fabrication of dynamic 1:1 inclusion complexes of metal nanoparticles inside oxide nanocups with high ...

  10. Complexing of variable-valence metals with alcohols

    International Nuclear Information System (INIS)

    Labile paramagnetic complexes of the compounds of metals of variable valence (Mo, W, V) with methanol, ethanol, and tret-butanol have been investigated by the PMR method. The data on the structure and thermodynamics of the complexes make possible the assumption that alcohol molecules can compete with hydroperoxides as far as complexing is concerned and hinder the reaction of epoxidation at the stage of deep hydroperoxide conversion

  11. Preparation and Characterization of Double Metal Cyanide Complex Catalysts

    Directory of Open Access Journals (Sweden)

    Weilin Guo

    2003-01-01

    Full Text Available A series of double metal cyanide (DMC complex catalysts were prepared in two different methods by using ß-cyclodextrin, PEG-1000 and Tween-60 as an additional complex ligands respectively. It was showed that a mixture of crystalline and amorphous DMC was synthesized by using traditional method in which the additional complex ligand was added after the precipitation of DMC. Amorphous and dispersed DMC with higher activity could be obtained when the additional complex ligand was added in the reactant solution before reaction. The effect of additional complex ligand and preparation method on the crystalline state and catalytic property of DMC were also investigated.

  12. Complex metallic alloys as new materials for additive manufacturing

    International Nuclear Information System (INIS)

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal–matrix composites or of polymer–matrix composites with improved properties. Functional parts using these alloys are now commercialized. (review)

  13. Ni(II, Cu(II, AND Zn(II COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z-(3-METHYLPYRIDIN-2- YLEIMINOMETHYLPHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

    Directory of Open Access Journals (Sweden)

    Masoumeh Orojloo

    2015-11-01

    Full Text Available Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II, Cu(II, and Zn(II are described. All three compounds have the general formula [M(L2(H2O2], where L = deprotonated phenol in the Schiff base 2-((z-(3-methylpyridin-2-yleiminomethylphenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD, and room temperature magnetic moments. The Cu(II and Ni(II complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature showed a typical ΔMS = ± 1 transition. The complexes ([M(L2(H2O2] were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

  14. Gold based bulk metallic glass

    OpenAIRE

    Schroers, Jan; Lohwongwatana, Boonrat; Johnson, William L.; Peker, Atakan

    2005-01-01

    Gold-based bulk metallic glass alloys based on Au-Cu-Si are introduced. The alloys exhibit a gold content comparable to 18-karat gold. They show very low liquidus temperature, large supercooled liquid region, and good processibility. The maximum casting thickness exceeds 5 mm in the best glassformer. Au49Ag5.5Pd2.3Cu26.9Si16.3 has a liquidus temperature of 644 K, a glass transition temperature of 401 K, and a supercooled liquid region of 58 K. The Vickers hardness of the alloys in this system...

  15. Metamaterial metal-based bolometers

    OpenAIRE

    Niesler, Fabian B. P.; Gansel, Justyna K.; Fischbach, Sarah; Wegener, Martin

    2012-01-01

    We demonstrate metamaterial metal-based bolometers, which take advantage of resonant absorption in that a spectral and/or polarization filter can be built into the bolometer. Our proof-of-principle gold-nanostructure-based devices operate around 1.5 \\mum wavelength and exhibit room-temperature time constants of about 134 \\mus. The ultimate detectivity is limited by Johnson noise, enabling room-temperature detection of 1 nW light levels within 1 Hz bandwidth. Graded bolometer arrays might allo...

  16. Heavy metal complexes with 2-hydroxyarylazothiophenes

    International Nuclear Information System (INIS)

    Spectrophotometric methods have been used to study 2-(3', 4'-dioxiphenyl)-azo-3-cyano-4-methyl-5-ethoxy-carbonylthiophene (I) and its complex compounds with Ge(IV)-, Zr(IV)-, and v(V)-ions. Ionization ionstants (I) in aqueous ethanol solution are determined to be pK=6.29+-0.02; pK2=11.53+-0.02. The maximum of the non-ionized form (I) is observed at 460 nr (E460=2.15x104). In a weakly acidic medium complexes (I) with germanium (IV)-, zirconium (IV)- and vanadium (5)aions are formed. Their molar absorption coefficients are 2.87x104; 250x104; 3.61x104 respectively. The composition of compleXes determined by the Asmus method, equilibrium shift and relative outpUt is M:R=1.1 The equilibrium constants are determined. The Beer law is obserVed in the range of 0.6-4 μg/ml Ge, 0.2-3.6 μg/ml Zr, and 0.2-3.2 μg/ml V

  17. Dipicolinate complexes of main group metals with hydrazinium cation

    Indian Academy of Sciences (India)

    K Saravanan; S Govindarajan

    2002-02-01

    Some new coordination complexes of hydrazinium main group metal dipicolinate hydrates of formulae (N2H5)2M(dip)2.H2O (where, M =Ca, Sr, Ba or Pb and = 0, 2, 4 and 3 respectively and dip = dipicolinate), N2H5Bi(dip)2.3H2O and (N2H5)3Bi(dip)3.4H2O have been prepared and characterized by physico-chemical techniques. The infrared spectra of the complexes reveal the presence of tridentate dipicolinate dianions and non-coordinating hydrazinium cations. Conductance measurements show that the mono, di and trihydrazinium complexes behave as 1:1, 2:1 and 3:1 electrolytes respectively, in aqueous solution. Thermal decomposition studies show that these compounds lose water followed by endothermic decomposition of hydrazine to give respective metal hydrogendipicolinate intermediates, which further decompose exothermically to the final product of either metal carbonates (Ca, Sr, Ba and Pb) or metal oxycarbonates (Bi). The coordination numbers around the metal ions differ from compound to compound. The various coordination numbers exhibited by these metals are six (Ca), seven (Ba), eight (Sr) and nine (Pb and Bi). In all the complexes the above coordination number is attained by tridentate dipicolinate dianions and water molecules. The X-ray diffraction patterns of these compounds differ from one another suggesting that they are not isomorphous.

  18. Metal-Organic Frameworks Based on Main Group Metals

    OpenAIRE

    Zhao, Xiang

    2011-01-01

    Metal-organic frameworks (MOFs) represent a large family of crystalline porous materials which have been extensively studied during the past decade. Due to their great porosity, precise and uniform pore size and functional organic linkers, they have found applications in the area of gas storage, separation, ion-exchange, catalysis and sensors. While previous studies in this area emphasize more on transition metal based MOFs, the main group metal based MOFs have been relatively less explored, ...

  19. Studies On Some Acid Divalent-Metal Nitrilotriacetate Complexes

    Directory of Open Access Journals (Sweden)

    N. E. Milad

    2000-10-01

    Full Text Available IR and 1H-NMR studies on nitrilotriacetic acid (H3NTA suggest that the acid exists in the zwitterion form, which allows the existence of intermolecular hydrogen bonding. A tetrahedral structure is established for eleven (1:1 anhydrous acid-metal (II nitrilotriacetates complexes. The ten Dq values for the colored complexes were determined spectrophotometrically. The pKa values for the eleven acid metal complexes [M(HNTA].(OH23] were determined and compared with the corresponding pKa values of the [M(OH2n]+2 ions and also with the log β1 values of the corresponding [M(NTA]- complexes. X-ray diffraction studies on the ligand and on eight of these complexes are described.

  20. Inkjet printing of 3D metallic silver complex microstructures

    OpenAIRE

    Wits, Wessel W.; Sridhar, Ashok

    2010-01-01

    To broaden the scope of inkjet printing, this paper focuses on printing of an organic silver complex ink on glass substrates towards the fabrication of metallic 3D microstructures. The droplet formation sequence of the inkjet printer is optimised to print continuous layers of metal. A brief discussion on orientation trials, aimed at optimising the print parameters, is followed by two different methodologies of printing 3D microstructures: wet-in-wet and wet-in-dry. The surface topography of t...

  1. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    OpenAIRE

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2011-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt,...

  2. Homogeneous Catalysis with Metal Complexes Fundamentals and Applications

    CERN Document Server

    Duca, Gheorghe

    2012-01-01

    The book about homogeneous catalysis with metal complexes deals with the description of the reductive-oxidative, metal complexes  in a liquid phase (in polar solvents, mainly in water, and less in nonpolar solvents). The exceptional importance of the redox processes in chemical systems, in the reactions occuring in living organisms, the environmental processes, atmosphere, water, soil, and in industrial technologies (especially in food-processing industries) is discussed. The detailed practical aspects of the established regularities are explained for solving the specific practical tasks in various fields of industrial chemistry, biochemistry, medicine, analytical chemistry and ecological chemistry. The main scope of the book is the survey and systematization of the latest advances in homogeneous catalysis with metal complexes. It gives an overview of the research results and practical experience accumulated by the author during the last decade.

  3. Preparation of nanoporous metal foam from high nitrogen transition metal complexes

    Science.gov (United States)

    Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

    2006-11-28

    Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

  4. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    Science.gov (United States)

    Beck, M.

    1979-01-01

    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  5. Magnetite-sulfide-metal complexes in the Allende meteorite

    Science.gov (United States)

    Haggerty, S. E.; Mcmahon, B. M.

    1979-01-01

    A model of liquid immiscibility is presented that seemingly accounts for the sulfide-oxide-metal complexes that are present in olivine-rich chondrules in the Allende meteorite. The four major assemblages that are identified are: (1) magnetite + Ni-Fe metal; (2) magnetite + troilite + Ni-Fe metal; (3) magnetite + troilite + pentlandite + Ni-Fe metal; and (4) troilite + or - pentlandite. Specific attention is focused on oxide-metal associations and experimental data confirm earlier suggestions that magnetite results from the oxidation of an initially high-Fe-content metal alloy. Oxidation decreases the modal abundance of the Fe metal and this is accompanied by substantial increases in Ni contents which reach a maximum of approximately 70 wt % Ni. The proposed oxidation mechanism is entirely consistent with condensation of Fe-metal + olivine (Fa5) that subsequently reequilibrated at lower temperatures. Although the sulfide constituents could also have formed by the reaction of Fe-Ni metal + gaseous H2S, sulfide immiscibility under increased conditions of partial O2 pressure is the preferred process.

  6. Complexation-induced supramolecular assembly drives metal-ion extraction.

    Science.gov (United States)

    Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

    2014-09-26

    Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. PMID:25169678

  7. Physicochemical and biological properties of new steroid metal complexes

    International Nuclear Information System (INIS)

    The aim of this investigation was to prepare stable steroid metal chelates by chemical conversion of the natural steroid hormones testerone, 5α-dihydrotestosterone (5α-DHT) and estradiol and to characterize these by means of their spectroscopic and other physico-chemical properties. In addition, various measuring techniques for the qualitative and quantitative study of complex stabilities and hydrolytic properties were employed. The distribution of some tritiated steroid metal complexes in the tissues of rats was tested using whole animal autoradiography, mainly with a view to identifying whether selective concentration occurs in certain organs. (orig.)

  8. Radio-metal production and complexation for imaging and therapy

    International Nuclear Information System (INIS)

    Full text of publication follows. Radioactive metals (radio-metals) are regularly used for diagnosis and therapy in nuclear medicine. The most commonly used radio-metal is Tc-99m and due to recent shortages there are a number of new methods being explored to produce it at the levels needed to meet current demand. Production should result in a radio-metal with high chemical purity and specific activity in a form easily incorporated into the desired final radiopharmaceutical. Single photon emission computed tomography or positron emission tomography are the two mostly commonly used imaging techniques, whereas radio-metals with particles emissions such as alpha, beta or auger electrons can be used for tumor cell kill. Only a few radio-metals are able to be used in their native chemical form, the majority either require attachment to a targeting vector or incorporation into a chemical ligand that determines there in vivo fate. It is critical that these radio-metal complexes are stable and kinetically inert in vivo as loss of radio-metal can result in inaccurate diagnosis and toxicity to normal tissues. For imaging it is necessary to choose radio-metals that decay with emissions that are easily detected in high yield externally from the body and with appropriate half-lives with minimal particle emission. Therapy requires particle emissions and half-lives that meet the biological half-lives of the final radiopharmaceutical and nuclear decay that results in a small production of image-producing gamma to allow for determination of distribution and dosimetry. An overview will be presented of radio-metals that are of interest for nuclear medicine imaging and therapy with a discussion of their production techniques and modes of complexation. (author)

  9. Electrochemical Studies of Eight New Divalent Transition Metal Benzenesulphonate Ternary Complexes with 1,10-Phenanthroline

    Institute of Scientific and Technical Information of China (English)

    LU Yao; GUO Li-ping; MA Jian-fang; YANG Jin; WU Dongmei

    2004-01-01

    The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1,10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltammetry(CV). Based on the CV data the influences of various coordination modes on the electrochemical behavior of the complexes were discussed. The diffusion coefficient Dc and rate constant ks of those complexes in DMF systems were estimated according to CV and the results show that these processes were all quasi-reversible.

  10. Tailoring optical complex fields with nano-metallic surfaces

    Directory of Open Access Journals (Sweden)

    Rui Guanghao

    2015-04-01

    Full Text Available Recently there is an increasing interest in complex optical fields with spatially inhomogeneous state of polarizations and optical singularities. Novel effects and phenomena have been predicted and observed for light beams with these unconventional states. Nanostructured metallic thin film offers unique opportunities to generate, manipulate and detect these novel fields. Strong interactions between nano-metallic surfaces and complex optical fields enable the development of highly compact and versatile functional devices and systems. In this review, we first briefly summarize the recent developments in complex optical fields. Various nano-metallic surface designs that can produce and manipulate complex optical fields with tailored characteristics in the optical far field will be presented. Nano-metallic surfaces are also proven to be very effective for receiving and detection of complex optical fields in the near field. Advances made in this nascent field may enable the design of novel photonic devices and systems for a variety of applications such as quantum optical information processing and integrated photonic circuits.

  11. The Peculiarities of Formation of the Metal Nanoparticles in Irradiated Polymer-Metal Complexes

    International Nuclear Information System (INIS)

    Preparation of nanocomposite polymeric materials with metal particles attracts growing interest in view of a large number of potential applications. The radiation-chemical approaches may be very useful for reduction of metal ions and preparation of nanoparticles in multicomponent systems due to their flexibility and selectivity of the radiation-induced processes. Interpolyelectrolytic complexes with relatively high content of metal ions form films, which are insoluble in the water-alcohol mixtures. For this reason, such complexes may be considered as containers for metal ions, which can be reduced to yield nanoparticles stabilized in a polymeric matrix. The films of triple polymer metal complexes (polyethyleneimin (PEI) - polyacrylic acid (PAC) with ions Cu2+ or Ni2+) were used for study of the peculiarities of formation of metal nanoparticles under irradiation. The samples of interpolyelectrolytic complexes in alcohol-water environment were irradiated at 293 K in vacuum using a 60Co irradiator. The degree of reduction of the copper ions was controlled by EPR spectroscopy. Electron microscopy was used for characterization of the resulting nanocomposite polymeric materials. The study of microstructure of irradiated films has demonstrated the presence of spherical metal nanoparticles. The dimension of nanoparticles varied from 2 to 5 nm. It was found that the efficiency of reduction of ions in polymer films depended on the composition of complexes. The efficiency of reduction of Cu2+ ions under irradiation increases with increase in the relative number of PAC units. On the other hand, no significant reduction of Ni2+ ions was observed for the films containing excess amount of PAC. Analysis of the EPR spectra shows remarkable difference in reduction effect for copper ions in various ligand environment. The mechanisms of reduction of metal ions in heterogeneous systems (swelled films of interpolyelectrolytic complexes in water-alcohol environment) and the effect of

  12. Magnetic Exchange Couplings in Transition Metal Complexes from DFT

    Science.gov (United States)

    Peralta, Juan

    In this talk I will review our current efforts for the evaluation of magnetic exchange couplings in transition metal complexes from density functional theory. I will focus on the performance of different DFT approximations, including a variety of hybrid density functionals, and show that hybrid density functionals containing approximately 30% Hartree-Fock type exchange are in general among the best choice in terms of accuracy. I will also describe a novel computational method to evaluate exchange coupling parameters using analytic self-consistent linear response theory. This method avoids the explicit evaluation of energy differences, which can become impractical for large systems. Our approach is based on the evaluation of the transversal magnetic torque between two magnetic centers for a given spin configuration using explicit constraints of the local magnetization direction via Lagrange multipliers. This method is applicable in combination with any modern density functional with a noncollinear spin generalization and can be utilized as a ``black-box''. I will show proof-of-concept calculations in frustrated Fe7IIIdisk-shaped clusters, and dinuclear CuII, FeIII, and heteronuclear complexes. NSF DMR-1206920.

  13. New Transition metal assisted complex borohydrides for hydrogen storage

    International Nuclear Information System (INIS)

    High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH4)2] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH4/MgH2 catalyzed with ZnCl2 has been synthesized and characterized using various analytical techniques. (authors)

  14. Diffusion coefficients of metals and metal complexes in hydrogels used in diffusive gradients in thin films

    International Nuclear Information System (INIS)

    Diffusion coefficients of metal ions and metal-ligand complexes in hydrogels were measured at ionic strengths of 0.1-100 mmol L-1 using a diffusion cell. The three different types of hydrogel were all based on polyacrylamide and have been commonly used in the technique of diffusive gradients in thin films (DGT), where accurate diffusion coefficients are essential for the assessment of the concentrations of labile metal in solution. There was little difference in the diffusion coefficients of either Cu and Cd measured in gels with thicknesses of 0.4, 0.8 and 1.6 mm, showing that any diffusion boundary layer in solution was negligibly small. The diffusion coefficients of Pb, Ni, Cu and Cd in simple inorganic solutions was independent of ionic strength (1-100 mmol L-1), except at very low ionic strengths (0.1 mmol L-1) where the value of D was 50% lower. This observation is consistent with the gel having a positive charge that creates a Donnan partitioning of cations at the gel surface. Diffusion coefficient of Pb complexes decreased with increasing size of the ligand, in the order of diglycolic acid (DGA), nitrilotriacetic acid (NTA), fulvic acid and humic acid. In freshwaters the contribution of fulvic acid species to measured DGT mass should be considered. No significant difference was found between the rate of diffusion of Cu and Cd through the mostly commonly used gel and the filter membrane at the face of the DGT device. Diffusion coefficients obtained using a gel with small pore size (restricted gel) plus filter membrane were higher than those obtained using the restricted gel alone. It may be necessary to modify the standard DGT equation for restricted gel deployments, to take into account the difference in diffusion between the gel and the filter membrane

  15. Gold based bulk metallic glass

    Science.gov (United States)

    Schroers, Jan; Lohwongwatana, Boonrat; Johnson, William L.; Peker, Atakan

    2005-08-01

    Gold-based bulk metallic glass alloys based on Au-Cu-Si are introduced. The alloys exhibit a gold content comparable to 18-karat gold. They show very low liquidus temperature, large supercooled liquid region, and good processibility. The maximum casting thickness exceeds 5mm in the best glassformer. Au49Ag5.5Pd2.3Cu26.9Si16.3 has a liquidus temperature of 644K, a glass transition temperature of 401K, and a supercooled liquid region of 58K. The Vickers hardness of the alloys in this system is ˜350Hv, twice that of conventional 18-karat crystalline gold alloys. This combination of properties makes the alloys attractive for many applications including electronic, medical, dental, surface coating, and jewelry.

  16. Gold based bulk metallic glass

    International Nuclear Information System (INIS)

    Gold-based bulk metallic glass alloys based on Au-Cu-Si are introduced. The alloys exhibit a gold content comparable to 18-karat gold. They show very low liquidus temperature, large supercooled liquid region, and good processibility. The maximum casting thickness exceeds 5 mm in the best glassformer. Au49Ag5.5Pd2.3Cu26.9Si16.3 has a liquidus temperature of 644 K, a glass transition temperature of 401 K, and a supercooled liquid region of 58 K. The Vickers hardness of the alloys in this system is ∼350 Hv, twice that of conventional 18-karat crystalline gold alloys. This combination of properties makes the alloys attractive for many applications including electronic, medical, dental, surface coating, and jewelry

  17. Fluorescence properties of metal complexes of 2-N-Anilino pyrimidine

    International Nuclear Information System (INIS)

    2-N-Anilino pyrimidine was used as specific binder towards selected transition metals ion such as Mn (II), Ni (II) and Cr (II) in a 1:2 ratio (metal: ligand) to give their respective complexes. The structures of the ligand and complexes were confirmed by spectroscopic analysis. Fluorescence studies of metal complexes of 2-N-Anilino pyrimidine and the ligand itself were carried out under various conditions using methanol as the solvent. In general, metal ions, especially paramagnetic ions, are able to quench the fluorescence of organic ligands. The fluorescence intensity was studied based on several factors such as pH, capped and uncapped conditions. The compounds showed higher intensity in capped samples compared to uncapped samples. (author)

  18. Chemistry of Platinum and Palladium Metal Complexes in Homogeneous and Heterogeneous Catalysis: A Mini Review

    Directory of Open Access Journals (Sweden)

    Mehrban Ashiq

    2013-04-01

    Full Text Available Transition metal complexes of platinum and palladium are most widely used in catalysis. Many synthetic reactions have been carried out with such complexes (used as a catalyst which have specifically polymer ligands, through hydrosilylation, acetoxylation, hydrogenation, hydro-formylation, oligo-merisation and polymerization. Almost many platinum and palladium catalysts are heterogeneous in nature i.e. the reaction taking place on a solid surface. Now from few years homogeneous catalysts which are completely soluble in the liquid phase reactant, has acknowledged too much attention, yet having small industrial applications, mainly due to the striving of platinum and palladium complexes separation from the catalytic products. More recently a transitional type of platinum and palladium catalysts have been synthesized through attachment of the activated transition metal complexes on the surface of polymer support particularly insoluble which has been establish to offer encouraging new collection of catalysts for effective research on synthesis. Many of such complexes will be based on the palladium and platinum metals group. The major objective of this review is to inaugurate the relationship among the reactivity’s of homogeneous platinum and palladium complexes and heterogeneous complexes of these metals (those bonded to the surface of metals.

  19. Transition metal complexes with pyrazole-based ligands.Part 29. Reactions of zinc(II) and mercury(II) thiocyanate with 4-acetyl-3-amino-5-methylpyrazole

    OpenAIRE

    KATALIN MÉSZÁROS SZÉCSÉNYI; BERTA HOLLÓ; VUKADIN M. LEOVAC; Bogdanović, Goran A.; Jaćimović, Željko K.

    2009-01-01

    The work is concerned with the crystal and molecular structures of zinc(II) and mercury(II) complexes with 4-acetyl-3-amino-5-methyl-pyrazole (aamp) of the coordination formulae [Zn(NCS)2(aamp)2] and (Haamp)2[Hg(SCN)4]. The zinc(II) complex was obtained by the reaction of a warm methanolic solution of aamp with a mixture of zinc(II) nitrate and ammonium thiocyanate, whereas the mercury(II) complex was prepared by the reaction of a warm ethanolic solution of aamp and a warm, slightly acidified...

  20. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Energy Technology Data Exchange (ETDEWEB)

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  1. Radiolabelled metal complexes as possible interwell water tracers

    International Nuclear Information System (INIS)

    This proposal concentrates on water tracers for interwell studies in oil reservoirs. The main objective is to conduct further studies of a previously somewhat investigated class of metal complex water tracers. This class is composed of a selection of metal cyanide. The metals (or central cation) should preferably also have stable isotopes with high activation cross-section for analysis with thermal or epithermal neutron activation analysis. These properties offer the possibility to use also the non-radioactive metal complexes as water tracers. The metal ion selected is cobalt to make Co(CN)63- with the possible radiolabels 56Co, 57Co, 58Co, 60Co and 14C, nickel to make Ni (CN)42- with the possible radiolabel 63Ni, silver to make Ag (CN)2- with the possible radiolabel 110mAg and gold to make Au (CN)2- and/or Au(CN)4- with the possible radiolabel 195Au. In addition, new classes of complexes will be considered for further studies. This part will mainly be a concept study to prepare for future experimental investigation

  2. Reaction ability of nitrosyl group in transition metal complexes

    International Nuclear Information System (INIS)

    Transformations of the intraspheric nitrosyl group in complexes of transition metals are reviewed. All the reactions involving these groups are divided into two types: reactions associated with the electrophilic properties of the nitrosyl group; reactions associated with the nucleophilic properties of the nitrosyl group. Attempts to correlate the reactivity of the nitrosyl group with its structure and spectral characteristics are considered

  3. Group 4 Metal Complexes of Chelating Cyclopentadienyl-ketimide Ligands

    Czech Academy of Sciences Publication Activity Database

    Večeřa, M.; Varga, Vojtěch; Císařová, I.; Pinkas, Jiří; Kucharczyk, P.; Sedlařík, V.; Lamač, Martin

    2016-01-01

    Roč. 35, č. 5 (2016), s. 785-798. ISSN 0276-7333 R&D Projects: GA ČR(CZ) GA14-08531S; GA MŠk(CZ) LO1504 Institutional support: RVO:61388955 Keywords : group 4 metal complexes * cyclopentadienyl-ketimide ligands * metallocenes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.126, year: 2014

  4. Method for synthesizing metal bis(borano) hypophosphite complexes

    Science.gov (United States)

    Cordaro, Joseph G.

    2013-06-18

    The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

  5. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    Directory of Open Access Journals (Sweden)

    Yedil Yergozhin

    2013-05-01

    Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

  6. Synthesis and Spectroscopic Characterization of New Ligand and Its Pd(II, Cu(II Metal Complexes

    Directory of Open Access Journals (Sweden)

    Isam Hussain Al-Karkhi

    2013-08-01

    Full Text Available A novel Schiff base ligand containing nitrogen and sulfur donor atoms was synthesized by condensing thioamide (TA with imidothioic acid (IT to form 1, 4 dithiane-2, 3-diamine (TAIT. Metal complexes of this ligand were prepared using Cu (II chloride dihydrates and Pd (III chloride. These complexes have been characterized using various physico-chemical and spectroscopic techniques. Based on physico-chemical and spectroscopic analyses, the structure of Cu (II complex is expected to be octahedral, while Pd (II complex is proposed to be square planner geometry. Schiff base and its metal complexes were expected to show strong bioactivity against microbes and cancer cells.

  7. Bivalent transition metal complexes of coumarin-3-yl thiosemicarbazone derivatives: Spectroscopic, antibacterial activity and thermogravimetric studies

    Science.gov (United States)

    Refat, Moamen S.; El-Deen, Ibrahim M.; Anwer, Zeinab M.; El-Ghol, Samir

    2009-02-01

    Schiff base complexes of Cu(II), Co(II) and Ni(II) with two coumarin-3-yl thiosemicarbazone derivatives (1E)-1-(1-(2-oxo-2H-chromen-3-yl)ethylidene)thiosemicarbazide (OCET) and (1E)-1-(1-(6-bromo-2-oxo-2H-chromen-3-yl)ethylidene)thiosemicarbazide (BOCET) were synthesized by the reaction of Cu(II), Co(II) and Ni(II) chlorides with each mentioned ligand with molar ratio 1:2 metal-to-ligand. Both ligands and their metal complexes were characterized by different physicochemical methods, elemental analysis, molar conductivity, (UV-vis, Mass, Infrared, 1H NMR spectra) and also thermal analysis (TG and DTG) techniques. The discussion of the outcome data of the prepared complexes indicate that the coumarin-3-yl thiosemicarbazone derivatives ligands behave as a bidentate ligand through both thione sulphur and azomethine nitrogen with 1:2 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The kinetic thermodynamic parameters such as: E∗, Δ H∗, Δ S∗and Δ G∗are calculated from the DTG curves, all complexes are more ordered except Ni(II) complexes. The antibacterial activity of the coumarin-3-yl thiosemicarbazone derivatives and their metal complexes was evaluated against some kinds of Gram positive and Gram negative bacteria.

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

    Directory of Open Access Journals (Sweden)

    Enis Nadia Md Yusof

    2015-05-01

    Full Text Available 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(NS2] 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.

  9. METAL CONTAMINANTS PROMOTE DEGRADATION OF LIPID/DNA COMPLEXES DURING LYOPHILIZATION

    OpenAIRE

    Molina, Marion d.C.; Anchordoquy, Thomas J.

    2006-01-01

    Oxidation reactions represent an important degradation pathway of nucleic acid-based pharmaceuticals. To evaluate the role of metal contamination and chelating agents in the formation of reactive oxygen species (ROS) during lyophilization, ROS generation and the stability of lipid/DNA complexes were investigated. Trehalose-containing formulations were lyophilized with different levels of transition metals. ROS generation was examined by adding proxyl fluorescamine to the formulations prior to...

  10. Effect of Metal Ions on Melanin – Local Anaesthetic Drug Complexes

    OpenAIRE

    Ewa Buszman; Bożena Betlej; Dorota Wrześniok; Bożena Radwańska-Wala

    2003-01-01

    The affinity of melanin biopolymers for metal ions, drugs and other organic compounds is an important factor in the etiology of toxic retinopathy, hiperpigmentation, otic lesions and irreversible extrapyramidal disorders. The aim of the presented work was to examine the interaction of local anaesthetic drugs used in ophthalmology with model DOPA-melanin in the presence of metal ions. It has been demonstrated that the analyzed drugs form complexes with melanin biopolymer. Based on the .values ...

  11. Humic substances in natural waters and their complexation with trace metals and radionuclides: a review

    International Nuclear Information System (INIS)

    Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empirically determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. Larger values of stability constants indicate greater complex stability. The stability of radionuclide-organic complexes is affected both by concentration variables and envionmental factors. In general, complexing is favored by increased of radionuclide, increased pH, and decreased ionic strength. Actinide elements are generally most soluble in their higher oxidation states. Radionuclides can also form stable, insoluble complexes with humic materials that tend to reduce radionuclide mobility. These insoluble complexes may be radionuclide-humate colloids that subsequently precipitate from solution, or complexes of radionuclides and humic substances that sorb to clay minerals or other soil particulates strongly enough to immobilize the radionuclides. Colloid formation appears to be favored by increased radionuclide concentration and lowered pH; however, the conditions that favor formation of insoluble complexes that sorb to particulates are still poorly understood. 129 refs., 25 figs., 19 tabs

  12. Coupling of metal-based light-harvesting antennas and electron-donor subunits: Trinuclear Ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands

    DEFF Research Database (Denmark)

    Campagna, Sebastiano; Serroni, Scolastica; Puntoriero, Fausto;

    2002-01-01

    )(4,4'-Mebpy)](2+) (4,4'-Mebpy = 4,4'-dimethyl-2,2'-bipyridine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy)](6+). The absorption spectra and redox behavior of all the new metal compounds can be interpreted by a multicomponent approach, in which specific absorption features and redox processes can be assigned to......(mu-2,3-dpp)}(2)Ru(bpy-TTF1)](PF6)(6) (9; bpy=2,2'-bipyridine; 2,3-dpp = 2,3-bis(2'-pyridyl)pyrazine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy-TTF2)](PF6)(6) (10). These compounds can be viewed as coupled antennas and charge-separation systems, in which the multichromophoric trinuclear metal subunits act...... compounds in fluid solution at room temperature. Time-resolved transient absorption spectroscopy confirmed that the potentially luminescent MLCT states of 7-10 are significantly shorter lived than the corresponding states of the model species. Photoinduced electron-transfer processes from the TTF moieties...

  13. Closo-Carborane-metal complexes containing metal-carbon and metal-boron sigma-bonds

    International Nuclear Information System (INIS)

    This paper examines the metal derivatives of the closo-carboranes formed through carborane carbon-metal and carborane boron-metal bonds. In order to provide a better perspective of the closo-carborane-metal compounds the authors include derivatives containing carboranyl groups bonded to boron and silicon, which are normally classified as nonmetals. The structures, nomenclature system, and general preparative methods of the closo-carboranes are examined

  14. Synthesis of some novel divalent transition metal complexes as antimicrobials

    Institute of Scientific and Technical Information of China (English)

    Kaushal K. Oza; Paresh N. Patel; Hasmukh S. Patel

    2011-01-01

    A novel series of transition metal complexes have been synthesized from the reaction of 5-((3-(methylthio)-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-ylamino)methyl)quinolin-8-ol with transition metal salts. The structures of these compounds have been elucidated by elemental and spectral analysis. Furthermore, compounds were screened for in vitro antimicrobial activity against the representative panel of two Gram-positive and two Gram-negative bacteria and two strains of fungus. The various compounds show potent inhibitory action against test organisms.

  15. Metal complexes of 4,5-dimethylpyrazole-3-carboxaldehyde phenylthiosemicarbazone

    Science.gov (United States)

    El-Dissouky, Ali

    Several new transition metal complexes derived from 4,5-dimethyl-3-carboxaldehyde phenyl- thiosemicarbazone, LH, have been synthesized. The complexes are of stoichiometry, [CoL 2]X, X = Cl -, Br -, ClO -4 or NO -3, [MnL 2] and [CuX nL m], X = Cl -, Br -, NCS - or N -3; n = 1 or 0; m = 1 or 2 and L = the anion of LH. All complexes have been characterized by elemental analysis, spectral (i.r., electronic, NMR, ESR) and magnetic measurements. The ligand acts as tridentate monobasic co-ordinated to the metal ion via azomethine, pyrazole (N 2) nitrogen atoms and the thiolo-sulphur. The ligand field and ESR parameters are used to interpret the nature of bonding of LH with the metal ion, ground state and the ligand field strength of LH and the various co-ordinated simple ions. The coupling constants of various co-ordinated nuclei with copper (II) are estimated from ESR spectra of copper (II) complexes.

  16. Conventional and microwave synthesis, spectral, thermal and antimicrobial studies of some transition metal complexes containing 2-amino-5-methylthiazole moiety

    Directory of Open Access Journals (Sweden)

    A.P. Mishra

    2014-12-01

    Full Text Available Schiff base metal complexes of Cr(III, Co(II, Ni(II and Cu(II derived from 5-chlorosalicylidene-2-amino-5-methylthiazole (HL1 and 2-hydroxy-1-naphthylidene-2-amino-5-methylthiazole (HL2 have been synthesized by conventional as well as microwave methods. These compounds have been characterized by elemental analysis, FT-IR, FAB-mass, molar conductance, electronic spectra, 1H-NMR, ESR, magnetic susceptibility, thermal, electrical conductivity and XRD analyses. The complexes exhibit coordination number 4 or 6. The complexes are coloured and stable in air. Analytical data reveal that all the complexes exhibit 1:2 (metal:ligand ratio. IR data show that the ligand coordinates with the metal ions in a bidentate manner through the phenolic oxygen and azomethine nitrogen. FAB-mass and thermal data show degradation pattern of the complexes. The thermal behaviour of metal complexes shows that the hydrated complexes lose water molecules of hydration in the first step; followed by decomposition of ligand molecules in the subsequent steps. XRD patterns indicate crystalline nature for the complexes. The Schiff bases and metal complexes show good activity against the Gram-positive bacteria; Staphylococcus aureus and Gram-negative bacteria; Escherichia coli and fungi Aspergillus niger and Candida albicans. The antimicrobial results also indicate that the metal complexes are better antimicrobial agents as compared to the Schiff bases.

  17. Inhomogeneous complexation of trace metals in water with organic nano-complexants

    Science.gov (United States)

    Dolgin, Bella; Bulatov, Valery; Hadar-Abuhatzira, Hodayah; Japarov, Julia; Schechter, Israel

    2011-12-01

    The complexation of heavy metals, such as Cd 2+ and Ni 2+, with organic complexants such as 1-(2-pyridylazo)-2-naphthol (PAN) and 1-(2-thiazolylazo)-2-naphthol (TAN) in water has been investigated. Under such conditions, both the reagents and the products form nano-particulates. These materials are important because their spectrum changes upon exposure to heavy metals and they may be used for design of new optical detectors. The kinetic schemes so far suggested for these complexation reactions are not valid for such experimental conditions, since they assume homogeneous behavior. We provide evidences to the inhomogeneous nature of these reactions. The complexation has been studied using TEM imaging, zeta-potentiometry, time-dependent particulate size analysis and time-dependent spectroscopy. Many of the experimental results are explained in terms of the nature of the nano-particulates of these two complexants. Several processes were identified, including crystal growing of the complexant, its reaction with metal ions in solution and on the surface area, chemical erosion of complexant crystallites and their decomposition, re-crystallization of the formed complexes and long term aggregation of both the complexant and the resulted complex. It was found that the needle-like nano-structures on the surface of the TAN particulates governs its reaction and particulate behavior. The known optimal complexation conditions, such as pH, and delay time are now understood in terms of the zeta-potential minima of the suspensions and in terms of the kinetic parameters. Also the interferences of some ions in the Ni-TAN complexation are now quantified and the kinetic data indicate the best delay time when the interfering effects are minimal.

  18. Metal-Based Antibacterial and Antifungal Agents: Synthesis, Characterization, and In Vitro Biological Evaluation of Co(II), Cu(II), Ni(II), and Zn(II) Complexes With Amino Acid-Derived Compounds

    OpenAIRE

    Zahid H. Chohan; Arif, M.; Akhtar, Muhammad A.; Supuran, Claudiu T.

    2006-01-01

    A series of antibacterial and antifungal amino acid-derived compounds and their cobalt(II), copper(II), nickel(II), and zinc(II) metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, and IR, and electronic spectral measurements. Ligands (L1)−(L5) were derived by condensation of β-diketones with glycine, phenylalanine, valine, and histidine and act as bidentate towards metal ions (cobalt, copper, nickel, and zinc) via the azo...

  19. Estimating the acidity of transition metal hydride and dihydrogen complexes by adding ligand acidity constants.

    Science.gov (United States)

    Morris, Robert H

    2014-02-01

    A simple equation (pKa(THF) = ∑AL + Ccharge + Cnd + Cd6) can be used to obtain an estimate of the pKa of diamagnetic transition metal hydride and dihydrogen complexes in tetrahydrofuran, and, by use of conversion equations, in other solvents. It involves adding acidity constants AL for each of the ligands in the 5-, 6-, 7-, or 8-coordinate conjugate base complex of the hydride or dihydrogen complex along with a correction for the charge (Ccharge = -15, 0 or 30 for x = +1, 0 or -1 charge, respectively) and the periodic row of the transition metal (Cnd = 0 for 3d or 4d metal, 2 for 5d metal) as well as a correction for d(6) octahedral acids (Cd6 = 6 for d(6) metal ion in the acid, 0 for others) that are not dihydrogen complexes. Constants AL are provided for 13 commonly occurring ligand types; of these, nine neutral ligands are correlated with Lever's electrochemical ligand parameters EL. This method gives good estimates of the over 170 literature pKa values that range from less than zero to 50 with a standard deviation of 3 pKa units for complexes of the metals chromium to nickel, molybdenum, ruthenium to palladium, and tungsten to platinum in the periodic table. This approach allows a quick assessment of the acidity of hydride complexes found in nature (e.g., hydrogenases) and in industry (e.g., catalysis and hydrogen energy applications). The pKa values calculated for acids that have bulky or large bite angle chelating ligands deviate the most from this correlation. The method also provides an estimate of the base strength of the deprotonated form of the complex. PMID:24410025

  20. A polarographic method for elucidating the position of complexing in metal ion-azo-dyestuffs complexes

    International Nuclear Information System (INIS)

    The location of chosen metal ions (M = Be, La, Ce, Nd, Gd, Lu, Y) in their chelates of azo-dyestuffs like arsenazo 1, arsenazo 3, chlorophosphonazo 3, nitrosulphonazo 3 has been studied by direct current polarography, differential pulse polarography and adsorptive stripping voltammetry. It has been noticed, that the cathodic wave (peak) of a complex has appeared when the azo-group was involved in forming the complex. On the basis of the received results and a survey of the literature it has been stated, that the polarographic method can be used as a criterion which solves the location of a metal ion in its chelate of a electrochemically active, multifunctional ligand

  1. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    Science.gov (United States)

    Siddiqi, K. S.; Khan, Sadaf; Nami, Shahab A. A.; El-ajaily, M. M.

    2007-07-01

    Sn(tch) 2{MCl 2} 2 was prepared from the precursor Sn(tch) 2 and MCl 2. It was subsequently allowed to react with diethyldithiocarbamate which yielded the trinuclear complexes of the type Sn(tch) 2{M 2(dtc) 4}, where tch = thiocarbohydrazide, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and dtc = diethyldithiocarbamate. They were characterized on the basis of microanalytical, thermal (TGA/DSC), spectral (IR, UV-vis, EPR, 1H NMR) studies, conductivity measurement and magnetic moment data. On the basis of spectral data a tetrahedral geometry has been proposed for the halide complexes, Sn(tch) 2{MCl 2} 2 except for Cu(II) which exhibits a square planar coordination although the transition metal ion in Sn(tch) 2{M 2(dtc) 4} achieves an octahedral geometry where the dithiocarbamato moiety acts as a symmetrical bidentate ligand. The bidentate nature has been established by the appearance of a sharp single ν(C-S) around 1000 cm -1. A downfield shift observed in NH a and NH b protons on moving from Sn(tch) 2 to Sn(tch) 2{MCl 2} 2 is due to the drift of electrons toward metal atoms. A two-step pyrolysis has been observed in the Sn(tch) 2{MCl 2} 2 complexes while their dithiocarbamato derivatives exhibit a three-stage degradation pattern. Finally, the in vitro antibacterial activity of Sn(tch) 2{M 2(dtc) 4} and the mononuclear Sn(tch) 2 has been carried out on bacterial strains Escherichia coli and Salmonella typhi. The compounds were found to be active against the test organisms. The activity of the complexes is enhanced with increasing concentration. The maximum activity in both the strains was achieved by cobalt(II) dithiocarbamate complex. Minimum activity was found for Sn(tch) 2 which generally increases with the introduction of transition metal ion in the complex.

  2. Syntheses, Crystal Structures and Properties of Two Metal-organic Complexes Based on 5-(4-Pyridyl)-methoxyl Isophthalic Acid

    Institute of Scientific and Technical Information of China (English)

    TAO Zhao-Lin; QIN Ling; ZHENG He-Gen

    2013-01-01

    Two new metal-organic frameworks,[Co3L2(NO2)2(H2O)2]n (1) and{[Ni(L)(H2O)5]·(H2O)2·DMF}n (2,H2L =5-(4-pyridyl)-methoxyl isophthalic acid),have been synthesized by the hydrothermal method and characterized by elemental analysis,infrared spectroscopy,thermogravimetric analysis (TGA) and X-ray crystallography.Compound 1 crystallizes in the monoclinic system with space group P2/c and adopts a slightly distorted octahedral configuration.In compound 1,the 2D bilayered structures are linked by O-H…O and O-H…N hydrogen bonds to form a 3D framework.Compound 2 crystallizes in the monoclinic system with space group P21/n,and the central nickel atoms are octa-coordinated with five O atoms from coordinated water molecules and one N atom from one H2L ligand.The abundant O-H…O hydrogen bonds and π…π interactions link the molecules into a 3D framework.In addition,compounds 1 and 2 exhibit strong ultraviolet absorption in the solid state at room temperature.

  3. Preparation and physical properties of grafted bagasse pulp metal complexes

    International Nuclear Information System (INIS)

    The effect of grafting on the electrical properties of bleached bagasse pulp has been investigated over a frequency range 1-200 Khz. The conductivity increases upon grafting with acrylic acid or acrylonitrile. Grafted bleached bagasse pulp with acrylic acid showed an increase in the dielectric constant ε and dielectric loss ε. The bagasse/acrylic acid copolymer metal complexes have shown further increase in the conductivity. The conductivity decreases as the degree of grafting increased from 25% to 215%, indicating slower rate of complexation at higher grafting percentage

  4. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Science.gov (United States)

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-01

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

  5. Photactivatable metal complexes : from theory to applications in biotechnology and medicine

    OpenAIRE

    Smith, N. A.; Sadler, P. J.

    2013-01-01

    This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal–carbonyl complexes is still...

  6. Interplay of metal-allyl and metal-metal bonding in dimolybdenum allyl complexes.

    Energy Technology Data Exchange (ETDEWEB)

    Trovitch, R. J.; John, K. D.; Martin, R. L.; Obrey, S. J.; Sattelberger, A. P.; Scott, B. L.; Baker, R. T.; LANL; Univ. of Ottawa

    2009-01-01

    Addition of PMe{sub 3} to Mo{sub 2}(allyl){sub 4} afforded Mo{sub 2}(allyl){sub 4}(PMe{sub 3}){sub 2}, in which two of the allyl groups adopt an unprecedented {mu}{sub 2}-{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the roles of the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  7. Effects of microwave irradiation on metal hydrides and complex hydrides

    International Nuclear Information System (INIS)

    Effects of single-mode microwave irradiation on metal hydrides, MHn (LiH, MgH2, CaH2, TiH2, VH0.81, ZrH2, and LaH2.48) and complex hydrides MBH4 (LiBH4, NaBH4, and KBH4) were systematically investigated. Among the metal hydrides, TiH2, VH0.81, ZrH2, and LaH2.48 exhibit a rapid heating by microwave irradiation, where small amount of hydrogen (less than 0.5 mass%) are desorbed. On the other hand, LiBH4 is heated above 380 K by microwave irradiation, where 13.7 mass% of hydrogen is desorbed. The rapid heating of metal hydrides such as TiH2, VH0.81, ZrH2, and LaH2.48 are mainly due to the conductive loss. Meanwhile the microwave heating in LiBH4 is attributed to the conductive loss which is caused by a structural transition. The difference in the amount of desorbed hydrogen between metal hydrides and complex hydrides might be caused by the different microwave penetration depth and/or the temperature saturation in the microwave irradiation process. Microwave heating might be applied to hydrogen storage system, though further development of hydrides themselves and engineering techniques are required

  8. Ionic products of metal complexes with dithiocarbonic acid derivatives

    International Nuclear Information System (INIS)

    Ionic products of the complexes of certain sulfide-forming metal ions (In, Cd, Te, etc.) with alkyl derivates of dithiocarbonic acid have been defined. The possibility to use ionic products of alkyl xanthates for predicting the practicability of employing alkyl xanthates as analytic reagents in titrimetric methods of analysis, in extractional methods of separation and determination of elements, increase in the determination selectivity, is shown. 11 refs., 1 fig., 1 tab

  9. Electrochemistry of metal complexes and their use in amperometric sensors

    OpenAIRE

    Somasundrum, Mithran

    1994-01-01

    This thesis concerns the utilization of metal complexes in amperometric sensors. Chapter One provides a general introduction to the area. The electrochemical theories relating to the development and use of amperometric sensors, are described, and applications for such sensors are outlined. These include trace element analysis for environmental and clinical use and the determination of NADH for the detection of clinical analytes. In Chapter Two, the electrochemical changes oc...

  10. Physical properties of the complex metallic alloy phases in the Al-Pd-Mn system

    OpenAIRE

    Dolinsek, Janez; Jaglicic, Zvonko; Smontara, Ana

    2005-01-01

    Abstract The Al-Pd-Mn system of intermetallics contains complex metallic alloy (CMA) phases, whose crystal structures are based on giant unit cells comprising up to more than a thousand atoms per cell. We performed investigation of the magnetic, electrical, thermal transport and thermoelectric properties of the i' phase and the related ? phase on single-crystalline samples.

  11. Synthesis of N4 donor macrocyclic Schiff base ligands and their Ru (II), Pd (II), Pt (II) metal complexes for biological studies and catalytic oxidation of didanosine in pharmaceuticals

    Science.gov (United States)

    Ravi krishna, E.; Muralidhar Reddy, P.; Sarangapani, M.; Hanmanthu, G.; Geeta, B.; Shoba Rani, K.; Ravinder, V.

    2012-11-01

    A series of tetraaza (N4 donor) macrocyclic ligands (L1-L4) were derived from the condensation of o-phthalaldehyde (OPA) with some substituted aromatic amines/azide, and subsequently used to synthesize the metal complexes of Ru(II), Pd(II) and Pt(II). The structures of macrocyclic ligands and their metal complexes were characterized by elemental analyses, IR, 1H &13C NMR, mass and electronic spectroscopy, thermal, magnetic and conductance measurements. Both the ligands and their complexes were screened for their antibacterial activities against Gram positive and Gram negative bacteria by MIC method. Besides, these macrocyclic complexes were investigated as catalysts in the oxidation of pharmaceutical drug didanosine. The oxidized products were further treated with sulphanilic acid to develop the colored products to determine by spectrophotometrically. The current oxidation method is an environmentally friendly, simple to set-up, requires short reaction time, produces high yields and does not require co-oxidant.

  12. Creating Complex Hollow Metal Geometries Using Additive Manufacturing and Metal Plating

    OpenAIRE

    McCarthy, David Lee

    2012-01-01

    Additive manufacturing introduces a new design paradigm that allows the fabrication of geometrically complex parts that cannot be produced by traditional manufacturing and assembly methods. Using a cellular heat exchanger as a motivational example, this thesis investigates the creation of a hybrid manufacturing approach that combines selective laser sintering with an electroforming process to produce complex, hollow, metal geometries. The developed process uses electroless nickel plating on l...

  13. Metal-Based Antibacterial and Antifungal Agents: Synthesis, Characterization, and In Vitro Biological Evaluation of Co(II, Cu(II, Ni(II, and Zn(II Complexes with Amino Acid-Derived Compounds

    Directory of Open Access Journals (Sweden)

    Zahid H. Chohan

    2006-01-01

    Full Text Available A series of antibacterial and antifungal amino acid-derived compounds and their cobalt(II, copper(II, nickel(II, and zinc(II metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, and IR, and electronic spectral measurements. Ligands (L1–(L5 were derived by condensation of β-diketones with glycine, phenylalanine, valine, and histidine and act as bidentate towards metal ions (cobalt, copper, nickel, and zinc via the azomethine-N and deprotonated-O of the respective amino acid. The stoichiometric reaction between the metal(II ion and synthesized ligands in molar ratio of M: L (1: 1 resulted in the formation of the metal complexes of type [M(L(H2O4]Cl (where M = Co(II, Cu(II, and Zn(II and of M: L (1: 2 of type [M(L2(H2O2] (where M = Co(II, Cu(II, Ni(II, and Zn(II. The magnetic moment data suggested for the complexes to have an octahedral geometry around the central metal atom. The electronic spectral data also supported the same octahedral geometry of the complexes. Elemental analyses and NMR spectral data of the ligands and their metal(II complexes agree with their proposed structures. The synthesized ligands, along with their metal(II complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexeneri, Pseudomonas aeruginosa, and Salmonella typhi and two Gram-positive (Bacillus subtilis and Staphylococcus aureus bacterial strains and for in vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani, and Candida glaberata. The results of these studies show the metal(II complexes to be more antibacterial/antifungal against one or more species as compared to the uncomplexed ligands. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties. Five compounds, (3, (7, (10, (11, and (22, displayed potent cytotoxic

  14. Metal-Based Antibacterial and Antifungal Agents: Synthesis, Characterization, and In Vitro Biological Evaluation of Co(II), Cu(II), Ni(II), and Zn(II) Complexes With Amino Acid-Derived Compounds.

    Science.gov (United States)

    Chohan, Zahid H; Arif, M; Akhtar, Muhammad A; Supuran, Claudiu T

    2006-01-01

    A series of antibacterial and antifungal amino acid-derived compounds and their cobalt(II), copper(II), nickel(II), and zinc(II) metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, and IR, and electronic spectral measurements. Ligands (L(1))-(L(5)) were derived by condensation of beta-diketones with glycine, phenylalanine, valine, and histidine and act as bidentate towards metal ions (cobalt, copper, nickel, and zinc) via the azomethine-N and deprotonated-O of the respective amino acid. The stoichiometric reaction between the metal(II) ion and synthesized ligands in molar ratio of M : L (1 : 1) resulted in the formation of the metal complexes of type [M(L)(H(2)O)(4)]Cl (where M = Co(II), Cu(II), and Zn(II)) and of M : L (1 : 2) of type [M(L)(2)(H(2)O)(2)] (where M = Co(II), Cu(II), Ni(II), and Zn(II)). The magnetic moment data suggested for the complexes to have an octahedral geometry around the central metal atom. The electronic spectral data also supported the same octahedral geometry of the complexes. Elemental analyses and NMR spectral data of the ligands and their metal(II) complexes agree with their proposed structures. The synthesized ligands, along with their metal(II) complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexeneri, Pseudomonas aeruginosa, and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and for in vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani, and Candida glaberata. The results of these studies show the metal(II) complexes to be more antibacterial/antifungal against one or more species as compared to the uncomplexed ligands. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties. Five compounds, (3), (7), (10), (11), and (22

  15. Mononuclear metal complexes of organic carboxylic acid derivatives: Synthesis, spectroscopic characterization, thermal investigation and antimicrobial activity

    Science.gov (United States)

    Abd El-Wahab, Zeinab H.

    2007-05-01

    Two Schiff base ligands bearing organic acid moiety, vis., N-(2-thienylmethylidene)-2-amino-4-chlorobenzoic acid (HL 1) and N-(2-hydroxybenzylidene)-2-amino-4-chlorobenzoic acid (H 2L 2) have been synthesized by the interaction of 2-thiophenecarboxaldehyde and 2-hydroxybenzaldehyde with 2-amino-4-chlorobenzoic acid. Co(II), Ni(II), Cu(II) and Zn(II) complexes of these ligands have been prepared. They are characterized on the basis of analytical data, molar conductance, IR, 1H NMR, UV-vis, mass spectra, magnetic measurements, thermal analysis and X-ray powder diffraction technique. The molar conductance data reveal that these complexes are non-electrolytes. The ligands are coordinated to the metal ions in a terdentate manner with ONO/ONS donor sites of the carbonyl oxygen, azomethine nitrogen and phenolic oxygen or thiophenic sulphur. An octahedral structure is proposed for the prepared metal complexes and some ligand field parameters ( Dq, B and β) in addition to CFSE were calculated. The thermal stability of the metal complexes is evaluated. The Schiff base ligands and their metal complexes have been tested against four species of bacteria as well as four species of fungi and the results have been compared with some known antibiotics.

  16. Synthesis and antibacterial activity of some Schiff base complexes

    Directory of Open Access Journals (Sweden)

    R. NAIR

    2006-07-01

    Full Text Available Two Schiff bases were synthesized from raceacetophenone: 1 ADS1: 4-ethyl-6-{(E-1-[(3-nitrophenylimino]ethyl}benzene-1,3-diol and 2 ADS3: 4-ethyl-6-{(E-1-[(2-nitrophenylimino]ethyl}benzene-1,3-diol. Then their metal complexes were formed. The metals selected for the preparation of complexes were copper, nickel, iron and zinc. Hence, in total 8 metal complexes were synthesized and screened for antibacterial activity against some clinically important bacteria, such as Pseudomonas aeruginosa, Proteus vulgaris, Proteus mirabilis, Klebsiella pneumoniae and Staphylococcus aureus. The in vitro antibacterial activity was determined by the Agar Ditch technique using DMF (polar and 1,4-dioxane (non polar as solvents. The Schiff bases showed greater activity than theirmetal complexes; themetal complexes showed differential effects on the bacterial strains investigated and the solvent used, suggesting that the antibacterial activity is dependent on the molecular structure of the compound, the solvent used and the bacterial strain under consideration. The Schiff base ADS3 in the polar solvent DMF showed better antibacterial activity towards the investigated bacterial strains. Amongst the four metals, Zn showed the best antibacterial activity followed by Fe in 1,4-dioxane while Ni followed by Zn and Fe showed the best antibacterial activity in DMF. P. vulgaris was the most resistant bacteria.

  17. Metal complexes as antibacterial agents: Synthesis, characterization and antibacterial activity of some 3d metal complexes of sulphadimidine

    Directory of Open Access Journals (Sweden)

    Adedibu Clement Tella

    2010-06-01

    Full Text Available Metal complexes of Sulphadimidine(SAD were synthesized.The complexes were formulated as [Co(SAD2Cl2], [Cu(SAD2 (H2O2], [Ni (SAD2 Cl2 H2O], [Cd (SAD2 Br2], [Fe (SAD3](H­2O­3 and [Mn (SAD2Cl2] characterized by elemental Analysis, conductivity, IR , UV-Vis, Magnet moment and 1H-NMR and Mass spectroscopies. Co(II, Mn (II,  and Ni(II sulphadimidine complexes consist of metal ion which coordinates through amino nitrogen of the terminal NH2 group and oxygen of sulfonamidic group of the two molecules of sulphadimidine ligand and two halide ions to form octahedral structure while Cd(II coordinates with sulphadimidine through amino nitrogen of the terminal NH2 group with two bromine ions to complete tetrahedral structure. In Cu(II sulphadimidine complex, copper ion coordinates through both pyrimidinic nitrogen (heterocyclic nitrogen and sulfonamidic nitrogen of the two molecules of sulphadimidine. Fe(III coordinates to three molecules of sulphadimidine through heterocyclic nitrogen (pyrimidinic nitrogen and sulfonamidic nitrogen,with three molecules of water outside the coordination sphere. Both Fe(III and Cu(II complexes exhibit octahedral geometry. The antibacterial activity of the complexes and the ligands was investigated against Esherichia coli,  Staphylococcus aureus and Klebsiella pneumonia .  The data obtained revealed that the complexes showed greater activity against the three micro-organisms when compared to parent compound. Stability constant of the complexes were evaluated for the metal salts, the order of stability constant b was found to be Cu (II > Fe (III >Ni(II> Co (II > Cd (II.The values of stability constant (b was found to be log 6.31, 5.93, 5.29, 4.63 and 3.92, respectively. The stability constant data revealed that this ligand may be used as antidote or chelating agent for medical treatment of metals overload or poisoning.

  18. Synthesis, structural characterization and biological studies of some nalidixic acid-metal complexes: Metalloantibiotic complexes of some divalent and trivalent metal ions

    Science.gov (United States)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.

    2015-08-01

    This article describes the synthesis, characterization, computational and biological assessments of some divalent and trivalent metal (Ca(II), Fe(III), Pd(II) and Au(III)) complexes of nalidixic acid (nixH). The structures of these complexes were assigned using elemental analyses and spectral measurements e.g., IR, Raman, 1H NMR, 13C NMR and electronic techniques. These results indicated that, nalidixic acid reacts as a bidentate ligand bound to the metal ion through the oxygen atoms of carbonyl and carboxylate groups. The molar conductance measurements of the complexes in DMSO correspond to be non-electrolyte nature. Thus, these complexes may be formulated as [Ca(nix)(Cl)(H2O)3]. H2O, [Fe(nix)(Cl)2(H2O)2]·3H2O, [Pd(nix)(Cl)(H2O)] and [Au(nix)(Cl)2]. Base on the Coats-Redfern and Horowitz-Metzeger methods, the kinetic thermodynamic parameters (E∗, ΔS∗, ΔH∗ and ΔG∗) of the thermal decomposition reactions have been calculated from thermogravimetric curves of TG and DTG. The nano-scale range of the nalidixic acid complexes have been discussed using X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) analyzer. The computational studies for the synthesized complexes have been estimated.

  19. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity

    Science.gov (United States)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL1 and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL2 derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML(1-2)2 have been synthesized, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate ? coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mn Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu > Mn > Ni > Co > Zn.

  20. Ab initio calculations on the magnetic properties of transition metal complexes

    International Nuclear Information System (INIS)

    We present a protocol for the ab initio determination of the magnetic properties of mono- and polynuclear transition metal compounds. First, we obtain the low lying electronic states by multireference methods. Then, we include spin-orbit coupling and an external magnetic field for the determination of zero-field splitting and g-tensors. For the polynuclear complexes the magnetic exchange coupling constants are determined by a modified complete active space self consistent field method. Based on the results of the ab initio calculations, magnetic data such as magnetic susceptibility or magnetization are simulated and compared to experimental data. The results obtained for the polynuclear complexes are further analysed by calculations on model complexes where part of the magnetic centers are substituted by diamagnetic ions. The methods are applied to different Co and Ni containing transition metal complexes

  1. Organodioxygen complexes of some group 4B metal ions

    International Nuclear Information System (INIS)

    Organodioxygen complexes of some group 4B metal ions, viz., zirconium(IV), tin(IV) and lead(II) containing monodentate, bidentate and tridentate ligands were synthesized and characterized. The complexes have the compositions of [Zr(O)(O2)2C5H5N.H2O], [Zr(O)(O2-)2.2OPPh3], [Sn(O2)(C9H6NO)2], [Sn(02)2.(CH2)2(NH2)2], [Pb(O2-)(C5H5N)2NO3], [Pb(O2)(C8H6NOH)], [Pb(O2-)(det)NO3] and [PbO2-) (C5H4NCOOH)NO3.H2O]. Because of apparent linearity of M- O2 grouping, the V1(O-O) stretching modes were only Raman active, giving bands at 810- 841 cm1 for the peroxo complexes (1, 3, ,4 and 6), while the bands in the superoxo complexes (2, 5, 7 and 8) appeared at 1020- 1100 cm-1. The peroxo complex of Zr(IV) containing monodentate ligands were found to oxidize trans-stilbene to trans-stilbene oxide under stoichiometric conditions. The organoperoxo complexes of tin and lead were insensitive to oxidative processes. (author)

  2. STUDY ON SYNTHESIS AND RELAXIVITY OF PARAMAGNETIC POLYESTER METAL COMPLEXES FOR MRI

    Institute of Scientific and Technical Information of China (English)

    Ouyangming; ZhuoRenxi; 等

    1995-01-01

    Fifteen new polyester ligands were prepared by copolymerization of EDTA (ethylenediaminetertraacetic acid)dianhydride or DTPA (diethylenetriamine pentaacetic acid) dianhydride and dihydric alcohol or dihydric phenol.Their paramagnetic metal complexes were also synthesized.All polyester ligands and metal complexes were characterized by 1HNMR,IR spectra and elemental analyses.Preliminary study showed that the polyester metal complexes had higher relaxation effectiveness as compared to corresponding small molecular metal complexes.

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

    Science.gov (United States)

    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.

  4. Transition metal M(II complexes with isonicotinoylhydrazone-9-anthraldehyde

    Directory of Open Access Journals (Sweden)

    Dianu M.L.

    2010-01-01

    Full Text Available New complexes of isonicotinoylhydrazone-9-anthraldehyde with Cu(II, Co(II and Ni(II have been prepared and characterized by analytical and physico-chemical techniques, such as elemental and thermal analyses, magnetic susceptibility and conductivity measurements, and electronic, EPR and IR spectral studies. The infrared spectral studies revealed the bidentate or monodentate nature of the Schiff base in the complexes; the pyridine nitrogen does not participate in the coordination. A tetrahedral geometry is suggested for the nitrate-complexes and an octahedral geometry for the others. Thermal studies support the chemical formulation of these complexes.

  5. Synthesis, characterization and antimicrobial studies of Schiff base complexes

    Science.gov (United States)

    Zafar, Hina; Ahmad, Anis; Khan, Asad U.; Khan, Tahir Ali

    2015-10-01

    The Schiff base complexes, MLCl2 [M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by the template reaction of respective metal ions with 2-acetylpyrrole and 1,3-diaminopropane in 1:2:1 M ratio. The complexes have been characterized by elemental analyses, ESI - mass, NMR (1H and 13C), IR, XRD, electronic and EPR spectral studies, magnetic susceptibility and molar conductance measurements. These studies show that all the complexes have octahedral arrangement around the metal ions. The molar conductance measurements of all the complexes in DMSO indicate their non-electrolytic nature. The complexes were screened for their antibacterial activity in vitro against Gram-positive (Streptococcus pyogenes) and Gram-negative (Klebsiella pneumoniae) bacteria. Among the metal complexes studied the copper complex [CuLCl2], showed highest antibacterial activity nearly equal to standard drug ciprofloxacin. Other complexes also showed considerable antibacterial activity. The relative order of activity against S. Pyogenes is as Cu(II) > Zn(II) > Co(II) = Fe(II) > Ni(II) and with K. Pneumonia is as Cu(II) > Co(II) > Zn(II) > Fe(II) > Ni(II).

  6. Reactions of transition metal complexes with cyclic ethers

    International Nuclear Information System (INIS)

    Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

  7. Structural models for alkali-metal complexes of polyacetylene

    Science.gov (United States)

    Murthy, N. S.; Shacklette, L. W.; Baughman, R. H.

    1990-02-01

    Structural models for a stage-2 complex are proposed for polyacetylene doped with less than about 0.1 potassium or rubidium atoms per carbon. These structures utilize as a basic motif an alkali-metal column surrounded by four planar-zig-zag polyacetylene chains, a structure found at the highest dopant levels. In the new stage-2 structures, each polyacetylene chain neighbors only one alkali-metal column, so the phase contains four polymer chains per alkali-metal column. Basic structural aspects for stage-1 and stage-2 structures are now established for both potassium- and rubidium-doped polyacetylene. X-ray-diffraction and electrochemical data show that undoped and doped phases coexist at low dopant concentrations (<0.06 K atom per C). X-ray-diffraction data, down to a Bragg spacing of 1.3 Å, for polyacetylene heavily doped with potassium (0.125-0.167 K atom per C) is fully consistent with our previously proposed stage-1 tetragonal unit cell containing two polyacetylene chains per alkali-metal column. There is no evidence for our samples requiring a distortion to a monoclinic unit cell as reported by others for heavily doped samples. The nature of structural transformations and the relationship between structure and electronic properties are discussed for potassium-doped polyacetylene.

  8. Metal complexation inhibits the effect of oxalic acid in aerosols as cloud condensation nuclei (CCN

    Directory of Open Access Journals (Sweden)

    T. Furukawa

    2010-11-01

    Full Text Available Atmospheric aerosols have both a direct and an indirect cooling effect that influences the radiative balance at the Earth's surface. It has been estimated that the degree of cooling is large enough to cancel the warming effect of carbon dioxide. Among the cooling factors, secondary organic aerosols (SOA play a key role in the solar radiation balance in the troposphere as SOA can act as cloud condensation nuclei (CCN and extend the lifespan of clouds because of their high hygroscopic and water soluble nature. Oxalic acid is one of the major components of SOA, and is produced via several formation pathways in the atmosphere. However, it is not certain whether oxalic acid exists as free oxalic acid or as metal oxalate complexes in aerosols, although there is a marked difference in their solubility in water and their hygroscopicity. We employed X-ray absorption fine structure spectroscopy to characterize the calcium (Ca and zinc (Zn in aerosols collected at Tsukuba in Japan with fractionation based on particle size using an impactor aerosol sampler. It was shown that 10–60% and 20–100% of the total Ca and Zn in the finer particles (<2.1 μm were present as Ca and Zn oxalate complexes, respectively. Oxalic acid can act as CCN because of its hygroscopic properties, while metal complexes are not hygroscopic, and so cannot be CCN. Based on the concentration of noncomplexed and metal-complexed oxalate species, we found that most of the oxalic acid is present as metal oxalate complexes in the aerosols, suggesting that oxalic acid does not act as CCN in the atmosphere. Similar results are expected for other dicarboxylic acids, such as malonic and succinic acids. Thus, it is possible that the cooling effect of organic aerosols assumed in various climate modeling studies is overestimated because of the lack of information on metal oxalate complexes in aerosols.

  9. Complex metal borohydrides: multifunctional materials for energy storage and conversion.

    Science.gov (United States)

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-01

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world's energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future. PMID:27384871

  10. Complex metal borohydrides: multifunctional materials for energy storage and conversion

    Science.gov (United States)

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-01

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world’s energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future.

  11. Synthesis and Application of Zeolite-encapsulated Nickel Schiff-base Complex

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Transition-metal complex-catalyzed oxidation of organic substrates with molecular oxygen is gaining importance as a viable alternative to the environmentally hazardous metal-oxide-based reagents. The complexes have received much attention recently due to the potential application of these complexes as oxidation catalysts for the oxidation of alkene, enolizable, aldehydes and other organic substrates. Recent studies of our group showed that metal complexes catalyzed the oxidation of organic substrates selectively in the presence of molecular oxygen 1,5. Here, it is reported that zeolite-encapsulated Ni (I) Schiff-base complex exhibit a catalytic activity and selectivity for the oxidation of styrene.

  12. Model Based Metal Transfer Control

    DEFF Research Database (Denmark)

    Thomsen, Jesper Sandberg

    In pulsed gas metal arc welding (pulsed GMAW) current pulses are used for detaching drops at the tip of the electrode. To obtain a high weld quality one drop should be detached for every pulse, and moreover, the amount of energy used for detachment should be kept at a minimum. Thus, each pulse mu...

  13. Transition metal complexes with thiosemicarbazide-based ligands. Part46. Synthesis and physico-chemical characterization of mixed ligand cobalt(III-complexes with salicylaldehyde semi-, thiosemi- and isothiosemicarbazone and pyridine

    Directory of Open Access Journals (Sweden)

    VUKADIN M. LEOVAC

    2003-12-01

    Full Text Available Mixed ligand octahedral cobalt(III complexes with the tridentate salicylaldehyde semi-, thiosemi- and isothiosemicarbazone and pyridine of general formula [CoIII(L11-3(py3]X (H2L1 = salicylaldehyde semicarbazone, X = [CoIICl3(py]-, ClO4- . H2O, I- . 0.5 I2; H2L2 = salicylaldehyde thiosemicarbazone, X = [CoIICl3(py]-, [CoIIBr3(py]-, ClO4- . H2O, I3-; H2L3 = salicylaldehyde S-methylisothiosemicarbazone, X = [ CoIIBr3(py ]-, ClO4- . H2O, BF4- were synthesized. The tridentate coordination of all the three dianionic forms of the ligands involves the phenol oxygen, hydrazine nitrogen and the chalcogen (O or S in case of salicylaldehyde semi-, thiosemicarbazone and the terminal nitrogen atom in the case of isothiosemicarbazone. For all the complexes, a meridial octahedral arrangement is proposed, which is a consequence of the planarity of the chelate ligand. The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility, IR and electronic absorption spectra. The thermal decomposition of the complexes was investigated by thermogravimetry, coupled TG-MS measurements and DSC.

  14. Structural relationships in complex hydrides of the late transition metals

    International Nuclear Information System (INIS)

    Literature data on complex hydrides of the late transition metals (groups 7-10), such as the hydrogen storage material Mg2NiH4, are reviewed with respect to order-disorder phase transitions and structural relationships. They are analysed in terms of crystallographic group-subgroup trees and their use in understanding the different crystal structures from a symmetry point of view is demonstrated. New data are presented on the low temperature behaviour of magnesium iridium hydrides and strontium rhodium hydrides studied by powder X-ray diffraction. (orig.)

  15. Microwave synthesis, spectral, thermal, and antimicrobial activities of some transition metal complexes involving 5-bromosalicylaldehyde moiety

    Directory of Open Access Journals (Sweden)

    Rajendra K. Jain

    2012-07-01

    Full Text Available The coordination complexes of Co(II, Ni(II and Cu(II derived from 5-bromosalicylidene-3,4-dimethylaniline (BSMA and 5-bromosalicylidene-3,4-dichloroaniline (BSCA have been synthesized by conventional as well as microwave methods. These compounds have been characterized by elemental analysis, FT-IR, molar conductance, electronic spectra, 1H-NMR, FAB-mass, ESR, magnetic susceptibility, electrical conductivity and thermal analysis. The complexes are coloured and stable in air. Analytical data revealed that all the complexes exhibited 1:2 (metal: ligand ratio with coordination number 4 or 6. IR data shows that the ligand coordinates with the metal ions in a bidentate manner through the phenolic oxygen and azomethine nitrogen. FAB-mass and thermal data show degradation pattern of the complexes. Solid state electrical conductivity studies reflect semiconducting nature of the complexes. The Schiff base and metal complexes show a good activity against the Gram-positive bacteria; Staphylococcus aureus and Gram-negative bacteria; Escherichia coli and fungi Aspergillus niger and Candida albicans.

  16. MCPB.py: A Python Based Metal Center Parameter Builder.

    Science.gov (United States)

    Li, Pengfei; Merz, Kenneth M

    2016-04-25

    MCPB.py, a python based metal center parameter builder, has been developed to build force fields for the simulation of metal complexes employing the bonded model approach. It has an optimized code structure, with far fewer required steps than the previous developed MCPB program. It supports various AMBER force fields and more than 80 metal ions. A series of parametrization schemes to derive force constants and charge parameters are available within the program. We give two examples (one metalloprotein example and one organometallic compound example), indicating the program's ability to build reliable force fields for different metal ion containing complexes. The original version was released with AmberTools15. It is provided via the GNU General Public License v3.0 (GNU_GPL_v3) agreement and is free to download and distribute. MCPB.py provides a bridge between quantum mechanical calculations and molecular dynamics simulation software packages thereby enabling the modeling of metal ion centers. It offers an entry into simulating metal ions in a number of situations by providing an efficient way for researchers to handle the vagaries and difficulties associated with metal ion modeling. PMID:26913476

  17. A series of 2D metal-quinolone complexes: Syntheses, structures, and physical properties

    Energy Technology Data Exchange (ETDEWEB)

    He, Jiang-Hong [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Xiao, Dong-Rong, E-mail: xiaodr98@yahoo.com.cn [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Chen, Hai-Yan; Sun, Dian-Zhen; Yan, Shi-Wei; Wang, Xin; Ye, Zhong-Li [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Luo, Qun-Li, E-mail: qlluo@swu.edu.cn [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Wang, En-Bo, E-mail: wangeb889@nenu.edu.cn [Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2013-02-15

    Six novel 2D metal-quinolone complexes, namely [Cd(cfH)(bpdc)]{center_dot}H{sub 2}O (1), [M(norfH)(bpdc)]{center_dot}H{sub 2}O (M=Cd (2) and Mn (3)), [Mn{sub 2}(cfH)(odpa)(H{sub 2}O){sub 3}]{center_dot}0.5H{sub 2}O (4), [Co{sub 2}(norfH)(bpta)({mu}{sub 2}-H{sub 2}O)(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O (5) and [Co{sub 3}(saraH){sub 2}(Hbpta){sub 2}(H{sub 2}O){sub 4}]{center_dot}9H{sub 2}O (6) (cfH=ciprofloxacin, norfH=norfloxacin, saraH=sarafloxacin, bpdc=4,4 Prime -biphenyldicarboxylate, odpa=4,4 Prime -oxydiphthalate, bpta=3,3 Prime ,4,4 Prime -biphenyltetracarboxylate) have been synthesized and characterized. Compounds 1-3 consist of 2D arm-shaped layers based on the 1D {l_brace}M(COO){r_brace}{sub n}{sup n+} chains. Compounds 4 and 5 display 2D structures based on tetranuclear manganese or cobalt clusters with (3,6)-connected kgd topology. Compound 6 exhibits a 2D bilayer structure, which represents the first example of metal-quinolone complexes with 2D bilayer structure. By inspection of the structures of 1-6, it is believed that the long aromatic polycarboxylate ligands are important for the formation of 2D metal-quinolone complexes. The magnetic properties of compounds 3-6 was studied, indicating the existence of antiferromagnetic interactions. Furthermore, the luminescent properties of compounds 1-2 are discussed. - Graphical abstract: Six novel 2D metal-quinolone complexes have been prepared by self-assemblies of the quinolones and metal salts in the presence of long aromatic polycarboxylates. Highlights: Black-Right-Pointing-Pointer Compounds 1-3 consist of novel 2D arm-shaped layers based on the 1D {l_brace}M(COO){r_brace}{sub n}{sup n+} chains. Black-Right-Pointing-Pointer Compounds 4 and 5 are two novel 2D layers based on tetranuclear Mn or Co clusters with kgd topology. Black-Right-Pointing-Pointer Compound 6 is the first example of metal-quinolone complexes with 2D bilayer structure. Black-Right-Pointing-Pointer Compounds 1-6 represent six unusual

  18. Phosphorescence of the subgroup 4B metal complexes

    International Nuclear Information System (INIS)

    Phosphorescence properties of Cp2M4+Cl2 complexes, where Cp=η5-C5H5, M=Zr (1), Hf (2), were studied by the methods of emission and absorption spectroscopy. Results of comparative analysis of low-lying electron-excited states in the series Ti, Zr, Hf were provided. It was ascertained that phosphorescence excitation spectra actually coincide with absorption spectra and they do not depend on wavelength of exciting light. Radiation lifetime of T1→S0 transitions in isostructural series of the complexes studied depends strictly on metal nature, being equal to ∼2 ms (for Zr) and to 0.3 ms (for Hf)

  19. Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Baba, Shintaro; Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Oku, Takeo [Department of Materials Science, The University of Shiga Prefecture. 2500 Hassaka, Hikone, Shiga 522-8533 (Japan)

    2016-02-01

    Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in {sup 13}C-nuclear magnetic resonance ({sup 13}C-NMR), principle g-tensor, A-tensor, V-tensor of electric field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.

  20. Salicylaldiminato derivatives of cyclotriveratrylene: flexible strategy for new rim-metalated CTV complexes.

    Science.gov (United States)

    Bohle, D S; Stasko, D J

    2000-12-11

    The amino-derivatized cyclotriveratrylene analogue, triaminotrimethoxytribenzocyclononene [CTV(NH2)3(OMe)3], 1, is readily converted into triply substituted imine compounds [CTV(sal)3(OMe)3], 2, in high yield by treatment of the acid salt of 1 with a variety of substituted salicylaldehydes. Cleavage of the protecting methoxy group generates the tristridentate chelate CTV(sal)3(OH)3, 3, which is readily converted into new rim-metalated species CTV(sal)3(ONiL)3, 4a (a, L = pyrrolidine; b, L = 1-n-butyl-imidazole). Taken together, these results illustrate the remarkable synthetic flexibility that is possible for the CTV-based metal complexes by alteration of the metal, the salicylaldehyde component of the CTV ligand, or the ancillary ligands coordinated to the metal. PMID:11151378

  1. Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

    Science.gov (United States)

    Baba, Shintaro; Suzuki, Atsushi; Oku, Takeo

    2016-02-01

    Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in 13C-nuclear magnetic resonance (13C-NMR), principle g-tensor, A-tensor, V-tensor of electric field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.

  2. Four transition metal complexes with a semicarbazone ligand bearing pyrazine unit

    Science.gov (United States)

    Chen, Hong; Ma, Xiu-qin; Lv, Yan-yun; Jia, Lei; Xu, Jun; Wang, Yuan; Ge, Zhi-jun

    2016-04-01

    Four new complexes based on L (where L = 3-ethyl-2-acetylpyrazine semicarbazone), namely [CoL2]Cl2·0.5H2O (1), [CoL2](NO3)2 (2), [CdL(H2O)2(NO3)](NO3)·H2O (3) and [CuL(CH3OH)Cl2]·[CuLCl2] (4) have been synthesized and characterized by X-ray diffraction analyses. The results show that the semicarbazone acts as a tridentate neutral ligand in all complexes. Each of complex 1 and 2 reveals a distorted octahedral geometry around the metal ion provided by two units of the ligand, while the ratio of the ligand and metal is 1:1 in complexes 3 and 4. The effect of complexes 1-4 on cell proliferation, apoptosis of human pancreatic cancer (Patu8988), human gastric cancer (SGC7901) and human hepatic cancer (SMMC7721) cell lines have been detected by MTT assay, Annexin V/PI double staining flow cytometry and TUNEL assay. The results show that complexes 1-4 can inhibit cell proliferation of Patu8988, SGC7901 and SMMC7721 cells, significantly higher than the effect of the ligand. However, the complex 4 reveals higher apoptosis rate, and displays up-regulated expression level of caspase 3, detected by western blotting, which also indicates the complex 4 can induce caspase-dependent cell apoptosis in SMMC7721.

  3. Facile Synthesis of Functionalized Carbene Metal Complexes from Coordinated Isonitriles.

    Science.gov (United States)

    Lothschütz, Christian; Wurm, Thomas; Zeiler, Anna; Freiherr V Falkenhausen, Alexander; Rudolph, Matthias; Rominger, Frank; Hashmi, A Stephen K

    2016-02-01

    The scope and limitations of the isonitrile-based NHC template synthesis were investigated with a series of precursors containing a nucleophilic amine in combination with tethered electrophiles. In the case of alkynes and phosphonic esters as electrophiles no ring closure was observed and new functionalized NAC gold complexes were obtained. By the use of unsaturated esters and phosphonic esters as Michael acceptors in the amine precursors, ester-modified gold and palladium NHC complexes were accessible in high efficiency. PMID:26033484

  4. The QSAR study of flavonoid-metal complexes scavenging rad OH free radical

    Science.gov (United States)

    Wang, Bo-chu; Qian, Jun-zhen; Fan, Ying; Tan, Jun

    2014-10-01

    Flavonoid-metal complexes have antioxidant activities. However, quantitative structure-activity relationships (QSAR) of flavonoid-metal complexes and their antioxidant activities has still not been tackled. On the basis of 21 structures of flavonoid-metal complexes and their antioxidant activities for scavenging rad OH free radical, we optimised their structures using Gaussian 03 software package and we subsequently calculated and chose 18 quantum chemistry descriptors such as dipole, charge and energy. Then we chose several quantum chemistry descriptors that are very important to the IC50 of flavonoid-metal complexes for scavenging rad OH free radical through method of stepwise linear regression, Meanwhile we obtained 4 new variables through the principal component analysis. Finally, we built the QSAR models based on those important quantum chemistry descriptors and the 4 new variables as the independent variables and the IC50 as the dependent variable using an Artificial Neural Network (ANN), and we validated the two models using experimental data. These results show that the two models in this paper are reliable and predictable.

  5. Radical AdoMet enzymes in complex metal cluster biosynthesis.

    Science.gov (United States)

    Duffus, Benjamin R; Hamilton, Trinity L; Shepard, Eric M; Boyd, Eric S; Peters, John W; Broderick, Joan B

    2012-11-01

    Radical S-adenosylmethionine (AdoMet) enzymes comprise a large superfamily of proteins that engage in a diverse series of biochemical transformations through generation of the highly reactive 5'-deoxyadenosyl radical intermediate. Recent advances into the biosynthesis of unique iron-sulfur (FeS)-containing cofactors such as the H-cluster in [FeFe]-hydrogenase, the FeMo-co in nitrogenase, as well as the iron-guanylylpyridinol (FeGP) cofactor in [Fe]-hydrogenase have implicated new roles for radical AdoMet enzymes in the biosynthesis of complex inorganic cofactors. Radical AdoMet enzymes in conjunction with scaffold proteins engage in modifying ubiquitous FeS precursors into unique clusters, through novel amino acid decomposition and sulfur insertion reactions. The ability of radical AdoMet enzymes to modify common metal centers to unusual metal cofactors may provide important clues into the stepwise evolution of these and other complex bioinorganic catalysts. This article is part of a Special Issue entitled: Radical SAM enzymes and Radical Enzymology. PMID:22269887

  6. Synthesis, Characterization and Biocidal Evaluation of Azole-Based Ligandsmetal Complexes

    Directory of Open Access Journals (Sweden)

    S. A. Olagboye

    2013-12-01

    Full Text Available Different metal complexes of the azole-based ligands have been synthesized and characterized based on the solubility, percentage yield, melting points and conductivity a well as the antimicrobial evaluations on the selected fungi species of plant pathogens. The studies revealed that solid metal complexes were soluble in 80% water and 20% (DMSO dimethylsulphuroxide and the percentage yields were of appreciable high while the conductivity results showed that metal complexes were non-electrolytes. The solid complexes were also screened against the fungi species: Rhizoctonia solani,Pythium aphaindermatum,Rhizoctonia cerealis,Sclerotium rofisil ,Phyphotoria palmivora (causative agent of black pod diseases and Benlate a commercial anti fungi agent (as control.The results of the present studies confirmed that metal complexes had good inhibitory actions on the growth of the fungi species and metal complexes appeared to be more proactive on the tested organisms than the free ligands.

  7. Synthesis, characterization, antibacterial and antifungal studies of some transition and rare earth metal complexes of N-benzylidene-2-hydroxybenzohydrazide

    Directory of Open Access Journals (Sweden)

    T.K. Chondhekar

    2011-12-01

    Full Text Available The solid complexes of Cu(II, Co(II, Mn(II, La(III and Ce(III were prepared from bidentate Schiff base, N-benzylidene-2-hydroxybenzohydrazide. The Schiff base ligand was synthesized from 2-hyhdroxybenzohydrazide and benzaldehyde. These metal complexes were characterized by molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, FTIR, 1H-NMR, UV-Vis and mass spectroscopy. The analytical data of these metal complexes showed metal:ligand ratio of 1:2. The physico-chemical study supports the presence of square planar geometry around Cu(II and octahedral geometry around Mn(II, Co(II, La(III and Ce(III ions. The IR spectral data reveal that the ligand behaves as bidentate with ON donor atom sequence towards central metal ion. The molar conductance values of metal complexes suggest their non-electrolyte nature. The X-ray diffraction data suggest monoclinic crystal system for these complexes. Thermal behavior (TG/DTA and kinetic parameters calculated by Coats-Redfern method are suggestive of more ordered activated state in complex formation. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma.

  8. Thermodynamic data-base for metal fluorides

    International Nuclear Information System (INIS)

    This study is aimed at collecting useful data of thermodynamic properties of various metal fluorides. Many thermodynamic data for metal fluorides are needed for the effective development, but no report of data-base was published. Accordingly, the objective of this report is to rearrange systematically the existing thermodynamic data based on metal fluorides and is to use it as basic data for the development of pyrochemical process. The physicochemical properties of various metal fluorides and metals were collected from literature and such existing data base as HSC code, TAPP code, FACT code, JANAF table, NEA data-base, CRC handbook. As major contents of the thermodynamic data-base, the physicochemical properties such as formation energy, viscosity, density, vapor pressure, etc. were collected. Especially, some phase diagrams of eutectic molten fluorides are plotted and thermodynamic data of liquid metals are also compiled. In the future, the technical report is to be used as basic data for the development of the pyrochemical process which is being carried out as a long-term nuclear R and D project

  9. Thermodynamic data-base for metal fluorides

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Jae Hyung; Lee, Byung Gik; Kang, Young Ho and others

    2001-05-01

    This study is aimed at collecting useful data of thermodynamic properties of various metal fluorides. Many thermodynamic data for metal fluorides are needed for the effective development, but no report of data-base was published. Accordingly, the objective of this report is to rearrange systematically the existing thermodynamic data based on metal fluorides and is to use it as basic data for the development of pyrochemical process. The physicochemical properties of various metal fluorides and metals were collected from literature and such existing data base as HSC code, TAPP code, FACT code, JANAF table, NEA data-base, CRC handbook. As major contents of the thermodynamic data-base, the physicochemical properties such as formation energy, viscosity, density, vapor pressure, etc. were collected. Especially, some phase diagrams of eutectic molten fluorides are plotted and thermodynamic data of liquid metals are also compiled. In the future, the technical report is to be used as basic data for the development of the pyrochemical process which is being carried out as a long-term nuclear R and D project.

  10. Spectroscopic and Thermal Characterization of Gliclazide, Glibenclamide and Glimeperide Complexes with Transition and Inner Transition Metals

    Directory of Open Access Journals (Sweden)

    MOHAMMAD TAWKIR

    2012-12-01

    Full Text Available Metal complxes of Gliclazide, Glibenclamide and Glimeperide drugs were prepared and characterized based on elemental analysis, FT-IR, Molar conductance and thermal analysis (TGA and DTG technique. From elemental analysis data, the complexes were proposed to have general formulae (GLZ2Co2H2O, (GLZ2Cu, (GLB2Co2H2O, Cu(GLB 2, (GLM 2Hg and (GLM 2La2H2O. The molar conductance data reveal that all the metal complexes are non-electrolytic, IR spectra shows that GLZ, GLB and GLM are coordinated to metal ions in a neutral bidentate manner from the ESR spectra and XRD-spectra. It is found that the geometrical structures of these complexes are tetrahedral Cu(II ,Hg(II and octrahedral Co(II, La(II. The thermal behavior of these complexes studied using thermogravimetric analysis (TGA and DTG techniques. The results obtained shows that the hydrated complexes lose water molecules of hydration followed immediately by decomposition of the anions and ligand molecules in the successive unseparate steps. Thermogravimetric analysis was carried out to study the decomposition and various kinetic parameters. Freeman Carroll and Sharp Wentworth method have been applied for calculation of kinetic parameters. While data from freeman Carroll method have been used to determine various thermodynamic parameters such as order of reactions, energy of activation, frequency factor, entropy change, free energy change and apparent entropy change and order of reaction..

  11. Graphene oxide-based flexible metal-insulator-metal capacitors

    Science.gov (United States)

    Bag, A.; Hota, M. K.; Mallik, S.; Maiti, C. K.

    2013-05-01

    This work explores the fabrication of graphene oxide (GO)-based metal-insulator-metal (MIM) capacitors on flexible polyethylene terephthalate (PET) substrates. Electrical properties are studied in detail. A high capacitance density of ˜4 fF µm-2 measured at 1 MHz and permittivity of ˜6 have been obtained. A low voltage coefficient of capacitance, VCC-α, and a low dielectric loss tangent indicate the potential of GO-based MIM capacitors for RF applications. The constant voltage stressing study has shown a high reliability against degradation up to a projected period of 10 years. Degradation in capacitance of the devices on flexible substrates has been studied by bending radius down to 1 cm even up to 6000 times of repeated bending.

  12. Complex Wavelet Based Modulation Analysis

    DEFF Research Database (Denmark)

    Luneau, Jean-Marc; Lebrun, Jérôme; Jensen, Søren Holdt

    2008-01-01

     polynomial trends. Moreover an analytic Hilbert-like transform is possible with complex wavelets implemented as an orthogonal filter bank. By working in an alternative transform domain coined as “Modulation Subbands”, this transform shows very promising denoising capabilities and suggests new approaches for joint...... spectro-temporal analytic processing of slow frequency and phase varying signals....

  13. Metal-metal interactions in weakly coupled mixed-valence E- and Z-diferrocenylethylene complexes.

    Science.gov (United States)

    Chen, Y J; Pan, D S; Chiu, C F; Su, J X; Lin, S J; Kwan, K S

    2000-03-01

    To study metal-to-metal interactions in mixed-valence states of two weakly coupling ferrocenyl groups assembled in E or Z conformation on an ethylenic double bond, E-1,2-dimethyldiferrocenylethylene (1), Z-1,2-dimethyldi-ferrocenylethylene (2), and 1,2-diferrocenylcyclohexene (3) were synthesized and structurally characterized. Crystals of 1 are triclinic, P1, with a = 7.494(9) A, b = 10.801(3) A, c = 11.971(2) A, alpha = 102.17(2) degrees, beta = 106.12(9) degrees, gamma = 90.42(2) degrees, V = 907.8 A3, and Z = 2. Crystals of 2 are monoclinic, P2(1)/c, with a = 13.601(8) A, b = 11.104(4) A, c = 13.732(1) A, beta = 114.26(7) degrees, V = 1890.8(3) A3, and Z = 4. Crystals of 3 are orthorhombic, P2(1)2(1)2(1), with a = 5.766(2) A, b = 13.090(1) A, c = 26.695(2) A, V = 2014.9(3) A3, and Z = 4. Intervalence transition spectra (IT) and electrochemical data have been determined and compared with those of diferrocenyl-benzene (para, ortho, and meta). The comproportionation constants in nitrobenzene at 25 degrees C were found to be 490 and 813 for 1 and 3, respectively. That of 2 was not measured because of the fact that 2+ isomerizes rapidly in all solvents tested, yielding nearly a racemic mixture of E and Z conformers. This finding helps to clear the paradoxical phenomenon between experimental results of mixed-valence complexes of E- and Z-1,2-bis(1'-ethyl-1-ferrocenyl)-1,2-dimethylethylene and theories. The stability of the mixed-valence species was discussed in terms of resonance delocalization, Coulomb repulsion energy, inductive effect, magnetic interaction, structural factors, and statistical factor. According to our analysis based on the Hush formalism, the contribution due to Coulomb repulsion energy dominates the overall stability of the mixed-valence state in 1+, 2+, and 3+. Stabilization that arises from resonance delocalization is only minor and contributes less than 4% to the overall stability, even in 3+ where linked Cp rings and the ethylenic plane are

  14. Metal ion cage complexes as imaging agents for cancer cells

    International Nuclear Information System (INIS)

    Full text: Cage ligands are very attractive for use in radiolabelling antibodies. Their synthesis is based around Co(III) octahedral co-ordination chemistry and they may be easily derivatised for attachment to antibodies. They are known to form kinetically inert metal complexes. Copper-64 (t1/2 = 12.7 h) has been identified as having potential value in diagnostic and therapeutic application. Its positron annihilation radiation is useful for PET imaging, while its beta (Emax 578 keV, 37.2 %) emissions may also be suitable for therapy. In the current study, the new hexa-aza-cryptand, 1 -N-(4-amino-benzyl)-3,6,10,13,16,19-hexaaza-bicyclo[6.6.6]eicosane- 1,8-diamine, or SarAr, has been synthesised specifically for radiolabelling antibodies with 64Cu and a kit formulation has been produced. The resulting radiolabelled immunoconjugate (64Cu-SarArB-72.3) was injected into nude mice bearing LS174t colorectal carcinoma. Clearance of 64CuSarAr-B72.3 from the liver and kidneys was typical of a whole IgG antibody. Tumour localisation was comparable to similar radiolabelled immunoconjugates (38± 5 % ID/g at 48 hours). Biodistribution studies of 123I- and 111In- radiolabelled B72.3 were conducted in the same animal model. MIRDOSE 3 was used to compare target to non-target dose of their analogous therapeutic counterparts (90Y and 131I respectively) with 64Cu-SarAr-B72.3. Total body dose for 64Cu-SarAr-B72.3 was significantly lower (0.09 rad/mCi) than analogous products (131I-B72.3, 2.64 rad/mCi; 90Y- B72.3, 2.387 rad/mCi) while still providing enough dose to small tumours to be potentially therapeutic. In order to assess therapeutic effect of 64Cu, a biological study was conducted over a 12 month period. Nude mice bearing tumours between 3.5 - 5.5 mm in length were injected with various doses (0, 10, 20, 30, 40 MBq) of 64Cu-SarAr-B72.3. Animals were regularly monitored for tumour size, animal mass, behavioural and physical abnormalities (e.g. movement / gait, food intake and

  15. Metal-polybenzimidazole complexes as a nonviral gene carrier: effects of the DNA affinity on gene delivery.

    Science.gov (United States)

    Huang, Xueying; Dong, Xiongwei; Li, Xue; Meng, Xianggao; Zhang, Dan; Liu, Changlin

    2013-12-01

    The metal complex-based carriers are emerging likely as a new type of gene-delivery systems prone to systematic structural alteration and chemical tailoring. In our work, the DNA affinity of metal complexes with polybenzimidazoles was found to be one of the determinants that can regulate expression of the transgenes. Here, the correlations between the DNA affinity and transfection efficacy were explored by characterizing gene-delivering properties of a series of Co(2+)- and Ca(2+)-polybenzimidazole complexes. The binding equilibrium constants (Kobs) of the divalent metal complexes to DNA, which is considered as a measure of the DNA affinity of metal complexes, were evaluated by isothermal titration calorimetry (ITC) and UV-visible absorption titration. The properties of DNA condensates formed with the metal complexes including sizes, ζ potential and morphology were observed to be altered with Kobs values. The monodispersed spherical condensates were found only for the Ca(2+) complexes whose DNA affinity is weaker than that of the Co(2+) complexes. However, the cell internalization examination indicated that cell uptake of the DNA condensates is independent of homogeneity in their sizes and morphology. The comparison of transgene expression showed that that the Ca(2+) complex-mediated transfection has higher efficiency than the Co(2+) complexes under the conditions tested, and the transfection efficacy cannot be correlated with the cell uptake of DNA condensates. Moreover, the Ca(2+) complexes and their DNA condensates had lower cytotoxicity than the Co(2+) complexes. Thus, the DNA affinity should be one of the factors to be capable of regulating the gene-delivering property of metal complexes. PMID:24099694

  16. The Effect of the Serum Amino Acid Levels Thiosemicarbazone Derivatives and its Metal Complexes on Rats

    OpenAIRE

    Karatepe, Mustafa; Kaman, Dilara

    2013-01-01

    Advers biological activities of Thiosemicarbazone (TSC) and Schiff base (SB) derivatives have been widely studied in rats and in other animal species using different doses, times and routes of administration. To date, no attempt has been made to study alterations occurring in the amino acid profile in the effects of the thiosemicarbazone derivative and its metal complexes on the rats. At this study, the rats were injected subcutaneously with a new thiosemicarbazone and its LH-Zn and LH-Cu com...

  17. Metal based drugs: design, synthesis and in-vitro antimicrobial screening of Co(II), Ni(II), Cu(II) and Zn(II) complexes with some new carboxamide derived compounds: crystal structures of N-[ethyl(propan-2-yl)carbamothioyl]thiophene-2-carboxamide and its copper(II) complex.

    Science.gov (United States)

    Sumrra, Sajjad H; Hanif, Muhammad; Chohan, Zahid H; Akram, Muhammad Safwan; Akhtar, Javeed; Al-Shehri, Saad M

    2016-08-01

    A new series of compounds derived from thiophene-2-carboxamide were synthesized and characterized by IR, (1)H-NMR and (13)C-NMR, mass spectrometry and elemental analysis. These compounds were further used to prepare their Co(II), Ni(II), Cu(II) and Zn(II) metal complexes. All metal(II) complexes were air and moisture stable. Physical, spectral and analytical data have shown the Ni(II) and Cu(II) complexes to exhibit distorted square-planar and Co(II) and Zn(II) complexes tetrahedral geometries. The ligand (L(1)) and its Cu(II) complex were characterized by the single-crystal X-ray diffraction method. All the ligands and their metal(II) complexes were screened for their in-vitro antimicrobial activity. The antibacterial and antifungal bioactivity data showed that the metal(II) complexes were found to be more potent than the parent ligands against one or more bacterial and fungal strains. PMID:26067080

  18. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  19. Electron spin resonance of radicals and metal complexes

    International Nuclear Information System (INIS)

    The materials are a collection of extended synopsis of papers presented at the conference sessions. The broad area of magnetic techniques applications has been described as well as their spectra interpretation methods. The ESR, NMR, ENDOR and spin echo were applied for studying the radiation and UV induced radicals in chemical and biological systems. Also in the study of complexes of metallic ions (having the paramagnetic properties) and their interaction with the matrix, the magnetic techniques has been commonly used. They are also very convenient tool for the study of reaction kinetics and mechanism as well as interaction of paramagnetic species with themselves and crystal lattice or with the surface as for thee catalytic processes

  20. Base Metal Co-Fired Multilayer Piezoelectrics

    Directory of Open Access Journals (Sweden)

    Lisheng Gao

    2016-03-01

    Full Text Available Piezoelectrics have been widely used in different kinds of applications, from the automobile industry to consumer electronics. The novel multilayer piezoelectrics, which are inspired by multilayer ceramic capacitors, not only minimize the size of the functional parts, but also maximize energy efficiency. Development of multilayer piezoelectric devices is at a significant crossroads on the way to achieving low costs, high efficiency, and excellent reliability. Concerning the costs of manufacturing multilayer piezoelectrics, the trend is to replace the costly noble metal internal electrodes with base metal materials. This paper discusses the materials development of metal co-firing and the progress of integrating current base metal chemistries. There are some significant considerations in metal co-firing multilayer piezoelectrics: retaining stoichiometry with volatile Pb and alkaline elements in ceramics, the selection of appropriate sintering agents to lower the sintering temperature with minimum impact on piezoelectric performance, and designing effective binder formulation for low pO2 burnout to prevent oxidation of Ni and Cu base metal.

  1. Friction and solid-solid adhesion on complex metallic alloys

    International Nuclear Information System (INIS)

    The discovery in 1987 of stable quasicrystals in the Al–Cu–Fe system was soon exploited to patent specific coatings that showed reduced friction in ambient air against hard antagonists. Henceforth, it was possible to develop a number of applications, potential or commercially exploited to date, that will be alluded to in this topical review. A deeper understanding of the characteristics of complex metallic alloys (CMAs) may explain why material made of metals like Al, Cu and Fe offers reduced friction; low solid–solid adhesion came later. It is linked to the surface energy being significantly lower on those materials, in which translational symmetry has become a weak property, that is determined by the depth of the pseudo-gap at the Fermi energy. As a result, friction is anisotropic in CMAs that builds up according to the translation symmetry along one direction, but is aperiodic along the other two directions. A review is given in this article of the most salient data found along these lines during the past two decades or so. (focus issue)

  2. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    Science.gov (United States)

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  3. Oxalate metal complexes in aerosol particles: implications for the hygroscopicity of oxalate-containing particles

    Directory of Open Access Journals (Sweden)

    T. Furukawa

    2011-05-01

    Full Text Available Atmospheric aerosols have both a direct and an indirect cooling effect that influences the radiative balance at the Earth's surface. It has been estimated that the degree of cooling is large enough to weaken the warming effect of carbon dioxide. Among the cooling factors, secondary organic aerosols (SOA play an important role in the solar radiation balance in the troposphere as SOA can act as cloud condensation nuclei (CCN and extend the lifespan of clouds because of their high hygroscopic and water soluble nature. Oxalic acid is an important component of SOA, and is produced via several formation pathways in the atmosphere. However, it is not certain whether oxalic acid exists as free oxalic acid or as metal oxalate complexes in aerosols, although there is a marked difference in their solubility in water and their hygroscopicity. We employed X-ray absorption fine structure spectroscopy to characterize the calcium (Ca and zinc (Zn in aerosols collected at Tsukuba in Japan. Size-fractionated aerosol samples were collected for this purpose using an impactor aerosol sampler. It was shown that 10–60% and 20–100% of the total Ca and Zn in the finer particles (<2.1 μm were present as Ca and Zn oxalate complexes, respectively. Oxalic acid is hygroscopic and can thus increase the CCN activity of aerosol particles, while complexes with various polyvalent metal ions such as Ca and Zn are not hygroscopic, which cannot contribute to the increase of the CCN activity of aerosols. Based on the concentrations of noncomplexed and metal-complexed oxalate species, we found that most of the oxalic acid is present as metal oxalate complexes in the aerosols, suggesting that oxalic acid does not always increase the hygroscopicity of aerosols in the atmosphere. Similar results are expected for other dicarboxylic acids, such as malonic and succinic acids. Thus, it is advisable that the cooling effect of organic aerosols should be estimated by including the

  4. Effect of metal complexation on the conductance of single-molecular wires measured at room temperature.

    Science.gov (United States)

    Ponce, Julia; Arroyo, Carlos R; Tatay, Sergio; Frisenda, Riccardo; Gaviña, Pablo; Aravena, Daniel; Ruiz, Eliseo; van der Zant, Herre S J; Coronado, Eugenio

    2014-06-11

    The present work aims to give insight into the effect that metal coordination has on the room-temperature conductance of molecular wires. For that purpose, we have designed a family of rigid, highly conductive ligands functionalized with different terminations (acetylthiols, pyridines, and ethynyl groups), in which the conformational changes induced by metal coordination are negligible. The single-molecule conductance features of this series of molecular wires and their corresponding Cu(I) complexes have been measured in break-junction setups at room temperature. Experimental and theoretical data show that no matter the anchoring group, in all cases metal coordination leads to a shift toward lower energies of the ligand energy levels and a reduction of the HOMO-LUMO gap. However, electron-transport measurements carried out at room temperature revealed a variable metal coordination effect depending on the anchoring group: upon metal coordination, the molecular conductance of thiol and ethynyl derivatives decreased, whereas that of pyridine derivatives increased. These differences reside on the molecular levels implied in the conduction. According to quantum-mechanical calculations based on density functional theory methods, the ligand frontier orbital lying closer to the Fermi energy of the leads differs depending on the anchoring group. Thereby, the effect of metal coordination on molecular conductance observed for each anchoring could be explained in terms of the different energy alignments of the molecular orbitals within the gold Fermi level. PMID:24831452

  5. Binding Isotherms and Cooperative Effects for Metal-DNA Complexes

    CERN Document Server

    Gelagutashvili, Eteri

    2008-01-01

    The stoichiometric binding constants of Nickel(II), Cobalt(II), Manganese(II), Silver(I), Zinc(II) ions with DNA, from Spirulina platensis were determined from their binding isotherms by equilibrium dialysis and atomic absorption spectroscopy. It was shown, that the nature of these ions interaction with DNA, from S .platensis is different. For Cobalt(II), Zinc(II) ions were observed cooperative effects and existence of two different types of the binding sites. Nickel(II)_, Silver(I) -DNA complexes shows independent and identical binding sites and Manganese(II)_ negative cooperative interaction. The logarithm of binding constants for Cobalt (II)_, Nickel (II)_, Manganese (II)_, Zinc (II)_, Silver (I) - DNA, from S. platensis in 3 mM Na(I) are 5.11; 5.18; 4.77; 5.05; 5.42; respectively. The linear correlation of logarithm of binding constants (for complexes of metal-DNA from S. platensis) and the covalent index of Pauling are observed.

  6. From ligand to complexes: inhibition of HIV-1 Integrase by beta-diketo acid metal complexes

    OpenAIRE

    Sechi, Mario; BACCHI, Alessia; Carcelli, Mauro; Fisicaro, Emilia; Rogolino, Dominga; Gates, Paul; Derudas, Marco; Al-Mawsawi, Laith Q.; Neamati, Nouri

    2006-01-01

    Recently, a class of compounds bearing a β-diketo acid moiety have emerged as the most promising lead in anti-HIV-1 IN drug discovery. It is believed that the β-diketo acid pharmacophoric motif could be involved in a functional sequestration of one or both divalent metal ions, which are critical cofactors at the enzyme catalytic site. This would subsequently block the transition state of the IN-DNA complex. In this scenario, it is of paramount importance to acquire information ...

  7. Effects of humic acid-metal complexes on hepatic carnitine palmitoyltransferase, carnitine acetyltransferase and catalase activities

    Energy Technology Data Exchange (ETDEWEB)

    Fungjou Lu; Youngshin Chen (National Taiwan Univ., Taipei (Taiwan, Province of China). Dept. of Biochemistry); Tienshang Huang (National Taiwan Univ., Taipei (Taiwan, Province of China). Dept. of Medicine)

    1994-03-01

    A significant increase in activities of hepatic carnitine palmitoyltransferase and carnitine acetyltransferase was observed in male Balb/c mice intraperitoneally injected for 40 d with 0.125 mg/0.1 ml/d humic acid-metal complexes. Among these complexes, the humic acid-As complex was relatively effective, whereas humic acid-25 metal complex was more effective, and humic acid-26 metal complex was most effective. However, humic acid or metal mixtures, or metal such as As alone, was not effective. Humic acid-metal complexes also significantly decreased hepatic catalase activity. A marked decrease of 60-kDa polypeptide in liver cytoplasm was also observed on SDS-polyacrylamide gel electrophoresis after the mice had been injected with the complexes. Morphological analysis of a histopathological biopsy of such treated mice revealed several changes in hepatocytes, including focal necrosis and cell infiltration, mild fatty changes, reactive nuclei, and hypertrophy. Humic acid-metal complexes affect activities of metabolic enzymes of fatty acids, and this results in accumulation of hydrogen peroxide and increase of the lipid peroxidation. The products of lipid peroxidation may be responsible for liver damage and possible carcinogenesis. Previous studies in this laboratory had shown that humic acid-metal complex altered the coagulation system and that humic acid, per se, caused vasculopathy. Therefore, humic acid-metal complexes may be main causal factors of not only so-called blackfoot disease, but also the liver cancer prevailing on the southwestern coast of Taiwan.

  8. Base metals in the new economic environment

    International Nuclear Information System (INIS)

    The focus of this paper was on the demand side of the base metals industry. It is expected that in the next decade more than 50 per cent of global demand growth will come from China and other countries of the former Eastern block. Following the large decline in base metals demand in 2001, it is expected that a large growth in metals supply will be needed over the next decade and there is a real possibility that the mining industry will struggle to meet demand growth. While industry performance is usually driven by economic growth and its impact on metals demand, analysts realize that every cycle is different and it can be easily affected by unpredicted, economic and geopolitical events. The author suggests that the while next few years will be a period of slower growth in the traditional consuming countries, this will be offset by the significant rise in the importance of China and the possible resurgence in demand growth in the Former Soviet Union and Eastern Europe. The paper presented a brief historical overview of the different growth phases for metals over the past 50 years. Strong metal demand in the 1990s was driven by the telecommunications and computer revolutions. Stainless steel/nickel, zinc/galvanized applications and aluminium were used to save on maintenance costs and to improve energy efficiency. The paper also discussed the shifting pattern of copper and aluminium demand by decade. 2 tabs., 7 figs

  9. Atomic Resolution Imaging of Nanoscale Structural Ordering in a Complex Metal Oxide Catalyst

    KAUST Repository

    Zhu, Yihan

    2012-08-28

    The determination of the atomic structure of a functional material is crucial to understanding its "structure-to-property" relationship (e.g., the active sites in a catalyst), which is however challenging if the structure possesses complex inhomogeneities. Here, we report an atomic structure study of an important MoVTeO complex metal oxide catalyst that is potentially useful for the industrially relevant propane-based BP/SOHIO process. We combined aberration-corrected scanning transmission electron microscopy with synchrotron powder X-ray crystallography to explore the structure at both nanoscopic and macroscopic scales. At the nanoscopic scale, this material exhibits structural and compositional order within nanosized "domains", while the domains show disordered distribution at the macroscopic scale. We proposed that the intradomain compositional ordering and the interdomain electric dipolar interaction synergistically induce the displacement of Te atoms in the Mo-V-O channels, which determines the geometry of the multifunctional metal oxo-active sites.

  10. Sub-monolayer film growth of a volatile lanthanide complex on metallic surfaces

    Directory of Open Access Journals (Sweden)

    Hironari Isshiki

    2015-12-01

    Full Text Available We deposited a volatile lanthanide complex, tris(2,2,6,6-tetramethyl-3,5-heptanedionatoterbium(III, onto metal surfaces of Cu(111, Ag(111 and Au(111 in vacuum and observed well-ordered sub-monolayer films with low temperature (5 K scanning tunneling microscopy. The films show a distorted three-fold symmetry with a commensurate structure. Scanning tunneling spectroscopy reveals molecular orbitals delocalized on the ligands of the molecule. Our results imply that this complex can be transferred onto the metal substrates without molecular decomposition or contamination of the surface. This new rare-earth-based class of molecules broadens the choice of molecular magnets to study with scanning tunneling microscopy.

  11. A series of 2D metal-quinolone complexes: Syntheses, structures, and physical properties

    Science.gov (United States)

    He, Jiang-Hong; Xiao, Dong-Rong; Chen, Hai-Yan; Sun, Dian-Zhen; Yan, Shi-Wei; Wang, Xin; Ye, Zhong-Li; Luo, Qun-Li; Wang, En-Bo

    2013-02-01

    Six novel 2D metal-quinolone complexes, namely [Cd(cfH)(bpdc)]rad H2O (1), [M(norfH)(bpdc)]rad H2O (M=Cd (2) and Mn (3)), [Mn2(cfH)(odpa)(H2O)3]rad 0.5H2O (4), [Co2(norfH)(bpta)(μ2-H2O)(H2O)2]rad H2O (5) and [Co3(saraH)2(Hbpta)2(H2O)4]rad 9H2O (6) (cfH=ciprofloxacin, norfH=norfloxacin, saraH=sarafloxacin, bpdc=4,4'-biphenyldicarboxylate, odpa=4,4'-oxydiphthalate, bpta=3,3',4,4'-biphenyltetracarboxylate) have been synthesized and characterized. Compounds 1-3 consist of 2D arm-shaped layers based on the 1D {M(COO)}nn+ chains. Compounds 4 and 5 display 2D structures based on tetranuclear manganese or cobalt clusters with (3,6)-connected kgd topology. Compound 6 exhibits a 2D bilayer structure, which represents the first example of metal-quinolone complexes with 2D bilayer structure. By inspection of the structures of 1-6, it is believed that the long aromatic polycarboxylate ligands are important for the formation of 2D metal-quinolone complexes. The magnetic properties of compounds 3-6 was studied, indicating the existence of antiferromagnetic interactions. Furthermore, the luminescent properties of compounds 1-2 are discussed.

  12. Complexation of metal ion with poly(1-vinylimidazole) resin prepared by radiation-induced polymerization with template metal ion

    International Nuclear Information System (INIS)

    Poly(1-vinylimidazole) (PVI) resin was prepared with Ni2+, CO2+, or Zn2+ as a template to study the adsorption of metal ions. The metal-1-vinylimidazole complex was copolymerized and cross-linked with 1-vinyl-2-pyrrolidone by γ-ray irradiation and the template metal ion was removed by treating the polymer complex with an acid. These PVI resins adsorbed metal ions more effectively than the PVI resin prepared without the template. The number of adsorption sites (As) and the stability constant (K) of Ni2+ complex were larger for the PVI resin prepared with the Ni ion template caused by the smaller dissociation rate constant of Ni ion from the resin. The composition of the Ni2+ complex in the resin remained constant. This suggests that the complexation proceeded via a one-step mechanism

  13. Potentials and challenges of integration for complex metal oxides in CMOS devices and beyond

    International Nuclear Information System (INIS)

    This review focuses on recent accomplishments on complex metal oxide based multifunctional materials and the potential they hold in advancing integrated circuits. It begins with metal oxide based high-κ materials to highlight the success of their integration since 45 nm complementary metal–oxide–semiconductor (CMOS) devices. By simultaneously offering a higher dielectric constant for improved capacitance as well as providing a thicker physical layer to prevent the quantum mechanical tunnelling of electrons, high-κ materials have enabled the continued down-scaling of CMOS based devices. The most recent technology driver has been the demand to lower device power consumption, which requires the design and synthesis of novel materials, such as complex metal oxides that exhibit remarkable tunability in their ferromagnetic, ferroelectric and multiferroic properties. These properties make them suitable for a wide variety of applications such as magnetoelectric random access memory, radio frequency band pass filters, antennae and magnetic sensors. Single-phase multiferroics, while rare, offer unique functionalities which have motivated much scientific and technological research to ascertain the origins of their multiferroicity and their applicability to potential devices. However, due to the weak magnetoelectric coupling for single-phase multiferroics, engineered multiferroic composites based on magnetostrictive ferromagnets interfacing piezoelectrics or ferroelectrics have shown enhanced multiferroic behaviour from effective strain coupling at the interface. In addition, nanostructuring of the ferroic phases has demonstrated further improvement in the coupling effect. Therefore, single-phase and engineered composite multiferroics consisting of complex metal oxides are reviewed in terms of magnetoelectric coupling effects and voltage controlled ferromagnetic properties, followed by a review on the integration challenges that need to be overcome to realize the

  14. Applications of "Hot" and "Cold" Bis(thiosemicarbazonato) Metal Complexes in Multimodal Imaging.

    Science.gov (United States)

    Cortezon-Tamarit, Fernando; Sarpaki, Sophia; Calatayud, David G; Mirabello, Vincenzo; Pascu, Sofia I

    2016-06-01

    The applications of coordination chemistry to molecular imaging has become a matter of intense research over the past 10 years. In particular, the applications of bis(thiosemicarbazonato) metal complexes in molecular imaging have mainly been focused on compounds with aliphatic backbones due to the in vivo imaging success of hypoxic tumors with PET (positron emission tomography) using (64) CuATSM [copper (diacetyl-bis(N4-methylthiosemicarbazone))]. This compound entered clinical trials in the US and the UK during the first decade of the 21(st) century for imaging hypoxia in head and neck tumors. The replacement of the ligand backbone to aromatic groups, coupled with the exocyclic N's functionalization during the synthesis of bis(thiosemicarbazones) opens the possibility to use the corresponding metal complexes as multimodal imaging agents of use, both in vitro for optical detection, and in vivo when radiolabeled with several different metallic species. The greater kinetic stability of acenaphthenequinone bis(thiosemicarbazonato) metal complexes, with respect to that of the corresponding aliphatic ATSM complexes, allows the stabilization of a number of imaging probes, with special interest in "cold" and "hot" Cu(II) and Ga(III) derivatives for PET applications and (111) In(III) derivatives for SPECT (single-photon emission computed tomography) applications, whilst Zn(II) derivatives display optical imaging properties in cells, with enhanced fluorescence emission and lifetime with respect to the free ligands. Preliminary studies have shown that gallium-based acenaphthenequinone bis(thiosemicarbazonato) complexes are also hypoxia selective in vitro, thus increasing the interest in them as new generation imaging agents for in vitro and in vivo applications. PMID:27149900

  15. Adaptive Beamforming Based on Complex Quaternion Processes

    Directory of Open Access Journals (Sweden)

    Jian-wu Tao

    2014-01-01

    Full Text Available Motivated by the benefits of array signal processing in quaternion domain, we investigate the problem of adaptive beamforming based on complex quaternion processes in this paper. First, a complex quaternion least-mean squares (CQLMS algorithm is proposed and its performance is analyzed. The CQLMS algorithm is suitable for adaptive beamforming of vector-sensor array. The weight vector update of CQLMS algorithm is derived based on the complex gradient, leading to lower computational complexity. Because the complex quaternion can exhibit the orthogonal structure of an electromagnetic vector-sensor in a natural way, a complex quaternion model in time domain is provided for a 3-component vector-sensor array. And the normalized adaptive beamformer using CQLMS is presented. Finally, simulation results are given to validate the performance of the proposed adaptive beamformer.

  16. 21 CFR 872.3710 - Base metal alloy.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Base metal alloy. 872.3710 Section 872.3710 Food... DEVICES DENTAL DEVICES Prosthetic Devices § 872.3710 Base metal alloy. (a) Identification. A base metal alloy is a device composed primarily of base metals, such as nickel, chromium, or cobalt, that...

  17. Antimicrobial Activity of Metal & Metal Oxide Nanoparticles Interfaced With Ligand Complexes Of 8-Hydroxyquinoline And α-Amino Acids

    Science.gov (United States)

    Bhanjana, Gaurav; Kumar, Neeraj; Thakur, Rajesh; Dilbaghi, Neeraj; Kumar, Sandeep

    2011-12-01

    Antimicrobial nanotechnology is a recent addition to the fight against disease causing organisms, replacing heavy metals and toxins. In the present work, mixed ligand complexes of metals like zinc, silver etc. and metal oxide have been synthesized using 8-hydroxyquinoline (HQ) as a primary ligand and N-and/O-donor amino acids such as L-serine, L-alanine, glycine, cysteine and histidine as secondary ligands. These complexes were characterized using different spectroscopic techniques. The complexes were tested for antifungal and antibacterial activity by using agar well diffusion bioassay.

  18. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Guodong Du

    2004-12-19

    products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of {alpha}-ketols to {alpha}-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

  19. Metals complexation with humic acids in surface water of different natural–climatic zones

    Directory of Open Access Journals (Sweden)

    Dinu M. I.

    2013-04-01

    Full Text Available Humic acids extracted from different soils. The stability constants of metal humates and acid dissociation constant humic acids were calculated. Forms of metals in natural waters was determined with use account their chemical composition and content and properties of organic matter. We assessed metals speciation in water objects with account for competitive reactions resulting in formation of hydroxide, hydrocarbonate, sulfate, and chloride metal complexes and obtained a competitive series of metal activity in natural waters of the zones considered.

  20. Interplay between Theory and Experiment for Ammonia Synthesis Catalyzed by Transition Metal Complexes.

    Science.gov (United States)

    Tanaka, Hiromasa; Nishibayashi, Yoshiaki; Yoshizawa, Kazunari

    2016-05-17

    Nitrogen fixation is an essential chemical process both biologically and industrially. Since the discovery of the first transition-metal-dinitrogen complex in 1965, a great deal of effort has been devoted to the development of artificial nitrogen fixation systems that work under mild reaction conditions. However, the transformation of chemically inert dinitrogen using homogeneous catalysts is still challenging because of the difficulty in breaking the strong triple bond of dinitrogen, and a very limited number of transition metal complexes have exhibited the catalytic activity for the direct transformation of dinitrogen into ammonia with low turnover numbers. To develop more effective nitrogen fixation systems, it is necessary to retrieve as much information as possible from the limited successful examples. Computational chemistry will provide valuable insights in the understanding of the reaction mechanisms involving unstable intermediates that are hard to isolate or characterize. We have been applying it for clarifying detailed mechanisms of dinitrogen activation and functionalization by transition metal complexes as well as for designing new catalysts for more effective nitrogen fixation. This Account summarizes recent progress in the elucidation of catalytic mechanisms of nitrogen fixation by using mono- and dinuclear molybdenum complexes, as well as cubane-type metal-sulfido clusters from a theoretical point of view. First, we briefly introduce experimental and theoretical contributions to the elucidation of the reaction mechanism of nitrogen fixation catalyzed by a mononuclear Mo-triamidoamine complex. Special attention is paid to our recent studies on Mo-catalyzed nitrogen fixation using dinitrogen-bridged dimolybdenum complexes. A possible catalytic mechanism is proposed based on theoretical and experimental investigations. The catalytic mechanism involves the formation of a monuclear molybdenum-nitride (Mo≡N) intermediate, as well as the regeneration of

  1. Synthesis, thermal and spectroscopic behaviors of metal-drug complexes: La(III), Ce(III), Sm(III) and Y(III) amoxicillin trihydrate antibiotic drug complexes

    Science.gov (United States)

    Refat, Moamen S.; Al-Maydama, Hussein M. A.; Al-Azab, Fathi M.; Amin, Ragab R.; Jamil, Yasmin M. S.

    2014-07-01

    The metal complexes of Amoxicillin trihydrate with La(III), Ce(III), Sm(III) and Y(III) are synthesized with 1:1 (metal:Amox) molar ratio. The suggested formula structures of the complexes are based on the results of the elemental analyses, molar conductivity, (infrared, UV-visible and fluorescence) spectra, effective magnetic moment in Bohr magnetons, as well as the thermal analysis (TG), and characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results obtained suggested that Amoxicillin reacted with metal ions as tridentate ligands, coordinating the metal ion through its amino, imino, and β-lactamic carbonyl. The kinetic thermodynamic parameters such as: Ea, ΔH*, ΔS* and ΔG* were estimated from the DTG curves.

  2. Structural and biological evaluation of some metal complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone

    Science.gov (United States)

    Yousef, T. A.; Abu El-Reash, G. M.; Al-Jahdali, M.; El-Rakhawy, El-Bastawesy R.

    2013-12-01

    The synthesis and characterization of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and U(VI)O2 complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone (H2PVT) are reported. Theoretical calculations have been performed to obtain IR spectra of ligand and its complexes using AM1, Zindo/1, MM+ and PM3, methods. The Schiff base and its metal complexes have been screened for antibacterial Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis and Staphylococcus saprophyticus. H2VPT shows no apparent digestion effect on the egg albumin while Mn(II), Hg(II) and Cu(II) complexes exhibited a considerable digestion effect following the order Cu(II) > Mn(II) > Hg(II). Moreover, Ni(II) and Co(II) complexes revealed strong digestion effect. Fe(II), Mn(II), Cu(II), Zn(II) and Ni(II) acted as metal co- SOD enzyme factors, which are located in different compartments of the cell.

  3. High antioxidative potential and low toxic effects of selenosemicarbazone metal complexes

    Directory of Open Access Journals (Sweden)

    Dekanski Dragana

    2013-01-01

    Full Text Available Novel metal-based compounds with therapeutic potential became the subject of intense investigation in inorganic chemistry and biomedical science. Recently, strong dose-dependent cytotoxic activity against several human cancer cell lines of selenosemicarbazone metal complexes was demonstrated. The aim of the present study was to investigate in vitro antioxidative potential of Ni(II, Cd(II and Zn(II selenosemicarbazone complexes. All three investigated complexes exhibited high ABTS radical scavenging capacity, comparable with ascorbic acid. In the acute toxicity study, administration of the compounds was performed orally to the mice at the single doses and they were observed for clinical signs, body weight effects, and mortality for 14 days after which they were sacrificed for gross organ necropsy. Body weight did not vary after administration, and the autoptic analysis failed to show appreciable macroscopic alterations of internal organs. Generally, the compounds exhibited low toxic effects as required for further in vivo therapeutic studies. [Projekat Ministarstva nauke Republike Srbije, br. 451-03-2372-IP type 1/79: Antioxidants based on selenium complex compounds - research and development

  4. A metal-based inhibitor of NEDD8-activating enzyme.

    Directory of Open Access Journals (Sweden)

    Hai-Jing Zhong

    Full Text Available A cyclometallated rhodium(III complex [Rh(ppy(2(dppz](+ (1 (where ppy=2-phenylpyridine and dppz=dipyrido[3,2-a:2',3'-c]phenazine dipyridophenazine has been prepared and identified as an inhibitor of NEDD8-activating enzyme (NAE. The complex inhibited NAE activity in cell-free and cell-based assays, and suppressed the CRL-regulated substrate degradation and NF-κB activation in human cancer cells with potency comparable to known NAE inhibitor MLN4924. Molecular modeling analysis suggested that the overall binding mode of 1 within the binding pocket of the APPBP1/UBA3 heterodimer resembled that for MLN4924. Complex 1 is the first metal complex reported to suppress the NEDDylation pathway via inhibition of the NEDD8-activating enzyme.

  5. Synthesis, magnetic and spectral studies on polystyrene-anchored coordination complexes of bi-, tri-, tetra- and hexavalent metal ions with unsymmetrical dibasic tetradentate ONNO donor Schiff base derived from 3-formylsalicylic acid, ethylenediamine and 2-benzoylacetanilide

    Indian Academy of Sciences (India)

    Dinesh Kumar; Arun Syamal; Jaipal; Lalit Kumar Sharma

    2009-01-01

    Polystyrene-anchored Cu(II), Zn(II), Cd(II), Ni(II), Mn(II), MoO2(II), UO2(II), Fe(III) and Zr(IV), complexes of the unsymmetrical dibasic tetradentate ONNO donor Schiff base derived from the condensation of chloromethylated polystyrene, 3-formylsalicylic acid, ethylenediamine and 2-benzoylacetanilide (PS-LH2) has been synthesized. The polystyrene anchored complexes have the formulae: PS-LM (where M = Cu, Zn, Cd, Ni, MoO2, UO2), PS-LFeCl.DMF, PS-LMn.2DMF and PS-LZr(OH)2.DMF. The polystyrene-anchored coordination compounds have been characterized by elemental analysis, IR, reflectance, ESR and magnetic susceptibility measurements. The per cent reaction conversion of polystyrene anchored Schiff base to polystyrene supported coordination compounds lies between 28.98 and 85.9. The coordinated dimethylformamide is completely lost on heating the complexes. The shifts of the ν(C=N)(azomethine) and ν(C-O)(phenolic) stretches have been monitored in order to find out the donor sites of the ligands. The Cu(II) complex is paramagnetic with square planar structure; the Ni(II) complex is diamagnetic with square planar structure; the Zn(II) and Cd(II) complexes are diamagnetic and have tetrahedral structure; the Mn(II) and Fe(III) complexes are paramagnetic and have octahedral structure; the MoO2(II) and UO2(II) complexes are diamagnetic and have octahedral structure and the Zr(IV) complexes are diamagnetic and have pentagonal bipyramidal structure.

  6. Alkali Metal Complexes: Mixed Ligand Complexes of Some Alkali Metal Salts of Some Organic Acids with Isonitroso-PMethylace to phenone

    Directory of Open Access Journals (Sweden)

    O.P. Gupta

    2016-02-01

    Full Text Available A number of mixed ligand complexes of alkali metal salts of o-nitrophenol,2,4-dinitrophenol, 2,4,6,- trinitrophenol, 1-nitroso-2- naphthol and 8- hydroxyquinoline with Insoniroso–p methylacetopheone have been synthesized in absolute ethanol & characterized by elemental analysis and I .B. spectral data. Their I.R spectral data indicate the presence of hydrogen bonding in them, which many be one of the dominant factors of their stability. Further appreciable shift in 1650 cm-1 band (possibly vC=O and 1600 cm-1 band (possibly vC=NSuggests their coordination behavior in these mixed ligand complexes The reactions that take place in natural systems are highly specific and selective. Alkali metal ions actively participate in most of the reaction occurring in the biological systems, which are dominated by mixed ligand complexes. Studies of such mixed ligand complexes of alkali metals can threw light in understanding the role and mechanism of selective absorption of alkali metals ions by plants Coordinating ability of alkali metal with isonitrosoacetophenone1-2 and transition metals with isonitrosoacetophenone3 and isonitroso-p-methylacetophenone4 have been reported earlier. In the present paper we report the mixed ligand complexes of alkali metal salts having the general formula ML.HL, ‘ where M=Li, Na & K and L=deprotonated o- nitrophenol, 2,4 dinitrophenol, 2, 4, 6- trinitrophenol, 1-nitroso-2-naphthol or 8- hydroxquinoline; HL’= p -MeHINAP (isonitroso-p-methylacetophenone.

  7. Complex band structures of transition metal dichalcogenide monolayers with spin–orbit coupling effects

    Science.gov (United States)

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-09-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin–orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed.

  8. Reductive Cleavage of CO2 by Metal-Ligand-Cooperation Mediated by an Iridium Pincer Complex.

    Science.gov (United States)

    Feller, Moran; Gellrich, Urs; Anaby, Aviel; Diskin-Posner, Yael; Milstein, David

    2016-05-25

    A unique mode of stoichiometric CO2 activation and reductive splitting based on metal-ligand-cooperation is described. The novel Ir hydride complexes [((t)Bu-PNP*)Ir(H)2] (2) ((t)Bu-PNP*, deprotonated (t)Bu-PNP ligand) and [((t)Bu-PNP)Ir(H)] (3) react with CO2 to give the dearomatized complex [((t)Bu-PNP*)Ir(CO)] (4) and water. Mechanistic studies have identified an adduct in which CO2 is bound to the ligand and metal, [((t)Bu-PNP-COO)Ir(H)2] (5), and a di-CO2 iridacycle [((t)Bu-PNP)Ir(H)(C2O4-κC,O)] (6). DFT calculations confirm the formation of 5 and 6 as reversibly formed side products, and suggest an η(1)-CO2 intermediate leading to the thermodynamic product 4. The calculations support a metal-ligand-cooperation pathway in which an internal deprotonation of the benzylic position by the η(1)-CO2 ligand leads to a carboxylate intermediate, which further reacts with the hydride ligand to give complex 4 and water. PMID:27124097

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Complex band structures of transition metal dichalcogenide monolayers with spin-orbit coupling effects.

    Science.gov (United States)

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-09-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin-orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed. PMID:27367475

  11. Preparation, Physicochemical Characterization and Biological Evaluation of some Hesperidin Metal Complexes

    OpenAIRE

    Daoud, Safa; Afifi, Fatma U.; Amal G Al-Bakri; Kasabri, Violet; Hamdan, Imad I

    2014-01-01

    The ability of hesperidin (HP) to form complexes with five metals; cobalt, nickel, zinc, calcium and magnesium was investigated. The complexation was studied using U.V spectroscopic titration, in methanol as well as aqueous buffer solutions (physiological conditions). Potential complexes were studied by IR and NMR spectroscopy, melting point and their solubility were also evaluated. The interaction of HP and its metal complexes with DNA was investigated by U.V spectroscopy. HP and its potenti...

  12. A macrocyclic approach to transition metal and uranyl Pacman complexes

    OpenAIRE

    Love, J. B.

    2009-01-01

    Multielectron redox chemistry involving small molecules such as O-2, H2O, N-2, CO2, and CH4 is intrinsic to the chemical challenges surrounding sustainable, low-carbon energy generation and exploitation. Compounds with more than one metal reaction site facilitate this chemistry by providing both unique binding environments and combined redox equivalents. However, controlling the aggregation of metal cations is problematic, as both the primary coordination spheres of the metals and the metal-m...

  13. Isotope exchange study of the dissociation of metal-humic complexes

    International Nuclear Information System (INIS)

    Prediction of the migration of toxic metals and radionuclides in the environment requires knowledge of equilibrium and kinetic parameters characterising their interaction with humic substance (HS). In this work, isotope exchange of Eu and Co in the systems containing HS has been used to study dissociation of the cations from their complexes with HS under quasi-stationary conditions. In the experimental arrangement of the so-called diaphragm method, a dialysis membrane divides two compartments containing solutions of metal and HS, identical in both half-cells but for radiolabeling (152Eu and 60Co) applied only in one cell. The membrane is permeable for free metal cation but not for the metal-HS complex. The slow dissociation of metal cation from HS is reflected by retardation (compared to a reference system in the absence of HS) of the rate of the isotope exchange between the two compartments. However, only an apparent dissociation rate can be observed, as detection of fast dissociation is limited by the rate of diffusion of dissociated cations through membrane and by their recombination with available binding sites of HS. The rate of isotope exchange of Eu and Co in the systems with HS (Aldrich sodium humate, soil humic and fulvic acid) was monitored as function of pH (4 and 6), ionic strength (0.01 and 0.1 M), and the degree of HS loading with metal ([M]0 = 10-7 - 2x10-5 M at 10 mg/L HS). For Co, the rate of 60Co2+ diffusion through the membrane showed up to control the rate of the isotope exchange indicating that the Co-HS dissociation is too fast to be followed by the diaphragm method, and that the abundance of non-complexed Co is not negligible. The apparent rate of Eu-HS dissociation was found to be enhanced by decreasing pH value, increasing ionic strength, and increasing metal loading (i.e., metal/HS ratio). For interpretation of the experimental kinetic data, a discrete 2-component model (bi-exponential decay function) was applied. Based on comparison of

  14. Automotive cooling systems based on metal hydrides

    OpenAIRE

    Linder, Marc

    2010-01-01

    The present work focuses on metal hydride sorption systems as an alternative technology for automotive air-conditioning systems. Although this technology offers the possibility to increase the energy efficiency of a car (by utilising waste heat) and consequently reduces the CO2 emissions, its weight specific cooling power has so far been the main obstacle for an automotive application. Based on investigations of various metal hydrides, two alloys (LmNi4.91Sn0.15 and Ti0.99Zr0.01V0.43Fe0.09Cr0...

  15. Digermylene Oxide Stabilized Group 11 Metal Iodide Complexes.

    Science.gov (United States)

    Yadav, Dhirendra; Siwatch, Rahul Kumar; Sinhababu, Soumen; Karwasara, Surendar; Singh, Dharmendra; Rajaraman, Gopalan; Nagendran, Selvarajan

    2015-12-01

    Use of a substituted digermylene oxide as a ligand has been demonstrated through the isolation of a series of group 11 metal(I) iodide complexes. Accordingly, the reactions of digermylene oxide [{(i-Bu)2ATIGe}2O] (ATI = aminotroponiminate) (1) with CuI under different conditions afforded [({(i-Bu)2ATIGe}2O)2(Cu4I4)] (2) with a Cu4I4 octahedral core, [({(i-Bu)2ATIGe}2O)2(Cu3I3)] (3) with a Cu3I3 core, and [{(i-Bu)2ATIGe}2O(Cu2I2)(C5H5N)2] (4) with a butterfly-type Cu2I2 core. The reactions of compound 1 with AgI and AuI produced [({(i-Bu)2ATIGe}2O)2(Ag4I4)] (5) with a Ag4I4 octahedral core and [{(i-Bu)2ATIGe}2O(Au2I2)] (6) with a Au2I2 core, respectively. The presence of metallophilic interactions in these compounds is shown through the single-crystal X-ray diffraction and atom-in-molecule (AIM) studies. Preliminary photophysical studies on compound 6 are also carried out. PMID:26558406

  16. Oxidation of limonene catalyzed by Metal(Salen complexes

    Directory of Open Access Journals (Sweden)

    L. F. Lima

    2006-03-01

    Full Text Available The compound R-(+limonene is available and cheap than its oxidized products. Consequently, the selective oxidation of R(+limonene has attracted attention as a promising process for the production of compounds with a higher market value, such as cis/trans-1,2-limoneneoxide, cis/trans-carveol and/or carvone. One of the these processes, described in the recent literature, is submission of R-(+limonene to an oxidation reaction catalyzed by neutral or cationic Metal(Salen complexes, in the presence of effective terminal oxidants such as NaOCl or PhIO. These reactions are commonly carried out in organic solvents (dichromethane, ethyl acetate, acetonitrile or acetone. Thus, the main objective of the present work was to study the effect of several factors (type of oxidant, catalyst, solvent and time on reaction selectivity for the high-priced compounds referred to above. For this purposes, experimental statistical multivariate analysis was used in conjunction with a complete experimental design. From the results it was observed that for the three targeted products (1,2-limoneneoxide, carveol or carvone some factors, including the nature of the terminal oxidant and the catalyst, were significant for product selectivity (with a confidence level of 95%. Therefore, this statistical analysis proved to be suitable for choosing of the best reaction conditions for a specific desired product.

  17. Capillary electrophoresis application in metal speciation and complexation characterization

    Science.gov (United States)

    Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

  18. Synthesis, characterization, optical band gap, in vitro antimicrobial activity and DNA cleavage studies of some metal complexes of pyridyl thiosemicarbazone

    Science.gov (United States)

    Yousef, T. A.; Abu El-Reash, G. M.; El-Gammal, O. A.; Bedier, R. A.

    2013-03-01

    A new series of Cr(III), Mn(II), Ni(II), Zn(II) and Hg(II) complexes of Schiff-bases derived from the condensation of 4-(2-pyridyl)-3-thiosemicarbazide and pyruvic acid (H2PTP) have been synthesized and characterized by spectroscopic studies. Schiff-base exhibit thiol-thione tautomerism wherein sulfur plays an important role in the coordination. The coordination possibility of the Schiff-bases towards metal ions have been proposed in the light of elemental analysis, spectral (IR, UV-vis, 1H NMR and 13C NMR), magnetic and thermal studies. IR spectra show that H2PTP is coordinated to the metal ions in a mononegative tridentate manner except in Cr(III) complex in which the ligand exhibits mononegative bidentate manner. The parameters total energy, binding energy, isolated atomic energy, electronic energy, heat of formation, dipole moment, HOMO and LUMO were calculated for the ligand and its complexes. Furthermore, the kinetic and thermodynamic parameters for the different decomposition steps were calculated using the Coats-Redfern and Horowitz-Metzger methods. Also, the optical band gap (Eg) of the metal complexes has been calculated. The optical transition energy (Eg) is direct and equals 3.20, 3.27 and 3.26 eV for Cr, Mn and Ni complexes, respectively. The synthesized ligand, in comparison to its metal complexes is screened for its antibacterial activity against the bacterial species, Bacillus thuringiensis, Staphylococcus aureus, Pseudomonas aeuroginosa and Escherichia coli. The results show that the metal complexes be more potent in activity antibacterial than the parent Shciff base ligand towards one or more bacterial species. Finally, the biochemical studies showed that, Mn complex have powerful and complete degradation effect on DNA.

  19. DNA interaction and efficient antimicrobial activities of 4N chelating metal complexes.

    Science.gov (United States)

    Packianathan, S; Arun, T; Raman, N

    2015-07-01

    A new series of metal(II) complexes using a symmetric Schiff base ligand, obtained by the condensation reaction of 4-formyl-N,N-dimethylaniline with benzene-1,2-diamine were synthesized and characterized. The various physico-chemical data indicate that the complexes have octahedral geometry. The intrinsic binding constant of the complexes with DNA is explored. The UV-Vis., circular dichorism, fluorescence emission spectral data and the viscosity measurements indicate that the complexes bind to calf thymus DNA (CT DNA) by intercalative mode. The intrinsic binding constants of Cu(II), Ni(II), Co(II) and Zn(II) complexes are found to be 7.1×10(4), 5.2×10(4), 1.8×10(5) and 6.3×10(4) M(-1), respectively. The cleavage studies of these complexes are investigated by gel electrophoresis method in the presence of peroxide. The complexes exhibit enhanced biological activities compared to the free ligand. PMID:25931401

  20. Chemoelectronic circuits based on metal nanoparticles

    Science.gov (United States)

    Yan, Yong; Warren, Scott C.; Fuller, Patrick; Grzybowski, Bartosz A.

    2016-07-01

    To develop electronic devices with novel functionalities and applications, various non-silicon-based materials are currently being explored. Nanoparticles have unique characteristics due to their small size, which can impart functions that are distinct from those of their bulk counterparts. The use of semiconductor nanoparticles has already led to improvements in the efficiency of solar cells, the processability of transistors and the sensitivity of photodetectors, and the optical and catalytic properties of metal nanoparticles have led to similar advances in plasmonics and energy conversion. However, metals screen electric fields and this has, so far, prevented their use in the design of all-metal nanoparticle circuitry. Here, we show that simple electronic circuits can be made exclusively from metal nanoparticles functionalized with charged organic ligands. In these materials, electronic currents are controlled by the ionic gradients of mobile counterions surrounding the ‘jammed’ nanoparticles. The nanoparticle-based electronic elements of the circuitry can be interfaced with metal nanoparticles capable of sensing various environmental changes (humidity, gas, the presence of various cations), creating electronic devices in which metal nanoparticles sense, process and ultimately report chemical signals. Because the constituent nanoparticles combine electronic and chemical sensing functions, we term these systems ‘chemoelectronic’. The circuits have switching times comparable to those of polymer electronics, selectively transduce parts-per-trillion chemical changes into electrical signals, perform logic operations, consume little power (on the scale of microwatts), and are mechanically flexible. They are also ‘green’, in the sense that they comprise non-toxic nanoparticles cast at room temperature from alcohol solutions.

  1. Humic substances in natural waters and their complexation with trace metals and radionuclides: a review. [129 references

    Energy Technology Data Exchange (ETDEWEB)

    Boggs, S. Jr.; Livermore, D.; Seitz, M.G.

    1985-07-01

    Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empirically determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. Larger values of stability constants indicate greater complex stability. The stability of radionuclide-organic complexes is affected both by concentration variables and envionmental factors. In general, complexing is favored by increased of radionuclide, increased pH, and decreased ionic strength. Actinide elements are generally most soluble in their higher oxidation states. Radionuclides can also form stable, insoluble complexes with humic materials that tend to reduce radionuclide mobility. These insoluble complexes may be radionuclide-humate colloids that subsequently precipitate from solution, or complexes of radionuclides and humic substances that sorb to clay minerals or other soil particulates strongly enough to immobilize the radionuclides. Colloid formation appears to be favored by increased radionuclide concentration and lowered pH; however, the conditions that favor formation of insoluble complexes that sorb to particulates are still poorly understood. 129 refs., 25 figs., 19 tabs.

  2. Mechanism of electrochemical charge transport in individual transition metal complexes.

    Science.gov (United States)

    Albrecht, Tim; Guckian, Adrian; Kuznetsov, Alexander M; Vos, Johannes G; Ulstrup, Jens

    2006-12-27

    We used electrochemical scanning tunneling microscopy (STM) and spectroscopy (STS) to elucidate the mechanism of electron transport through individual pyridyl-based Os complexes. Our tunneling data obtained by two-dimensional electrochemical STS and STM imaging lead us to the conclusion that electron transport occurs by thermally activated hopping. The conductance enhancement around the redox potential of the complex, which is reminiscent of switching and transistor characterics in electronics, is reflected both in the STM imaging contrast and directly in the tunneling current. The latter shows a biphasic distance dependence, in line with a two-step electron hopping process. Under conditions where the substrate/molecule electron transfer (ET) step is dominant in determining the overall tunneling current, we determined the conductance of an individual Os complex to be 9 nS (Vbias = 0.1 V). We use theoretical approaches to connect the single-molecule conductance with electrochemical kinetics data obtained from monolayer experiments. While the latter leave some controversy regarding the degree of electronic coupling, our results suggest that electron transport occurs in the adiabatic limit of strong electronic coupling. Remarkably, and in contrast to established ET theory, the redox-mediated tunneling current remains strongly distance dependent due to the electronic coupling, even in the adiabatic limit. We exploit this feature and apply it to electrochemical single-molecule conductance data. In this way, we attempt to paint a unified picture of electrochemical charge transport at the single-molecule and monolayer levels. PMID:17177467

  3. A biomimicing approach to the mixed ligand complexes of bivalent transition metal

    Directory of Open Access Journals (Sweden)

    Bipin Bihari Prasad

    2013-03-01

    Full Text Available Metal complexes of the type ML1L2[M=Cu(II, Ni(II, and Co(II, L1=,'-dipyridyl(dipy., L2=2-hydroxybenzalidine anthranilic acid (HBAA] have been synthesized by using ,'-dipyridyl(dipy., 2-hdroxybenzalidine anthranilic acid (HBAA and metal(II acetate. The resulting mixed ligand metal complexes have been characterized on the basis of elemental analysis, IR-spectra, electronic spectra, magnetic susceptibilities and molar conductance measurements. The antifungal and antibacterial activities of ligands and there metal complexes have been screened against Aspergillus flavus, Aspergillus fumigatus, Aspergillus niger, Escherichia coli and Staphylococcus aureus.

  4. Infrared Spectroscopic Analysis of Linkage Isomerism in Metal-Thiocyanate Complexes

    Science.gov (United States)

    Baer, Carl; Pike, Jay

    2010-01-01

    We developed an experiment suitable for an advanced inorganic chemistry laboratory that utilizes a cooperative learning environment, which allows students to develop an empirical method of determining the bonding mode of a series of unknown metal-thiocyanate complexes. Students synthesize the metal-thiocyanate complexes and obtain the FT-IR…

  5. Complexation with dissolved organic matter and solubility control of heavy metals in sandy soil

    NARCIS (Netherlands)

    Weng, L.; Temminghoff, E.J.M.; Lofts, S.; Tipping, E.; Riemsdijk, van W.H.

    2002-01-01

    The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The res

  6. On the possibility of removing of transition metal ions from sewage using polymeric complexes

    International Nuclear Information System (INIS)

    The possibility of using of complexation in the system polyethylene-imine transition metal ions (Cu2+, Ni2+, Co2+)-surface active substance for removing of metal ions from solution and sewage has been investigated. It is shown, that pH of medium, hydro-fugitive of system and ratio between component of the triply complex effect on purification of solution. (author)

  7. Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

    OpenAIRE

    Kiefe, Claude; Bestgen, Sebastian; Gamer, Michael T.; Lebedkin, Sergei; Kappes, Manfred M.; Roesky, Peter W.

    2015-01-01

    Phenylpropynyl-functionalized imidazolium salts, as well as their gold complexes, were prepared in excellent yields affording suitable starting materials for metal cluster synthesis. The reactions of these gold complexes with coinage metal phenylacetylides [M(CCPh)]x (M = Cu, Ag) resulted in the formation of novel heterometallic hexanuclear clusters which exhibit mixed metallophillic interactions and intense white photoluminescence at low temperature.

  8. Metal complexes of 2((ethylthio)methyl)-4-aminophenol as oxidation inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Rarog, B.G.; Ivanov, V.A.; Potekhin, V.M.; Nesterov, M.V.

    1983-07-10

    Interest in the use of complex compounds as inhibitors of liquid-phase oxidation of hydrocarbons has increased in recent years. Sulfur- and nitrogen-containing metal complexes are known whose inhibiting properties are determined to a considerable extent by the composition of the chelate system, the nature of the metal, and the structure of the complex. At the same time, there is no information on metal compounds whose molecules contain functional groups not included in the chelate system but capable of taking part in inhibition reactions, and there are no data on the possible influence of the metal in the chelate system on the antioxidant activity of these groups. Accordingly, the inhibiting properties of metal complexes of 2((ethylthio)-methyl)-4-aminophenol, having a free amino group, in liquid-phase oxidation of hydrocarbons were studied. Decalin was chosen as the model oxidizable compound in studies of the antioxidant action of metal chelates.

  9. A study of the formation constants of ternary and quaternary complexes of some bivalent transition metals

    Directory of Open Access Journals (Sweden)

    MADHURJYA NEOG

    2010-01-01

    Full Text Available The formation of hetero-ligand 1:1:1, M(II-Opda-Sal/Gly ternary and 1:1:1:1, M(II-Opda-Sal-Gly quaternary complexes, where M(II = Ni, Cu, Zn and Cd; Opda = o‑phenylenediamine, Sal = salicylic acid, Gly = glycine, was studied pH-metrically in aqueous medium. The formation constants for the resulting ternary and quaternary complexes were evaluated at a constant ionic strength, μ = 0.20 mol dm-3 and temperature, 30±0.1 °C. The order of the formation constants in terms of the metal ion for both type of complexes was found to be Cu(II > Ni(II > Zn(II > Cd(II. This order was explained based on the increasing number of fused rings, the coordination number of the metal ions, the Irving – William order and the stability of various species. The expected species formed in solution were pruned with the Fortran IV program SPEPLOT and the stability of the ternary and quaternary complexes is explained.

  10. Synthesis, characterization, structural analysis of metal(II) complexes of N'-[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxybenzohydrazide-Multisubstituted Schiff base as a F(-) and Cu(2+) ions selective chemosensor.

    Science.gov (United States)

    Sundar, A; Prabhu, M; Indra Gandhi, N; Marappan, M; Rajagopal, G

    2014-08-14

    New colorimetric chemosensor, N'-[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxybenzohydrazide, containing OH and NH groups as binding sites have been synthesized and characterized by spectral UV, IR, NMR and ESR. The molecular structure of ligand is determined by X-ray crystallography and it has the monoclinic space group P21/c with cell parameters a=15.1058(6), b=14.3433(6), c=17.5800(8)Å and Z=8. The electronic spectral measurements show that Co(2+), Ni(2+) and Zn(2+) complexes have tetrahedral geometry, while Cu(2+) complex has square planar geometry. Magnetic measurements show that Cu(2+), Co(2+) and Ni(2+) complexes have paramagnetic behavior and Zn(2+) complex has diamagnetic behavior. Anion binding studies carried out using (1)H NMR and UV-visible spectrophotometric titrations revealed that these receptors exhibit selective recognition towards F(-) over other halide anions. The selectivity for F(-) among the halides is attributed mainly to the hydrogen-bond interaction of the receptor with F(-). Receptor (5 × 10(-5)M) shows color change from colorless to yellow in the presence of tetrabutylammonium fluoride (TBAF, 1.5 × 10(-3)M). Moreover, F(-)-induced color changes remain the same even in the presence of large excess of Cl(-), Br(-) and I(-). The binding constant is found to be higher towards F(-) ion and this may be due to presence of OH group, which offers extra binding site. Chromogenic receptor undergoes distinct color changes from colorless to green on gradual addition of Cu(2+) can be used as colorimetric probes for spectrophotometric and visual analysis of Cu(2+) in the presence of other transition metal ions such as Co(2+), Ni(2+) and Zn(2+). PMID:24759756

  11. Colour interceptions, thermal stability and surface morphology of polyester metal complexes

    International Nuclear Information System (INIS)

    Chelating copolymers via grafting of acrylic acid (AAc) and acrylamide (AAm/AAc) comonomer mixture onto polyester micro fiber fabrics (PETMF) using gamma-radiation technique were prepared. The prepared graft chains (PETMF-g-AAc) and (PETMF-g-PAAc/PAAm) acted as chelating sites for some selected transition metal ions. The prepared graft copolymers and their metal complexes were characterized using thermogravimetric analysis (TGA), colour parameters and surface morphology measurements. The colour interception and strength measurements showed that the metal complexation is homogeneously distributed. The results showed that the thermal stability of PETMF was improved after graft copolymerization and metal complexes. Moreover, the degree of grafting enhanced the thermal stability values of the grafted and complexed copolymers up to 25% of magnitude, on the other hand the activation energy of the grafted-copolymer with acrylic acid increased up to 80%. The SEM observation gives further supports to the homogenous distribution of grafting and metal complexation

  12. The influence of metal substrates and porcelains on the shade of metal-ceramic complex: A spectrophotometric study

    OpenAIRE

    Kavitha Janardanan; Sreelal Thankappan Pillai; Harshakumar Karunakaran

    2012-01-01

    Background: The final esthetic outcome of a metal-ceramic restoration is influenced by several factors including the type of the underlying metal as well as the brand of the ceramic. Settings and Design: An in vitro study. Aims: The purpose of the in vitro study was to investigate the influence of four types of metal-ceramic alloys and two porcelain systems on the color co-ordinates of the metal-ceramic complex. It also aimed at establishing a color index which correlated the color of t...

  13. Spectrophotometric study of some metal ions using some Schiff's bases

    International Nuclear Information System (INIS)

    In this work two schiff bases namely N,N Bis(benzoyl acetone)-o-phenylene diamine (NNBBPD) and N,N Bis(benzoyl acetone)-isopropylene diamine (NNBBAID) were prepared by direct coupling of benzoyl acetone with o-phenylene and isopropylene diamine respectively. The two reagents were identified by IR spectra, thin layer chromatography (TLC) and determination of the percentage of nitrogen contents (N%). It is found that the two reagents form coloured chelates with Fe (II), Fe (III), Cu (II), U (VI), Ni (II) and Co (II). The two reagents were used for the determination of Fe (II), Fe (III) and U (VI). The formulate of these metal ion complexes were obtained using continuous variations, mole ratio and slope ratio methods. Effect of two micelles, namely sodium n-dodecyl sulphate (SDS) and hexadecyl pyridinum broinide monohydrate (HPB) on metal ion complexes were studied. It is found that both of them increase the solubility and the absorbances of the metal ion complexes with variable effects of the absorption maxima. Calibration curves for Fe (II), Fe (II) and U (VI) were obtained in optimum conditions of pH and micelles solutions. (Author)

  14. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    Science.gov (United States)

    Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

    2016-01-01

    The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

  15. Compartmentation and complexation of metals in hyperaccumulator plants

    OpenAIRE

    Leitenmaier, Barbara; Küpper, Hendrik

    2013-01-01

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their “strange” behavior in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defense against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of ...

  16. Compartmentation and complexation of metals in hyperaccumulator plants

    OpenAIRE

    Barbara eLeitenmaier; Hendrik eKüpper

    2013-01-01

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their strange behaviour in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defence against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of c...

  17. Dithiocarbamate Complexes as Single Source Precursors to Metal Sulfide Nanoparticles for Applications in Catalysis

    OpenAIRE

    Roffey, A. R.

    2014-01-01

    Herein we report the solvothermal decomposition of a range of metal dithiocarbamate complexes for the synthesis of metal sulfide nanoparticles. Metal sulfides exist in a variety of structural phases, some of which are known to be catalytically active towards various processes. The aim of this work was to synthesise a variety of different metal sulfide phases for future catalysis testing, particularly the iron sulfide greigite (Fe3S4, a thiospinel containing Fe2+ and Fe3+) which is to be teste...

  18. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    Science.gov (United States)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  19. (BB)-Carboryne Complex of Ruthenium: Synthesis by Double B-H Activation at a Single Metal Center.

    Science.gov (United States)

    Eleazer, Bennett J; Smith, Mark D; Popov, Alexey A; Peryshkov, Dmitry V

    2016-08-24

    The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B-H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B-Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne-carboranyl transformations reported herein represent a new mode of cooperative metal-ligand reactivity of boron-based complexes. PMID:27526855

  20. Synthesis of Dichloride-Diphenylacetonitrile Palladium and Metal-Polymer Composite Based on Uhmwpe

    Directory of Open Access Journals (Sweden)

    A. M. Nemeryuk

    2016-05-01

    Full Text Available New complex of Pd (II with phenylacetonitrile, suitable for use as a precursor of palladium nano particles in the composition of metal-based composite UHMWPE was obtained. The thermodynamic characteristics of metal-polymer composite, found the effect of nano particles of palladium in the crystallization processes in UHMWPE and other characteristics of the material.

  1. Liquid chromatography of uranium complexes of tetradentate Schiff bases.

    Science.gov (United States)

    Khuhawar, M Y; Lanjwani, S N; Jehangir, T M

    2004-08-01

    Dioxouranium together with copper(II), nickel(II) and iron(II) were extracted in chloroform as complexes of bis(salicylaldehyde)-dl-stilbenediimine (dl-H2SA2S) or bis(salicylaldehyde)-meso-stilbenediimine (meso-H2SA2S), and separated by liquid chromatography with UV detection. The linear calibration range and detection limits were 40 - 200 ng and 10 ng/injection for each metal ion. The method was applied to the determination of uranium from mineral ore samples at concentrations of 30 - 700 microg/g with coefficients of variation from 3.6 to 5.5%. The relative elution of dioxouranium complexes of different Schiff bases was examined from reversed-phase HPLC; the substitution of methyl and phenyl groups at the bridge position enhanced the column retention of uranyl complexes. PMID:15352510

  2. The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

    Directory of Open Access Journals (Sweden)

    Malcolm A. Halcrow

    2016-05-01

    Full Text Available The relationship between chemical structure and spin state in a transition metal complex has an important bearing on mechanistic bioinorganic chemistry, catalysis by base metals, and the design of spin crossover materials. The latter provide an ideal testbed for this question, since small changes in spin state energetics can be easily detected from shifts in the spin crossover equilibrium temperature. Published structure-function relationships relating ligand design and spin state from the spin crossover literature give varied results. A sterically crowded ligand sphere favors the expanded metal–ligand bonds associated with the high-spin state. However, steric clashes at the molecular periphery can stabilize either the high-spin or the low-spin state in a predictable way, depending on their effect on ligand conformation. In the absence of steric influences, the picture is less clear since electron-withdrawing ligand substituents are reported to favor the low-spin or the high-spin state in different series of compounds. A recent study has shed light on this conundrum, showing that the electronic influence of a substituent on a coordinated metal ion depends on its position on the ligand framework. Finally, hydrogen bonding to complexes containing peripheral N‒H groups consistently stabilizes the low-spin state, where this has been quantified.

  3. Coordination Chemistry of Disilylated Stannylenes with Group 10 d10 Transition Metals: Silastannene vs Stannylene Complexation

    OpenAIRE

    Arp, Henning; Marschner, Christoph; Baumgartner, Judith; Zark, Patrick; Müller, Thomas

    2013-01-01

    The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners. While with nickel stannylene complex formation was observed, coordination of the stannylenes to palladium and platinum compounds led to unusual si...

  4. Synthesis and properties of 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl] porphyrin and its metal complexes

    Directory of Open Access Journals (Sweden)

    Lian Wenhui

    2012-01-01

    Full Text Available A novel 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl]porphyrin and its transition metal complexes are reported in this paper. Their molecular structures were characterized by elemental analysis, IR spectra, 1HNMR spectra and UV-Vis spectra. Their spectroscopic properties were studied by Raman spectra, fluorescence spectra and X-ray photoelectron spectra (XPS. The fluorescence quantum yields have been measured at room temperature. The fluorescence intensity of porphyrin ligand was stronger than that of the complexes. In Raman spectra, there was much difference between porphyrin ligand and its metal complexes due to changes of the symmetry of porphyrin plane. In the XPS spectra, the replacement of the free-base protons by a metal ion to form the metalloporphyrin increases the symmetry of the molecule also introduces an electron with-drawing group into the center of the porphyrin ligand which increases the N1s binding energy.

  5. Tuning carrier density at complex oxide interface with metallic overlayer

    Science.gov (United States)

    Zhou, Y.; Shi, Y. J.; Jiang, S. W.; Yue, F. J.; Wang, P.; Ding, H. F.; Wu, D.

    2016-06-01

    We have systematically investigated the electronic transport properties of the LaAlO3/SrTiO3 interfaces with several different metal capping layers. The sheet carrier density can be tuned in a wide range by the metallic overlayer without changing the carrier mobility. The sheet carrier density variation is found to be linearly dependent on the size of metal work function. This behavior is explained by the mechanism of the charge transfer between the oxide interface and the metal overlayer across the LaAlO3 layer. Our results confirm the existence of a built-in electric field in LaAlO3 film with an estimated value of 67.7 eV/Å. Since the metallic overlayer is essential for devices, the present phenomena must be considered for future applications.

  6. Study of the Complexation Behavior of Calixarene with Transition Metal Cations by UV—vis and Fluorescent Spectra

    Institute of Scientific and Technical Information of China (English)

    杨俊林; 郑企雨; 等

    2002-01-01

    A new fluorescent compound based on calix[4] arene skeleton was synthesized.Its complexation ability with transition metal ions,such as Fe3+,Co2+,Ni2+,Cu2+,Zn2+ and Ag+,Was investigated by UV-vis and fluorescent spectra.

  7. Study of the Complexation Behavior of Calixarene with Transition Metal Cations by UV-vis and Fluorescent Spectra

    Institute of Scientific and Technical Information of China (English)

    YANG,Jun-Lin(杨俊林); ZHENG,Qi-Yu(郑企雨); AN,Li-Na(安丽娜); CHEN,Chuan-Feng(陈传峰); LIN,Hong-Zhen(蔺洪振); BAI,Feng-Lian(白凤莲); HUANG,Zhi-Tang(黄志镗)

    2002-01-01

    A new fluorescent compound based on calix[4]arene skeleton was synthesized. Its complexation ability with transition metal ions, such as Fe3+, Co2+, Ni2+, Cu2+, Zn2+ and Ag+, was investigated by UV-vis and fluorescent spectra.

  8. Recovery of rare-metal elements from their EDTA complex solution by means of electrodialysis accompanied by metal substitution reaction

    International Nuclear Information System (INIS)

    The electrodialyzer used for the experiments was composed of five compartments divided by a cation-exchange membrane, C, and an anion-exchange membrane, A. The compartments were set in the order of Anode, Feed, Reaction, Strip, and Cathode compartments, and were partitioned with the A, C, C and A membranes, respectively. The Feed solution, the Reaction solution, and the Strip solution, each of which flowed through the corresponding compartment, contained CuCl2, rare metal-EDTA complex, and HCl solution, respectively. The electrodialysis for the recovery of rare-metal elements was expected to proceed as follows: When voltage is applied to the electrodialyzer, Cu2+ should proceed from the Feed compartment to the Reaction compartment, and act as the substitute for rare-metal elements in the EDTA complexes. The resultant free ions of rare-metal elements move to the Strip compartment, and are recovered. In the experiments, Co, La, Gd, Y, and Ni were selected as rare-metal elements. In the electrodialysis experiment for the Co-EDTA system, Cu2+ from the Feed compartment was immediately substituted for Co, and part of the resultant Co2+ moved to the Strip compartment. No permeation of Cu-EDTA and free Cu2+ was observed during the dialysis. The flux of Co2+ increased with an increase in current density. For the systems of La-EDTA, Gd-EDTA, and Y-EDTA, the permeation behavior of metal ions was almost the same as that for the Co-EDTA system. For the Ni-EDTA system, however, Cu2+ as well as Ni2+ proceeded to the Strip compartment: This suggests that for the Ni-EDTA system the metal substitution reaction is much slower than that for the other metal elements. Moreover, the substitution reaction rates of Cu for the rare-metal elements in the EDTA complexes were measured spectroscopically and analyzed with due consideration of dinuclear complex intermediates. (J.P.N.)

  9. Synthesis and characterization of group 4 metal alkoxide complexes containing imine based bis-bidentate ligands: effective catalysts for the ring opening polymerization of lactides, epoxides and polymerization of ethylene.

    Science.gov (United States)

    Roymuhury, Sagnik K; Chakraborty, Debashis; Ramkumar, Venkatachalam

    2015-06-14

    A series of Ti(iv), Zr(iv) and Hf(iv) complexes containing imine based bis-bidentate ligands were synthesized and characterized by various spectroscopic techniques, elemental analysis and X-ray crystallography. The ligands m-xysal-((t)Bu)4 (L(1)((t)Bu)4), m-xysal-(Me)2((t)Bu)2 (L(2)Me2((t)Bu)2) and m-xysal-(Cl)4 (L(3)Cl4) were reacted with Ti(O(i)Pr)4, Zr(O(i)Pr)4·(i)PrOH and Hf(O(t)Bu)4 in a 1 : 1 stoichiometric ratio to form complexes (L2M2(OR)4, where L = m-xysal-((t)Bu)4, m-xysal-(Me)2((t)Bu)2 and m-xysal-(Cl)4, M = Ti and R = (i)Pr, (L2M2(OR)4, where L = m-xysal-((t)Bu)4, m-xysal-(Me)2((t)Bu)2 and m-xysal-(Cl)4, M = Zr and R = (i)Pr and (L3M3(OR)6, where L = m-xysal-((t)Bu)4, m-xysal-(Me)2((t)Bu)2 and m-xysal-(Cl)4, M = Hf and R = (t)Bu respectively. Complex was crystallized from a 1 : 1 : 1 mixture of chloroform, ethanol and toluene to yield an ethoxy substituted complex (L2M2(OR)4, L = m-xysal-(Me)2((t)Bu)2, M = Zr and R = Et. The X-ray structures of , and illustrate that and are binuclear helical complexes, whereas is trinuclear. These complexes were found to be active for the ring opening polymerization (ROP) of lactides (rac-LA, l-LA) and epoxides. All the complexes produced atactic poly(lactic acid) (PLA) with good number average molecular weight (Mn) and narrow molecular weight distributions (MWDs). The magnetic isotropic shielding constants were calculated using the GIAO/B3LYP/LANL2DZ approach and correlated with the experimental values. The HOMO-LUMO energy band gaps and Mulliken charges were calculated using the DFT method to explain the reactivity of these complexes according to the relationship between chemical hardness and reactivity established by Pearson. In addition, complexes , activated by methylaluminoxane (MAO), were used and found to be moderately active for ethylene polymerization. PMID:25970486

  10. Structure and catalytic properties of metal β-diketonate complexes with oxygen-containing compounds

    International Nuclear Information System (INIS)

    The results of researches published in recent 15-20 years of complexes of metal β-diketonates (including Cr3+, VO2+, MoOΛ22+, Co3+, Mn3+, Ni2+, Fe3+) with oxygen-containing compounds (alcohols, glycols, phenols, hydroperoxides, aldehydes, esters, etc.) playing an important role in catalytic processes of oxidation, addition, polymerization and copolymerization are reviewed. Data on the nature of chemical bond of oxygen-containing reacting agents with metal β-diketonates, on structure of metal β-diketonate complexes with oxygen-containing reacting agents and thermodynamics of complexing as well as on activation of reacting agents in complexes and catalytic properties of metal β-diketonates are discussed. Stored materials make it possible to exercise directed control of metal β-diketonate activity

  11. Process for the displacement of cyanide ions from metal-cyanide complexes

    Science.gov (United States)

    Smith, Barbara F.; Robinson, Thomas W.

    1997-01-01

    The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

  12. Synthesis, thermal and optical properties of metal(II) complexes with a novel ligand derived from pyrazolone-5

    Science.gov (United States)

    Li, Xiaoyi; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

    2011-03-01

    Three novel metal(II) complexes, CoL2, NiL2 and CuL2 (L = (Z)-4-(2-(1,3-dimethyl-5-oxo-1H-pyrazol-4(5H)-ylidene)hydrazinyl)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one were synthesized. Their structures were postulated based on elemental analyses, 1H NMR, ESI-MS, FT-IR spectra and UV-vis spectra. The effect of different central metal(II) ions on absorption bands of the metal(II) complexes in CHCl3 solutions was researched. The result indicates that the bathochromic shift is CuL2 > NiL2 > CoL2. The absorption properties of thin films and thermal stability of these complexes are also discussed. In addition, the optical constants (complex refractive index N= n+ ik) and thickness of the complex thin films on polished single-crystal silicon substrates were measured by spectroscopic ellipsometry. Results indicate that the metal(II) complexes would be a promising recording medium candidate for blu-ray recordable optical storage system due to good absorption at 405 nm, high thermal stability and sharp thermal decomposition, and a high n values of 1.35-1.45 and a low k values of 0.33-0.39.

  13. Preparation and characterisation of some transition metal complexes of niacinamide (vitamin b3)

    International Nuclear Information System (INIS)

    Niacinamide forms metal complexes of general formula (M(C/sub 6/H/sub 6/N/sub 2/O)2)Cl/sub 2/; where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) in the aqueous medium. The complexes were formulated by comparing the experimental and calculated data for C, H, N and metal. The prepared complexes were characterized by different physicochemical methods. The UV-vis, FTIR spectral analysis and thermo gravimetric analysis (TGA). TGA of these complexes have been discussed. Magnetic susceptibility values indicate that all complexes except Zn complex are paramagnetic in nature. The redox properties of the metal ions in the Mn, Cu and Zn complexes have been discussed from the cyclic voltammetric studies. In all cases the systems are quasi reversible. (author)

  14. ANTIBACTERIAL ACTIVITY OF BENZIMIDAZOLES 2-THIO, 2-AMINODERIVATIVES AND COMPLEXES OF BENZIMIDAZOLES WITH TRANSITIONAL METALS

    Directory of Open Access Journals (Sweden)

    E. I. Mayboroda

    2014-01-01

    Full Text Available The literature data about antibacterial properties of benzimidazole 2-thio-, 2-aminoderivatives and benzimidazole complexes have been generalized and systematized in the review. Today prevention and treatment of diseases caused by microorganisms is an actual problem of modern therapy. Therefore, the search for active molecules, the based on them development of some new, more effective antimicrobial agents is an important task of modern pharmaceutical chemistry. Promising compounds for solving these problems are benzimidazole derivatives. They are available, functionally capable, stable and have a wide spectrum of biological activities (antiviral, anthelmintic, antibacterial, anticancer, antidiabetic.The purpose of this paper is to generalize and systematize information about the antimicrobial action of 2-thio-, 2-amino-substituted benzimidazoles and benzimidazole derivatives complexes with transition metals.These compounds and their complexes with transition metals are active against pathogenic strains Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Salmonella typhimurium, Proteus vulgaris, Bacillus cereus, Micrococcus luteus, Helicobacter рylori and others.

  15. Thermokinetic Study on the Complexation Reaction of the First-Row Transitional Metal Chlorides with Histidine

    Institute of Scientific and Technical Information of China (English)

    CHEN,San-Ping(陈三平); GAO,Sheng-Li(高胜利); SHI,Qi-Zhen(史启祯)

    2004-01-01

    The enthalpy change of the complexation reactions of the first-row transitional metal chlorides including CrCl3,MnCl2, FeCl2, CoCl2, NiCl2 and CuCl2 with L-α-histidine in water were determined by a microcalorimeter at 298.15-323.15 K. The standard enthalpy of formation of Cr(His)3+2 (aq) and M(His)2+2 (aq) (M=Mn, Fe, Co,Ni and Cu) were calculated. Based on the thermodynamic and kinetic equations of the reactions, three thermodynamic parameters (the activation enthalpy, the activation entropy, the activation free energy), the rate constants, and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) are obtained. The solid complexes of CrCl3, MnCl2, FeCl2, CoCl2, NiCl2 and CuCl2 with histidine were prepared and acterized by IR as well. The results showed that, with the atomic number increasing, three thermodynamic parameters, △G≠(-), △H≠(-) and △S≠(-) of the complexation reaction of these metal chlorides with L-α-histidine in water present an analogy regularity.

  16. Investigation on the gas-phase radiolysis of metal complexes

    International Nuclear Information System (INIS)

    Gas-phase radiolysis of metal carbonyls has been performed. These carbonyls with iron, chromium and cobalt are sublimed easily by heating under atmospheric condition, and formed fine powder by gamma-ray-or electron-irradiation. Chemical compositions of fine powders prepared by electron beam irradiation are estimated as metal oxide after physical analysis such as microscopic observation, particle sizing, thermal and chemical analysis. These metal oxides thus obtained contain CO2, H2O, and some carbonic compounds, and they are removed easily by heating up to 400degC. (author)

  17. Determination of stability constants of aminoglycoside antibiotics with their metal complexes

    Science.gov (United States)

    Tiwow, Vanny M. A.

    2014-03-01

    One group of aminoglycoside antibiotics contains aminosugars. The aminosugar neomycin B with its derivate product neamine (2-Deoxy-4-0-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyl)-D-Streptamine) was identified as a free ligands and metal complexes. In particular, the stability constants of metal complexes by potentiometric titration techniques were investigated. Our previous study had determined the acid dissociation constants of these aminosugars with few metal complexes in fair depth. In this work, the complexation of two pyridine-containing amino alcohols and an amino sugar (neamine) have been measured potentiometrically. For instance, the stability constant of copper(II) complexation were determine and the model system generated an excellent fit. Stability constants with several metals have been determined and will be reported.

  18. Photochemical activation and reactivity of polynuclear transition metal complex molecules. Final report

    International Nuclear Information System (INIS)

    Several bi- and trinuclear metal complexes containing ligands from β-polyketonates have been synthesized and characterized including homo- and hetero-polynuclear complexes. New synthetic approaches to the preparation of heterobi- and trinuclear complexes have been developed that allow the preparation of a large number of molecules containing heavy-metal ions such as Pd2+ or UO22+ and a first-row transition-metal ion. The electrochemical properties of these complexes have been investigated and many exhibit the ability to transfer two electrons at very nearly the same potential. Photochemical studies on binuclear Cu(II) and Ni(II) showed that these compounds yielded reduced metal species and decomposition upon irradiation. Luminescence of hetero-complexes of uranyl polyketonates is observed at 770K with the UO22+ moiety functioning as an isolated chromophore in which emission is observed only on direct excitation of UO22+ and energy transfer to lower states in the molecule is not observed

  19. Transition metal complexing with polymetric sulfur-containing fibrous ligand

    International Nuclear Information System (INIS)

    A study was made on interaction of Cr4, V5, Cu2 transition metals with thioamidated polymeric PVS-PAN-T ligand of fibrous structure. Sorption characteristics of PVS-PAN-T, depending on pH and temperature of solutions of copper, chromium and vanadium salts were determined. Parameters of ESR spectra of PVS-PAN-T compounds with transition metals enabled to determine the structure of formed coordination centers

  20. A quantitative structure-activity approach for lipophilicity estimation of antitumor complexes of different metals using microemulsion electrokinetic chromatography.

    Science.gov (United States)

    Foteeva, Lidia S; Trofimov, Denis A; Kuznetsova, Olga V; Kowol, Christian R; Arion, Vladimir B; Keppler, Bernhard K; Timerbaev, Andrei R

    2011-06-01

    Microemulsion electrokinetic chromatography (MEEKC) offers a valuable tool for the rapid and highly productive determination of lipophilicity for metal-based anticancer agents. In this investigation, the MEEKC technique was applied for estimation of n-octanol-water partition coefficient (logP(oct)) of a series of antiproliferative complexes of gallium(III) and iron(III) with (4)N-substituted α-N-heterocyclic thiosemicarbazones. Analysis of relationships between the experimental logP(oct) and the retention factors of compounds showed their satisfactory consistency in the case of single metal sets, as well as for both metals. Since none of available calculation programs allows for evaluating the contribution of central metal ion into logP(oct) (i.e. ΔlogP(oct)) of complexes of different metals, this parameter was measured experimentally, by the standard 'shake-flask' method. Extension of the logP(oct) programs by adding ΔlogP(oct) data resulted in good lipophilicity predictions for the complexes of gallium(III) and iron(III) included in one regression set. Comparison of metal-thiosemicarbazonates under examination in terms of logP(oct) vs. antiproliferative activities (i.e. 50% inhibitory concentration in cancer cells) provided evidence that their cytotoxic potency is associated with the ability to cross the lipid bilayer of the cell-membrane via passive diffusion. PMID:21382684

  1. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Timothy J. Deming

    2013-01-01

    Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  2. The influence of the chelated metal ion on the fragmentation pathways of metal complexes of 5-nitro-octaethylporphyrin

    International Nuclear Information System (INIS)

    Tandem mass spectrometric analyses of suite of 10 divalent complexes of 5-nitro-octaethylporphyrin reveals that the fragmentation pathway is influenced by the chelated metal ion. The porphyrins undergo a novel cleavage of the macrocyclic ring. Surprisingly, the expected β-cleavage of the alkyl substituents is not very significant for many of the complexes. In this paper the mass spectra of the metalloporphyrins are compared and the role of the chelated metal ion will be discussed. The effect of the rate of heating on the mass spectra of the molecules will also be discussed

  3. Critical survey of stability constants of EDTA complexes critical evaluation of equilibrium constants in solution stability constants of metal complexes

    CERN Document Server

    Anderegg, G

    2013-01-01

    Critical Survey of Stability Constants of EDTA Complexes focuses on the computations, values, and characteristics of stability constants. The book emphasizes that for a critical discussion of experimentally determined stability constants, it is important to consider the precision of the values that manifests the self-consistency of the constant, taking into consideration the random errors. The publication reviews the stability constants of metal complexes. The numerical calculations affirm the reactions and transformations of metal ions when exposed to varying conditions. The text also present

  4. Synthesis, Characterization, Antibacterial and Anti-Inflammatory Activities of Enoxacin Metal Complexes

    Directory of Open Access Journals (Sweden)

    Saeed Arayne

    2009-01-01

    Full Text Available The present work comprises the synthesis of enoxacin (Heno complexes with various transition metals. Two types of complexes [M(eno2(H2O2]3H2O(M=CuII, NiII or MnII and [M(eno(H2O2]Cl⋅4H2O  (M=FeIII were obtained. The complexes were characterized by different physicochemical, spectroscopic, and elemental analysis. Results suggest that enoxacin interacts with the metals as a monoanionic bidentate ligand. These complexes were also tested for their antibacterial activity against eleven (11 different microorganisms, and the results were compared with the parent drug. Moreover all the metal complexes were also tested for their ability to scavenge reactive oxygen species where by MnII and CuII complexes exhibited potential to mediate anti-inflammatory response.

  5. Structure Characterization and Properties of Metal-Surfactant Complexes Dispersed in Organic Solvents.

    Science.gov (United States)

    de la Iglesia, Pablo; Jaeger, Vance W; Xi, Yuyin; Pfaendtner, Jim; Pozzo, Lilo D

    2015-08-25

    This work describes the synthesis and characterization of metal-surfactant complexes. Dioctyl sulfosuccinate and dodecylbenzenesulfonate are associated with multivalent aluminum, iron, and vanadium ions using an ion exchange reaction. The metal complexes are dispersible in various organic solvents. In solvents with low polarity, the complexes form "inverse" macromolecular structures with multiple metal ions. In contrast, in alcohols, the complex size is reduced, showing a more disperse conformation. The metal and surfactant ions are still strongly bonded to each other in all the solvents probed. Small-angle X-ray and neutron scattering (SAXS and SANS) are used to characterize the structures. Simultaneous fitting of neutron and X-ray scattering spectra is performed in order to obtain an accurate description of the system. Scattering results are also validated by performing molecular dynamics (MD) simulations. The conductive and electrochemical properties of the complexes in solution are also evaluated. The dispersion of metal-organic complexes significantly increases electric conductivity, and some metal ions in the core of the complexes are shown to be electrochemically active in apolar solvents. PMID:26212253

  6. Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: Complexation versus mixture

    International Nuclear Information System (INIS)

    Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC50 values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. - Highlights: ► The complex of antibiotic with metal is a mixture of various complexation modes. ► Antibiotic and metal act as various combined interactions when their complexation is ignored. ► Antibiotic, metal, and their complex act as concentration addition interaction. ► Complex commonly is the highest toxicant. ► Neglecting complexation renders improper classification of risks for antibiotics. - Antibiotic, heavy metal and their complex act primarily as concentration addition interaction and the complex commonly is highest toxic.

  7. Effects of complexing compounds on sorption of metal ions to cement

    Energy Technology Data Exchange (ETDEWEB)

    Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry

    2005-12-15

    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  8. Effects of complexing compounds on sorption of metal ions to cement

    International Nuclear Information System (INIS)

    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  9. Multiheteromacrocycles that complex metal ions. Third progress report, 1 May 1976--30 April 1977

    International Nuclear Information System (INIS)

    The overall objective of this research is to design, synthesize and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes and clusters. Host organic compounds consist of strategically placed solvating, coordinating and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The specific compounds synthesized and their complexing and lipophilizing properties are summarized

  10. Formation of Complexes of Flavonoids and Metals. Determination of the Stoichiometry and Stability Constants

    OpenAIRE

    Pomilio, A. B.; L. D. Slep; R. Alonso Werner; Barolli, M. G.

    2000-01-01

    The complexes between some flavonoids and metals (Co(II), Cu(II), Mn(II), Mg(II), Sn(II)) have been studied by spectrophotometric methods in order to determine the stoichiometry and stability constants.

  11. SIMULTANEOUS DETERMINATION OF HEAVY METAL IONS BY CAILLARY ZONE ELECTROPHORESIS USING A COMPLEX SELECTOR

    OpenAIRE

    Neudachina, L. K.; Lebedeva, E. L.

    2014-01-01

    The usage of diglycylglycine (GGG) was proposed to improve the separation of the complexes of heavy metal ions with EDTA by capillary zone electrophoresis. The tripeptide can interact with the complexes in capillary and thereby acts as a complex selector.The influence of GGG on the electrophoretic behavior of ten metal complexes (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) and Bi(III)) was studied in an acidic media using a negative polarity voltage supply. Three ...

  12. Development of a polymer based fiberoptic magnetostrictive metal detector system

    OpenAIRE

    Hua, Wei Shu; Hooks, Joshua Rosenberg; Wu, Wen Jong; Wang, Wei Chih

    2010-01-01

    This paper presents a new metal detector using a fiberoptic magnetostriction sensor. The metal sensor uses a fiber-optic Mach-Zehnder interferometer with a newly developed ferromagnetic polymer as the magnetostrictive sensing material. This polymeric magnetostrictive fiberoptic metal sensor is simple to fabricate, small in size, and resistant to RF interference (which is common in typical electromagnetic type metal detectors). Metal detection is based on disruption of the ma...

  13. Manipulation of a Schlenk Line: Preparation of Tetrahydrofuran Complexes of Transition-Metal Chlorides

    Science.gov (United States)

    Davis, Craig M.; Curran, Kelly A.

    2007-01-01

    Before taking an inorganic laboratory course few students have experience handling air-sensitive materials using Schlenk techniques. This exercise introduces them to techniques they will employ in later syntheses. The procedure involves the formation of anhydrous tetrahydrofuran complexes of transition-metal chlorides from metal-chloride hydrates;…

  14. Synthesis and Complexation Properties Towards Metal Ions of New Tri-substituted Thiacalix[4]arenes

    OpenAIRE

    FELIX, Caroline; Vocanson, Francis; Dumazet-Bonnamour, Isabelle

    2009-01-01

    Abstract New thiacalix[4]arenes appended with three amide functions have been prepared. Their conformations have been solved thanks to 1H NMR 2D COSY and NOESY. The complexation ability of these ligands towards various metal ions (Cd2+, Pb2+, Pd2+; Ni2+, Hg2+, Hg+, Ag+, Zn2+ and Cu2+) has been investigated by UV-vis absorption and the stoichiometry of the metal-ligand complexes was determined

  15. Sulfonate Functionalisation of Transition Metal Complexes: A Versatile Tool Towards Catalyst Recovery

    OpenAIRE

    Virboul, M.A.N.

    2011-01-01

    This thesis describes the synthesis and application of sulfonate-functionalised ligands in organometallic chemistry and (aqueous) catalysis. Due to their ability to trigger specific solubility, different NHC ligand precursors bearing a butyl-sulfonate chain were synthesised. The formation of transition metal complexes containing gold and rhodium was enabled by a simple procedure involving the initial synthesis of a silver complex and a transmetallation with a suitable metal precursor and an o...

  16. Quantum Chemical Calculations of EPR-Hyperfine Coupling Constants for Transition Metal Complex

    International Nuclear Information System (INIS)

    In this this study the performance of various density functional approaches for calculation of electron paramagnetic resonance hyperfine coupling constants in transition metal complexes was studied. Several gradient-corrected as well as hybrid functionals have been validated by comparison with experimental data and high-level coupled-cluster calculation for 21 systems, representing a variety of bonding situations. Second part of this work represents an analysis and interpretation of spin-polarization effects in first transition metal complexes

  17. New trends for metal complexes with anticancer activity

    NARCIS (Netherlands)

    Bruijnincx, P.C.A.; Sadler, Peter J.

    2008-01-01

    Medicinal inorganic chemistry can exploit the unique properties of metal ions for the design of new drugs. This has, for instance, led to the clinical application of chemotherapeutic agents for cancer treatment, such as cisplatin. The use of cisplatin is, however, severely limited by its toxic side-

  18. Synthesis and Reactivity of Tripodal Complexes Containing Pendant Bases

    Energy Technology Data Exchange (ETDEWEB)

    Blacquiere, Johanna M.; Pegis, Michael L.; Raugei, Simone; Kaminsky, Werner; Forget, Amelie; Cook, Sarah; Taguchi, Taketo; Borovik, Andrew S.; Mayer, James M.

    2014-09-02

    The synthesis of a new tripodal ligand family is reported, with tertiary-amine groups in the second-coordination sphere. The ligands are tris(amido)amine derivatives, with the pendant amines attached via a peptide coupling strategy. They were designed to be used in new catalysts for the oxygen reduction reaction (ORR), in which the pendant acid/base group could improve catalyst performance. Two members of the new ligand family were each metallated with Co(II) and Zn(II) to afford trigonal monopyramidal complexes. Reaction of the cobalt complexes, [Co(L)]-, with dioxygen reversibly generates a small amount of a Co(III)-superoxo species, which was characterized by EPR. Protonation of the zinc complex Zn[N{CH2CH2NC(O)CH2N(CH2Ph)2}3)-– ([Zn(TNBn)]-) with one equivalent of acid occurs with displacement and dissociation of an amide ligand. Addition of excess acid to the any of the complexes [M(L)]- results in complete proteolysis and formation of the ligands H3L. This decomposition limits the use of these complexes as catalysts for the ORR. An alternative ligand with two pyridyl arms was also prepared but could not be metallated. These studies highlight the importance of stability of the primary-coordination sphere of ORR electrocatalysts to both oxidative and acidic conditions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  19. Structural diversity in binuclear complexes of alkaline earth metal ions with 4,6-diacetylresorcinol

    Science.gov (United States)

    Shebl, Magdy; Khalil, Saied M. E.; Taha, A.; Mahdi, M. A. N.

    2012-11-01

    A new series of binuclear and mixed-ligand complexes with the general formula: [M 2(LO)yClz]; where M = Mg(II), Ca(II), Sr(II) and Ba(II); H2L = 4,6-diacetylresorcinol, the secondary ligand L' = acetylacetone (acac), 8-hydroxyquinoline (8-HQ) or 2,2'-bipyridyl (Bipy), n = 0-2, m = 1, 2, x = 0, 1, 2, 4, y = 0, 2, 4, 5 and z = 0-2; have been synthesized. They have been characterized by the analytical and spectral methods (IR, 1H NMR and mass) as well as TGA and molar conductivity measurements. The spectroscopic and conductance data suggested that the H2L ligand behaves as a neutral, monobasic or dibasic tetradentate ligand, depending on the basicity of the secondary ligand, through the two phenolic and two carbonyl groups. Binuclear octahedral geometry has been assigned to all of the prepared complexes in various molar ratios 2:2; 2:2:2; 1:2:1 and 1:2:4 (L:M:L'). Molecular orbital calculations were performed for the ligands and their complexes using Hyperchem 7.52 program on the bases of PM3 level and the results were correlated with the experimental data. The ligand and some of its alkaline metal(II) complexes showed antibacterial activity towards some of Gram-positive and Gram-negative bacteria, yeast (Candida albicans) and fungus (Aspergillus fumigatus).

  20. Magnetic and transport properties of Co–Si–B metallic glasses with complex dopants

    International Nuclear Information System (INIS)

    The structure, magnetic and resistivity characteristics of Co–Si–B metallic glasses containing complex dopants have been investigated. The intervals of thermal stability of the phases existing in the alloys studied have been determined. The temperature dependences of the resistivity were shown to be essentially nonlinear up to a certain temperature, evidencing for the contribution of several scattering mechanisms. Magnetic and resistivity behavior of these alloys are substantially governed by the phase separation within the region of the amorphous state stability and magnetic clusters formation. In the as-cast alloys these clusters are estimated to contain 2–4 Co atoms. Heat treatment significantly affects the structure and magnetic properties. It leads to increase of the Curie temperature and localized magnetic moment, whereas the crystallization temperature remains almost invariable. - Highlights: • We study magnetic and transport properties of Co–Si–B based metallic glasses. • Intervals of thermal stability of the existing phases have been determined. • We calculated paramagnetic moments per transition metal atom μTM. • Possibility of the cluster structure of studied alloys is discussed. • Influence of heat treatment on μTM and the Curie temperature is defined

  1. Chemical Sensors Based on Metal Oxide Nanostructures

    Science.gov (United States)

    Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Mike J.; Liu, Chung-Chiun

    2006-01-01

    This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

  2. Near-infrared dichroism of a mesogenic transition metal complex and its solubility in nematic hosts

    International Nuclear Information System (INIS)

    A transition metal complex possessing the nematic phase, bis (p-n-butylstyryl-1, 2-dithiolato) nickel, was synthesized and its optical properties and solubility in the nematic hosts K15 and MBBA were investigated. The metal complex displayed a high solubility in both host materials (up to 10% wt/wt) and a strong near-infrared absorption band centered at 860 nm. A blocking extinction of greater than OD = 3 was obtained with a 100 micron pathlength of a 0.5% wt/wt mixture of the nematic metal complex in K15, suggesting its usefulness for passive blocking of near infrared radiation. A 24 micron thick, homogeneously aligned guest-host cell containing a 1% wt/wt mixture of the metal complex in K15 possessed a contrast ratio of nearly 5:1 and a blocking extinction of OD = 3.5 at 860 nm, demonstrating for the first time the existence of near-infrared dichroism in this class of materials. The solubility and blocking extinction of the mesogenic metal complex in K15 was considerably superior to the non-mesogenic near ir laser dye bis(dimethylaminodithiobenzil) nickel in the same host. An interaction of the nematic metal complex in mixtures with MBBA which resulted in the creation of a new absorption band at 1050 nm was also observed. 21 refs., 9 figs

  3. Development of the aza-crown ether metal complexes as artificial hydrolase.

    Science.gov (United States)

    Yu, Lan; Li, Fang-zhen; Wu, Jiao-yi; Xie, Jia-qing; Li, Shuo

    2016-01-01

    Hydrolases play a crucial role in the biochemical process, which can catalyze the hydrolysis of various compounds like carboxylic esters, phosphoesters, amides, nucleic acids, peptides, and so on. The design of artificial hydrolases has attracted extensive attention due to their scientific significance and potential applications in the field of gene medicine and molecular biology. Numerous macrocyclic metal complexes have been used as artificial hydrolase in the catalytic hydrolysis of the organic substrate. Aza-crown ether for this comment is a special class of the macrocyclic ligand containing both the nitrogen atoms and oxygen atoms in the ring. The studies showed that the aza-crown complexes exhibited high activity of hydrolytic enzyme. However, the aza-crown ether metal complex as artificial hydrolase is still very limited because of its difficulty in synthesis. This review summarizes the development of the aza-crown ether metal complexes as the artificial hydrolase, including the synthesis and catalysis of the transition metal complexes and lanthanide metal complexes of aza-crown ethers. The purpose of this review is to highlight: (1) the relationship between the structure and hydrolytic activity of synthetic hydrolase; (2) the synergistic effect of metal sites and ligands in the course of organic compound hydrolysis; and (3) the design strategies of the aza-crown ethers as hydrolase. PMID:26460062

  4. On the complexing of certain transition metal bromides with trimecaine

    International Nuclear Information System (INIS)

    Synthesis and IR spectroscopy of the structure of cadmium bromide coordination compounds and certain other elements with trimecaine (diethylamino-2,4-6-trymethylacetanilidine, L) are carried out. Complexes of the CdLBr2(1) and Cd(LH)2Br4(2) composition are prepared, this molecular structure is established. In complex 1 cadmium atom is shown to be coordinately related to the nitrogen atom of the ternary aminogroup; in complex 2 the bond between the CdBr42- anion and ternary nitrogen atom of the ligand is of the ionic character

  5. Investigations of tris(1,10-phenanthroline) metal complexes and related mixed ligand complexes associated with DNA

    International Nuclear Information System (INIS)

    One of the most interesting problems in research on the interactions of small molecules with DNA is the delineation of factors involved in recognition of specific DNA sequences and conformations. We have studied tris(1,10-phenanthroline) metal complexes of several transition metals and related mixed ligand complexes in an effort to elucidate the effect of chirality, charge, hydrophobicity and size of the complex on DNA binding properties. 1H NMR spectroscopy of [Ru(phen)3]Cl2, [Rh(phen)3]Cl3, [Co(phen)3]Cl3 bound to oligonucleotides demonstrated that the complexes bind enantoselectively. Enantioselectivity is influenced by the charge of the complex, with +2 complexes displaying a Δ preference, and +3 complexes having a Λ preference. DNA unwinding and 31P NMR experiments have revealed that the difference in enantioselectivity observed for [Ru(phen)3]Cl2 and [Rh(phen)3]Cl3 may result from enhanced affinity of the surface binding mode as charge is increased. This is the first example in which the DNA-binding mode of a complex has been studied as a function of its charge

  6. Application of Δ- and Λ-Isomerism of Octahedral Metal Complexes for Inducing Chiral Nematic Phases

    Directory of Open Access Journals (Sweden)

    Hisako Sato

    2009-10-01

    Full Text Available The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(β-diketonatometal(III complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III, Cr(III and Ru(III complexes with C2 symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described.

  7. Transition metal complexes of some biologically active ligands; synthesis characterization and bioactivities

    International Nuclear Information System (INIS)

    Transition/representative transition metals complexes of biologically active chelating agent 1,2-dipyrolodinoethane were synthesized and characterized through spectral and analytical data. The complexes are of the formula (M(L)X/sub 2/). Where (M = Co (II), Ni (II), Cu (II), Zn (II), Hg (II) and Cd (II) and X = CI, Br, NO/sub 3/). Tetrahedral geometry has been proposed to these-metal complexes with the help of magnetic measurements, elemental analysis, chemical stoichiometry and spectroscopic data Antibacterial activity of the ligand and its metal complexes were screened against Eschereschi coli, Klebsiello pneumonia, Proteus mirabilis, Proteus vulhari, Streptococcus pneumonia, Salmonella Iyphi, Bacilh,s anthrax, Streptococcus fecalis and Staphylococcus aureus. Complexes were found to be active against Eschereschi coli, Klebsiella pneumonia, Proteus mirabilis and Proteus vulharis. (author)

  8. The first uranyl-lanthanide hetero metallic complexes: metal-organic frameworks with DOTA and oxalato ligands

    International Nuclear Information System (INIS)

    Reaction of uranyl and lanthanide nitrates with DOTA (H4L) under hydrothermal conditions gave the first uranyl-lanthanide hetero metallic complexes, [(UO2)2Ln(L)(C2O4)(OH)(H2O)]· 3H2O [Ln = Gd (1) or Eu (2)]. (author)

  9. Synthesis of monomeric and polymeric alkali and alkaline earth metal complexes using a phosphinoselenoic amide ligand in metal coordination sphere

    Indian Academy of Sciences (India)

    Jayeeta Bhattacharjee; Ravi K Kottalanka; Harinath Adimulam; Tarun K Panda

    2014-09-01

    We report the monomeric complexes of magnesium and calcium of composition [M(THF){2-Ph2P(Se)N(CMe3)}2] [M= Mg (3), n = 1 andM = Ca (4), n = 2)] and polymeric complexes of potassium and barium of composition [K(THF)2{Ph2P(Se)N(CMe3)}] (2) and [K(THF)Ba{Ph2P(Se)N(CMe3)}3](5) respectively. The potassium complex 2 was readily prepared by the reaction of potassium bis(trimethylsilyl)amide with phosphinoselenoic amide ligand (1) at ambient temperature. The calcium complex 4 was prepared by two synthetic routes: in the first method, commonly known as salt metathesis reaction, the potassium complex 2 was made to react with alkaline earth metal diiodide at room temperature to afford the corresponding calcium complex. The metal bis(trimethylsilyl)amides were made to react with protic ligand 1 in the second method to eliminate the volatile bis(trimethyl)silyl amine. The magnesium complex 3 and barium complex 5 were prepared only through the first method. Solid-state structures of all the new complexes were established by single crystal X-ray diffraction analysis. The smaller ionic radii of Mg2+ (0.72Å) and Ca2+ (0.99Å) ions form the monomeric complex, whereas the larger ions K+ (1.38Å) and Ba2+ (1.35Å) were found to form onedimensional polymeric complexes with monoanionic ligand 1. Compound 2 serves an example of magnesium complex with a Mg-Se direct bond.

  10. Network Percolation Based on Complex Network

    Directory of Open Access Journals (Sweden)

    Yong Zhang

    2013-08-01

    Full Text Available Network percolation model is an abstraction of many practical problems, while the spread of the disease model can be described by percolation model. The problem of the spread of the disease has been the focus of academia and the medical. Recently years, the complex network is a true reflection of the some important characteristics of the system, which is the effective means to study realistic network. In this paper, we will introduce the complex networks and network percolation. We will research the disease propagation model while research the network percolation based on complex network. We will summary and analysis the two traditional disease propagation model—SIR and SIS. And it can provide some important reference for controlling the spread of the virus.  In this paper we will analyze the propagation of SIR model when consider the propagation media and the reflection SIS model. At last we will use some experiments to verify the results of those two models. And we can know that the complex network can accurate analyze the network percolation model such as disease propagation model.

  11. Efficient waveguide coupler based on metal materials

    Science.gov (United States)

    Wu, Wenjun; Yang, Junbo; Chang, Shengli; Zhang, Jingjing; Lu, Huanyu

    2015-10-01

    Because of the diffraction limit of light, the scale of optical element stays in the order of wavelength, which makes the interface optics and nano-electronic components cannot be directly matched, thus the development of photonics technology encounters a bottleneck. In order to solve the problem that coupling of light into the subwavelength waveguide, this paper proposes a model of coupler based on metal materials. By using Surface Plasmon Polaritons (SPPs) wave, incident light can be efficiently coupled into waveguide of diameter less than 100 nm. This paper mainly aims at near infrared wave band, and tests a variety of the combination of metal materials, and by changing the structural parameters to get the maximum coupling efficiency. This structure splits the plane incident light with wavelength of 864 nm, the width of 600 nm into two uniform beams, and separately coupled into the waveguide layer whose width is only about 80 nm, and the highest coupling efficiency can reach above 95%. Using SPPs structure will be an effective method to break through the diffraction limit and implement photonics device high-performance miniaturization. We can further compress the light into small scale fiber or waveguide by using the metal coupler, and to save the space to hold more fiber or waveguide layer, so that we can greatly improve the capacity of optical communication. In addition, high-performance miniaturization of the optical transmission medium can improve the integration of optical devices, also provide a feasible solution for the photon computer research and development in the future.

  12. Inherent structure length in metallic glasses: simplicity behind complexity.

    Science.gov (United States)

    Wu, Yuan; Wang, Hui; Cheng, Yongqiang; Liu, Xiongjun; Hui, Xidong; Nieh, Taigang; Wang, Yandong; Lu, Zhaoping

    2015-01-01

    One of the central themes in materials science is the structure-property relationship. In conventional crystalline metals, their mechanical behaviour is often dictated by well-defined structural defects such as dislocations, impurities, and twins. However, the structure-property relationship in amorphous alloys is far from being understood, due to great difficulties in characterizing and describing the disordered atomic-level structure. Herein, we report a universal, yet simple, correlation between the macroscopic mechanical properties (i.e., yield strength and shear modulus) and a unique characteristic structural length in metallic glasses (MGs). Our analysis indicates that this characteristic length can incorporate effects of both the inter-atomic distance and valence electron density in MGs, and result in the observed universal correlation. The current findings shed lights on the basic understanding of mechanical properties of MGs from their disordered atomic structures. PMID:26245801

  13. Capsules, secondary interactions and unusual multi-metallic complexes

    OpenAIRE

    Hart, John Stewart

    2012-01-01

    Research into inorganic supramolecular chemistry is burgeoning, in particular that which focuses on the formation of capsular molecules and the effects that these unique environments have on catalytic reactions. With the aim of producing new ligand designs that could not only support reactive metals, but also partake in supramolecular aggregation to provide a capsular microenvironment, new tripodal ligands and wide span imines and amines have been synthesised. Furthermore, t...

  14. Methanogens, sulphate and heavy metals: a complex system

    OpenAIRE

    Luz Ferreira Martins Paulo, Da, L.; Stams, A. J. M.; Machado de Sousa, D.Z.

    2015-01-01

    Anaerobic digestion (AD) is a well-established technology used for the treatment of wastes and wastewaters with high organic content. During AD organic matter is converted stepwise to methane-containing biogasa renewable energy carrier. Methane production occurs in the last AD step and relies on methanogens, which are rather sensitive to some contaminants commonly found in wastewaters (e.g. heavy metals), or easily outcompeted by other groups of microorganisms (e.g. sulphate reducing bacteria...

  15. Controlled Assembly of Endohedrally-Functionalized Metal-Ligand Supramolecular Complexes

    OpenAIRE

    Johnson, Amber

    2014-01-01

    An area of supramolecular chemistry that has recently been growing in popularity is the synthesis of metal-ligand cages. These are most commonly comprised of organic ligands and transition metal ions. Cage complexes often take the form of geometric polyhedra such as tetrahedra and octahedra, where the ligands act as the edges or faces and the metals serve as the vertices. Because these complexes have a polyhedral design, there is a central cavity in the cage, and this has been exploited for g...

  16. Synthesis, characterization and antimicrobial investigation of some moxifloxacin metal complexes

    Science.gov (United States)

    Sadeek, Sadeek A.; El-Shwiniy, Walaa H.; El-Attar, Mohamed S.

    2011-12-01

    The new complexes of moxifloxacin (MOX), with Ti(IV), Y(III), Pd(II) and Ce(IV) have been synthesized. These complexes were then characterized by melting point, magnetic studies and spectroscopic techniques involving infrared spectra (IR), UV-Vis, 1H NMR. C, H, N and halogen elemental analysis and thermal behavior of complexes also investigated. The results suggested that the molar ratio for all complexes is M: MOX = 1:2 where moxifloxacin acts as a bidentate via one of the oxygen atoms of the carboxylate group and through the ring carbonyl group and the complexes have the following formula [Ti(MOX) 2](SO 4) 2·7H 2O, [Y(MOX) 2Cl 2]Cl·12H 2O, [Pd(MOX) 2(H 2O) 2]Cl 2·6H 2O and [Ce(MOX) 2](SO 4) 2·2H 2O. The activation energies, E*, enthalpies, Δ H*, entropies, Δ S* and Gibbs free energies, Δ G*, of the thermal decomposition reactions have been derived from thermogravimetric (TGA) and differential thermogravimetric (DrTG) curves, using Coats-Redfern (CR) and Horowitz-Metzger (HM) methods. The antimicrobial activity of these complexes has been evaluated against three Gram-positive and three Gram-negative bacteria and compared with the reference drug moxifloxacin. The antibacterial activity of Ti(IV) complex is significant for E. coli K32 and highly significant for S. aureus K1, B. subtilis K22, Br. otitidis K76, P. aeruginosa SW1 and K. oxytoca K42 compared with free moxifloxacin.

  17. Capillary Electrophoresis for the Simultaneous Determination of Metals by Using Ethylenediamine Tetraacetic Acid as Complexing Agent and Vancomycin as Complex Selector

    Institute of Scientific and Technical Information of China (English)

    THREEPROM, Jirasak; SOM-AUM, Waraporn; LIN, Jin-Ming

    2006-01-01

    A new separation system of capillary electrophoresis for the simultaneous determination of metals by using ethylenediamine tetraacetic acid (EDTA) as complexing agent and employing vancomycin as complex selector was described. The Z-shape cell capillary electrophoresis was used to enhance the sensitivity for the determination of the complexes of Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ) and Fe(Ⅲ) with EDTA. The partial filling method (co-current mode) was used in order to increase the selectivity of the electrophoretic method, meanwhile vancomycin was not present at the detector path during the detection of metal-EDTA complexes. The vancomycin concentration, phosphate concentration and pH of the buffer strongly influenced mobility, resolution and selectivity of the studied analytes. Under the optimal condition, the relative standard deviations (n=5) of the migration time and the peak area were less than 3.14% and 7.35%, respectively. Application of the Z-shape cell capillary electrophoresis method with UV detection and vancomycin loading led to the reliable determination of these metal ions in tap water and the recoveries were 97%-101%. The detection limits based on a signal to noise ratio of 3: 1 were found in the range of 2-10 μg·L-1.

  18. Reactivities of d~0 transition metal complexes toward oxygen:Synthetic and mechanistic studies

    Institute of Scientific and Technical Information of China (English)

    CHEN ShuJian; ZHANG XinHao; LIN ZhenYang; WU YunDong; XUE ZiLing

    2009-01-01

    Transition metals such as Fe in porphyrin complexes are known to bind or react with O_2,and such reactions are critical to many biological functions and catalytic oxidation using O_2.The transition metals in these reactions often contain valence d electrons,and oxidation of metals is an important step.In recent years,reactions of O_2 with d~0 transition metal complexes such as Hf(NR_2)_4 (R=alkyl) have been used to make metal oxide thin films as insulating gate materials in new microelectronic devices.This feature article discusses our recent studies of such reactions and the formation of TiO_2 thin films.In contrast to the reactions of many d~n complexes where metals are often oxidized,reactions of d~0 complexes such as Hf(Nme_2)_4 and Ta(Nme_2)_4(SiR_3) with O_2 usually lead to the oxidation of ligands,forming,e.g.,-ONMe_2 and-OSiR_3 from-Nme_2 and-SiR_3 ligands,respectively.Mechanistic and theoretical studies of these reactions have revealed pathways in the formation of the metal oxide thin films as microelectronic materials.

  19. Modification of radiation response by metal complexes: a review with emphasis of nonplatinum studies

    International Nuclear Information System (INIS)

    There is a need to develop compounds which alter the effects of radiation, particularly in the hypoxic radioresistant cell, following the limited success to date of the electron-affinic nitroimidazoles. The chemistry of transition metals is briefly outlined to point out certain aspects which might be exploited in the design of radiosensitizers. The best known clinical example of a metal complex which enhances the effect of radiation in hypoxic cells is the successful antineoplastic cisplatin. Past studies on enhancement of radiation damage by complexes of metals other than platinum, mainly in bacterial spores and bacterial and mammalian cells, have been summarized according to the metal used. The many mechanisms by which metal complexes could interact with radiation are outlined, and examples are given where possible. This survey emphasizes the need for a systematic study of the effect of metal/ligand variation on radiosensitization with regard to mechanisms of action to assess the potential of these compounds as radiosensitizers. Metal complexes offer many advantages, both for the study of mechanisms by which radiation kills cells and for drug development. 146 references

  20. Systematic change in relative stabilities of REE-humic complexes at various metal loading levels

    International Nuclear Information System (INIS)

    Complexation of rare earth elements (REEs) with humic substances (HSs) at various REE loading levels was studied by solvent extraction and equilibrium dialysis methods coupled with inductively coupled plasma-mass spectrometry (ICP-MS). Apparent stability constants (βM-HS) of REE ions with standard Suwannee River humic acid (SRHA) were determined simultaneously for all REEs except for Pm. βM-HS depends on the REE loading level to HSs, where βM-HS decreases with an increase in the REE loading level at a lower REE loading region, whereas βM-HS is almost constant beyond a certain REE loading level. The variation in βM-HS with the REE loading level suggests the existence of several types of binding sites of REEs in HSs. Next, βM-HS was converted into KMA (Which is the REE-HS interaction parameter for Tipping's 'Humic Ion-Binding Model VI') to be compared with the data by previous studies on REE-HS complexation at various REE loading levels in terms of relative differences among REEs (i.e., REE pattern). In the case of solvent extraction, the REE pattern of logKMA changes with variation in the REE loading level; a peak around Sm and Eu was observed in the REE pattern of logKMA at a higher REE loading region, whereas logKMA increases with an increase in the atomic number of REEs at a lower REE loading region. On the other hand, such variation in the REE pattern of logKMA was not observed in the results of equilibrium dialysis. This difference in the REE pattern of logKMA can be explained by the total metal loading level, including the contributions of Fe3+ and Al3+ originally contained in HS. The main binding sites of REEs in HSs were determined by comparing the REE pattern of logKMA experimentally obtained for HSs with those estimated based on the linear free-energy relationship (LFER) for carboxylates. Similarity of the REE pattern suggested that simple carboxylates are the main binding sites of REEs at a higher metal loading region, whereas chelating sites play a

  1. Synthesis and antimalarial activity of metal complexes of cross-bridged tetraazamacrocyclic ligands

    OpenAIRE

    Timothy J. Hubin; Amoyaw, Prince N. -A.; Roewe, Kimberly D.; Simpson, Natalie C.; Maples, Randall D.; Carder Freeman, TaRynn N.; Amy N. Cain; Le, Justin G.; Stephen J Archibald; Khan, Shabana I.; Tekwani, Babu L.; Khan, M. O. Faruk

    2014-01-01

    Using transition metals such as manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), several new metal complexes of cross-bridged tetraazamacrocyclic chelators namely, cyclen- and cyclam-analogs with benzyl groups, were synthesized and screened for in vitro antimalarial activity against chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum. The metal-free chelators tested showed little or no antimalarial activity. All the metal comple...

  2. Complexes of 3.6 kDa Maltodextrin with Some Metals

    Directory of Open Access Journals (Sweden)

    Christopher H. Schilling

    2004-06-01

    Full Text Available Preparation of magnesium, lanthanum, and bismuth(III complexes of 3.6 kDa maltodextrin and some properties of the resulting materials are presented. The metal derivatives contain metals bound to the oxygen atoms of the hydroxyl groups of maltodextrin. Additionally, the metal atoms are coordinated to the hydroxyl groups of the D-glucose units of the macroligand. Such coordination stabilized the metal – oxygen bond against hydrolysis, even in boiling water. The presence of magnesium and lanthanum atoms increased the thermal stability of maltodextrin, whereas bismuth atoms decreased it.

  3. Direct micro/nano metal patterning based on two-step transfer printing of ionic metal nano-ink

    International Nuclear Information System (INIS)

    We present a direct metal patterning method by a two-step transfer printing process of non-particle, ionic metal nano-ink solution. This fabrication method allows a simple direct patterning of various micro/nanoscale metallic structures. Complex structures such as multilayer line arrays, patterns along non-flat topologies, and micro/nanoscale hybrid patterns can be achieved by using this process. Also, the low temperature and pressure process conditions are compatible with the fabrication of electronic structures and devices on flexible substrates such as polyimide film and photographic papers. As an application of this process, we fabricated ZnO nanowire-based flexible UV sensors, where metal electrodes were fabricated by two-step transfer printing. In the case of ZnO nanowire sensors, highly sensitive and fast responding performances to UV illumination and good mechanical robustness against repeated bending conditions could be verified. (paper)

  4. Half-sandwich pentamethylcyclopentadienyl group 9 metal complexes of 2-aminopyridyl ligands: Synthesis, spectral and molecular study

    Indian Academy of Sciences (India)

    Mahesh Kalidasan; Scott Forbes; Yurij Mozharivskyj; Mohan Rao Kollipara

    2015-06-01

    Thereaction of [Cp*M(-Cl)Cl]2 (M = Rh, Ir) with 2-aminopyridyl based ligands lead to the formation of mononuclear neutral complexes of general formula [Cp*MCl2(L)] {where L1= 2-aminopyridine, L2= 2-amino-3-picoline, L3= 2-amino-3-nirtopyridine, and L4= 2-amino-3-pyridine carboxyaldehyde}. The complexes have been characterized by FT-IR, UV-Vis, 1H-13C NMR and mass spectroscopic methods. X-ray crystallographic studies of the complexes have shown typical piano-stool geometry around the metal centre in which 2-aminopyridyl ligand acts as an N-monodentate ligand and the amino functionality is not involved in metal coordination. The intra/intermolecular arrangement is due to hydrogen bonding.

  5. Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex

    DEFF Research Database (Denmark)

    Hao, Xian; Zhu, Nan; Gschneidtner, Tina;

    2013-01-01

    Coordination chemistry has been a consistently active branch of chemistry since Werner's seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal-ligand interactions at the single-molecule level...... remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold...... significant impact on the metal-ligand interactions. The present approach represents a major advancement in unravelling the nature of metal-ligand interactions and could have broad implications in coordination chemistry....

  6. Synthesis, Structure and Characterization of a Series of Transition Metal Complexes with Tripodal Polyimidazole Ligand

    Institute of Scientific and Technical Information of China (English)

    任颜卫; 吴爱芝; 李珺; 张逢星; 张金花

    2005-01-01

    Five new metal transition metal complexes formed with tripodal polyimidazole ligand tri{2-[2-(1-methyl)imidazoly](methylimino)ethyl}amine ((min)3tren), [Zn(min)3tren](ClO4)2 (1) [Cu(min)3tren](ClO4)2 (2), [Ni(min)3tren]-(ClO4)2 (3), [Co(min)3tren](ClO4)2 (4), and [Mn(min)3tren](ClO4)2·CH3CN (5) were synthesized and characterized by elemental analysis, molar conductances, IR and electronic spectra. Analytical results show 1 : 1 metal-ligand stoichiometry and 2 : 1 type of electrolyte in all metal complexes. The crystal structures of 4 and 5 have been determined. The metal atoms in 4 and 5, being in distorted [MN6] octahedra, are coordinated with three imine nitrogen atoms and three imidazole nitrogen atoms.

  7. Metal ion complexation by ionizable crown ethers. Progress report, January 1, 1991--December 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, R.A.

    1993-07-01

    Cyclic and acyclic polyether compounds with pendent carboxylic acid, phosphonic acid monoethyl ester, sulfonic acid, phosphinic acid and hydroxamic acid groups have been synthesized. The proton-ionizable polyethers can come with and without lipophilic groups. Two types of lipophilic di-ionizable lariat ethers have been prepared. Conformations of proton-ionizable lariat ethers have been probed. Competitive alkali metal cation transport by syn-(decyl)dibenzo-16-crown-5-oxyacetic acid and lipophilic proton-ionizable dibenzo lariat ethers in polymer-supported liquid membranes was studied. Complexation of alkali metal cations with ionized lariat ethers was studied. Condensation polymerization of cyclic and acyclic dibenzo polyethers containing pendent mono-ionizable groups with formaldehyde produces novel ion exchange resins with both ion exchange sites for metal ion complexation and polyether binding sites for metal ion recognition. Resins prepared from lariat ether dibenzo phosphonic acid monoethyl esters show strong sorption of divalent heavy metal cations with selectivity for Pb{sup 2+}.

  8. Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Kexi; Lei, Yinkai; Wang, Guofeng, E-mail: guw8@pitt.edu [Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania 15261 (United States)

    2013-11-28

    Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O{sub 2} adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N{sub 4} chelation, as well as the molecular and electronic structures for the O{sub 2} adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O{sub 2} on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d{sub z{sup 2}}, d{sub xy}, d{sub xz}, and d{sub yz}) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O{sub 2} adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

  9. Remarkable metal-complexed phosphorus analogues of the cyclopropenylcarbene–cyclobutadiene rearrangement

    OpenAIRE

    Lyaskovskyy, V.; Elders, N.; Ehlers, A.W.; Lutz, M.; Slootweg, J.C.; Lammertsma, K.

    2011-01-01

    In situ-generated metal carbonyl-complexed cyclopropenylphosphinidenes undergo a sequence of structural changes leading to phosphorus analogues of Pettit’s seminal (η4-cyclobutadiene)iron tricarbonyl complex via multiple valence isomers along the reaction pathway and the elimination of one molecule of carbon monoxide.

  10. Gallium(III) and indium(III) dithiolate complexes: Versatile precursors for metal sulfides

    Indian Academy of Sciences (India)

    Shamik Ghoshal; Vimal K Jain

    2007-11-01

    The chemistry of classical and organometallic complexes of gallium and indium with dithiolate ligands, i.e., dithiocarboxylates, xanthates, dithiocarbamates, dithiophosphates, dithiophophinates and dithioarsenates, has been reviewed. Synthesis, spectroscopic and structural aspects of these complexes are described. Their emerging role as single source molecular precursors for the preparation of metal sulfide thin films and nano-particles has been discussed.

  11. Confirmation of molecular formulas of metallic complexes through X-ray fluorescence quantitative analysis

    International Nuclear Information System (INIS)

    X-ray fluorescence spectrophotometry was employed to determined the metal content in a series of five transition element complexes (Mn, Ti, Zn, V). The results confirmed the molecular formulas of these complexes, already proposed on the basis of elemental microanalysis, solution condutimetry and other analytical methods. (C.L.B.)

  12. Light induced electron transfer reactions of metal complexes

    International Nuclear Information System (INIS)

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  13. Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Matsunaga, P.T.

    1991-11-01

    The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

  14. Unveiling the complex electronic structure of amorphous metal oxides

    OpenAIRE

    Arhammar, C.; Pietzsch, A; Bock, N.; Holmstrom, E.; Araujo, C. M.; Grasjo, J.; Zhao, S.; Green, S; Peery, T.; Hennies, F.; Amerioun, S.; Fohlisch, A.; Schlappa, J.; Schmitt, T; Strocov, V. N.

    2011-01-01

    Amorphous materials represent a large and important emerging area of material’s science. Amorphous oxides are key technological oxides in applications such as a gate dielectric in Complementary metal-oxide semiconductor devices and in Silicon-Oxide-Nitride-Oxide-Silicon and TANOS (TaN-Al2O3-Si3N4-SiO2-Silicon) flash memories. These technologies are required for the high packing density of today’s integrated circuits. Therefore the investigation of defect states in these structures is crucial....

  15. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity

    Science.gov (United States)

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-11-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

  16. Hydrogen bond and protonation in carbonyl nitrosyl complexes of transition metals

    International Nuclear Information System (INIS)

    Infrared spectroscopy was used to study interaction of CoM(CO)2(NO) π-complexes, where M=Cr, Mo, Cp=η5-C5H5, with perfluorotert butanol (PFTB) and HCl in liquid Xe solutions at low temperatures. It is shown that mentioned complexes can form earlier unknown type of hydrogen bond with PFTB and HCl by oxygen atom of nitrosyl group of transition metal atom. Protonation of complexes dissolved in liquid Xe by transition metal atom during their interaction with HCl was reveald

  17. Catalytic hydrolysis of phosphate diester (BNPP) and plasmid DNA by mononuclear macrocyclic polyamine metal complexes

    Institute of Scientific and Technical Information of China (English)

    Qing Xiang Xiang; Li Qun Zhang; Xiao Qi Yu; Ru Gang Xie

    2009-01-01

    The activities of the catalytic hydrolysis of phosphate diester (BNPP) [bis(p-nitrophenyl)phosphate diester]and plasmid DNA (pUC 18) by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper.The results showed that the highest activity in hydrolysis of BNPP was obtained with le-Zn(II) complex (composed of lipophilic group) as catalyst.The hydrolysis rate enhancement is up to 3.64 × 104 fold.These metal complexes could effectively promote the cleavage of plasmid DNA (pUC18) at physiological conditions.

  18. Mixed amido-cyclopentadienyl group 4 metal complexes

    Czech Academy of Sciences Publication Activity Database

    Havlík, Aleš; Lamač, Martin; Pinkas, Jiří; Růžička, A.; Horáček, Michal

    2015-01-01

    Roč. 5, č. 73 (2015), s. 59154-59166. ISSN 2046-2069 R&D Projects: GA ČR GAP106/10/0924 Institutional support: RVO:61388955 Keywords : BOND COVALENT RADII * IMIDO COMPLEXES * SIDE-ON Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.840, year: 2014

  19. Interaction of porphyrins with adenine and adenosine complexes. Effect of a metal nature

    International Nuclear Information System (INIS)

    Reactions of complex formation of 5,10,15,20-tetraphenylporphine (H2TPP) and tetra-tert-butylphthalocyanine (H2(t-Bu)4Pc) with adenine and adenosine complexes of d-metals (M=Cd, Co, Cu, Hg, Zn) in DMSO and ethanol are studied. It was found that H2TPP reacts with Cu(II) and Hg(II) adeninates and adenosinates in DMSO, but does not react with Zn(II), Co(II), and Cd(II) adeninates and adenosinates (with both bridging and monodentate type of the ligand coordination). H2(t-Bu)4Pc enters the complex formation reaction with adeninates and adenosinates of all studied metals in DMSO at almost equal rates. The states of adenine and adenosine complexes of different d-metals in DMSO and ethanol are proposed on the basis of kinetic data obtained

  20. Fabrication of carbon nanotube films from alkyne-transition metal complexes

    Science.gov (United States)

    Iyer, Vivekanantan S.; Vollhardt, K. Peter C.

    2007-08-28

    A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

  1. A Heteroepitaxial Perovskite Metal-Base Transistor

    Energy Technology Data Exchange (ETDEWEB)

    Yajima, T.; Hikita, Y.; /Tokyo U.; Hwang, H.Y.; /Tokyo U. /JST, PRESTO /SLAC

    2011-08-11

    'More than Moore' captures a concept for overcoming limitations in silicon electronics by incorporating new functionalities in the constituent materials. Perovskite oxides are candidates because of their vast array of physical properties in a common structure. They also enable new electronic devices based on strongly-correlated electrons. The field effect transistor and its derivatives have been the principal oxide devices investigated thus far, but another option is available in a different geometry: if the current is perpendicular to the interface, the strong internal electric fields generated at back-to-back heterojunctions can be used for oxide electronics, analogous to bipolar transistors. Here we demonstrate a perovskite heteroepitaxial metal-base transistor operating at room temperature, enabled by interface dipole engineering. Analysis of many devices quantifies the evolution from hot-electron to permeable-base behaviour. This device provides a platform for incorporating the exotic ground states of perovskite oxides, as well as novel electronic phases at their interfaces.

  2. Metal-based biologically active azoles and β-lactams derived from sulfa drugs.

    Science.gov (United States)

    Ebrahimi, Hossein Pasha; Hadi, Jabbar S; Almayah, Abdulelah A; Bolandnazar, Zeinab; Swadi, Ali G; Ebrahimi, Amirpasha

    2016-03-01

    Metal complexes of Schiff bases derived from sulfamethoxazole (SMZ) and sulfathiazole (STZ), converted to their β-lactam derivatives have been synthesized and experimentally characterized by elemental analysis, spectral (IR, (1)H NMR, (13)C NMR, and EI-mass), molar conductance measurements and thermal analysis techniques. The structural and electronic properties of the studied molecules were investigated theoretically by performing density functional theory (DFT) to access reliable results to the experimental values. The spectral and thermal analysis reveals that the Schiff bases act as bidentate ligands via the coordination of azomethine nitrogen to metal ions as well as the proton displacement from the phenolic group through the metal ions; therefore, Cu complexes can attain the square planner arrangement and Zn complexes have a distorted tetrahedral structure. The thermogravimetric (TG/DTG) analyses confirm high stability for all complexes followed by thermal decomposition in different steps. In addition, the antibacterial activities of synthesized compounds have been screened in vitro against various pathogenic bacterial species. Inspection of the results revealed that all newly synthesized complexes individually exhibit varying degrees of inhibitory effects on the growth of the tested bacterial species, therefore, they may be considered as drug candidates for bacterial pathogens. The free Schiff base ligands (1-2) exhibited a broad spectrum antibacterial activity against Gram negative Escherichia coli, Pseudomonas aeruginosa, and Proteus spp., and Gram positive Staphylococcus aureus bacterial strains. The results also indicated that the β-lactam derivatives (3-4) have high antibacterial activities on Gram positive bacteria as well as the metal complexes (5-8), particularly Zn complexes, have a significant activity against all Gram negative bacterial strains. It has been shown that the metal complexes have significantly higher activity than corresponding

  3. Rhodium and ruthenium tetracarboxylate nitrosyl complexes: electronic structure and metal-metal bond

    International Nuclear Information System (INIS)

    The electronic structure of the tetracarboxylates M2(μ-O2CH)4, M2(μ-O2CH)4(L)2 (M = Ru, Rh; L= H2O, NO) was analyzed by the density functional theory with full geometry optimization. The inclusion of nitrogen oxide orbitals into the molecular orbitals forming the metal-metal bond affects all of the main characteristics of this bond and the concomitant properties. In the case of rhodium tetracarboxylates, one can consider destruction of the Rh-Rh covalent σ-bond and reorientation of two electrons from the internal region of the Rh2(μ-O2CH)4 core to the outside, toward the axial ligands to give Rh-N covalent bonds. The axial coordination of nitrogen oxide in Ru2(μ-O2CR)4 is accompanied by destruction of the metal-metal π-bond

  4. Fluorescent zinc and copper complexes for detection of adrafinil in paper-based microfluidic devices.

    Science.gov (United States)

    Caglayan, Mehmet Gokhan; Sheykhi, Sara; Mosca, Lorenzo; Anzenbacher, Pavel

    2016-07-01

    Recognition of electroneutral Lewis bases and anions in aqueous media is extremely difficult. We show that fluorescent coordinatively unsaturated metal complexes can recognize various Lewis bases while providing an easy-to-detect fluorescence response. This approach is applied to the detection of adrafinil, a banned performance-enhancing drug. PMID:27293080

  5. Bivalent transition metal complexes of ONO donor hydrazone ligand: Synthesis, structural characterization and antimicrobial activity.

    Science.gov (United States)

    Bhaskar, Ravindra; Salunkhe, Nilesh; Yaul, Amit; Aswar, Anand

    2015-12-01

    Mononuclear transition metal complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a new hydrazone ligand derived from pyrazine-2-carbohydrazide and 2-hydroxyacetophenone have been synthesized. The isolated complexes were characterized by elemental analysis, spectral and analytical methods including elemental analyses, IR, diffuse reflectance, (1)H-NMR, mass spectra, molar conductance, magnetic moment, ESR, XRD, TG and SEM analysis. From the elemental analyses data, the stoichiometry of the complexes was found to be 1:1 (metal:ligand) having the general formulae [M(HL)(Cl)(H2O)2], [M=Mn(II), Co(II), Ni(II) and Cu(II)] and [M(L)(H2O)], [M=Zn(II) and Cd(II)]. The molar conductance values indicate the nonelectrolytic nature of metal complexes. The IR spectral data suggest that the ligand behaves as tridentate moiety with ONO donor atoms sequence towards central metal ion. The Mn(II), Co(II), Ni(II) and Cu(II) complexes have been assigned a monomeric octahedral geometry whereas tetrahedral to Zn(II) and Cd(II) complexes. The antibacterial and antifungal activities of the ligand and its metal complexes were studied against bacterial species Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, Enterococcus faecalis and Streptococcus pyogenes and fungi Candida albicans, Aspergillus niger and Aspergillus clavatus. The activity data show that the metal complexes have a promising biological activity comparable with the parent ligand against all bacterial and fungal species. PMID:26163785

  6. Poly-functional description of metal complexation by natural organic matter: theory and practice

    International Nuclear Information System (INIS)

    The Differential Equilibrium Function (DEF) approach to metal complexation interpretation and prediction is compared to other models or approaches. The basic features of DEF are summarized, both from the experimental and theoretical points of view. The relation of DEF with key environmental concepts or parameters, in particular minor vs major complexing sites, the buffering intensity of natural organic matter (NOM), and their poly functional vs polyelectrolyte properties, is discussed. The relation between DEF and Freundlich isotherm is described quantitatively. The practical applications of DEF are discussed for (i) interpretation of metal complexation by NOM, and (ii) prediction of metal complexation by NOM. It is shown that DEF (i.e. sound extrapolation is possible with care). DEF cans be readily incorporated in metal species distribution codes (e.g. MINEQL). DEF is not equivalent to a molecular complexation model which describes complexation at each individual site; DEF gives a rigorous representation of complexation by NOM as a whole chemical system. (authors). 23 refs., 6 figs

  7. Synthesis of complex plutonium oxides with alkaline-earth metals

    International Nuclear Information System (INIS)

    Complex plutonium(IV) oxides with strontium and barium, SuPuO3 and BaPuO3, were synthesized and their crystal structure was analyzed. Compacted mixture of plutonium dioxide powder and the carbonate of strontium or barium was heated in a stream of argon gas using a cell with a small orifice. The products obtained were found to be composed of a nearly single phase showing the structure of orthorhombic slightly distorted from cubic. (author)

  8. Reactions of aliphatic free radicals with transition metal complexes

    International Nuclear Information System (INIS)

    A pulse radiolytic study of the reactions of copper ions with free aliphatic radicals was carried out. It was found that all the aliphatic radicals studied react with Cusub(aq)sup(+) and Cusub(aq)sup(2+), forming an unstable compound, with a carbon-copper σ bond, according to the reaction Mnsub(aq)sup(n+)+ . CR1R2R3 → M-CR1R2Rsub(3)sup(n+). It was also found that the rates of formation of the intermediate compounds, their half-lives and their decomposition mechanism depend on the properties of the radical and the cation. Experiments for the determination of the influence of macrocyclic ligands of the Curtis type on the stability of intermediate compounds failed because of insufficient concentrations of these ligands. The processes of ligand hydridization, isomerization and decomposition for the macrocylic complexes Cusup(I)L were also studied. These complexes, which are unstable, are formed as a result of the reaction of the stable Cusup(II)L complexes with certain free aliphatic radicals

  9. Synthesis and catalytic activities of porphyrin-based PCP pincer complexes.

    OpenAIRE

    Fujimoto, Keisuke; Yoneda, Tomoki; Yorimitsu, Hideki; Osuka, Atsuhiro

    2013-01-01

    2,18-Bis(diphenylphosphino)porphyrins undergo peripheral cyclometalation with group 10 transition-metal salts to afford the corresponding porphyrin-based PCP pincer complexes. The porphyrinic plane and the PCP-pincer unit are apparently coplanar, with small strain. The catalytic activities of the porphyrin-based pincer complexes at the periphery were investigated in the allylation of benzaldehyde with allylstannane and in the 1,4-reduction of chalcone to discover the electronic interplay betw...

  10. Selective Decontamination Effect of Metal Ions in Soil Using Supercritical CO2 and TBP Complex

    International Nuclear Information System (INIS)

    Decontamination of soil pollution is difficult because the type of contamination largely depends on the characteristics of the pollutant and the area. Also, existing soil decontamination methods generate large quantities of secondary waste and additional process costs. For this reason, new decontamination methods are always under active investigation. A method involving the use of supercritical carbon dioxide with excellent permeability in place of chemical solvents is currently being studied. Unlike other heavy metals in fission products, uranium is used as fuel, and must be handled carefully. Therefore, in this paper, we studied a supercritical carbon dioxide method for decontaminating heavy metal ions in soil using tri-n-butyl phosphate(TBP), which is well known as a ligand for the extraction of metal ions of actinium. We investigated the decontamination effect of heavy metal ions in the soil using TBP-HNO3 Complex and supercritical carbon dioxide. The study results showed that when heavy metals in soil are extracted using supercritical carbon dioxide, the extraction efficiency is different according to the type of pollutant metal ions in the soil. When TBP-HNO3 Complex is used with an extractant, uranium extraction is very effective, but lithium, strontium, and cesium extraction is not effective. Therefore, in the case of a mixture of uranium and other metals such as lithium, strontium, cesium, and so on in soil contaminated by fission product leaks from nuclear power plants, we can selectively decontaminate uranium with supercritical carbon dioxide and TBP-HNO3 Complex

  11. Exploring Coordination Modes: Late Transition Metal Complexes with a Methylene-bridged Macrocyclic Tetra-NHC Ligand.

    Science.gov (United States)

    Altmann, Philipp J; Weiss, Daniel T; Jandl, Christian; Kühn, Fritz E

    2016-05-20

    A tetranuclear silver(I) N-heterocyclic carbene (NHC) complex bearing a macrocyclic, exclusively methylene-bridged, tetracarbene ligand was synthesized and employed as transmetalation agent for the synthesis of nickel(II), palladium(II), platinum(II), and gold(I) derivatives. The transition metal complexes exhibit different coordination geometries, the coinage metals being bound in a linear fashion forming molecular box-type complexes, whereas the group 10 metals adapt an almost ideal square planar coordination geometry within the ligand's cavity, resulting in saddle-shaped complexes. Both the Ag(I) and the Au(I) complexes show ligand-induced metal-metal contacts, causing photoluminescence in the blue region for the gold complex. Distinct metal-dependent differences of the coordination behavior between the group 10 transition metals were elucidated by low-temperature NMR spectroscopy and DFT calculations. PMID:27017146

  12. A Superlens Based on Metal-Dielectric Composites

    OpenAIRE

    Cai, Wenshan; Genov, Dentcho A.; Shalaev, Vladimir M.

    2005-01-01

    Pure noble metals are typically considered to be the materials of choice for a near-field superlens that allows subwavelength resolution by recovering both propagating and evanescent waves. However, a superlens based on bulk metal can operate only at a single frequency for a given dielectric host. In this Letter, it is shown that a composite metal-dielectric film, with an appropriate metal filling factor, can operate at practically any desired wavelength in the visible and near-infrared range...

  13. Synthesis, physical characterization and biological evaluation of Schiff base M(II complexes

    Directory of Open Access Journals (Sweden)

    Mahasin Alias

    2014-04-01

    Full Text Available Metal (II complexes of Cu, Ni, and Co with Schiff base derived from potassium 2-N (4-N,N-dimethylaminobenzyliden- 4-trithiocarbonate 1,3,4-thiadiazole (L were synthesized and characterized by standard physico-chemical procedures i.e. (metal analysis A.A, elemental chemical analysis C.H.N.S, FTIR, UV–vis, thermal analysis TGA, magnetic susceptibility and conductometric measurements. On the basis of these studies, a six coordinated octahedral geometry for all these complexes has been proposed. The Schiff base ligand and its complexes were also tested for their antibacterial activity to assess their inhibiting potential against Pseudomonas aeruginosa (as gram negative bacteria and Staphylococcus aureus (as gram positive bacteria using two different concentrations (5 and 10 mM. The results showed the Ni(II complex have the higher rate in antibacterial activity than other complexes and ligand when compared them with ampicillin as standard drug.

  14. Dissociative CdSe/ZnS Quantum Dot-Molecule Complex for Luminescent Sensing of Metal Ions in Aqueous Solutions

    OpenAIRE

    Baranov, A. V.; Orlova, A. O.; Maslov, V. G.; Toporova, Yu. A.; Ushakova, E. V.; Federov, A.; Artemyev, M. V.; Perova, T. S.; Berwick, Kevin

    2010-01-01

    The optical properties of dissociative luminescent sensors based on a complex consisting of highly luminescent hydrophobic core/shell CdSe/ZnS quantum dots (QDs) and 1-(2-pyridilazo)-2-naphtol (PAN) molecules in organic solutions and a polymer film are reported. It is demonstrated, using Ni2+ and Co2+ ions as an illustrative example, that the QD/PAN sensor may have applications in the quantitative luminescent sensing of metal ions in aqueous solutions.

  15. Synthesis, spectral studies, thermal behavior, and antibacterial activity of Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) complexes with an ONO tridentate Schiff base

    Institute of Scientific and Technical Information of China (English)

    Mohammad Azarkish; Tahereh Sedaghat

    2012-01-01

    Three new transition metal complexes have been synthesized with a Schiff base,3-(2-hydroxy-5-chlorophenylimino)-1,3-diphenylpropen- 1-one.In all complexes Schiff base is completely deprotonated and coordinated to metal as tridentate ligand via phenolic and enolic oxygens and imine nitrogen.Thermal decomposition of the complexes has been studied by thermogravimetry.The in vitro antibacterial activity of Schiff bases and their complexes has been evaluated and compared with the standard drugs.

  16. Investigation of aromatase inhibitory activity of metal complexes of 8-hydroxyquinoline and uracil derivatives

    Directory of Open Access Journals (Sweden)

    Prachayasittikul V

    2014-08-01

    Full Text Available Veda Prachayasittikul,1 Ratchanok Pingaew,2 Chanin Nantasenamat,3 Supaluk Prachayasittikul,3 Somsak Ruchirawat,4,5 Virapong Prachayasittikul1 1Department of Clinical Microbiology and Applied Technology, Faculty of Medical Technology, Mahidol University, Bangkok, Thailand; 2Department of Chemistry, Faculty of Science, Srinakharinwirot University, Bangkok, Thailand; 3Center of Data Mining and Biomedical Informatics, Faculty of Medical Technology, Mahidol University, Bangkok, Thailand; 4Laboratory of Medicinal Chemistry, Chulabhorn Research Institute, 5Chulabhorn Graduate Institute, Bangkok, Thailand Purpose: Estrogens play important roles in the pathogenesis and progression of breast cancer as well as estrogen-related diseases. Aromatase is a key enzyme in the rate-limiting step of estrogen production, in which its inhibition is one strategy for controlling estrogen levels to improve prognosis of estrogen-related cancers and diseases. Herein, a series of metal (Mn, Cu, and Ni complexes of 8-hydroxyquinoline (8HQ and uracil derivatives (4–9 were investigated for their aromatase inhibitory and cytotoxic activities. Methods: The aromatase inhibition assay was performed according to a Gentest™ kit using CYP19 enzyme, wherein ketoconazole and letrozole were used as reference drugs. The cytotoxicity was tested on normal embryonic lung cells (MRC-5 using 3-(4,5-dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT assay. Results: Only Cu complexes (6 and 9 exhibited aromatase inhibitory effect with IC50 0.30 and 1.7 µM, respectively. Cytotoxicity test against MRC-5 cells showed that Mn and Cu complexes (5 and 6, as well as free ligand 8HQ, exhibited activity with IC50 range 0.74–6.27 µM. Conclusion: Cu complexes (6 and 9 were found to act as a novel class of aromatase inhibitor. Our findings suggest that these 8HQ–Cu–uracil complexes are promising agents that could be potentially developed as a selective anticancer agent for breast cancer

  17. DNA binding mode of novel tetradentate amino acid based 2-hydroxybenzylidene-4-aminoantipyrine complexes

    Science.gov (United States)

    Raman, N.; Sobha, S.; Selvaganapathy, M.; Mahalakshmi, R.

    2012-10-01

    Few transition metal complexes of tetradentate N2O2 donor Schiff base ligands containing 2-hydroxybenzylidene-4-aminoantipyrine and amino acids (alanine/valine) abbreviated to KHL1/KHL2 have been synthesized. All the metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The Schiff bases KHL1/KHL2 are found to act as tetradentate ligands using N2O2 donor set of atoms leading to a square-planar geometry for the complexes around the metal ions. The binding behaviors of the complexes to calf thymus DNA have been investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The DNA binding constants reveal that all these complexes interact with DNA through minor groove binding mode. The studies on mechanism of photocleavage reveal that singlet oxygen (1O2) and superoxide anion radical (O2rad -) may play an important role in the photocleavage. The Schiff bases and their metal complexes have been screened for their in vitro antibacterial activities against Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae and antifungal activities against Aspergillus niger, Fusarium solani, Culvularia lunata, Rhizoctonia bataicola and Candida albicans by MIC method.

  18. First-row transition-metal-diborane and -borylene complexes.

    Science.gov (United States)

    Sharmila, Dudekula; Mondal, Bijan; Ramalakshmi, Rongala; Kundu, Sangita; Varghese, Babu; Ghosh, Sundargopal

    2015-03-23

    A combined experimental and quantum chemical study of Group 7 borane, trimetallic triply bridged borylene and boride complexes has been undertaken. Treatment of [{Cp*CoCl}2 ] (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) with LiBH4 ⋅thf at -78 °C, followed by room-temperature reaction with three equivalents of [Mn2 (CO)10 ] yielded a manganese hexahydridodiborate compound [{(OC)4 Mn}(η(6) -B2 H6 ){Mn(CO)3 }2 (μ-H)] (1) and a triply bridged borylene complex [(μ3 -BH)(Cp*Co)2 (μ-CO)(μ-H)2 MnH(CO)3 ] (2). In a similar fashion, [Re2 (CO)10 ] generated [(μ3 -BH)(Cp*Co)2 (μ-CO)(μ-H)2 ReH(CO)3 ] (3) and [(μ3 -BH)(Cp*Co)2 (μ-CO)2 (μ-H)Co(CO)3 ] (4) in modest yields. In contrast, [Ru3 (CO)12 ] under similar reaction conditions yielded a heterometallic semi-interstitial boride cluster [(Cp*Co)(μ-H)3 Ru3 (CO)9 B] (5). The solid-state X-ray structure of compound 1 shows a significantly shorter boron-boron bond length. The detailed spectroscopic data of 1 and the unusual structural and bonding features have been described. All the complexes have been characterized by using (1) H, (11) B, (13) C NMR spectroscopy, mass spectrometry, and X-ray diffraction analysis. The DFT computations were used to shed light on the bonding and electronic structures of these new compounds. The study reveals a dominant B-H-Mn, a weak B-B-Mn interaction, and an enhanced B-B bonding in 1. PMID:25689833

  19. Metal-metal multiply bonded complexes of technetium. 1. Synthesis and structural characterization of phosphine complexes that contain a Tc-Tc multiple bond

    International Nuclear Information System (INIS)

    A series of triply metal-metal bonded ditechnetium(II) phosphine complexes with the general formula Tc2Cl4(PR3)4 (PR3 = PEt3, PPrn3, PMePh2, PMe2Ph) have been prepared from mononuclear Tc(IV) precursors and fully characterized. Two-electron reduction of the Tc(IV) bis(phosphine) complexes TcCl4(PR3)2 (PR3 = PEt3, PPrn3, PMePh2, PMe2Ph) with finely divided zinc in aromatic solvents or tetrahydrofuran results in the formation of the corresponding electron-rich triply bonded compounds Tc2Cl4(PR3)4 in high yield. These are the first phosphine complexes of technetium that possess a metal-metal bond. The solid-state structures of the PEt3, PMe2Ph, and PMePh2 derivatives have been investigated by X-ray crystallography and are described in detail. Similar to the analogous dirhenium(II) complexes, the molecules adopt an eclipsed M2L8 conformation with approximate D2d symmetry. The Tc-Tc bond lengths are 2.133(3), 2.127(1), and 2.1384(5) angstrom for Tc2Cl4(PEt3)4, Tc2Cl4(PEt3)4, Tc2Cl4(PMe2Ph)4, and Tc2Cl4(PMePh2)4, respectively. Structural and spectroscopic evidence indicates that these dimers contain an electron-rich Tc-Tc triple bond with a σ2-π-4δ2δ*2 ground-state electronic configuration. Electrochemical studies reveal that each compound undergoes two reversible one-electron oxidation processes, which presumably produce the corresponding Tc25+ and Tc26+ dinuclear species. 1H HMR, 31P(1H) NMR, and UV-vis spectroscopic data are presented for each compound

  20. Synthesis of new microbial pesticide metal complexes derived from coumarin-imine ligand.

    Science.gov (United States)

    Elhusseiny, Amel F; Aazam, Elham S; Al-Amri, Huda M

    2014-07-15

    A series of metal complexes of zinc(II), cadmium(II), copper(II), nickel(II) and palladium(II) have been synthesized from coumarin-imine ligand, 8-[(1E)-1-(2-aminophenyliminio)ethyl]-2-oxo-2H-chromen-7-olate, [HL]. The structures of the complexes were proposed in the light of their spectroscopic, molar conductance, magnetic and thermal studies. The ligand coordinated in a tridentate manner through the azomethine nitrogen, the phenolic oxygen and the amine nitrogen and all complexes were non-electrolytes with different geometrical arrangements around the central metal ion. Photoluminescence data unambiguously showed remarkable fluorescence enhancement to Zn(2+) over other cations. The antimicrobial screening tests revealed that copper(II) complex exhibited the highest potency and its minimum inhibitory concentration on the enzymatic activities of the tested microbial species was determined. No toxin productivity was detected for all tested toxigenic species upon the exposure of copper complex. PMID:24704603

  1. In vitro anticancer activities of Schiff base and its lanthanum complex

    Science.gov (United States)

    Neelima; Poonia, Kavita; Siddiqui, Sahabjada; Arshad, Md; Kumar, Dinesh

    2016-02-01

    Schiff base metal complexes are well-known to intercalate DNA. The La(III) complexes have been synthesized such that they hinder with the role of the topoisomerases, which control the topology of DNA during the cell-division cycle. Although several promising chemotherapeutics have been developed, on the basis of Schiff base metal complex DNA intercalating system they did not proceed past clinical trials due to their dose-limiting toxicity. Herein, we discuss an alternative compound, the La(III) complex, [La(L1)2Cl3]·7H2O based on a Schiff base ligand 2,3-dihydro-1H-indolo-[2,3-b]-phenazin-4(5H)-ylidene)benzothiazole-2-amine (L1), and report in vitro cell studies. Results of antitumor activity using cell viability assay, reactive oxygen species (ROS) generation and nuclear condensation in PC-3 (Human, prostate carcinoma) cells show that the metal complex is more potent than ligand. La(III) complexes have been synthesized by reaction of lanthanum(III) salt in 1:2 M ratio with ligands L1 and 3-(ethoxymethylene)-2,3-dihydro-1H-indolo[2,3-b]-phenazin-4(5H)-ylidene)benzathiazole-2-amine (L2) in methanol. The ligands and their La(III) complexes were characterized by molar conductance, magnetic susceptibility, elemental analyses, FT-IR, UV-Vis, 1H/13C NMR, thermogravimetric, XRD, and SEM analysis.

  2. Computer-based sensing and visualizing of metal transfer mode in gas metal arc welding

    Institute of Scientific and Technical Information of China (English)

    Chen Maoai; Wu Chuansong; Lü Yunfei

    2008-01-01

    Using Xenon lamp lights to overcome the strong interference from the welding arc, a computer-based system is developed to sense and visualize the metal transfer in GMAW. This system combines through-the-arc sensing of the welding current and arc voltage with high speed imaging of the metal transfer. It can simultaneously display the metal transfer processes and waveforms of electrical welding parameters in real-time The metal transfer videos and waveforms of electrical welding parameters can be recorded. Metal transfers under various welding conditions have been investigated with the system developed.

  3. Cage Opening of a Carborane Ligand by Metal Cluster Complexes.

    Science.gov (United States)

    Adams, Richard D; Kiprotich, Joseph; Peryshkov, Dmitry V; Wong, Yuen Onn

    2016-05-01

    The reaction of Os3 (CO)10 (NCMe)2 with closo-o-C2 B10 H10 has yielded two interconvertible isomers Os3 (CO)9 (μ3 -4,5,9-C2 B10 H8 )(μ-H)2 (1 a) and Os3 (CO)9 (μ3 -3,4,8-C2 B10 H8 )(μ-H)2 (1 b) formed by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster. Two BH bonds of the o-C2 B10 H10 were activated in its addition to the osmium cluster. A second triosmium cluster was added to the 1 a/1 b mixture to yield the complex Os3 (CO)9 (μ-H)2 (μ3 -4,5,9-μ3 -7,11,12-C2 B10 H7 )Os3 (CO)9 (μ-H)3 (2) that contains two triosmium triangles attached to the same carborane cage. When heated, 2 was transformed to the complex Os3 (CO)9 (μ-H)(μ3 -3,4,8-μ3 -7,11,12-C2 B10 H8 )Os3 (CO)9 (μ-H) (3) by a novel opening of the carborane cage with loss of H2 . PMID:26971388

  4. Finite element simulations of sheet metal forming under complex strain paths

    Institute of Scientific and Technical Information of China (English)

    CHEN Wei; YANG Jichang; WU Xiaofeng; LU Dun; GUO Weigang

    2007-01-01

    Fracture is a common defect in sheet metal forming and it is essentially caused by tensile instability. This paper analyzes some experiments and theories for building forming limit diagrams of sheet metal and points out the advantages and disadvantages of current experiments and theories. According to this, a method that integrates the finite element simulation and experiment was used to research the forming limit diagrams of the sheet metal under complex strain paths. Taking the rear hanger that undergoes twice stamping as an example, the strain paths of the dangerous point of the rear hanger is investigated. Finally, the forming method of the rear hanger is confirmed. Results indicate that finite element method (FEM) can achieve the complex strain paths and different strain paths will have great impacts on the result of the sheet metal forming.

  5. Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes.

    Science.gov (United States)

    Engelmann, Xenia; Monte-Pérez, Inés; Ray, Kallol

    2016-06-27

    The selective functionalization of strong C-H bonds and the oxidation of water by cheap and nontoxic metals are some of the key targets of chemical research today. It has been proposed that high-valent iron-, manganese-, and copper-oxo cores are involved as reactive intermediates in important oxidation reactions performed by biological systems, thus making them attractive targets for biomimetic synthetic studies. The generation and characterization of metal-oxo model complexes of iron, manganese, and copper together with detailed reactivity studies can help in understanding how the steric and electronic properties of the metal centers modulate the reactivity of the metalloenzymes. This Review provides a focused overview of the advances in the chemistry of biomimetic high-valent metal-oxo complexes from the last 5-10 years that can be related to our understanding of biological systems. PMID:27311082

  6. Interaction of natural complexing agents with soil bound heavy metals -geochemical and environmental technical aspects

    International Nuclear Information System (INIS)

    The sanitation of heavy metal polluted soils requires the application of an adequate technology, which should be consistent in its ecological aims and methodology. Therefore a research programme has been developed at the 'Institute of Ecological Chemistry' of the 'GSF-Research Center', Neuherberg, which has its starting point in the study of influences of natural organic complexing agents on the chemical activity and dynamic of heavy metals in soils. The groundlaying idea is to elevate the concentration of complexing agents in the soil solution by additional application and possible stimulation of their microbial production to such an extent, that heavy metals will be enhanced solubilized, mobilized and removed together with the seepage water. Batch experiments in order to extract heavy metals from typical soil components (bentonite, peat) by amino acids demonstrate, that removal rates up to 95% can be obtained. (orig.)

  7. Complexes of zinc, cadmium and mercury with some schiff bases

    International Nuclear Information System (INIS)

    Two type of complexes with different stoichiometries were isolated for zinc (II), cadmium(II) and mercury (II). These complexes having the general formulate [M (H2L)] X2 and [M(L)] (where H2L and L represent the neutral and dibasic from of the ligand derived from the condensation of benzoin with o-phenylene diamine and X2 CI- or NO3-) were prepared by the reaction of the mentioned metal salts with the ligand in both neutral and alkaline solutions. Characterization of the complexes was carried out by analytical, spectral and physical studies. In type I complexes, the ligand coordinates through both azomethine nitrogen and alcohlic oxygen atoms acting as neutral tetradentate. For type II complexes, the coordination occurs through both azomethine nitrogen and deprotonated alcoholic oxygen atoms, for which the ligand acts as dibasic tetradentate. In all complexes, the metal ions are tetracoordinated with the most probable tetrahedral geometry (author). 17 refs.; 1 fig., 3 tabs

  8. Homoleptic transition metal complexes of the 7-azaindolide ligand featuring κ(1)-N1 coordination.

    Science.gov (United States)

    Przyojski, Jacob A; Kiewit, Monica L; Fillman, Kathlyn L; Arman, Hadi D; Tonzetich, Zachary J

    2015-10-01

    Homoleptic complexes of the anion of 7-azaindole (AzaIn) were synthesized and characterized for a series of 3d transition metals. For Mn(II), Fe(II), and Co(II), complexes of formula Na2[M(AzaIn)4]·2L (L = tetrahydrofuran (THF), 2-MeTHF, toluene, or benzene) were isolated by treatment of the corresponding metal chloride salts with 7-azaindole in the presence of sodium hexamethyldisilazide. The complexes adopt tetrahedral geometries with exclusive coordination to the transition metal ion through the pyrrolic N1 nitrogen atoms of the AzaIn ligands. Solid-state structures of the complexes demonstrate that the sodium cations remain tightly associated with the coordination entities through interaction with both the pyrrolic and pyridine nitrogen atoms of the azaindolide ligands. For Fe(II), replacement of the sodium cations by other alkali metal ions (Li or K) generates new complexes that demonstrate similar coordination geometries to the sodium salts. As a means of comparison, the Fe(II) complex of 4-azaindolide was also investigated. Na2[Fe(4-AzaIn)4]·2L adopts a similar solution structure to the 7-azaindolide complexes as judged by NMR spectroscopy and cyclic voltammetry. Density functional theory calculations were performed to investigate the bonding in the 7-azaindolide complexes. Results demonstrate that 7-azaindolide-κ(1)-N1 is a nearly pure sigma donor ligand that features a high degree of ionic character in its bonding to mid 3d transition metal ions. PMID:26378471

  9. Pore-controlled formation of 0D metal complexes in anionic 3D metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, MW; Bosch, M; Zhou, HC

    2015-01-01

    The host-guest chemistry between a series of anionic MOFs and their trapped counterions was investigated by single crystal XRD. The PCN-514 series contains crystallographically identifiable metal complexes trapped in the pores, where their formation is controlled by the size and shape of the MOF pores. A change in the structure and pore size of PCN-518 indicates that the existence of guest molecules may reciprocally affect the formation of host MOFs.

  10. DNA based computing for understanding complex shapes.

    Science.gov (United States)

    Ullah, A M M Sharif; D'Addona, Doriana; Arai, Nobuyuki

    2014-03-01

    This study deals with a computing method called DNA based computing (DBC) that takes inspiration from the Central Dogma of Molecular Biology. The proposed DBC uses a set of user-defined rules to create a DNA-like sequence from a given piece of problem-relevant information (e.g., image data) in a dry-media (i.e., in an ordinary computer). It then uses another set of user-defined rules to create an mRNA-like sequence from the DNA. Finally, it uses the genetic code to translate the mRNA (or directly the DNA) to a protein-like sequence (a sequence of amino acids). The informational characteristics of the protein (entropy, absence, presence, abundance of some selected amino acids, and relationships among their likelihoods) can be used to solve problems (e.g., to understand complex shapes from their image data). Two case studies ((1) fractal geometry generated shape of a fern-leaf and (2) machining experiment generated shape of the worn-zones of a cutting tool) are presented elucidating the shape understanding ability of the proposed DBC in the presence of a great deal of variability in the image data of the respective shapes. The implication of the proposed DBC from the context of Internet-aided manufacturing system is also described. Further study can be carried out in solving other complex computational problems by using the proposed DBC and its derivatives. PMID:24447435

  11. Equilibrium study of the complex formation of some trivalent metal ion chelates of Schiff bases derived from 2-hydroxy-3-phenyl benzaldehyde and evaluation of these reagents from their anticoagulant activity

    International Nuclear Information System (INIS)

    Potentiometric studies have been carried out on metal chelates of La3+, Pr3+, Gd3+, Tb3+, Dy3+, Er3+ and Yb3+ with N-(2-hydroxy-3-phenylbenz ylidene)-aniline and N-(2-hydroxy-3-phenylbenzylidene)-3, 4, 5 trimethoxyaniline. The dissociatio n constants of the reagents and formation constants of their metal chelates have been determine d by Calvin-Bjerrum pH titration technique as adopted by Irving and Rossotti and at 28 ± 0.1degC at ionic strength 0.1 M in 75:25 (v/v) dioxane-water mediium. (author). 7 figs., 5 refs

  12. Synthesis, Characterization and Antibacterial Activity of a Novel Curcumin Metal Complex

    OpenAIRE

    Anindya Bagchi; Prosenjit Mukherjee; Sarmistha Bhowmick; Anusree Raha

    2015-01-01

    In the present work a central transition metal cation (Ferrous sulphate) was selected where curcumin acts as ligand which ultimately give a chelate that is formed with enolic form of curcumin and because curcumin having anti-inflammatory activity, so a novel curcumin metal complex was synthesized with establishing their characterization spectrophotometrically and also in-vitro anti-inflammatory activity has been measured with comparing with the pure curcumin.

  13. Synthesis, Characterization and Antibacterial Activity of a Novel Curcumin Metal Complex

    Directory of Open Access Journals (Sweden)

    Anindya Bagchi

    2015-06-01

    Full Text Available In the present work a central transition metal cation (Ferrous sulphate was selected where curcumin acts as ligand which ultimately give a chelate that is formed with enolic form of curcumin and because curcumin having anti-inflammatory activity, so a novel curcumin metal complex was synthesized with establishing their characterization spectrophotometrically and also in-vitro anti-inflammatory activity has been measured with comparing with the pure curcumin.

  14. Structural and Spectral Properties of Curcumin and Metal- Curcumin Complex Derived from Turmeric (Curcuma longa)

    Science.gov (United States)

    Bich, Vu Thi; Thuy, Nguyen Thi; Binh, Nguyen Thanh; Huong, Nguyen Thi Mai; Yen, Pham Nguyen Dong; Luong, Tran Thanh

    Structural and spectral properties of curcumin and metal- curcumin complex derived from turmeric (Curcuma longa) were studied by SEM and vibrational (FTIR and Raman) techniques. By comparison between curcumin commercial, fresh turmeric and a yellow powder obtained via extraction and purification of turmeric, we have found that this insoluble powder in water is curcumin. The yellow compound could complex with certain ion metal and this metal-curcumin coloring complex is water soluble and capable of producing varying hues of the same colors and having antimicrobial, cytotoxicity activities for use in foodstuffs and pharmacy. The result also demonstrates that Micro-Raman spec-troscopy is a valuable non-destructive tool and fast for investigation of a natural plant even when occurring in low concentrations.

  15. Ethylenediamine complexes of transition metals in zeolite X

    International Nuclear Information System (INIS)

    Single-crystal X-ray diffraction studies of two ion-exchanged zeolite forms of the faujasite type are performed. Form I, NaCu[Cu(en)2]X [a=25.013(5) A, space group Fd3, 315F(hkl), R=0.050], is obtained by the treatment of zeolite NaX crystals with a [Cu(en)2]SO4 solution. Form II, NaCo[Co(en)x]X [a=25.000(5) A, space group Fd3, 532F(hkl), R=0.051], is obtained by the treatment of zeolite NaCoX with an ethylenediamine solution. Along with Na, Cu, and Co ions situated at the positions typical of zeolite X, the cationic complexes [Cu(en)2]2+ and [Co(en)x]2+ are found to be located in the large-sized zeolite cavities

  16. Synthesis and chemistry of cationic d{sup 0} metal alkyl complexes. Progress report, July 1988--May 1991

    Energy Technology Data Exchange (ETDEWEB)

    Jordan, R.F.

    1991-12-31

    The objective of this project is to develop new types of electrophilic metal alkyl complexes for catalytic C-H activation and olefin polymerization chemistry, and associated fundamental mechanistic studies. We have focused our efforts on four classes of early metal alkyl complexes: (1) cationic group 4 Cp{sub 2}M(R){sup +} complexes (1) which are active species in Cp{sub 2}MX{sub 2}-based Ziegler-Natta olefin polymerization catalyst systems and which catalyze productive C-H activation reactions of heterocycles, (2) neutral (dicarbollide)(Cp*)M(R) complexes (2) which are structurally are electronically very similar to 1, (3) half-sandwich complexes CpM(R){sub 2}(L){sub n}{sup +} which are highly coordinatively and electronically unsaturated, and (4) new group 5 (dicarbollide)(Cp)MR{sub 2} and (dicarbollide){sub 2} MR complexes which are more unsaturated than group 5 Cp{sub 2}M systems due to incorporation of the dicarbollide ligand.

  17. Stromatolites, Metals, Statistics and Microbial Mats: A Complex Interplay

    Science.gov (United States)

    Spear, J. R.

    2014-12-01

    Initially thought to be relatively 'simple' ecosystems for study, microbial mats have long been considered ideal for any number of research questions. Microbial mats can be found in any number of environments, both natural and manmade, and are typically dependent upon the physiochemical environment for their structure, maintenance and longevity. Ultimately, these and other parameters govern community whereby a microbial mat provides overall ecosystem services to their environment. On the edge of a hotspring in Yellowstone National Park we have found an active microbial mat community that can form a laminated, lithified, accretionary structure that is likely the best example of a living and growing stromatolite. In the outfall channel of the sulfidic Stinking Spring, Utah, we have found examples of both naturally occurring laminated and floating mats where the carbon flux is controlled by abiotic degassing of CO2 rather than metabolism. δ13C-bicarbonate uptake experiments reveal an autotrophic growth rate of 0 - 0.16%/day while δ13C-acetate reveals a higher heterotrophic growth rate of 0.03 - 0.65%/day, which highlights the role of heterotrophs in these mats. Similar growth experiments on Little Hot Creek, California laminated microbial mats reveal a trend for top-down microbial growth with similar microbial taxonomy and diversity to other mat-types. Of a curious note is that incubation experiments with Little Hot Creek mats reveals the importance of particular metals in mat structure and function. Statistically, alpha- and beta-diversity metrics are often used to characterize microbial communities in such systems, but from an analysis of a wastewater treatment system, Hill diversities can better interpret the effective number of species to produce an ecologically intuitive quantity to better understand a microbial mat ecosystem.

  18. Alkali Metal Variation and Twisting of the FeNNFe Core in Bridging Diiron Dinitrogen Complexes.

    Science.gov (United States)

    McWilliams, Sean F; Rodgers, Kenton R; Lukat-Rodgers, Gudrun; Mercado, Brandon Q; Grubel, Katarzyna; Holland, Patrick L

    2016-03-21

    Alkali metal cations can interact with Fe-N2 complexes, potentially enhancing back-bonding or influencing the geometry of the iron atom. These influences are relevant to large-scale N2 reduction by iron, such as in the FeMoco of nitrogenase and the alkali-promoted Haber-Bosch process. However, to our knowledge there have been no systematic studies of a large range of alkali metals regarding their influence on transition metal-dinitrogen complexes. In this work, we varied the alkali metal in [alkali cation]2[LFeNNFeL] complexes (L = bulky β-diketiminate ligand) through the size range from Na(+) to K(+), Rb(+), and Cs(+). The FeNNFe cores have similar Fe-N and N-N distances and N-N stretching frequencies despite the drastic change in alkali metal cation size. The two diketiminates twist relative to one another, with larger dihedral angles accommodating the larger cations. In order to explain why the twisting has so little influence on the core, we performed density functional theory calculations on a simplified LFeNNFeL model, which show that the two metals surprisingly do not compete for back-bonding to the same π* orbital of N2, even when the ligand planes are parallel. This diiron system can tolerate distortion of the ligand planes through compensating orbital energy changes, and thus, a range of ligand orientations can give very similar energies. PMID:26925968

  19. Infrared Multiple-Photon Dissociation spectroscopy of group II metal complexes with salicylate

    Energy Technology Data Exchange (ETDEWEB)

    Ryan P. Dain; Gary Gresham; Gary S. Groenewold; Jeffrey D. Steill; Jos Oomens; Michael J. van Stipdonk

    2011-07-01

    Ion-trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations were used to characterize singly-charged, 1:1 complexes of Ca2+, Sr2+ and Ba2+ with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO2 and (b) formation of [MOH]+ where M=Ca2+, Sr2+ or Ba2+. DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cation is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 – 1650 cm-1, and the best correlation between theoretical and experimental spectra for the structure that features coordination of the metal ion by phenoxide and the carbonyl group of the carboxylic acid group, consistent with calculated energies for the respective species.

  20. Structure and properties of alizarin complex formed with alkali metal hydroxides in methanol solution.

    Science.gov (United States)

    Jeliński, Tomasz; Cysewski, Piotr

    2016-06-01

    Quantum chemical computations were used for prediction of the structure and color of alizarin complex with alkali metal hydroxides in methanolic solutions. The color prediction relying on the single Gaussian-like band once again proved the usefulness of the PBE0 density functional due to the observed smallest color difference between computed and experimentally derived values. It was found that the alkali metal hydroxide molecules can bind to the two oxygen atoms of both hydroxyl groups of alizarin or to one of these atoms and the oxygen atom from the keto group in a complex with three methanol molecules. This means that two electronic transitions need to be taken into account when considering the spectra of the studied complexes. The resulting bond lengths and angles are correlated with the properties of the alkali metal atoms. The molar mass, the atomic radius, and the Pauling electronegativity of studied metals are quite accurate predictors of the geometric properties of hydroxide complexes with alizarin in methanol solution. Graphical abstract The spectra of the neutral and monoanionic form of alizarin together with color changes resulting from addition of different metal hydroxides and represented in CIE color space. PMID:27178415

  1. The stability of some metal EDTA, DTPA and DOTA complexes. Application as tracers in groundwater studies

    International Nuclear Information System (INIS)

    Studies of the stability of various metal EDTA, DTPA and DOTA complexes in order to evaluate their applicability as non-sorbing tracers have been performed. In laboratory tests, the stability generally increases for the individual metal ions in the EDTA-, for example had a breakthrough and recovery which were very similar to the non-sorbing tracers used. According to the extremely low tracers concentrations used, thermodynamic data indicate that all metal EDTA tracers should have been decomplexed as a result of the competition with the naturally occurring cations in the groundwater. This was not found, which indicates that the decomplexation rate and sorption mechanism are important in estimating the applicability of the metal complexes as tracers. The DOTA complexes of elements in the middle of the lanthanide series have indicated high stability in the laboratory tests and therefore appear to be good candidates as non-sorbing tracers. However, in contrary to the metal EDTA tracers, the DOTA complexes of La3+ and Lu3+ seemed to be slightly delayed in the in situ experiment. (author)

  2. Improved ORR activity of non-noble metal electrocatalysts by increasing ligand and metal ratio in synthetic complex precursors

    Energy Technology Data Exchange (ETDEWEB)

    Wang Liucheng [School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001 (China); Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC V6T 1W5 (Canada); Zhang Lei, E-mail: lei.zhang@nrc-cnrc.gc.ca [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC V6T 1W5 (Canada); Zhang Jiujun [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC V6T 1W5 (Canada)

    2011-06-30

    Highlights: > Various mole ratios between precursor Fe(II) and nitrogen-containing ligand of tripyridyl triazine (TPTZ) were investigated in order to further improve the ORR activity of Fe-N{sub x}/C catalyst. > The research results revealed that as the Fe to TPTZ mole ratio in the precursor complex was decreased, the catalytic ORR activity of Fe-N{sub x}/C increased monotonically in the mole ratio range of 1:2-1:6. > Increasing the amount of ligand in the precursor metal complex was demonstrated to be an effective way to compress the decomposition of ORR active site density and thereby enhance the ORR activity of Fe-N{sub x}/C. - Abstract: In an effort to improve oxygen reduction reaction (ORR) activity by increasing the catalytic active site density in carbon-supported non-noble metal catalysts, several nitrogen-containing catalysts were synthesized through a heat treatment process at 900 deg. C using precursor complexes of Fe(II) and tripyridyl triazine (TPTZ). Fe to TPTZ mole ratios of 1:2, 1:3, 1:4, 1:5, 1:6, and 1:7 were used to prepare the precursor complexes. X-ray diffraction and surface electrochemical techniques were used to characterize these catalysts (Fe-N{sub x}/C), and revealed that when the amount of TPTZ in the precursor complex was increased, the decomposition of Fe-N{sub x} sites, which are considered active sites for the ORR, was effectively reduced, resulting in higher Fe-N{sub x} site density and thus improving the catalysts' ORR activity. This beneficial effect was validated through rotating disk electrode tests and analysis of the ORR kinetics catalyzed by these catalysts. The obtained results showed that as the Fe to TPTZ mole ratio in the precursor complex was decreased, the catalytic ORR activity of Fe-N{sub x}/C increased monotonically in the mole ratio range of 1:2-1:6. Therefore, increasing the amount of ligand in the precursor metal complex was demonstrated to be an effective way to reduce the decomposition of ORR active site

  3. Extraction-mass spectrometric determination of platinum metals in materials of complex composition

    International Nuclear Information System (INIS)

    A method is developed for the extraction mass-spectrometric determination of platinum metals, including ruthenium. The loWer limit of detectable contents is 1.6x10-6 mass.% (a coefficient of concentration is 50). The relative standard deviation is 0.19-0.38. Relative sensitivity coefficients determined experimentally with the aid of reference samples for platinum metals enable the systematic errors of analysis results to be taken into account. The method is most advisably used for the simultaneous determination of platinum metals in complex objects (minerals, rocks, etc.)

  4. Thermochemistry of complex oxides of uranium(6), arsenic and alkali metals

    International Nuclear Information System (INIS)

    Standard reaction enthalpies for stoichiometric mixtures of mono-potassium orthoarsenate, uranium(6) and alkali metal nitrate oxides as well as mixtures of complex oxides of the M1AsUO6 (M1 = Li, Na, K, Rb, Cs) general formulas and potassium nitrate with hydrofluoric acid are determined in adiabatic calorimeter at the temperature of 298.15 K. Standard enthalpies for formation of complex oxides of uranium(6), arsenic and alkali metals at the temperature of 298.15 K are calculated by the obtained results. 8 refs., 1 tab

  5. Transition Metal Complexes of Naproxen: Synthesis, Characterization, Forced Degradation Studies, and Analytical Method Verification

    Science.gov (United States)

    Hasan, Md. Sharif; Kayesh, Ruhul; Begum, Farida; Rahman, S. M. Abdur

    2016-01-01

    The aim of our current research was to synthesize some transition metal complexes of Naproxen, determine their physical properties, and examine their relative stability under various conditions. Characterizations of these complexes were done by 1H-NMR, Differential Scanning Calorimetry (DSC), FT-IR, HPLC, and scanning electron microscope (SEM). Complexes were subjected to acidic, basic, and aqueous hydrolysis as well as oxidation, reduction, and thermal degradation. Also the reversed phase high-performance liquid chromatography (RP-HPLC) method of Naproxen outlined in USP was verified for the Naproxen-metal complexes, with respect to accuracy, precision, solution stability, robustness, and system suitability. The melting points of the complexes were higher than that of the parent drug molecule suggesting their thermal stability. In forced degradation study, complexes were found more stable than the Naproxen itself in all conditions: acidic, basic, oxidation, and reduction media. All the HPLC verification parameters were found within the acceptable value. Therefore, it can be concluded from the study that the metal complexes of Naproxen can be more stable drug entity and offer better efficacy and longer shelf life than the parent Naproxen. PMID:27034891

  6. Transition Metal Complexes of Naproxen: Synthesis, Characterization, Forced Degradation Studies, and Analytical Method Verification.

    Science.gov (United States)

    Hasan, Md Sharif; Kayesh, Ruhul; Begum, Farida; Rahman, S M Abdur

    2016-01-01

    The aim of our current research was to synthesize some transition metal complexes of Naproxen, determine their physical properties, and examine their relative stability under various conditions. Characterizations of these complexes were done by 1H-NMR, Differential Scanning Calorimetry (DSC), FT-IR, HPLC, and scanning electron microscope (SEM). Complexes were subjected to acidic, basic, and aqueous hydrolysis as well as oxidation, reduction, and thermal degradation. Also the reversed phase high-performance liquid chromatography (RP-HPLC) method of Naproxen outlined in USP was verified for the Naproxen-metal complexes, with respect to accuracy, precision, solution stability, robustness, and system suitability. The melting points of the complexes were higher than that of the parent drug molecule suggesting their thermal stability. In forced degradation study, complexes were found more stable than the Naproxen itself in all conditions: acidic, basic, oxidation, and reduction media. All the HPLC verification parameters were found within the acceptable value. Therefore, it can be concluded from the study that the metal complexes of Naproxen can be more stable drug entity and offer better efficacy and longer shelf life than the parent Naproxen. PMID:27034891

  7. Crystallization Kinetics of Misch Metal Based Bulk Metallic Glasses

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The crystallization kinetics of Mm55Al25Cu10Ni5Co5 bulk metallic glass (BMG) was investigated by means of differential scanning calorimetry (DSC) in the mode of continuous heating or isothermal annealing. It was found that the apparent activation energy Eg, Ex and Ep of the BMG calculated by Kissinger's method were 189.58, 170.68 and 170.41 kJ·mol-1, respectively, which was bigger than those of La55Al25Cu10Ni5Co5 BMG indicating that thermal stability of the former was higher than that of the latter. The local activation energy obtained using Ozawa equation decreased as crystallization proceeded except for the initial stage. The Avrami exponents were calculated to be in the range of 3.26~5.23 for different crystallization stages and isothermal temperatures. This implied that crystallization of Mm55Al25Cu10Ni5Co5 BMG was governed by diffusion-controlled three-dimensional growth with either reduced or increased nucleation rate, depending on isothermal temperature. Inconsistency of thermal stability with glass-forming ability for Mm(La)-Al-Cu-Ni-Co BMGs was discussed.

  8. Development of metal based thermal barrier coatings

    Science.gov (United States)

    Shin, Dong-Il

    In this work, metal-based thermal barrier coatings (MBTBCs) have been produced, using high frequency induction plasma spraying (IPS) of iron-based nanostructured alloy powders. Important advances have been made over recent years to the development of ceramic-based thermal barrier coatings (TBCs) for internal combustion engines application, but they are not yet applied in mass production situations. Besides the important economic considerations, the reliability of ceramic: TBCs is also an issue, being associated with the difficulty of predicting their "in-service" lifetime. Through engineering of the nano/amorphous structure of MBTBCs, their thermal conductivity can be made as low as those of ceramic-based TBCs, with reduced mean free paths of the electrons/phonons scattering. In this work, nano/amorphous structured coatings were deposited by IPS using the following spray parameters: spraying distance (210 ˜ 270 mm), plasma gas composition (Ar/N2), IPS torch power (24kW), and powder feed-rate (16g/min.). The structure and properties of the deposited layers were characterized through SEM (Scanning Electron Microscopy) observations. The thermal diffusivity (alpha) properties of the MBTBCs were measured using a laser flash method. Density (rho) and specific heat (Cp) of the MBTBCs were also measured, and their thermal conductivity (k) calculated (k =alpharhoCp). The thermal conductivity of MBTBCs was found to be as low as 1.99 W/m/K. The heat treatment study showed that crystal structure changes, and grain size growth from a few nanometers to tenth of nanometers occurred at 550°C under static exposure conditions. Thermal expansion coefficient (TEC) of MBTBCs was 13E-6/K, which is close to the TEC of cast iron and thus, closer to the TEC values of aluminium alloys than are conventional TBCs. Fracture toughness of MBTBCs has also been assessed by use of Vickers hardness tests, with a 500 g load for 15 s, and the results show that there are no measurable crack

  9. Antimicrobial and Thermal Properties of Metal Complexes of Grafted Fabrics with Acrylic Acid by Gamma Irradiation

    International Nuclear Information System (INIS)

    Cotton, cotton/PET blend and PET fabrics were treated against microbial effect by radiation - induced grafting of acrylic acid followed by metal complexation with some divalent transition metal ions Co (II), Ni (II) and Cu (II). The microbial resistance was evaluated by testing the mechanical properties of the treated fabrics after burring for one and two weeks in a moist soil reach with microorganisms. Also, the growth of microorganisms was examined by scanning electron microscope (SEM). Moreover, the effect of this treatment on the thermal decomposition behavior was investigated by thermogravimetric analysis (TGA). On the basis of microbial studies, it was found that the metal complexation of the grafted fabrics with acrylic acid enhanced the antimicrobial resistance of the fabrics and the antimicrobial resistance could be arranged according to the metal ions as follows: copper> nickel> cobalt. Also, the thermal stability of different fabrics could be arranged as follow: grafted fabrics complexed with Cu (II) > grafted fabrics complexed with Ni (II) > grafted fabrics complexed with Co (II)

  10. Magnetic interactions as a stabilizing factor of semiquinone species of lawsone by metal complexation

    Energy Technology Data Exchange (ETDEWEB)

    Valle-Bourrouet, Grettel [Universidad de Costa Rica, Escuela de Quimica, San Jose (Costa Rica); Ugalde-Saldivar, Victor M. [Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, C.P. 04510, Mexico, D.F. (Mexico); Gomez, Martin [Departamento de Sistemas Biologicos, Universidad Autonoma Metropolitana-Xochimilco, C.P. 04960, Mexico, D.F. (Mexico); Ortiz-Frade, Luis A. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Parque Tecnologico Queretaro, Sanfandila, 76703, Pedro Escobedo, Queretaro (Mexico); Gonzalez, Ignacio [Universidad Autonoma Metropolitana - Iztapalapa, Departamento de Quimica, Area de Electroquimica, Apartado postal 55-534, 09340, Mexico, D.F. (Mexico); Frontana, Carlos, E-mail: ultrabuho@yahoo.com.m [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. Instituto Politecnico Nacional No. 2508 Col. San Pedro Zacatenco, C.P. 07360, Mexico, D.F. (Mexico)

    2010-12-01

    Changes in electrochemical reactivity for lawsone anions (lawsone, 2-hydroxy-1,4-naphthoquinone, HLw) being coordinated to a series of metallic ions in dimethylsulfoxide solution were evaluated. Upon performing cyclic voltammetry experiments for metal complexes of this quinone with pyridine (Py) - structural formula M(II)(Lw{sup -}){sub 2}(Py){sub 2}; M: Co(II), Ni(II), Zn(II) - it was found that the reduction of coordinated Lw{sup -} units occurs during the first and second electron uptake in the analyzed compounds. The stability of the electrogenerated intermediates for each complex depends on the d electron configuration in each metal center and is determined by magnetic interactions with the available spins considering an octahedral conformation for all the compounds. This was evidenced by in situ spectroelectrochemical-ESR measurements in the Zn(II) complex in which due to the lack of magnetic interaction owing to its electron configuration, the structure of the coordinated anion radical species was determined. Successive reduction of the associated Lw{sup -} units leads to partial dissociation of the complex, determined by the identification of free radical dianion structures in solution. These results show some insights on how metal-lawsone complexation can modify the solution reactivity and stability of the electrogenerated radical species.

  11. Metal oxalate complexes as novel inorganic dopants: Studies on their effect on conducting polyaniline

    Indian Academy of Sciences (India)

    R Murugesan; E Subramanian

    2002-12-01

    Doped polyaniline materials with metal oxalate complexes of Cr, Fe, Mn, Co and Al were synthesized by in situ chemical oxidative polymerization of aniline using potassium perdisulphate as oxidant in aqueous sulphuric acid medium. These polymer materials were characterized by chemical analyses, spectral studies (UV-visible and IR), X-ray diffraction and thermal techniques and also by conductivity measurements by four-probe technique. The presence of complex anion in polyaniline material was confirmed by chemical and spectral analyses. The yield and conductivity of metal oxalate doped polyanilines were found to be high when compared to the simple sulphate ion doped polyaniline prepared under similar condition. UV-visible and IR spectral features not only confirmed the polyaniline doping by complex anions but also substantiated their facilitating effect on conductivity. The X-ray diffraction patterns indicated some crystalline nature in metal oxalate doped polyaniline and amorphous in polyaniline sulphate salt. The conductivity of the polymer samples strongly depended on the degree of crystallinity induced by complex counter anions as dopant. All the polymer materials, as evident from TGA curves, were observed to undergo three-step degradation of water loss, de-doping and decomposition of polymer. Further, the thermal stability of polyaniline was found to improve on doping with metal oxalate complex.

  12. On the Nature of the Bonding in Metal-Silane sigma-Complexes

    CERN Document Server

    McGrady, G Sean; Chatterton, Nicholas P; Ostermann, Andreas; Gatti, Carlo; Altmannshofer, Sandra; Herz, Verena; Eickerling, Georg; Scherer, Wolfgang

    2008-01-01

    The nature of metal silane sigma-bond interaction has been investigated in several key systems by a range of experimental and computational techniques. The structure of [Cp'Mn(CO)2(eta2-HSiHPh2)] 1 has been determined by single crystal neutron diffraction, and the geometry at the Si atom is shown to approximate to a trigonal bipyramid. This complex is similar to [Cp'Mn(CO)2(eta2-HSiFPh2)] 2, whose structure and bonding characteristics have recently been determined by charge density studies based on high-resolution X-ray and neutron diffraction data. The geometry at the Si atom in these sigma-bond complexes is compared with that in other systems containing hypercoordinate silicon. The Mn-H distances for 1 and 2 in solution have been estimated using NMR T1 relaxation measurements, giving a value of 1.56(3) AA in each case, in excellent agreement with the distances deduced from neutron diffraction. DFT calculations have been employed to explore the bonding in the Mn-H-Si unit in 1 and 2 and in the related system...

  13. Metal Complexes Containing Natural and and Artificial Radioactive Elements and Their Applications

    Directory of Open Access Journals (Sweden)

    Oxana V. Kharissova

    2014-07-01

    Full Text Available Recent advances (during the 2007–2014 period in the coordination and organometallic chemistry of compounds containing natural and artificially prepared radionuclides (actinides and technetium, are reviewed. Radioactive isotopes of naturally stable elements are not included for discussion in this work. Actinide and technetium complexes with O-, N-, N,O, N,S-, P-containing ligands, as well π-organometallics are discussed from the view point of their synthesis, properties, and main applications. On the basis of their properties, several mono-, bi-, tri-, tetra- or polydentate ligands have been designed for specific recognition of some particular radionuclides, and can be used in the processes of nuclear waste remediation, i.e., recycling of nuclear fuel and the separation of actinides and fission products from waste solutions or for analytical determination of actinides in solutions; actinide metal complexes are also usefulas catalysts forcoupling gaseous carbon monoxide,as well as antimicrobial and anti-fungi agents due to their biological activity. Radioactive labeling based on the short-lived metastable nuclide technetium-99m (99mTc for biomedical use as heart, lung, kidney, bone, brain, liver or cancer imaging agents is also discussed. Finally, the promising applications of technetium labeling of nanomaterials, with potential applications as drug transport and delivery vehicles, radiotherapeutic agents or radiotracers for monitoring metabolic pathways, are also described.

  14. Metal complexes containing natural and and artificial radioactive elements and their applications.

    Science.gov (United States)

    Kharissova, Oxana V; Méndez-Rojas, Miguel A; Kharisov, Boris I; Méndez, Ubaldo Ortiz; Martínez, Perla Elizondo

    2014-01-01

    Recent advances (during the 2007-2014 period) in the coordination and organometallic chemistry of compounds containing natural and artificially prepared radionuclides (actinides and technetium), are reviewed. Radioactive isotopes of naturally stable elements are not included for discussion in this work. Actinide and technetium complexes with O-, N-, N,O, N,S-, P-containing ligands, as well π-organometallics are discussed from the view point of their synthesis, properties, and main applications. On the basis of their properties, several mono-, bi-, tri-, tetra- or polydentate ligands have been designed for specific recognition of some particular radionuclides, and can be used in the processes of nuclear waste remediation, i.e., recycling of nuclear fuel and the separation of actinides and fission products from waste solutions or for analytical determination of actinides in solutions; actinide metal complexes are also usefulas catalysts forcoupling gaseous carbon monoxide,as well as antimicrobial and anti-fungi agents due to their biological activity. Radioactive labeling based on the short-lived metastable nuclide technetium-99m ((99m)Tc) for biomedical use as heart, lung, kidney, bone, brain, liver or cancer imaging agents is also discussed. Finally, the promising applications of technetium labeling of nanomaterials, with potential applications as drug transport and delivery vehicles, radiotherapeutic agents or radiotracers for monitoring metabolic pathways, are also described. PMID:25061724

  15. Photochemical activation and reactivity of polynuclear transition-metal-complex molecules. Progress report, June 1981-May 31, 1982

    International Nuclear Information System (INIS)

    Significant results obtained during the year are summarized for the following programs: (1) reversible, two electron transfer at a single potential in binuclear complexes; (2) photophysics of polyketonate complexes; (3) synthetic strategies and characterization of heavy metal heterobinuclear complexes; (4) high yield synthesis of ligands capable of binding 3 and 4 metal ions per molecule. Electrochemical studies have uncovered a number of new binuclear metal complexes that undergo reversible two-electron reduction at single potential including Cu(II) complexes with two different coordination environments, mixed Ni(II), Cu(II) complexes and binuclear Ni(II) complexes. In each case the species that exhibit these electron transfer properties have been shown to be Na+ ion-paired complexes. Several new trinuclear molecular complexes have been prepared and characterized that contain two UO22+ ions and one transition metal ion. The electrochemistry, absorption spectra, and luminescence have been investigated

  16. Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: Bonding, electronic structure, and comparison with actinides and other electropositive metals

    OpenAIRE

    Huang, W.; Diaconescu, PL

    2015-01-01

    © 2015 The Royal Society of Chemistry. Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, m...

  17. Solventless acid-free synthesis of mesostructured titania: Nanovessels for metal complexes and metal nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Dag, Oe.; Celik, Oe.; Ozin, G.A. [Department of Chemistry, Bilkent University, 06533 Ankara (Turkey); Soten, I.; Polarz, S.; Coombs, N. [Materials Chemistry Research Group, Chemistry Department, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada)

    2003-01-01

    A new and highly reproducible method to obtain mesostructured titania materials is introduced in this contribution. The mesostructured titania is obtained by employing self-assembled structures of non-ionic alkyl-poly(ethylene oxide) surfactants as templates. The materials are produced without additional solvents such as alcohols, or even water. Only the titanium(IV) ethoxide and the surfactant (C{sub 12}EO{sub 10}) are needed. Water, in the form of that attached to the surfactant and from the atmosphere, induces growth of titania nanoclusters in the synthesis sol. It is indicated that these nanoclusters interact with the surfactant EO-head groups to form a new titanotropic amphiphile. The new amphiphiles self-assemble into titanium nanocluster-surfactant hybrid lyotropic phases, which are transformed to the final mesostructured materials by further condensation of the titania network. The titania materials can be obtained also with noble-metal particles immobilized in the mesostructured framework. It is seen that when different metal salts are used as the metal precursors, different interactions with the titania walls are found. The materials are characterized by X-ray diffraction (XRD), polarization optical microscopy (POM), transmission electron microscopy (TEM), UV-vis spectroscopy, and micro-Raman analysis. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  18. Chemistry of Platinum and Palladium Metal Complexes in Homogeneous and Heterogeneous Catalysis: A Mini Review

    OpenAIRE

    Mehrban Ashiq; Fareeha Mukhtar; Sineen Bari; Muhammad Danish; Muhammad Ali Mohsin

    2013-01-01

    Transition metal complexes of platinum and palladium are most widely used in catalysis. Many synthetic reactions have been carried out with such complexes (used as a catalyst) which have specifically polymer ligands, through hydrosilylation, acetoxylation, hydrogenation, hydro-formylation, oligo-merisation and polymerization. Almost many platinum and palladium catalysts are heterogeneous in nature i.e. the reaction taking place on a solid surface. Now from few years homogeneou...

  19. Synthesis, Characterization and Metal Ion Detection of Novel Fluoroionophores Based on Heterocyclic Substituted Alanines

    Directory of Open Access Journals (Sweden)

    M. Manuela M Raposo

    2007-10-01

    Full Text Available The synthesis of new fluorescent probes containing the thiophene andbenzoxazole moieties combined with an alanine residue is described. The resulting highlyfluorescent heterocyclic alanine derivatives respond via a quenching effect, withparamagnetic Cu(II and Ni(II metal ions and with diamagnetic Hg(II, as shown by theabsorption and steady-state fluorescence spectroscopy studies. The formation ofmononuclear or dinuclear metal complexes was postulated based on the presence of thefree carboxylic acid as binding site and also with the interaction with the donor atoms inthe chromophore. Interaction with other important biological metal ions such as Zn(II,Ca(II and Na(I was also explored.

  20. Single crystal growth of europium and ytterbium based intermetallic compounds using metal flux technique

    Indian Academy of Sciences (India)

    Sumanta Sarkar; Sebastian C Peter

    2012-11-01

    This article covers the use of indium as a potential metal solvent for the crystal growth of europium and ytterbium-based intermetallic compounds. A brief view about the advantage of metal flux technique and the use of indium as reactive and non-reactive flux are outlined. Large single crystals of EuGe2, EuCoGe3 and Yb2AuGe3 compounds were obtained in high yield from the reactions of the elements in liquid indium. The results presented here demonstrate that considerable advances in the discovery of single crystal growth of complex phases are achievable utilizing molten metals as solvents.