WorldWideScience

Sample records for cobalt phthalocyanine molecules

  1. Molecular mechanics calculations on cobalt phthalocyanine dimers

    NARCIS (Netherlands)

    Heuts, J.P.A.; Schipper, E.T.W.M.; Piet, P.; German, A.L.

    1995-01-01

    In order to obtain insight into the structure of cobalt phthalocyanine dimers, molecular mechanics calculations were performed on dimeric cobalt phthalocyanine species. Molecular mechanics calculations are first presented on monomeric cobalt(II) phthalocyanine. Using the Tripos force field for the

  2. Perfluorinated cobalt phthalocyanine effectively catalyzes water electrooxidation

    KAUST Repository

    Morlanes, Natalia Sanchez

    2014-12-08

    Efficient electrocatalysis of water oxidation under mild conditions at neutral pH was achieved by a fluorinated cobalt phthalocyanine immobilized on fluorine-doped tin oxide (FTO) surfaces with an onset potential at 1.7 V vs. RHE. Spectroscopic, electrochemical, and inhibition studies indicate that phthalocyanine molecular species are the operational active sites. Neither free cobalt ions nor heterogeneous cobalt oxide particles or films were observed. During long-term controlled-potential electrolysis at 2 V vs. RHE (phosphate buffer, pH 7), electrocatalytic water oxidation was sustained for at least 8 h (TON ≈ 1.0 × 105), producing about 4 μmol O2 h-1 cm-2 with a turnover frequency (TOF) of about 3.6 s-1 and no measurable catalyst degradation.

  3. Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode

    International Nuclear Information System (INIS)

    Mashazi, Philani N.; Westbroek, Philippe; Ozoemena, Kenneth I.; Nyokong, Tebello

    2007-01-01

    Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards L-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for L-cysteine at potentials where metal oxidation (M III /M II ) takes place and this metal oxidation mediates the catalytic oxidation of L-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards L-cysteine at potentials where Mn IV /Mn III redox peak occurs and this redox peak mediates L-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10 -7 mol L -1 and good linearity for a studied concentration range up to 60 μmol L -1

  4. Graphene-enhanced intermolecular interaction at interface between copper- and cobalt-phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Dou, Wei-Dong [Department of Physics, Shaoxing University, Shaoxing 312000 (China); Center of Super-Diamond and Advanced Films (COSDAF) and Department of Physics and Material Science, City University of Hong Kong, Hong Kong (China); Huang, Shu-Ping [Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069 (United States); Lee, Chun-Sing, E-mail: apcslee@cityu.edu.hk [Center of Super-Diamond and Advanced Films (COSDAF) and Department of Physics and Material Science, City University of Hong Kong, Hong Kong (China)

    2015-10-07

    Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π–π interaction between CoPc and CuPc. Analysis based on X-ray photoelectron spectroscopy and density functional theory reveals that the decrease in the work function for the CuPc/CoPc/graphene system is induced by the intermolecular interaction between CuPc and CoPc which is enhanced owning to the peculiar electronic properties at the CoPc-graphene interface.

  5. Layer-by-layer construction of graphene/cobalt phthalocyanine composite film on activated GCE for application as a nitrite sensor

    International Nuclear Information System (INIS)

    Cui, Lili; Pu, Tao; Liu, Ying; He, Xingquan

    2013-01-01

    Graphical abstract: A novel nitrite sensor was prepared by using LBL technique which for the first time used the activated positively charged glassy carbon electrode (A-GCE) as the substrate. The nitrite sensor shows super stability for consecutive CV testing and rather low detection limit. -- Abstract: In this paper, a novel graphene/cobalt phthalocyanine composite film was prepared by layer-by-layer (LBL) technique which for the first time used the activated positively charged glassy carbon electrode (A-GCE) as the substrate. The surface morphology of graphene/cobalt phthalocyanine composite film was characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM). It is found that graphene/cobalt phthalocyanine composite film modified GCE exhibits good catalytic activity toward the oxidation of nitrite. The oxidation current barely decreases in consecutive CV test. Furthermore, the modified GCE shows long-term stability after 70 days. The super good stability can be attributed to the immobilization and dispersion of electroactive cobalt phthalocyanine by graphene, and using A-GCE as substrate which can enhance the interaction force between GCE and electroactive cobalt phthalocyanine. The nitrite sensor shows rather low detection limit of 0.084 μM at a signal-to-noise ratio = 3 (S/N = 3)

  6. The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule

    Directory of Open Access Journals (Sweden)

    Jing Zhou

    2016-03-01

    Full Text Available To shed some light on the metal 3d ground state configuration of cobalt phthalocyanines system, so far in debate, we present an investigation by X-ray absorption spectroscopy (XAS at Co L2,3 edge and theoretical calculation. The density functional theory calculations reveal highly anisotropic covalent bond between central cobalt ion and nitrogen ligands, with the dominant σ donor accompanied by weak π-back acceptor interaction. Our combined experimental and theoretical study on the Co-L2,3 XAS spectra demonstrate a robust ground state of 2A1g symmetry that is built from 73% 3d7 character and 27% 3 d 8 L ¯ ( L ¯ denotes a ligand hole components, as the first excited-state with 2Eg symmetry lies about 158 meV higher in energy. The effect of anisotropic and isotropic covalency on the ground state was also calculated and the results indicate that the ground state with 2A1g symmetry is robust in a large range of anisotropic covalent strength while a transition of ground state from 2A1g to 2Eg configuration when isotropic covalent strength increases to a certain extent. Here, we address a significant anisotropic covalent effect of short Co(II-N bond on the ground state and suggest that it should be taken into account in determining the ground state of analogous cobalt complexes.

  7. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

    KAUST Repository

    Ziani, Ahmed

    2016-11-04

    The decoration of (photo)electrodes for efficient photoresponse requires the use of electrocatalysts with good dispersion and high transparency for efficient light absorption by the photoelectrode. As a result of the ease of thermal evaporation and particulate self-assembly growth, the phthalocyanine molecular species can be uniformly deposited layer-by-layer on the surface of substrates. This structure can be used as a template to achieve a tunable amount of catalysts, high dispersion of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a phthalocyanine metal precursor. Cobalt phthalocyanine (CoPc) films with different thicknesses were deposited by thermal evaporation on different substrates. The films were annealed at 400 °C in air to form a material with the cobalt oxide phase. The final Co oxide catalysts exhibit high transparency after thermal treatment. Their OER measurements demonstrate well expected mass activity for OER. Thermally evaporated and treated transition metal oxide nanoparticles are attractive for the functionalization of (photo)anodes for water oxidation.

  8. Sulphonated cobalt phthalocyanine-MCM-41: An active photocatalyst for degradation of 2,4-dichlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Zanjanchi, M.A., E-mail: zanjanchi@guilan.ac.ir [Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Namjoo St., Rasht 41335 (Iran, Islamic Republic of); Ebrahimian, A.; Arvand, M. [Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Namjoo St., Rasht 41335 (Iran, Islamic Republic of)

    2010-03-15

    The photocatalytic activity of sulphonated cobalt phthalocyanine immobilized onto MCM-41 was investigated for decomposition of 2,4-dichlorophenol (2,4-DCP) in aqueous solutions. Immobilization of anion sulpho-cobalt phthalocyanine to the walls of MCM-41 was performed by pre-anchorage of 3-(aminopropyl)-triethoxysilane (APTES) onto MCM-41 via post-synthesis method. X-ray diffraction, nitrogen physisorption, diffuse reflectance spectroscopy, energy-dispersive X-ray and FT-IR methods were used to characterize the product. Photocatalytic efficiency of the prepared catalyst for degradation of 2,4-DCP was tested under illumination of UV-A and visible light. The results obtained reveal that the photocatalyst is very active in degradation of 2,4-DCP. The photodegradation process is completed within 3 h using a dose of 0.6 g/L of the catalyst under UV irradiation. The reactions follow a pseudo-first-order kinetics and the observed rate constant values change with 2,4-DCP concentrations. The reproducibility of the catalyst was tested. The reaction intermediates were identified by gas chromatoghraphy-mass spectrometery (GC-MS) technique.

  9. Dynamics of copper-phthalocyanine molecules on Au/Ge(001)

    NARCIS (Netherlands)

    Sotthewes, Kai; Heimbuch, Rene; Zandvliet, Henricus J.W.

    2015-01-01

    Spatially resolved current-time scanning tunneling spectroscopy combined with current-distance spectroscopy has been used to characterize the dynamic behavior of copper-phthalocyanine (CuPc) molecules adsorbed on a Au-modified Ge(001) surface. The analyzed CuPc molecules are adsorbed in a “molecular

  10. The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yuhao; Reddy, Ramana G. [Department of Metallurgical and Materials Engineering, The University of Alabama, P.O. Box 870202, Tuscaloosa, AL 35487 (United States)

    2007-02-01

    The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 C, 635 C and 980 C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H{sub 2}SO{sub 4} solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 C or 635 C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC. (author)

  11. Simultaneous Reduction of CO 2 and Splitting of H 2 O by a Single Immobilized Cobalt Phthalocyanine Electrocatalyst

    KAUST Repository

    Morlanes, Natalia Sanchez; Takanabe, Kazuhiro; Rodionov, Valentin

    2016-01-01

    Perfluorinated cobalt phthalocyanine (CoFPc) immobilized on carbon electrodes was found to electrocatalyze the reduction of CO2 selectively to CO in an aqueous solution. The conversion of CO2 became apparent at -0.5 V vs RHE, and the Faradaic

  12. Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

    Energy Technology Data Exchange (ETDEWEB)

    Massimi, Lorenzo, E-mail: lorenzo.massimi@uniroma1.it; Angelucci, Marco; Gargiani, Pierluigi; Betti, Maria Grazia [Dipartimento di Fisica, Università di Roma La “Sapienza,” 00185 Roma (Italy); Montoro, Silvia [IFIS Litoral, CONICET-UNL, Laboratorio de Fisica de Superficies e Interfaces, Güemes 3450, Santa Fe (Argentina); Mariani, Carlo, E-mail: carlo.mariani@uniroma1.it [Dipartimento di Fisica, CNISM, Università di Roma La “Sapienza,” 00185 Roma (Italy)

    2014-06-28

    Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption, and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.

  13. Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes, chitosan and cobalt (II) phthalocyanine

    International Nuclear Information System (INIS)

    Sousa Luz, Roberto A. de; Martins, Marccus Victor A.; Magalhaes, Janildo L.; Siqueira, Jose R.; Zucolotto, Valtencir; Oliveira, Osvaldo N.; Crespilho, Frank N.; Cantanhede da Silva, Welter

    2011-01-01

    Highlights: → Platforms were assembled from cobalt phthalocyanine, chitosan and carbon nanotubes. → Supramolecular organization of multilayer films was investigated. → Increase of the supramolecular charge transfer after carbon nanotube incorporation. → Functional modulation based on constitutional dynamic chemistry was achieved. - Abstract: The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {Chit/CoTsPc} n and {Chit-SWCNTs/CoTsPc} n (n = 1-10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E 1/2 at -0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)] 5- /[CoTsPc(II)] 4- and CoTsPc(II) to CoTsPc(III), respectively. The {Chit-SWCNTs/CoTsPc} 5 multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the electrode surface.

  14. Electrocatalytic behahiour of cobalt tetraamino-phthalocyanine in the presence of a composite of reduced graphene nanosheets and of multi-walled carbon nanotubes

    International Nuclear Information System (INIS)

    Nyoni, Stephen; Nyokong, Tebello

    2014-01-01

    Graphical abstract: A composite of multi-walled carbon nanotubes, reduced graphene nanosheets and cobalt tetraamino phthalocyanine was used for electrode modification, resulting in a rough surface as judged by scanning electrochemical microscopy. - Highlights: • Conjugates of multi-walled carbon nanotubes and reduced graphene nanosheets were used to modify glassy carbon electrode. • The electrode was further modified with cobalt tetraamino phthalocyanine. • The modified electrode was employed for the detection of paraquat. • A mechanism for paraquat detection using the composite electrodes is proposed. - Abstract: A composite of multi-walled carbon nanotubes (MWCNT) with reduced graphene nanosheets (rGNS-2) was developed in order to minimize the restacking of the latter. The composite was used to modify a glassy carbon electrode (GCE). GCE was further modified with cobalt tetraamino phthalocyanine (CoTAPc). The modified electrode is represented as rGNS-2-MWCNT-CoTAPc-GCE. X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electrochemical microscopy and Raman spectroscopy were used to explore into surface functionalities, morphology and topography of the nanocomposite. The rGNS-2-MWCNT-CoTAPc-GCE had a low limit of detection of 3.32 × 10 −8 M towards the detection of paraguat as a test analyte. A mechanism for paraquat detection using an rGNS-2-MWCNT-CoTAPc-GCE is also proposed in this work

  15. Comparative study of electronic and magnetic properties of Pc ( = Fe, Co) molecules physisorbed on 2D MoS and graphene

    KAUST Repository

    Haldar, Soumyajyoti; Bhandary, Sumanta; Vovusha, Hakkim; Sanyal, Biplab

    2017-01-01

    In this paper, we have done a comparative study of electronic and magnetic properties of iron phthalocyanine (FePc) and cobalt phthalocyanine (CoPc) molecules physisorbed on monolayer of MoS$_2$ and graphene by using density functional theory

  16. Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes, chitosan and cobalt (II) phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Sousa Luz, Roberto A. de; Martins, Marccus Victor A.; Magalhaes, Janildo L. [Departamento de Quimica, Centro de Ciencias da Natureza, Universidade Federal do Piaui, Teresina - PI, CEP 64049-550 (Brazil); Siqueira, Jose R. [Instituto de Ciencias Exatas, Naturais e Educacao, Universidade Federal do Triangulo Mineiro, Uberaba - MG, CEP 38025-180, Brazil (Brazil); Zucolotto, Valtencir; Oliveira, Osvaldo N. [Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Sao Carlos - SP, CEP 13560-970 (Brazil); Crespilho, Frank N. [Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC, Santo Andre - SP, CEP 09210-170 (Brazil); Cantanhede da Silva, Welter, E-mail: welter@ufpi.edu.br [Departamento de Quimica, Centro de Ciencias da Natureza, Universidade Federal do Piaui, Teresina - PI, CEP 64049-550 (Brazil)

    2011-11-01

    Highlights: {yields} Platforms were assembled from cobalt phthalocyanine, chitosan and carbon nanotubes. {yields} Supramolecular organization of multilayer films was investigated. {yields} Increase of the supramolecular charge transfer after carbon nanotube incorporation. {yields} Functional modulation based on constitutional dynamic chemistry was achieved. - Abstract: The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {l_brace}Chit/CoTsPc{r_brace}{sub n} and {l_brace}Chit-SWCNTs/CoTsPc{r_brace}{sub n} (n = 1-10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E{sub 1/2} at -0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)]{sup 5-}/[CoTsPc(II)]{sup 4-} and CoTsPc(II) to CoTsPc(III), respectively. The {l_brace}Chit-SWCNTs/CoTsPc{r_brace}{sub 5} multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the

  17. Effects of analytes on the fluorescence properties of CdTe@ZnS quantum dots decorated with cobalt tetraamino-phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Adegoke, Oluwasesan; Nyokong, Tebello, E-mail: t.nyokong@ru.ac.za

    2014-02-15

    In this work, we have carried out an investigation on the effects of different biologically active analytes on the fluorescence response of glutathione-capped CdTe@ZnS quantum dots (QDs)-colbalt tetraamino-phthalocyanine nanoconjugate system. Firstly, fluorescence quenching occurred. Experimental results showed that some analytes either “turned on”, others further quenched or showed no effect on the fluorescence emission of the nanoprobe. -- Highlights: • A conjugate between CdTe@ZnS quantum dots and cobalt tetraamino-phthalocyanine is formed. • The fluorescence of quantum dots is quenched on coordination. • The fluorescence is enhanced by analytes such as cystamine, hydroxyl radical, glutathione, and perchlorate.

  18. Novel non-symmetrical bifunctionally-substituted phthalonitriles and corresponding d-metal phthalocyaninates

    Science.gov (United States)

    Vashurin, Artur; Maizlish, Vladimir; Tikhomirova, Tatiyana; Nemtseva, Marina; Znoyko, Serafima; Aleksandriiskii, Viktor

    2018-05-01

    The work reports synthesis of 4-(2-tert-butyl-4,5-dicyanophenylsulfonyl)benzene and its analogue containing carboxyl group in phenyl fragment by nucleophilic substitution of nitro-group of 4-tert-butyl-5-nitrophthalonitrile. Unique structure of the obtained compounds is explained by presence of bulky tert-butyl substituent in combination with carboxyl group, which being part of phthalocyanine molecule impart it higher solubility within different solvents (organic and water mediums) and act as anchoring groups. Based on obtained nitriles phthalocyanine complexes of copper, nickel, cobalt and magnesium are synthesized with good yields. Demetallization of initial magnesium phthalocyanine by hydrochloric acid was performed in order to obtain ligand of phthalocyanine. Synthetic and purification techniques are described in detail. Obtained substances are of specific structure making them to be applied in sensorics for smart materials production, as sensitizers or part of molecular magnets. The structure, NMR and IR spectra are modeled using special software. Resulting experimental and theoretical data are compared. The results show sufficient correlation that confirms correctness of chosen methods and its applicability for theoretical studying compounds related to investigated ones.

  19. Synthesis and electrochemical and in situ spectroelectrochemical characterization of manganese, vanadyl, and cobalt phthalocyanines with 2-naphthoxy substituents

    International Nuclear Information System (INIS)

    Ozcesmeci, Ibrahim; Koca, Atif; Guel, Ahmet

    2011-01-01

    Highlights: → Metallo (Mn, Co, VO) phthalocyanines bearing peripheral 2-naphthoxy-groups were synthesized by cyclotetramerisation of the corresponding phthalonitrile derivative. → Incorporation of the redox active metal ions into the phthalocyanine core extends the redox capabilities of the Pc ring. → The presence of O 2 in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes. → Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. - Abstract: Metallo (Mn, Co, VO) phthalocyanines bearing peripheral 2-naphthoxy groups were synthesized by cyclotetramerisation of the corresponding phthalonitrile derivative. The phthalocyanine compounds were characterized by elemental analyses, mass, FT-IR and UV-vis spectral data. Three intense bands in the electronic spectra clearly indicate the absorptions resulting from naphthyl groups along with the Q and B bands of the phthalocyanines. Electrochemical and spectroelectrochemical measurements exhibit that incorporation of redox active metal ions, Co II and Mn III , into the phthalocyanine core extends the redox capabilities of the Pc ring including the metal-based reduction and oxidation couples of the metal. Presence of molecular oxygen in the electrolyte system affects the voltammetric and spectroelectrochemical responses of the cobalt and manganese phthalocyanines due to the interaction between the complexes and molecular oxygen. Interaction reaction of oxygen with CoPc occurs via an 'inner sphere' chemical catalysis process. While CoPc gives the intermediates [O 2 - -Co II Pc -2 ] - and [O 2 2 -Co II Pc -2 ] 2- , MnPc forms μ-oxo MnPc species. An in situ electrocolorimetric method has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for possible electrochromatic applications.

  20. In situ metalation of free base phthalocyanine covalently bonded to silicon surfaces

    Directory of Open Access Journals (Sweden)

    Fabio Lupo

    2014-11-01

    Full Text Available Free 4-undecenoxyphthalocyanine molecules were covalently bonded to Si(100 and porous silicon through thermic hydrosilylation of the terminal double bonds of the undecenyl chains. The success of the anchoring strategy on both surfaces was demonstrated by the combination of X-ray photoelectron spectroscopy with control experiments performed adopting the commercially available 2,3,9,10,16,17,23,24-octakis(octyloxy-29H,31H-phthalocyanine, which is not suited for silicon anchoring. Moreover, the study of the shape of the XPS N 1s band gave relevant information on the interactions occurring between the anchored molecules and the substrates. The spectra suggest that the phthalocyanine ring interacts significantly with the flat Si surface, whilst ring–surface interactions are less relevant on porous Si. The surface-bonded molecules were then metalated in situ with Co by using wet chemistry. The efficiency of the metalation process was evaluated by XPS measurements and, in particular, on porous silicon, the complexation of cobalt was confirmed by the disappearance in the FTIR spectra of the band at 3290 cm−1 due to –NH stretches. Finally, XPS results revealed that the different surface–phthalocyanine interactions observed for flat and porous substrates affect the efficiency of the in situ metalation process.

  1. Structural and electrical studies on tetrameric cobalt phthalocyanine and polyaniline composites

    International Nuclear Information System (INIS)

    Saravanan, S.; Anantharaman, M.R.; Venkatachalam, S.

    2006-01-01

    Polyaniline and oligomeric cobalt phthalocyanine are blended in different proportions by chemical methods. These blends are characterised by spectroscopic methods and dielectric measurements. Dielectric studies on the conducting polymer blends are carried out in the frequency range of 100 kHz to 5 MHz from room temperature (300 K) to 373 K. Dielectric permittivity and dielectric loss of these blends are explained on the basis of interfacial polarisation. From the dielectric permittivity studies, ac conductivity of the samples were calculated and the results are correlated. In order to understand the exact conduction mechanism of the samples, dc electrical conductivity of the blends is carried out in the temperature range of 70-300 K. By applying Mott's theory, it is found that the conducting polymer composites obey a 3D variable range hopping mechanism. The values of Mott's temperature (T 0 ), density of states at the Fermi energy (N(E F )), range of hopping (R) and hopping energy (W) for the composites are calculated and presented

  2. Direct observation of hindered eccentric rotation of an individual molecule : Cu-phthalocyanine on C60

    NARCIS (Netherlands)

    Stöhr, Meike; Wagner, T; Gabriel, M; Weyers, B; Moller, R

    2002-01-01

    Individual Cu-phthalocyanine molecules have been investigated by scanning tunnel microscopy on a closed packed film of C-60 at various temperatures. The molecules are found to bind asymmetrically to one C-60. While they remain in one position at low temperature, they can hop between six equivalent

  3. On-surface manipulation of atom substitution between cobalt phthalocyanine and the Cu(111) substrate

    DEFF Research Database (Denmark)

    Shen, Kongchao; Narsu, Bai; Ji, Gengwu

    2017-01-01

    On-surface fabrication of controllable nanostructures is an appealing topic in the field of molecular electronics. Herein, the adsorption of cobalt phthalocyanine (CoPc) on a Cu(111) surface is investigated utilizing a combination of photoelectron spectroscopy (PES) and density functional theory ...... state environment may offer an encouraging approach towards the artificial engineering of organometallic nanostructures and related properties for surface catalysts, molecular electronics and so on....... and thermal annealing, and the tendency to form Co–Cu alloy at the interface. While CoPc has been successfully utilized in electrocatalysts for fuel cell applications and CuPc is commonly used as a leading material in organic solar cells, this report of interface transmetalation from CoPc to CuPc in a solid...

  4. Electronic and magnetic coupling of iron and copper phthalocyanine to ferromagnetic Co(100) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Felix; Sauther, Jens; Lach, Stefan; Ziegler, Christiane [Department of Physics, University of Kaiserslautern, Erwin Schroedinger Str. 56, D-67663 Kaiserslautern (Germany); Ali, Ehesan; Oppeneer, Peter [Department of Physics and Materials Science, Box 530, Uppsala University, S-75121 Uppsala (Sweden)

    2009-07-01

    Metallo-phthalocyanines are organic semiconductors which show in certain cases promising magnetic properties, advertising them for use in organic spintronics. Here, copper (CuPc) and iron phthalocyanine (FePc) were grown on ultra thin layers of Co(100) substrates with well known highly spin-polarized electron injection capability. Photoelectron spectroscopy (XPS) reveals different interactions between the pyrolytic nitrogen atoms and the cobalt surface for the two phthalocyanines. The analysis of the different multiplet structures appearing for the nitrogen core levels in the submonolayer regime and UPS investigations of the valence band electronic structure of the Co dominated region near the Fermi level indicates a particularly electronic coupling and a rehybridisation of the molecular orbitals with the cobalt orbitals. In order to clarify the influence of the two different central atoms on the electronic- and subsequently the magnetic coupling to the Co substrate, theoretical calculations using the GGA and GGA+U methodologies on a structure of Fe/Cu-phthalocyanine adsorbed on a 3-layered cobalt surface were performed indicating a ferromagnetic coupling between FePc and Co.

  5. Hindered rotation of a copper phthalocyanine molecule on C60 : Experiments and molecular mechanics calculations

    NARCIS (Netherlands)

    Fendrich, M.; Wagner, Th.; Stöhr, M.; Möller, R.

    2006-01-01

    If copper phthalocyanine (CuPc) molecules are deposited on a Au(111) surface covered with a monolayer of C60, the molecules are found to adsorb individually onto the close-packed layer of C60. As the adsorption site of the CuPc is not symmetric with respect to the underlying C60 layer, the CuPc

  6. Fast Response and High Sensitivity of ZnO Nanowires-Cobalt Phthalocyanine Heterojunction Based H2S Sensor.

    Science.gov (United States)

    Kumar, Ashwini; Samanta, Soumen; Singh, Ajay; Roy, Mainak; Singh, Surendra; Basu, Saibal; Chehimi, Mohmad M; Roy, Kallol; Ramgir, Niranjan; Navaneethan, M; Hayakawa, Y; Debnath, Anil K; Aswal, Dinesh K; Gupta, Shiv K

    2015-08-19

    The room temperature chemiresistive response of n-type ZnO nanowire (ZnO NWs) films modified with different thicknesses of p-type cobalt phthalocyanine (CoPc) has been studied. With increasing thickness of CoPc (>15 nm), heterojunction films exhibit a transition from n- to p-type conduction due to uniform coating of CoPc on ZnO. The heterojunction films prepared with a 25 nm thick CoPc layer exhibit the highest response (268% at 10 ppm of H2S) and the fastest response (26 s) among all samples. The X-ray photoelectron spectroscopy and work function measurements reveal that electron transfer takes place from ZnO to CoPc, resulting in formation of a p-n junction with a barrier height of 0.4 eV and a depletion layer width of ∼8.9 nm. The detailed XPS analysis suggests that these heterojunction films with 25 nm thick CoPc exhibit the least content of chemisorbed oxygen, enabling the direct interaction of H2S with the CoPc molecule, and therefore exhibit the fastest response. The improved response is attributed to the high susceptibility of the p-n junctions to the H2S gas, which manipulates the depletion layer width and controls the charge transport.

  7. Importance of semicore states in GW calculations for simulating accurately the photoemission spectra of metal phthalocyanine molecules.

    Science.gov (United States)

    Umari, P; Fabris, S

    2012-05-07

    The quasi-particle energy levels of the Zn-Phthalocyanine (ZnPc) molecule calculated with the GW approximation are shown to depend sensitively on the explicit description of the metal-center semicore states. We find that the calculated GW energy levels are in good agreement with the measured experimental photoemission spectra only when explicitly including the Zn 3s and 3p semicore states in the valence. The main origin of this effect is traced back to the exchange term in the self-energy GW approximation. Based on this finding, we propose a simplified approach for correcting GW calculations of metal phthalocyanine molecules that avoids the time-consuming explicit treatment of the metal semicore states. Our method allows for speeding up the calculations without compromising the accuracy of the computed spectra.

  8. Electronic structure of CoPc adsorbed on Ag(100): Evidence for molecule-substrate interaction mediated by Co 3d orbitals

    Czech Academy of Sciences Publication Activity Database

    Salomon, E.; Amsalem, P.; Marom, N.; Vondráček, Martin; Kronik, L.; Koch, N.; Angot, T.

    2013-01-01

    Roč. 87, č. 7 (2013), "075407-1"-"075407-9" ISSN 1098-0121 R&D Projects: GA MŠk(CZ) LG12003 Institutional support: RVO:68378271 Keywords : cobalt-phthalocyanine * molecule-substrate interaction * photoemission spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.664, year: 2013

  9. Photorefractive IR-spectrum composites prepared from polyimide and ruthenium(II) tetra-15-crown-5-phthalocyaninate with axially coordinated triethylenediamine molecules

    International Nuclear Information System (INIS)

    Vannikov, A.V.; Grishina, A.D.; Gorbunova, Yu.G.; Enakieva, Yu.Yu.; Krivenko, T.V.; Savel'ev, V.V.; Tsivadze, A.Yu.

    2006-01-01

    Photoelectric, non-linear optical, and photorefractive properties of aromatic polyimine doped with ruthenium(II) complex with tetra-15-crown-5-phthalocyanine and axially coordinated triethylenediamine molecules, (R 4 Pc)Ru(TED) 2 , where R 4 Pc 2- and TED denote 4,5,4',5',4'',5'',4''',5'''-tetrakis-(1,4,7,10,13- pentaoxatridecamethylene)phthalocyaninate ion and triethylenediamine molecule, respectively, were studied. It is established that supramolecular ensembles on the basis of the complex make an aromatic polyimide layer photoelectrically sensitive to 1064-nm Nd : YAG laser radiation, exhibit third-order susceptibility, and, consequently, impart photorefractive properties to the polymer layer at this wavelength [ru

  10. Valence electronic structure of cobalt phthalocyanine from an optimally tuned range-separated hybrid functional.

    Science.gov (United States)

    Brumboiu, Iulia Emilia; Prokopiou, Georgia; Kronik, Leeor; Brena, Barbara

    2017-07-28

    We analyse the valence electronic structure of cobalt phthalocyanine (CoPc) by means of optimally tuning a range-separated hybrid functional. The tuning is performed by modifying both the amount of short-range exact exchange (α) included in the hybrid functional and the range-separation parameter (γ), with two strategies employed for finding the optimal γ for each α. The influence of these two parameters on the structural, electronic, and magnetic properties of CoPc is thoroughly investigated. The electronic structure is found to be very sensitive to the amount and range in which the exact exchange is included. The electronic structure obtained using the optimal parameters is compared to gas-phase photo-electron data and GW calculations, with the unoccupied states additionally compared with inverse photo-electron spectroscopy measurements. The calculated spectrum with tuned γ, determined for the optimal value of α = 0.1, yields a very good agreement with both experimental results and with GW calculations that well-reproduce the experimental data.

  11. Studies on the Optical Properties and Surface Morphology of Cobalt Phthalocyanine Thin Films

    Directory of Open Access Journals (Sweden)

    Benny Joseph

    2008-01-01

    Full Text Available Thin films of Cobalt Phthalocyanine (CoPc are fabricated at a base pressure of 10-5 m.bar using Hind-Hivac thermal evaporation plant. The films are deposited on to glass substrates at various temperatures 318, 363, 408 and 458K. The optical absorption spectra of these thin films are measured. The present studies reveal that the optical band gap energies of CoPc thin films are almost same on substrate temperature variation. The structure and surface morphology of the films deposited on glass substrates of temperatures 303, 363 and 458K are studied using X-ray diffractograms and Scanning Electron Micrographs (SEM, which show that there is a change in the crystallinity and surface morphology due to change in the substrate temperatures. Full width at half maximum (FWHM intensity of the diffraction peaks is also found reduced with increasing substrate temperatures. Scanning electron micrographs show that these crystals are needle like, which are interconnected at high substrate temperatures. The optical band gap energy is almost same on substrate temperature variation. Trap energy levels are also observed for these films.

  12. The photophysical and photochemical properties of new unmetallated and metallated phthalocyanines bearing four 5-chloroquinolin-8-yloxy substituents on peripheral sites

    Energy Technology Data Exchange (ETDEWEB)

    Nas, Asiye; Demirbaş, Ümit [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey); Pişkin, Mehmet [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy-Istanbul (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze, 41400 Kocaeli (Turkey); Kantekin, Halit, E-mail: halit@ktu.edu.tr [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2014-01-15

    The synthesis and characterization of novel peripherally tetrakis-(5-chloroquinolin-8-yloxy) substituted metal-free (4), zinc(II) (5), lead(II) (6), cobalt(II) (7), copper(II) (8) and nickel(II) (9) phthalocyanines are described for the first time in this study. The spectroscopic, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen production and photodegradation under light irradiation) of metal-free (4), zinc(II) (5) and lead(II) (6) phthalocyanines are investigated in N,N-dimetilformamid (DMF). The newly synthesized cobalt(II) (7), copper(II) (8) and nickel(II) (9) phthalocyanine compounds were not evaluated for this purpose due to open shell nature of these central metals in the phthalocyanine cavity. The influence of various the nature of the central metal ion (zinc, lead or without metal) on these properties has also been investigated and compared. -- Highlights: • The synthesis and characterization of novel peripherally tetrakis-(5-chloroquinolin-8-yloxy) substituted metal-free (4), zinc(II) (5), lead(II) (6), cobalt(II) (7), copper(II) (8) and nickel(II) (9) phthalocyanines. • The spectroscopic, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties of metal-free (4), zinc(II) (5) and lead(II) (6)phthalocyanines in N, N-dimetilformamid (DMF). • The influence of various the nature of the central metal ion (zinc, lead or without metal) on these properties.

  13. Two-electron oxidation of cobalt phthalocyanines by thionyl chloride: Implications for lithium/thionyl chloride batteries. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    Bernstein, P.A.; Lever, A.B.

    1989-10-20

    Cyclic voltammetry, DPV and electronic spectroscopy are used to study the reaction between thionyl chloride and cobalt phthalocyanine. SOCl2 reacts with (Co(I)Tn Pc(2-)) and Co(II)Tn Pc(2-) to give two-electron oxidized species. Implications for Li/SOCl2 batteries are discussed. Thionyl chloride also forms a mono SOCl2 adduct with Co(II)TnPc(2-). Driving forces (Delta E values) were calculated for CoTnPc comproportionation and CoTnPc + SOCl2 reactions. Rest potential measurements of a Li/SOCl2 cells show that addition of AlCl3 stabilizes the LiCl product as LiAlCl4. A catalytic two-electron mechanism is indicated for the reduction of thionyl chloride in a Li/SOCl2/(CoTnPc,C) battery.

  14. Short-lived γ-emitting metal isotopes phthalocyanine tetrasulfonic acid

    International Nuclear Information System (INIS)

    Lier, J. Van; Rousseau, J.; Autenrieth, D.

    1981-01-01

    New phthalocyanine tetrasulfonic acid metal complexes selected from technetium-99m, gallium-67, gallium-68, copper-64, chromium-51, cobalt-57, indium-111, mercury-197 and zinc-62 have been found to have affinity for malignant growth and thus are useful in detecting the presence, size and location thereof with radiation imaging device. (author)

  15. Manipulating individual dichlorotin phthalocyanine molecules on Cu(100) surface at room temperature by scanning tunneling microscopy

    International Nuclear Information System (INIS)

    Li, Chao; Xiang, Feifei; Wang, Zhongping; Liu, Xiaoqing; Jiang, Danfeng; Wang, Li; Wang, Guang; Zhang, Xueao; Chen, Wei

    2014-01-01

    Single molecule manipulations have been achieved on dichlorotin phthalocyanine(SnCl 2 Pc) molecules adsorbed on Cu (100) at room temperature. Scanning tunneling microscopy observations directly demonstrate that the individual SnCl 2 Pc molecules can be moved along the [100] direction on Cu(100) surface by employing a scanning tunneling microscope tip fixed at the special position of the molecules. The orientation of the molecule can be switched between two angles of ±28° with respect to the [011] surface direction in the same way. Dependences of the probability of molecular motion on the distances between the tip and the molecules reveal that the mechanism for such manipulation of a SnCl 2 Pc molecule is dominated by the repulsive interactions between the tip and the molecules. With the assistance of this manipulation process, a prototype molecular storage array with molecular orientation as information carrier and an artificial hydrogen bonded supramolecular structure have been constructed on the surface. (paper)

  16. Voltammetric, in-situ spectroelectrochemical and in-situ electrocolorimetric characterization of phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Koca, Atif [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey)], E-mail: akoca@eng.marmara.edu.tr; Bayar, Serife; Dincer, Hatice A. [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey); Gonca, Erguen [Department of Chemistry, Fatih University, TR34500 B.Cekmece, Istanbul (Turkey)

    2009-04-01

    In this work, electrochemical, and in-situ spectroelectrochemical characterization of the metallophthalocyanines bearing tetra-(1,1-(dicarbethoxy)-2-(2-methylbenzyl))-ethyl 3,10,17,24-tetra chloro groups were performed. Voltammetric and in-situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. The redox processes are generally diffusion-controlled, reversible and one-electron transfer processes. Differently lead phthalocyanine demetallized during second oxidation reaction while it was stable during reduction processes. An in-situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l'Eclairage) system of colorimetry, has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for the first time in this study.

  17. Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

    Science.gov (United States)

    Yang, Yang

    2010-12-23

    Si-E bondings in hexacoordinate silicon phthalocyanine were analyzed using bond order (BO), energy partition, atoms in molecules (AIM), electron localization function (ELF), and localized orbital locator (LOL). Bond models were proposed to explain differences between hexacoordinate and tetracoordinate Si-E bondings. Aromaticity of silicon phthalocyanine was investigated using nucleus-independent chemical shift (NICS), harmonic oscillator model of aromaticity (HOMA), conceptual density functional theory (DFT), ring critical point (RCP) descriptors, and delocalization index (DI). Structure, energy, bonding, and aromaticity of tetracoordinate silicon phthalocyanine were studied and compared with hexacoordinate one.

  18. Room temperature ferromagnetism in a phthalocyanine based carbon material

    International Nuclear Information System (INIS)

    Honda, Z.; Sato, K.; Sakai, M.; Fukuda, T.; Kamata, N.; Hagiwara, M.; Kida, T.

    2014-01-01

    We report on a simple method to fabricate a magnetic carbon material that contains nitrogen-coordinated transition metals and has a large magnetic moment. Highly chlorinated iron phthalocyanine was used as building blocks and potassium as a coupling reagent to uniformly disperse nitrogen-coordinated iron atoms on the phthalocyanine based carbon material. The iron phthalocyanine based carbon material exhibits ferromagnetic properties at room temperature and the ferromagnetic phase transition occurs at T c  = 490 ± 10 K. Transmission electron microscopy observation, X-ray diffraction analysis, and the temperature dependence of magnetization suggest that the phthalocyanine molecules form three-dimensional random networks in the iron phthalocyanine based carbon material

  19. Room temperature ferromagnetism in a phthalocyanine based carbon material

    Energy Technology Data Exchange (ETDEWEB)

    Honda, Z., E-mail: honda@fms.saitama-u.ac.jp; Sato, K.; Sakai, M.; Fukuda, T.; Kamata, N. [Graduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570 (Japan); Hagiwara, M.; Kida, T. [KYOKUGEN (Center for Quantum Science and Technology under Extreme Conditions), Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)

    2014-02-07

    We report on a simple method to fabricate a magnetic carbon material that contains nitrogen-coordinated transition metals and has a large magnetic moment. Highly chlorinated iron phthalocyanine was used as building blocks and potassium as a coupling reagent to uniformly disperse nitrogen-coordinated iron atoms on the phthalocyanine based carbon material. The iron phthalocyanine based carbon material exhibits ferromagnetic properties at room temperature and the ferromagnetic phase transition occurs at T{sub c} = 490 ± 10 K. Transmission electron microscopy observation, X-ray diffraction analysis, and the temperature dependence of magnetization suggest that the phthalocyanine molecules form three-dimensional random networks in the iron phthalocyanine based carbon material.

  20. Supramolecular assemblies of pyridyl porphyrin and diazadithia phthalocyanine

    Directory of Open Access Journals (Sweden)

    OZER BEKAROGLU

    1999-08-01

    Full Text Available In this paper we report for the first time on a mixed complex between the cationic porphyrin 5, 10, 15, 20-tetra-N- -methyl-pyrydinium-p-il porphyrin (TMPyP and a new metal phthalocyanine with four 16-membered diazadithia macrocycles (denoted here as Pc16, in order to obtain an active complex with an intense absorption on the lower energy side of the visible spectrum and with a higher sensitivity in photodynamic therapy of cancer. The dimerization constant for Pc16 and also the ratio between the oscillator strengths for monomeric and dimeric forms of this compound, were evaluated. The ratio between these oscillator strengths was 2.01 showing a certain dimerization process. The Job mathematical method allowed the establishment of the stoichiometry and the formation constants for the heteroaggregates between the porphyrin and the phthalocy- anine (a diad between one phthalocyanine molecule and one porphyrin molecule and a triad between two phthalocyanine molecules and only one porphyrin molecule. The coulombic attraction resulting from the p-p interaction of the two highly conjugated macrocycles and from the interaction between the substituents, favors a face-to-face geometry.

  1. Screen-Printed Carbon Electrodes Modified with Cobalt Phthalocyanine for Selective Sulfur Detection in Cosmetic Products

    Directory of Open Access Journals (Sweden)

    Ying Shih

    2011-06-01

    Full Text Available Cobalt phthalocyanine (CoPc films were deposited on the surface of a screen-printed carbon electrode using a simple drop coating method. The cyclic voltammogram of the resulting CoPc modified screen-printed electrode (CoPc/SPE prepared under optimum conditions shows a well-behaved redox couple due to the (CoI/CoII system. The CoPc/SPE surface demonstrates excellent electrochemical activity towards the oxidation of sulfur in a 0.01 mol·L−1 NaOH. A linear calibration curve with the detection limit (DL, S/N = 3 of 0.325 mg·L−1 was achieved by CoPc/SPE coupled with flow injection analysis of the sulfur concentration ranging from 4 to 1120 mg·L−1. The precision of the system response was evaluated (3.60% and 3.52% RSD for 12 repeated injections, in the range of 64 and 480 mg·L−1 sulfur. The applicability of the method was successfully demonstrated in a real sample analysis of sulfur in anti-acne creams, and good recovery was obtained. The CoPc/SPE displayed several advantages in sulfur determination including easy fabrication, high stability, and low cost.

  2. Structural and luminescence properties of GaN nanowires grown using cobalt phthalocyanine as catalyst

    Science.gov (United States)

    Yadav, Shivesh; Rodríguez-Fernández, Carlos; de Lima, Mauricio M.; Cantarero, Andres; Dhar, Subhabrata

    2015-12-01

    Catalyst free methods have usually been employed to avoid any catalyst induced contamination for the synthesis of GaN nanowires with better transport and optical properties. Here, we have used a catalytic route to grow GaN nanowires, which show good optical quality. Structural and luminescence properties of GaN nanowires grown by vapor-liquid-solid technique using cobalt phthalocyanine as catalyst are systematically investigated as a function of various growth parameters such as the growth temperature and III/V ratio. The study reveals that most of the nanowires, which are several tens of microns long, grow along [ 10 1 ¯ 0 ] direction. Interestingly, the average wire diameter has been found to decrease with the increase in III/V ratio. It has also been observed that in these samples, defect related broad luminescence features, which are often present in GaN, are completely suppressed. At all temperatures, photoluminescence spectrum is found to be dominated only by a band edge feature, which comprises of free and bound excitonic transitions. Our study furthermore reveals that the bound excitonic feature is associated with excitons trapped in certain deep level defects, which result from the deficiency of nitrogen during growth. This transition has a strong coupling with the localized vibrational modes of the defects.

  3. Simultaneous Reduction of CO 2 and Splitting of H 2 O by a Single Immobilized Cobalt Phthalocyanine Electrocatalyst

    KAUST Repository

    Morlanés, Natalia

    2016-04-12

    Perfluorinated cobalt phthalocyanine (CoFPc) immobilized on carbon electrodes was found to electrocatalyze the reduction of CO2 selectively to CO in an aqueous solution. The conversion of CO2 became apparent at -0.5 V vs RHE, and the Faradaic efficiency for the CO production reached as high as 93% at -0.8 V vs RHE. Highly stable electrolysis of CO2/H2O into CO/O2 was achieved for 12 h by applying the same catalyst as the cathode for CO2 reduction and the anode for water oxidation. This result indicates the highly robust nature of the CoFPc at wide range of potentials from -0.9 V to +2.2 V vs RHE, demonstrating the potential bipolar electrolytic system for CO2/H2O electrolysis, using the single-site molecular CoFPc-based electrocatalyst, which is simple, inexpensive, robust, and efficient. © 2016 American Chemical Society.

  4. Filler size effects on the conductivity of polymer nanocomposites: semiconductive phthalocyanine nanoparticles in epoxy matrices

    NARCIS (Netherlands)

    Yuan, M.; Brokken-Zijp, J.C.M.; Huijbregts, L.J.; With, de G.

    2008-01-01

    Three Cobalt(III) phthalocyanine (Phthalcon) powders with different particle sizes and chemical compositions, but almost equal XRD spectra and powder conductivity were synthesized and used as conductive fillers in crosslinked epoxy matrices. Two of these Phthalcons are new compounds. The relation

  5. Multi-polar resistance switching and memory effect in copper phthalocyanine junctions

    International Nuclear Information System (INIS)

    Qiao Shi-Zhu; Kang Shi-Shou; Li Qiang; Zhong Hai; Kang Yun; Yu Shu-Yun; Han Guang-Bing; Yan Shi-Shen; Mei Liang-Mo; Qin Yu-Feng

    2014-01-01

    Copper phthalocyanine junctions, fabricated by magnetron sputtering and evaporating methods, show multi-polar (unipolar and bipolar) resistance switching and the memory effect. The multi-polar resistance switching has not been observed simultaneously in one organic material before. With both electrodes being cobalt, the unipolar resistance switching is universal. The high resistance state is switched to the low resistance state when the bias reaches the set voltage. Generally, the set voltage increases with the thickness of copper phthalocyanine and decreases with increasing dwell time of bias. Moreover, the low resistance state could be switched to the high resistance state by absorbing the phonon energy. The stability of the low resistance state could be tuned by different electrodes. In Au/copper phthalocyanine/Co system, the low resistance state is far more stable, and the bipolar resistance switching is found. Temperature dependence of electrical transport measurements demonstrates that there are no obvious differences in the electrical transport mechanism before and after the resistance switching. They fit quite well with Mott variable range hopping theory. The effect of Al 2 O 3 on the resistance switching is excluded by control experiments. The holes trapping and detrapping in copper phthalocyanine layer are responsible for the resistance switching, and the interfacial effect between electrodes and copper phthalocyanine layer affects the memory effect. (interdisciplinary physics and related areas of science and technology)

  6. The complex nature of phthalocyanine/gold interfaces

    International Nuclear Information System (INIS)

    Lindner, Susi; Treske, Uwe; Knupfer, Martin

    2013-01-01

    We compare the electronic properties of the interface between Au(1 0 0) and cobalt phthalocyanine (CoPc), fluorinated F 16 CoPc as well as CuPc using X-ray photoemission spectroscopy and valence band ultra-violet photoemission spectroscopy. Our results show that in addition to the formation of an interface dipole at the interfaces of CoPc and F 16 CoPc to gold, there is a local charge transfer to the central Co ion, which as a result is reduced to Co(I).

  7. Synthesis, photophysical and electrochemical properties of water–soluble phthalocyanines bearing 8-hydroxyquinoline-5-sulfonicacid derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Günsel, Armağan; Kocabaş, Sibel; Bilgiçli, Ahmet T. [Department of Chemistry, Sakarya University, 54140 Esentepe, Sakarya (Turkey); Güney, Sevgi [Department of Chemistry, Istanbul Technical University, 34469 Maslak, Istanbul (Turkey); Kandaz, Mehmet, E-mail: mkandaz@sakarya.edu.tr [Department of Chemistry, Sakarya University, 54140 Esentepe, Sakarya (Turkey)

    2016-08-15

    We have presented in this paper, the synthesis, characterization, photophysical properties and electrochemical characterization of water soluble phthalocyanines (Pcs) bearing 8-hydroxyquinoline-5-sulfonicacid conjugates and their cationic quaternized counterpart that play important roles their application in photodynamic therapy (PDT). The periphery and non-periphery substituted phthalocyanines show high solubility and low aggregation tendency due to bulky 8-hydroxyquinoline-5-sulfonicacid steric hindrance moieties and axially bound counter chlorine anion. Singlet oxygen quantum yields, photodegradation quantum yields, photophysical properties and also the nature of the substituent and solvent effect on the photophysical and photochemical parameters of α-ZnPc and β-ZnPc are reported. In electrovalent cobalt (II) and manganese (III) compounds, metal based electron transfer reactions have been observed in addition to the common phthalocyanine ring-based electron transfer processes. The effect of point of substitution on the electrochemical properties of newly synthesized phthalocyanines substituted with 8-hydroxyquinoline-5-sulfonicacid group were evaluated.

  8. Cobalt phthalocyanine modified electrodes utilised in electroanalysis: nano-structured modified electrodes vs. bulk modified screen-printed electrodes.

    Science.gov (United States)

    Foster, Christopher W; Pillay, Jeseelan; Metters, Jonathan P; Banks, Craig E

    2014-11-19

    Cobalt phthalocyanine (CoPC) compounds have been reported to provide electrocatalytic performances towards a substantial number of analytes. In these configurations, electrodes are typically constructed via drop casting the CoPC onto a supporting electrode substrate, while in other cases the CoPC complex is incorporated within the ink of a screen-printed sensor, providing a one-shot economical and disposable electrode configuration. In this paper we critically compare CoPC modified electrodes prepared by drop casting CoPC nanoparticles (nano-CoPC) onto a range of carbon based electrode substrates with that of CoPC bulk modified screen-printed electrodes in the sensing of the model analytes L-ascorbic acid, oxygen and hydrazine. It is found that no "electrocatalysis" is observed towards L-ascorbic acid using either of these CoPC modified electrode configurations and that the bare underlying carbon electrode is the origin of the obtained voltammetric signal, which gives rise to useful electroanalytical signatures, providing new insights into literature reports where "electrocatalysis" has been reported with no clear control experiments undertaken. On the other hand true electrocatalysis is observed towards hydrazine, where no such voltammetric features are witnessed on the bare underlying electrode substrate.

  9. Controlling the Orbital Sequence in Individual Cu-Phthalocyanine Molecules

    NARCIS (Netherlands)

    Uhlmann, C.; Swart, I.; Repp, J.

    2013-01-01

    We report on the controlled change of the energetic ordering of molecular orbitals. Negatively charged copper(II)phthalocyanine on NaCl/Cu(100) undergoes a Jahn–Teller distortion that lifts the degeneracy of two frontier orbitals. The energetic order of the levels can be controlled by Au and Ag

  10. Comparative study of electronic and magnetic properties of Pc ( = Fe, Co) molecules physisorbed on 2D MoS and graphene

    KAUST Repository

    Haldar, Soumyajyoti

    2017-09-13

    In this paper, we have done a comparative study of electronic and magnetic properties of iron phthalocyanine (FePc) and cobalt phthalocyanine (CoPc) molecules physisorbed on monolayer of MoS$_2$ and graphene by using density functional theory. Various different types of physisorption sites have been considered for both surfaces. Our calculations reveal that the $M$Pc molecules prefer the S-top position on MoS$_2$. However, on graphene, FePc molecule prefers the bridge position while CoPc molecule prefers the top position. The $M$Pc molecules are physisorbed strongly on the MoS$_2$ surface than the graphene ($\\\\sim$ 2.5 eV higher physisorption energy). Analysis of magnetic properties indicates the presence of strong spin dipole moment opposite to the spin moment and hence a huge reduction of effective spin moment can be observed. Our calculations of magnetic anisotropy energies using both variational approach and $2^{nd}$ order perturbation approach indicate no significant changes after physisorption. In case of FePc, an out-of-plane easy axis and in case of CoPc, an in-plane easy axis can be seen. Calculations of work function indicate a reduction of MoS$_2$ work function $\\\\sim$ 1 eV due to physisorption of $M$Pc molecules while it does not change significantly in case of graphene.

  11. Cobalt Phthalocyanine Modified Electrodes Utilised in Electroanalysis: Nano-Structured Modified Electrodes vs. Bulk Modified Screen-Printed Electrodes

    Directory of Open Access Journals (Sweden)

    Christopher W. Foster

    2014-11-01

    Full Text Available Cobalt phthalocyanine (CoPC compounds have been reported to provide electrocatalytic performances towards a substantial number of analytes. In these configurations, electrodes are typically constructed via drop casting the CoPC onto a supporting electrode substrate, while in other cases the CoPC complex is incorporated within the ink of a screen-printed sensor, providing a one-shot economical and disposable electrode configuration. In this paper we critically compare CoPC modified electrodes prepared by drop casting CoPC nanoparticles (nano-CoPC onto a range of carbon based electrode substrates with that of CoPC bulk modified screen-printed electrodes in the sensing of the model analytes L-ascorbic acid, oxygen and hydrazine. It is found that no “electrocatalysis” is observed towards L-ascorbic acid using either of these CoPC modified electrode configurations and that the bare underlying carbon electrode is the origin of the obtained voltammetric signal, which gives rise to useful electroanalytical signatures, providing new insights into literature reports where “electrocatalysis” has been reported with no clear control experiments undertaken. On the other hand true electrocatalysis is observed towards hydrazine, where no such voltammetric features are witnessed on the bare underlying electrode substrate.

  12. Surface properties of self-assembled monolayer films of tetra-substituted cobalt, iron and manganese alkylthio phthalocyanine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Akinbulu, Isaac Adebayo; Khene, Samson [Department of Chemistry, Rhodes University, Grahamstown 6140 (South Africa); Nyokong, Tebello, E-mail: t.nyokong@ru.ac.z [Department of Chemistry, Rhodes University, Grahamstown 6140 (South Africa)

    2010-09-30

    Self-assembled monolayer (SAM) films of iron (SAM-1), cobalt (SAM-2) and manganese (SAM-3) phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the non-peripheral positions, were formed on gold electrode in dimethylformamide (DMF). Electrochemical, impedimentary and surface properties of the SAM films were investigated. Cyclic voltammetry was used to investigate the electrochemical properties of the films. Ability of the films to inhibit common faradaic processes on bare gold surface (gold oxidation, solution redox chemistry of [Fe(H{sub 2}O){sub 6}]{sup 3+}/[Fe(H{sub 2}O){sub 6}]{sup 2+} and underpotential deposition (UDP) of copper) was investigated. Electrochemical impedance spectroscopy (EIS), using [Fe(CN){sub 6}]{sup 3-/4-} redox process as a probe, offered insights into the electrical properties of the films/electrode interfaces. Surface properties of the films were probed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The films were employed for the electrocatalytic oxidation of the pesticide, carbofuran. Electrocatalysis was evidenced from enhanced current signal and less positive oxidation potential of the pesticide on each film, relative to that observed on the bare gold electrode. Mechanism of electrocatalytic oxidation of the pesticide was studied using rotating disc electrode voltammetry.

  13. Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

    Science.gov (United States)

    Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

    2008-07-31

    Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

  14. Investigation of interaction between alkoxy substituted phthalocyanines with different lengths of alkyl residue and bovine serum albumin

    Energy Technology Data Exchange (ETDEWEB)

    Lebedeva, Natalya Sh., E-mail: nsl@isc-ras.ru [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaya, 1, 153045 Ivanovo (Russian Federation); Gubarev, Yury A.; Vyugin, Anatoly I. [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaya, 1, 153045 Ivanovo (Russian Federation); Koifman, Oscar I. [Research Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, 153000 Ivanovo (Russian Federation)

    2015-10-15

    Interaction between bovine serum albumin and alkoxy substituted phthalocyanines was studied by means of electron absorption spectroscopy, fluorescence spectroscopy and viscosimetry. The binding constants and binding distance were calculated. It was found that ZnPc(4-NH-CO-C{sub 6}H{sub 4}-OC{sub 10}H{sub 21}){sub 4} prevents twisting of BSA molecule and localizes between subdomains IB and IIA in protein globule. ZnPc(4-NH-CO-C{sub 6}H{sub 4}-OC{sub 6}H{sub 13}){sub 4} and ZnPc(4-NH-CO-C{sub 6}H{sub 4}-OC{sub 8}H{sub 17}){sub 4} are located on the outer surface of the protein globule. In the case of ZnPc(4-NH-CO-C{sub 6}H{sub 4}-OC{sub 3}H{sub 7}){sub 4} it can be assumed that the phthalocyanine molecule is in the immediate vicinity of the subdomains IB and IIA. - Highlights: • Interaction between bovine serum albumin and alkoxy substituted phthalocyanines was studied by means of electron absorption spectroscopy, fluorescence spectroscopy and viscosimetry. • The binding constants and binding distance were calculated by using the Scatchard method. • Photochemical characteristics of phthalocyanines of studied phthalocyanines are defined. • Localization of phthalocyanines on the protein globule is defined.

  15. Adsorption of metal-phthalocyanine molecules onto the Si(111) surface passivated by δ doping: Ab initio calculations

    Science.gov (United States)

    Veiga, R. G. A.; Miwa, R. H.; McLean, A. B.

    2016-03-01

    We report first-principles calculations of the energetic stability and electronic properties of metal-phthalocyanine (MPc) molecules (M = Cr, Mn, Fe, Co, Ni, Cu, and Zn) adsorbed on the δ -doped Si(111)-B (√{3 }×√{3 }) reconstructed surface. (i) It can be seen that CrPc, MnPc, FePc, and CoPc are chemically anchored to the topmost Si atom. (ii) Contrastingly, the binding of the NiPc, CuPc, and ZnPc molecules to the Si (111 ) -B (√{3 }×√{3 }) surface is exclusively ruled by van der Waals interactions, the main implication being that these molecules may diffuse and rearrange to form clusters and/or self-organized structures on this surface. The electronic structure calculations reveal that in point (i), owing to the formation of the metal-Si covalent bond, the net magnetic moment of the molecule is quenched by 1 μB , remaining unchanged in point (ii). In particular, the magnetic moment of CuPc (1 μB ) is preserved after adsorption. Finally, we verify that the formation of ZnPc, CuPc, and NiPc molecular (self-assembled) arrangements on the Si(111)-B (√{3 }×√{3 } ) surface is energetically favorable, in good agreement with recent experimental findings.

  16. Zinc phthalocyanine thin film and chemical analyte interaction studies by density functional theory and vibrational techniques

    International Nuclear Information System (INIS)

    Saini, G S S; Singh, Sukhwinder; Kumar, Ranjan; Tripathi, S K; Kaur, Sarvpreet; Sathe, Vasant

    2009-01-01

    Thin films of zinc phthalocyanine have been deposited on KBr and glass substrates by the thermal evaporation method and characterized by the x-ray diffraction, optical, infrared and Raman techniques. The observed x-ray diffraction and infrared absorption spectra of as-deposited thin films suggest the presence of an α crystalline phase. Infrared and Raman spectra of thin films after exposure to vapours of ammonia and methanol have also been recorded. Shifts in the position of some IR and Raman bands in the spectra of exposed films have been observed. Some bands also show changes in their intensity on exposure. Increased charge on the phthalocyanine ring and out-of-plane distortion of the core due to interaction between zinc phthalocyanine and vapour molecules involving the fifth coordination site of the central metal ion may be responsible for the band shifts. Changes in the intensity of bands are interpreted in terms of the lowering of molecular symmetry from D 4h to C 4v due to doming of the core. Molecular parameters and Mulliken atomic charges of zinc phthalocyanine and its complexes with methanol and ammonia have been calculated from density functional theory. The binding energy of the complexes have also been calculated. Calculated values of the energy for different complexes suggest that axially coordinated vapour molecules form the most stable complex. Calculated Mulliken atomic charges show net charge transfer from vapour molecules to the phthalocyanine ring for the most stable complex.

  17. Optimized adsorption of sulfonated phthalocyanines on ZnO electrodes and their characterization in dye- sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Falgenhauer, Jane; Loewenstein, Thomas; Schlettwein, Derck [Institute of Applied Physics, Justus-Liebig-University Giessen (Germany)

    2010-07-01

    Phthalocyanines belong to the most stable industrial dyes and show some of the highest molar extinction coefficients in the visible range. ZnO is known as a wide band gap semiconductor material which can be conveniently prepared as a porous electrode from solution-based processes. Sulfonated phthalocyanines were adsorbed at such electrodeposited porous ZnO thin films to work as a photosensitizer in a dye sensitized solar cell (DSSC). The adsorption solution of the phthalocyanine was modified in its composition and by adding different detergents in different concentrations. The adsorption solutions and the sensitized ZnO films were investigated by UV/Vis spectroscopy to characterize the aggregation of the dye molecules. Most of the detergents used could minimize the aggregation of the dye molecules in the adsorption solution without hindering the adsorption of the phthalocyanine on the ZnO surface. The photoelectrochemical characteristics of the resulting test cells were determined using a standard liquid electrolyte. The efficiency of the cells did not reach the expected level and reasons for this are discussed based on film morphology, amount of adsorbed dye molecules, competition by detergent adsorption, the optical absorbance of the dyes in the film and aggregate formation.

  18. Functionalization of nanocrystalline diamond films with phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Petkov, Christo [Institute of Nanostructure Technologies and Analytics (INA), Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel (Germany); Reintanz, Philipp M. [Institute of Chemistry, Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel (Germany); Kulisch, Wilhelm [Institute of Nanostructure Technologies and Analytics (INA), Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel (Germany); Degenhardt, Anna Katharina [Institute of Chemistry, Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel (Germany); Weidner, Tobias [Max Planck Institute for Polymer Research, Mainz (Germany); Baio, Joe E. [School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, OR (United States); Merz, Rolf; Kopnarski, Michael [Institut für Oberflächen- und Schichtanalytik (IFOS), Kaiserslautern (Germany); Siemeling, Ulrich [Institute of Chemistry, Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel (Germany); Reithmaier, Johann Peter [Institute of Nanostructure Technologies and Analytics (INA), Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel (Germany); Popov, Cyril, E-mail: popov@ina.uni-kassel.de [Institute of Nanostructure Technologies and Analytics (INA), Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel (Germany)

    2016-08-30

    Highlights: • Grafting of phthalocyanines on nanocrystalline diamond films with different terminations. • Pc with different central atoms and side chains synthesized and characterized. • Attachment of Pc on H- and O-terminated NCD studied by XPS and NEXAFS spectroscopy. • Orientation order of phthalocyanine molecules on NCD surface. - Abstract: Phthalocyanine (Pc) derivatives containing different central metal atoms (Mn, Cu, Ti) and different peripheral chains were synthesized and comprehensively characterized. Their interaction with nanocrystalline diamond (NCD) films, as-grown by hot-filament chemical vapor deposition or after their modification with oxygen plasma to exchange the hydrogen termination with oxygen-containing groups, was studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The elemental composition as determined by XPS showed that the Pc were grafted on both as-grown and O-terminated NCD. Mn, Cu and Ti were detected together with N stemming from the Pc ring and S in case of the Ti-Pc from the peripheral ligands. The results for the elemental surface composition and the detailed study of the N 1s, S 2p and O 1s core spectra revealed that Ti-Pc grafted better on as-grown NCD but Cu-Pc and Mn-Pc on O-terminated films. Samples of Mn-Pc on as-grown and O-terminated NCD were further investigated by NEXAFS spectroscopy. The results showed ordering of the grafted molecules, laying flat on the H-terminated NCD surface while only the macrocycles were oriented parallel to the O-terminated surface with the peripheral chains perpendicular to it.

  19. Synthesis of mesogenic phthalocyanine-C60 donor–acceptor dyads designed for molecular heterojunction photovoltaic devices

    Directory of Open Access Journals (Sweden)

    Yves Henri Geerts

    2009-10-01

    Full Text Available A series of phthalocyanine-C60 dyads 2a–d was synthesized. Key steps in their synthesis are preparation of the low symmetry phthalocyanine intermediate by the statistical condensation of two phthalonitriles, and the final esterification of the fullerene derivative bearing a free COOH group. Structural characterization of the molecules in solution was performed by NMR spectroscopy, UV–vis spectroscopy and cyclic voltammetry. Preliminary studies suggest formation of liquid crystalline (LC mesophases for some of the prepared dyads. To the best of our knowledge, this is the first example of LC phthalocyanine-C60 dyads.

  20. Spectroscopic insights on selfassembly and excited state interactions between rhodamine and phthalocyanine molecules.

    Science.gov (United States)

    Geng, Hao; Zhang, Xian-Fu

    2015-03-15

    The absorption and fluorescence spectra as well as fluorescence lifetimes of tetrasulfonated zinc phthalocyanine ZnPc(SO3Na)4 were measured in the absence and presence of four rhodamine dyes, Rhodamine B (RB), Ethyl rhodamine B (ERB), Rhodamine 6G (R6G), Rhodamine 110 (R110), and Pyronine B (PYB). The ground state complexes of phthalocyanine-(Rhodamine)2 were observed which exhibit new absorption bands. The binding constants are all very large (0.86×10(5)-0.22×10(8) M(-1)), suggesting rhodamine-phthalocyanine pairs are very good combinations for efficient selfassembly. Both the fluorescence intensity and the lifetime values of ZnPc(SO3Na)4 were decreased by the presence of rhodamines. The structural effect of rhodamines on selfassembly is significant. The ground state binding and dynamic quenching capability is PYB>R6G>ERB>RB>R110. The dynamic fluorescence quenching is due to the photoinduced electron transfer (PET). The PET rate constant is very large and in the order of 10(13) M(-1) s(-1), much greater than kf and kic (in the order of 10(8) M(-1) s(-1)), which means that the PET efficiency is almost 100%. Therefore the non-covalent Pc-rhodamine is a very good pair of donor/acceptor for potential efficient solar energy conversion. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Electroanalysis of formetanate hydrochloride by a cobalt phthalocyanine functionalized multiwalled carbon nanotubes modified electrode: characterization and application in fruits

    International Nuclear Information System (INIS)

    Ribeiro, Francisco Wirley Paulino; Souza Lucas, Francisco Willian de; Mascaro, Lucia H.; Morais, Simone; Naftali da Silva Casciano, Paulo; Lima-Neto, Pedro de; Correia, Adriana N.

    2016-01-01

    Highlights: • A Co-phthalocyanine functionalized MWCNT modified carbon electrode was developed. • Formetanate (FMT) electroanalytical behavior is consistent with an ECE mechanism. • CoPc-fMWCNT/GCE exhibited good analytical performance to quantify FMT. • CoPc-fMWCNT/GCE was successfully applied to fruits (recoveries ≥ 94.2%). - Abstract: This study characterizes the electroanalytical behavior of the carbamate pesticide formetanate hydrochloride (FMT) at a cobalt phthalocyanine (CoPc) functionalized multiwalled carbon nanotubes (fMWCNT) modified glassy carbon electrode (CoPc-fMWCNT/GCE). Nafion ® was used to improve solubility and dispersibility of fMWCNT. The construction of the developed electrode was characterized by high-resolution field-emission gun scanning electron microscopy, Raman spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. FMT exhibited a behavior consistent with a three-step reaction of the electrochemical-chemical-electrochemical mechanistic type at CoPc-fMWCNT/GCE (three anodic peaks at 0.26, 0.55 and 1.2 V, and two cathodic peaks at 0.35 and 0.50 V vs. Ag/AgCl/3 M KCl). Highly reproducible and well-defined peaks were obtained at the optimum experimental conditions (Britton-Robinson buffer at pH 5.0, accumulation potential 1.55 V, accumulation time 5 s, frequency 100 s −1 , amplitude 30 mV, and scan increment 3 mV). Peak currents were found to be proportional to the FMT concentrations in the range of 9.80 × 10 −8 to 3.92 × 10 −6 mol dm −3 with a detection limit (LOD) of 9.7 × 10 −8 mol dm −3 . The modification of GCE with CoPc-fMWCNT enhanced the electrocatalytic activity and provided high sensitivity (3.51 A mol −1 dm 3 ). The developed electroanalytical methodology was successfully applied to FMT residue analysis in mango and grape samples with recoveries in the range of 94.2 ± 4.5 to 105.7 ± 1.8%. The proposed electroanalytical approach represents a reliable, sensitive and environmental

  2. Bioinspired catalytic generation of high-valent cobalt-oxo species by the axially coordinated CoPc on pyridine-functionalized MWCNTs for the elimination of organic contaminants

    Science.gov (United States)

    Li, Nan; Wang, Ying; Wu, Chenren; Lu, Wangyang; Pei, Kemei; Chen, Wenxing

    2018-03-01

    Enzymes have always been a source of inspiration for the design and improvement of catalysts. Many examples are occurring in heme/non-heme metalloenzymes with the generation of active high-valent metal-oxo intermediates that are controlled by the surrounding amino acids/protein and axial residue ligands, facilitating the efficient oxidation of substrates in biochemical processes. Here, the high-valent cobalt-oxo species have been formed during the heterolysis of H2O2 activated by the bioinspired catalyst, axially coordinated cobalt phthalocyanine (CoPc) on pyridine-functionalized multi-walled carbon nanotubes (MWCNTs-Py), characterized by ultraviolet-visible and X-ray photoelectron spectroscopy. Formation process of the active cobalt-oxo species has been further confirmed by electrospray ionization mass spectrometry analysis and the results from the density functional theory (B3LYP/6-311G) calculations. Such high-valent cobalt-oxo species exhibit high reactivity and enough persistence for the oxidation of the target substrate, C.I. Acid Red 1. The oxidation products are nearly biodegradable small molecules identified by ultra-performance liquid chromatography/high-definition mass spectrometry. This strategy provides a foundation on developing efficient and persistent catalytic system, in particular oxidation processes based on the complex catalysts with N4 macrocycle structures.

  3. Comparison of interaction mechanisms of copper phthalocyanine and nickel phthalocyanine thin films with chemical vapours

    Science.gov (United States)

    Ridhi, R.; Singh, Sukhdeep; Saini, G. S. S.; Tripathi, S. K.

    2018-04-01

    The present study deals with comparing interaction mechanisms of copper phthalocyanine and nickel phthalocyanine with versatile chemical vapours: reducing, stable aromatic and oxidizing vapours namely; diethylamine, benzene and bromine. The variation in electrical current of phthalocyanines with exposure of chemical vapours is used as the detection parameter for studying interaction behaviour. Nickel phthalocyanine is found to exhibit anomalous behaviour after exposure of reducing vapour diethylamine due to alteration in its spectroscopic transitions and magnetic states. The observed sensitivities of copper phthalocyanine and nickel phthalcyanine films are different in spite of their similar bond numbers, indicating significant role of central metal atom in interaction mechanism. The variations in electronic transition levels after vapours exposure, studied using UV-Visible spectroscopy confirmed our electrical sensing results. Bromine exposure leads to significant changes in vibrational bands of metal phthalocyanines as compared to other vapours.

  4. Adsorption of Cu phthalocyanine on Pt modified Ge(001): A scanning tunneling microscopy study

    NARCIS (Netherlands)

    Saedi, A.; Berkelaar, Robin P.; Kumar, Avijit; Poelsema, Bene; Zandvliet, Henricus J.W.

    2010-01-01

    The adsorption configurations of copper phthalocyanine (CuPc) molecules on platinum-modified Ge(001) have been studied using scanning tunneling microscopy. After deposition at room temperature and cooling down to 77 K the CuPc molecules are still dynamic. However, after annealing at 550±50 K, the

  5. Photophysical, Photochemical, and BQ Quenching Properties of Zinc Phthalocyanines with Fused or Interrupted Extended Conjugation

    Directory of Open Access Journals (Sweden)

    Gülşah Gümrükçü

    2014-01-01

    Full Text Available The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II phthalocyanines containing four Schiff’s base substituents attached directly and through phenyleneoxy-bridges on peripheral positions are reported. The group effects on peripheral position and the continual and intermittent conjugation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen, and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO, dimethylformamide (DMF, and tetrahydrofurane (THF. Among the different substituents, phthalocyanines with cinnamaldimine moieties (1c and 2c have the highest singlet oxygen quantum yields (ΦΔ and those with nitro groups (1a and 2a have the highest fluorescence quantum yields in all the solvents used. The fluorescence of the substituted zinc(II phthalocyanine complexes is effectively quenched by 1,4-benzoquinone (BQ in these solvents.

  6. Electronic and transport properties of Cobalt-based valence tautomeric molecules and polymers

    Science.gov (United States)

    Chen, Yifeng; Calzolari, Arrigo; Buongiorno Nardelli, Marco

    2011-03-01

    The advancement of molecular spintronics requires further understandings of the fundamental electronic structures and transport properties of prototypical spintronics molecules and polymers. Here we present a density functional based theoretical study of the electronic structures of Cobalt-based valence tautomeric molecules Co III (SQ)(Cat)L Co II (SQ)2 L and their polymers, where SQ refers to the semiquinone ligand, and Cat the catecholate ligand, while L is a redox innocent backbone ligand. The conversion from low-spin Co III ground state to high-spin Co II excited state is realized by imposing an on-site potential U on the Co atom and elongating the Co-N bond. Transport properties are subsequently calculated by extracting electronic Wannier functions from these systems and computing the charge transport in the ballistic regime using a Non-Equilibrium Green's Function (NEGF) approach. Our transport results show distinct charge transport properties between low-spin ground state and high-spin excited state, hence suggesting potential spintronics devices from these molecules and polymers such as spin valves.

  7. Immobilization of glucose oxidase on graphene and cobalt phthalocyanine composite and its application for the determination of glucose.

    Science.gov (United States)

    Mani, Veerappan; Devasenathipathy, Rajkumar; Chen, Shen-Ming; Huang, Sheng-Tung; Vasantha, V S

    2014-11-01

    We described a simple and facile chemical reduction strategy for the preparation of graphene (GR)-cobalt phthalocyanine (CoPc) composite and explored it for the enzymatic determination of glucose. CoPc is an active mediator and electrocatalysts for the immobilization of GOx and determination of glucose. However, it is not stable on the electrode surface and also suffers from lack of conductivity. Here, we have employed GR as the suitable support to stabilize CoPc through simple chemical reduction method and the resulting composite has been used for the glucose biosensor application. Scanning electron microscopy, X-ray diffraction and Energy-dispersive X-ray spectroscopy studies confirmed the successful formation of composite. Direct electron transfer of glucose oxidase (GOx) was observed with well defined redox peaks at the formal potential of -0.44 V. The amount of electroactive GOx (Г) and electron transfer rate constant (ks) were calculated to be 3.77×10(-10) mol cm(-2) and 3.57 s(-1), respectively. The fabricated amperometric biosensor detects glucose in wide linear concentration range from 10 μM to 14.8 mM with high sensitivity of 5.0 9μA mM(-1) cm(-2). The sensor offered very low detection limit (LOD) of 1.6 μM. In addition, practical feasibility of the sensor has been explored in screen printing carbon electrode with accurate determination of glucose present in human blood serum and urine samples. Furthermore, the sensor exhibited appreciable stability, repeatability and reproducibility results. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. Binary molecular layers of C-60 and copper phthalocyanine on Au(111) : Self-organized nanostructuring

    NARCIS (Netherlands)

    Stöhr, Meike; Wagner, Thorsten; Gabriel, Markus; Weyers, Bastian; Möller, Rolf

    The binary molecular system of C-60 and copper phthalocyanine(CuPc) molecules has been investigated by scanning tunneling microscopy (STM) at room temperature and at 50 K. As substrate Au(111) was chosen. When C-60 and CuPc molecules are sequentially deposited, it is found that well-ordered domains

  9. Electronic properties and orbital-filling mechanism in Rb-intercalated copper phthalocyanine

    NARCIS (Netherlands)

    Evangelista, F.; Gotter, R.; Mahne, N.; Nannarone, S.; Ruocco, A.; Rudolf, P.

    2008-01-01

    The evolution of the electronic properties of a thin film of copper phthalocyanine deposited on Al(100) and progressively intercalated with rubidium atoms was followed by photoemission and X-ray absorption spectroscopies. Electron donation from the Rb atoms to the C32H16N8Cu molecules results in the

  10. Organização supramolecular da ftalocianina de cobalto(II e seu efeito na oxidação do aminoácido cisteína Supramolecular organization of cobalt (II phthalocyanine on the pathway of cysteine oxidation

    Directory of Open Access Journals (Sweden)

    Amanda Costa Santos

    2010-01-01

    Full Text Available The interest in the chemistry of cobalt (II tetrasulfonated phthalocyanine (PcTsCo comes mainly from its macrocycle-ligand structure combined with their special chemical characteristics, such as high solubility, well-defined redox reactions and remarkable optical absorption in the visible region. In this work, we use layer-by-layer technique in order to assemble CoTsPc and poly(allylaminehydrochloride (PAH in hybrid supramolecular system. The electronic spectroscopy and cyclic voltammetry techniques were utilized to study PAH/CoTsPc multilayers growth and the cysteine catalytic oxidation. PAH/CoTsPc showed high electrochemical stability and worthwhile to mention is the remarkable influence of supramolecular arrangement on the final redox properties of the system.

  11. Novel zinc(II)phthalocyanines bearing azo-containing schiff base: Determination of pKa values, absorption, emission, enzyme inhibition and photochemical properties

    Science.gov (United States)

    Kantar, Cihan; Mavi, Vildan; Baltaş, Nimet; İslamoğlu, Fatih; Şaşmaz, Selami

    2016-10-01

    Azo-containing schiff bases are well known and there are many studies about their various properties in literature. However, phthalocyanines bearing azo-containing schiff bases, their spectral, analytical and biological properties are unknown. Therefore, new zinc (II) phthalocyanines bearing azo-containing schiff base were synthesized and investigated to determine pKa values, absorption, emission, enzyme inhibition and photochemical properties. Emission spectra were reported and large Stokes shift values were determined for all compounds, indicating that all molecules exhibit excited state intramolecular proton transfer. These phthalocyanines were the first examples of phthalocyanine showing excited state intramolecular proton transfer. Singlet oxygen quantum yields of zinc (II) phthalocyanines were determined. pKa values and indicator properties of all compounds were investigated by potentiometry. All compounds were assayed for inhibitory activity against bovine milk xanthine oxidase and acetylcholinesterase enzyme in vitro. Compound 2 showed the high inhibitory effect against xanthine oxidase (IC50 = 0.24 ± 0.01 μM). However, phthalocyanine compounds did not show enzyme inhibitor behavior.

  12. Atomic-Scale Control of Electron Transport through Single Molecules

    DEFF Research Database (Denmark)

    Wang, Y. F.; Kroger, J.; Berndt, R.

    2010-01-01

    Tin-phthalocyanine molecules adsorbed on Ag(111) were contacted with the tip of a cryogenic scanning tunneling microscope. Orders-of-magnitude variations of the single-molecule junction conductance were achieved by controllably dehydrogenating the molecule and by modifying the atomic structure...

  13. Cobalt-phthalocyanine-derived ultrafine Co{sub 3}O{sub 4} nanoparticles as high-performance anode materials for lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Heng-guo, E-mail: wanghengguo@cust.edu.cn; Zhu, Yanjie; Yuan, Chenpei; Li, Yanhui; Duan, Qian, E-mail: duanqian88@hotmail.com

    2017-08-31

    Highlights: • Transition-metal oxides nanoparticles are prepared by deriving from metal-phthalocyanine. • Co{sub 3}O{sub 4}, Fe{sub 2}O{sub 3}, and CuO nanoparticles can be prepared due to the adjustability of central metals. • This present strategy is simple, general, effective yet mass-production. • The Co{sub 3}O{sub 4} nanoparticles exhibit good lithium storage performances. - Abstract: In this work, we present a simple, general, effective yet mass-production strategy to prepare transition-metal oxides (TMOs) nanoparticles using the metal-phthalocyanine as both the precursor and the starting self-sacrificial template. As the central metals of metal-phthalocyanine are easily tunable, various TMOs nanoparticles including Co{sub 3}O{sub 4}, Fe{sub 2}O{sub 3}, and CuO have been successfully prepared by deriving from the corresponding metal-phthalocyanine. As a proof-of-concept demonstration of the application of such nanostructured TMOs, Co{sub 3}O{sub 4} nanoparticles were evaluated as anode materials for LIBs, which show high initial capacity (1132.9 mAh g{sup −1} at 0.05 A g{sup −1}), improved cycling stability (585.6 mAh g{sup −1} after 200 cycles at 0.05 A g{sup −1}), and good rate capability (238.1 mAh g{sup −1} at 2 A g{sup −1}) due to the unique properties of the ultrafine Co{sub 3}O{sub 4} nanoparticles. This present strategy might open new avenues for the design of a series of transition metal oxides using organometallic compounds for a range of applications.

  14. Conjugated Molecules for the Smart Filtering of Intense Radiations

    Directory of Open Access Journals (Sweden)

    Danilo Dini

    2003-04-01

    Full Text Available Abstract: The practical realization of smart optical filters, i.e. devices which change their optical transmission in a suitable way to keep a working state for a general light sensitive element , can involve the use of conjugated molecules whose light absorption properties are light- intensity dependent (nonlinear optical effect. The verification of optical limiting displayed by some particular conjugated molecules, e.g. phthalocyanines, is quite noteworthy and can be successfully exploited for the realization of such smart optical devices. In the present contribution the analysis of the relevant molecular feature of a phthalocyanine are analyzed with the aim of determining useful correlations between optical limiting performance and phthalocyanine chemical structure. In particular , the electronic nature of the substituent is considered as a key factor for the explanation of some observed optical limiting trends.

  15. Iron phthalocyanine on Cu(111): Coverage-dependent assembly and symmetry breaking, temperature-induced homocoupling, and modification of the adsorbate-surface interaction by annealing.

    Science.gov (United States)

    Snezhkova, Olesia; Bischoff, Felix; He, Yuanqin; Wiengarten, Alissa; Chaudhary, Shilpi; Johansson, Niclas; Schulte, Karina; Knudsen, Jan; Barth, Johannes V; Seufert, Knud; Auwärter, Willi; Schnadt, Joachim

    2016-03-07

    We have examined the geometric and electronic structures of iron phthalocyanine assemblies on a Cu(111) surface at different sub- to mono-layer coverages and the changes induced by thermal annealing at temperatures between 250 and 320 °C by scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy. The symmetry breaking observed in scanning tunneling microscopy images is found to be coverage dependent and to persist upon annealing. Further, we find that annealing to temperatures between 300 and 320 °C leads to both desorption of iron phthalocyanine molecules from the surface and their agglomeration. We see clear evidence of temperature-induced homocoupling reactions of the iron phthalocyanine molecules following dehydrogenation of their isoindole rings, similar to what has been observed for related tetrapyrroles on transition metal surfaces. Finally, spectroscopy indicates a modified substrate-adsorbate interaction upon annealing with a shortened bond distance. This finding could potentially explain a changed reactivity of Cu-supported iron phthalocyanine in comparison to that of the pristine compound.

  16. Unexpected Rotamerism at the Origin of a Chessboard Supramolecular Assembly of Ruthenium Phthalocyanine.

    Science.gov (United States)

    Mattioli, Giuseppe; Larciprete, Rosanna; Alippi, Paola; Bonapasta, Aldo Amore; Filippone, Francesco; Lacovig, Paolo; Lizzit, Silvano; Paoletti, Anna Maria; Pennesi, Giovanna; Ronci, Fabio; Zanotti, Gloria; Colonna, Stefano

    2017-11-16

    We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc) 2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru-Ru bond, (RuPc) 2 can be found in two stable rotameric forms separated by a low-energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard-like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π-stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc) 2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Water soluble peripheral and non-peripheral tetrasubstituted zinc phthalocyanines: Synthesis, photochemistry and bovine serum albumin binding behavior

    Energy Technology Data Exchange (ETDEWEB)

    Çakır, Volkan; Çakır, Dilek [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Pişkin, Mehmet [Department of Food Technology, Çanakkale Vocational School of Technical Sciences, Çanakkale Onsekiz Mart University, 17100 Çanakkale (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze 41400, Kocaeli (Turkey); Bıyıklıoğlu, Zekeriya, E-mail: zekeriya_61@yahoo.com [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2014-10-15

    The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituted zinc(II) phthalocyanine complexes (2a and 3a) and their quaternized amphiphilic derivatives (2b and 3b) have been synthesized and characterized using UV–vis, FT-IR, {sup 1}H-NMR, {sup 13}C-NMR, MS spectroscopic data and elemental analysis for the first time. The quaternized complexes (2b and 3b) show excellent solubility in water and DMSO which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines are investigated in dimethylsulfoxide (DMSO) for non-quaternized complexes and in DMSO, phosphate buffered solution (PBS) or PBS+triton X-100 (TX) solution for quaternized complexes. In this study, the effects of the aggregation of the molecules, quaternization, position of the substituents (peripherally or non-peripherally) and nature of the solvents (DMSO, PBS or PBS+triton X-100) on the photochemical parameters of the zinc (II) phthalocyanines are also reported. In addition, a spectroscopic investigation of the binding behavior of the quaternized zinc(II) phthalocyanine complexes to bovine serum albumin (BSA) is also presented in this work. - Highlights: • Synthesis of zinc phthalocyanines is performed. • Photophysical and photochemical properties of phthalocyanines are studied. • Photodynamic therapy studies are performed.

  18. Water soluble peripheral and non-peripheral tetrasubstituted zinc phthalocyanines: Synthesis, photochemistry and bovine serum albumin binding behavior

    International Nuclear Information System (INIS)

    Çakır, Volkan; Çakır, Dilek; Pişkin, Mehmet; Durmuş, Mahmut; Bıyıklıoğlu, Zekeriya

    2014-01-01

    The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituted zinc(II) phthalocyanine complexes (2a and 3a) and their quaternized amphiphilic derivatives (2b and 3b) have been synthesized and characterized using UV–vis, FT-IR, 1 H-NMR, 13 C-NMR, MS spectroscopic data and elemental analysis for the first time. The quaternized complexes (2b and 3b) show excellent solubility in water and DMSO which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines are investigated in dimethylsulfoxide (DMSO) for non-quaternized complexes and in DMSO, phosphate buffered solution (PBS) or PBS+triton X-100 (TX) solution for quaternized complexes. In this study, the effects of the aggregation of the molecules, quaternization, position of the substituents (peripherally or non-peripherally) and nature of the solvents (DMSO, PBS or PBS+triton X-100) on the photochemical parameters of the zinc (II) phthalocyanines are also reported. In addition, a spectroscopic investigation of the binding behavior of the quaternized zinc(II) phthalocyanine complexes to bovine serum albumin (BSA) is also presented in this work. - Highlights: • Synthesis of zinc phthalocyanines is performed. • Photophysical and photochemical properties of phthalocyanines are studied. • Photodynamic therapy studies are performed

  19. Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

    Directory of Open Access Journals (Sweden)

    Satoru Mori

    2017-10-01

    Full Text Available Phthalocyanines and subphthalocyanines are attracting attention as functional dyes that are applicable to organic solar cells, photodynamic therapy, organic electronic devices, and other applications. However, phthalocyanines are generally difficult to handle due to their strong ability to aggregate, so this property must be controlled for further applications of phthalocyanines. On the other hand, trifluoroethoxy-substituted phthalocyanines are known to suppress aggregation due to repulsion of the trifluoroethoxy group. Furthermore, the electronic characteristics of phthalocyanines are significantly changed by the strong electronegativity of fluorine. Therefore, it is expected that trifluoroethoxy-substituted phthalocyanines can be applied to new industrial fields. This review summarizes the synthesis and application of trifluoroethoxy-substituted phthalocyanine and subphthalocyanine derivatives.

  20. Relevance of the Interaction between the M-Phthalocyanines and Carbon Nanotubes in the Electroactivity toward ORR.

    Science.gov (United States)

    González-Gaitán, Carolina; Ruiz-Rosas, Ramiro; Morallón, Emilia; Cazorla-Amorós, Diego

    2017-10-31

    In this work, the influence of the interaction between the iron and cobalt-phthalocyanines (FePc and CoPc) and carbon nanotubes (CNTs) used as support in the electroactivity toward oxygen reduction reaction (ORR) in alkaline media has been investigated. A series of thermal treatments were performed on these materials in order to modify the interaction between the CNTs and the phthalocyanines. The FePc-based catalysts showed the highest activity, with comparable performance to the state-of-the-art Pt-Vulcan catalyst. A heat treatment at 400 °C improved the activity of FePc-based catalysts, while the use of higher temperatures or oxidative atmosphere rendered the decomposition of the macrocyclic compound and consequently the loss of the electrochemical activity of the complex. CoPc-based catalysts performance was negatively affected for all of the tested treatments. Thermogravimetric analyses demonstrated that the FePc was stabilized when loaded onto CNTs, while CoPc did not show such a feature, pointing to a better interaction of the FePc instead of the CoPc. Interestingly, electrochemical measurements demonstrated an improvement of the electron transfer rate in thermally treated FePc-based catalysts. They also allowed us to assess that only 15% of the iron in the catalyst was available for direct electron transfer. This is the same iron amount that remains on the catalyst after a strong acid washing with concentrated HCl (ca. 0.3 wt %), which is enough to deliver a comparable ORR activity. Durability tests confirmed that the catalysts deactivation occurs at a slower rate in those catalysts where FePc is strongly attached to the CNT surface. Thus, the highest ORR activity seems to be provided by those FePc molecules that are strongly attached to the CNT surface, pointing out the relevance of the interaction between the support and the FePc in these catalysts.

  1. High-resolution spectroscopy in superfluid helium droplets. Investigation of vibrational fine structures in electronic spectra of phthalocyanine and porphyrin derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Riechers, Ricarda Eva Friederike Elisabeth

    2011-03-22

    Since a considerably large variety of substituted compounds is commercially available and the electronic excitation spectra fit well into the spectral range covered by the continuous wave dye laser used for this study several porphyrin and phthalocyanine derivatives substituted with different types and numbers of alkyl and aryl groups were chosen as molecular probes. Recording fluorescence excitation and dispersed emission spectra revealed exclusively sharp transitions for all species. A change of the molecule's electrostatic moments, primarily and most effectively, a change of the molecular dipole moment regarding both magnitude and orientation, was identified as the main contribution for line broadening effects. Apart from the sharp lines presented in their fluorescence excitation spectra, the phthalocyanine derivatives investigated for this study, namely chloro-aluminium-phthalocyanine (AlClPc) and tetra-tertbutyl-phthalocyanine (TTBPc), exhibited more than one emission spectrum.

  2. High-resolution spectroscopy in superfluid helium droplets. Investigation of vibrational fine structures in electronic spectra of phthalocyanine and porphyrin derivatives

    International Nuclear Information System (INIS)

    Riechers, Ricarda Eva Friederike Elisabeth

    2011-01-01

    Since a considerably large variety of substituted compounds is commercially available and the electronic excitation spectra fit well into the spectral range covered by the continuous wave dye laser used for this study several porphyrin and phthalocyanine derivatives substituted with different types and numbers of alkyl and aryl groups were chosen as molecular probes. Recording fluorescence excitation and dispersed emission spectra revealed exclusively sharp transitions for all species. A change of the molecule's electrostatic moments, primarily and most effectively, a change of the molecular dipole moment regarding both magnitude and orientation, was identified as the main contribution for line broadening effects. Apart from the sharp lines presented in their fluorescence excitation spectra, the phthalocyanine derivatives investigated for this study, namely chloro-aluminium-phthalocyanine (AlClPc) and tetra-tertbutyl-phthalocyanine (TTBPc), exhibited more than one emission spectrum.

  3. Self-Assembly of Individually Addressable Complexes of C-60 and Phthalocyanines on a Metal Surface : Structural and Electronic Investigations

    NARCIS (Netherlands)

    Samuely, Tomas; Liu, Shi-Xia; Haas, Marco; Decurtins, Silvio; Jung, Thomas A.; Stoehr, Meike

    2009-01-01

    The hosting properties of a close-packed layer of phenoxy-substituted phthalocyanine derivatives adsorbed on Ag(III) were investigated for the adsorption of C-60 molecules. The C-60 molecules bind to two clearly distinguishable sites, namely, to the underlying metal substrate in between two adjacent

  4. Electronic structure of copper phthalocyanine : An experimental and theoretical study of occupied and unoccupied levels

    NARCIS (Netherlands)

    Evangelista, Fabrizio; Carravetta, Vincenzo; Stefani, Giovanni; Jansik, Branislav; Alagia, Michele; Stranges, Stefano; Ruocco, Alessandro

    2007-01-01

    An experimental and theoretical study of the electronic structure of copper phthalocyanine (CuPc) molecule is presented. We performed x-ray photoemission spectroscopy (XPS) and photoabsorption [x-ray absorption near-edge structure (XANES)] gas phase experiments and we compared the results with

  5. Atomic contributions to the valence band photoelectron spectra of metal-free, iron and manganese phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Bidermane, I., E-mail: ieva.bidermane@physics.uu.se [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Institut des Nanosciences de Paris, UPMC Univ. Paris 06, CNRS UMR 7588, F-75005 Paris (France); Brumboiu, I.E. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Totani, R. [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, Coppito, I-67010 L’Aquila (Italy); Grazioli, C. [CNR-IOM, Laboratorio TASC, ss. 14 km. 163.5, Basovizza, 34149 Trieste (Italy); Departement of Chemical and Pharmaceutical Sciences, University of Trieste (Italy); Shariati-Nilsson, M.N.; Herper, H.C.; Eriksson, O.; Sanyal, B. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Ressel, B. [University of Nova Gorica, Vipavska Cesta 11c, 5270 Ajdovščina (Slovenia); Simone, M. de [CNR-IOM, Laboratorio TASC, ss. 14 km. 163.5, Basovizza, 34149 Trieste (Italy); Lozzi, L. [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, Coppito, I-67010 L’Aquila (Italy); Brena, B.; Puglia, C. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden)

    2015-11-15

    Highlights: • In detail comparison between the valence band structure of H{sub 2}Pc, FePc and MnPc. • Comparison between the gas phase samples and thin evaporated films on Au (1 1 1). • Detailed analysis of the atomic orbital contributions to the valence band features. • DFT/HSE06 study of the valence band electronic structure of H{sub 2}Pc, FePc and MnPc. - Abstract: The present work reports a photoelectron spectroscopy study of the low-energy region of the valence band of metal-free phthalocyanine (H{sub 2}Pc) compared with those of iron phthalocyanine (FePc) and manganese phthalocyanine (MnPc). We have analysed in detail the atomic orbital composition of the valence band both experimentally, by making use of the variation in photoionization cross-sections with photon energy, and theoretically, by means of density functional theory. The atomic character of the Highest Occupied Molecular Orbital (HOMO), reflected on the outermost valence band binding energy region, is different for MnPc as compared to the other two molecules. The peaks related to the C 2p contributions, result in the HOMO for H{sub 2}Pc and FePc and in the HOMO-1 for MnPc as described by the theoretical predictions, in very good agreement with the experimental results. The DFT simulations, discerning the atomic contribution to the density of states, indicate how the central metal atom interacts with the C and N atoms of the molecule, giving rise to different partial and total density of states for these three Pc molecules.

  6. The influence of phthalocyanine aggregation in complexes with CdSe/ZnS quantum dots on the photophysical properties of the complexes

    Directory of Open Access Journals (Sweden)

    Irina V. Martynenko

    2016-07-01

    Full Text Available The formation of nonluminescent aggregates of aluminium sulfonated phthalocyanine in complexes with CdSe/ZnS quantum dots causes a decrease of the intracomplex energy transfer efficiency with increasing phthalocyanine concentration. This was confirmed by steady-state absorption and photoluminescent spectroscopy. A corresponding physical model was developed that describes well the experimental data. The results can be used at designing of QD/molecule systems with the desired spatial arrangement for photodynamic therapy.

  7. Ordering of Zn-centered porphyrin and phthalocyanine on TiO2(011: STM studies

    Directory of Open Access Journals (Sweden)

    Piotr Olszowski

    2017-01-01

    Full Text Available Zn(IIphthalocyanine molecules (ZnPc were thermally deposited on a rutile TiO2(011 surface and on Zn(IImeso-tetraphenylporphyrin (ZnTPP wetting layers at room temperature and after elevated temperature thermal processing. The molecular homo- and heterostructures were characterized by high-resolution scanning tunneling microscopy (STM at room temperature and their geometrical arrangement and degree of ordering are compared with the previously studied copper phthalocyanine (CuPc and ZnTPP heterostructures. It was found that the central metal atom may play some role in ordering and growth of phthalocyanine/ZnTPP heterostructures, causing differences in stability of upright standing ZnPc versus CuPc molecular chains at given thermal annealing conditions.

  8. Adsorption energy of iron-phthalocyanine on crystal surfaces

    International Nuclear Information System (INIS)

    Struzzi, C.; Scardamaglia, M.; Angelucci, M; Massimi, L.; Mariani, C.; Betti, G.

    2013-01-01

    The adsorption energy of iron-phthalocyanine (FePc) deposited on different crystal surfaces is studied by thermal desorption spectroscopy. A thin film of molecules has been absorbed on highly oriented pyrolytic graphite (HOPG), on graphene epitaxially grown on Ir(111), and on Au(110). Activation energies for the desorption of a molecular thin film and for the FePc single layer are determined at the three surfaces. The desorption temperature measured for the thin films is only slightly dependent on the substrate, since it is mostly dominated by molecule-molecule interactions. A definitely different desorption temperature is found at the single-layer coverage: we find an increasing desorption temperature going from HOPG, to graphene/Ir, to the Au(110) surface. The different adsorption energies of the first FePc layer in contact with the substrate surface are discussed taking into account the interaction and the growth morphology.

  9. Synthesis and photophysical properties of indium(III) phthalocyanine derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Özceşmeci, İbrahim, E-mail: ozcesmecii@itu.edu.tr [Department of Chemistry, Technical University of Istanbul, Maslak 34469, Istanbul (Turkey); Gelir, Ali [Department of Physics, Technical University of Istanbul, Maslak 34469, Istanbul (Turkey); Gül, Ahmet [Department of Chemistry, Technical University of Istanbul, Maslak 34469, Istanbul (Turkey)

    2014-03-15

    Three chloroindium(III) phthalocyanine derivatives bearing four aromatic (naphthalene or pyrene) or aliphatic (hexylthio) groups were prepared from corresponding phthalonitrile compounds. The indium(III) phthalocyanine derivatives were characterized with elemental analyses, mass, proton nuclear magnetic resonance ({sup 1}H NMR), Fourier transform infrared spectroscopy (FT-IR) and ultraviolet–visible spectroscopy (UV–vis) techniques. Quantum yields and the energy transfer from the substituents to phthalocyanine core were examined. No energy transfer was observed for 5. The energy transfer efficiency from pyrene units to indium phthalocyanine core was calculated as 0.27 for 6. Quantum yields of all samples were very small due to heavy atom effect of indium atom in the core. It was also observed that upon binding of pyrene and naphthalene units to indium phthalocyanine as substituents, the quantum yields of indium phthalocyanine parts of 5 and 6 decreased. -- Highlights: • Three chloroindium(III) phthalocyanines were prepared and characterized. • Aggregation properties of these compounds were investigated. • The energy transfer efficiency was examined. • Quantum yield of these systems were calculated.

  10. Controlling molecular condensation/diffusion of copper phthalocyanine by local electric field induced with scanning tunneling microscope tip

    Science.gov (United States)

    Nagaoka, Katsumi; Yaginuma, Shin; Nakayama, Tomonobu

    2018-02-01

    We have discovered the condensation/diffusion phenomena of copper phthalocyanine (CuPc) molecules controlled with a pulsed electric field induced by the scanning tunneling microscope tip. This behavior is not explained by the conventional induced dipole model. In order to understand the mechanism, we have measured the electronic structure of the molecule by tunneling spectroscopy and also performed theoretical calculations on molecular orbitals. These data clearly indicate that the molecule is positively charged owing to charge transfer to the substrate, and that hydrogen bonding exists between CuPc molecules, which makes the molecular island stable.

  11. Iron phthalocyanine supported on amidoximated PAN fiber as effective catalyst for controllable hydrogen peroxide activation in oxidizing organic dyes

    International Nuclear Information System (INIS)

    Han, Zhenbang; Han, Xu; Zhao, Xiaoming; Yu, Jiantao; Xu, Hang

    2016-01-01

    Iron(II) phthalocyanine was immobilized onto amidoximated polyacrylonitrile fiber to construct a bioinspired catalytic system for oxidizing organic dyes by H 2 O 2 activation. The amidoxime groups greatly helped to anchor Iron(II) phthalocyanine molecules onto the fiber through coordination interaction, which has been confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and UV diffuse reflectance spectroscopy analyses. Electron spin resonance studies indicate that the catalytic process of physically anchored Iron(II) phthalocyanine performed via a hydroxyl radical pathway, while the catalyst bonded Iron(II) phthalocyanine through coordination effect could selectively catalyze the H 2 O 2 decomposition to generate high-valent iron-oxo species. This may result from the amidoxime groups functioning as the axial fifth ligands to favor the heterolytic cleavage of the peroxide O−O bond. This feature also enables the catalyst to only degrade the dyes adjacent to the catalytic active centers and enhances the efficient utilization of H 2 O 2 . In addition, this catalyst could effectively catalyze the mineralization of organic dyes and can be easily recycled without any loss of activity.

  12. Adsorption of gas molecules on a manganese phthalocyanine molecular device and its possibility as a gas sensor.

    Science.gov (United States)

    Zou, Dongqing; Zhao, Wenkai; Cui, Bin; Li, Dongmei; Liu, Desheng

    2018-01-17

    A theoretical investigation of the gas detection performance of manganese(ii) phthalocyanine (MnPc) molecular junctions for six different gases (NO, CO, O 2 , CO 2 , NO 2 , and NH 3 ) is executed through a non-equilibrium Green's function technique in combination with spin density functional theory. Herein, we systematically studied the adsorption structural configurations, the adsorption energy, the charge transfer, and the spin transport properties of the MnPc molecular junctions with these gas adsorbates. Remarkably, NO adsorption can achieve an off-state of the Mn spin; this may be an effective measure to switch the molecular spin. In addition, our results indicate that by measuring spin filter efficiency and the changes in total current through the molecular junctions, the CO, NO, O 2 , and NO 2 gas molecules can be detected selectively. However, the CO 2 and NH 3 gas adsorptions are difficult to be detected due to weak van der Waals interaction between these two gases and central Mn atom. Our findings provide important clues to the application of nanosensors for highly sensitive and selective based on MnPc molecular junction systems.

  13. Nucleation and growth of copper phthalocyanine aggregates deposited from solution on planar surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ghani, Fatemeh [Department of Theory & Bio-Systems, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1 Golm, 14476 Potsdam (Germany); Gojzewski, Hubert, E-mail: hubert.gojzewski@put.poznan.pl [Department of Theory & Bio-Systems, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1 Golm, 14476 Potsdam (Germany); Institute of Physics, Poznan University of Technology, Piotrowo 3, 60-965 Poznan (Poland); Riegler, Hans [Department of Theory & Bio-Systems, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1 Golm, 14476 Potsdam (Germany)

    2015-10-01

    Graphical abstract: - Highlights: • Copper phthalocyanine deposited on planar surfaces by 3 solution process methods. • Aggregate morphology examined for coverage extending over 3 orders of magnitude. • Morphologies vary from small individual domains to mesh-like multilayers. • Nucleation and growth model explains the observed deposit morphologies. - Abstract: Copper phthalocyanine (CuPc) dissolved in trifluoroacetic acid (TFA) is deposited on solid SiO{sub 2} surfaces by solvent evaporation. The deposited CuPc aggregates are investigated by atomic force microscopy (AFM). The CuPc deposits were prepared by spin casting, dip coating, and spray deposition. Depending on the amount of deposited CuPc the aggregate morphology ranges from small individual domains to mesh-like multilayers. Each domain/layer consists of many parallel stacks of CuPc molecules with the square, plate-like molecules piled face-wise within each stack. The parallel stacks are attached sideways (i.e., edgewise attachment molecularly) to the substrate forming “nanoribbons” with uniform thickness of about 1 nm and varying width. The thickness reflects the length of a molecular edge, the width the number of stacks. A nucleation and growth model is presented that explains the observed aggregate and multilayer morphologies as result of the combination of nucleation, transport processes and a consequence of the anisotropic intermolecular interactions due to the shape of the CuPc molecule.

  14. Sulphonated metal phthalocyanine complexes as redox indicators in micro titrations with cerium(IV) sulphate

    Energy Technology Data Exchange (ETDEWEB)

    Gowda, H S; Achar, B N [Mysore Univ. (India). Dept. of Chemistry

    1980-01-01

    Tetrasodium salts of copper(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine 2-hydrate, nickel(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine, nickel(II) 3,3', 3'', 3'''-tetrasulphophthalocyanine and cobalt(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine 2-hydrate, and copper phthalocyanine trisulphonic acid are prepared in pure state. The molar absorptivity and formal redox potentials of the complexes are determined. The complexes are proposed as sensitive redox indicators in the micro determination of iron(II), arsenic(III), molybdenum(V), uranium(IV) and hydroquinone with 0.001-0.0005N cerium(IV) sulphate in sulphuric, hydrochloric and acetic acid media. They give sharp colour change from light turquoise blue to pale purple colour at the equivalence point. They have advantages over a few existing redox indicators.

  15. Effects of complexation of oppositely charged water-soluble cobaltphthalocyanines on catalytic mercaptoethanol autoxidation

    NARCIS (Netherlands)

    Schipper, E.T.W.M.; Heuts, J.P.A.; Piet, P.; Beelen, T.P.M.; German, A.L.

    1994-01-01

    In order to elucidate the different promoting effects polycations have on cobalt(II) phthalocyanine-catalyzed autoxidn. of 2-mercaptoethanol, the properties of mixts. of oppositely charged water-sol. cobalt(II) phthalocyanines were studied. The contribution of polycation-induced dimerization of the

  16. Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

    Science.gov (United States)

    Zhang, Tiantian; Ma, Dongdong; Pan, Sujuan; Wu, Shijun; Jiang, Yufeng; Zeng, Di; Yang, Hongqin; Peng, Yiru

    2016-10-01

    Photo-induced electron transfer (PET) is an important and fundamental process in natural photosynthesis. To mimic such interesting PET process, a suitable donor and acceptor couple were properly chosen. Dendrimer phthalocyanines and their derivatives have emerged as promising materials for artificial photosynthesis systems. In this paper, the electron transfer between the light harvest dendrimer phthalocyanine (donor) and the 1,4-benzoquinone (acceptor) was studied by UV/Vis and fluorescence spectroscopic methods. It was found that fluorescence of phthalocyanine was quenched by benzoquinone (BQ) via excited state electron transfer, from the phthalocyanine to the BQ upon excitation at 610 nm. The Stern-Volmer constant (KSV) of electron transfer was calculated. Our study suggests that this dendritic phthalocyanine is an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.

  17. Iron phthalocyanine supported on amidoximated PAN fiber as effective catalyst for controllable hydrogen peroxide activation in oxidizing organic dyes

    Energy Technology Data Exchange (ETDEWEB)

    Han, Zhenbang, E-mail: hzbang@aliyun.com [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China); Key Laboratory of Advanced Textile Composite Materials, Ministry of Education of China, Tianjin 300387 (China); Han, Xu [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China); Zhao, Xiaoming, E-mail: zhaoxiaoming@tjpu.edu.cn [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China); Key Laboratory of Advanced Textile Composite Materials, Ministry of Education of China, Tianjin 300387 (China); Yu, Jiantao; Xu, Hang [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China)

    2016-12-15

    Iron(II) phthalocyanine was immobilized onto amidoximated polyacrylonitrile fiber to construct a bioinspired catalytic system for oxidizing organic dyes by H{sub 2}O{sub 2} activation. The amidoxime groups greatly helped to anchor Iron(II) phthalocyanine molecules onto the fiber through coordination interaction, which has been confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and UV diffuse reflectance spectroscopy analyses. Electron spin resonance studies indicate that the catalytic process of physically anchored Iron(II) phthalocyanine performed via a hydroxyl radical pathway, while the catalyst bonded Iron(II) phthalocyanine through coordination effect could selectively catalyze the H{sub 2}O{sub 2} decomposition to generate high-valent iron-oxo species. This may result from the amidoxime groups functioning as the axial fifth ligands to favor the heterolytic cleavage of the peroxide O−O bond. This feature also enables the catalyst to only degrade the dyes adjacent to the catalytic active centers and enhances the efficient utilization of H{sub 2}O{sub 2}. In addition, this catalyst could effectively catalyze the mineralization of organic dyes and can be easily recycled without any loss of activity.

  18. Photophysical studies of zinc phthalocyanine and chloroaluminum phthalocyanine incorporated into liposomes in the presence of additives

    Directory of Open Access Journals (Sweden)

    S.M.T. Nunes

    2004-02-01

    Full Text Available The photophysical properties of zinc phthalocyanine (ZnPC and chloroaluminum phthalocyanine (AlPHCl incorporated into liposomes of dimyristoyl phosphatidylcholine in the presence and absence of additives such as cholesterol or cardiolipin were studied by time-resolved fluorescence, laser flash photolysis and steady-state techniques. The absorbance of the drugs changed linearly with drug concentration, at least up to 5.0 µM in homogeneous and heterogeneous media, indicating that aggregation did not occur in these media within this concentration range. The incorporation of the drugs into liposomes increases the dimerization constant by one order of magnitude (for ZnPC, 3.6 x 10(4 to 1.0 x 10(5 M-1 and for AlPHCl, 3.7 x 10(4 to 1.5 x 10(5 M-1, but this feature dose does not rule out the use of this carrier, since the incorporation of these hydrophobic drugs into liposomes permits their systemic administration. Probe location in biological membranes and predominant positions of the phthalocyanines in liposomes were inferred on the basis of their fluorescence and triplet state properties. Both phthalocyanines are preferentially distributed in the internal regions of the liposome bilayer. The additives affect the distribution of these drugs within the liposomes, a fact that controls their delivery when both are used in a biological medium, retarding their release. The addition of the additives to the liposomes increases the internalization of phthalocyanines. The interaction of the drugs with a plasma protein, bovine serum albumin, was examined quantitatively by the fluorescence technique. The results show that when the drugs were incorporated into small unilamellar liposomes, the association with albumin was enhanced when compared with organic media, a fact that should increase the selectivity of tumor targeting by these phthalocyanines (for ZnPC, 0.71 x 10(6 to 1.30 x 10(7 M-1 and for AlPHCl, 4.86 x 10(7 to 3.10 x 10(8 M-1.

  19. Copper phthalocyanine and metal free phthalocyanine bulk heterojunction photodetector

    Energy Technology Data Exchange (ETDEWEB)

    Farooq, Amjad, E-mail: amjad.farooq1212@hotmail.com [Wah Engineering College, University of Wah, Wah Cantt. 47040 (Pakistan); GIK Institute of Engineering Sciences and Technology, Topi 23640, Swabi (Pakistan); Karimov, Kh.S. [GIK Institute of Engineering Sciences and Technology, Topi 23640, Swabi (Pakistan); Physical Technical Institute, Aini St. 299/1, Dushanbe 734063 (Tajikistan); Ahmed, Nisar; Ali, Taimoor [GIK Institute of Engineering Sciences and Technology, Topi 23640, Swabi (Pakistan); Khalid Alamgir, M. [National Institute of Vacuum Science and Technology, NCP complex, Islamabad 44000 (Pakistan); Usman, Muhammad [Experimental Physics Laboratories, National Centre for Physics, Quaid-i-Azam University, Islamabad 44000 (Pakistan)

    2015-01-15

    In this study we present the dependence of electrical properties of copper phthalocyanine (CuPc) and metal free phthalocyanine (H{sub 2}Pc) bulk heterojunction structure under different illumination levels. To fabricate the device on ITO coated glass substrate the bulk heterojunction thin film of CuPc and H{sub 2}Pc with thickness varying from 100 nm to 300 nm are deposited by thermal evaporator. Aluminum thin film was deposited by thermal evaporation as a top contact. The optical properties of the fabricated device are investigated using UV–vis spectroscopy. The current-voltage characteristics in dark and under illumination show that the device is sensitive towards visible light. The absorption spectrum describes its photo sensitivity in the range of wavelength from 200 nm to 850 nm. Simulation of current-intensity of light curve is carried out and experimental results are found in good agreement with simulated ones.

  20. Copper phthalocyanine and metal free phthalocyanine bulk heterojunction photodetector

    International Nuclear Information System (INIS)

    Farooq, Amjad; Karimov, Kh.S.; Ahmed, Nisar; Ali, Taimoor; Khalid Alamgir, M.; Usman, Muhammad

    2015-01-01

    In this study we present the dependence of electrical properties of copper phthalocyanine (CuPc) and metal free phthalocyanine (H 2 Pc) bulk heterojunction structure under different illumination levels. To fabricate the device on ITO coated glass substrate the bulk heterojunction thin film of CuPc and H 2 Pc with thickness varying from 100 nm to 300 nm are deposited by thermal evaporator. Aluminum thin film was deposited by thermal evaporation as a top contact. The optical properties of the fabricated device are investigated using UV–vis spectroscopy. The current-voltage characteristics in dark and under illumination show that the device is sensitive towards visible light. The absorption spectrum describes its photo sensitivity in the range of wavelength from 200 nm to 850 nm. Simulation of current-intensity of light curve is carried out and experimental results are found in good agreement with simulated ones

  1. Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads

    NARCIS (Netherlands)

    Niemi, Marja; Tkachenko, Nikolai V.; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

    2008-01-01

    Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C-60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results

  2. Photodynamics of charge separation and recombination in solid alternating films of phthalocyanine or phthalocyanine-fullerene dyad and perylene dicarboximide

    NARCIS (Netherlands)

    Lehtivuori, Heli; Kumpulainen, Tatu; Hietala, Matti; Efimov, Alexander; Helge, Lemmetyinen; Kira, Aiko; Imahori, Hiroshi; Tkachenko, Nikolai V.

    2009-01-01

    Alternate bilayer structures of N,N'-bis(2,5-di-tert-butylphenyl)-3,4,9,10- perylene dicarboximide (PDI), freebase phthalocyanines (Pc), and double-linked free-base phthalocyanine-fullerene dyad (Pc-C 60) were prepared by the Langmuir-Schäfer method and studied using a range of optical spectroscopy

  3. An ultrafast study of Zinc Phthalocyanine in DMSO

    CSIR Research Space (South Africa)

    Ombinda-Lemboumba, Saturnin

    2010-10-01

    Full Text Available The ultrafast dynamics of Zinc Phthalocyanine was studied using trasient absorption pump probe spectroscopy. Zinc Phthalocyanine was excited (pumped) at 672nm and probed by a white light continuum. The pump-probe technique used in this study...

  4. Real-time single-molecule imaging of quantum interference.

    Science.gov (United States)

    Juffmann, Thomas; Milic, Adriana; Müllneritsch, Michael; Asenbaum, Peter; Tsukernik, Alexander; Tüxen, Jens; Mayor, Marcel; Cheshnovsky, Ori; Arndt, Markus

    2012-03-25

    The observation of interference patterns in double-slit experiments with massive particles is generally regarded as the ultimate demonstration of the quantum nature of these objects. Such matter-wave interference has been observed for electrons, neutrons, atoms and molecules and, in contrast to classical physics, quantum interference can be observed when single particles arrive at the detector one by one. The build-up of such patterns in experiments with electrons has been described as the "most beautiful experiment in physics". Here, we show how a combination of nanofabrication and nano-imaging allows us to record the full two-dimensional build-up of quantum interference patterns in real time for phthalocyanine molecules and for derivatives of phthalocyanine molecules, which have masses of 514 AMU and 1,298 AMU respectively. A laser-controlled micro-evaporation source was used to produce a beam of molecules with the required intensity and coherence, and the gratings were machined in 10-nm-thick silicon nitride membranes to reduce the effect of van der Waals forces. Wide-field fluorescence microscopy detected the position of each molecule with an accuracy of 10 nm and revealed the build-up of a deterministic ensemble interference pattern from single molecules that arrived stochastically at the detector. In addition to providing this particularly clear demonstration of wave-particle duality, our approach could also be used to study larger molecules and explore the boundary between quantum and classical physics.

  5. Conducting Polymers Functionalized with Phthalocyanine as Nitrogen Dioxide Sensors

    Directory of Open Access Journals (Sweden)

    S. D. Deshpande

    2002-05-01

    Full Text Available The conducting polymers such as polyaniline, polypyrrole and polythiophene were functionalized with copper phthalocyanine using chemical oxidation method. The obtained polymers viz. PANI-CuPc, PPy-CuPc and PT-CuPc were studied as chemical sensors by their response characteristics after exposure to various chemical vapors such as methanol, ammonia and nitrogen dioxide. The results obtained showed that these polymers have moderate sensitivity towards the methanol as well as ammonia vapors whereas they show tremendous sensitivity towards nitrogen dioxide vapors. The sensitivity factor of as high as 50,000 was obtained for PT-CuPc polymers in nitrogen dioxide. In comparison to this, the sensitivity factors of about 100 and 40 were obtained, when these polymers were exposed to ammonia and methanol vapors. The very high selectivity towards the nitrogen dioxide was explained on the basis of charge transfer complex formed between, the phthalocyanine donor and nitrogen dioxide acceptor molecules. On the other hand, ammonia becomes a competing electron donor in CuPc containing conducting polymers. The very low response towards the methanol may be explained on the basis very little charge transfer / interaction between CuPc containing polymers and methanol. Thus, CuPc incorporated conducting polymers have much higher selectivity than their original homopolymer.

  6. Pinning of fullerene lowest unoccupied molecular orbital edge at the interface with standing up copper phthalocyanine

    International Nuclear Information System (INIS)

    Wang, Chenggong; Irfan, Irfan; Turinske, Alexander J.; Gao, Yongli

    2012-01-01

    The electronic structure evolution of interfaces of fullerene (C 60 ) with copper phthalocyanine (CuPc) on highly oriented pyrolitic graphite (HOPG) and on native silicon oxide has been investigated with ultra-violet photoemission spectroscopy and inverse photoemission spectroscopy. The lowest unoccupied molecular orbital edge of C 60 was found to be pinned at the interface with CuPc on SiO 2 . A substantial difference in the electron affinity of CuPc on the two substrates was observed as the orientation of CuPc is lying flat on HOPG and standing up on SiO 2 . The ionization potential and electron affinity of C 60 were not affected by the orientation of CuPc due to the spherical symmetry of C 60 molecules. We observed band bending in C 60 on the standing-up orientation of CuPc molecules, while the energy levels of C 60 on the flat lying orientation of CuPc molecules were observed to be flat. - Highlights: ► Orientation of copper phthalocyanine (CuPc) on ordered graphite and silicon oxide. ► Pinning of lowest unoccupied molecular orbital edge of C60 to the Fermi level on CuPc. ► No C60 pinning or band bending was observed on flat laying CuPc. ► Results are useful for organic photovoltaic and organic light emitting diode research.

  7. Resonance Raman spectra of phthalocyanine monolayers on different supports. A normal mode analysis of zinc phthalocyanine by means of the MNDO method

    NARCIS (Netherlands)

    Palys, Barbara J.; van den Ham, Dirk M.W.; van den Ham, D.M.W.; Briels, Willem J.; Feil, D.; Feil, Dirk

    1995-01-01

    Resonance Raman spectra of monolayers of transition metal phthalocyanines reveal specific interaction with the support. To elucidate its mechanism, Raman spectra of zinc phthalocyanine monolayers were studied. The analysis was based largely on the results of MNDO calculations. Calculated wavenumbers

  8. Thermosetting Phthalocyanine Polymers

    Science.gov (United States)

    Fohlen, G.; Parker, J.; Achar, B.

    1985-01-01

    Group of phthalocyanine polymers resist thermal degradation. Polymers expected semiconducting. Principal applications probably in molded or laminated parts that have to withstand high temperatures. Polymers made from either of two classes of monomer: Bisphthalonitriles with imide linkages or Bisphthalonitriles with ester-imide linkages.

  9. Synthesis of phthalocyanine doped sol-gel materials

    Science.gov (United States)

    Dunn, Bruce

    1993-01-01

    The synthesis of sol-gel silica materials doped with three different types of metallophthalocyanines has been studied. Homogeneous materials of good optical quality were prepared and the first optical limiting measurements of dyes in sol-gel hosts were carried out. The properties of these solid state limiters are similar to limiters based on phthalocyanine (Pc) in solution. Sol-gel silica materials containing copper, tin and germanium phthalocyanines were investigated. The initial step in all cases was to prepare silica sols by the sonogel method using tetramethoxy silane (TMOS), HCl and distilled water. Thereafter, the synthesis depended upon the specific Pc and its solubility characteristics. Copper phthalocyanine tetrasulfonic acid tetra sodium salt (CuPc4S) is soluble in water and various doping levels (1 x 10 (exp -4) M to 1 x 10 (exp -5) M) were added to the sol. The group IV Pc's, SnPc(OSi(n-hexyl)3)2 and GePc(OSi(n-hexyl)3)2, are insoluble in water and the process was changed accordingly. In these cases, the compounds were dissolved in THF and then added to the sol. The Pc concentration in the sol was 2 x 10(exp -5)M. The samples were then aged and dried in the standard method of making xerogel monoliths. Comparative nanosecond optical limiting experiments were performed on silica xerogels that were doped with the different metallophthalocyanines. The ratio of the net excited state absorption cross section (sigma(sub e)) to the ground state cross section (sigma(sub g)) is an important figure of merit that is used to characterize these materials. By this standard the SnPc sample exhibits the best limiting for the Pc doped sol-gel materials. Its cross section ratio of 19 compares favorably with the value of 22 that was measured in toluene. The GePc materials appear to not be as useful as those containing SnPc. The GePc doped solids exhibit a higher onset energy (2.5 mj and lower cross section ratio, 7. The CuPc4S sol-gel material has a still lower cross

  10. Some Phthalocyanine and Naphthalocyanine Derivatives as Corrosion Inhibitors for Aluminium in Acidic Medium: Experimental, Quantum Chemical Calculations, QSAR Studies and Synergistic Effect of Iodide Ions

    Directory of Open Access Journals (Sweden)

    Masego Dibetsoe

    2015-08-01

    Full Text Available The effects of seven macrocyclic compounds comprising four phthalocyanines (Pcs namely 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (Pc1, 2,3,9,10,16,17,23,24-octakis(octyloxy-29H,31H-phthalocyanine (Pc2, 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (Pc3 and 29H,31H-phthalocyanine (Pc4, and three naphthalocyanines namely 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (nPc1, 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (nPc2 and 2,3-naphthalocyanine (nP3 were investigated on the corrosion of aluminium (Al in 1 M HCl using a gravimetric method, potentiodynamic polarization technique, quantum chemical calculations and quantitative structure activity relationship (QSAR. Synergistic effects of KI on the corrosion inhibition properties of the compounds were also investigated. All the studied compounds showed appreciable inhibition efficiencies, which decrease with increasing temperature from 30 °C to 70 °C. At each concentration of the inhibitor, addition of 0.1% KI increased the inhibition efficiency compared to the absence of KI indicating the occurrence of synergistic interactions between the studied molecules and I− ions. From the potentiodynamic polarization studies, the studied Pcs and nPcs are mixed type corrosion inhibitors both without and with addition of KI. The adsorption of the studied molecules on Al surface obeys the Langmuir adsorption isotherm, while the thermodynamic and kinetic parameters revealed that the adsorption of the studied compounds on Al surface is spontaneous and involves competitive physisorption and chemisorption mechanisms. The experimental results revealed the aggregated interactions between the inhibitor molecules and the results further indicated that the peripheral groups on the compounds affect these interactions. The calculated quantum chemical parameters and the QSAR results revealed the possibility of strong interactions between the studied inhibitors and metal surface. QSAR

  11. Photoconductivity study of acid on Zinc phthalocyanine pyridine thin films

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Sukhwinder, E-mail: ss7667@gmail.com [Department of Physics, Govt. College for Girls, Ludhiana (India); Saini, G. S. S.; Tripathi, S. K. [Department of Physics, Panjab University, Chandigarh (India)

    2016-05-06

    The Metal Phthalocyanine (MPc) have attracted much interest because of chemical and high thermal stability. Molecules forming a crystal of MPc are held together by weak attractive Vander Waals forces. Organic semiconductors have π conjugate bonds which allow electrons to move via π-electron cloud overlaps. Conduction mechanisms for organic semiconductor are mainly through tunneling; hopping between localized states, mobility gaps, and phonon assisted hopping. The photo conductivity of thin films of these complexes changes when exposed to oxidizing and reducing gases. Arrhenius plot is used to find the thermal activation energy in the intrinsic region and impurity scattering region. Arrhenius plotsare used to find the thermal activation energy.

  12. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    International Nuclear Information System (INIS)

    Li Xiaofang; Zhao Shuang; Yang Min; Sun Changqing; Guo, Liping

    2005-01-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF 2 and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior

  13. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaofang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Zhao Shuang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Yang Min [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Sun Changqing [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China)]. E-mail: sunchq@mail.jlu.edu.cn; Guo, Liping [Department of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2005-05-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF{sub 2} and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior.

  14. Peculiarities of spin polarization inversion at a thiophene/cobalt interface

    KAUST Repository

    Wang, Xuhui; Manchon, Aurelien; Schwingenschlö gl, Udo; Zhu, Zhiyong

    2013-01-01

    We perform ab initio calculations to investigate the spin polarization at the interface between a thiophene molecule and cobalt substrate. We find that the reduced symmetry in the presence of a sulfur atom (in the thiophene molecule) leads to a

  15. The composite phthalocyanine-based Langmuir-Blodgett films: structural peculiarities and NO-sensitive properties

    Energy Technology Data Exchange (ETDEWEB)

    Emelianov, I.L.; Khatko, V.V. [Nat. Acad. of Sci., Minsk (Belarus). Phys. Tech. Inst.

    1999-10-08

    Surface pressure versus area per molecule isotherms of the Langmuir monolayers of copper tetra-tert-butyl phthalocyanine (abbreviated as CuTTBPc), arachidic acid (abbreviated as AA), and their mixtures were measured depending upon the film component ratio and ionic content of the subphase. Substantial deviations of the mixed monolayer behaviour from an ideal one, which is characteristic of fully immiscible compounds forming separate surface domains on the liquid subphase, were observed if the molar fraction of AA in mixed monolayers exceeded 50%. This abnormality in the monolayer behaviour correlated with the drastic changes in the kinetics responses to NO gas of the sensors based on the mixed Langmuir-Blodgett (LB) films. The comparison and analysis of the results obtained suggest that the gas-sensitive properties of the two-component LB films are determined by two features of their structure, namely, hole-like defects existing in the AA matrix and interlayer cavities. The corresponding structure model of the mixed films is proposed. The results obtained may be useful for understanding the gas-sensitive mechanism of the composite phthalocyanine-based LB films. (orig.)

  16. Optical and infrared spectroscopic studies of chemical sensing by copper phthalocyanine thin films

    International Nuclear Information System (INIS)

    Singh, Sukhwinder; Tripathi, S.K.; Saini, G.S.S.

    2008-01-01

    Thin films of copper phthalocyanine have been deposited on KBr and glass substrates by thermal evaporation method and characterized by the X-ray diffraction and optical absorption techniques. The observed X-ray pattern suggests the presence of α crystalline phase of copper phthalocyanine in the as-deposited thin films. Infrared spectra of thin films on the KBr pallet before and after exposure to the vapours of ammonia and methanol have been recorded in the wavenumber region of 400-1650 cm -1 . The observed infrared bands also confirm the α crystalline phase. On exposure, change in the intensity of some bands is observed. A new band at 1385 cm -1 , forbidden under ideal D 4h point group symmetry, is also observed in the spectra of exposed thin films. These changes in the spectra are interpreted in terms of the lowering of molecular symmetry from D 4h to C 4v . Axial ligation of the vapour molecules on fifth coordination site of the metal ion is responsible for lowering of the molecular symmetry

  17. Development of Smart Phthalocyanine-based Photosensitizers for Photodynamic Therapy

    Science.gov (United States)

    Chow, Yun Sang

    Phthalocyanines are versatile functional dyes that have shown great potential in cancer theranostics, especially in photodynamic therapy (PDT). This research work aims to develop "smart" phthalocyanine-based photosensitizers for targeted PDT. This thesis describes the synthesis, spectroscopic characterization, photophysical properties, and in vitro photodynamic activities of several series of carefully designed phthalocyanine-based photosensitizers. Chapter 1 presents an overview of PDT, including its historical development, photophysical mechanisms, and biological mechanisms. Various classes of photosensitizers are introduced with emphasis putting on phthalocyanines, which exhibit ideal characteristics of photosensitizers for PDT. In recent years, several approaches have been used to develop photosensitizers with higher tumor selectivity and minimal skin photosensitivity after PDT. Activatable photosensitizers can provide a "turn on" mechanism to offer an additional control of the specificity of treatment. Photosensitizers can also work cooperatively with the tumor-targeting groups or anticancer drugs so as to achieve targeted or dual therapy, which can enhance the efficacy of PDT. The novel approaches mentioned above have been widely used and combined to form multi-functional photosensitizing agents. These novel concepts and development of PDT are discussed and illustrated with relevant examples at the end of this chapter. To minimize the prolonged skin photosensitivity, photosensitizers that can only be activated by tumor-associated stimuli have been developed. Due to the abnormal metabolism in tumor tissues, their surface usually exhibits a lower pH compared to that of the normal tissues. Also, the pH difference between the intracellular and the physiological environment provides a pH-activation mechanism. Chapter 2 presents the synthesis and spectroscopic characterization of a pH-responsive zinc(II) phthalocyanine tetramer, in which the phthalocyanine units

  18. Single NdPc2 molecules on surfaces. Adsorption, interaction, and molecular magnetism

    International Nuclear Information System (INIS)

    Fahrendorf, Sarah

    2013-01-01

    They have huge potential for application in molecular-spin-transistors, molecular-spinvalves, and molecular quantum computing. SMMs are characterized by high spin ground states with zero-field splitting leading to high relaxation barriers and long relaxation times. A relevant class of molecules are the lanthanide double-decker phthalocyanines (LaPc 2 ) with only one metal atom sandwiched between two organic phthalocyanine (Pc) ligands. For envisaged spintronic applications it is important to understand the interaction between the molecules and the substrate and its influence on the electronic and magnetic properties. The subject of this thesis is the investigation of the adsorbed neodymium double-decker phthalocyanine (NdPc 2 ) by means of low temperature scanning tunneling microscopy and spectroscopy (STM and STS). The molecules are deposited by sublimation onto different substrates. It is observed that a large fraction of the double-decker molecules decomposes during deposition. The decomposition probability strongly depends on the chosen substrate. Therefore it is concluded that the substrate modifies the electronic structure of the molecule leading to a stabilization or destabilization of the molecular entity. Charge transfer from the surface to the molecule is identified as a potential stabilizing mechanism. The electronic and magnetic properties are investigated in detail for adsorbed NdPc 2 molecules on Cu(100). The results of the experimental study are compared to state-of-the-art density functional theory calculations performed by our colleagues from the Peter Gruenberg Institute (PGI-1) at the Forschungszentrum Juelich. Interestingly, the lower Pc ring of the molecule hybridizes intensely with the substrate leading to strong chemisorption of the molecule, while the upper Pc ring keeps its molecular type electronic states, which can be energetically shifted by an external electric field. Importantly, it is possible to get direct access to the spin

  19. Electronic transport properties of (fluorinated) metal phthalocyanine

    KAUST Repository

    Fadlallah, M M; Eckern, U; Romero, A H; Schwingenschlö gl, Udo

    2015-01-01

    The magnetic and transport properties of the metal phthalocyanine (MPc) and F16MPc (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ag) families of molecules in contact with S–Au wires are investigated by density functional theory within the local density approximation, including local electronic correlations on the central metal atom. The magnetic moments are found to be considerably modified under fluorination. In addition, they do not depend exclusively on the configuration of the outer electronic shell of the central metal atom (as in isolated MPc and F16MPc) but also on the interaction with the leads. Good agreement between the calculated conductance and experimental results is obtained. For M = Ag, a high spin filter efficiency and conductance is observed, giving rise to a potentially high sensitivity for chemical sensor applications.

  20. Electronic transport properties of (fluorinated) metal phthalocyanine

    KAUST Repository

    Fadlallah, M M

    2015-12-21

    The magnetic and transport properties of the metal phthalocyanine (MPc) and F16MPc (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ag) families of molecules in contact with S–Au wires are investigated by density functional theory within the local density approximation, including local electronic correlations on the central metal atom. The magnetic moments are found to be considerably modified under fluorination. In addition, they do not depend exclusively on the configuration of the outer electronic shell of the central metal atom (as in isolated MPc and F16MPc) but also on the interaction with the leads. Good agreement between the calculated conductance and experimental results is obtained. For M = Ag, a high spin filter efficiency and conductance is observed, giving rise to a potentially high sensitivity for chemical sensor applications.

  1. Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

    Science.gov (United States)

    Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

    2018-06-01

    Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

  2. Sensing response of copper phthalocyanine salt dispersed glass with organic vapours

    Energy Technology Data Exchange (ETDEWEB)

    Ridhi, R.; Sachdeva, Sheenam; Saini, G. S. S.; Tripathi, S. K., E-mail: surya@pu.ac.in [Department of Physics, Center of Advanced Study in Physics, Panjab University, Chandigarh-160 014 (INDIA) Fax: +91-172-2783336; Tel.:+91-172-2544362 (India)

    2016-05-06

    Copper Phthalocyanine and other Metal Phthalocyanines are very flexible and tuned easily to modify their structural, spectroscopic, optical and electrical properties by either functionalizing them with various substituent groups or by replacing or adding a ligand to the central metal atom in the phthalocyanine ring and accordingly can be made sensitive and selective to various organic species or gaseous vapours. In the present work, we have dispersed Copper Phthalocyanine Salt (CuPcS) in sol-gel glass form using chemical route sol-gel method and studied its sensing mechanism with organic vapours like methanol and benzene and found that current increases onto their exposure with vapours. A variation in the activation energies was also observed with exposure of vapours.

  3. Fabrication and characterization of tetracyanoquinodimethane/phthalocyanine solar cells

    International Nuclear Information System (INIS)

    Suzuki, Atsushi; Ohtsuki, Takahiro; Oku, Takeo; Akiyama, Tsuyoshi

    2012-01-01

    Highlights: ► Heterojunction solar cells of tetracyanoquinodimethane (TCNQ)/copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) were fabricated and characterized. ► The light-induced charge separation with charge transfer was investigated by light-induced current density and optical absorption.. ► In both solar cells of TCNQ/CuPc and TCNQ/ZnPc, the TCNQ thin film worked for strong electron-accepting layer. ► These behaviors would be originated in charge transfer of excited electron from CuPc and ZnPc to TCNQ. ► The photovoltaic mechanism was discussed by the experimental results. - Abstract: Fabrication and characterization of heterojunction solar cells of tetracyanoquinodimethane (TCNQ)/copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) were carried out. The light-induced charge separation with charge transfer was investigated by light-induced current density and optical absorption. In both cases of the TCNQ/CuPc and TCNQ/ZnPc solar cells, the TCNQ thin film worked for strong electron-accepting layer as n-type semiconductor. These behaviors would be originated in charge transfer of excited electron from CuPc and ZnPc to TCNQ. The photovoltaic mechanism was discussed on the basis of the experimental results.

  4. Double-decker phthalocyanine complex: Scanning tunneling microscopy study of film formation and spin properties

    Science.gov (United States)

    Komeda, Tadahiro; Katoh, Keiichi; Yamashita, Masahiro

    2014-05-01

    We review recent studies of double-decker and triple-decker phthalocyanine (Pc) molecules adsorbed on surfaces in terms of the bonding configuration, electronic structure and spin state. The Pc molecule has been studied extensively in surface science. A Pc molecule can contain various metal atoms at the center, and the class of the molecule is called as metal phthalocyanine (MPc). If the center metal has a large radius, like as lanthanoid metals, it becomes difficult to incorporate the metal atom inside of the Pc ring. Pc ligands are placed so as to sandwich the metal atom, where the metal atom is placed out of the Pc plane. The molecule in this configuration is called as a multilayer-decker Pc molecule. After the finding that the double-decker Pc lanthanoid complex shows single-molecule magnet (SMM) behavior, it has attracted a large attention. This is partly due to a rising interest for the ‘molecular spintronics’, in which the freedoms of spin and charge of an electron are applied to the quantum process of information. SMMs represent a class of compounds in which a single molecule behaves as a magnet. The reported blocking temperature, below which a single SMM molecule works as an quantum magnet, has been increasing with the development in the molecular design and synthesis techniques of multiple-decker Pc complex. However, even the bulk properties of these molecules are promising for the use of electronic materials, the films of multi-decker Pc molecules is less studied than those for the MPc molecules. An intriguing structural property is expected for the multi-decker Pc molecules since the Pc planes are linked by metal atoms. This gives an additional degree of freedom to the rotational angle between the two Pc ligands, and they can make a wheel-like symmetric rotation. Due to a simple and well-defined structure of a multi-decker Pc complex, the molecule can be a model molecule for molecular machine studies. The multi-decker Pc molecules can provide

  5. Nonlinear optical properties of systems based on ruthenium(II) tetra-15-crown-5-phthalocyaninate

    International Nuclear Information System (INIS)

    Grishina, A.D.; Gorbunova, Yu.G.; Enakieva, Yu.Yu.; Krivenko, T.V.; Savel'ev, V.V.; Vannikov, A.V.; Tsivadze, A.Yu.

    2008-01-01

    The third-order nonlinear optical properties of the ruthenium (II) complex with tetra-15-crown-5-phthalocyanine and axially coordinated triethylenediamine molecules (R 4 Pc)Ru(TED) 2 were analyzed by means of the z-scanning technique. A solution of (R 4 Pc)Ru(TED) 2 in tetrachloroethane was exposed to nanosecond laser pulses at a wavelength of 1064 nm. It was found that the third-order molecular polarizability of the Ru(II) complex is 4.5 x 10 -32 cm 4 /C (esu). The polarizability per molecule increases by a factor of 3.6 when the single molecule occurs in a supramolecular assembly of (R 4 Pc)Ru(TED) 2 complexes. The photoelectric and photorefractive properties at 1064 nm of polymer composites, determined by the supramolecular assemblies that exhibits optical absorption and photoelectric sensitivity in the near IR region, are reported [ru

  6. Photoinduced charge and energy transfer in phthalocyanine-functionalized gold nanoparticles

    NARCIS (Netherlands)

    Kotiaho, Anne; Lahtinen, Riikka; Efimov, Alexander; Metsberg, Hanna Kaisa; Sariola, Essi; Lehtivuori, Heli; Tkachenko, Nikolai V.; Lemmetyinen, Helge

    2010-01-01

    Photoinduced processes in phthalocyanine-functionalized gold nanoparticles (Pc-AuNPs) have been investigated by spectroscopic measurements. The metal-free phthalocyanines used have two linkers with thioacetate groups for bonding to the gold nanoparticle surface, and the attachment was achieved using

  7. Single NdPc{sub 2} molecules on surfaces. Adsorption, interaction, and molecular magnetism

    Energy Technology Data Exchange (ETDEWEB)

    Fahrendorf, Sarah

    2013-01-24

    They have huge potential for application in molecular-spin-transistors, molecular-spinvalves, and molecular quantum computing. SMMs are characterized by high spin ground states with zero-field splitting leading to high relaxation barriers and long relaxation times. A relevant class of molecules are the lanthanide double-decker phthalocyanines (LaPc{sub 2}) with only one metal atom sandwiched between two organic phthalocyanine (Pc) ligands. For envisaged spintronic applications it is important to understand the interaction between the molecules and the substrate and its influence on the electronic and magnetic properties. The subject of this thesis is the investigation of the adsorbed neodymium double-decker phthalocyanine (NdPc{sub 2}) by means of low temperature scanning tunneling microscopy and spectroscopy (STM and STS). The molecules are deposited by sublimation onto different substrates. It is observed that a large fraction of the double-decker molecules decomposes during deposition. The decomposition probability strongly depends on the chosen substrate. Therefore it is concluded that the substrate modifies the electronic structure of the molecule leading to a stabilization or destabilization of the molecular entity. Charge transfer from the surface to the molecule is identified as a potential stabilizing mechanism. The electronic and magnetic properties are investigated in detail for adsorbed NdPc{sub 2} molecules on Cu(100). The results of the experimental study are compared to state-of-the-art density functional theory calculations performed by our colleagues from the Peter Gruenberg Institute (PGI-1) at the Forschungszentrum Juelich. Interestingly, the lower Pc ring of the molecule hybridizes intensely with the substrate leading to strong chemisorption of the molecule, while the upper Pc ring keeps its molecular type electronic states, which can be energetically shifted by an external electric field. Importantly, it is possible to get direct access to the

  8. Thin film formation at the air-water interface and on solid substrates of soluble axial substituted cis-bis-decanoate tin phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Campos-Teran, Jose, E-mail: jcampos@correo.cua.uam.mx [Departamento de Procesos y Tecnologia, DCNI, Universidad Autonoma Metropolitana-Cuajimalpa, Artificios 40-sexto piso, Col. Hidalgo, D. F., 001120 (Mexico); Garza, Cristina [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, P. O. Box 20-364, D. F., 01000 (Mexico); Beltran, Hiram I. [Departamento de Ciencias Naturales, DCNI, Universidad Autonoma Metropolitana-Cuajimalpa, Artificios 40-sexto piso, Col. Hidalgo, D. F., 001120 (Mexico); Castillo, Rolando [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, P. O. Box 20-364, D. F., 01000 (Mexico)

    2012-01-01

    Herein we study thin films of a recent kind of soluble axial substituted cis-bis-decanoate-tin{sup IV} phthalocyanine (PcSn10) at the air/water interface, which were compressed isothermally and observed with Brewster Angle Microscopy. The air/water interfacial behavior of the films suggests that there are strong interactions among the PcSn10 molecules, which produces multilayers and 3D self-assemblies that prevent the formation of a Langmuir monolayer. Langmuir-Blodgett deposits of these films on both mica (negatively charged) and mild steel (positively charged) surfaces were developed. Information about the morphology of the film was obtained by using atomic force microscopy. We found structural differences in the PcSn10 thin films deposited on both substrates, suggesting that a combination of {pi}-{pi}, {sigma}-{pi} and Van der Waals interactions are the leading factors for the deposition, and consequently, for the control of supramolecular order. Our findings provide insights in the design of phthalocyanine molecules for the development of highly ordered and reproducible thin films.

  9. Thin film formation at the air–water interface and on solid substrates of soluble axial substituted cis-bis-decanoate tin phthalocyanine

    International Nuclear Information System (INIS)

    Campos-Terán, José; Garza, Cristina; Beltrán, Hiram I.; Castillo, Rolando

    2012-01-01

    Herein we study thin films of a recent kind of soluble axial substituted cis-bis-decanoate-tin IV phthalocyanine (PcSn10) at the air/water interface, which were compressed isothermally and observed with Brewster Angle Microscopy. The air/water interfacial behavior of the films suggests that there are strong interactions among the PcSn10 molecules, which produces multilayers and 3D self-assemblies that prevent the formation of a Langmuir monolayer. Langmuir–Blodgett deposits of these films on both mica (negatively charged) and mild steel (positively charged) surfaces were developed. Information about the morphology of the film was obtained by using atomic force microscopy. We found structural differences in the PcSn10 thin films deposited on both substrates, suggesting that a combination of π–π, σ–π and Van der Waals interactions are the leading factors for the deposition, and consequently, for the control of supramolecular order. Our findings provide insights in the design of phthalocyanine molecules for the development of highly ordered and reproducible thin films.

  10. Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands

    International Nuclear Information System (INIS)

    Fester, J.; García-Melchor, M.; Walton, A. S.; Bajdich, M.

    2017-01-01

    Here, transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress in the development of highly active oxide nanostructures is hampered by a lack of knowledge of the location and nature of the active sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy and computational modelling, how hydroxyls form from water dissociation at under coordinated cobalt edge sites of cobalt oxide nanoislands. Surprisingly, we find that an additional water molecule acts to promote all the elementary steps of the dissociation process and subsequent hydrogen migration, revealing the important assisting role of a water molecule in its own dissociation process on a metal oxide. Inspired by the experimental findings, we theoretically model the oxygen evolution reaction activity of cobalt oxide nanoislands and show that the nanoparticle metal edges also display favourable adsorption energetics for water oxidation under electrochemical conditions.

  11. Phthalocyanines as sensitizers for photodynamic water disinfection

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsova, N.; Slivka, L.; Kaliya, O.; Lukyanets, E.; Negrimovsky, V.; Vorozhtsov, G. [Organic Intermediates and Dyes Inst., Moscow (Russian Federation); Nedachin, E.; Artemova, T.; Ivanova, L.; Lavrova, D. [A.N. Sysin Research Inst. of Human Ecology and Environmental Health of Russian Academy of Medical Sciences, Moscow (Russian Federation)

    2003-07-01

    New octapyridiniomethyl-substituted phthalocyanines of Al and Zn have been synthesized. These octacationic complexes are readily soluble in water, show monomeric behavior and sensitize formation of singlet oxygen efficiently. They are of high photodynamic potential in killing both Gram-negative and Gram-positive bacteria in contrast to negatively charged sulfonated derivatives, which are substantially less effective, particularly towards coliform bacteria in natural or sewage water. The present study confirms that cationic phthalocyanines represent a class of photosensitizing agents with an efficient antibacterial activity. (orig.)

  12. Cobalt

    Science.gov (United States)

    Slack, John F.; Kimball, Bryn E.; Shedd, Kim B.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Cobalt is a silvery gray metal that has diverse uses based on certain key properties, including ferromagnetism, hardness and wear-resistance when alloyed with other metals, low thermal and electrical conductivity, high melting point, multiple valences, and production of intense blue colors when combined with silica. Cobalt is used mostly in cathodes in rechargeable batteries and in superalloys for turbine engines in jet aircraft. Annual global cobalt consumption was approximately 75,000 metric tons in 2011; China, Japan, and the United States (in order of consumption amount) were the top three cobalt-consuming countries. In 2011, approximately 109,000 metric tons of recoverable cobalt was produced in ores, concentrates, and intermediate products from cobalt, copper, nickel, platinum-group-element (PGE), and zinc operations. The Democratic Republic of the Congo (Congo [Kinshasa]) was the principal source of mined cobalt globally (55 percent). The United States produced a negligible amount of byproduct cobalt as an intermediate product from a PGE mining and refining operation in southeastern Montana; no U.S. production was from mines in which cobalt was the principal commodity. China was the leading refiner of cobalt, and much of its production came from cobalt ores, concentrates, and partially refined materials imported from Congo (Kinshasa).The mineralogy of cobalt deposits is diverse and includes both primary (hypogene) and secondary (supergene) phases. Principal terrestrial (land-based) deposit types, which represent most of world’s cobalt mine production, include primary magmatic Ni-Cu(-Co-PGE) sulfides, primary and secondary stratiform sediment-hosted Cu-Co sulfides and oxides, and secondary Ni-Co laterites. Seven additional terrestrial deposit types are described in this chapter. The total terrestrial cobalt resource (reserves plus other resources) plus past production, where available, is calculated to be 25.5 million metric tons. Additional resources of

  13. Individual Magnetic Molecules on Ultrathin Insulating Surfaces

    Science.gov (United States)

    El Hallak, Fadi; Warner, Ben; Hirjibehedin, Cyrus

    2012-02-01

    Single molecule magnets have attracted ample interest because of their exciting magnetic and quantum properties. Recent studies have demonstrated that some of these molecules can be evaporated on surfaces without losing their magnetic properties [M. Mannini et al., Nature 468, 417, (2010)]. This remarkable progress enhances the chances of real world applications for these molecules. We present STM imaging and spectroscopy data on iron phthalocyanine molecules deposited on Cu(100) and on a Cu2N ultrathin insulating surface. These molecules have been shown to display a large magnetic anisotropy on another thin insulating surface, oxidized Cu(110) [N. Tsukahara et al., Phys. Rev. Lett. 102, 167203 (2009)]. By using a combination of elastic and inelastic electron tunnelling spectroscopy, we investigate the binding of the molecules to the surface and the impact that the surface has on their electronic and magnetic properties.

  14. Synthesis, photophysical and photochemical properties of zinc phthalocyanines bearing fluoro-functionalized substituents

    International Nuclear Information System (INIS)

    Aktaş, Ayşe; Pişkin, Mehmet; Durmuş, Mahmut; Bıyıklıoğlu, Zekeriya

    2014-01-01

    In this study, the synthesis of phthalonitrile derivatives bearing fluoro-functionalized groups and their peripherally-tetra substituted zinc phthalocyanine complexes were reported. The phthalonitrile derivatives 2a–5a were prepared by nucleophilic substitution of 4-nitrophthalonitrile with 2-[3-(trifluoromethyl)phenoxy]ethanol, 2-{2-[3-(trifluoromethyl) phenoxy]ethoxy}ethanol, 2-(2,3,5,6-tetrafluorophenoxy)ethanol, 2-[2-(2,3,5,6-tetrafluorophenoxy)ethoxy]ethanol, respectively. Zinc phthalocyanines bearing fluoro-functionalized groups (2b–5b) were obtained from the corresponding phthalonitrile derivatives. The newly synthesized phthalocyanines displayed good solubility in organic solvents such as chloroform (CHCl 3 ), dichloromethane (DCM), tetrahydrofuran (THF), toluene, dimethylformamide (DMF) and dimethylsulfoxide (DMSO). On the other hand, the singlet oxygen, photodegradation, fluorescence quantum yields and fluorescence lifetime of these complexes were determined in DMSO. The effects of the substitution with fluoro-functionalized groups on these parameters were also compared. -- Highlights: • Synthesis of peripherally substituted zinc phthalocyanines. • Photophysical and photochemical properties in DMSO for phthalocyanines. • Photodynamic therapy studies

  15. Synthesis, photophysical and photochemical properties of zinc phthalocyanines bearing fluoro-functionalized substituents

    Energy Technology Data Exchange (ETDEWEB)

    Aktaş, Ayşe [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Pişkin, Mehmet [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadikoy-Istanbul (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze 41400, Kocaeli (Turkey); Bıyıklıoğlu, Zekeriya, E-mail: zekeriya_61@yahoo.com [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2014-01-15

    In this study, the synthesis of phthalonitrile derivatives bearing fluoro-functionalized groups and their peripherally-tetra substituted zinc phthalocyanine complexes were reported. The phthalonitrile derivatives 2a–5a were prepared by nucleophilic substitution of 4-nitrophthalonitrile with 2-[3-(trifluoromethyl)phenoxy]ethanol, 2-{2-[3-(trifluoromethyl) phenoxy]ethoxy}ethanol, 2-(2,3,5,6-tetrafluorophenoxy)ethanol, 2-[2-(2,3,5,6-tetrafluorophenoxy)ethoxy]ethanol, respectively. Zinc phthalocyanines bearing fluoro-functionalized groups (2b–5b) were obtained from the corresponding phthalonitrile derivatives. The newly synthesized phthalocyanines displayed good solubility in organic solvents such as chloroform (CHCl{sub 3}), dichloromethane (DCM), tetrahydrofuran (THF), toluene, dimethylformamide (DMF) and dimethylsulfoxide (DMSO). On the other hand, the singlet oxygen, photodegradation, fluorescence quantum yields and fluorescence lifetime of these complexes were determined in DMSO. The effects of the substitution with fluoro-functionalized groups on these parameters were also compared. -- Highlights: • Synthesis of peripherally substituted zinc phthalocyanines. • Photophysical and photochemical properties in DMSO for phthalocyanines. • Photodynamic therapy studies.

  16. Ratiometric Fluorescent Detection of Pb2+ by FRET-Based Phthalocyanine-Porphyrin Dyads.

    Science.gov (United States)

    Zhang, Dongli; Zhu, Mengliang; Zhao, Luyang; Zhang, Jinghui; Wang, Kang; Qi, Dongdong; Zhou, Yang; Bian, Yongzhong; Jiang, Jianzhuang

    2017-12-04

    Sensitive and selective detection of Pb 2+ is a very worthwhile endeavor in terms of both human health and environmental protection, as the heavy metal is fairly ubiquitous and highly toxic. In this study, we designed phthalocyanine-porphyrin (Pc-Por) heterodyads, namely, H 2 Pc-α-ZnPor (1) and H 2 Pc-β-ZnPor (2), by connecting a zinc(II) porphyrin moiety to the nonperipheral (α) or peripheral (β) position of a metal-free phthalocyanine moiety. Upon excitation at the porphyrin Soret region (420 nm), both of the dyads exhibited not only a porphyrin emission (605 nm) but also a phthalocyanine emission (ca. 700 nm), indicating the occurrence of intramolecular fluorescence resonance energy transfer (FRET) processes from the porphyrin donor to the phthalocyanine acceptor. The dyads can selectively bind Pb 2+ in the phthalocyanine core leading to a red shift of the phthalocyanine absorption and thus a decrease of spectral overlap between the porphyrin emission and phthalocyanine absorption, which in turn suppresses the intramolecular FRET. In addition, the binding of Pb 2+ can highly quench the emission of phthalocyanine by heavy-metal ion effects. The synergistic coupled functions endow the dyads with remarkable ratiometric fluorescent responses at two distinct wavelengths (F 605 /F 703 for 1 and F 605 /F 700 for 2). The emission intensity ratio increased as a linear function to the concentration of Pb 2+ in the range of 0-4.0 μM, whereas the detection limits were determined to be 3.4 × 10 -9 and 2.2 × 10 -8 M for 1 and 2, respectively. Furthermore, by comparative study of 1 and 2, the effects of distance and relative orientation between Pc and ZnPor fluorophores on the FRET efficiency and sensing performance were highlighted, which is helpful for further optimizing such FRET systems.

  17. Photophysical properties of a novel axially substituted tetra-α-(pentyloxy) Titanium(IV) Phthalocyanine - Hematoxylin

    Science.gov (United States)

    Jiang, Yufeng; Lv, Huafei; Yu, Xinxin; Pan, Sujuan; Zhang, Tiantian; Huang, Yide; Wang, Yuhua; Xie, Shusen; Yang, Hongqin; Peng, Yiru

    2017-06-01

    Metal phthalocyanines (MPcs) are a very important class of widespread application compounds. They are not only used as dyes but also used as catalysts, data storage, electron charge carriers in photocopiers, photoconductors in chemical sensors, and photo-antenna devices in photosysthesis, photovoltaic cells. A particular application of Pcs is that it was used as a photosensitizers (PS) for treatment of certain cancer by photodynamic therapy of cancer and non-cancer diseases. However, the molecular aggregation of phthalocyanines, which is an intrinsic property of these large π-π conjugated systems, provides an efficient non-radioactive energy relaxation pathway, thereby shortening the excited state lifetimes, and reducing the photosensitizing and target efficiency. To overcome these problems, the introduction of axial ligands to phthalocyanine can prevent the formation of aggregation to some extend. In this paper, hematoxylin axially substituted tetra-α-(pentoxy) titanium (IV) phthalocyanine (TiPc(OC5H11)4-Hematoxylin) were characterized by elemental analysis, IR, 1H NMR, UV-Vis, fluorescence spectra. No obviously Q band change was observed after the hematoxylin was substituted at the peripheral position of substituted phthalocyanine ring. Because of the rigidity structure of the hematoxylin, the fluorescence intensity of hematoxylin peripheral substituted phthalocyanine decreased compared with free substituted phthalocyanines. The fluorescence lifetimes of axially substituted phthalocyanine was fitted to be 3.613 ns. This compound may be considered as a promising photosensitizer for PDT.

  18. Layer-by-layer assembled highly absorbing hundred-layer films containing a phthalocyanine dye: Fabrication and photosensibilization by thermal treatment

    International Nuclear Information System (INIS)

    Sergeeva, Alena S.; Volkova, Elena K.; Bratashov, Daniil N.; Shishkin, Mikhail I.; Atkin, Vsevolod S.; Markin, Aleksey V.; Skaptsov, Aleksandr A.; Volodkin, Dmitry V.; Gorin, Dmitry A.

    2015-01-01

    Highly absorbing hundred-layer films based on poly(diallyldimethylammonium chloride) (PDADMAC) of various molecular weights and on sulfonated copper phthalocyanine (CuPcTs) were prepared using layer-by-layer assembly. The multilayer films grew linearly up to 54 bilayers, indicating that the same amount of CuPcTs was adsorbed at each deposition step. This amount, however, was dependent on the molecular weight of PDADMAC in the range 100-500 kDa: the higher the molecular weight, the more CuPcTs molecules were adsorbed. This can be explained by the larger surface charge number density specific to longer polymer chains. Domains of pure PDADMAC and of the PDADMAC/CuPcTs complex were formed in the films during the assembly. Uniform distribution of CuPcTs over the films could be achieved by thermal treatment, leading to an α → β phase transition in phthalocyanine at 300 °C. Annealing caused changes in the film absorbance spectra, resulting in a 30-nm red shift of the peak maxima and in a strong (up to 62%) decrease in optical density. Thermogravimetric analysis revealed thermodegradation of PDADMAC during annealing above 270 °C, giving rise to micrometer-sized cracks within the films, as evidenced by scanning electron microscopy. - Highlights: • The films exhibit the linear dependence of the adsorption on the bilayer number varied from 2 until 54. • Polyelectrolyte of the highest MW shows the maximal adsorption of copper phthalocyanine molecules. • Annealing of the films causes a red-shift of the maxima in the absorbance spectra. • Cracks and micropores emerged in the multilayer films during the annealing

  19. Competitive Adsorption-Assisted Formation of One-Dimensional Cobalt Nanochains with High CO Hydrogenation Activity

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Xin [State; Ren, Zhibo [State; Institute; Zhu, Xiaolin [State; Zhang, Qinwei [State; Mei, Donghai [Institute; Chen, Biaohua [State

    2017-10-31

    In the present work, cobalt nanochains have been successfully synthesized by a novel co assisted self-assembling formation strategy. A dramatic morphology transformation from cobalt nanoparticles to nanochains are observed when co molecules were introduced into the synthetic system. DFT calculations further confirm that competitive co-adsorbed co and oleylamine over the cobalt nanoparticles facilitates the formation of cobalt nanochains, which show higher co hydrogenation performance. The present work provides a new strategic and promising method for controllable synthesis of catalyst nanomaterials with the preferred surface structure and morphology.

  20. Photoinduced electron transfer between the dendritic zinc phthalocyanines and anthraquinone

    Science.gov (United States)

    Chen, Kuizhi; Wen, Junri; Liu, Jiangsheng; Chen, Zhenzhen; Pan, Sujuan; Huang, Zheng; Peng, Yiru

    2015-03-01

    The intermolecular electron transfer between the novel dendritic zinc (II) phthalocyanines (G1-DPcB and G2-DPcB) and anthraquinone (AQ) was studied by steady-state fluorescence and UV/Vis absorption spectroscopic methods. The effect of dendron generation on intermolecular electron transfer was investigated. The results showed that the fluorescence emission of these dendritic phthalocyanines could be greatly quenched by AQ upon excitation at 610 nm. The Stern- Volmer constant (KSV) of electron transfer was decreased with increasing the dendron generations. Our study suggested that these novel dendritic phthalocyanines were effective new electron donors and transmission complexes and could be used as a potential artifical photosysthesis system.

  1. Photoelectric characteristics of lead phthalocyanine/titanium oxide structures

    CERN Document Server

    Ray, A K; Hodgson, S N B

    2003-01-01

    A study has been carried out into the conduction, charge transfer/electron injection and photovoltaic conversion properties of TiO sub 2 -lead phthalocyanine (PbPc) heterojunctions. The results indicate that although the heterojunction area, and hence overall conversion efficiency, was low for the planar device structures used in the investigation, electron injection and effective charge separation across the dye-TiO sub 2 interface was achieved, with open circuit voltages in the region of 0.3 V. The conversion efficiency was found to be a function of the thickness of the phthalocyanine layer, increasing by a factor of more than 30 times as the thickness of the dye layer was reduced from 500 to 100 nm. The results suggest that under appropriate deposition conditions, to ensure effective coating of the inorganic phase, such phthalocyanine dyes may offer potential for use in dye sensitized photovoltaic cells.

  2. Continuous wasteless ecologically safe technology of propylenecarbonate production in presence of phthalocyanine catalysts

    Science.gov (United States)

    Afanasiev, Vladimir Vasilievich [Moscow, RU; Zefirov, Nikolai Serafimovich [Moscow, RU; Zalepugin, Dmitry Yurievich [Moscow, RU; Polyakov, Victor Stanislavovich [Moscow, RU; Tilkunova, Nataliya Alexandrovna [Moscow, RU; Tomilova, Larisa Godvigovna [Moscow, RU

    2009-09-08

    A continuous method of producing propylenecarbonate includes carboxylation of propylene oxide with carbon dioxide in presence of phthalocyanine catalyst on an inert carrier, using as the phthalocyanine catalyst at least one catalyst selected from the group consisting of not-substituted, methyl, ethyl, butyl, and tret butyl-substituted phthalocyanines of metals, including those containing counterions, and using as the carrier a hydrophobic carrier.

  3. Influence of Exchange-Correlation Functional in the Calculations of Vertical Excitation Energies of Halogenated Copper Phthalocyanines using Time-Dependent Density Functional Theory (TD-DFT)

    International Nuclear Information System (INIS)

    Lee, Sang Uck

    2013-01-01

    The accurate prediction of vertical excitation energies is very important for the development of new materials in the dye and pigment industry. A time-dependent density functional theory (TD-DFT) approach coupled with 22 different exchange-correlation functionals was used for the prediction of vertical excitation energies in the halogenated copper phthalocyanine molecules in order to find the most appropriate functional and to determine the accuracy of the prediction of the absorption wavelength and observed spectral shifts. Among the tested functional, B3LYP functional provides much more accurate vertical excitation energies and UV-vis spectra. Our results clearly provide a benchmark calibration of the TD-DFT method for phthalocyanine based dyes and pigments used in industry

  4. Phthalocyanine doping to improve critical current densities in MgB2 tapes

    International Nuclear Information System (INIS)

    Zhang Xianping; Ma Yanwei; Wang Dongliang; Gao Zhaoshun; Wang Lei; Qi Yanpeng; Awaji, Satoshi; Watanabe, Kazuo; Mossang, Eric

    2009-01-01

    Phthalocyanine-doped MgB 2 tapes were prepared by the in situ powder-in-tube method. The relationships between the critical current properties, crystallinity and microstructure were studied as a function of the phthalocyanine doping level. It is found that both H irr and H c2 were improved when MgB 2 samples were doped with phthalocyanine, which are mainly attributed to the effective carbon substitution and enhanced flux pinning strength caused by very fine grain sizes. Furthermore, compared to pure samples, the MgO content remained almost unchanged in all doped tapes, which is very beneficial to having better grain connectivity in MgB 2 . Significantly improved J c was obtained in the phthalocyanine-doped MgB 2 tapes, especially under high magnetic fields.

  5. Enhancement in photovoltaic performance of phthalocyanine-sensitized solar cells by attapulgite nanoparticles

    International Nuclear Information System (INIS)

    Jin Ling; Chen Dajun

    2012-01-01

    Highlights: ► Dye-sensitized solar cells sensitized by zinc octacarboxylic phthalocyanine. ► Attapulgite nanoparticles have been used to suppress phthalocyanine aggregation. ► Adding attapulgite improves the photovoltaic performance of the dye-sensitized solar cells. - Abstract: Attapulgite nanoparticles were used to improve photovoltaic performance of phthalocyanine-sensitized solar cells. The effects of attapulgite on the devices were investigated in details. Adding of attapulgite into TiO 2 electrodes not only reduced the adsorption of zinc octacarboxylic phthalocyanine but also prevented phthalocyanine aggregation effect, which greatly improved photovoltaic performance of the dye-sensitized solar cell. The solar cell with 10 mg attapulgite nanoparticles dispersed in the dye solution exhibited nearly three times larger photoelectric conversion efficiency under simulated AM 1.5 G irradiation (100 mW cm −2 ) when compared to the pure dye, which was further characterized by the electrochemical impedance spectroscopy (EIS). The EIS studies showed that attapulgite decreased the charge-transfer resistances at the TiO 2 /dye/electrolyte interface, which can promote electron transport.

  6. Photochemical and Photophysical Properties of Phthalocyanines Modified with Optically Active Alcohols

    Directory of Open Access Journals (Sweden)

    Aline A. Ramos

    2015-07-01

    Full Text Available Three phthalocyanine derivatives were synthesized and characterized: one modified with a racemic mixture of 1-(4-bromophenylethanol and two other macrocycles modified with each one of the enantioenriched isomers (R-1-(4-bromophenylethanol and (S-1-(4-bromophenylethanol. The compounds were characterized by 1H-NMR spectroscopy, mass spectrometry, UV-Vis absorption, and excitation and emission spectra. Additionally, partition coefficient values and the quantum yield of the generation of oxygen reactive species were determined. Interestingly, the phthalocyanine containing a (R-1-(4-bromophenylethoxy moiety showed higher quantum yield of reactive oxygen species generation than other compounds under the same conditions. In addition, the obtained fluorescence microscopy and cell viability results have shown that these phthalocyanines have different interactions with mammary MCF-7 cells. Therefore, our results indicate that the photochemical and biological properties of phthalocyanines with chiral ligands should be evaluated separately for each enantiomeric species.

  7. Adsorption of phthalocyanines on noble metal surfaces; Adsorption von Phthalocyaninen auf Edelmetalloberflaechen

    Energy Technology Data Exchange (ETDEWEB)

    Kroeger, Ingo

    2011-05-20

    In this thesis the adsorbate systems CuPc/Ag(111), CuPc/Au(111), CuPc/Cu(111), H2Pc and TiOPc/Ag(111) were investigated and characterized in great detail using complementary methods. The focus of the experiments was the determination of lateral geometric structures with spot-profile-analysis low energy electron diffraction (SPA-LEED) and scanning tunneling microscopy (STM), as well as the measurement of adsorption heights using the method of normal incidence X-ray standing waves (NIXSW). High resolution electron energy loss spectroscopy (HREELS) was used to characterize the vibronic properties of the molecule and the interface dynamical charge transfer (IDCT). The electronic structure and the charge transfer into the molecule were investigated with ultraviolet photoelectron spectroscopy (UPS). The most important results of this work are related with the interplay between adsorbate-substrate and adsorbate-adsorbate interaction of Phthalocyanines in the submonolayer regime. (orig.)

  8. Corrections to the density-functional theory electronic spectrum: Copper phthalocyanine

    DEFF Research Database (Denmark)

    Vazquez, Hector; Jelinek, P.; Brandbyge, Mads

    2009-01-01

    A method for improving the electronic spectrum of standard Density-Functional Theory (DFT) calculations (i.e., LDA or GGA approximations) is presented, and its application is discussed for the case of the copper phthalocyanine (CuPc) molecule. The method is based on a treatment of exchange...... and correlation in a many-body Hamiltonian, and it leads to easy-to-evaluate corrections to the DFT eigenvalues. Self-interaction is largely corrected, so that the modified energy levels do not suffer from spurious crossings, as often encountered for CuPc in DFT, and they remedy the standard underestimation...... or semiempirical functionals for molecular levels, it can be easily applied to any local-orbital DFT approach, improving on several important limitations of standard DFT methods....

  9. Nanocrystalline Axially Bridged Iron Phthalocyanine Polymeric Conductor: (μ-Thiocyanato(phthalocyaninatoiron(III

    Directory of Open Access Journals (Sweden)

    Eiza Shimizu

    2016-01-01

    Full Text Available Skewered Iron(III phthalocyanine conducting polymer can be constructed with the utilization of axial thiocyanato ligands ((μ-thiocyanato(phthalocyaninatoiron(III; (FeIII(Pc(SCNn thereby creating additional avenues for electron transport through a linear SCN bridge, apart from the intermolecular π-π orbital overlap between the Pc molecules. In this paper, we report on the conversion of bulk FeIII(Pc(SCNn polymeric organic conductor into crystalline nanostructures through horizontal vapor phase growth process. The needle-like nanostructures are deemed to provide more ordered and, thus, more π-π interactive interskewer FeIII(Pc(SCNn polymer orientation, resulting in a twofold increase of its electrical conductivity per materials density unit.

  10. Phthalocyanines in batteries and supercapacitors

    CSIR Research Space (South Africa)

    Oni, J

    2012-08-01

    Full Text Available of their lower cost. This review article looks through a very narrow window of the applications of phthalocyanines in batteries and supercapacitors as a means of improving the qualities such as cycle property, energy density, capacity, open circuit voltage, etc...

  11. Realisation and study of poly-phthalocyanine thin films grafted on solid substrate

    International Nuclear Information System (INIS)

    Huc, Vincent

    1999-01-01

    The aim of this work is to develop thin films of phthalocyanines covalently grafted to solid substrates. These thin films are formed of successive monomolecular layers of macrocycles, deposited on the substrate by a 'Merrifield' sequential method. These phthalocyanines have in their centre a metallic ion (such as ruthenium) which ensures the bonding of phthalocyanines on the substrate and the assembling of monolayers consecutive together. The deposition of these monolayers is provided by a succession of two spontaneous exchange ligands reactions between the labile groups L initially bound to ruthenium and to those present on the substrate (preliminary functionalized). The repetition of these two steps allows to consider the controlled formation of phthalocyanines multilayers by self-assembling. The main substrates used are the silicon oxide and the gold. Their different characteristics have imposed the development of separate functionalization and characterization methods. The results obtained with these two substrates are separately described. A second method of construction of successive monolayers of phthalocyanines is described involving a chemical coupling between an amine function carried out by the substrate and an aldehyde function present on the ligands bound on ruthenium. (author) [fr

  12. Localization Study of Co-Phthalocyanines in Cells by Raman Micro(spectro)scopy

    NARCIS (Netherlands)

    Arzhantsev, S.Y.; Arzhantsev, S.Y.; Chikishev, A.Y.; Chikishev, A.Y.; Koroteev, N.I.; Greve, Jan; Otto, Cornelis; Sijtsema, N.M.

    1999-01-01

    An investigation of intracellular localization of Co-phthalocyanines is reported. The Raman images of K562 cells stained with phthalocyanine were acquired. To understand the peculiarities of the Raman images, measurements were performed at different z-axis positions. The intracellular concentration

  13. Localization study of Co-phthalocyanines in cells by Raman micro(spectro)scopy

    NARCIS (Netherlands)

    Arzhantsev, S Y; Chikishev, A Y; Koroteev, N I; Greve, J; Otto, C; Sijtsema, N M

    An investigation of intracellular localization of Co-phthalocyanines is reported. The Raman images of K562 cells stained with phthalocyanine were acquired. To understand the peculiarities of the Raman images, measurements were performed at different z-axis positions. The intracellular concentration

  14. Synthesis of phthalocyanine conjugates with gold nanoparticles and liposomes for photodynamic therapy

    CSIR Research Space (South Africa)

    Nombona, N

    2012-02-01

    Full Text Available -damage of cancer cells. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizer were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either...

  15. Decolorization Treatment of Copper Phthalocyanine Textile Dye Wastewater by Electrochemical Methods

    Directory of Open Access Journals (Sweden)

    K. Dermentzis

    2013-01-01

    Full Text Available Electrochemical decolorization and degradation treatment of aqueous copper phthalocyanine reactive dye solutions was comparatively studied by electrocoagulation, electrooxidation and electro-Fenton processes. In the electrocoagulation process with aluminum electrodes the colored aqueous solutions of initial pH 6.4 containing 50 mg L-1 copper phthalocyanine and 6 g L-1 NaCl were treated at applied current densities of 2.5 and 5 mA cm-2. Fast and 100% decolorization was achieved in 4 and 2 minutes of electroprocessing respectively. The indirect electrooxidation process was conducted in acidic electrolyte solutions containing 50 mg L-1 copper phthalocyanine and 6 g L-1 NaCl with Ti/Pt and graphite plate electrodes at the applied current density of 10 mA cm-2. Even after 90 minutes of electrolysis time the dye remained by 23 and 18.8 % respectively undegradable. By the direct and indirect electrooxidation with the same amount of Na2SO4 electrolyte and added H2O2 respectively and using the same electrodes, the copper phthalocyanine dye was not or was only barely degraded respectively. In the electro-Fenton process with Fe electrodes and added amounts of H2O2 at pH 3 and an applied current density of 5 mA/cm2 complete degradation of copper phthalocyanine occurred in 15 minutes.

  16. Hole Mobility of Molecular β-Copper Phthalocyanine Crystal

    International Nuclear Information System (INIS)

    Pengmanayol, S.; Osotchan, T.; Suewattana, M.; Ingadapa, N.; Girdpun, J.

    2011-01-01

    A Monte Carlo approach is used to estimate hole mobilities in molecular β-copper phthalocyanine (CuPc) crystal for different applied electric field directions. Due to the crystal symmetry, the twelve neighboring molecules in the three-dimensional crystal are selected in the hopping rate calculation. Density functional theory is employed to derive the molecular interaction between the central and neighboring molecules for various applied electric fields. The derived molecular hopping rate is applied to 80 × 80 × 80 lattice sites under periodic boundary conditions. In order to achieve accurate statistics, each calculation includes 6561 particles with more than 10000 hopping steps under an applied electric field of 0.5–3.5 MV/cm. The results indicate that the molecular hopping strongly depends on the molecular orientation and neighboring sites related to the applied electric field direction. The estimated carrier mobility can be described by the percentage occupation in each neighboring site and the obtained hole mobility value is in the same range of the measured values of single crystal CuPc. The calculated mobility for applied electric field along the c crystal axis exhibits the highest values while the mobility along the b axis has the smallest value. (condensed matter: structure, mechanical and thermal properties)

  17. Recent Studies in Phthalocyanine Chemistry.

    Science.gov (United States)

    1986-07-01

    desulfurisation ) etc. Many of the uses cited In the preceding sentence involve a redox process in which two or more electrons are exchanged per reaction...phthalocyanine as a catalyst for desulfurisation of residues, effluents etc 144]. Acknowledgmnts We ars Indebted to the Natural Sciences and Engineering

  18. Cobalt(II phthalocyanine bonded to 3-n-propylimidazole immobilized on silica gel surface: preparation and electrochemical properties

    Directory of Open Access Journals (Sweden)

    Fujiwara Sergio T.

    1999-01-01

    Full Text Available Co-Phthalocyanine complex was immobilized on 3-n-propylimidazole groups grafted on a porous SiO2 surface (specific surface area S BET = 500 m² g-1 and efficiently electrocatalyzed the oxalic acid oxidation on a carbon paste electrode surface made of this material. Intermolecular interactions of the complex species which can normally interfere in the redox process practically are not observed in the present case because of a low average surface density, delta = 4.7 x 10-13 mol cm-2 (delta = Nf/S BET, where Nf is the amount of adsorbed Co-phtalocyanine per gram of modified silica gel of the complex species material prepared. The linear response of the electrode to oxalic acid concentration, between 6.5 x 10-4 and 3.2 x 10-3 mol L-1, associated with its high chemical stability makes the covalently immobilized Co-phtalocyanine complex material very attractive in preparing a new class of chemical sensors.

  19. Film formation of non-planar phthalocyanines on copper(i) iodide

    OpenAIRE

    Ramadan, A. J.; Fearn, S.; Jones, T. S. (Tim S.); Heutz, S.; Rochford, L. A. (Luke A.)

    2016-01-01

    Structural templating is frequently used in organic photovoltaic devices to control the properties of the functional layers and therefore improve efficiencies. Modification of the substrate temperatures has also been shown to impact the structure and morphology of phthalocyanine thin films. Here we combine templating by copper iodide and high substrate temperature growth and study its effect on the structure and morphology of two different non-planar phthalocyanines, chloroaluminium (ClAlPc) ...

  20. Synthesis, spectral and photophysical properties of novel phthalocyanines bearing bulky phenantroxy moiety

    International Nuclear Information System (INIS)

    Erdogmuş, Ali; Lütfi Ugur, Ahmet; Memişoglu, Abdussamed; Erden, İbrahim

    2013-01-01

    The synthesis, characterization, spectral and photophysical properties of soluble 9-Phenanthroxy substituted oxo-titanium (IV), zinc, magnesium and nickel phthalocyanines (1a, 1b, 1c and 1d) are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, 1 H–NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for spectral, fluorescence properties and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO) and toluene. All phthalocyanine complexes (1a to 1d) exhibited excellent solubility in organic solvents such as dichloromethane, chloroform, THF, toluene, DMF and DMSO. - Highlights: ► New metallophthalocyanines (1a–1d) were synthesized. ► These new phthalocyanine derivatives show the enhanced solubility in organic solvents. ► The spectral and photophysical properties of TiO(IV), zinc (II) and Mg(II) phthalocyanine (1a–1c) are investigated in DMSO and toluene. ► Ground state electronic absorption and fluorescence spectra.

  1. Deposition and properties of cobalt- and ruthenium-based ultra-thin films

    Science.gov (United States)

    Henderson, Lucas Benjamin

    Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165°C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350°C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis(trimethylphosphine)cobalt

  2. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

    KAUST Repository

    Ziani, Ahmed; Shinagawa, Tatsuya; Stegenburga, Liga; Takanabe, Kazuhiro

    2016-01-01

    of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a

  3. Charge transfer from and to manganese phthalocyanine: bulk materials and interfaces

    Directory of Open Access Journals (Sweden)

    Florian Rückerl

    2017-08-01

    Full Text Available Manganese phthalocyanine (MnPc is a member of the family of transition-metal phthalocyanines, which combines interesting electronic behavior in the fields of organic and molecular electronics with local magnetic moments. MnPc is characterized by hybrid states between the Mn 3d orbitals and the π orbitals of the ligand very close to the Fermi level. This causes particular physical properties, different from those of the other phthalocyanines, such as a rather small ionization potential, a small band gap and a large electron affinity. These can be exploited to prepare particular compounds and interfaces with appropriate partners, which are characterized by a charge transfer from or to MnPc. We summarize recent spectroscopic and theoretical results that have been achieved in this regard.

  4. Covalentely Attached Multilayer Films Comprising Phthalocyanine and Their Photoelectron Conversion Properties

    Institute of Scientific and Technical Information of China (English)

    ZANG Mao-feng; YAO Qiao-hong; YANG Zhao-hui; HUANG Chun-hui; CAO Wei-xiao

    2004-01-01

    The photosensitive multilayer films from sulfonated metal-free, sulfonated copper-, and sulfonated nickel-phthalocyanines were fabricated with diazoresin layer by layer on a substrate via electrostatic interaction by the self-assembly technique. Under UV irradiation, the linkage nature between the layers of the film is converted from the electrostatic bonding to covalent bonding. The covalently attached multilayer films are very stable towards polar solvents and salt aqueous solutions. The photovoltaic properties of the covalently attached film can be determined by means of a traditional three-electrode photoelectrochemical cell in aqueous solutions with KCl as the supporting electrolyte. The photocurrent determination has shown that the sulfonated copper-containing phthalocyanine films possess a higher photocurrent value than sulfonated metalfree and sulfonated nickel-containing phthalocyanine films.

  5. Soluble substituted phthalocyanines for OFET applications

    Czech Academy of Sciences Publication Activity Database

    Chaidogiannos, G.; Petraki, F.; Glezos, N.; Kennou, S.; Nešpůrek, Stanislav

    2008-01-01

    Roč. 152, - (2008), s. 105-108 ISSN 0921-5107. [International Workshop on Nanosciences and Nanotechnologies. Thessaloniki, 16.08.2007-18.07.2007] Institutional research plan: CEZ:AV0Z40500505 Keywords : organic electronic transistors * phthalocyanines Subject RIV: CD - Macromolecular Chemistry

  6. Separation of copper-64 from copper phthalocyanine

    International Nuclear Information System (INIS)

    Battaglin, R.I.M.

    1979-01-01

    The separation of copper-64 from irradiated copper phthalocyanine by Szilard-Chalmers effect is studied. Two methods of separation are used: one of them is based on the dissolution of the irradiated dry compound in concentrated sulfuric acid following its precipitation in water. In the other one the compound is irradiated with water in paste form following treatment with water and hydrochloric acid. The influence of the crystal form of the copper phthalocyanine on the separation yield of copper-64 is shown. Preliminary tests using the ionic exchange technique for purification and changing of copper-64 sulfate to chloride form are carried out. The specific activity using the spectrophotometric technique, after the determination of the copper concentration in solution of copper-64, is calculated. (Author) [pt

  7. Enhancing photophysical and photochemical properties of zinc(II) phthalocyanine dyes by substitution of triptycene moieties

    Energy Technology Data Exchange (ETDEWEB)

    Al-Sohaimi, Bander Roshadan [Department of Chemistry, Faculty of Science, Taibah University, P.O. Box 344, Al-Madinah Al Munawwrah (Saudi Arabia); Pişkin, Mehmet [Çanakkale Onsekiz Mart University, Vocational School of Technical Sciences, Department of Food Technology, Çanakkale 17100 (Turkey); Aljuhani, Ateyatallah; Al-Raqa, Shaya Y. [Department of Chemistry, Faculty of Science, Taibah University, P.O. Box 344, Al-Madinah Al Munawwrah (Saudi Arabia); Durmuş, Mahmut, E-mail: durmus@gtu.edu.tr [Gebze Technical University, Department of Chemistry, P.O. Box 141, Gebze 41400, Kocaeli (Turkey)

    2016-05-15

    The symmetrical zinc(II) phthalocyanines conjugated with 9,10-dioctyl-6,7-dimethoxy-2,3-dioxytriptycene or 9,10-diundecyl-6,7-dimethoxy-2,3-dioxytriptycene moieties were synthesized in this study. These novel phthalocyanines were characterized by standard characterization techniques such as {sup 1}H-NMR, FT-IR, UV–vis, Mass and Elemental Analysis. All these phthalocyanines showed highly solubility and formed non-aggregated monomeric species in most of the organic solvents. Their photochemical properties such as singlet oxygen, and photodegradation quantum yields, and photophysical properties including fluorescence quantum yields and lifetimes were investigated in toluene. The fluorescence quenching behavior of the studied zinc(II) phthalocyanines by the addition of 1,4-benzoquinone were also described in toluene.

  8. Enhancing photophysical and photochemical properties of zinc(II) phthalocyanine dyes by substitution of triptycene moieties

    International Nuclear Information System (INIS)

    Al-Sohaimi, Bander Roshadan; Pişkin, Mehmet; Aljuhani, Ateyatallah; Al-Raqa, Shaya Y.; Durmuş, Mahmut

    2016-01-01

    The symmetrical zinc(II) phthalocyanines conjugated with 9,10-dioctyl-6,7-dimethoxy-2,3-dioxytriptycene or 9,10-diundecyl-6,7-dimethoxy-2,3-dioxytriptycene moieties were synthesized in this study. These novel phthalocyanines were characterized by standard characterization techniques such as 1 H-NMR, FT-IR, UV–vis, Mass and Elemental Analysis. All these phthalocyanines showed highly solubility and formed non-aggregated monomeric species in most of the organic solvents. Their photochemical properties such as singlet oxygen, and photodegradation quantum yields, and photophysical properties including fluorescence quantum yields and lifetimes were investigated in toluene. The fluorescence quenching behavior of the studied zinc(II) phthalocyanines by the addition of 1,4-benzoquinone were also described in toluene.

  9. Synthesis and characterization of near-IR absorbing metal-free and zinc(II phthalocyanines modified with aromatic azo groups

    Directory of Open Access Journals (Sweden)

    Mukaddes Özçeşmeci

    2015-05-01

    Full Text Available Metal-free and zinc(II phthalocyanine complexes bearing peripheral (E-4-((2-hydroxynaphthalen-1-yldiazenyl units have been synthesized. Novel phthalonitrile derivative required for the preparation of phthalocyanine complexes was prepared by coupling 4-aminophthalonitrile and 2-naphthol. The structures of these new compounds were characterized by using elemental analyses, proton nuclear magnetic resonance, fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, fluorescence spectroscopy and mass spectrometry. In the UV-Vis spectra a broad absorption band appears for phthalocyanine complexes at around 450–500 nm resulting from azo-group introduced onto the phthalocyanine ring. The photophysical properties of metal-free and zinc(II phthalocyanines were studied in tetrahydrofuran.

  10. Sandwich-cell-type bulk-heterojunction organic solar cells utilizing liquid crystalline phthalocyanine

    Science.gov (United States)

    Nakata, Yuya; Usui, Toshiki; Nishikawa, Yuki; Nekelson, Fabien; Shimizu, Yo; Fujii, Akihiko; Ozaki, Masanori

    2018-03-01

    Sandwich-cell-type bulk-heterojunction organic solar cells utilizing the liquid crystalline phthalocyanine, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2), have been fabricated and their photovoltaic properties have been studied. The short-circuit current (J SC) and power conversion efficiency (PCE) depended on the blend ratio of donor and acceptor molecules, and the maximum performance, such as J SC of 3.4 mA/cm2 and PCE of 0.67%, was demonstrated, when the blend ratio of the acceptor was 10 mol %. The photovoltaic properties were discussed by taking the relationship between the column axis direction of C6PcH2 and the carrier mobility in the active layer into consideration.

  11. Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Atsushi; 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 properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of {sup 13}C, {sup 14}N and {sup 1}H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in {sup 13}C, {sup 14}N and {sup 1}H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

  12. Solvent Effect, Photochemical and Photophysical Properties of Phthalocyanines with Different Metallic Nuclei

    Directory of Open Access Journals (Sweden)

    Charles Biral Silva

    2017-12-01

    Full Text Available Photophysical and photochemical properties of lithium phthalocyanine (1, gallium(III phthalocyanine chloride (2, titanium(IV phthalocyanine dichloride (3 and iron(II phthalocyanine (4 were investigated in dimethyl sulfoxide (DMSO, tetrahydrofuran (THF and DMSO-THF mixtures. The influence of the central metal on these properties was analyzed according to solvent type, axial ligands and their paramagnetic and diamagnetic effect. Fluorescence lifetimes were recorded using a time correlated single photon counting setup (TCSPC technique. In order to demonstrate the generation of reactive oxygen species under light irradiation, the indirect method (applying 1,3-diphenylisobenzofuran (DPBF as chemical suppressor and the direct method (analyzing the phosphorescence decay curves of singlete oxygen at 1270 nm were employed. Compounds 1, 2 and 3 showed a monomeric behavior in all media while compound 4 presented low aggregation in DMSO, but a very pronounced aggregation behavior in THF. Steady-state fluorescence anisotropy was compared with emission spectra and complex 4 presented values beyond the expected limits. DOI: http://dx.doi.org/10.17807/orbital.v9i5.1047 

  13. Realization and utilization of a harmonic light scattering experiment to select new molecules with great optical nonlinearity

    International Nuclear Information System (INIS)

    Dhenaut, Christophe

    1995-01-01

    Conception of new organic materials for nonlinear optics is generally driven by a molecular engineering approach. The usual technique for determining the quadratic hyper polarizability of designed molecules is the electric field induced second harmonic (EFISH) experiment. However this technique is limited to neutral molecules with a permanent dipole moment. We have realized an harmonic light scattering (HLS) experiment which allow the measurement of any kind of molecules, polar or non polar, neutral or ionic. Using this technique we have been able to demonstrate experimentally the validity of the octupole concept (molecules without dipole moment) which has been proposed recently. We have studied molecules corresponding to various octupolar geometries. Nonlinearities are found to be comparable to those of the best dipolar compounds. We have also investigated other molecular families with different symmetry such as polyenes, sub-phthalocyanines and phthalocyanines by EFISH and HLS techniques. We have confronted results obtained by the two experiments. It appears that these results are not easy to compare, the tensorial components accessible by each experiment being different. The two experiments seems complementary. HLS experiments allow the observation of a quadratic hyper polarizability for centrosymmetric molecules. This surprising observation could be explained by the contribution of a vibration al part to the hyper polarizability measured by HLS (but not present in EFISH). Interpretation of this dynamic process is still in progress. (author) [fr

  14. Water soluble {2-[3-(diethylamino)phenoxy]ethoxy} substituted zinc(II) phthalocyanine photosensitizers

    Energy Technology Data Exchange (ETDEWEB)

    Çakır, Dilek [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Göl, Cem [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze, 41400, Kocaeli (Turkey); Çakır, Volkan [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze, 41400, Kocaeli (Turkey); Bıyıklıoğlu, Zekeriya, E-mail: zekeriya_61@yahoo.com [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Kantekin, Halit [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2015-03-15

    The new peripherally and non-peripherally tetra-{2-[3-(diethylamino)phenoxy] ethoxy} substituted zinc phthalocyanines (2a and 3a) were synthesized by cyclotetramerization of phthalonitrile derivatives (2 and 3). 2-[3-(diethylamino)phenoxy] ethoxy group was chosen as substituent because the quaternization of the diethylamino functionality on the structure of this group produced water soluble zinc phthalocyanines (2b and 3b). The water solubility is very important for many different applications such as photosensitizers in the photodynamic therapy of cancer because the water soluble photosensitizers can be injected directly to the body and they can transport to cancer cells through blood stream. The new compounds were characterized by using elemental analysis, UV–vis, IR, {sup 1}H NMR, {sup 13}C NMR and mass spectroscopies. The photophysical and photochemical properties of these novel photosensitizer compounds were examined in DMSO (both non-ionic and ionic complexes) and in PBS (for ionic complexes) solutions. The investigation of these properties is very important for the usage of the compounds as photosensitizers for PDT because determination of these properties is the first stage of potential of the compounds as photosensitizers. The bovine serum albumin (BSA) and DNA binding behaviour of the studied water soluble zinc (II) phthalocyanines were also investigated in PBS solutions for the determination of biological activity of these compounds. - Highlights: • Synthesis of water soluble zinc phthalocyanines. • Photophysical and photochemical properties for phthalocyanines. • Photodynamic therapy studies.

  15. Water soluble {2-[3-(diethylamino)phenoxy]ethoxy} substituted zinc(II) phthalocyanine photosensitizers

    International Nuclear Information System (INIS)

    Çakır, Dilek; Göl, Cem; Çakır, Volkan; Durmuş, Mahmut; Bıyıklıoğlu, Zekeriya; Kantekin, Halit

    2015-01-01

    The new peripherally and non-peripherally tetra-{2-[3-(diethylamino)phenoxy] ethoxy} substituted zinc phthalocyanines (2a and 3a) were synthesized by cyclotetramerization of phthalonitrile derivatives (2 and 3). 2-[3-(diethylamino)phenoxy] ethoxy group was chosen as substituent because the quaternization of the diethylamino functionality on the structure of this group produced water soluble zinc phthalocyanines (2b and 3b). The water solubility is very important for many different applications such as photosensitizers in the photodynamic therapy of cancer because the water soluble photosensitizers can be injected directly to the body and they can transport to cancer cells through blood stream. The new compounds were characterized by using elemental analysis, UV–vis, IR, 1 H NMR, 13 C NMR and mass spectroscopies. The photophysical and photochemical properties of these novel photosensitizer compounds were examined in DMSO (both non-ionic and ionic complexes) and in PBS (for ionic complexes) solutions. The investigation of these properties is very important for the usage of the compounds as photosensitizers for PDT because determination of these properties is the first stage of potential of the compounds as photosensitizers. The bovine serum albumin (BSA) and DNA binding behaviour of the studied water soluble zinc (II) phthalocyanines were also investigated in PBS solutions for the determination of biological activity of these compounds. - Highlights: • Synthesis of water soluble zinc phthalocyanines. • Photophysical and photochemical properties for phthalocyanines. • Photodynamic therapy studies

  16. Light-harvesting dendrimer zinc-phthalocyanines chromophores labeled single-wall carbon nanotube nanoensembles: Synthesis and photoinduced electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hongqin [Key Laboratory of Optoelectronic Science and Technology for Medicine, Ministry of Education and Fujian Provincial Key Laboratory for Photonics Technology, Fujian Normal University, Fuzhou 350007 (China); Pan, Sujuan; Ma, Dongdong; He, Dandan; Wang, Yuhua [College of Chemistry & Engineering, Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, Fuzhou 350007 (China); Xie, Shusen [Key Laboratory of Optoelectronic Science and Technology for Medicine, Ministry of Education and Fujian Provincial Key Laboratory for Photonics Technology, Fujian Normal University, Fuzhou 350007 (China); Peng, Yiru, E-mail: yirupeng@fjnu.edu.cn [College of Chemistry & Engineering, Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, Fuzhou 350007 (China)

    2016-11-15

    A novel series of light-harvesting dendrimer zinc-phthalocyanines chromophores labeled-single-wall carbon nanotubes (SWNTs) nanoparticles, in which 0–2 generations dendrimer zinc phthalocyanines covalently linked with SWNTs using either ethylenediamine or hexamethylenediamine as the space linkers were prepared. The structures and morphologies of these nanoconjugates were comprehensively characterized by Raman spectroscopy, transmission electron microscopy and thermal gravimetric analysis methods. Their photophysical properties were investigated by fluorescence and time-resolved spectroscopic methods. The photoinduced intramolecular electron transfer occurred from phthalocyanines (donors) to SWNTs (acceptors). Besides, the electron transfer exchange rates and exchange efficacies between the dendritic phthalocyanines and single-wall carbon nanotubes increased as the length of spacer linker decreased, or as the dendritic generation increased. Cyclic voltammetry (CV) method further confirmed thermodynamics possibility of the electron transfer from phthalocyanines to single-wall carbon nanotubes. These new nanoconjugates are fundamentally important due to the synergy effects of both carbon nanotubes and dendrimer phthalocyanines, which may find potential applications in the fields of drug delivery, biological labeling, or others.

  17. Cobalt Cardiomyopathy Secondary to Hip Arthroplasty: An Increasingly Prevalent Problem

    Directory of Open Access Journals (Sweden)

    Russel Tilney

    2017-01-01

    Full Text Available A forty-year-old man experienced worsening heart failure four years following bilateral complicated total hip replacement. His condition was extensively worked up but no underlying pathology was immediately evident. Given the cobalt-chromium alloy component present in the hip arthroplasties, the raised cobalt blood levels, and a fitting clinical picture coupled with radiological findings, the patient underwent right hip revision. Evidence of biotribocorrosion was present on direct visualisation intraoperatively. The patient subsequently experienced symptomatic improvement (NYHA class III to class I and echocardiography showed recovery of ejection fraction. Cobalt exists as a bivalent and trivalent molecule in circulation and produces a cytotoxicity profile similar to nanoparticles, causing neurological, thyroid, and cardiological pathology. Blood levels are not entirely useful as there is no identifiable conversion factor for levels in whole blood, serum, and erythrocytes which seem to act independently of each other. Interestingly cobalt cardiomyopathy is frequently compounded by other possible causes of cardiomyopathy such as alcohol and a link has been postulated. Definitive treatment is revision of the arthroplasty as other treatments are unproven.

  18. Effect of thickness and temperature of copper phthalocyanine films on their properties

    Directory of Open Access Journals (Sweden)

    Alieva Kh. S.

    2012-06-01

    Full Text Available The research has shown that copper phthalocyanine films, having a set of unique properties, can be successfully used as gas-sensitive coating of resistive structures. The thickness of the film, in contrast to its temperature, is not the determining factor for high sensitivity. Low operating temperature of structures with copper phthalocyanine films allows to exploit them in economy mode.

  19. An effective zinc phthalocyanine derivative for photodynamic antimicrobial chemotherapy

    International Nuclear Information System (INIS)

    Chen, Zhuo; Zhou, Shanyong; Chen, Jincan; Li, Linsen; Hu, Ping; Chen, Song; Huang, Mingdong

    2014-01-01

    Bacterial infection is a common clinical problem. The emergence of antibiotic resistant bacteria posts a severe challenge to medical practice worldwide. Photodynamic antimicrobial chemotherapy (PACT) uses laser light at specific wavelength to activate oxygen molecule in the human tissue into reactive oxygen species as antimicrobial agent. This activation of oxygen by laser light is mediated through a photosensitizer. Two key properties for potent photosensitizer are its absorbance of light in the infrared region (630–700 nm), which promotes tissue penetration depth, and the selective accumulation on bacteria instead of human tissue. We herein report a zinc phthalocyanine derivative, pentalysine β-carbonylphthalocyanine zinc (ZnPc-(Lys) 5 ) and its antimicrobial effects in vitro and in an animal infection model. This photosensitizer has strong capability to kill bacteria at 670 nm. Chemically, it is a water-soluble and cationic photosensitizer carrying positive charge under physiological pH, and can specifically target to bacteria which usually bears negative charges on its surface. Compared with anionic ZnPc counterparts, ZnPc-(Lys) 5 shows a higher phototoxicity toward bacteria. PACT studies of ZnPc-(Lys) 5 in experimental infection animal model showed a significant bacteria inhibition compared to controls, and high selectivity of ZnPc-(Lys) 5 toward bacteria. These findings suggest ZnPc-(Lys) 5 is a promising antimicrobial photosensitizer for the treatment of infectious diseases. - Highlights: • Photodynamic antimicrobial chemotherapy (PACT) with water-soluble zinc phthalocyanine derivative offers a promising measure to deal with antibiotic resistance of bacteria. • The use of portable LED light sources that are battery-powered and with low cost may make possible the deployment of systems that can be used for wound decontamination. • ZnPc-(Lys) 5 is a potent photosensitizer for treatment of infectious diseases

  20. An effective zinc phthalocyanine derivative for photodynamic antimicrobial chemotherapy

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Zhuo, E-mail: zchen@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry and Danish-Chinese Centre for Proteases and Cancer, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Zhou, Shanyong; Chen, Jincan [State Key Laboratory of Structural Chemistry and Danish-Chinese Centre for Proteases and Cancer, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Li, Linsen [Department of Biochemistry, Shenyang Medical College, Shenyang, Liaoning 110034 (China); Hu, Ping; Chen, Song [State Key Laboratory of Structural Chemistry and Danish-Chinese Centre for Proteases and Cancer, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Huang, Mingdong, E-mail: mhuang@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry and Danish-Chinese Centre for Proteases and Cancer, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2014-08-01

    Bacterial infection is a common clinical problem. The emergence of antibiotic resistant bacteria posts a severe challenge to medical practice worldwide. Photodynamic antimicrobial chemotherapy (PACT) uses laser light at specific wavelength to activate oxygen molecule in the human tissue into reactive oxygen species as antimicrobial agent. This activation of oxygen by laser light is mediated through a photosensitizer. Two key properties for potent photosensitizer are its absorbance of light in the infrared region (630–700 nm), which promotes tissue penetration depth, and the selective accumulation on bacteria instead of human tissue. We herein report a zinc phthalocyanine derivative, pentalysine β-carbonylphthalocyanine zinc (ZnPc-(Lys){sub 5}) and its antimicrobial effects in vitro and in an animal infection model. This photosensitizer has strong capability to kill bacteria at 670 nm. Chemically, it is a water-soluble and cationic photosensitizer carrying positive charge under physiological pH, and can specifically target to bacteria which usually bears negative charges on its surface. Compared with anionic ZnPc counterparts, ZnPc-(Lys){sub 5} shows a higher phototoxicity toward bacteria. PACT studies of ZnPc-(Lys){sub 5} in experimental infection animal model showed a significant bacteria inhibition compared to controls, and high selectivity of ZnPc-(Lys){sub 5} toward bacteria. These findings suggest ZnPc-(Lys){sub 5} is a promising antimicrobial photosensitizer for the treatment of infectious diseases. - Highlights: • Photodynamic antimicrobial chemotherapy (PACT) with water-soluble zinc phthalocyanine derivative offers a promising measure to deal with antibiotic resistance of bacteria. • The use of portable LED light sources that are battery-powered and with low cost may make possible the deployment of systems that can be used for wound decontamination. • ZnPc-(Lys){sub 5} is a potent photosensitizer for treatment of infectious diseases.

  1. Fluorescence behavior and singlet oxygen generating abilities of aluminum phthalocyanine in the presence of anisotropic gold nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Mthethwa, Thandekile; Nyokong, Tebello, E-mail: t.nyokong@ru.ac.za

    2015-01-15

    Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs. - Highlights: • Gold nanoparticles (spheres, rods and bipyramids) were synthesized. • Gold nanoparticles were then conjugated to a quaternized ClAl phthalocyanine. • Conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields. • An increase in the singlet oxygen quantum yields was observed for the phthalocyanine in the presence of nanoparticles.

  2. Recovery of Cobalt as Cobalt Oxalate from Cobalt Tailings Using Moderately Thermophilic Bioleaching Technology and Selective Sequential Extraction

    Directory of Open Access Journals (Sweden)

    Guobao Chen

    2016-07-01

    Full Text Available Cobalt is a very important metal which is widely applied in various critical areas, however, it is difficult to recover cobalt from minerals since there is a lack of independent cobalt deposits in nature. This work is to provide a complete process to recover cobalt from cobalt tailings using the moderately thermophilic bioleaching technology and selective sequential extraction. It is found that 96.51% Co and 26.32% Cu were extracted after bioleaching for four days at 10% pulp density. The mean compositions of the leach solutions contain 0.98 g·L−1 of Co, 6.52 g·L−1 of Cu, and 24.57 g·L−1 of Fe (III. The copper ion was then recovered by a solvent extraction process and the ferric ions were selectively removed by applying a goethite deironization process. The technological conditions of the above purification procedures were deliberately discussed. Over 98.6% of copper and 99.9% of ferric ions were eliminated from the leaching liquor. Cobalt was finally produced as cobalt oxalate and its overall recovery during the whole process was greater than 95%. The present bioleaching process of cobalt is worth using for reference to deal with low-grade cobalt ores.

  3. Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

    International Nuclear Information System (INIS)

    Ramesh, Thimmasandra Narayan

    2010-01-01

    The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co 3 O 4 . The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co 3 O 4 phase.

  4. Peculiarities of spin polarization inversion at a thiophene/cobalt interface

    KAUST Repository

    Wang, Xuhui

    2013-03-20

    We perform ab initio calculations to investigate the spin polarization at the interface between a thiophene molecule and cobalt substrate. We find that the reduced symmetry in the presence of a sulfur atom (in the thiophene molecule) leads to a strong spatial dependence of the spin polarization of the molecule. The two carbon atoms far from the sulfur acquire a polarization opposite to that of the substrate, while the carbon atoms bonded directly to sulfur possess the same polarization as the substrate. We determine the origin of this peculiar spin interface property as well as its impact on the spin transport.

  5. Graphene and Carbon-Nanotube Nanohybrids Covalently Functionalized by Porphyrins and Phthalocyanines for Optoelectronic Properties.

    Science.gov (United States)

    Wang, Aijian; Ye, Jun; Humphrey, Mark G; Zhang, Chi

    2018-04-01

    In recent years, there has been a rapid growth in studies of the optoelectronic properties of graphene, carbon nanotubes (CNTs), and their derivatives. The chemical functionalization of graphene and CNTs is a key requirement for the development of this field, but it remains a significant challenge. The focus here is on recent advances in constructing nanohybrids of graphene or CNTs covalently linked to porphyrins or phthalocyanines, as well as their application in nonlinear optics. Following a summary of the syntheses of nanohybrids constructed from graphene or CNTs and porphyrins or phthalocyanines, explicit intraconjugate electronic interactions between photoexcited porphyrins/phthalocyanines and graphene/CNTs are introduced classified by energy transfer, electron transfer, and charge transfer, and their optoelectronic applications are also highlighted. The major current challenges for the development of covalently linked nanohybrids of porphyrins or phthalocyanines and carbon nanostructures are also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Soluble phthalocyanines - new materials for optoelectronics

    Czech Academy of Sciences Publication Activity Database

    Biler, M.; Zhivkov, I.; Rakušan, J.; Karásková, M.; Pochekailov, S.; Wang, G.; Nešpůrek, Stanislav

    2005-01-01

    Roč. 7, č. 3 (2005), s. 1365-1370 ISSN 1454-4164 R&D Projects: GA MPO FT-TA/036; GA MŠk ME 700 Institutional research plan: CEZ:AV0Z40500505 Keywords : phthalocyanine * poly[3,4-(ethylenedioxy)thiophene] * electrical properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.138, year: 2005

  7. Nanotoxicity of cobalt induced by oxidant generation and glutathione depletion in MCF-7 cells.

    Science.gov (United States)

    Akhtar, Mohd Javed; Ahamed, Maqusood; Alhadlaq, Hisham A; Alshamsan, Aws

    2017-04-01

    There are very few studies regarding the biological activity of cobalt-based nanoparticles (NPs) and, therefore, the possible mechanism behind the biological response of cobalt NPs has not been fully explored. The present study was designed to explore the potential mechanisms of the cytotoxicity of cobalt NPs in human breast cancer (MCF-7) cells. The shape and size of cobalt NPs were characterized by scanning and transmission electron microscopy (SEM and TEM). The crystallinity of NPs was determined by X-ray diffraction (XRD). The dissolution of NPs was measured in phosphate-buffered saline (PBS) and culture media by atomic absorption spectroscopy (AAS). Cytotoxicity parameters, such as [3-(4,5-dimethyl thiazol-2-yl)-2,5-diphenyl tetrazolium bromide] (MTT), neutral red uptake (NRU), and lactate dehydrogenase (LDH) release suggested that cobalt NPs were toxic to MCF-7 cells in a dose-dependent manner (50-200μg/ml). Cobalt NPs also significantly induced reactive oxygen species (ROS) generation, lipid peroxidation (LPO), mitochondrial outer membrane potential loss (MOMP), and activity of caspase-3 enzymes in MCF-7 cells. Moreover, cobalt NPs decreased intracellular antioxidant glutathione (GSH) molecules. The exogenous supply of antioxidant N-acetyl cysteine in cobalt NP-treated cells restored the cellular GSH level and prevented cytotoxicity that was also confirmed by microscopy. Similarly, the addition of buthionine-[S, R]-sulfoximine, which interferes with GSH biosynthesis, potentiated cobalt NP-mediated toxicity. Our data suggested that low solubility cobalt NPs could exert toxicity in MCF-7 cells mainly through cobalt NP dissolution to Co 2+ . Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Theoretical investigation of the electronic structure of a substituted nickel phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Prabhjot, E-mail: prabhphysics@gmail.com; Sachdeva, Ritika [Department of Physics, Panjab University Chandigarh-160014, Chandigarh (India); Singh, Sukhwinder [Department of Physics, Govt. College for Girls, Ludhiana-141008, Ludhiana (India)

    2016-05-23

    The optimized geometry and electronic structure of an organic compound nickel phthalocyanine tetrasulfonic acid tetra sodium salt have been investigated using density functional theory. We have also optimized the structure of nickel phthalocyanine tetrasulfonic acid tetra sodium salt in dimethyl sulfoxide to study effects of solvent on the electronic structure and transitions. Experimentally, the electronic transitions have been studied using UV-VIS spectroscopic technique. It is observed that the electronic transitions obtained from the theoretical studies generally agree with the experiment.

  9. Blood doping by cobalt. Should we measure cobalt in athletes?

    Directory of Open Access Journals (Sweden)

    Guidi Gian

    2006-07-01

    Full Text Available Abstract Background Blood doping is commonplace in competitive athletes who seek to enhance their aerobic performances through illicit techniques. Presentation of the hypothesis Cobalt, a naturally-occurring element with properties similar to those of iron and nickel, induces a marked and stable polycythemic response through a more efficient transcription of the erythropoietin gene. Testing the hypothesis Although little information is available so far on cobalt metabolism, reference value ranges or supplementation in athletes, there is emerging evidence that cobalt is used as a supplement and increased serum concentrations are occasionally observed in athletes. Therefore, given the athlete's connatural inclination to experiment with innovative, unfair and potentially unhealthy doping techniques, cobalt administration might soon become the most suited complement or surrogate for erythropoiesis-stimulating substances. Nevertheless, cobalt administration is not free from unsafe consequences, which involve toxic effects on heart, liver, kidney, thyroid and cancer promotion. Implications of the hypothesis Cobalt is easily purchasable, inexpensive and not currently comprehended within the World Anti-Doping Agency prohibited list. Moreover, available techniques for measuring whole blood, serum, plasma or urinary cobalt involve analytic approaches which are currently not practical for antidoping laboratories. Thus more research on cobalt metabolism in athletes is compelling, along with implementation of effective strategies to unmask this potentially deleterious doping practice

  10. Unsymmetrical extended π-conjugated zinc phthalocyanine for ...

    Indian Academy of Sciences (India)

    Administrator

    mental compatibility compared to the ruthenium dyes. 2–6 ... for the development of efficient light-to-energy con- version devices. .... solution and compared to that of the phthalocyanine adsorbed onto 2 μm .... of dark current. 25. In this study ...

  11. Effect of alignment on adsorption characteristics of self-oriented multi-walled carbon nanotube arrays

    International Nuclear Information System (INIS)

    Zilli, D; Bonelli, P R; Cukierman, A L

    2006-01-01

    The adsorption characteristics of self-oriented multi-walled carbon nanotube (MWCNT) arrays are examined from N 2 (-196 deg. C) adsorption measurements. The arrays were synthesized in a laboratory by in situ chemical vapour deposition of iron or cobalt phthalocyanines at 880 and 950 deg. C, under otherwise constant conditions, in an attempt to obtain different morphological structures. For both precursors, increasing the temperature leads to MWCNT arrays with lower Brunauer-Emmett-Teller (BET) surface area and total pore volume, though the effect is more pronounced for those arising from the iron-based compound. Despite this, precursor yields of individual nanotubes of larger diameter, higher BET area and total pore volume characterize the resulting arrays compared to those arising from cobalt phthalocyanine for the same temperatures. As evidenced by SEM and TEM images, the arrays synthesized from iron phthalocyanine at 880 deg. C show better vertical alignment and denser structures than those obtained from this compound at 950 deg. C, and also from cobalt phthalocyanine at both temperatures. Further ultrasonication of the arrays produced from the iron compound brings about a significant reduction in their adsorption capacity, attributable to the pronounced disarrangement of the resulting structures. The present results demonstrate that the alignment of MWCNT arrays plays a crucial role in their N 2 adsorption characteristics

  12. Tetra- and octa-[4-(2-hydroxyethyl)phenoxy bearing novel metal-free and zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysicochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Köksoy, Baybars [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, 41400 Gebze, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey)

    2015-05-15

    In this study, four novel phthalonitriles (1–4) and their corresponding metal-free (5–8) and zinc(II) phthalocyanine derivatives (9–12) bearing 4-(hydroxyethyl)phenoxy groups were synthesized. These novel compounds were characterized by IR, elemental analyses, {sup 1}H-NMR, UV–vis, and MALDI-TOF spectral data. Furthermore, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen generation and photodegradation quantum yields) of these phthalocyanines were investigated in dimethylsulfoxide. The studied zinc(II) phthalocyanines generated highly singlet oxygen which is very important for the photodynamic therapy (PDT) of cancer. The fluorescence quenching behaviour of the newly synthesized phthalocyanine compounds were also investigated using 1,4-benzoquinone. - Highlights: • Octa and tetra 4-(hydroxyethyl)phenoxy substituted metal-free and zinc(II) phthalocyanines. • Study of photophysicochemical properties of eight new phthalocyanines. • Highly singlet oxygen generation for novel zinc(II) phthalocyanine photosensitizers.

  13. Cobalt (III) complexes as novel matrix metalloproteinase-9 inhibitors

    International Nuclear Information System (INIS)

    Lee, Jiyoun

    2012-01-01

    We have synthesized a series of novel MMP-9 inhibitors containing cobalt(III) complexes. The synthesized cobalt(III) complexes are effective as enzyme inhibitors and the attachment of a biphenyl group enhanced the efficiency of enzyme inhibition up to 6-fold. When compared to the reported non-hydroxamate MMP inhibitors, the synthesized complexes showed comparable in vitro potency. The enzyme assay showed that the cobalt(III) complex can disrupt the zinc binding active site of MMP-9 and is proposed to work via a ligand exchange mechanism. Since histidine residues are essential for the catalytic activity of a large percentage of enzymes and zinc finger proteins, these cobalt(III) complexes can serve as a prototype inhibitor towards various zinc containing enzymes and proteins. Matrix metalloproteinases (MMPs) are a family of zinc binding endopeptidases that play crucial roles in various physiological processes and diseases such as embryogenic growth, angiogenesis, arthritis, skin ulceration, liver fibrosis and tumor metastasis. Because of their implications in a wide range of diseases, MMPs are considered as intriguing drug targets. The majority of MMP inhibitors are organic small molecules containing a hydroxamate functionality for the zinc binding group. This hydroxamate group binds to a zinc(II) center in a bidentate fashion and creates a distorted trigonal bipyramidal geometry

  14. Cobalt (III) complexes as novel matrix metalloproteinase-9 inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jiyoun [Sungshin Women' s Univ., Seoul (Korea, Republic of)

    2012-04-15

    We have synthesized a series of novel MMP-9 inhibitors containing cobalt(III) complexes. The synthesized cobalt(III) complexes are effective as enzyme inhibitors and the attachment of a biphenyl group enhanced the efficiency of enzyme inhibition up to 6-fold. When compared to the reported non-hydroxamate MMP inhibitors, the synthesized complexes showed comparable in vitro potency. The enzyme assay showed that the cobalt(III) complex can disrupt the zinc binding active site of MMP-9 and is proposed to work via a ligand exchange mechanism. Since histidine residues are essential for the catalytic activity of a large percentage of enzymes and zinc finger proteins, these cobalt(III) complexes can serve as a prototype inhibitor towards various zinc containing enzymes and proteins. Matrix metalloproteinases (MMPs) are a family of zinc binding endopeptidases that play crucial roles in various physiological processes and diseases such as embryogenic growth, angiogenesis, arthritis, skin ulceration, liver fibrosis and tumor metastasis. Because of their implications in a wide range of diseases, MMPs are considered as intriguing drug targets. The majority of MMP inhibitors are organic small molecules containing a hydroxamate functionality for the zinc binding group. This hydroxamate group binds to a zinc(II) center in a bidentate fashion and creates a distorted trigonal bipyramidal geometry.

  15. Chemical wiring and soldering toward all-molecule electronic circuitry.

    Science.gov (United States)

    Okawa, Yuji; Mandal, Swapan K; Hu, Chunping; Tateyama, Yoshitaka; Goedecker, Stefan; Tsukamoto, Shigeru; Hasegawa, Tsuyoshi; Gimzewski, James K; Aono, Masakazu

    2011-06-01

    Key to single-molecule electronics is connecting functional molecules to each other using conductive nanowires. This involves two issues: how to create conductive nanowires at designated positions, and how to ensure chemical bonding between the nanowires and functional molecules. Here, we present a novel method that solves both issues. Relevant functional molecules are placed on a self-assembled monolayer of diacetylene compound. A probe tip of a scanning tunneling microscope is then positioned on the molecular row of the diacetylene compound to which the functional molecule is adsorbed, and a conductive polydiacetylene nanowire is fabricated by initiating chain polymerization by stimulation with the tip. Since the front edge of chain polymerization necessarily has a reactive chemical species, the created polymer nanowire forms chemical bonding with an encountered molecular element. We name this spontaneous reaction "chemical soldering". First-principles theoretical calculations are used to investigate the structures and electronic properties of the connection. We demonstrate that two conductive polymer nanowires are connected to a single phthalocyanine molecule. A resonant tunneling diode formed by this method is discussed. © 2011 American Chemical Society

  16. Sulphonated Phthalocyanines as Effective Oxidation Photocatalysts

    Czech Academy of Sciences Publication Activity Database

    Klusoň, P.; Drobek, M.; Strašák, Tomáš; Krýsa, J.; Karásková, M.; Rakušak, J.

    2008-01-01

    Roč. 272, 1-2 (2008), s. 213-219 ISSN 1381-1169 R&D Projects: GA ČR(CZ) GD203/03/H140; GA AV ČR(CZ) KAN400720701 Institutional research plan: CEZ:AV0Z40720504 Keywords : phthalocyanines * 4-Chlorophenol * photocatalysis Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.814, year: 2008

  17. The Synthesis And Characterization Of Wolfram Phthalocyanine For The Target Material Of High Specific Activity Radioisotope Wolfram - 188 (188W)

    International Nuclear Information System (INIS)

    Setiawan, Duyeh

    2000-01-01

    The application of 188 Re radioisotope separation on aluminia column through elution solution has increased significantly since the last two decades. The 188 Re radioisotope has been done fram 188 Re beta-decay through a neutron capture radiation on wolfram -186 target. In trhe column separation, high specific activity of 188 W radioisotope is required to get sufficient activity in small quality 188 W radioisotope has been carried out in this research. Wolfram-phthalocyanine compound was prepared by refluxing a mixture of wolfram trioxyde, (WO 3 ) and phthalonitrile, (C 8 H 4 N 2 ) at 250 o C for two hours. The synthesis of wolfram phthalocyanine is 70% purity yield, the product are green crystals, have a 193,0-193,8 o C melting points, and has a molecular formula C 3 2H 1 6 N8 WO 2 . The infra red spectrum of wolfram-phthalocyanine was the absorption band at 964,3 cm - 1 was due to the vibration of W=O bond of the wolfram dioxy-phthalocyanine. The x-ray diffraction of the wolfram dioxy-phthalocyanine was similar with molybdenum dioxy-phthalocyanine compound. This fact showed that the product was wolfram dioxy-phthalocyanine

  18. Cobalt release from inexpensive jewellery

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten Stendahl; Menné, Torkil

    2010-01-01

    . Conclusions: This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future......Objectives: The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. Methods: The cobalt spot test was used to assess cobalt release from all items...

  19. Antibacterial effect of cationic porphyrazines and anionic phthalocyanine and their interaction with plasmid DNA

    Science.gov (United States)

    Hassani, Leila; Hakimian, Fatemeh; Safaei, Elham; Fazeli, Zahra

    2013-11-01

    Resistance to antibiotics is a public health issue and identification of new antibacterial agents is one of the most important goals of pharmacological research. Among the novel developed antibacterial agents, porphyrin complexes and their derivatives are ideal candidates for use in medical applications. Phthalocyanines differ from porphyrins by having nitrogen atoms link the individual pyrrol units. The aza analogues of the phthalocyanines (azaPcs) such as tetramethylmetalloporphyrazines are heterocyclic Pc analogues. In this investigation, interaction of an anionic phthalocyanine (Cu(PcTs)) and two cationic tetrapyridinoporphyrazines including [Cu(2,3-tmtppa)]4+ and [Cu(3,4-tmtppa)]4+ complexes with plasmid DNA was studied using spectroscopic and gel electrophoresis methods. In addition, antibacterial effect of the complexes against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria was investigated using dilution test method. The results indicated that both porphyrazines have significant antibacterial properties, but Cu(PcTs) has weak antibacterial effect. Compairing the binding of the phthalocyanine and the porphyrazines to DNA demonstrated that the interaction of cationic porphyrazines is stronger than the anionic phthalocyanine remarkably. The extent of hypochromicity and red shift of absorption spectra indicated preferential intercalation of the two porphyrazine into the base pairs of DNA helix. Gel electrophoresis result implied Cu(2,3-tmtppa) and Cu(3,4-tmtppa) are able to perform cleavage of the plasmid DNA. Consequently, DNA binding and cleavage might be one of the antibacterial mechanisms of the complexes.

  20. sup(60)Co hot atom chemistry of tris(acetylacetonato) cobalt(III) adsorbed on silica gel

    International Nuclear Information System (INIS)

    Nishioji, H.; Sakai, Y.; Tominaga, T.

    1985-01-01

    The sup(60)Co hot atom reactions were studied in tris(acetylacetonato)cobalt(III) adsorbed on silica gel surface. sup(57)Fe Moessbauer spectra of tris(acetylacetonato)iron(III) in the corresponding system were also measured in order to examine the state of dispersion of complex molecules on silica gel. The retention formation processes were discussed in terms of the dependence of sup(60)Co retention on the adsorbed amount (concentration) of cobalt(III) complexes. (author)

  1. Synthesis of superconducting cobalt oxyhydrates using a novel method: Electrolyzed and oxidized water

    International Nuclear Information System (INIS)

    Liu, C.-J.; Wu, T.-H.; Hsu, L.-L.; Wang, J.-S.; Chen, S.-Y.

    2007-01-01

    By deintercalation of Na + followed by inserting bilayers of water molecules into the host lattice, the layered cobalt oxide of γ-Na 0.7 CoO 2 undergoes a topotactic transformation to a layered cobalt oxyhydrate of Na 0.35 (H 2 O) 1.3 CoO 2-δ with the c-axis expanded from c ∼ 10.9 A to c ∼ 19.6 A. In this paper, we demonstrate that the superconducting phase of c ∼ 19.6 A can be directly obtained by simply immersing γ-Na 0.7 CoO 2 powders in electrolyzed/oxidized (EO) water, which is readily available from a commercial electrolyzed water generator. We found that high oxidation-reduction potential of EO water drives the oxidation of the cobalt ions accompanying by the formation of the superconductive c ∼ 19.6 A phase. Our results demonstrate how EO water can be used to oxidize the cobalt ions and hence form superconducting cobalt oxyhydrates in a clean and simple way and may provide an economic and environment-friendly route to oxidize the transition metal of complex metal oxides

  2. Synthesis of superconducting cobalt oxyhydrates using a novel method: Electrolyzed and oxidized water

    Science.gov (United States)

    Liu, Chia-Jyi; Wu, Tsung-Hsien; Hsu, Lin-Li; Wang, Jung-Sheng; Chen, Shu-Yo

    2007-09-01

    By deintercalation of Na+ followed by inserting bilayers of water molecules into the host lattice, the layered cobalt oxide of γ-Na0.7CoO2 undergoes a topotactic transformation to a layered cobalt oxyhydrate of Na0.35(H2O)1.3CoO2-δ with the c-axis expanded from c ≈ 10.9 Å to c ≈ 19.6 Å. In this paper, we demonstrate that the superconducting phase of c ≈ 19.6 Å can be directly obtained by simply immersing γ-Na0.7CoO2 powders in electrolyzed/oxidized (EO) water, which is readily available from a commercial electrolyzed water generator. We found that high oxidation-reduction potential of EO water drives the oxidation of the cobalt ions accompanying by the formation of the superconductive c ≈ 19.6 Å phase. Our results demonstrate how EO water can be used to oxidize the cobalt ions and hence form superconducting cobalt oxyhydrates in a clean and simple way and may provide an economic and environment-friendly route to oxidize the transition metal of complex metal oxides.

  3. Synthesis of superconducting cobalt oxyhydrates using a novel method: Electrolyzed and oxidized water

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C.-J. [Department of Physics, National Changhua University of Education, Changhua 50007, Taiwan (China)], E-mail: liucj@cc.ncue.edu.tw; Wu, T.-H.; Hsu, L.-L.; Wang, J.-S.; Chen, S.-Y. [Department of Physics, National Changhua University of Education, Changhua 50007, Taiwan (China)

    2007-09-01

    By deintercalation of Na{sup +} followed by inserting bilayers of water molecules into the host lattice, the layered cobalt oxide of {gamma}-Na{sub 0.7}CoO{sub 2} undergoes a topotactic transformation to a layered cobalt oxyhydrate of Na{sub 0.35}(H{sub 2}O){sub 1.3}CoO{sub 2-{delta}} with the c-axis expanded from c {approx} 10.9 A to c {approx} 19.6 A. In this paper, we demonstrate that the superconducting phase of c {approx} 19.6 A can be directly obtained by simply immersing {gamma}-Na{sub 0.7}CoO{sub 2} powders in electrolyzed/oxidized (EO) water, which is readily available from a commercial electrolyzed water generator. We found that high oxidation-reduction potential of EO water drives the oxidation of the cobalt ions accompanying by the formation of the superconductive c {approx} 19.6 A phase. Our results demonstrate how EO water can be used to oxidize the cobalt ions and hence form superconducting cobalt oxyhydrates in a clean and simple way and may provide an economic and environment-friendly route to oxidize the transition metal of complex metal oxides.

  4. Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

    Science.gov (United States)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil; Lidén, Carola; Julander, Anneli; Møller, Per; Johansen, Jeanne Duus

    2010-08-01

    Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure. The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. The cobalt spot test was used to assess cobalt release from all items. Microstructural characterization was made using scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS). Cobalt release was found in 4 (1.1%) of 354 items. All these had a dark appearance. SEM/EDS was performed on the four dark appearing items which showed tin-cobalt plating on these. This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future. Industries may not be fully aware of the potential cobalt allergy problem.

  5. Cobalt

    International Nuclear Information System (INIS)

    Stolyarova, I.A.; Bunakova, N.Yu.

    1983-01-01

    The neutron-activation method for determining cobalt in rocks, polymetallic and iron ores and rockforming minerals at 2x10 -6 -5x10 -3 % content is developed. Cobalt determination is based on the formation under the effect of thermal neutrons of nuclear reactor of the 60 Co radioactive isotope by the 59 Co (n, γ) 60 Co reaction with radiation energy of the most intensive line of 1333 keV. Cobalt can be determined by the scheme of the multicomponent analysis from the sample with other elements. Co is determined in the solution after separation of all determinable by the scheme elements. The 60 Co intensity is measured by the mUltichannel gamma-spectrometer with Ge(Li)-detector

  6. Spontaneous Adsorption of a Co-Phthalocyanine Ionic Derivative on HOPG. An In Situ EPR Study

    Czech Academy of Sciences Publication Activity Database

    Tarábek, Ján; Klusáčková, Monika; Janda, Pavel; Tarábková, Hana; Rulíšek, Lubomír; Plšek, Jan

    2014-01-01

    Roč. 118, č. 8 (2014), s. 4198-4206 ISSN 1932-7447 R&D Projects: GA ČR(CZ) GA14-31419S Institutional support: RVO:61388963 ; RVO:61388955 Keywords : scanning tunneling microscopy * electron paramagnetic resonance * metal phthalocyanine s * copper phthalocyanine Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.772, year: 2014

  7. An application of the coincidence Doppler spectroscopy for substances of chemical interest: phthalocyanine and acetylacetonate complexes

    International Nuclear Information System (INIS)

    Ito, Y.; Suzuki, T.

    2000-01-01

    Coincidence Doppler spectroscopy, which is particularly powerful when one is concerned with high momentum components of positron annihilation gamma-rays, has been applied to two different kinds of organo-metallic ligands: metal phthalocyanines and metal acetylacetonates. The energy (momentum) profiles of the annihilation gamma-rays were the same for metal phthalocyanines indicating that positron and/or positronium are not interacting with the metal ions. However, the profiles for the metal acetylacetonates evidently showed a dependence on the kind of metal ions. Discussion is made on the features of positron interaction which are different for phthalocyanines and acetylacetonates.

  8. Cobalt release from implants and consumer items and characteristics of cobalt sensitized patients with dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Menne, Torkil; Liden, Carola

    2012-01-01

    -containing dental alloys and revised hip implant components.Results. Six of eight dental alloys and 10 of 98 revised hip implant components released cobalt in the cobalt spot test, whereas none of 50 mobile phones gave positive reactions. The clinical relevance of positive cobalt test reactions was difficult......-tested dermatitis patients in an attempt to better understand cobalt allergy.Materials and methods. 19 780 dermatitis patients aged 4-99 years were patch tested with nickel, chromium or cobalt between 1985 and 2010. The cobalt spot test was used to test for cobalt ion release from mobile phones as well as cobalt...

  9. Electrochemistry and spectroelectrochemistry of tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine, Lu2Pc4 and dimeric lutetium(III) phthalocyanine, Lu2Pc2(OAc)2

    International Nuclear Information System (INIS)

    Koca, Atif; Ceyhan, Tanju; Erbil, Mehmet K.; Ozkaya, Ali Riza; Bekaroglu, Ozer

    2007-01-01

    In this study, electrochemical, electrochromic and spectroelectrochemical properties of a tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine (Lu 2 Pc 4 2) were investigated explicitly as compared with a tert-butylcalix[4]arene bridged dimeric lutetium(III) phthalocyanine [Lu 2 Pc 2 (OAc) 2 1]. Distinctive differences between electrochemical and electrochromic properties of 1 and 2 were detected. Moreover, the properties of 1 and 2 were compared with previously reported S 4 (CH 2 ) 4 bridged Lu 2 Pc 2 (OAc) 2 and Lu 2 Pc 4 . The calixarene bridged phthalocyanine (Pc) compounds, 1 and 2 showed well-defined electrochromic behaviour with green-blue and blue-purple colour transitions. The enhanced electrochromic properties of 2, as compared to 1, were attributed to its double-decker structure, probably allowing the formation of suitable ion channels for the counter ion movement in the solid film

  10. Towards the anti-fibrillogenic activity of phthalocyanines with out-of-plane ligands: correlation with self-association proneness

    Directory of Open Access Journals (Sweden)

    Kovalska V. B.

    2013-11-01

    Full Text Available Aim. The activity of five hafnium phthalocyanines containing out-of-plane ligands as inhibitors of reaction of insulin fibril formation is studied and correlation between their inhibitory properties and tendency to self-association is discussed. Methods. Fluorescence and absorption spectroscopy. Results. For the complexes with weak proneness to self-association PcHfDbm2, PcHfPyr2, and PcHfBtfa2 the values of inhibitory activity were estimated as 60–73 %. For phthalocyanines with the pronounced tendency to self-association PcHfPiromelit and PcHfCl2 the noticeably higher inhibitory activity values (about 95 % were shown. In the presence of native or fibrilar insulin the destruction of self-associates of metal complex occurs in buffer pH 7.9, Besides upon the conditions of insulin fibrillization reaction (0.1 M HCl phthalocyanines exist predominantly as monomers. Conclusions. The phthalocyanines with out-of-plane ligands with higher tendency to self-association have shown higher inhibitory activity in the insulin fibril formation comparing with the poorly aggregated metal complexes. At the same time low-order self-associates are not involved directly in the mechanism of inhibition of insulin fibrillization and the phthalocyanines bind with protein in monomeric form. Tendency of phthalocyanines to self-association in aqueous media seems to be an «indicator» of their proneness to stack with protein aromatic amino-acids and thus of anti-fibrilogenic properties.

  11. The beneficial effects of mixing spiro-OMeTAD with n-butyl-substituted copper phthalocyanine for perovskite solar cells

    International Nuclear Information System (INIS)

    Nouri, Esmaiel; Wang, Yu-Long; Chen, Qian; Xu, Jia-Ju; Dracopoulos, Vassilios; Sygellou, Lamprini; Xu, Zong-Xiang; Mohammadi, Mohammad Reza; Lianos, Panagiotis

    2016-01-01

    Highlights: • Soluble n-butyl substituted copper phthalocyanine. • Mixture with spiro-OMeTAD and employment in perovskite solar cells. • Impressive improvement of perovskite solar cell efficiency. • n-Butyl derivative gives better results than tert-butyl derivative - Abstract: Perovskite solar cells have been constructed under ambient conditions by using 2,2',7,7'-Tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) mixed with a small quantity of soluble tetra-n-butyl substituted copper phthalocyanine as hole transporting material. The introduction of the phthalocyanine derivative resulted in an impressive increase of cell efficiency, which changed from 10.4% in the absence to 15.4% in the presence of phthalocyanine. This effect is related to the creation of deep traps in the hole transporting phase which block back-travelling electrons as well as to the improvement of the structural quality of the spiro-OMeTAD film in the presence of phthalocyanine. Both functionalities decrease shunt paths within the hole transporting phase resulting in increasing the fill factor and the open-circuit voltage of the cell.

  12. Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections

    International Nuclear Information System (INIS)

    Lüder, Johann; Eriksson, Olle; Sanyal, Biplab; Brena, Barbara

    2014-01-01

    We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μ B distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based on the total and on the spin-resolved differential charge densities are provided for bias voltages of −1.45 and 1.45 eV

  13. Active and passive control of zinc phthalocyanine photodynamics

    NARCIS (Netherlands)

    Sharma, Divya; Huijser, Jannetje Maria; Savolainen, Janne; Steen, Gerrit Willem; Herek, Jennifer Lynn

    2013-01-01

    In this work we report on the ultrafast photodynamics of the photosensitizer zinc phthalocyanine (ZnPc) and manipulation thereof. Two approaches are followed: active control via pulse shaping and passive control via strategic manipulation in the periphery of the molecular structure. The objective of

  14. Kinetic of the Intracellular Incorporation of New Phthalocyanines Synthesized in mexico and Its Potential as Photosensibilizers in the Photodynamic Therapy

    International Nuclear Information System (INIS)

    Aragon-Aguilar, Hector; Ramon-Gallegos, Eva; Arenas-Huertero, Francisco Jesus; Contreras-Ramos, Alejandra; Cruz-Orea, Alfredo; Sosa-Sanchez, Jose Luis; Garcia Miranda, Maribel

    2008-01-01

    The search of more specific and efficient photosensitizer in low oxygen tensions is a need in the Photodynamic Therapy (PDT). Phthalocyanines have demonstrated to have the above mentioned activity. The aim of this work was to determine the efficiency of PDT using two phthalocyanines synthesized in Mexico to eliminate melanoma cells. B16F0 melanoma mouse cells were exposed to concentrations from 8.95x10 -5 to 0.733 m/mL of F16VoPc and F16NbPcC13 during 24h, afterwards cellular mortality was measured. One kinetic was realized to determine the intracellular incorporation of phthalocyanines by confocal microscopy at 1, 2, 4, 8, 16 and 24 h of exposition. The PDT was applied exposing the cells to innocuous concentration (that does not provoke cellular death with out irradiation) and irradiating with an argon laser at 100 J/cm 2 . For each phthalocyanine a control group was used; one group was not treated neither with light nor with phthalocyanine, the other group it was only irradiated. 24 h after treatment the citotoxicity was measured by Alamar blue assay. The innocuous concentration found for the phthalocyanines F16VoPc and F16NbPcC13 were 4.58x10-2 and 2.29xl0 -2 mg/mL, respectively. The time of maximum intracellular accumulation for both phthalocyanines was 24 h. Only the F16VoPc had anticancerous activity and induced 31.7% of cellular death. The PDT might offer a potential alternative to the treatment of this cancer when is used the phthalocyanine F16VoPc

  15. Antiferromagnetic coupling of TbPc2 molecules to ultrathin Ni and Co films

    Directory of Open Access Journals (Sweden)

    David Klar

    2013-05-01

    Full Text Available The magnetic and electronic properties of single-molecule magnets are studied by X-ray absorption spectroscopy and X-ray magnetic circular dichroism. We study the magnetic coupling of ultrathin Co and Ni films that are epitaxially grown onto a Cu(100 substrate, to an in situ deposited submonolayer of TbPc2 molecules. Because of the element specificity of the X-ray absorption spectroscopy we are able to individually determine the field dependence of the magnetization of the Tb ions and the Ni or Co film. On both substrates the TbPc2 molecules couple antiferromagnetically to the ferromagnetic films, which is possibly due to a superexchange interaction via the phthalocyanine ligand that contacts the magnetic surface.

  16. Synthesis of the iron phthalocyaninate radical cation μ-nitrido dimer and its interaction with hydrogen peroxide

    Science.gov (United States)

    Grishina, E. S.; Makarova, A. S.; Kudrik, E. V.; Makarov, S. V.; Koifman, O. I.

    2016-03-01

    The iron phthalocyaninate μ-nitrido dimer radical cation, as well as the μ-nitrido dimer complexes of iron phthalocyaninate, was found to have high catalytic activity in the oxidation of organic compounds. It was concluded that this compound is of interest as a model of active intermediates—catalase and oxidase enzymes.

  17. Immobilization of Zinc Phthalocyanines in Silicate Matrices and Investigation of Their Photobactericidal Effect on E.coli

    Directory of Open Access Journals (Sweden)

    Spas Artarsky

    2006-01-01

    Full Text Available The aim of the present investigation was to immobilize zinc phthalocyanines in a silicate matrix and to test the photobactericidal properties of the matrices so prepared toward Esherichia coli in model aqueous media. For the purpose, tetra tertiary butyl zinc phthalocyanine (TBZnPc and zinc phthalocyanine tetrasulfonic acid (ZnPcTS were used. The abilities of these two photosensitizers to generate singlet oxygen in solution were compared by following the rate of photobleaching of 1,3-diphenylisobenzofuran (DPBF at 430 nm in dimethylformamide (DMF.The results of this study show clearly that, under the conditions used here, the TBZnPc is the more effective generator of singlet oxygen; with it the DPBF was virtually completely photobleached in 4 min, while with the ZnPcTS under the same conditions, it took 12 min to reach this point. Glass conjugates with the two phthalocyanines were obtained by the sol-gel technique and were characterized by a well-defined color due to the phthalocyanine incorporated in the silicate matrix. Glasses with an intense, but inhomogeneous, green color were obtained when the tetrasulfonic derivative of the zinc phthalocyanine was used, while blue glasses of evenly distributed coloration were formed from the tetra tertiary butyl derivative.The ZnPcTS conjugate demonstrates more effective singlet oxygen evolution than is the case with the TBZnPc conjugate. These results are the opposite of those obtained for the free phthalocyanines in solution. The structural formulae of the compounds show that TBZnPc has a more pronounced hydrophobic character than the sulfonic derivative. In our view, the relative reactivities of the conjugates can be explained by the tetrasulfonic derivative being situated mainly in the surface parts of the glass matrix where the hydrophilic character is prevailing, while the tertiary butyl derivative is mainly present in the internal parts of the matrix as a result of which it is less accessible and

  18. Photoconductivity study of acid on Zinc phthalocyanine pyridine thin films

    Science.gov (United States)

    Singh, Sukhwinder; Saini, G. S. S.; Tripathi, S. K.

    2016-05-01

    The Metal Phthalocyanine (MPc) have attracted much interest because of chemical and high thermal stability. Molecules forming a crystal of MPc are held together by weak attractive Vander Waals forces. Organic semiconductors have π conjugate bonds which allow electrons to move via π-electron cloud overlaps. Conduction mechanisms for organic semiconductor are mainly through tunneling; hopping between localized states, mobility gaps, and phonon assisted hopping. The photo conductivity of thin films of these complexes changes when exposed to oxidizing and reducing gases. Arrhenius plot is used to find the thermal activation energy in the intrinsic region and impurity scattering region. Arrhenius plotsare used to find the thermal activation energy. The original version of this article supplied to AIP Publishing contained erroneous text at the end of the abstract. "Arrhenius plots are used to find the thermal activation energy." was deleted as it does not pertain to the article. In addition, a figure citation was cited incorrectly and an equation was missing. This has been corrected in the updated version republished on 4 December 2017.

  19. Dynamical propagation of nanosecond pulses in Naphthalocyanines and Phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Quan, E-mail: qmiao2013@yahoo.com [College of Electronics, Communication and Physics, Shandong University of Science and Technology, Qingdao 266590, Shandong (China); Liang, Min; Liu, Qixin [College of Electronics, Communication and Physics, Shandong University of Science and Technology, Qingdao 266590, Shandong (China); College of Electrical Engineering and Automation, Shandong University of Science and Technology, Qingdao 266590, Shandong (China); Wang, Jing-Jing [College of Electronics, Communication and Physics, Shandong University of Science and Technology, Qingdao 266590, Shandong (China); Sun, Erping; Xu, Yan [College of Electronics, Communication and Physics, Shandong University of Science and Technology, Qingdao 266590, Shandong (China); College of Electrical Engineering and Automation, Shandong University of Science and Technology, Qingdao 266590, Shandong (China)

    2016-11-30

    Highlights: • We study the dynamical processes of nanoseconds lasers in Naphthalocyanines and Phthalocyanines. • We provide theoretical evidences of the main mechanism of optical power limiting. • The central metals play more important roles in the dynamical processes. • The main reason is the central metals enhance the spin–orbit coupling. - Abstract: Dynamical propagation and optical limiting of nanosecond pulses in peripherally substituted Naphthalocyanines (Npcs) and Phthalocyanines (Pcs) with central metals gallium and indium were theoretically studied using paraxial field and rate equations. The results demonstrated that both Npcs and Pcs have good optical limiting performances, and Npc with heavier central mental indium shows better optical limiting properities due to the stronger reverse saturable absorption, which is mainly strengthened by the larger one-photo absorption cross section of excited state and the faster intersystem crossing rate.

  20. Supramolecular Structure, Physical Properties, and Langmuir-Blodgett Film Formation of an Optically Active Liquid-Crystalline Phthalocyanine

    NARCIS (Netherlands)

    Nostrum, Cornelus F. van; Bosman, Anton W.; Gelinck, Gerwin H.; Schouten, Pieter G.; Warman, John M.; Devillers, Marinus A.C.; Meijerink, Andries; Picken, Stephen J.; Sohling, Ulrich; Schouten, Arend-Jan; Nolte, Roeland J.M.

    The structure and physical properties of optically active, metal-free 2,3,9,10,16,17,23,24-octa(S-3,7-dimethyloctoxy)phthalocyanine ((S)-Pc(8,2)) are reported and compared with those of the phthalocyanine with (R,S) side chains (mixture of 43 stereoisomers). Unlike the latter compound, (S)-Pc(8,2)

  1. Synthesis, characterization, photophysical, and photochemical properties of novel zinc(II) and indium(III) phthalocyanines containing 2-phenylphenoxy units

    Energy Technology Data Exchange (ETDEWEB)

    Ali, Haytham Elzien Alamin [Department of Chemistry, Marmara University, Istanbul 34722 (Turkey); University of Khartoum, Department of Chemistry, Faculty of Science, P.O. Box 321, Khartoum, 11115 (Sudan); Pişkin, Mehmet [Çanakkale Onsekiz Mart University, Vocational School of Technical Sciences, Department of Food Technology, Çanakkale 17100 (Turkey); Altun, Selçuk [Department of Chemistry, Marmara University, Istanbul 34722 (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, P.O. Box 141, Gebze, Kocaeli 41400 (Turkey); Odabaş, Zafer, E-mail: zodabas@marmara.edu.tr [Department of Chemistry, Marmara University, Istanbul 34722 (Turkey)

    2016-05-15

    The synthesis of highly soluble and non-aggregated peripherally/non-peripherally Zn and In(OAc) phthalocyanines was achieved by 3-/ and 4-(2-phenylphenoxy)phthalonitrile as starting materials. The novel compounds were characterized by elemental analyses, FT-IR, {sup 1}H-NMR (for phthalonitriles), UV–vis and MALDI-TOF mass (for Pcs) spectroscopic techniques. Additionally, photophysical, photochemical and spectral properties of the phthalocyanines were reported. Especially, the indium(OAc) phthalocyanines showed good singlet oxygen quantum yields in DMSO and they can be appropriate candidates as Type II photosensitizers in photodynamic therapy (PDT) applications.

  2. Synthesis, characterization, photophysical, and photochemical properties of novel zinc(II) and indium(III) phthalocyanines containing 2-phenylphenoxy units

    International Nuclear Information System (INIS)

    Ali, Haytham Elzien Alamin; Pişkin, Mehmet; Altun, Selçuk; Durmuş, Mahmut; Odabaş, Zafer

    2016-01-01

    The synthesis of highly soluble and non-aggregated peripherally/non-peripherally Zn and In(OAc) phthalocyanines was achieved by 3-/ and 4-(2-phenylphenoxy)phthalonitrile as starting materials. The novel compounds were characterized by elemental analyses, FT-IR, 1 H-NMR (for phthalonitriles), UV–vis and MALDI-TOF mass (for Pcs) spectroscopic techniques. Additionally, photophysical, photochemical and spectral properties of the phthalocyanines were reported. Especially, the indium(OAc) phthalocyanines showed good singlet oxygen quantum yields in DMSO and they can be appropriate candidates as Type II photosensitizers in photodynamic therapy (PDT) applications.

  3. Novel homo- and heterobinuclear ball-type phthalocyanines: synthesis and electrochemical, electrical, EPR and MCD spectral properties.

    Science.gov (United States)

    Odabaş, Zafer; Dumludağ, Fatih; Ozkaya, Ali Riza; Yamauchi, Seigo; Kobayashi, Nagao; Bekaroğlu, Ozer

    2010-09-21

    The mononuclear Fe(II) phthalocyanine 2 and ball-type homobinuclear Fe(II)-Fe(II) and Cu(II)-Cu(II) phthalocyanines, 3 and 4 respectively, were synthesized from the corresponding 4,4'-[1,1'-methylenebis-(naphthalene-2,1-diyl)]bis(oxy)diphthalonitrile 1, and then ball-type heterobinuclear Fe(II)-Cu(II) phthalocyanine 5 was synthesized from 2. The novel compounds 4 and 5 have been characterized by elemental analysis, UV/vis, IR and MALDI-TOF mass spectroscopies. Electron paramagnetic resonance and magnetic circular dichroism measurements of 3, 4 and 5 were also examined. The voltammetric measurements of the complexes showed the formation of various electrochemically stable ligand- and metal-based mixed-valence species, due to the intramolecular interactions between the two MPc units, especially in ball-type binuclear iron(II) phthalocyanine. Impedance spectroscopy and d.c. conductivity measurements of 4 and 5 were performed as a function of temperature (295-523 K) and frequency (40-10(5) Hz). While room temperature impedance spectra consist of a curved line, a transformation into a full semicircle with increasing temperature was observed for both compounds.

  4. Passivation and corrosion behaviours of cobalt and cobalt-chromium-molybdenum alloy

    International Nuclear Information System (INIS)

    Metikos-Hukovic, M.; Babic, R.

    2007-01-01

    Passivation and corrosion behaviour of the cobalt and cobalt-base alloy Co30Cr6Mo was studied in a simulated physiological solution containing chloride and bicarbonate ions and with pH of 6.8. The oxido-reduction processes included solid state transformations occurring at the cobalt/electrolyte interface are interpreted using theories of surface electrochemistry. The dissolution of cobalt is significantly suppressed by alloying it with chromium and molybdenum, since the alloy exhibited 'chromium like' passivity. The structural and protective properties of passive oxide films formed spontaneously at the open circuit potential or during the anodic polarization were studied using electrochemical impedance spectroscopy in the wide frequency range

  5. CoPc and CoPcF16 on gold: Site-specific charge-transfer processes

    Directory of Open Access Journals (Sweden)

    Fotini Petraki

    2014-04-01

    Full Text Available Interface properties of cobalt(II phthalocyanine (CoPc and cobalt(II hexadecafluoro-phthalocyanine (CoPcF16 to gold are investigated by photo-excited electron spectroscopies (X-ray photoemission spectroscopy (XPS, ultraviolet photoemission spectroscopy (UPS and X-ray excited Auger electron spectroscopy (XAES. It is shown that a bidirectional charge transfer determines the interface energetics for CoPc and CoPcF16 on Au. Combined XPS and XAES measurements allow for the separation of chemical shifts based on different local charges at the considered atom caused by polarization effects. This facilitates a detailed discussion of energetic shifts of core level spectra. The data allow the discussion of site-specific charge-transfer processes.

  6. Molecular dynamics simulations of H2 adsorption in tetramethyl ammonium lithium phthalocyanine crystalline structures.

    Science.gov (United States)

    Lamonte, Kevin; Gómez Gualdrón, Diego A; Cabrales-Navarro, Fredy A; Scanlon, Lawrence G; Sandi, Giselle; Feld, William; Balbuena, Perla B

    2008-12-11

    Tetramethyl ammonium lithium phthalocyanine is explored as a potential material for storage of molecular hydrogen. Density functional theory calculations are used to investigate the molecular structure and the dimer conformation. Additional scans performed to determine the interactions of a H2 molecule located at various distances from the molecular sites are used to generate a simple force field including dipole-induced-dipole interactions. This force field is employed in molecular dynamics simulations to calculate adsorption isotherms at various pressures. The regions of strongest adsorption are quantified as functions of temperature, pressure, and separation between molecules in the adsorbent phase, and compared to the regions of strongest binding energy as given by the proposed force field. It is found that the total adsorption could not be predicted only from the spatial distribution of the strongest binding energies; the available volume is the other contributing factor even if the volume includes regions of much lower binding energy. The results suggest that the complex anion is primarily involved in the adsorption process with molecular hydrogen, whereas the cation serves to provide access for hydrogen adsorption in both sides of the anion molecular plane, and spacing between the planes.

  7. Application of aluminum phthalocyanine nanoparticles for fluorescent diagnostics in dentistry and skin autotransplantology.

    Science.gov (United States)

    Vasilchenko, Sergey Yu; Volkova, Anna I; Ryabova, Anastasiya V; Loschenov, Victor B; Konov, Vitaly I; Mamedov, Adil A; Kuzmin, Sergey G; Lukyanets, Evgeniy A

    2010-06-01

    This paper deals with the possibility of application of aluminum phthalocyanine (AlPc) nanoparticles in clinical practice. AlPc fluoresces in the molecular form but in the form of nanoparticles it does not. Separation of molecules from an AlPc nanoparticle and therefore the appearance of fluorescence occurs under the effect of a number of biochemo-physical factors. Owing to this feature the application of AlPc nanoparticles followed by the measurement of fluorescence spectra is proposed as a diagnostics method. It was shown that after AlPc nanoparticle application on a tooth surface the fluorescence intensity in the enamel microdamage area is 2-3 times higher than that in the normal enamel area. The appearance of fluorescence after application of AlPc nanoparticles on skin autografts testifies to the presence of inflammation. (c) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Elicitation threshold of cobalt chloride

    DEFF Research Database (Denmark)

    Fischer, Louise A; Johansen, Jeanne D; Voelund, Aage

    2016-01-01

    : On the basis of five included studies, the ED10 values of aqueous cobalt chloride ranged between 0.0663 and 1.95 µg cobalt/cm(2), corresponding to 30.8-259 ppm. CONCLUSIONS: Our analysis provides an overview of the doses of cobalt that are required to elicit allergic cobalt contactdermatitis in sensitized...

  9. Zinc Phthalocyanine Labelled Polyethylene Glycol: Preparation, Characterization, Interaction with Bovine Serum Albumin and Near Infrared Fluorescence Imaging in Vivo

    Directory of Open Access Journals (Sweden)

    Tianjun Liu

    2012-05-01

    Full Text Available Zinc phthalocyanine labelled polyethylene glycol was prepared to track and monitor the in vivo fate of polyethylene glycol. The chemical structures were characterized by nuclear magnetic resonance and infrared spectroscopy. Their light stability and fluorescence quantum yield were evaluated by UV-Visible and fluorescence spectroscopy methods. The interaction of zinc phthalocyanine labelled polyethylene glycol with bovine serum albumin was evaluated by fluorescence titration and isothermal titration calorimetry methods. Optical imaging in vivo, organ aggregation as well as distribution of fluorescence experiments for tracking polyethylene glycol were performed with zinc phthalocyanine labelled polyethylene glycol as fluorescent agent. Results show that zinc phthalocyanine labelled polyethylene glycol has good optical stability and high emission ability in the near infrared region. Imaging results demonstrate that zinc phthalocyanine labelled polyethylene glycol can track and monitor the in vivo process by near infrared fluorescence imaging, which implies its potential in biomaterials evaluation in vivo by a real-time noninvasive method.

  10. Synthesis and Supramolecular Chemistry of Novel Liquid Crystalline Crown Ether-Substituted Phthalocyanines : Toward Molecular Wires and Molecular Ionoelectronics

    NARCIS (Netherlands)

    Nostrum, Cornelus F. van; Picken, Stephen J.; Schouten, Arend-Jan; Nolte, Roeland J.M.

    1995-01-01

    The synthesis of the metal-free and the dihydroxysilicon derivatives of tetrakis[4’,5’-bis(decoxy)benzo-18-crown-6]phthalocyanine is described. The metal-free phthalocyanine is liquid crystalline and exhibits a crystalline phase to mesophase transition at 148 °C. The structures of the crystalline

  11. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

  12. 1D and 2D Cobalt(II) Coordination Polymers, Co(ox)(en):Synthesis, Structures and Magnetic Properties

    International Nuclear Information System (INIS)

    Kang, Jae Un; Lee, Yu Mi; Kim, Seung Joo; Yun, Ho Seop; Do, Jung Hwan

    2014-01-01

    Two ethylenediamine cobalt(II) oxalate complexes Co(ox)(en), 1 and Co(ox)(en)·2H 2 O, 2 have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In 1, Co atoms are coordinated by two bis-bidentate oxalate ions in transconfiguration to form Co(ox) chains, which are further bridged by ethylenediamine molecules to produce 2D grid layers, Co(ox)(en). In 2, Co atoms are coordinated by bridging oxalate ions in cis - configuration to form Co(ox) chains, and the additional chelation of ethylenediamine to Co atoms completes 1D zigzag chain, Co(en)(ox). Two lattice water molecules stabilize the chains through hydrogen bonding. Magnetic susceptibility measurements indicate that both complexes exhibit weak antiferromagnetic coupling between cobalt(II) ions with the susceptibility maxima at 23 K for 1 and 20 K for 2, respectively. In 1 and 2, the oxalate ligands afford a much shorter and more effective pathway for the magnetic interaction between cobalt ions compared to the ethylenediamine ligands, so the magnetic behaviors of both complexes could be well described with 1D infinite magnetic chain model

  13. 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.

  14. Spectroscopic investigation of sulfonate phthalocyanine to probe enzyme reactions for heavy metals detection

    Energy Technology Data Exchange (ETDEWEB)

    Chaure, Shweta; Paul, Deepen; Vadagma, Pankaj [School of Engineering and Material Science, Queen Mary, University of London, London E1 4NS (United Kingdom); Ray, Asim K., E-mail: a.k.ray@qmul.ac.uk [School of Engineering and Material Science, Queen Mary, University of London, London E1 4NS (United Kingdom)

    2010-01-15

    Optical absorption and Raman spectra of the sulfonated copper phthalocyanine (CuTsPc) layer were exploited for detection of cadmium (Cd) contaminants in water. Acetylcholine esterase was immobilized by freely suspending them in calcium alginate microbeads and this gel was then spincoated on the drop cast sulfonated copper phthalocyanine film on a glass substrate to form a bilayer. The inhibition of catalytic reaction between acetylcholine chloride and enzyme due to Cd contaminants was monitored by recording changes in spectra of drop cast CuTsPc as an indicator. The detection limit of cadmium content in water was found to be 1 ppm.

  15. Spectroscopic investigation of sulfonate phthalocyanine to probe enzyme reactions for heavy metals detection

    International Nuclear Information System (INIS)

    Chaure, Shweta; Paul, Deepen; Vadagma, Pankaj; Ray, Asim K.

    2010-01-01

    Optical absorption and Raman spectra of the sulfonated copper phthalocyanine (CuTsPc) layer were exploited for detection of cadmium (Cd) contaminants in water. Acetylcholine esterase was immobilized by freely suspending them in calcium alginate microbeads and this gel was then spincoated on the drop cast sulfonated copper phthalocyanine film on a glass substrate to form a bilayer. The inhibition of catalytic reaction between acetylcholine chloride and enzyme due to Cd contaminants was monitored by recording changes in spectra of drop cast CuTsPc as an indicator. The detection limit of cadmium content in water was found to be 1 ppm.

  16. Giant Magnetoresistance in Carbon Nanotubes with Single-Molecule Magnets TbPc2.

    Science.gov (United States)

    Krainov, Igor V; Klier, Janina; Dmitriev, Alexander P; Klyatskaya, Svetlana; Ruben, Mario; Wernsdorfer, Wolfgang; Gornyi, Igor V

    2017-07-25

    We present experimental results and a theoretical model for the gate-controlled spin-valve effect in carbon nanotubes with side-attached single-molecule magnets TbPc 2 (Terbium(III) bis-phthalocyanine). These structures show a giant magnetoresistance up to 1000% in experiments on single-wall nanotubes that are tunnel-coupled to the leads. The proposed theoretical model combines the spin-dependent Fano effect with Coulomb blockade and predicts a spin-spin interaction between the TbPc 2 molecules, mediated by conducting electrons via the charging effect. This gate-tuned interaction is responsible for the stable magnetic ordering of the inner spins of the molecules in the absence of magnetic field. In the case of antiferromagnetic arrangement, electrons with either spin experience the scattering by the molecules, which results in blocking the linear transport. In strong magnetic fields, the Zeeman energy exceeds the effective antiferromagnetic coupling and one species of electrons is not scattered by molecules, which leads to a much lower total resistance at the resonant values of gate voltage, and hence to a supramolecular spin-valve effect.

  17. Characterization of titanyl phthalocyanine (TiOPc) thin films by microscopic and spectroscopic method

    Science.gov (United States)

    Skonieczny, R.; Makowiecki, J.; Bursa, B.; Krzykowski, A.; Szybowicz, M.

    2018-02-01

    The titanyl phthalocyanine (TiOPc) thin film deposited on glass, silicon and gold substrate have been studied using Raman spectroscopy, atomic force microscopy (AFM), absorption and profilometry measurements. The TiOPc thin layers have been deposited at room temperature by the quasi-molecular beam evaporation technique. The Raman spectra have been recorded using micro Raman system equipped with a confocal microscope. Using surface Raman mapping techni que with polarized Raman spectra the polymorphic forms of the TiOPc thin films distribution have been obtained. The AFM height and phase image were examined in order to find surface features and morphology of the thin films. Additionally to compare experimental results, structure optimization and vibrational spectra calculation of single TiOPc molecule were performed using DFT calculations. The received results showed that the parameters like polymorphic form, grain size, roughness of the surface in TiOPc thin films can well characterize the obtained organic thin films structures in terms of their use in optoelectronics and photovoltaics devices.

  18. Photosensitive heterostructures made of sulfonamide zinc phthalocyanine and organic semiconductor

    Czech Academy of Sciences Publication Activity Database

    Lutsyk, P.; Vertsimakha, Ya.; Nešpůrek, Stanislav; Pomaz, I.

    2011-01-01

    Roč. 535, - (2011), s. 18-29 ISSN 1542-1406 Institutional research plan: CEZ:AV0Z40500505 Keywords : heterostructure * reversal of sign in photovoltage spectra * sulphonamide-substituted phthalocyanine Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.580, year: 2011

  19. Crystal structures of bis(phenoxysilicon phthalocyanines: increasing π–π interactions, solubility and disorder and no halogen bonding observed

    Directory of Open Access Journals (Sweden)

    Benoît H. Lessard

    2016-07-01

    Full Text Available We report the syntheses and characterization of three solution-processable phenoxy silicon phthalocyanines (SiPcs, namely bis(3-methylphenoxy(phthalocyaninesilicon [(3MP2-SiPc], C46H30N8O2Si, bis(2-sec-butylphenoxy(phthalocyaninesilicon [(2secBP2-SiPc], C44H24I2N8O2Si, and bis(3-iodophenoxy(phthalocyaninesilicon [(3IP2-SiPc], C52H42N8O2Si. Crystals grown of these compounds were characterized by single-crystal X-ray diffraction and the π–π interactions between the aromatic SiPc cores were studied. It was determined that (3MP2-SiPc has similar interactions to previously reported bis(3,4,5-trifluorophenoxysilicon phthalocyanines [(345 F2-SiPc] with significant π–π interactions between the SiPc groups. (3IP2-SiPc and (2secBP2-SiPc both experienced a parallel stacking of two of the peripheral aromatic groups. In all three cases, the solubility of these molecules was increased by the addition of phenoxy groups while maintaining π–π interactions between the aromatic SiPc groups. The solubility of (2secBP2-SiPc was significantly higher than other bis-phenoxy-SiPcs and this was exemplified by the higher observed disorder within the crystal structure.

  20. Effect of iodine doping of phthalocyanine on the photocurrent generation in a phthalocyanine/C_<60> heterojunction

    OpenAIRE

    Mizuta, Shinsei; Iyota, Masatoshi; Tanaka, Senku; Hiromitsu, Ichiro

    2012-01-01

    Photocurrent generation in an indium?tin oxide (ITO)/iodine-doped Ni-phthalocyanine (NiPc-I_x)/C_/In/Al heterojunction device with x~1 was studied. By keeping the device in air after preparation, the device slowly reached a stationary state in which the sign of the photocurrent is opposite to that of a non-doped ITO/NiPc/C_/In/Al device although the rectification direction for the dark current is the same. By a simulation of incident photon-to-current conversion efficiency spectra and a measu...

  1. Inhibition of cobalt active dissolution by benzotriazole in slightly alkaline bicarbonate aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Gallant, Danick [Departement de Chimie, Universite Laval, Quebec (Canada); Departement de Biologie, Chimie et Geographie, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Quebec (Canada); E-mail: danick.gallant.1@ulaval.ca; Pezolet, Michel [Departement de Chimie, Universite Laval, Quebec (Canada)]. E-mail: michel.pezolet@chm.ulaval.ca; Simard, Stephan [Departement de Chimie, Universite Laval, Quebec (Canada); Departement de Biologie, Chimie et Geographie, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Quebec (Canada); E-mail: stephan_simard@uqar.qc.ca

    2007-04-20

    The efficiency of benzotriazole as inhibiting agent for the corrosion of cobalt was probed at pH ranging from 8.3 to 10.2 in a sodium bicarbonate solution, chosen to simulate mild natural environments. From electrochemical, Raman spectroscopy, atomic force microscopy and ellipsometry experiments, we have demonstrated that benzotriazole markedly affects the electrodissolution reactions, which become modeled by the formation of a [Co(II)(BTA){sub 2}.H{sub 2}O] {sub n} film according to two different mechanisms. Surface-enhanced Raman spectroscopy has shown that the polarization of a cobalt electrode at cathodic potentials with respect to its potential of zero charge allows a mechanism of specific adsorption of the neutral form of benzotriazole to take place through a suspected metal-to-molecule electron transfer and which follows Frumkin's adsorption isotherms. At the onset of the anodic dissolution, some experimental evidence suggests that these adsorbed neutral benzotriazole molecules deprotonate to yield a very thin [Co(II)(BTA){sub 2}.H{sub 2}O] {sub n} polymer-like and water-insoluble protective film, responsible for the inhibition of active dissolution processes occurring at slightly more anodic potentials. In the anodic dissolution region, deprotonated benzotriazole species present in the bulk solution favors the formation of a multilayered [Co(II)(BTA){sub 2}.H{sub 2}O] {sub n} film, which also contributes to the inhibition of any further cobalt dissolution usually observed at higher electrode potentials.

  2. Photophysicochemical, calf thymus DNA binding and in vitro photocytotoxicity properties of tetra-morpholinoethoxy-substituted phthalocyanines and their water-soluble quaternized derivatives.

    Science.gov (United States)

    Koçan, Halit; Kaya, Kerem; Özçeşmeci, İbrahim; Sesalan, B Şebnem; Göksel, Meltem; Durmuş, Mahmut; Burat, Ayfer Kalkan

    2017-12-01

    In this study, morpholinoethoxy-substituted metal-free (3), zinc(II) (4) and indium(III) (5) phthalocyanines were synthesized. These phthalocyanines were converted to their water-soluble quaternized derivatives (3Q-5Q) using excess methyl iodide as a quaternization agent. All these phthalocyanines (Pcs) were characterized by elemental analysis and different spectroscopic methods such as FT-IR, 1 H NMR, UV-Vis and mass spectrometry. The photophysical and photochemical properties such as fluorescence and generation of singlet oxygen were investigated for determination of these phthalocyanines as photosensitizers in photodynamic therapy (PDT) applications. The binding properties of quaternized phthalocyanines (3Q-5Q) to calf thymus DNA (CT-DNA) were investigated by UV-Vis and fluorescence spectrophotometric methods. The quenching effect of all quaternized phthalocyanines on the fluorescence intensity of SYBR Green-DNA complex was determined. The mixtures of 3Q, 4Q or 5Q and DNA solutions were used to determine the change in T m of double helix DNA with thermal denaturation profile. In addition, thermodynamic parameters considering their aggregation in buffer solution, which shows the spontaneity of the reactions between DNA and quaternized Pcs were investigated. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method. Peripherally tetra-substituted neutral and quaternized metal-free and metallophthalocyanines (MPcs) (Zn, In) bearing morpholinoethoxy groups were prepared. The binding of quaternized compounds (3Q-5Q) to CT-DNA were examined using UV-Vis, fluorescence spectra, thermal denaturation profiles and K SV values. Besides, thermodynamic studies indicated that binding of 3Q-5Q to DNA was spontaneous. On the other hand, in vitro phototoxicity and

  3. Spin-polarized scanning tunneling microscopy of magnetic nanostructures at the example of bcc-Co/Fe(110), Fe/Mo(110), and copper phthalocyanine/Fe(1110); Spinpolarisierte Rastertunnelmikroskopie magnetischer Nanostrukturen am Beispiel von bcc-Co/Fe(110), Fe/Mo(110) und Kupfer-Phthalocyanin/Fe(110)

    Energy Technology Data Exchange (ETDEWEB)

    Methfessel, Torsten

    2010-12-09

    This thesis provides an introduction into the technique of spin-polarized scanning tunnelling microscopy and spectroscopy as an experimental method for the investigation of magnetic nanostructures. Experimental results for the spin polarized electronic structure depending on the crystal structure of ultrathin Co layers, and depending on the direction of the magnetization for ultrathin Fe layers are presented. High-resolution measurements show the position-dependent spin polarization on a single copper-phthalocyanine molecule deposited on a ferromagnetic surface. Co was deposited by molecular beam epitaxy on the (110) surface of the bodycentered cubic metals Cr and Fe. In contrast to previous reports in the literature only two layers of Co can be stabilized in the body-centered cubic (bcc) structure. The bcc-Co films on the Fe(110) surface show no signs of epitaxial distortions. Thicker layers reconstruct into a closed-packed structure (hcp / fcc). The bcc structure increases the spin-polarization of Co to P=62 % in comparison to hcp-Co (P=45 %). The temperature-dependent spin-reorientation of ultrathin Fe/Mo(110) films was investigated by spin-polarized spectroscopy. A reorientation of the magnetic easy axis from the [110] direction along the surface normal to the in-plane [001] axis is observed at T (13.2{+-}0.5) K. This process can be identified as a discontinuous reorientation transition, revealing two simultaneous minima of the free energy in a certain temperature range. The electronic structure of mono- and double-layer Fe/Mo(110) shows a variation with the reorientation of the magnetic easy axis and with the direction of the magnetization. The investigation of the spin-polarized charge transport through a copper-phthalocyanine molecule on the Fe/Mo(110) surface provides an essential contribution to the understanding of spin-transport at the interface between metal and organic molecule. Due to the interaction with the surface of the metal the HOMO-LUMO energy

  4. Enhanced power conversion efficiency of p-i-n type organic solar cells by employing a p-layer of palladium phthalocyanine

    KAUST Repository

    Kim, Inho; Haverinen, Hanna M.; Li, Jian; Jabbour, Ghassan E.

    2010-01-01

    We demonstrate an enhancement in the power conversion efficiency (PCE) of p-i-n type organic solar cells consisting of zinc phthalocyanine (ZnPc) and fullerene (C60) using a p-layer of palladium phthalocyanine (PdPc). Solar cells employing three

  5. Structural and magnetic characterization of copper sulfonated phthalocyanine grafted onto treated polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Reznickova, A., E-mail: alena.reznickova@vscht.cz [Department of Solid State Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic); Kolska, Z. [Department of Solid State Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic); Faculty of Science, J.E. Purkyne University, 400 96 Usti nad Labem (Czech Republic); Orendac, M.; Cizmar, E. [Faculty of Science, P.J. Safarik University, Park Angelinum 9, 04013 Kosice (Slovakia); Sajdl, P. [Department of Power Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic); Svorcik, V. [Department of Solid State Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic)

    2016-08-30

    Highlights: • Polyethylene (PE) surface was activated by argon plasma discharge. • Monolayer of copper phthalocyanine was achieved. • ESR proved that CuPc coated PE surface exhibits magnetic properties. • The studied structures may have potential application in spintronics and data storage. - Abstract: This study focuses on high density polyethylene (HDPE) activated by Ar plasma treatment, subsequently grafted with copper sulfonated phthalocyanine (CuPc) especially pointing out to the surface and magnetic properties of those composites. Properties of pristine PE and their plasma treated counterparts were studied by different experimental techniques: X-ray photoelectron spectroscopy (XPS), UV–vis spectroscopy, zeta potential and by electron spin resonance (ESR). XPS analysis confirmed the successful grafting of phthalocyanine. The highest absorption was found for the sample grafted with {sup b}CuPc for 1 h. Electrokinetic analysis also confirmed the plasma treatment and also subsequent CuPc grafting influence significantly the surface chemistry and charge. These results correspond well with XPS determination. ESR studies confirmed the presence of CuPc grafted on HDPE. It was found, that grafting is mediated by magnetically inactive functional groups, rather than radicals. Magnetic properties of CuPc do not seem to change significantly after grafting CuPc on polyethylene surface.

  6. Fabrication and characterization of inverted organic solar cells using shuttle cock-type metal phthalocyanine and PCBM:P3HT

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-02-27

    Inverted organic solar cells using shuttle cock-type phthalocyanine, semiconducting polymer and fullerenes were fabricated and characterized. Photovoltaic and optical properties of the solar cells with inverted structures were investigated by optical absorption, current density-voltage characteristics. The photovoltaic properties of the tandem organic solar cell using titanyl phthalocyanine, vanadyl phthalocyanine, poly(3-hexylthiophene) (P3HT) and [6, 6]-phenyl C{sub 61}-butyric acid methyl ester (PCBM) were improved. Effect of annealing and solvent treatment on surface morphologies of the active layer was investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed for improvement of the photovoltaic performance.

  7. Fabrication and characterization of inverted organic solar cells using shuttle cock-type metal phthalocyanine and PCBM:P3HT

    International Nuclear Information System (INIS)

    Suzuki, Atsushi; Furukawa, Ryo; Akiyama, Tsuyoshi; Oku, Takeo

    2015-01-01

    Inverted organic solar cells using shuttle cock-type phthalocyanine, semiconducting polymer and fullerenes were fabricated and characterized. Photovoltaic and optical properties of the solar cells with inverted structures were investigated by optical absorption, current density-voltage characteristics. The photovoltaic properties of the tandem organic solar cell using titanyl phthalocyanine, vanadyl phthalocyanine, poly(3-hexylthiophene) (P3HT) and [6, 6]-phenyl C 61 -butyric acid methyl ester (PCBM) were improved. Effect of annealing and solvent treatment on surface morphologies of the active layer was investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed for improvement of the photovoltaic performance

  8. Electrochemistry and spectroelectrochemistry of tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine, Lu{sub 2}Pc{sub 4} and dimeric lutetium(III) phthalocyanine, Lu{sub 2}Pc{sub 2}(OAc){sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Koca, Atif [Chemical Engineering Department, Engineering Faculty, Marmara University, TR34722 Goeztepe, Istanbul (Turkey); Ceyhan, Tanju; Erbil, Mehmet K. [Department of Biochemistry, Division of Organic Chemistry, Guelhane Medical Academy (GATA), Ankara (Turkey); Ozkaya, Ali Riza [Department of Chemistry, Marmara University, TR34722 Goeztepe, Istanbul (Turkey)], E-mail: aliozkaya@marmara.edu.tr; Bekaroglu, Ozer [Department of Chemistry, Technical University of Istanbul, TR34469 Maslak, Istanbul (Turkey)], E-mail: obek@itu.edu.tr

    2007-11-09

    In this study, electrochemical, electrochromic and spectroelectrochemical properties of a tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine (Lu{sub 2}Pc{sub 4}2) were investigated explicitly as compared with a tert-butylcalix[4]arene bridged dimeric lutetium(III) phthalocyanine [Lu{sub 2}Pc{sub 2}(OAc){sub 2}1]. Distinctive differences between electrochemical and electrochromic properties of 1 and 2 were detected. Moreover, the properties of 1 and 2 were compared with previously reported S{sub 4}(CH{sub 2}){sub 4} bridged Lu{sub 2}Pc{sub 2}(OAc){sub 2} and Lu{sub 2}Pc{sub 4}. The calixarene bridged phthalocyanine (Pc) compounds, 1 and 2 showed well-defined electrochromic behaviour with green-blue and blue-purple colour transitions. The enhanced electrochromic properties of 2, as compared to 1, were attributed to its double-decker structure, probably allowing the formation of suitable ion channels for the counter ion movement in the solid film.

  9. Zinc(II) phthalocyanines immobilized in mesoporous silica Al-MCM-41 and their applications in photocatalytic degradation of pesticides

    Energy Technology Data Exchange (ETDEWEB)

    Silva, M. [Departamento de Quimica, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra (Portugal); Laboratoire de Photochimie Moleculaire et Macromoleculaire, UMR CNRS 6505, Universite Blaise Pascal, F-63177 Aubiere cedex (France); Calvete, M.J.F.; Goncalves, N.P.F.; Burrows, H.D. [Departamento de Quimica, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra (Portugal); Sarakha, M. [Laboratoire de Photochimie Moleculaire et Macromoleculaire, UMR CNRS 6505, Universite Blaise Pascal, F-63177 Aubiere cedex (France); Fernandes, A.; Ribeiro, M.F. [Instituto para a Biotecnologia e Bioengenharia, Centro para a Engenharia Biologica e Quimica, Instituto Superior Tecnico - Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Azenha, M.E., E-mail: meazenha@ci.uc.pt [Departamento de Quimica, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra (Portugal); Pereira, M.M., E-mail: mmpereira@qui.uc.pt [Departamento de Quimica, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra (Portugal)

    2012-09-30

    Highlights: Black-Right-Pointing-Pointer Complete immobilization of zinc(II) phthalocyanines accomplished in Al-MCM-41. Black-Right-Pointing-Pointer Efficient photodegradation of model pesticides achieved using 365 nm irradiation. Black-Right-Pointing-Pointer Sodium azide experiments showed the involvement of singlet oxygen ({sup 1}O{sub 2}). - Abstract: In the present study the authors investigated a set of three new zinc(II) phthalocyanines (zinc(II) tetranitrophthalocyanine (ZnTNPc), zinc(II) tetra(phenyloxy)phthalocyanine (ZnTPhOPc) and the tetraiodide salt of zinc(II)tetra(N,N,N-trimethylaminoethyloxy) phthalocyaninate (ZnTTMAEOPcI)) immobilized into Al-MCM-41 prepared via ship-in-a-bottle methodology. The samples were fully characterized by diffuse reflectance-UV-vis spectroscopy (DRS-UV-vis), luminescence, thermogravimetric analysis (TG/DSC), N{sub 2} adsorption techniques and elemental analysis. A comparative study was made on the photocatalytic performance upon irradiation within the wavelength range 320-460 nm of these three systems in the degradation of pesticides fenamiphos and pentachlorophenol. ZnTNPc-Al-MCM-41 and ZnTTMAEOPcI-Al-MCM-41 were found to be the most active systems, with the best performance observed with the immobilized cationic phthalocyanine, ZnTTMAEOPcI-Al-MCM-41. This system showed high activity even after three photocatalytic cycles. LC-MS product characterization and mechanistic studies indicate that singlet oxygen ({sup 1}O{sub 2}), produced by excitation of these immobilized photosensitizers, is a key intermediate in the photocatalytic degradation of both pesticides.

  10. Zinc(II) phthalocyanines immobilized in mesoporous silica Al-MCM-41 and their applications in photocatalytic degradation of pesticides

    International Nuclear Information System (INIS)

    Silva, M.; Calvete, M.J.F.; Gonçalves, N.P.F.; Burrows, H.D.; Sarakha, M.; Fernandes, A.; Ribeiro, M.F.; Azenha, M.E.; Pereira, M.M.

    2012-01-01

    Highlights: ► Complete immobilization of zinc(II) phthalocyanines accomplished in Al-MCM-41. ► Efficient photodegradation of model pesticides achieved using 365 nm irradiation. ► Sodium azide experiments showed the involvement of singlet oxygen ( 1 O 2 ). - Abstract: In the present study the authors investigated a set of three new zinc(II) phthalocyanines (zinc(II) tetranitrophthalocyanine (ZnTNPc), zinc(II) tetra(phenyloxy)phthalocyanine (ZnTPhOPc) and the tetraiodide salt of zinc(II)tetra(N,N,N-trimethylaminoethyloxy) phthalocyaninate (ZnTTMAEOPcI)) immobilized into Al-MCM-41 prepared via ship-in-a-bottle methodology. The samples were fully characterized by diffuse reflectance-UV–vis spectroscopy (DRS-UV–vis), luminescence, thermogravimetric analysis (TG/DSC), N 2 adsorption techniques and elemental analysis. A comparative study was made on the photocatalytic performance upon irradiation within the wavelength range 320–460 nm of these three systems in the degradation of pesticides fenamiphos and pentachlorophenol. ZnTNPc-Al-MCM-41 and ZnTTMAEOPcI-Al-MCM-41 were found to be the most active systems, with the best performance observed with the immobilized cationic phthalocyanine, ZnTTMAEOPcI-Al-MCM-41. This system showed high activity even after three photocatalytic cycles. LC–MS product characterization and mechanistic studies indicate that singlet oxygen ( 1 O 2 ), produced by excitation of these immobilized photosensitizers, is a key intermediate in the photocatalytic degradation of both pesticides.

  11. Photoemission from valence bands of transition metal-phthalocyanines

    International Nuclear Information System (INIS)

    Shang, Ming-Hui; Nagaosa, Mayumi; Nagamatsu, Shin-ichi; Hosoumi, Shunsuke; Kera, Satoshi; Fujikawa, Takashi; Ueno, Nobuo

    2011-01-01

    Research highlights: → The HOMO mainly comes from the carbon atoms of Pc rings and the central metal atoms almost have no contribution on the highest occupied molecular orbital (HOMO: a 1u ) distribution of CoPc as well as NiPc. → Influence by central metal atom on the photoemission intensities from the HOMO of two single molecule systems is negligible for the major. → The modification of the distribution for π-orbital upon adsorption as well as the scattering effects of the central metal on the photoemission intensities are negligible for the major. - Abstract: Angular dependencies of ultraviolet photoelectron spectrum of transition metal-phthalocyanines (TM-Pcs), NiPc and CoPc, have been studied by using multiple-scattering theory to explore the electronic structure of the organometallic complexes influenced by central metal atom. The calculated angular distributions of photoelectrons for the highest occupied molecular orbital (HOMO: a 1u ) from the two single systems are nearly the same and represent well the experimental results obtained for the well-ordered monolayer on the highly oriented pyrolytic graphite substrate. The central metal atoms almost have no contribution on the HOMO distribution, which mainly comes from the carbon atoms of Pc ring. Moreover, the modification of the distribution for π orbital upon adsorption as well as the scattering effects of the central metal on the photoemission intensities are negligible for the major.

  12. Reactive oxygen species produced by irradiation of some phthalocyanine derivatives

    Czech Academy of Sciences Publication Activity Database

    Černý, J.; Karásková, M.; Rakušan, J.; Nešpůrek, Stanislav

    2010-01-01

    Roč. 210, č. 1 (2010), s. 82-88 ISSN 1010-6030 R&D Projects: GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40500505 Keywords : singlet oxygen * photosensitizer * phthalocyanine Subject RIV: CG - Electrochemistry Impact factor: 2.243, year: 2010

  13. Cobalt metabolism and toxicology—A brief update

    International Nuclear Information System (INIS)

    Simonsen, Lars Ole; Harbak, Henrik; Bennekou, Poul

    2012-01-01

    Cobalt metabolism and toxicology are summarized. The biological functions of cobalt are updated in the light of recent understanding of cobalt interference with the sensing in almost all animal cells of oxygen deficiency (hypoxia). Cobalt (Co 2+ ) stabilizes the transcriptional activator hypoxia-inducible factor (HIF) and thus mimics hypoxia and stimulates erythropoietin (Epo) production, but probably also by the same mechanism induces a coordinated up-regulation of a number of adaptive responses to hypoxia, many with potential carcinogenic effects. This means on the other hand that cobalt (Co 2+ ) also may have beneficial effects under conditions of tissue hypoxia, and possibly can represent an alternative to hypoxic preconditioning. Cobalt is acutely toxic in larger doses, and in mammalian in vitro test systems cobalt ions and cobalt metal are cytotoxic and induce apoptosis and at higher concentrations necrosis with inflammatory response. Cobalt metal and salts are also genotoxic, mainly caused by oxidative DNA damage by reactive oxygen species, perhaps combined with inhibition of DNA repair. Of note, the evidence for carcinogenicity of cobalt metal and cobalt sulfate is considered sufficient in experimental animals, but is as yet considered inadequate in humans. Interestingly, some of the toxic effects of cobalt (Co 2+ ) have recently been proposed to be due to putative inhibition of Ca 2+ entry and Ca 2+ -signaling and competition with Ca 2+ for intracellular Ca 2+ -binding proteins. The tissue partitioning of cobalt (Co 2+ ) and its time-dependence after administration of a single dose have been studied in man, but mainly in laboratory animals. Cobalt is accumulated primarily in liver, kidney, pancreas, and heart, with the relative content in skeleton and skeletal muscle increasing with time after cobalt administration. In man the renal excretion is initially rapid but decreasing over the first days, followed by a second, slow phase lasting several weeks, and

  14. High carrier mobility of CoPc wires based field-effect transistors using bi-layer gate dielectric

    Directory of Open Access Journals (Sweden)

    Murali Gedda

    2013-11-01

    Full Text Available Polyvinyl alcohol (PVA and anodized Al2O3 layers were used as bi-layer gate for the fabrication of cobalt phthalocyanine (CoPc wire base field-effect transistors (OFETs. CoPc wires were grown on SiO2 surfaces by organic vapor phase deposition method. These devices exhibit a field-effect carrier mobility (μEF value of 1.11 cm2/Vs. The high carrier mobility for CoPc molecules is attributed to the better capacitive coupling between the channel of CoPc wires and the gate through organic-inorganic dielectric layer. Our measurements also demonstrated the way to determine the thicknesses of the dielectric layers for a better process condition of OFETs.

  15. Synthesis and spectral properties of europium phthalocyanine complexes

    International Nuclear Information System (INIS)

    Maksimova, K.N.; Bazyakina, N.L.; Kutyreva, V.V.; Suvorova, O.N.; Domrachev, G.A.

    2008-01-01

    Synthesis of europium monophthalocyanic complexes with thenoyltrifluroacetonate (tta) and ferrocenoyltrifluoroacetate (fta) ligands has been considered. Spectral characteristics of complexes PcEu(tta)(ttaH) and PcEu(fta)(ftaH) (Pc - phthalocyanine ligand) have been investigated. One of β-diketonate ligand is proposed to bind with europium ion covalently, and the second ligand saturates coordination sphere of europium due to donor-acceptor binding [ru

  16. Electronic and gas sensing properties of soluble phthalocyanines

    Czech Academy of Sciences Publication Activity Database

    Pochekaylov, Sergey; Rais, David; Nešpůrek, Stanislav; Rakušan, J.; Karásková, M.

    2009-01-01

    Roč. 27, č. 3 (2009), s. 781-795 ISSN 0137-1339. [International Conference on Electtrical and Related Properties of Organic Solids /11./. Wroclaw, 13.07.2008-17.07.2008] R&D Projects: GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40500505 Keywords : substituted phthalocyanine * nitrogen dioxide sensor * optical properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.384, year: 2009

  17. Application of nanophotosensitizers (aluminum phthalocyanine nanoparticles) for early diagnosis and prevention of inflammatory diseases

    Science.gov (United States)

    Kuznetsova, J. O.; Makarov, V. I.

    2016-08-01

    This paper deals with a possibility of new types of photosensitizers application - Aluminum Phthalocyanine nanoparticles (nAlPc) in clinical practice for diagnosis, prevention and therapy of inflammatory diseases in dentistry and traumatology. It was detected that the aluminum phthalocyanine (AlPc) fluoresces in the nanoparticle form in the presence of pathologic microflora or inflammation process. It will make possible to detect the local accumulation of pathological microflora on the enamel surface and also for diagnostics and treatment of inflammatory diseases. Experimental studies of interaction of NP-AlPc with tooth enamel and with biological joint tissue at arthrosis are presented.

  18. Application of nanophotosensitizers (aluminum phthalocyanine nanoparticles) for early diagnosis and prevention of inflammatory diseases

    International Nuclear Information System (INIS)

    Kuznetsova, J O; Makarov, V I

    2016-01-01

    This paper deals with a possibility of new types of photosensitizers application - Aluminum Phthalocyanine nanoparticles (nAlPc) in clinical practice for diagnosis, prevention and therapy of inflammatory diseases in dentistry and traumatology. It was detected that the aluminum phthalocyanine (AlPc) fluoresces in the nanoparticle form in the presence of pathologic microflora or inflammation process. It will make possible to detect the local accumulation of pathological microflora on the enamel surface and also for diagnostics and treatment of inflammatory diseases. Experimental studies of interaction of NP-AlPc with tooth enamel and with biological joint tissue at arthrosis are presented. (paper)

  19. Cobalt metabolism and toxicology-A brief update

    Energy Technology Data Exchange (ETDEWEB)

    Simonsen, Lars Ole, E-mail: LOSimonsen@dadlnet.dk; Harbak, Henrik; Bennekou, Poul

    2012-08-15

    Cobalt metabolism and toxicology are summarized. The biological functions of cobalt are updated in the light of recent understanding of cobalt interference with the sensing in almost all animal cells of oxygen deficiency (hypoxia). Cobalt (Co{sup 2+}) stabilizes the transcriptional activator hypoxia-inducible factor (HIF) and thus mimics hypoxia and stimulates erythropoietin (Epo) production, but probably also by the same mechanism induces a coordinated up-regulation of a number of adaptive responses to hypoxia, many with potential carcinogenic effects. This means on the other hand that cobalt (Co{sup 2+}) also may have beneficial effects under conditions of tissue hypoxia, and possibly can represent an alternative to hypoxic preconditioning. Cobalt is acutely toxic in larger doses, and in mammalian in vitro test systems cobalt ions and cobalt metal are cytotoxic and induce apoptosis and at higher concentrations necrosis with inflammatory response. Cobalt metal and salts are also genotoxic, mainly caused by oxidative DNA damage by reactive oxygen species, perhaps combined with inhibition of DNA repair. Of note, the evidence for carcinogenicity of cobalt metal and cobalt sulfate is considered sufficient in experimental animals, but is as yet considered inadequate in humans. Interestingly, some of the toxic effects of cobalt (Co{sup 2+}) have recently been proposed to be due to putative inhibition of Ca{sup 2+} entry and Ca{sup 2+}-signaling and competition with Ca{sup 2+} for intracellular Ca{sup 2+}-binding proteins. The tissue partitioning of cobalt (Co{sup 2+}) and its time-dependence after administration of a single dose have been studied in man, but mainly in laboratory animals. Cobalt is accumulated primarily in liver, kidney, pancreas, and heart, with the relative content in skeleton and skeletal muscle increasing with time after cobalt administration. In man the renal excretion is initially rapid but decreasing over the first days, followed by a second, slow

  20. Properties of uncharged water-soluble tetra({omega}-methoxypolyethyleneoxy)phthalocyanine free base: Viable switching of the optical response by means of H{sub 3}O{sup +} ions

    Energy Technology Data Exchange (ETDEWEB)

    Mineo, Placido [Department of Chemistry, University of Catania and INSTM UdR of Catania, Viale Andrea Doria 6, 95125 Catania (Italy); Istituto per i Processi Chimico Fisici - CNR, Viale Ferdinando Stagno D' Alcontres, 37, 98158 Messina (Italy); Lupo, Fabio; Fragala, Ignazio; Scamporrino, Emilio [Department of Chemistry, University of Catania and INSTM UdR of Catania, Viale Andrea Doria 6, 95125 Catania (Italy); Gulino, Antonino, E-mail: agulino@unict.it [Department of Chemistry, University of Catania and INSTM UdR of Catania, Viale Andrea Doria 6, 95125 Catania (Italy)

    2012-02-15

    An uncharged water-soluble tetra ({omega}-methoxypolyethyleneoxy)phthalocyanine was characterized by MALDI-TOF mass spectrometry, UV-vis and luminescence measurements. The polyether substituents render water soluble this uncharged phthalocyanine. Relevant changes are observed in emission measurements upon protonation. The phthalocyanine free base and its protonated forms can be switched alternating H{sub 3}O{sup +} and OH{sup -} ions as inputs, being the intensity of the luminescence spectra the output. Binary codes 1 or 0 can be assigned to the high luminescent phthalocyanine free base state or to the low luminescent protonated state, respectively. The read-out procedure is fast and the system is reversible. In addition, the exploiting of the luminescent properties of the present water soluble phthalocyanine could be of relevance also for biological applications (photosensitizers for the photodynamic therapy). Highlights: Black-Right-Pointing-Pointer An uncharged water soluble tetra ({omega}-methoxypolyethyleneoxy)phthalocyanine was characterized. Black-Right-Pointing-Pointer Phthalocyanine protonation changes the luminescence output. Black-Right-Pointing-Pointer The system can be switched alternating H{sub 3}O{sup +} and OH{sup -} as inputs. Black-Right-Pointing-Pointer The read-out procedure is fast and reversible. Black-Right-Pointing-Pointer Binary codes are assigned to the high and low luminescent states, respectively.

  1. Cobalt Fischer-Tropsch catalysts: influence of cobalt dispersion and titanium oxides promotion

    Energy Technology Data Exchange (ETDEWEB)

    Azib, H

    1996-04-10

    The aim of this work is to study the effect of Sol-Gel preparation parameters which occur in silica supported cobalt catalysts synthesis. These catalysts are particularly used for the waxes production in natural gas processing. The solids have been characterized by several techniques: transmission electron microscopy (TEM), X-ray absorption near edge spectroscopy (XANES), programmed temperature reduction (TPR), infrared spectroscopy (IR), ultraviolet spectroscopy (UV), Magnetism, thermodesorption of H{sub 2} (TPD). The results indicate that the control of the cobalt dispersion and oxide phases nature is possible by modifying Sol-Gel parameters. The catalytic tests in Fischer-Tropsch synthesis were conducted on a pilot unit under pressure (20 atm) and suggested that turnover rates were independent of Co crystallite size, Co phases in the solids (Co deg., cobalt silicate) and titanium oxide promotion. On the other methane, the C{sub 3}{sup +} hydrocarbon selectivity is increased with increasing crystallite size. Inversely, the methane production is favoured by very small crystallites, cobalt silicate increase and titanium addition. However, the latter, used as a cobalt promoter, has a benefic effect on the active phase stability during the synthesis. (author). 149 refs., 102 figs., 71 tabs.

  2. Ambipolar Cu- and Fe-phthalocyanine single-crystal field-effect transistors

    NARCIS (Netherlands)

    De Boer, R.W.I.; Stassen, A.F.; Craciun, M.F.; Mulder, C.L.; Molinari, A.; Rogge, S.; Morpurgo, A.F.

    2005-01-01

    We report the observation of ambipolar transport in field-effect transistors fabricated on single crystals of copper- and iron-phthalocyanine, using gold as a high work-function metal for the fabrication of source and drain electrodes. In these devices, the room-temperature mobility of holes reaches

  3. Cobalt accumulation and circulation by blackgum trees

    International Nuclear Information System (INIS)

    Thomas, W.A.

    1975-01-01

    Blackgum (Nyssa sylvatica Marsh.) trees accumulate far greater concentrations of cobalt in mature foliage than do other species on the same site (363 ppM in ash of blackgum, compared with about 3 ppM by mockernut hickory and about 1 ppM by red maple, tulip tree, and white oak). Cobalt concentrations in dormant woody tissues of blackgum also significantly exceed those in the other four species. Inoculation of six blackgums with 60 Co revealed that cobalt remains mobile in the trees for at least 3 years. Foliar concentrations of stable cobalt increase uniformly until senescence. In late August, foliage accounts for only 9 percent of total tree weight but 57 percent of total tree cobalt. Losses of cobalt from trees occur almost entirely by leaf abscission, and the loss rates of weight and cobalt from decomposing litter are similar. Retention of cobalt in the biologically active soil layers perpetuates zones of cobalt concentration created by this species in woodlands

  4. Phase and Texture of Solution-Processed Copper Phthalocyanine Thin Films Investigated by Two-Dimensional Grazing Incidence X-Ray Diffraction

    Directory of Open Access Journals (Sweden)

    Lulu Deng

    2011-07-01

    Full Text Available The phase and texture of a newly developed solution-processed copper phthalocyanine (CuPc thin film have been investigated by two-dimensional grazing incidence X-ray diffraction. The results show that it has β phase crystalline structure, with crystallinity greater than 80%. The average size of the crystallites is found to be about 24 nm. There are two different arrangements of crystallites, with one dominating the diffraction pattern. Both of them have preferred orientation along the thin film normal. Based on the similarities to the vacuum deposited CuPc thin films, the new solution processing method is verified to offer a good alternative to vacuum process, for the fabrication of low cost small molecule based organic photovoltaics.

  5. Cobalt-60 production in CANDU power reactors

    International Nuclear Information System (INIS)

    Slack, J.; Norton, J.L.; Malkoske, G.R.

    2003-01-01

    MDS Nordion has been supplying cobalt-60 sources to industry for industrial and medical purposes since 1946. These cobalt-60 sources are used in many market and product segments. The major application is in the health care industry where irradiators are used to sterilize single use medical products. These irradiators are designed and built by MDS Nordion and are used by manufacturers of surgical kits, gloves, gowns, drapes and other medical products. The irradiator is a large shielded room with a storage pool for the cobalt-60 sources. The medical products are circulated through the shielded room and exposed to the cobalt-60 sources. This treatment sterilizes the medical products which can then be shipped to hospitals for immediate use. Other applications for this irradiation technology include sanitisation of cosmetics, microbial reduction of pharmaceutical raw materials and food irradiation. The cobalt-60 sources are manufactured by MDS Nordion in their Cobalt Operations Facility in Kanata. More than 75,000 cobalt-60 sources for use in irradiators have been manufactured by MDS Nordion. The cobalt-60 sources are double encapsulated in stainless steel capsules, seal welded and helium leak tested. Each source may contain up to 14,000 curies. These sources are shipped to over 170 industrial irradiators around the world. This paper will focus on the MDS Nordion proprietary technology used to produce the cobalt-60 isotope in CANDU reactors. Almost 55 years ago MDS Nordion and Atomic Energy of Canada developed the process for manufacturing cobalt-60 at the Chalk River Labs, in Ontario, Canada. A cobalt-59 target was introduced into a research reactor where the cobalt-59 atom absorbed one neutron to become cobalt-60. Once the cobalt-60 material was removed from the research reactor it was encapsulated in stainless steel and seal welded using a Tungsten Inert Gas weld. The first cobalt-60 sources manufactured using material from the Chalk River Labs were used in cancer

  6. Electroplated zinc-cobalt alloy

    International Nuclear Information System (INIS)

    Carpenter, D.E.O.S.; Farr, J.P.G.

    2005-01-01

    Recent work on the deposition and use of ectrodeposited zinc-cobalt alloys is surveyed. Alloys containing lower of Nuclear quantities of cobalt are potentially more useful. The structures of the deposits is related to their chemical and mechanical properties. The inclusion of oxide and its role in the deposition mechanism may be significant. Chemical and engineering properties relate to the metallurgical structure of the alloys, which derives from the mechanism of deposition. The inclusion of oxides and hydroxides in the electroplate may provide evidence for this mechanism. Electrochemical impedance measurements have been made at significant deposition potentials, in alkaline electrolytes. These reveal a complex electrode behaviour which depends not only on the electrode potential but on the Co content of the electrolyte. For the relevant range of cathodic potential zinc-cobalt alloy electrodeposition occurs through a stratified interface. The formation of an absorbed layer ZnOH/sup +/ is the initial step, this inhibits the deposition of cobalt at low cathodic potentials, so explaining its 'anomalous deposition'. A porous layer of zinc forms on the adsorbed ZnOH/sup +/ at underpotential. As the potential becomes more cathodic, cobalt co- deposits from its electrolytic complex forming a metallic solid solution of Co in Zn. In electrolytes containing a high concentration of cobalt a mixed entity (ZnCo)/sub +/ is assumed to adsorb at the cathode from which a CoZn intermetallic deposits. (author)

  7. Cobalt allergy in hard metal workers

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, T; Rystedt, I

    1983-03-01

    Hard metal contains about 10% cobalt. 853 hard metal workers were examined and patch tested with substances from their environment. Initial patch tests with 1% cobalt chloride showed 62 positive reactions. By means of secondary serial dilution tests, allergic reactions to cobalt were reproduced in 9 men and 30 women. Weak reactions could not normally be reproduced. A history of hand eczema was found in 36 of the 39 individuals with reproducible positive test reactions to cobalt, while 21 of 23 with a positive initial patch test but negative serial dilution test had never had any skin problems. Hand etching and hand grinding, mainly female activities and traumatic to the hands, were found to involve the greatest risk of cobalt sensitization. 24 individuals had an isolated cobalt allergy. They had probably been sensitized by hard metal work, while the individuals, all women, who had simultaneous nickel allergy had probably been sensitized to nickel before their employment and then became sensitized to cobalt by hard metal work. A traumatic occupation, which causes irritant contact dermatitis and/or a previous contact allergy or atopy is probably a prerequisite for the development of cobalt allergy.

  8. Pharmacokinetics of inorganic cobalt and a vitamin B12 supplement in the Thoroughbred horse: Differentiating cobalt abuse from supplementation.

    Science.gov (United States)

    Hillyer, L L; Ridd, Z; Fenwick, S; Hincks, P; Paine, S W

    2018-05-01

    While cobalt is an essential micronutrient for vitamin B 12 synthesis in the horse, at supraphysiological concentrations, it has been shown to enhance performance in human subjects and rats, and there is evidence that its administration in high doses to horses poses a welfare threat. Animal sport regulators currently control cobalt abuse via international race day thresholds, but this work was initiated to explore means of potentially adding to application of those thresholds since cobalt may be present in physiological concentrations. To devise a scientific basis for differentiation between presence of cobalt from bona fide supplementation and cobalt doping through the use of ratios. Six Thoroughbred horses were given 10 mL vitamin B 12 /cobalt supplement (Hemo-15 ® ; Vetoquinol, Buckingham, Buckinghamshire, UK., 1.5 mg B 12 , 7 mg cobalt gluconate = 983 μg total Co) as an i.v. bolus then an i.v. infusion (15 min) of 100 mg cobalt chloride (45.39 mg Co) 6 weeks later. Pre-and post-administration plasma and urine samples were analysed for cobalt and vitamin B 12 . Urine and plasma samples were analysed for vitamin B 12 using an immunoassay and cobalt concentrations were measured via ICP-MS. Baseline concentrations of cobalt in urine and plasma for each horse were subtracted from their cobalt concentrations post-administration for the PK analysis. Compartmental analysis was used for the determination of plasma PK parameters for cobalt using commercially available software. On administration of a vitamin B 12 /cobalt supplement, the ratio of cobalt to vitamin B 12 in plasma rapidly increased to approximately 3 and then rapidly declined below a ratio of 1 and then back to near baseline over the next week. On administration of 100 mg cobalt chloride, the ratio initially exceeded 10 in plasma and then declined with the lower 95% confidence interval remaining above a ratio of 1 for 7 days. For two horses with extended sampling, the plasma ratio remained above one for

  9. Low voltage operating OFETs based on solution processed metal phthalocyanines

    Czech Academy of Sciences Publication Activity Database

    Chaidogiannos, G.; Petraki, F.; Glezos, N.; Kennou, S.; Nešpůrek, Stanislav

    2009-01-01

    Roč. 96, č. 3 (2009), s. 763-767 ISSN 0947-8396 R&D Projects: GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40500505 Keywords : field-effect transistors * thin-film transistors * copper phthalocyanine Subject RIV: CG - Electrochemistry Impact factor: 1.595, year: 2009

  10. COBALT SALTS PRODUCTION BY USING SOLVENT EXTRACTION

    Directory of Open Access Journals (Sweden)

    Liudmila V. Dyakova

    2010-06-01

    Full Text Available The paper deals with the extracting cobalt salts by using mixtures on the basis of tertiary amine from multicomponent solutions from the process of hydrochloride leaching of cobalt concentrate. The optimal composition for the extraction mixture, the relationship between the cobalt distribution coefficients and modifier’s nature and concentration, and the saltingout agent type have been determined. A hydrochloride extraction technology of cobalt concentrate yielding a purified concentrated cobalt solution for the production of pure cobalt salts has been developed and introduced at Severonikel combine.

  11. Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance

    International Nuclear Information System (INIS)

    Qi, B.; Andrew, J. S.; Arnold, D. P.

    2017-01-01

    This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe_6_6Co_3_4) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe_2O_4) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.

  12. Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance

    Energy Technology Data Exchange (ETDEWEB)

    Qi, B. [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States); Andrew, J. S. [University of Florida, Department of Materials Science and Engineering (United States); Arnold, D. P., E-mail: darnold@ufl.edu [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States)

    2017-03-15

    This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe{sub 66}Co{sub 34}) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.

  13. Synthesis, aggregation and spectroscopic studies of novel water soluble metal free, zinc, copper and magnesium phthalocyanines and investigation of their anti-bacterial properties

    Science.gov (United States)

    Bayrak, Rıza; Akçay, Hakkı Türker; Beriş, Fatih Şaban; Şahin, Ertan; Bayrak, Hacer; Demirbaş, Ümit

    2014-12-01

    In this study, novel phthalonitrile derivative (3) was synthesized by the reaction between 4-nitrophthalonitrile (2) and a triazole derivative (1) containing pyridine moiety. Crystal structure of compound (3) was characterized by X-ray diffraction. New metal free and metallo-phthalocyanine complexes (Zn, Cu, and Mg) were synthesized using the phthalonitrile derivative (3). Cationic derivatives of these phthalocyanines (5, 7, 9, and 11) were prepared from the non-ionic phthalocyanines (4, 6, 8, and 10). All proposed structures were supported by instrumental methods. The aggregation behaviors of the phthalocyanines (4-11) were investigated in different solvents such as dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), chloroform and water. Water soluble cationic Pcs (5, 7, 9, and 11) aggregated in water and sodium dodecyl sulfate was used to prevent the aggregation. The second derivatives of the UV-Vis spectra of aggregated Pcs were used for analyzing the Q and B bands of aggregated species. Thermal behaviors of the phthalocyanines were also studied. In addition, anti-bacterial properties of the phthalocyanines were investigated. We used four gram negative and two gram positive bacteria to determine antibacterial activity of these compounds. Compound 7 has the best activity against the all bacteria with 125 μg/mL of MIC value. Compounds 4, 6, and 10 have the similar effect on the bacteria with 250 μg/mL of MIC value.

  14. Enhanced Charge Separation Efficiency in Pyridine-Anchored Phthalocyanine-Sensitized Solar Cells by Linker Elongation.

    Science.gov (United States)

    Ikeuchi, Takuro; Agrawal, Saurabh; Ezoe, Masayuki; Mori, Shogo; Kimura, Mutsumi

    2015-11-01

    A series of zinc phthalocyanine sensitizers (PcS22-24) having a pyridine anchoring group are designed and synthesized to investigate the structural dependence on performance in dye-sensitized solar cells. The pyridine-anchor zinc phthalocyanine sensitizer PcS23 shows 79 % incident-photon to current-conversion efficiency (IPCE) and 6.1 % energy conversion efficiency, which are comparable with similar phthalocyanine dyes having a carboxylic acid anchoring group. Based on DFT calculations, the high IPCE is attributed with the mixture of an excited-state molecular orbital of the sensitizer and the orbitals of TiO2 . Between pyridine and carboxylic acid anchor dyes, opposite trends are observed in the linker-length dependence of the IPCE. The red-absorbing PcS23 is applied for co-sensitization with a carboxyl-anchor organic dye D131 that has a complementary spectral response. The site-selective adsorption of PcS23 and D131 on the TiO2 surface results in a panchromatic photocurrent response for the whole visible-light region of sun light. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Nickel acts as an adjuvant during cobalt sensitization

    DEFF Research Database (Denmark)

    Bonefeld, Charlotte Menne; Nielsen, Morten Milek; Vennegaard, Marie T.

    2015-01-01

    Metal allergy is the most frequent form of contact allergy with nickel and cobalt being the main culprits. Typically, exposure comes from metal-alloys where nickel and cobalt co-exist. Importantly, very little is known about how co-exposure to nickel and cobalt affects the immune system. We...... investigated these effects by using a recently developed mouse model. Mice were epicutaneously sensitized with i) nickel alone, ii) nickel in the presence of cobalt, iii) cobalt alone, or iv) cobalt in the presence of nickel, and then followed by challenge with either nickel or cobalt alone. We found...... that sensitization with nickel alone induced more local inflammation than cobalt alone as measured by increased ear-swelling. Furthermore, the presence of nickel during sensitization to cobalt led to a stronger challenge response to cobalt as seen by increased ear-swelling and increased B and T cell responses...

  16. Side chain polysiloxanes with phthalocyanine moieties

    Directory of Open Access Journals (Sweden)

    T. Ganicz

    2012-05-01

    Full Text Available Side chain polysiloxane with 5-(pentyloxy-3-methyloxy-9,10,16,17,23,24-hexakis(octenyloxyphthalocyanine moieties is synthesized by hydrosilylation reaction. The phase behavior and thermooptical properties of the polysiloxane and starting 2-(pent-4-enyloxy-3-methyloxy-9,10,16,17,23,24-hexakis(octenyloxyphthalocyanine is examined by POM (Polarizing optical microscopy, TOA (thermooptical analysis, DSC (differential scanning calorimetry, AFM (atomic force microscopy and SAXS (small angle X-ray scattering studies. The effect of the attachment of phthalocyanine to polysiloxane chains over phase transitions and phase morphology is discussed in details.

  17. Electrochemical study on the effect of Schiff base and its cobalt complex on the acid corrosion of steel

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Gaber, A.M. [Chemistry Department, Faculty of Science, Alexandria University, Ibrahimia, P.O. Box 426, Alexandria 21321 (Egypt)], E-mail: ashrafmoustafa@yahoo.com; Masoud, M.S.; Khalil, E.A.; Shehata, E.E. [Chemistry Department, Faculty of Science, Alexandria University, Ibrahimia, P.O. Box 426, Alexandria 21321 (Egypt)

    2009-12-15

    The effect of the Schiff base N,N'-bis (salicylaldehyde)-1,3-diaminopropane (Salpr) and its corresponding cobalt complex on the corrosion behaviour of steel in 1 M sulphuric acid solution were studied by electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization techniques. Spectrophotometry measurements were employed to investigate the stability of the complex in acid media. The inhibitive effect of Salpr and its stable octahedral cobalt complex is argued to their adsorption over the steel surface. Theoretical fitting of different isotherms, Langmuir, Flory-Huggins and the kinetic-thermodynamic model were tested to clarify the nature of adsorption. The data revealed that there might be non-ideal behaviour in the adsorption processes of Co(Salpr) complex on the steel surface. The Co(Salpr) could displace more water molecules from the steel surface than the corresponding Salpr. The bulky Co(Salpr) molecule could cover more than one active site.

  18. Effect of iodine doping of phthalocyanine on the photocurrent generation in a phthalocyanine/C{sub 60} heterojunction

    Energy Technology Data Exchange (ETDEWEB)

    Mizuta, Shinsei; Iyota, Masatoshi; Tanaka, Senku; Hiromitsu, Ichiro, E-mail: hiromitu@riko.shimane-u.ac.jp

    2012-06-30

    Photocurrent generation in an indium-tin oxide (ITO)/iodine-doped Ni-phthalocyanine (NiPc-I{sub x})/C{sub 60}/In/Al heterojunction device with x {approx} 1 was studied. By keeping the device in air after preparation, the device slowly reached a stationary state in which the sign of the photocurrent is opposite to that of a non-doped ITO/NiPc/C{sub 60}/In/Al device although the rectification direction for the dark current is the same. By a simulation of incident photon-to-current conversion efficiency spectra and a measurement of internal electric field by electroabsorption spectroscopy, it was elucidated that, in the doped device, the band bending near the phthalocyanine/C{sub 60} interface is absent and the photocurrent is generated by a weak Schottky barrier at the C{sub 60}/In interface. It is also shown that the C{sub 60} film encapsulates the doped iodine into the NiPc-I{sub x} layer to stabilize the doping level and prevent the reaction of iodine with In. - Highlights: Black-Right-Pointing-Pointer The C{sub 60} film deposited on a NiPc-I{sub x} film encapsulates the doped iodine. Black-Right-Pointing-Pointer An iodine-doped device generates a photocurrent of inverted direction. Black-Right-Pointing-Pointer The internal electric field is also inverted. Black-Right-Pointing-Pointer The activity of photocurrent generation at the heterojunction is quenched. Black-Right-Pointing-Pointer Photocurrent is generated at the C{sub 60}/In interface.

  19. Cobalt-60 production in CANDU reactors

    International Nuclear Information System (INIS)

    Ross, Michel; Lemire, Christian

    2002-01-01

    CANDU reactors can produce cobalt-60 very efficiently and with an interesting return on investment. This paper discusses what is needed to convert a CANDU reactor into a cobalt-60 producer: what are the different phases, the safety studies required, the physical modifications needed, and what is the minimum involvement of the utility owning the plant. The past ten years of experience of Hydro-Quebec as a cobalt-60 producer will be reviewed, including the management of the risk of both incident and electricity generation loss, and including the benefits for the utility and its personnel. Originally a simple metal used for centuries as a pigment, cobalt-59 today is transformed into cobalt-60, a radioactive element of unprecedented value. Well known in medicine for cancer treatment, cobalt-60 is also used to sterilize a wide range of disposable medical products used in hospitals and to sanitize pharmaceutical and cosmetic products. Cobalt-60 is proving to be a new and effective solution, in the food sector, for preserving harvests and controlling food-borne diseases, or to advantageously replace certain gases and chemical products which are suspected of being harmful or carcinogenic. There are also other applications, such as: hardening of some plastics, treatment of sewage sludge and elimination of harmful insect populations. With a half-life of 5,3 years, cobalt-60 is a metal not found in nature. It is a radioactive isotope produced by exposing stable nuclei of cobalt-59 to neutrons. One of the best places to find such an important neutron source is a nuclear reactor. High energy gamma rays are then emitted during the process of radioactive decay, where cobalt-60 seeks again its stable state

  20. Laser deposition of sulfonated phthalocyanines for gas sensors

    Czech Academy of Sciences Publication Activity Database

    Fitl, Přemysl; Vrňata, M.; Kopecký, D.; Vlček, J.; Škodová, J.; Bulíř, Jiří; Novotný, Michal; Pokorný, Petr

    2014-01-01

    Roč. 302, MAY (2014), s. 37-41 ISSN 0169-4332. [European-Materials-Research-Society Symposium on Laser Material Interactions for Micro- and Nano- Applications /5./. Strasbourg, 27.05.2013-31.05.2013] R&D Projects: GA ČR(CZ) GAP108/11/1298 Institutional support: RVO:68378271 Keywords : Matrix Assisted Pulsed Laser Evaporation * substituted phthalocyanine s * gas sensors * impedance measurements Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.711, year: 2014

  1. Synthesis of phthalocyanines-ALA conjugates: water-soluble compounds with low aggregation.

    Science.gov (United States)

    de Oliveira, Kleber T; de Assis, Francisco F; Ribeiro, Anderson O; Neri, Claudio R; Fernandes, Adjaci U; Baptista, Mauricio S; Lopes, Norberto P; Serra, Osvaldo A; Iamamoto, Yassuko

    2009-10-16

    Syntheses of two water-soluble phthalocyanines (Pc) containing 5-aminolevulinic acid (ALA) linked to the core structure are described. These compounds were prepared by using original functionalizations, and they present remarkable structural and photophysical features, indicating that they could be applied to photodynamic therapy (PDT).

  2. Degradation of natural toxins by phthalocyanines-example of cyanobacterial toxin, microcystin

    Czech Academy of Sciences Publication Activity Database

    Jančula, D.; Blahová, L.; Karásková, M.; Maršálek, Blahoslav

    2010-01-01

    Roč. 62, č. 2 (2010), s. 273-278 ISSN 0273-1223 R&D Projects: GA MŠk 1M0571 Institutional research plan: CEZ:AV0Z60050516 Keywords : microcystin * phthalocyanine * singled oxygen Subject RIV: EF - Botanics Impact factor: 1.056, year: 2010

  3. A Circularly Arranged Sextuple Triptycene Gear Molecule.

    Science.gov (United States)

    Ube, Hitoshi; Yamada, Ryo; Ishida, Jun-Ichi; Sato, Hiroyasu; Shiro, Motoo; Shionoya, Mitsuhiko

    2017-11-22

    Herein we report the synthesis of a circularly arranged sextuple triptycene gear molecule, hexakis(10-dodecyloxy-9-triptycyl)ethynylbenzene, via the trimerization of the corresponding triyne with a cobalt catalyst. The six triptycene gears are closely engaged with each other as confirmed by single crystal X-ray structure analysis, and their motion in solution was established by NMR spectroscopy. Notably, when one bulky RuCp* complex was attached to one triptycene gear, the whole movement of the six gears was highly restricted via their mechanical engagement. Development of such a multigear molecule would provide a structural basis for molecular motion transmission systems with a switching function.

  4. Self-assembly 2D zinc-phthalocyanine heterojunction: An ideal platform for high efficiency solar cell

    Science.gov (United States)

    Jiang, Xue; Jiang, Zhou; Zhao, Jijun

    2017-12-01

    As an alternative to silicon-based solar cells, organic photovoltaic cells emerge for their easy manufacture, low cost, and light weight but are limited by their less stability, low power conversion efficiencies, and low charge carrier mobilities. Here, we design a series of two-dimensional (2D) organic materials incorporating zinc-phthalocyanine (ZnPc) based building blocks which can inherit their excellent intrinsic properties but overcome those shortcomings. Our first-principles calculation shows that such 2D ZnPc-based materials exhibit excellent thermal stabilities, suitable bandgaps, small effective masses, and good absorption properties. The additional benzene rings and nitrogen atoms incorporated between ZnPc molecules are mainly responsible for the modifications of electronic and optical properties. Moreover, some heterojunction solar cells constructed using those 2D ZnPc monolayers as the donor and acceptor have an appropriate absorber gap and interface band alignment. Among them, a power conversion efficiency up to 14.04% is achieved, which is very promising for the next-generation organic solar cells.

  5. Coordination compounds of cobalt and cadmium with isobutyric acid amide

    International Nuclear Information System (INIS)

    Tsivadze, A.Yu.; Ivanova, I.S.; Solovkina, O.A.

    1983-01-01

    Coordination compounds of cobalt and cadmium with isobutyric acid amide (IBAA) of Co(NCS) 2 x(IBAA) 2 (H 2 O) 2 , CoCl 2 (IBAA) 4 , CoI 2 (IBAA) 8 (H 2 O) 2 , CdI 2 (IBAA) 2 composition have been synthesized and characterized. Their infrared absorption spectra (200-400 cm -1 ), electron reflection spectra (200-750 nm) were studied. It is shown that in all compounds there are IBAA molecUles coordinated through an oxygen atom. Thiocyanogroups are coordinated throUgh nitrogen atoms

  6. Influence of Cr doping on the stability and structure of small cobalt oxide clusters

    Energy Technology Data Exchange (ETDEWEB)

    Tung, Nguyen Thanh; Lievens, Peter; Janssens, Ewald, E-mail: ewald.janssens@fys.kuleuven.be [Laboratory of Solid-State Physics and Magnetism, KU Leuven, B-3001 Leuven (Belgium); Tam, Nguyen Minh; Nguyen, Minh Tho [Department of Chemistry, KU Leuven, B-3001 Leuven (Belgium)

    2014-07-28

    The stability of mass-selected pure cobalt oxide and chromium doped cobalt oxide cluster cations, Co{sub n}O{sub m}{sup +} and Co{sub n−1}CrO{sub m}{sup +} (n = 2, 3; m = 2–6 and n = 4; m = 3–8), has been investigated using photodissociation mass spectrometry. Oxygen-rich Co{sub n}O{sub m}{sup +} clusters (m ⩾ n + 1 for n = 2, 4 and m ⩾ n + 2 for n = 3) prefer to photodissociate via the loss of an oxygen molecule, whereas oxygen poorer clusters favor the evaporation of oxygen atoms. Substituting a single Co atom by a single Cr atom alters the dissociation behavior. All investigated Co{sub n−1}CrO{sub m}{sup +} clusters, except CoCrO{sub 2}{sup +} and CoCrO{sub 3}{sup +}, prefer to decay by eliminating a neutral oxygen molecule. Co{sub 2}O{sub 2}{sup +}, Co{sub 4}O{sub 3}{sup +}, Co{sub 4}O{sub 4}{sup +}, and CoCrO{sub 2}{sup +} are found to be relatively difficult to dissociate and appear as fragmentation product of several larger clusters, suggesting that they are particularly stable. The geometric structures of pure and Cr doped cobalt oxide species are studied using density functional theory calculations. Dissociation energies for different evaporation channels are calculated and compared with the experimental observations. The influence of the dopant atom on the structure and the stability of the clusters is discussed.

  7. Environmentally Friendly Phthalocyanine Catalysts for Water Decontamination - Non Photocatalytic Systems

    Czech Academy of Sciences Publication Activity Database

    Klusoň, Petr; Drobek, M.; Zsigmond, A.; Baranyi, J.; Bata, P.; Zárubová, Š.; Kalaji, A.

    2009-01-01

    Roč. 91, 3-4 (2009), s. 605-609 ISSN 0926-3373 R&D Projects: GA ČR GD203/03/H140; GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40720504 Keywords : phthalocyanines * phenol * chlorophenols Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 5.252, year: 2009

  8. Covalent Functionalization of Carbon Nanotube by Tetrasubtituted Amino Manganese Phthalocyanine

    Institute of Scientific and Technical Information of China (English)

    Zheng Long YANG; Hong Zheng CHEN; Lei CAO; Han Yin LI; Mang WANG

    2004-01-01

    The multiwall carbon nanotube (MWCNT) bonded to 2, 9, 16, 23-tetraamino manganese phthalocyanine (TAMnPc) was obtained by covalent functionalization, and its chemical structure was characterized by TEM. The photoconductivity of single-layered photoreceptors, where MWCNT bonded by TAMnPc (MWCNT-b-TAMnPc) served as the charge generation material (CGM), was also studied.

  9. Phthalocyanine as Sensitive Coatings for QCM Sensors-Experimental and Computational Approaches

    International Nuclear Information System (INIS)

    Erbahar, D. D.; Harbeck, M.; Guerol, I.; Musluoglu, E.; Oeztuerk, Z. Z.; Berber, S.

    2011-01-01

    Sorption of organic compounds from aqueous phase into phthalocyanines (Pc) is studied using QCM sensors and Density Functional Theory (DFT) for the first time. The focus is set on the influence of substitution type and central metal atom on the liquid sensing properties of the Pcs.

  10. Electrocatalytic performance evaluation of cobalt hydroxide and cobalt oxide thin films for oxygen evolution reaction

    Science.gov (United States)

    Babar, P. T.; Lokhande, A. C.; Pawar, B. S.; Gang, M. G.; Jo, Eunjin; Go, Changsik; Suryawanshi, M. P.; Pawar, S. M.; Kim, Jin Hyeok

    2018-01-01

    The development of an inexpensive, stable, and highly active electrocatalyst for oxygen evolution reaction (OER) is essential for the practical application of water splitting. Herein, we have synthesized an electrodeposited cobalt hydroxide on nickel foam and subsequently annealed in an air atmosphere at 400 °C for 2 h. In-depth characterization of all the films using X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) techniques, which reveals major changes for their structural, morphological, compositional and electrochemical properties, respectively. The cobalt hydroxide nanosheet film shows high catalytic activity with 290 mV overpotential at 10 mA cm-2 and 91 mV dec-1 Tafel slope and robust stability (24 h) for OER in 1 M KOH electrolyte compared to cobalt oxide (340 mV). The better OER activity of cobalt hydroxide in comparison to cobalt oxide originated from high active sites, enhanced surface, and charge transport capability.

  11. Optical spectra of phthalocyanines and related compounds a guide for beginners

    CERN Document Server

    Isago, Hiroaki

    2015-01-01

    This book displays how optical (absorption, emission, and magnetic circular dichroism) spectra of phthalocyanines and related macrocyclic dyes can be varied from their prototypical ones depending on conditions. As these compounds can be involved in colorful chemistry (which might be driven by impurities in solvents), their spectra behave like the sea-god Proteus in their mutability. Therefore, those who have been engaged with phthalocyanines for the first time, including even educated professional researchers and engineers, may have been embarrassed by the deceptive behavior of their compounds and could have, in the worst cases, given up their projects. This book is aimed not merely at reviewing the optical spectra, but also at helping such people, particularly beginners, to figure them out by showing some examples of their prototypical spectra and their variations in several situations. For the purpose of better understanding, the book also provides an introduction to their theoretical backgrounds as graphic...

  12. Type II photoinitiator substituted zinc phthalocyanine: Synthesis, photophysical and photopolymerization studies

    Energy Technology Data Exchange (ETDEWEB)

    Korkut, Sibel Eken [Department of Chemistry, Yıldız Technical University, 34210 Davutpaşa, İstanbul (Turkey); Temel, Gokhan [Department of Polymer Engineering, Yalova University, 77100 Yalova (Turkey); Balta, Demet Karaca [Department of Chemistry, Yıldız Technical University, 34210 Davutpaşa, İstanbul (Turkey); Arsu, Nergis, E-mail: narsu@yildiz.edu.tr [Department of Chemistry, Yıldız Technical University, 34210 Davutpaşa, İstanbul (Turkey); Şener, M. Kasım, E-mail: mkasimsener@gmail.com [Department of Chemistry, Yıldız Technical University, 34210 Davutpaşa, İstanbul (Turkey)

    2013-04-15

    The novel 4-(9-oxo-9 H-thioxanthen-2yloxy) phthalonitrile (TX-Pht) and its peripherally tetra substituted zinc phthalocyanine complex (TX-ZnPc) have been prepared and characterized by spectroscopic and elemental analysis techniques. Photoinitiated polymerization of methyl methacrylate (MMA) with TX-ZnPc has been investigated in the presence and absence of a co-initiator. Fluorescence and phosphorescence measurements have been also performed to determine the photophysical properties. Low fluorescence quantum yield (Φ{sub F}=0.08) compared to the unsubstituted ZnPc has been found. This allows initiator to undergo intersystem crossing into the triplet state and the lowest triplet state possesses π-π{sup ⁎} configuration. Highlights: ► Zinc phthalocyanine (ZnPc), peripherally functionalized with photoactive thioxanthone (TX) groups was synthesized. ► The photophysical and photochemical properties of resulting photoinitiator were studied in DMF. ► Photoinitiated polymerization of MMA with TX-ZnPc was investigated in the presence and absence of co-initiator.

  13. Cobalt sensitization and dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob P

    2012-01-01

    : This clinical review article presents clinical and scientific data on cobalt sensitization and dermatitis. It is concluded that cobalt despite being a strong sensitizer and a prevalent contact allergen to come up on patch testing should be regarded as a very complex metal to test with. Exposure...

  14. Tin-phthalocyanine adsorption and diffusion on Cu and Au (111) surfaces: A density functional theory study

    Science.gov (United States)

    Qin, Dan; Ge, Xu-Jin; Lü, Jing-Tao

    2018-05-01

    Through density functional theory based calculations, we study the adsorption and diffusion of tin phthalocyanine (SnPc) molecule on Au(111) and Cu(111) surfaces. SnPc has two conformers with Sn pointing to the vacuum (Sn-up) and substrate (Sn-down), respectively. The binding energies of the two conformers with different adsorption sites on the two surfaces, including top, bridge, fcc, hcp, are calculated and compared. It is found that the SnPc molecule binds stronger on Cu(111) surface, with binding energy about 1 eV larger than that on Au(111). Only the bridge and top adsorption sites are stable on Cu(111), while all the four adsorption sites are stable on Au(111), with small diffusion barriers between them. Moreover, the flipping barrier from Sn-up to Sn-down conformer is of the same magnitude on the two metal surfaces. These results are consistent with a recent experiment [Zhang, et al., Angew. Chem., 56, 11769 (2017)], which shows that conformation change from Sn-up to Sn-down on Cu(111) surface can be induced by a C60-functionalized STM tip, while similar change is difficult to realize on Au(111), due to smaller diffusion barrier on Au(111).

  15. Cobalt 60 availability for radiation processing

    International Nuclear Information System (INIS)

    Fraser, F.M.

    1986-01-01

    In the last 20 years, the steady and significant growth in the application of radiation processing to industrial sterilization has been seen. The principal application of this technology is the sterilization of disposable medical products, food irradiation, the irradiation of personal care goods and so on. At present, more than 70 million curies of cobalt-60 supplied by Atomic Energy of Canada Ltd. have been used for gamma processing in these applications. This is estimated to be more than 80 % of the total cobalt-60 in service in the world. Commercial food irradiation has an exciting future, and as to the impact of food irradiation on the availability of cobalt-60 over the next ten years, two principal factors must be examined, namely, the anticipated demand for cobalt-60 in all radiation processing applications, and the supply of cobalt-60 to reliably meet the expected demand. As for the cobalt-60 in service today, 90 % is used for the sterilization of disposable medical products, 5 % for food irradiation, and 5 % for other application. The demand for up to 30 million curies of cobalt-60 is expected over the next 10 years. Today, it is estimated that over 150,000 tons of spices, fruit and fish are irradiated. The potential cobalt-60 production could exceed 110 million curies per year. Gamma processing application will demand nearly 50 million curies in 1990. (Kako, I.)

  16. Electrocatalytic behavior of carbon paste electrode modified with metal phthalocyanines nanoparticles toward the hydrogen evolution

    International Nuclear Information System (INIS)

    Abbaspour, Abdolkarim; Norouz-sarvestani, Fatemeh; Mirahmadi, Ehsan

    2012-01-01

    Highlights: ► The new construction of a carbon paste electrode impregnated with nanoparticles of Zn and Ni phthalocyanine (nano ZnPc and nano NiPc). ► The decrease overpotential and higher current value obtained in nano ZnPc and nano NiPc compared to bulky ZnPc and bulky NiPc, respectively. ► Types of the catalyst and pH of the solution affect the electro catalytic proton reduction reaction considerably. - Abstract: This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of Zn and Ni phthalocyanine (nano ZnPc and nano NiPc). These new electrodes (nano ZnPc-CPE and nano NiPc-CPE) reveal interesting electrocatalytic behavior toward hydrogen evolution reaction (HER). Voltammetric characteristics indicated that the proposed electrodes display better electrocatalytic activity compared to their corresponding bulky modified metal phthalocyanines (MPcs) in minimizing overpotential and increasing the reduction current of HER. Electrocatalytic activities irregularly change with the pH of the solution. However by increasing the pH while nano MPcs are still active, bulky MPcs are almost inactive, and their corresponding ΔE increase by increasing the pH.

  17. An Electrochemical Quartz Crystal Microbalance Multisensor System Based on Phthalocyanine Nanostructured Films: Discrimination of Musts

    Directory of Open Access Journals (Sweden)

    Celia Garcia-Hernandez

    2015-11-01

    Full Text Available An array of electrochemical quartz crystal electrodes (EQCM modified with nanostructured films based on phthalocyanines was developed and used to discriminate musts prepared from different varieties of grapes. Nanostructured films of iron, nickel and copper phthalocyanines were deposited on Pt/quartz crystals through the Layer by Layer technique by alternating layers of the corresponding phthalocyanine and poly-allylamine hydrochloride. Simultaneous electrochemical and mass measurements were used to study the mass changes accompanying the oxidation of electroactive species present in must samples obtained from six Spanish varieties of grapes (Juan García, Prieto Picudo, Mencía Regadío, Cabernet Sauvignon, Garnacha and Tempranillo. The mass and voltammetric outputs were processed using three-way models. Parallel Factor Analysis (PARAFAC was successfully used to discriminate the must samples according to their variety. Multi-way partial least squares (N-PLS evidenced the correlations existing between the voltammetric data and the polyphenolic content measured by chemical methods. Similarly, N-PLS showed a correlation between mass outputs and parameters related to the sugar content. These results demonstrated that electronic tongues based on arrays of EQCM sensors can offer advantages over arrays of mass or voltammetric sensors used separately.

  18. Improved syntheses of high hole mobility phthalocyanines: A case of steric assistance in the cyclo-oligomerisation of phthalonitriles

    Directory of Open Access Journals (Sweden)

    Daniel J. Tate

    2012-01-01

    Full Text Available It has been shown that the base-initiated cyclo-oligomerisation of phthalonitriles is favoured by bulky α-substituents making it possible to obtain the metal-free phthalocyanine directly and in high yield. The phthalocyanine with eight α-isoheptyl substituents gives a high time-of-flight hole mobility of 0.14 cm2·V−1·s−1 within the temperature range of the columnar hexagonal phase, that is 169–189 °C.

  19. Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

    Science.gov (United States)

    Orellana, Walter

    2012-07-01

    The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

  20. Raman scattering in semiconductor structures based on monophthalocyanine and triphthalocyanine molecules incorporating erbium ions

    International Nuclear Information System (INIS)

    Belogorokhov, I. A.; Tikhonov, E. V.; Breusova, M. O.; Pushkarev, V. E.; Zoteev, A. V.; Tomilova, L. G.; Khokhlov, D. R.

    2007-01-01

    Semiconductor structures of the type of butyl-substituted erbium monophthalocyanine and triphthalocyanine are studied by Raman spectroscopy. It is shown that, when the sandwich-like structure of the molecule incorporating two complexing atoms between the ligands is considered instead of the planar molecular structure with one ligand and one metal atom, a series of lines appears in the Raman spectrum. In this series, the wave numbers of the lines represent an arithmetic progression with the arithmetical ratio ∼80 cm -1 . It is suggested that this feature is due to the larger number of organic molecules per metal atom in the triphthalocyanine complex, and the four Raman peaks at the frequencies 122, 208, 280, and 362 cm -1 are the manifestation of slight out-of-plane vibrations of the phthalocyanine ligands

  1. Antimicrobial photodisinfection with Zn(II) phthalocyanine adsorbed on TiO2 upon UVA and red irradiation

    Science.gov (United States)

    Mantareva, Vanya; Eneva, Ivelina; Kussovski, Vesselin; Borisova, Ekaterina; Angelov, Ivan

    2015-01-01

    The light exposure on a daily basis has been well accepted as a competitive method for decontamination of wastewater. The catalytic properties of TiO2 offer a great potential to reduce the transmission of pathogens in the environment. Although the titanium dioxide shows high activity against pathogens, its general usage in water cleaning is limited due to the insufficient excitation natural light (about 3% of the solar spectrum). A hydrophobic dodecylpyridyloxy Zn(II)-phthalocyanine with four peripheral hydrocarbon chains of C12 (ZnPcDo) was immobilized on a photocatalyst TiO2 anatase (P25). The resulted greenish colored nanoparticles of phthalocyanine were characterized by the means of absorption, fluorescence and infrared spectroscopy. The laser scanning confocal fluorescence microscopy was used to visualize the phthalocyanine dye by the red fluorescence emission (650 - 740 nm). The intensive Q-band in the far red visible spectral region (~ 690 nm) suggested a monomeric state of phthalocyanine on TiO2 nanoparticles. Two pathogenic bacterial strains (methicillin-resistant Staphylococcus aureus - MRSA and Salmonella enteritidis) associated with wastewater were photoinactivated with the suspension of the particles. The effective photoinactivation was observed with 1 g.L-1 TiO2 anatase at irradiation with UVA 364 nm as with UVA 364 nm and LED 643 nm. The gram-negative Salmonella enteritidis was fully photoinactivated with ZnPcDo-TiO2 and TiO2 alone at UVA 346 nm and at irradiation with two light sources (364 nm + 643 nm). The proposed conjugate appears as an useful composite material for antibacterial disinfection.

  2. Phthalocyanine identification in paintings by reflectance spectroscopy. A laboratory and in situ study

    Science.gov (United States)

    Poldi, G.; Caglio, S.

    2013-06-01

    The importance of identifying pigments using non invasive (n.i.) analyses has gained increasing importance in the field of spectroscopy applied to art conservation and art studies. Among the large set of pigments synthesized and marketed during 20th century, surely phthalocyanine blue and green pigments occupy an important role in the field of painting (including restoration) and printing, thanks to their characteristics like brightness and fastness. This research focused on the most used phthalocyanine blue (PB15:1 and PB15:3) and green pigments (PG7), and on the possibility to identify these organic compounds using a methodology like reflectance spectroscopy in the UV, visible and near IR range (UV-vis-NIR RS), performed easily through portable instruments. Laboratory tests and three examples carried out on real paintings are discussed.

  3. Sodium doping in copper-phthalocyanine/C60 heterojunction for organic photovoltaic applications

    International Nuclear Information System (INIS)

    Chen, Hui-Ju; Wu, Hsuan-Ta; Hung, Kuang-Teng; Fu, Sheng-Wen; Shih, Chuan-Feng

    2013-01-01

    Sodium was incorporating at the copper-phthalocyanine (CuPc)/C 60 interface in CuPc/C 60 -based small-molecular solar cells to enhance their power conversion efficiency. C 60 was deposited on slightly sodium-doped CuPc. Post-annealing improved the cell properties. Post-annealing doubled the conversion efficiency of the least sodium-doped devices (75 °C, 40 min). The electron/hole mobility ratio gradually approached unity as the annealing time increased, indicating that a reduction in the space charge accumulation was the main cause of the increase of the short-circuit current. The mechanism of enhancement of carrier transport by annealing was investigated by making capacitance–voltage measurements and performing corresponding depth-profile analyses. - Highlights: • Incorporate Na at copper-phthalocyanine/C 60 interface • Annealing importantly improved the cell efficiency of Na-doped devices. • Change in the carrier mobility and concentration was investigated

  4. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

    Science.gov (United States)

    Zelenay, Piotr; Wu, Gang

    2014-04-29

    A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

  5. Synthesis of new cobalt aluminophosphate framework by opening a cobalt methylphosphonate layered material

    Czech Academy of Sciences Publication Activity Database

    Zaarour, M.; Pérez, O.; Boullay, P.; Martens, J.; Mihailova, B.; Karaghiosoff, K.; Palatinus, Lukáš; Mintova, S.

    2017-01-01

    Roč. 19, č. 34 (2017), s. 5100-5105 ISSN 1466-8033 Institutional support: RVO:68378271 Keywords : cobalt aluminophosphate * cobalt methylphosphonate * layered materials * crystallic structure * X-ray diffraction Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.474, year: 2016

  6. Radio cobalt in French rivers

    International Nuclear Information System (INIS)

    Lambrechts, A.; Baudin-Jaulent, Y.

    1996-01-01

    The isotopes 58 and 60 of cobalt present in liquid wastes from nuclear plants or from fuel reprocessing plant of Marcoule are fixed in the different compartments of French rivers. The activity levels of radio-cobalt vary according to the sampled compartments nature (bryophyta > immersed plants > sediment > fish). Elsewhere, laboratory experimentations show that the contamination of fish occurs essentially from the water way rather than from food. Cobalt is mainly fixed by kidneys; muscles is no more than 30 % of the total fish activity. (author)

  7. Vibrational spectra of charge transfer complexes of lead phthalocyanine

    International Nuclear Information System (INIS)

    Oza, A.T.; Patel, S.G.; Patel, R.G.; Prajapati, S.M.; Vaidya, Rajiv

    2005-01-01

    Infrared spectra of six charge transfer complexes of lead phthalocyanine (PbPc), namely, PbPc-I 2 , PbPc-TCNQ, PbPc-DDQ, PbPc-chloranil, PbPc-TCNE and PbPc-TNF, where TCNQ=7,7,8,8-tetracyano-1,4-quinodimethane, DDQ=2,3-dichloro-5,6-dicyano-p-benzoquinone, TCNE=tetracyano-p-ethylene and TNF=2,4,5,7-tetranitro-9-fluorenone have been studied in the range of 400-4000 cm -1 . The analysis of featureless absorption is carried out for studying transition across the Peierls gap of 0.225 eV. The electronic absorption envelopes at 1500, 1100 and 3400 cm -1 are found to have Gaussian shapes and not the degenerate oscillators, as found in purely organic conductors. There is a pairing of two electrons on phthalocyanine ligand as required in Little's model, and consequently, the electronic absorption envelope is a doublet. Electronic absorption envelope is a doublet showing two peaks at 1500 and 1100 cm -1 , indicating a two-electron problem in PbPc. Metal-ligand vibrations between 400 and 700 cm -1 lead to indirect transition between the valence and conduction bands and phonon-mediated coupling between metal chains and the side chains

  8. Optical-limiting response of rare-earth metallo-phthalocyanine-doped copolymer matrix

    NARCIS (Netherlands)

    Aneeshkumar, B.N.; Gopinath, P.; Vallabhan, C.P.G.; Nampoori, V.P.N.; Radhakrishnan, P.; Thomas, J.

    2003-01-01

    The nanosecond optical-limiting characteristics (at 532 nm) of some rare-earth metallo-phthalocyanines (Sm(Pc)2, Eu(Pc)2, and LaPc) doped in a copolymer matrix of poly(Me methacrylate) and Me-2-cyanoacrylate were studied for the 1st time to the authors' knowledge. The optical-limiting response is

  9. Annealing assisted structural and surface morphological changes in Langmuir–Blodgett films of nickel octabutoxy phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Shilpa Harish, T.; Viswanath, P., E-mail: viswanath@cnsms.res.in

    2016-01-01

    We report our studies on thin films of metallo-phthalocyanine (MPc), Nickel(II)1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (NiPc(OBu){sub 8}) transferred in a well defined thermodynamic state over a self assembled monolayer (octadecyl trichlorosilane)/SiO{sub 2}/Si substrate using the Langmuir–Blodgett (LB) method. The films are characterized using differential scanning calorimetry (DSC), grazing incidence X-ray diffraction (GIXD) and atomic force microscopy (AFM) techniques. DSC studies on powdered samples in the bulk indicate enantiotropic solid–solid phase transition. GIXD studies on the as-deposited LB film show a Bragg peak indicating crystallinity of the thin film. Annealing (373 K) results in reduction of lattice spacing (1.21 Å) signifying changes in molecular packing within the unit cell. At this stage, an additional Bragg peak is observed which grows at the expense of the former one and they coexist between 373 K and 423 K. A discontinuity in lattice spacing from 20.73 to 15.12 Å with annealing indicates clearly a structural change of the underlying crystalline lattice. Correspondingly, the surface morphology images obtained using AFM show, with annealing, a transformation from spherical granular morphology to elongated, flat crystallites suggesting asymmetric growth process. Statistical parameters of the grain extracted from the AFM images show that the size, fractal dimension and circularity are affected by annealing. Based on these studies, we infer the structural and surface morphological changes of the meta-stable phase (Form I) to the stable phase (Form II) in annealed LB films of phthalocyanine. - Highlights: • Langmuir–Blodgett (LB) films of phthalocyanine subjected to thermal annealing. • Structural transformation and coexistence of polymorphs in LB films • Surface morphology changes from nanoscale grains to elongated crystallites. • Reduction of fractal dimension and circularity index reveals asymmetric growth.

  10. AN ELECTROPLATING METHOD OF FORMING PLATINGS OF NICKEL, COBALT, NICKEL ALLOYS OR COBALT ALLOYS

    DEFF Research Database (Denmark)

    1997-01-01

    An electroplating method of forming platings of nickel, cobalt, nickel alloys or cobalt alloys with reduced stresses in an electrodepositing bath of the type: Watt's bath, chloride bath or a combination thereof, by employing pulse plating with periodic reverse pulse and a sulfonated naphthalene...

  11. THE COORDINATION COMPOUNDS OF COBALT (II, III WITH DITHIOCARBAMIC ACID DERIVATIVES — MODIFICATORS OF HYDROLYTIC ENZYMES ACTIVITY

    Directory of Open Access Journals (Sweden)

    L. D. Varbanets

    2013-02-01

    Full Text Available Chloride, bromide and isothiocyanate complexes of cobalt(II with N-substituted thiocarbamoyl-N?-pentamethylenesulfenamides (1–(12, and also complexes of cobalt(II, Ш with derivatives of morpholine-4-carbodithioic acid (13–(18 have been used as modificators of enzymes of hydrolytic action — Bacillus thurin-giensis ІМВ В-7324 peptidases, Bacillus subtilis 147 and Aspergillus flavus var. oryzae 80428 amylases, Eupenicillium erubescens 248 and Cryptococcus albidus 1001 rhamnosidases. It was shown that cobalt (II, Ш compounds influence differently on the activity of enzymes tested, exerted both inhibitory and stimulatory action. It gives a possibility to expect that manifestation of activity by complex molecule depends on ligand and anion presence — Cl–, Br– or NCS–. The high activating action of cobalt(II complexes with N-substituted thiocarbamoyl-N?-pentamethylenesulphenamides (1–(12 on elastase and fibrinolytic activity of peptidases compared to tris(4-morpholinecarbodithioatocobalt(ІІІ (14 and products of its interaction with halogens (15–(17, causes inhibitory effect that is probably due to presence of a weekly S–N link, which is easy subjected to homolytic breaking. The studies of influences of cobalt(II complexes on activity of C. аlbidus and E. еrubescens ?-Lrhamnosidases showed, that majority of compounds inhibits of its activity, at that the most inhibitory effect exerts to C. аlbidus enzyme.To sum up, it is possible to state that character of influence of cobalt(II complexes with N-substituted thiocarbamoyl-N?-pentamethylenesulphenamides, and also cobalt(II, Ш complexes with derivatives of morpholine-4-carbodithioic acid varies depending on both strain producer and enzyme tested. The difference in complex effects on enzymes tested are due to peculiarities of building and functional groups of their active centers, which are also responsible for binding with modificators.

  12. Study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel

    International Nuclear Information System (INIS)

    Ismailova, M.M.; Egorova, L.A.; Khamidov, B.O.

    1993-01-01

    Present article is devoted to study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel. The condition of cobalt in various rate of oxidation in acrylamide aqueous solutions was studied. The concentration conditions of stability of system Co(II)-Co(III) were defined. The composition of coordination compounds of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel was determined.

  13. Dry Etching of Copper Phthalocyanine Thin Films: Effects on Morphology and Surface Stoichiometry

    Directory of Open Access Journals (Sweden)

    Michael J. Brett

    2012-08-01

    Full Text Available We investigate the evolution of copper phthalocyanine thin films as they are etched with argon plasma. Significant morphological changes occur as a result of the ion bombardment; a planar surface quickly becomes an array of nanopillars which are less than 20 nm in diameter. The changes in morphology are independent of plasma power, which controls the etch rate only. Analysis by X-ray photoelectron spectroscopy shows that surface concentrations of copper and oxygen increase with etch time, while carbon and nitrogen are depleted. Despite these changes in surface stoichiometry, we observe no effect on the work function. The absorbance and X-ray diffraction spectra show no changes other than the peaks diminishing with etch time. These findings have important implications for organic photovoltaic devices which seek nanopillar thin films of metal phthalocyanine materials as an optimal structure.

  14. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    Grodkowski, J.

    2004-01-01

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  15. The effect of the triblock properties on the morphologies and photophysical properties of nanoparticle loaded with carboxylic dendrimer phthalocyanine

    Science.gov (United States)

    Lv, Huafei; Chen, Zhe; Yu, Xinxin; Pan, Sujuan; Zhang, Tiantian; Xie, Shusen; Yang, Hongqin; Peng, Yiru

    2016-09-01

    Photodynamic therapy (PDT) is an emerging alternative treatment for various cancers and age-related macular degeneration. Phthalocyanines (Pcs) and their substituted derivatives are under intensive investigation as the second generation photosensitizers. A big challenge for the application of Pcs is poor solubility and limited accumulation in the tumor tissues, which severely reduced its PDT efficacy. Nano-delivery systems such as polymeric micelles are promising tools for increasing the solubility and improving delivery efficiency of Pcs for PDT application. In this paper, nanoparticles of amphiphilic triblock copolymer poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) were developed to encapsulate 1-2 generation carboxylic poly (benzyl aryl ether) dendrimer. The morphologies and photophysical properties of polymeric nanoparticles loaded with 1-2 generation dendritic phthalocyanines (G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m) were studied by AFM, UV/Vis and fluorescent spectroscopic method. The morphologies of self-assembled PLL-PEG-PLL aggregates exhibited concentration dependence. Its morphologies changed from cocoon-like to spheral. The diameters of G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m were in the range of 33-147 nm, increasing with the increase of the concentration of PLL-PEG-PLL. The morphologies of G2-ZnPc(COOH)16/m also changed from cocoon-like to sphere with the increase of the concentration of PLL-PEG-PLL. It was found that, the no obviously Q change was observed between the free phthalocyanines and nanoparticles. The fluorescence intensity of polymer nanoparticles were higher enhanced compared with free dendritic phthalocyanines. The dendrimer phthalocyanine loaded with poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) presented suitable physical stability, improved photophysical properties suggesting it may be considered as a promising formulation for PDT.

  16. Phosphorus introduction mechanism in electrodeposited cobalt films

    International Nuclear Information System (INIS)

    Kravtchenko, Jean-Francois

    1973-01-01

    The cathodic reduction of hypophosphite, phosphite and phosphate ions was studied using chrono-potentiometry and voltammetry. Then cobalt was deposited at constant current from a bath containing one of these three compounds. The current, while giving an electrodeposition of cobalt, also enhances at the same time a chemical deposition of cobalt. It is shown that high coercive forces in cobalt films are much more related to this chemical deposition than to the simple fact that the films contain some phosphorus. (author) [fr

  17. Synergetic Enhancement of the Photocatalytic Activity of TiO2 with Visible Light by Sensitization Using a Novel Push-Pull Zinc Phthalocyanine

    Directory of Open Access Journals (Sweden)

    A. Luna-Flores

    2017-01-01

    Full Text Available A new one-pot synthesis of a novel A3B-type asymmetric zinc phthalocyanine (AZnPc was developed. The phthalocyanine complex was characterized unambiguously and used to prepare a TiO2 hybrid photocatalyst to enhance its photocatalytic activity in the visible range. Different compositions of the phthalocyanine dye were tested in order to find the optimum amount of sensitizer to get the highest activity during the photocatalytic tests. The hybrid photocatalyst was characterized by UV-Vis diffuse reflectance (DRS and Fourier transform infrared spectroscopy (FT-IR and its photocatalytic activity was compared with that of the individual components considering the effects of sensitization on their efficiency to degrade Rhodamine B as a model reaction. A synergic improvement of the photocatalytic activity for the hybrid system was explained in terms of an improved electron injection from the photo-activated phthalocyanine to the TiO2. Considering the structural features of the phthalocyanine sensitizer and their effect on aggregation, some mechanistic aspects of its binding to TiO2 are suggested to account for the photocatalytic activity enhancement. Finally, the inhibitory effect on the sprouting of chia seeds (Salvia hispanica was evaluated in order to test the toxicity of the water effluent obtained after the photodegradation process. According to our growth inhibition assays, it was found that the Rh-B degradation by-products do not lead to an acute toxicity.

  18. Cobalt reduction of NSSS valve hardfacings for ALARA

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Joo Hak; Lee, Sang Sub [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1994-07-01

    This report informs NSSS designer that replacement of materials is one of the major means of ALARA implementation, and describes that NSSS valves with high-cobalt hardfacing are significant contributors to post-shutdown radiation fields caused by activation of cobalt-59 to cobalt-60. Generic procedures for implementing cobalt reduction programs for valves are presented. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. The nuclear safety issues involved with changing valve hardfacing materials are discussed. The common methods used to deposit hardfacing materials are described together with an explanation of the wear measurements. Wear resistance, corrosion resistance, friction coefficient, and mechanical properties of candidate hardfacing alloys are given. World-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The use of low-cobalt or cobalt-free alloys in other nuclear plant components is described. 17 figs., 38 tabs., 18 refs. (Author).

  19. Cobalt reduction of NSSS valve hardfacings for ALARA

    International Nuclear Information System (INIS)

    Kim, Joo Hak; Lee, Sang Sub

    1994-07-01

    This report informs NSSS designer that replacement of materials is one of the major means of ALARA implementation, and describes that NSSS valves with high-cobalt hardfacing are significant contributors to post-shutdown radiation fields caused by activation of cobalt-59 to cobalt-60. Generic procedures for implementing cobalt reduction programs for valves are presented. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. The nuclear safety issues involved with changing valve hardfacing materials are discussed. The common methods used to deposit hardfacing materials are described together with an explanation of the wear measurements. Wear resistance, corrosion resistance, friction coefficient, and mechanical properties of candidate hardfacing alloys are given. World-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The use of low-cobalt or cobalt-free alloys in other nuclear plant components is described. 17 figs., 38 tabs., 18 refs. (Author)

  20. The Role of External Inputs and Internal Cycling in Shaping the Global Ocean Cobalt Distribution: Insights From the First Cobalt Biogeochemical Model

    Science.gov (United States)

    Tagliabue, Alessandro; Hawco, Nicholas J.; Bundy, Randelle M.; Landing, William M.; Milne, Angela; Morton, Peter L.; Saito, Mak A.

    2018-04-01

    Cobalt is an important micronutrient for ocean microbes as it is present in vitamin B12 and is a co-factor in various metalloenzymes that catalyze cellular processes. Moreover, when seawater availability of cobalt is compared to biological demands, cobalt emerges as being depleted in seawater, pointing to a potentially important limiting role. To properly account for the potential biological role for cobalt, there is therefore a need to understand the processes driving the biogeochemical cycling of cobalt and, in particular, the balance between external inputs and internal cycling. To do so, we developed the first cobalt model within a state-of-the-art three-dimensional global ocean biogeochemical model. Overall, our model does a good job in reproducing measurements with a correlation coefficient of >0.7 in the surface and >0.5 at depth. We find that continental margins are the dominant source of cobalt, with a crucial role played by supply under low bottom-water oxygen conditions. The basin-scale distribution of cobalt supplied from margins is facilitated by the activity of manganese-oxidizing bacteria being suppressed under low oxygen and low temperatures, which extends the residence time of cobalt. Overall, we find a residence time of 7 and 250 years in the upper 250 m and global ocean, respectively. Importantly, we find that the dominant internal resupply process switches from regeneration and recycling of particulate cobalt to dissolution of scavenged cobalt between the upper ocean and the ocean interior. Our model highlights key regions of the ocean where biological activity may be most sensitive to cobalt availability.

  1. Preparation of new phthalocyanine complexes of some rare-earth elements

    International Nuclear Information System (INIS)

    Sugimoto, Hiroshi; Higashi, Teruaki; Mori, Masayasu

    1982-01-01

    The reaction of tris(1,3-diphenyl-1,3-propanedionato) complexes of heavier rare-earth elements, M 3+ (dbm) 3 and lithium phthalocyaninato (2-), Li 2 (pc) gave two types of new stable phthalocyanine complexes, [M 3+ (pc)(dbm)(dbmH)] and [M 3+ (pc)(dbm)] depending on the solvents used for the preparation. The structure of both types of complexes are tentatively proposed. (author)

  2. Van Der Waals Heterostructures between Small Organic Molecules and Layered Substrates

    Directory of Open Access Journals (Sweden)

    Han Huang

    2016-09-01

    Full Text Available Two dimensional atomic crystals, like grapheme (G and molybdenum disulfide (MoS2, exhibit great interest in electronic and optoelectronic applications. The excellent physical properties, such as transparency, semiconductivity, and flexibility, make them compatible with current organic electronics. Here, we review recent progress in the understanding of the interfaces of van der Waals (vdW heterostructures between small organic molecules (pentacene, copper phthalocyanine (CuPc, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA, and dioctylbenzothienobenzothiophene (C8-BTBT and layered substrates (G, MoS2 and hexagonal boron nitride (h-BN. The influences of the underlying layered substrates on the molecular arrangement, electronic and vibrational properties will be addressed.

  3. Accumulation of cobalt by cephalopods

    International Nuclear Information System (INIS)

    Nakahara, Motokazu

    1981-01-01

    Accumulation of cobalt by cephalopod mollusca was investigated by radiotracer experiments and elemental analysis. In the radiotracer experiments, Octopus vulgaris took up cobalt-60 from seawater fairly well and the concentration of the nuclide in whole body attained about 150 times the level of seawater at 25th day at 20 0 C. Among the tissues and organs measured, branchial heart which is the specific organ of cephalopods showed the highest affinity for the nuclide. The organ accumulated about 50% of the radioactivity in whole body in spite of its little mass as 0.2% of total body weight. On the other hand, more than 90% of the radioactivity taken up from food (soft parts of Gomphina melanaegis labelled with cobalt-60 previously in an aquarium) was accumulated in liver at 3rd day after the single administration and then the radioactivity in the liver seemed to be distributed to other organs and tissues. The characteristic elution profiles of cobalt-60 was observed for each of the organs and tissues in Sephadex gel-filtration experiment. It was confirmed by the gel-filtration that most of cobalt-60 in the branchial heart was combined with the constituents of low molecular weights. The average concentration of stable cobalt in muscle of several species of cephalopods was 5.3 +- 3.0 μg/kg wet and it was almost comparable to the fish muscle. On the basis of soft parts, concentration of the nuclide closed association among bivalve, gastropod and cephalopod except squid that gave lower values than the others. (author)

  4. Cobalt-free nickel-base superalloys

    International Nuclear Information System (INIS)

    Koizumi, Yutaka; Yamazaki, Michio; Harada, Hiroshi

    1979-01-01

    Cobalt-free nickel-base cast superalloys have been developed. Cobalt is considered to be a beneficial element to strengthen the alloys but should be eliminated in alloys to be used for direct cycle helium turbine driven by helium gas from HTGR (high temp. gas reactor). The elimination of cobalt is required to avoid the formation of radioactive 60 Co from the debris or scales of the alloys. Cobalt-free alloys are also desirable from another viewpoint, i.e. recently the shortage of the element has become a serious problem in industry. Cobalt-free Mar-M200 type alloys modified by the additions of 0.15 - 0.2 wt% B and 1 - 1.5 wt% Hf were found to have a creep rupture strength superior or comparable to that of the original Mar-M200 alloy bearing cobalt. The ductility in tensile test at 800 0 C, as cast or after prolonged heating at 900 0 C (the tensile test was done without removing the surface layer affected by the heating), was also improved by the additions of 0.15 - 0.2% B and 1 - 1.5% Hf. The morphology of grain boundaries became intricated by the additions of 0.15 - 0.2% B and 1 - 1.5% Hf, to such a degree that one can hardly distinguish grain boundaries by microscopes. The change in the grain boundary morphology was considered, as suggested previously by one of the authors (M.Y.), to be the reason for the improvements in the creep rupture strength and tensile ductility. (author)

  5. Structural templating in a nonplanar phthalocyanine using single crystal copper iodide

    OpenAIRE

    Rochford, L. A. (Luke A.); Ramadan, Alexandra J.; Keeble, Dean S.; Ryan, Mary P.; Heutz, Sandrine; Jones, T. S. (Tim S.)

    2015-01-01

    Solution-grown copper iodide crystals are used as substrates for the templated growth of the nonplanar vanadyl phthalocyanine using organic molecular beam deposition. Structural characterization reveals a single molecular orientation produced by the (111) Miller plane of the copper iodide crystals. These fundamental measurements show the importance of morphology and structure in templating interactions for organic electronics applications.

  6. Cobalt-60 production in CANDU power reactors

    International Nuclear Information System (INIS)

    Malkoske, G.R.; Norton, J.L.; Slack, J.

    2002-01-01

    MDS Nordion has been supplying cobalt-60 sources to industry for industrial and medical purposes since 1946. These cobalt-60 sources are used in many market and product segments, but are primarily used to sterilize single-use medical products including; surgical kits, gloves, gowns, drapes, and cotton swabs. Other applications include sanitization of cosmetics, microbial reduction of pharmaceutical raw materials, and food irradiation. The technology for producing the cobalt-60 isotope was developed by MDS Nordion and Atomic Energy of Canada Limited (AECL) almost 55 years ago using research reactors at the AECL Chalk River Laboratories in Ontario, Canada. The first cobalt-60 source produced for medical applications was manufactured by MDS Nordion and used in cancer therapy. The benefits of cobalt-60 as applied to medical product manufacturing, were quickly realized and the demand for this radioisotope quickly grew. The same technology for producing cobalt-60 in research reactors was then designed and packaged such that it could be conveniently transferred to a utility/power reactor. In the early 1970's, in co-operation with Ontario Power Generation (formerly Ontario Hydro), bulk cobalt-60 production for industrial irradiation applications was initiated in the four Pickering A CANDU reactors. As the demand and acceptance of sterilization of medical products grew, MDS Nordion expanded its bulk supply by installing the proprietary Canadian technology for producing cobalt-60 in additional CANDU reactors. CANDU is unique among the power reactors of the world, being heavy water moderated and fuelled with natural uranium. They are also designed and supplied with stainless steel adjusters, the primary function of which is to shape the neutron flux to optimize reactor power and fuel bum-up, and to provide excess reactivity needed to overcome xenon-135 poisoning following a reduction of power. The reactor is designed to develop full power output with all of the adjuster

  7. Experimental evidence for cobalt(III)-carbene radicals: key intermediates in cobalt(II)-based metalloradical cyclopropanation

    NARCIS (Netherlands)

    Lu, H.; Dzik, W.I.; Xu, X.; Wojtas, L.; de Bruin, B.; Zhang, X.P.

    2011-01-01

    New and conclusive evidence has been obtained for the existence of cobalt(III)-carbene radicals that have been previously proposed as the key intermediates in the underlying mechanism of metalloradical cyclopropanation by cobalt(II) complexes of porphyrins. In the absence of olefin substrates,

  8. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    Science.gov (United States)

    Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

    2009-12-15

    The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

  9. Coordination compounds of cobalt and cadmium with isobutyric acid amide

    Energy Technology Data Exchange (ETDEWEB)

    Tsivadze, A.Yu.; Ivanova, I.S.; Solovkina, O.A. (AN SSSR, Moscow. Inst. Obshchej i Neorganicheskoj Khimii)

    1983-06-01

    Coordination compounds of cobalt and cadmium with isobutyric acid amide (IBAA) of Co(NCS)/sub 2/x(IBAA)/sub 2/(H/sub 2/O)/sub 2/, CoCl/sub 2/(IBAA)/sub 4/, CoI/sub 2/(IBAA)/sub 8/(H/sub 2/O)/sub 2/, CdI/sub 2/(IBAA)/sub 2/ composition have been synthesized and characterized. Their infrared absorption spectra (200-400 cm/sup -1/), electron reflection spectra (200-750 nm) were studied. It is shown that in all compounds there are IBAA molecUles coordinated through an oxygen atom. Thiocyanogroups are coordinated through nitrogen atoms.

  10. Removal of Cobalt Ions by Precipitate Foam Flotation

    Energy Technology Data Exchange (ETDEWEB)

    Jung, In Ha; Lee, Jung Won [Korea Atomic Energy Research Institute, Taejon (Korea)

    1998-09-30

    Simulated waste liquid containing 50 ppm cobalt ion was tested by precipitate flotation using a sodium lauryl sulfate as a collector. The effects of initial cobalt ion concentration, pH, surfactant concentration, flotation time, gas flow rate and foreign ions on removal efficiency of cobalt ion were studied. Pretreatment of the waste liquid with 35% H{sub 2}O{sub 2} prior to precipitate flotation made shift of optimal flotation pH from the strong alkalinity to weak alkaline range and made a favorable flotation of cobalt ion in wide range of pH. For the result of this experiment, 99.8% removal efficiency was obtained on the conditions of initial cobalt ion concentration 50 ppm, pH 9.5, gas flow rate 70 ml/min, flotation time 30 min. The simulate ion was formed to be the most harmful ion against removal of cobalt by precipitate flotation of the species which were tested. The presence of 0.1 M of SO{sub 4}{sup 2-} ion decreased removal efficiency of cobalt to 90% while the cobalt were almost entirely removed in the absence of sulfate ion. (author). 11 refs., 8 figs.

  11. Cobalt: for strength and color

    Science.gov (United States)

    Boland, Maeve A.; Kropschot, S.J.

    2011-01-01

    Cobalt is a shiny, gray, brittle metal that is best known for creating an intense blue color in glass and paints. It is frequently used in the manufacture of rechargeable batteries and to create alloys that maintain their strength at high temperatures. It is also one of the essential trace elements (or "micronutrients") that humans and many other living creatures require for good health. Cobalt is an important component in many aerospace, defense, and medical applications and is a key element in many clean energy technologies. The name cobalt comes from the German word kobold, meaning goblin. It was given this name by medieval miners who believed that troublesome goblins replaced the valuable metals in their ore with a substance that emitted poisonous fumes when smelted. The Swedish chemist Georg Brandt isolated metallic cobalt-the first new metal to be discovered since ancient times-in about 1735 and identified some of its valuable properties.

  12. Effects of cobalt in nickel-base superalloys

    Science.gov (United States)

    Tien, J. K.; Jarrett, R. N.

    1983-01-01

    The role of cobalt in a representative wrought nickel-base superalloy was determined. The results show cobalt affecting the solubility of elements in the gamma matrix, resulting in enhanced gamma' volume fraction, in the stabilization of MC-type carbides, and in the stabilization of sigma phase. In the particular alloy studied, these microstructural and microchemistry changes are insufficient in extent to impact on tensile strength, yield strength, and in the ductilities. Depending on the heat treatment, creep and stress rupture resistance can be cobalt sensitive. In the coarse grain, fully solutioned and aged condition, all of the alloy's 17% cobalt can be replaced by nickel without deleteriously affecting this resistance. In the fine grain, partially solutioned and aged condition, this resistance is deleteriously affected only when one-half or more of the initial cobalt content is removed. The structure and property results are discussed with respect to existing theories and with respect to other recent and earlier findings on the impact of cobalt, if any, on the performance of nickel-base superalloys.

  13. Impact of the Anchoring Ligand on Electron Injection and Recombination Dynamics at the Interface of Novel Asymmetric Push-Pull Zinc Phthalocyanines and TiO2

    NARCIS (Netherlands)

    Sharma, Divya; Steen, Gerrit Willem; Korterik, Jeroen P.; Garcia-Iglesias, M.; Vazquez, P; Torres, T.; Herek, Jennifer Lynn; Huijser, Jannetje Maria

    2013-01-01

    Phthalocyanines are promising photosensitizers for dye-sensitized solar cells (DSSCs). A parameter that has been problematic for a long time involves electron injection (EI) into the TiO2. The development of push-pull phthalocyanines shows great potential to improve the ratio of EI to back electron

  14. Giant magnetoresistance through a single molecule.

    Science.gov (United States)

    Schmaus, Stefan; Bagrets, Alexei; Nahas, Yasmine; Yamada, Toyo K; Bork, Annika; Bowen, Martin; Beaurepaire, Eric; Evers, Ferdinand; Wulfhekel, Wulf

    2011-03-01

    Magnetoresistance is a change in the resistance of a material system caused by an applied magnetic field. Giant magnetoresistance occurs in structures containing ferromagnetic contacts separated by a metallic non-magnetic spacer, and is now the basis of read heads for hard drives and for new forms of random access memory. Using an insulator (for example, a molecular thin film) rather than a metal as the spacer gives rise to tunnelling magnetoresistance, which typically produces a larger change in resistance for a given magnetic field strength, but also yields higher resistances, which are a disadvantage for real device operation. Here, we demonstrate giant magnetoresistance across a single, non-magnetic hydrogen phthalocyanine molecule contacted by the ferromagnetic tip of a scanning tunnelling microscope. We measure the magnetoresistance to be 60% and the conductance to be 0.26G(0), where G(0) is the quantum of conductance. Theoretical analysis identifies spin-dependent hybridization of molecular and electrode orbitals as the cause of the large magnetoresistance.

  15. Hydrothermal synthesis, crystal structure and properties of a novel chain coordination polymer constructed by tetrafunctional phosphonate anions and cobalt ions

    International Nuclear Information System (INIS)

    Guan, Lei; Wang, Ying

    2015-01-01

    A novel cobalt phosphonate, [Co(HL)(H 2 O) 3 ] n (1) (L=N(CH 2 PO 3 H) 3 3− ) has been synthesized by hydrothermal reaction at 150 °C and structurally characterized by X-ray diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Complex 1 features a 1D chain structure with double-channel built from CoO 6 octahedra bridged together by the phosphonate groups. Each cobalt ion is octahedrally coordinated by three phosphonate oxygen atoms and three water molecules. The coordinated water molecules can form the hydrogen bonds with the phosphonate oxygen atoms to link the 1D chains, building a 2D layered structure, further resulting in a 3D network. The luminescence spectrum indicates an emission maximum at 435 nm. The magnetic susceptibility curve exhibits a dominant antiferromagnetic behavior with a weakly ferromagnetic component at low temperatures. - Graphical abstract: The connectivity between cobalt ions and the ligands results in a chain structure with a 1D double-channel structure, which is constructed by A-type subrings and B-type subrings. - Highlights: • The tetrafunctional phosphonate ligand was used as the ligand. • A novel chain structure can be formed by A-type rings and B-type rings. • Two types of rings can form a 1D double-channel structure, along the c-axis

  16. Cobalt: A vital element in the aircraft engine industry

    Science.gov (United States)

    Stephens, J. R.

    1981-01-01

    Recent trends in the United States consumption of cobalt indicate that superalloys for aircraft engine manufacture require increasing amounts of this strategic element. Superalloys consume a lion's share of total U.S. cobalt usage which was about 16 million pounds in 1980. In excess of 90 percent of the cobalt used in this country was imported, principally from the African countries of Zaire and Zambia. Early studies on the roles of cobalt as an alloying element in high temperature alloys concentrated on the simple Ni-Cr and Nimonic alloy series. The role of cobalt in current complex nickel base superalloys is not well defined and indeed, the need for the high concentration of cobalt in widely used nickel base superalloys is not firmly established. The current cobalt situation is reviewed as it applies to superalloys and the opportunities for research to reduce the consumption of cobalt in the aircraft engine industry are described.

  17. In search of the main properties of phthalocyanines participating in toxicity against cyanobacteria

    Czech Academy of Sciences Publication Activity Database

    Jančula, Daniel; Maršálek, Blahoslav; Novotná, Zlatica; Černý, J.; Karásková, M.; Rakušan, J.

    2009-01-01

    Roč. 77, č. 11 (2009), s. 1520-1525 ISSN 0045-6535 R&D Projects: GA MŠk 1M0571 Institutional research plan: CEZ:AV0Z60050516 Keywords : phthalocyanine s * cyanobycteria * toxicity Subject RIV: EF - Botanics Impact factor: 3.253, year: 2009

  18. Effect of mixed-sulfonated aluminium phthalocyanine on human skin fibroblasts for photodynamic therapy

    CSIR Research Space (South Africa)

    Ndhundhuma, IM

    2008-08-01

    Full Text Available of the study was to evaluate the effect of mixed-sulfonated aluminium phthalocyanine (AlPcSmix) used as photosensitizers for PDT, determined by changes in cell morphology and cell viability of human skin fibroblasts (WS1). Methods. Cells incubated with 5, 10...

  19. Noncovalent functionalization of pristine CVD single-walled carbon nanotubes with 3d metal(II) phthalocyanines by adsorption from the gas phase

    Science.gov (United States)

    Basiuk, Vladimir A.; Flores-Sánchez, Laura J.; Meza-Laguna, Victor; Flores-Flores, José Ocotlán; Bucio-Galindo, Lauro; Puente-Lee, Iván; Basiuk, Elena V.

    2018-04-01

    Noncovalent hybrids of carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of growing research effort focused on the development of new efficient organic photovoltaic cells, heterogeneous catalysts, lithium batteries, gas sensors, field effect transistors, among other possible applications. The main advantage of using unsubstituted Pcs is their very moderate cost and easy commercial availability. Unfortunately, the deposition of unsubstituted Pcs onto CNT sidewalls via the traditional liquid-phase strategy proves to be very problematic due to an extremely poor solubility of Pcs. At the same time, unsubstituted free-base H2Pc ligand and many of its transition metal complexes exhibit high thermal stability and volatility under reduced pressure, which allows for their physical vapor deposition onto solid surfaces. In the present work, we demonstrated the possibility of simple, fast, efficient and environmentally friendly noncovalent functionalization of single-walled CNTs (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me = Co, Ni, Cu and Zn. The functionalization can be performed at 400-500 °C under moderate vacuum, and takes about 2-3 h only. The nanohybrids obtained were characterized by means of Fourier-transform infrared, Raman, UV-vis and energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), scanning and transmission electron microscopy. TGA suggested that Pc weight content is 30%, 17% and 35% for NiPc, CuPc and ZnPc, respectively (CoPc exhibited anomalous behavior), which is close to the estimates from EDS spectra of 24-39%, 27-36% and 27-44% for CoPc, CuPc and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Pc hybrids, as compared to that of pristine nanotubes, was interpreted as very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the patterns of HOMO and LUMO distribution

  20. Feasibility Study for Cobalt Bundle Loading to CANDU Reactor Core

    International Nuclear Information System (INIS)

    Park, Donghwan; Kim, Youngae; Kim, Sungmin

    2016-01-01

    CANDU units are generally used to produce cobalt-60 at Bruce and Point Lepreau in Canada and Embalse in Argentina. China has started production of cobalt-60 using its CANDU 6 Qinshan Phase III nuclear power plant in 2009. For cobalt-60 production, the reactor’s full complement of stainless steel adjusters is replaced with neutronically equivalent cobalt-59 adjusters, which are essentially invisible to reactor operation. With its very high neutron flux and optimized fuel burn-up, the CANDU has a very high cobalt-60 production rate in a relatively short time. This makes CANDU an excellent vehicle for bulk cobalt-60 production. Several studies have been performed to produce cobalt-60 using adjuster rod at Wolsong nuclear power plant. This study proposed new concept for producing cobalt-60 and performed the feasibility study. Bundle typed cobalt loading concept is proposed and evaluated the feasibility to fuel management without physics and system design change. The requirement to load cobalt bundle to the core was considered and several channels are nominated. The production of cobalt-60 source is very depend on the flux level and burnup directly. But the neutron absorption characteristic of cobalt bundle is too high, so optimizing design study is needed in the future

  1. Feasibility Study for Cobalt Bundle Loading to CANDU Reactor Core

    Energy Technology Data Exchange (ETDEWEB)

    Park, Donghwan; Kim, Youngae; Kim, Sungmin [KHNP Central Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    CANDU units are generally used to produce cobalt-60 at Bruce and Point Lepreau in Canada and Embalse in Argentina. China has started production of cobalt-60 using its CANDU 6 Qinshan Phase III nuclear power plant in 2009. For cobalt-60 production, the reactor’s full complement of stainless steel adjusters is replaced with neutronically equivalent cobalt-59 adjusters, which are essentially invisible to reactor operation. With its very high neutron flux and optimized fuel burn-up, the CANDU has a very high cobalt-60 production rate in a relatively short time. This makes CANDU an excellent vehicle for bulk cobalt-60 production. Several studies have been performed to produce cobalt-60 using adjuster rod at Wolsong nuclear power plant. This study proposed new concept for producing cobalt-60 and performed the feasibility study. Bundle typed cobalt loading concept is proposed and evaluated the feasibility to fuel management without physics and system design change. The requirement to load cobalt bundle to the core was considered and several channels are nominated. The production of cobalt-60 source is very depend on the flux level and burnup directly. But the neutron absorption characteristic of cobalt bundle is too high, so optimizing design study is needed in the future.

  2. Comparison of chemical changes during photooxidation of polypropylene film and filament containing phthalocyanine pigment

    International Nuclear Information System (INIS)

    Ahmadi, Z.; Haghighat Kish, M.; Kotak, R.; Katbab, A. A.

    2008-01-01

    Photooxidation as an important process, which significantly affects the service life of the polypropylene products, has been the subject of much theoretical and experimental study. Pigments used often change the light stabilities of polypropylene. Out-door applications of pigmented polypropylene are now increasingly developed in products such as artificial grass. The aim of this work is to examine the effect of photo-oxidation on the structure of isotactic polypropylene (iPP) in film and filament forms, where phthalocyanine pigment is used. For production of films and filaments, iPP granules with MFI 25 g/10 min were used, with and without phthalocyanine pigment. Samples were exposed to xenon lamp for various time lengths. The extent of the changes in chemical and structural parameters was examined by differential scanning calorimetry, Fourier transform infrared spectroscopy and wide angle x-ray diffraction. The results show that carbonyl and hydroperoxide indices increase during the exposure to the radiation. The changes in melting points of the samples were not significant after irradiation process. The effects of phthalocyanine pigment in the photooxidation of film and filament were different. Crystalline fractions of the non-pigmented filament samples decreased during the irradiation time while increased in film samples. Build up of hydroperoxide and carbonyl group in filament was higher than in film samples; that could be due to the differences in structural parameters. Crystallinity variations during photooxidation are related to the nucleation effect of the pigment, chemical crystallization and phase transformation

  3. Comparison of Chemical Changes During Photooxidation of Polypropylene Film and Filament Containing Phthalocyanine Pigment

    Directory of Open Access Journals (Sweden)

    Z. Ahmadi

    2008-02-01

    Full Text Available Photooxidation as an important process, which significantly affects the service life of the polypropylene products, has been the subject of much theoretical and experimental study. Pigments used often change the light stabilities of polypropylene. Out-door applications of pigmented polypr-opylene are now increasingly developed in products such as artificial grass. The aim of this work is to examine the effect of photo-oxidation on the structure of isotactic polypropylene (iPP in film and filament forms, where phthalocyanine pigment is used. For production of films and filaments, iPP granules with MFI 25 g/10min were used, with and without phthalocyanine pigment. Samples were exposed to xenon lamp for various time lengths. The extent of the changes in chemical and structural parameters was examined by differential scanning calorimetry, Fourier transform infrared spectroscopy and wide angle x-ray diffraction. The results show that carbonyl and hydroperoxide indices increase during the exposure to the radiation. The changes in melting points of the samples were not significant after irradiation process. The effects of phthalocyanine pigment in the photooxidation of filmand filament were different. Crystalline fractions of the non-pigmented filament samples decreased during the irradiation time while increased in film samples. Build up of hydroperoxide and carbonyl group in filament was higher than in film samples; that could be due to the differences in structural parameters. Crystallinity variations during photooxidation are related to the nucleation effect of the pigment, chemical crystallization and phase transformation.

  4. Nickel, cobalt, and their alloys

    CERN Document Server

    2000-01-01

    This book is a comprehensive guide to the compositions, properties, processing, performance, and applications of nickel, cobalt, and their alloys. It includes all of the essential information contained in the ASM Handbook series, as well as new or updated coverage in many areas in the nickel, cobalt, and related industries.

  5. Permanent antistatic phthalocyanine/epoxy nanocomposites – Influence of crosslinking agent, solvent and processing temperature

    NARCIS (Netherlands)

    Yuan, M.; Brokken-Zijp, J.C.M.; With, de G.

    2010-01-01

    Cross-linked epoxy matrices containing small amounts of semi-conductive phthalocyanine (Phthalcon) nanoparticles were prepared using different crosslinking agents and processing temperatures. A starting mixture containing an optimum dispersion of these nanoparticles and with an almost equal and

  6. Cobalt sorption onto Savannah River Plant soils

    International Nuclear Information System (INIS)

    Hoeffner, S.L.

    1985-06-01

    A laboratory study of cobalt-60 sorption was conducted using Savannah River Plant soil and groundwater from the low-level waste burial ground. Systematic variation of soil and water composition indicates that cobalt sorption is most strongly a function of pH. Over a pH range of 2 to 9, the distribution coefficient ranged from 2 to more than 10,000 mL/g. Changes in clay content and in K + , Ca 2+ , or Mg 2+ concentrations influence cobalt sorption indirectly through the slight pH changes which result. The ions Na + , Cl - , and NO 3 - have no effect on cobalt sorption. Ferrous ion, added to groundwater to simulate the condition of water at the bottom of the waste trenches, accounts for part of the decrease in cobalt sorption observed with trench waters. 17 refs., 3 figs., 4 tabs

  7. Bis(2-methoxybenzylammonium diaquabis(dihydrogen diphosphato-κ2O,O′cobaltate(II dihydrate

    Directory of Open Access Journals (Sweden)

    Adel Elboulali

    2014-04-01

    Full Text Available The title compound, (C8H12NO2[Co(H2P2O72(H2O2]·2H2O, crystallizes isotypically with its MnII analogue. It consists of alternating layers of organic cations and inorganic complex anions, extending parallel to (100. The complex cobaltate(II anion exhibits -1 symmetry. Its Co2+ atom has an octahedral coordination sphere, defined by two water molecules in apical positions and two H2P2O72− ligands in equatorial positions. The cohesion between inorganic and organic layers is accomplished by a set of O—H...O and N—H...O hydrogen bonds involving the organic cation, the inorganic anion and the remaining lattice water molecules.

  8. Optical properties of zinc phthalocyanine thin films prepared by pulsed laser deposition

    Czech Academy of Sciences Publication Activity Database

    Novotný, Michal; Bulíř, Jiří; Bensalah-Ledoux, A.; Guy, S.; Fitl, P.; Vrňata, M.; Lančok, Ján; Moine, B.

    2014-01-01

    Roč. 117, č. 1 (2014), 377-381 ISSN 0947-8396 R&D Projects: GA ČR(CZ) GAP108/11/1298 Grant - others:AVČR(CZ) M100101271 Institutional support: RVO:68378271 Keywords : optical properties * zinc phthalocyanine * laser deposition Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.704, year: 2014

  9. Photodynamic effects of 31 different phthalocyanines on a human keratinocyte cell line

    Czech Academy of Sciences Publication Activity Database

    Jančula, Daniel; Maršálek, Blahoslav; Babica, Pavel

    2013-01-01

    Roč. 93, č. 6 (2013), s. 870-874 ISSN 0045-6535 R&D Projects: GA TA ČR TA01010356 Grant - others:European Commission(XE) FP/2007-2013 no.2SGA2858 Institutional support: RVO:67985939 Keywords : phthalocyanine s * photodynamics * toxicity Subject RIV: EF - Botanics Impact factor: 3.499, year: 2013

  10. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  11. Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state

    Energy Technology Data Exchange (ETDEWEB)

    Ferraudi, G J; Prasad, D R

    1874-01-01

    Laser flash excitations at 640 nm have been used to generate the transient spectra of the lowest-lying /sup 3/..pi pi../sup */ state of phthalocyaninatoruthenium(II) complexes. The properties of this excited state such as the properties of the maxima, lambda/sub max/ = 500 +/- 30 nm, and lifetimes, t/sub 1/2/ = 70-4500 ns, exhibit a large dependence on the electron-accepting and electron-withdrawing tendencies of the axial ligands. A similar influence was observed upon the rate of electron-transfer quenching of the /sup 3/..pi pi../sup */ state. Values between 10/sup 6/ and 10/sup 7/ dm/sup 3/ mol/sup -1/ s/sup -1/ for the self-exchange rate constant have been obtained, according to Marcus-Hush theoretical treatments, for (Ru(pc.)LL')/sup +//(/sup 3/..pi pi../sup */)(Ru(pc)LL') (L and L' = neutral axial ligands; pc = phthalocyaninate (2-)) and isoelectronic cobalt(III) and rhodium(III) couples. The redox properties of the ground and excited states are correlated with axial ligand-induced perturbations of the electronic structure.

  12. Synthesis and spectral properties of axially substituted zirconium(IV) and hafnium(IV) water soluble phthalocyanines in solutions

    International Nuclear Information System (INIS)

    Gerasymchuk, Y.S.; Volkov, S.V.; Chernii, V.Ya.; Tomachynski, L.A.; Radzki, St.

    2004-01-01

    Methods of synthesis of novel water soluble axially substituted Zr(IV) and Hf(IV) phthalocyanines with gallic, 5-sulfosalicyllic, oxalic acids, and methyl ester of gallic acid as axial ligands coordinated to the central atom metal of phthalocyanine are presented. The absorption spectra of complex solutions in various solvents were characterized. The dependence of the spectral red shift from Reichardt's empirical polarity parameter is described. The deviation from the linearity of Beer-Bouguer-Lambert law was investigated for the range of concentration 5x10 -6 to 10x10 -5 M. Fluorescent properties of axially substituted phthalocyaninato metal complexes in DMSO solutions were investigated

  13. Transport of cobalt-60 industrial radiation sources

    Science.gov (United States)

    Kunstadt, Peter; Gibson, Wayne

    This paper will deal with safety aspects of the handling of Cobalt-60, the most widely used industrial radio-isotope. Cobalt-60 is a man-made radioisotope of Cobalt-59, a naturally occurring non radioactive element, that is made to order for radiation therapy and a wide range of industrial processing applications including sterilization of medical disposables, food irradiation, etc.

  14. Photodynamic therapy: anti-tumour potentialities of bis (tri π-hexyl-siloxy) silicon phthalocyanine against malignant achromic M6 melanocytes. EPR study of the photo-toxic mechanism

    International Nuclear Information System (INIS)

    Decreau, R.; Viola, A.; Julliard, M.; Hadjur, Ch.; Richard, M.J.; Favier, A.; Jeunet, A.

    1997-01-01

    Photodynamic therapy of cancerous cells is a technique relying upon the irradiation of tumorous cells after selective incorporation of a photo-sensitizer. The bis (tri n-hexyl-siloxy) silicon phthalocyanine is a second generation photo-sensitizer. Anti-cancerous potentialities of this molecule have been evaluated against the melanotic M6 cell line. Results have evidenced a high phototoxicity at low concentration and no dark toxicity under the same conditions. EPR studies on the photochemical pathways involved in phototoxicity processes have been realised in solvent and model membranes (liposomes). Results provide evidences for the production of singlet oxygen ( 1 O 2 ) as well as superoxide (O 2 0- ) and hydroxyl radical ( 0 OH). (authors)

  15. Hazardous Waste Minimization Assessment: Fort Ord, CA

    Science.gov (United States)

    1991-06-01

    phthalocyanine sludge with chromium/lead pigments, oils, hydrocarbon solvents, waxes, cobalt/zinc, magneze oleates, plasticizers Making gravure cylinders acid...7896 10920 Paint Shops 11525 190 506 8294 1598 937 Photography, Printing. and Arts) Cnts Shops 11031 310 160 150 200 10191 20 Other 4105 80 3515 510

  16. The physiological effect of cobalt on watermelon cultivation

    International Nuclear Information System (INIS)

    Yao Naihua; Jin Yafang; Sun Yaochen; Huang Yiming

    1993-01-01

    Cobalt has essential physiological action on both animals and plants. For the latter it can raise plant's nitrogen-fixing ability and saccharine content. Spray of cobalt mixed with other nutritive elements can improve the germinatit of seeds and the yield of fruit. For specifying the nutritive function of cobalt upon watermelon, isotope 60 Co was mixed into a complex leaf nutritive aqua and the regularity of transferring and absorbing cobalt in the watermelon's body was investigated

  17. Relaxation resistance of heat resisting alloys with cobalt

    International Nuclear Information System (INIS)

    Borzdyka, A.M.

    1977-01-01

    Relaxation resistance of refractory nickel-chromium alloys containing 5 to 14 % cobalt is under study. The tests involve the use of circular samples at 800 deg to 850 deg C. It is shown that an alloy containing 14% cobalt possesses the best relaxation resistance exceeding that of nickel-chromium alloys without any cobalt by a factor of 1.5 to 2. The relaxation resistance of an alloy with 5% cobalt can be increased by hardening at repeated loading

  18. Sodium doping in copper-phthalocyanine/C{sub 60} heterojunction for organic photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hui-Ju; Wu, Hsuan-Ta; Hung, Kuang-Teng; Fu, Sheng-Wen [Department of Electrical Engineering, National Cheng Kung University, Tainan, 70101, Taiwan (China); Shih, Chuan-Feng, E-mail: cfshih@mail.ncku.edu.tw [Department of Electrical Engineering, National Cheng Kung University, Tainan, 70101, Taiwan (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan, 70101, Taiwan (China)

    2013-10-01

    Sodium was incorporating at the copper-phthalocyanine (CuPc)/C{sub 60} interface in CuPc/C{sub 60}-based small-molecular solar cells to enhance their power conversion efficiency. C{sub 60} was deposited on slightly sodium-doped CuPc. Post-annealing improved the cell properties. Post-annealing doubled the conversion efficiency of the least sodium-doped devices (75 °C, 40 min). The electron/hole mobility ratio gradually approached unity as the annealing time increased, indicating that a reduction in the space charge accumulation was the main cause of the increase of the short-circuit current. The mechanism of enhancement of carrier transport by annealing was investigated by making capacitance–voltage measurements and performing corresponding depth-profile analyses. - Highlights: • Incorporate Na at copper-phthalocyanine/C{sub 60} interface • Annealing importantly improved the cell efficiency of Na-doped devices. • Change in the carrier mobility and concentration was investigated.

  19. Environmentally friendly inhibition of pathogenic bacteria and algae propagation due phthalocyanine agents

    International Nuclear Information System (INIS)

    Rihova Ambrozova, J.; Bezdekova, E.; Louckova, E.; Nekovarova, J.

    2007-01-01

    From 2004, in the laboratory of The Institute of Chemical Technology in Prague is being solved the project FT-TA/034 'Environmentally friendly inhibition of pathogenic bacteria and algae propagation in the circulatory cooling systems of nuclear power stations and in other similar technological facilities' to determine effects of phthalocyanine agents. The project bearer is VUOS, Inc. in Rybitvi (Research Institute for Organic Synthesis Inc.), where are the new phthalocyanines synthesized. The aimed goal of the research is environmentally friendly liquidation of bacteria and algae by means of photodynamic generated singlet oxygen through impact of solar radiation in the circulation cooling waters of various technical and technological systems. The principle of the problem outlined is the applying of phthalocyanine agents on samples of pure bacterial, anabaenas and algae cultures to estimate the inhibition effect on the organism exposed. In the course of solution, it is assumed that in such way conducted inhibition of bacteria, anabaenas and algae as well of their proliferation would replace routinely used bactericidal and algicidal preparations, which demand permanent dosing into circulating waters or perhaps from time to time an application of shocking doses. The particular algicidal and bactericidal agents represents in this case in situ emerging singlet oxygen, that is harmless to water biocenoses and whose presence in the water is no reason to ban the outflow of waters treated in such a way into water streams. The goal should be also a direct estimation of the effect those agents on cooling waters samples e. g. from the nuclear power plant systems. The purpose of the tests performance is also elimination of filamentous green algae, emerging in the systems cooling towers. The applied preparations are not toxic and do not burden the living environment, they contain no substances interacting with surface materials of structures in the circulatory cooling circuit

  20. Heating-induced inner-sphere substitution and reduction-oxidation reactions of the solid phenanthroline containing cobalt (2) and cobalt (3) complexes

    International Nuclear Information System (INIS)

    Palade, D.M.

    1996-01-01

    The results of the differential thermal and thermogravimetric analyses of solid phenanthroline-containing complexes of cobalt (2) and cobalt (3) in the atmosphere of the air have been analyzed. Mechanism of redox reactions occurring when cobalt (3) complexes are heated has been discussed. It is shown that some of gaseous products of the redox processes appear as a result of secondary reactions and not the processes of the ligands oxidation by Co 3+ . The influence of certain inner-sphere and coordinated anions (of I, inclusively) on cobalt (3) complexes behaviour during heating has been considered

  1. Control of carbon nanotube growth using cobalt nanoparticles as catalyst

    International Nuclear Information System (INIS)

    Huh, Yoon; Green, Malcolm L.H.; Kim, Young Heon; Lee, Jeong Yong; Lee, Cheol Jin

    2005-01-01

    We have controllably grown carbon nanotubes using uniformly distributed cobalt nanoparticles as catalyst. Cobalt nanoparticles with a uniform size were synthesized by chemical reaction and colloidal solutions including the cobalt nanoparticles were prepared. The cobalt nanoparticles were uniformly distributed on silicon substrates by a spin-coating method. Carbon nanotubes with a uniform diameter were synthesized on the cobalt nanoparticles by thermal chemical vapor deposition of acetylene gas. The density and vertical alignment of carbon nanotubes could be controlled by adjusting the density of cobalt (Co) nanoparticles

  2. Energy transfer and electron transfer in dimers and polymers of porphyrin and phthalocyanines: from the liquid phase to Langmuir-Blodgett films

    International Nuclear Information System (INIS)

    Lipskier, Jean-Francois

    1991-01-01

    The understanding of phenomena of photo-induced transfer of energy and of electron between chromophores belonging to a same supra-molecular entity is necessary for the design and fabrication of molecule devices performing the conversion of a light signal into electric signal or chemical potential. As porphyrin oligomers and phthalocyanine oligomers are examples of interest for the systematic study of parameters governing these processes, the first part of this research thesis addresses the study of dimers and trimers bound by covalent bridges. The second part addresses the study of physical-chemical properties of complexes bound by the Van der Waals interaction as well as by the Coulomb attraction. An extension to Langmuir-Blodgett films is proposed, and the properties of complexes organised in thin films according to this methodology are compared with those of their homologues in solution [fr

  3. Dosing of anaerobic granular sludge bioreactors with cobalt: Impact of cobalt retention on methanogenic activity

    KAUST Repository

    Fermoso, Fernando G.

    2010-12-01

    The effect of dosing a metal limited anaerobic sludge blanket (UASB) reactor with a metal pulse on the methanogenic activity of granular sludge has thus far not been successfully modeled. The prediction of this effect is crucial in order to optimize the strategy for metal dosage and to prevent unnecessary losses of resources. This paper describes the relation between the initial immobilization of cobalt in anaerobic granular sludge cobalt dosage into the reactor and the evolution of methanogenic activity during the subsequent weeks. An operationally defined parameter (A0· B0) was found to combine the amount of cobalt immobilized instantaneously upon the pulse (B0) and the amount of cobalt immobilized within the subsequent 24. h (A0). In contrast with the individual parameters A0 and B0, the parameter A0· B0 correlated significantly with the methanogenic activity of the sludge during the subsequent 16 or 35. days. This correlation between metal retention and activity evolution is a useful tool to implement trace metal dosing strategies for biofilm-based biotechnological processes. © 2010.

  4. Cobalt(II) and Cobalt(III) Coordination Compounds.

    Science.gov (United States)

    Thomas, Nicholas C.; And Others

    1989-01-01

    Presents a laboratory experiment which illustrates the formation of tris(phenanthroline)cobalt complexes in the 2+ and 3+ oxidation states, the effect of coordination on reactions of the ligand, and the use of a ligand displacement reaction in recovering the transformed ligand. Uses IR, UV-VIS, conductivity, and NMR. (MVL)

  5. Combination of hyperthermia and photodynamic therapy on mesenchymal stem cell line treated with chloroaluminum phthalocyanine magnetic-nanoemulsion

    Energy Technology Data Exchange (ETDEWEB)

    Paula, Leonardo B. de [Departamento de Química, Centro de Nanotecnologia e Engenharia Tecidual, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14040-901 (Brazil); Departamento de Genética, Faculdade de Medicina de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14049-900 (Brazil); Primo, Fernando L. [Departamento de Química, Centro de Nanotecnologia e Engenharia Tecidual, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14040-901 (Brazil); Nanophoton Company, SUPERA Innovation and Technology Park, Av. Doutora Nadir de Aguiar, 1805, Universidade de São Paulo, Ribeirão Preto, P 14056-680 (Brazil); Pinto, Marcelo R. [Departamento de Química, Laboratório de Enzimologia, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14040-901 (Brazil); Morais, Paulo C. [Instituto de Física, Universidade de Brasília, Brasília, DF 70910-900 (Brazil); School of Automation, Huazhong University of Science and Technology, Wuhan 430074 (China); and others

    2015-04-15

    The present study reports on the preparation and the cell viability assay of two nanoemulsions loaded with magnetic nanoparticle and chloroaluminum phthalocyanine. The preparations contain equal amount of chloroaluminum phthalocyanine (0.05 mg/mL) but different contents of magnetic nanoparticle (0.15×10{sup 13} or 1.50×10{sup 13} particle/mL). The human bone marrow mesenchymal stem cell line was used as the model to assess the cell viability and this type of cell can be used as a model to mimic cancer stem cells. The cell viability assays were performed in isolated as well as under combined magnetic hyperthermia and photodynamic therapy treatments. We found from the cell viability assay that under the hyperthermia treatment (1 MHz and 40 Oe magnetic field amplitude) the cell viability reduction was about 10%, regardless the magnetic nanoparticle content within the magnetic nanoparticle/chloroaluminum phthalocyanine formulation. However, cell viability reduction of about 50% and 60% were found while applying the photodynamic therapy treatment using the magnetic nanoparticle/chloroaluminum phthalocyanine formulation containing 0.15×10{sup 13} or 1.50×10{sup 13} magnetic particle/mL, respectively. Finally, an average reduction in cell viability of about 66% was found while combining the hyperthermia and photodynamic therapy treatments. - Highlights: • Current protocols in nanotechnology allow for biocompatible magnetic nanoparticles being associated with photosensitizer photoactive drugs, which could lead to perfectly controlled drug release. • The combination of the HPT and PDT therapies can be useful to develop further protocols for both advanced in vitro and in vivo assays. • Magnetic nanodevices associated with therapies have led to the decreased of proliferation of cell population that provides a favorable environment for tumor progression.

  6. Combination of hyperthermia and photodynamic therapy on mesenchymal stem cell line treated with chloroaluminum phthalocyanine magnetic-nanoemulsion

    International Nuclear Information System (INIS)

    Paula, Leonardo B. de; Primo, Fernando L.; Pinto, Marcelo R.; Morais, Paulo C.

    2015-01-01

    The present study reports on the preparation and the cell viability assay of two nanoemulsions loaded with magnetic nanoparticle and chloroaluminum phthalocyanine. The preparations contain equal amount of chloroaluminum phthalocyanine (0.05 mg/mL) but different contents of magnetic nanoparticle (0.15×10 13 or 1.50×10 13 particle/mL). The human bone marrow mesenchymal stem cell line was used as the model to assess the cell viability and this type of cell can be used as a model to mimic cancer stem cells. The cell viability assays were performed in isolated as well as under combined magnetic hyperthermia and photodynamic therapy treatments. We found from the cell viability assay that under the hyperthermia treatment (1 MHz and 40 Oe magnetic field amplitude) the cell viability reduction was about 10%, regardless the magnetic nanoparticle content within the magnetic nanoparticle/chloroaluminum phthalocyanine formulation. However, cell viability reduction of about 50% and 60% were found while applying the photodynamic therapy treatment using the magnetic nanoparticle/chloroaluminum phthalocyanine formulation containing 0.15×10 13 or 1.50×10 13 magnetic particle/mL, respectively. Finally, an average reduction in cell viability of about 66% was found while combining the hyperthermia and photodynamic therapy treatments. - Highlights: • Current protocols in nanotechnology allow for biocompatible magnetic nanoparticles being associated with photosensitizer photoactive drugs, which could lead to perfectly controlled drug release. • The combination of the HPT and PDT therapies can be useful to develop further protocols for both advanced in vitro and in vivo assays. • Magnetic nanodevices associated with therapies have led to the decreased of proliferation of cell population that provides a favorable environment for tumor progression

  7. Cobalt-60 control in Ontario Hydro reactors

    International Nuclear Information System (INIS)

    Lacy, C.S.

    1988-01-01

    This paper discusses the impact of specifying reduced Cobalt-59 in the primary heat transport circuit materials of construction on the radiation fields developed around the primary circuit. An eight-fold reduction in steam generator radiation fields due to Cobalt-60 has been observed for two identical sets of reactors, one with and one without Cobalt-59 control. The comparison is between eight reactors at the Pickering Nuclear Generating Station (PNGS). Units 5 to 8 (PNGS-B) are identical to Units 1 to 4 (PNGS-A) except that PNGS-B has reduced impurity Cobalt-59 in the alloys of construction and a reduced use of stellite. The effects of chemistry control are also discussed

  8. An elevator for cobalt-60 source

    International Nuclear Information System (INIS)

    Tang Zaimin; Liang Donghu

    1990-07-01

    The elevator used for cobalt-60 source is a key device in the irradiation industry. It plays an important role in the safety and control of irradiation operation as well as the utilization rate of radiation source. From 1983 to 1986, Beijing Institute of Nuclear Engineering undertook designing of various size irradiation projects for different uses. Since then a kind of cobalt-60 source elevator suited for the irradiator of wet-source-storage has been chosen. It is reliable in the operation and complete in the function. An automatic control circuit brings the systems of cobalt-60 source elevator into an interlock system which ensures the irradiation operation safety. Besides introducing the structural features and performance of this elevator, the conditions of safety interlocking in raising or lowering the cobalt-60 source is also discussed. The discussion is from the safety viewpoint of operating an irradiator and irradiation technology

  9. Study of the degradation of organic molecules complexing radionuclides by using Advanced Oxidation Processes

    International Nuclear Information System (INIS)

    Rekab, K.

    2014-01-01

    This research thesis reports the study of the application of two AOPs (Advanced Oxidation Processes) to degrade and mineralise organic molecules which are complexing radio-elements, and thus to allow their concentrations by trapping on mineral matrices. EDTA (ethylene diamine tetraacetic acid) is chosen as reference organic complexing agent for preliminary tests performed with inactive cobalt 59 before addressing actual nuclear effluents with active cobalt 60. The author first presents the industrial context (existing nuclear wastes, notably liquid effluents and their processing) and proposes an overview of the state of the art on adsorption and precipitation of cobalt (natural and radioactive isotope). Then, the author presents the characteristics of the various studied oxides, the photochemical reactor used to perform tests, experimental techniques and operational modes. Results are then presented regarding various issues: adsorption of EDTA and the Co-EDTA complex, and cobalt precipitation; determination of the lamp photon flow by chemical actinometry and by using the Keitz method; efficiency of different processes (UV, UV/TiO 2 , UV/H 2 O 2 ) to degrade EDTA and to degrade the Co-EDTA complex; processing of a nuclear effluent coming from La Hague pools with determination of decontamination factors

  10. Interaction of nitrogen dioxide with sulfonamide-substituted phthalocyanines: Towards NO2 gas sensor

    Czech Academy of Sciences Publication Activity Database

    Pochekailov, Sergii; Nožár, Juraj; Nešpůrek, Stanislav; Rakušan, J.; Karásková, M.

    2012-01-01

    Roč. 169, 5 July (2012), s. 1-9 ISSN 0925-4005 R&D Projects: GA AV ČR KAN400720701; GA MPO FR-TI1/144 Institutional research plan: CEZ:AV0Z40500505 Keywords : phthalocyanine * sulfonamide * nitrogen dioxide Subject RIV: CG - Electrochemistry Impact factor: 3.535, year: 2012

  11. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium-cobalt-aluminum oxide. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining a...

  12. The effect of NO2 on spectroscopic and structural properties of evaporated ruthenium phthalocyanine dimer

    International Nuclear Information System (INIS)

    Alagna, Lucilla; Capobianchi, Aldo; Paoletti, Anna Maria; Pennesi, Giovanna; Rossi, Gentilina; Casaletto, Maria Pia; Generosi, Amanda; Paci, Barbara; Albertini, Valerio Rossi

    2006-01-01

    The chemical interaction between NO 2 gas and dimeric ruthenium phthalocyanine (RuPc) 2 (Pc = phthalocyanine ligand) films has been investigated by different techniques: UV-Visible spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and Extended X-ray Absorption Fine Structure (EXAFS). The optical spectra in the Q band region (700-500 nm) registered 'in situ' enabled to follow the evolution of the process in real time indicating that a two steps reaction, showing two clear isosbestic points, occurs. The first phase was essentially characterised by: (a) the rapid disappearance of the 608 and 420 nm shoulders; (b) the intensity decrease of the main absorption peak and (c) the appearance of a new adsorption band centred around 510 nm. In the second step the remarkable feature is a further lowering of the main peak with the simultaneous decrease of the new 510 nm absorption. These spectral changes suggested that a chemical reaction occurred between NO 2 and ruthenium phthalocyanine with the formation of a radical species due to the macrocycle oxidation. The kinetics indicates that the adsorption of gas by the evaporated (RuPc) 2 film is a complex process involving more than one independent mechanism. XPS and EXAFS spectra collected before and after gas exposure showed that the central metals (Ru) were also involved in the oxidation process. The reversibility of the process has been also tested by treating the films at different temperatures, the original optical spectrum being not completely recovered

  13. Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil

    2010-01-01

    Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure.......Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure....

  14. The role of cobalt on the creep of Waspaloy

    Science.gov (United States)

    Jarrett, R. N.; Chin, L.; Tien, J. K.

    1984-01-01

    Cobalt was systematically replaced with nickel in Waspaloy (which normally contains 13% Co) to determine the effects of cobalt on the creep behavior of this alloy. Effects of cobalt were found to be minimal on tensile strengths and microstructure. The creep resistance and the stress rupture resistance determined in the range from 704 to 760 C (1300 to 1400 C) were found to decrease as cobalt was removed from the standard alloy at all stresses and temperatures. Roughly a ten-fold drop in rupture life and a corresponding increase in minimum creep rate were found under all test conditions. Both the apparent creep activation energy and the matrix contribution to creep resistance were found to increase with cobalt. These creep effects are attributed to cobalt lowering the stacking fault energy of the alloy matrix. The creep resistance loss due to the removal of cobalt is shown to be restored by slightly increasing the gamma' volume fraction. Results are compared to a previous study on Udimet 700, a higher strength, higher gamma' volume fraction alloy with similar phase chemistry, in which cobalt did not affect creep resistance. An explanation for this difference in behavior based on interparticle spacing and cross-slip is presented.

  15. Limitations of superfluid helium droplets as host system revealed by electronic spectroscopy of embedded molecules

    Energy Technology Data Exchange (ETDEWEB)

    Premke, Tobias

    2016-02-19

    Superfluid helium nanodroplets serve a unique cryogenic host system ideal to prepare cold molecules and clusters. Structures as well as dynamic processes can be examined by means of high resolution spectroscopy. Dopant spectra are accompanied by helium-induced spectroscopic features which reveal information on the dopant to helium interaction. For this reason the experimental research focuses on the investigation of such helium-induced effects in order to provide new information on the microsolvation inside the droplets. Since the quantitative understanding of helium-induced spectral features is essential to interpret molecular spectra recorded in helium droplets, this study contributes further experimental details on microsolvation in superfluid helium droplets. For this purpose two contrary systems were examined by means of high resolution electronic spectroscopy. The first one, phthalocyanine (Pc), is a planar organic molecule offering a huge and planar surface to the helium atoms and thus, the non-superfluid helium solvation layer can form different structures. The second system is iodine and in contrast to Pc it is of simple molecular shape. That means that in this case different complex structures of the non-superfluid helium solvation layer and the dopant can be expected to be avoided. Thus, both molecules should show clear differences in their microsolvation behavior. In this work a detailed examination of different spectroscopic properties of phthalocyanine is given by means of fluorescence excitation and dispersed emission spectroscopy. It raises legitimate doubts about the assignment of experimentally observed signals to features predicted by the model of the microsolvation. Even though there are no experimental observations which disprove the empirical model for the solvation in helium droplets, an unambiguous assignment of the helium-induced spectroscopic structures is often not possible. In the second part of this work, the investigation of the

  16. Nickel-cobalt hydroxide nanosheets: Synthesis, morphology and electrochemical properties.

    Science.gov (United States)

    Schneiderová, Barbora; Demel, Jan; Zhigunov, Alexander; Bohuslav, Jan; Tarábková, Hana; Janda, Pavel; Lang, Kamil

    2017-08-01

    This paper reports the synthesis, characterization, and electrochemical performance of nickel-cobalt hydroxide nanosheets. The hydroxide nanosheets of approximately 0.7nm thickness were prepared by delamination of layered nickel-cobalt hydroxide lactate in water and formed transparent colloids that were stable for months. The nanosheets were deposited on highly oriented pyrolytic graphite by spin coating, and their electrochemical behavior was investigated by cyclic voltammetry in potassium hydroxide electrolyte. Our method of electrode preparation allows for studying the electrochemistry of nanosheets where the majority of the active centers can participate in the charge transfer reaction. The observed electrochemical response was ascribed to mutual compensation of the cobalt and nickel response via electron sharing between these metals in the hydroxide nanosheets, a process that differentiates the behavior of nickel-cobalt hydroxide nanosheets from single nickel hydroxide or cobalt hydroxide nanosheets or their physical mixture. The presence of cobalt in the nickel-cobalt hydroxide nanosheets apparently decreases the time of electrochemical activation of the nanosheet layer, which for the nickel hydroxide nanosheets alone requires more potential sweeps. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Fabrication and characterization of organic solar cells using metal complex of phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-02-27

    Fabrication and characterization of organic solar cells using shuttle-cock-type phthalocyanines were carried out. Photovoltaic properties of the solar cells with inverted structures were investigated by current density-voltage characteristics. Effects of phase transition between H and J aggregates on the photovoltaic and optical properties were investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed.

  18. Interaction of tricyclic drugs with copper phthalocyanine dye immobilized on magnetic carriers

    Czech Academy of Sciences Publication Activity Database

    Šafaříková, Miroslava; Šafařík, Ivo

    3(Suppl.2), - (2002), s. 188-191 ISSN 1473-2262. [International Conference on the Scientific and Clinical Applications of Magnetic Carriers /4./. Tallahassee, 09.05.2002-11.05.2002] R&D Projects: GA MŠk OC 523.80; GA AV ČR IBS6087204 Institutional research plan: CEZ:AV0Z6087904 Keywords : magnetic * tricyclic drugs * phthalocyanine Subject RIV: CE - Biochemistry

  19. Carbohydrate and alditol analysis by high-performance anion-exchange chromatography coupled with electrochemical detection at a cobalt-modified electrode.

    Science.gov (United States)

    Casella, Innocenzo G; Contursi, Michela

    2003-07-01

    A cobalt oxyhydroxide film dispersed on a carbon electrode surface was characterized and proposed as an amperometric sensor for determination of alditols and carbohydrates in flowing streams. Complex mixtures of carbohydrates were separated by anion-exchange chromatography using a moderately alkaline solution as mobile phase. The cobalt modified electrode (GC-Co) was employed under a constant applied potential of 0.5 V (vs Ag/AgCl). Under these experimental conditions the detection limits (S/N=3) for all analyzed electroactive molecules ranged between 0.3 micromol L(-1) and 1.5 micromol L(-1) and the dynamic linear ranges spanned generally three orders of magnitude above the relevant detection limits. Analytical determinations of carbohydrates and alditols in red and white wines, are reported.

  20. COBALT COMPOUNDS AS ANTIDOTES FOR HYDROCYANIC ACID.

    Science.gov (United States)

    EVANS, C L

    1964-12-01

    The antidotal potency of a cobalt salt (acetate), of dicobalt edetate, of hydroxocobalamin and of cobinamide against hydrocyanic acid was examined mainly on mice and rabbits. All the compounds were active antidotes for up to twice the LD50; under some conditions for larger doses. The most successful was cobalt acetate for rabbits (5xLD50), which was effective at a molar cyanide/cobalt (CN/Co) ratio of 5, but had as a side-effect intense purgation. Hydroxocobalamin was irregular in action, but on the whole was most effective for mice (4.5xLD50 at a molar ratio of 1), and had no apparent side effects. Dicobalt edetate, at molar ratios of up to 2, was more effective for rabbits (3xLD50) than for mice (2xLD50), but had fewer side effects than cobalt acetate. The effect of thiosulphate was to augment the efficacy of dicobalt edetate and, in mice, that of hydroxocobalamin; but, apparently, in rabbits, to reduce that of hydroxocobalamin. Cobinamide, at a molar ratio of 1, was slightly more effective than hydroxocobalamin on rabbits and also less irregular in its action. Cobalt acetate by mouth was effective against orally administered hydrocyanic acid. The oxygen uptake of the body, reduced by cyanide, is rapidly reinstated when one of the cobalt antidotes has been successfully administered.

  1. A synthesis method for cobalt doped carbon aerogels with high surface area and their hydrogen storage properties

    Energy Technology Data Exchange (ETDEWEB)

    Tian, H.Y.; Buckley, C.E. [Department of Imaging and Applied Physics, Curtin University of Technology, GPO Box U 1987, Perth 6845, WA (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia); Sheppard, D.A.; Paskevicius, M. [Department of Imaging and Applied Physics, Curtin University of Technology, GPO Box U 1987, Perth 6845, WA (Australia); Hanna, N. [CSIRO Process Science and Engineering, Waterford, WA (Australia)

    2010-12-15

    Carbon aerogels doped with nanoscaled Co particles were prepared by first coating activated carbon aerogels using a wet-thin layer coating process. The resulting metal-doped carbon aerogels had a higher surface area ({proportional_to}1667 m{sup 2} g{sup -1}) and larger micropore volume ({proportional_to}0.6 cm{sup 3} g{sup -1}) than metal-doped carbon aerogels synthesised using other methods suggesting their usefulness in catalytic applications. The hydrogen adsorption behaviour of cobalt doped carbon aerogel was evaluated, displaying a high {proportional_to}4.38 wt.% H{sub 2} uptake under 4.6 MPa at -196 C. The hydrogen uptake capacity with respect to unit surface area was greater than for pure carbon aerogel and resulted in {proportional_to}1.3 H{sub 2} (wt. %) per 500 m{sup 2} g{sup -1}. However, the total hydrogen uptake was slightly reduced as compared to pure carbon aerogel due to a small reduction in surface area associated with cobalt doping. The improved adsorption per unit surface area suggests that there is a stronger interaction between the hydrogen molecules and the cobalt doped carbon aerogel than for pure carbon aerogel. (author)

  2. Photochemical oxygen reduction by zinc phthalocyanine and silver/gold nanoparticle incorporated silica thin films

    Energy Technology Data Exchange (ETDEWEB)

    Pal, Manas; Ganesan, Vellaichamy, E-mail: velganesh@yahoo.com; Azad, Uday Pratap

    2012-12-15

    Silver or gold nanoparticles are synthesized using a borohydride reduction method and are anchored simultaneously into/onto the mercaptopropyl functionalized silica. Later, zinc phthalocyanine is adsorbed onto the above materials. Thin films of these materials are prepared by coating an aqueous colloidal suspension of the respective material onto glass plates. Visible light irradiation of these films in oxygen saturated, stirred aqueous solutions effectively reduces oxygen to hydrogen peroxide. The photocatalytic reduction of oxygen is explained on the basis of the semiconducting properties of the silica films. The back electron transfer reaction is largely prevented by means of a sacrificial electron donor, triethanolamine. - Highlights: Black-Right-Pointing-Pointer Zinc phthalocyanine adsorbed silica materials were prepared. Black-Right-Pointing-Pointer Thin films of these materials photocatalytically reduce oxygen. Black-Right-Pointing-Pointer The photocatalysis is explained based on semiconductor properties of the materials. Black-Right-Pointing-Pointer Metal nanoparticles increase the photocatalytic efficiency of the materials.

  3. Characterization of a Porous Carbon Material Functionalized with Cobalt-Oxide/Cobalt Core-Shell Nanoparticles for Lithium Ion Battery Electrodes

    KAUST Repository

    Anjum, Dalaver H.; Rasul, Shahid; Roldan-Gutierrez, Manuel A.; Da Costa, Pedro M. F. J.

    2016-01-01

    A nanoporous carbon (C) material, functionalized with Cobalt-Oxide/Cobalt (CoO/Co) core-shell nanoparticles (NPs), was structurally and chemically characterized with transmission electron microcopy (TEM) while its electrochemical response

  4. Cobalt mineral exploration and supply from 1995 through 2013

    Science.gov (United States)

    Wilburn, David R.

    2011-01-01

    The global mining industry has invested a large amount of capital in mineral exploration and development over the past 15 years in an effort to ensure that sufficient resources are available to meet future increases in demand for minerals. Exploration data have been used to identify specific sites where this investment has led to a significant contribution in global mineral supply of cobalt or where a significant increase in cobalt production capacity is anticipated in the next 5 years. This report provides an overview of the cobalt industry, factors affecting mineral supply, and circumstances surrounding the development, or lack thereof, of key mineral properties with the potential to affect mineral supply. Of the 48 sites with an effective production capacity of at least 1,000 metric tons per year of cobalt considered for this study, 3 producing sites underwent significant expansion during the study period, 10 exploration sites commenced production from 1995 through 2008, and 16 sites were expected to begin production by 2013 if planned development schedules are met. Cobalt supply is influenced by economic, environmental, political, and technological factors affecting exploration for and production of copper, nickel, and other metals as well as factors affecting the cobalt industry. Cobalt-rich nickel laterite deposits were discovered and developed in Australia and the South Pacific and improvements in laterite processing technology took place during the 1990s and early in the first decade of the 21st century when mining of copper-cobalt deposits in Congo (Kinshasa) was restricted because of regional conflict and lack of investment in that country's mining sector. There was also increased exploration for and greater importance placed on cobalt as a byproduct of nickel mining in Australia and Canada. The emergence of China as a major refined cobalt producer and consumer since 2007 has changed the pattern of demand for cobalt, particularly from Africa and

  5. Sandwich-type mixed tetrapyrrole rare-earth triple-decker compounds. Effect of the coordination geometry on the single-molecule-magnet nature.

    Science.gov (United States)

    Kan, Jinglan; Wang, Hailong; Sun, Wei; Cao, Wei; Tao, Jun; Jiang, Jianzhuang

    2013-08-05

    Employment of the raise-by-one step method starting from M(TClPP)(acac) (acac = monoanion of acetylacetone) and [Pc(OPh)8]M'[Pc(OPh)8] led to the isolation and free modulation of the two rare-earth ions in the series of four mixed tetrapyrrole dysprosium sandwich complexes {(TClPP)M[Pc(OPh)8]M'[Pc(OPh)8]} [1-4; TClPP = dianion of meso-tetrakis(4-chlorophenyl)porphyrin; Pc(OPh)8 = dianion of 2,3,9,10,16,17,23,24-octa(phenoxyl)phthalocyanine; M-M' = Dy-Dy, Y-Dy, Dy-Y, and Y-Y]. Single-crystal X-ray diffraction analysis reveals different octacoordination geometries for the two metal ions in terms of the twist angle (defined as the rotation angle of one coordination square away from the eclipsed conformation with the other) between the two neighboring tetrapyrrole rings for the three dysprosium-containing isostructural triple-decker compounds, with the metal ion locating between an inner phthalocyanine ligand and an outer porphyrin ligand with a twist angle of 9.64-9.90° and the one between two phthalocyanine ligands of 25.12-25.30°. Systematic and comparative studies over the magnetic properties reveal magnetic-field-induced single-molecule magnet (SMM), SMM, and non-SMM nature for 1-3, respectively, indicating the dominant effect of the coordination geometry of the spin carrier, instead of the f-f interaction, on the magnetic properties. The present result will be helpful for the future design and synthesis of tetrapyrrole lanthanide SMMs with sandwich molecular structures.

  6. The cytotoxicity and genotoxicity of soluble and particulate cobalt in human lung fibroblast cells

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Leah J.; Holmes, Amie L. [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Maine Center for Environmental Toxicology and Health, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Department of Applied Medical Science, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Kandpal, Sanjeev Kumar; Mason, Michael D. [Department of Chemical and Biological Engineering, University of Maine, Orono, ME (United States); Zheng, Tongzhang [Department of Environmental Health Sciences, Yale School of Public Health, New Haven, CT (United States); Wise, John Pierce, E-mail: John.Wise@usm.maine.edu [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Maine Center for Environmental Toxicology and Health, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Department of Applied Medical Science, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States)

    2014-08-01

    Cobalt exposure is increasing as cobalt demand rises worldwide due to its use in enhancing rechargeable battery efficiency, super-alloys, and magnetic products. Cobalt is considered a possible human carcinogen with the lung being a primary target. However, few studies have considered cobalt-induced toxicity in human lung cells. Therefore, in this study, we sought to determine the cytotoxicity and genotoxicity of particulate and soluble cobalt in human lung cells. Cobalt oxide and cobalt chloride were used as representative particulate and soluble cobalt compounds, respectively. Exposure to both particulate and soluble cobalt induced a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobalt ion levels. Based on intracellular cobalt ion levels, we found that soluble cobalt was more cytotoxic than particulate cobalt while particulate and soluble cobalt induced similar levels of genotoxicity. However, soluble cobalt induced cell cycle arrest indicated by the lack of metaphases at much lower intracellular cobalt concentrations compared to cobalt oxide. Accordingly, we investigated the role of particle internalization in cobalt oxide-induced toxicity and found that particle-cell contact was necessary to induce cytotoxicity and genotoxicity after cobalt exposure. These data indicate that cobalt compounds are cytotoxic and genotoxic to human lung fibroblasts, and solubility plays a key role in cobalt-induced lung toxicity. - Highlights: • Particulate and soluble cobalt are cytotoxic and genotoxic to human lung cells. • Soluble cobalt induces more cytotoxicity compared to particulate cobalt. • Soluble and particulate cobalt induce similar levels of genotoxicity. • Particle-cell contact is required for particulate cobalt-induced toxicity.

  7. Making a robust carbon-cobalt(III) bond

    DEFF Research Database (Denmark)

    Larsen, Erik; Madsen, Anders Østergaard; Kofod, Pauli

    2009-01-01

    The coordination ion with a well-characterized carbon-cobalt(III) bond, the (1,4,7-triazacyclononane)(1,6-diamino-3-thia-4-hexanido)cobalt(III) dication, [Co(tacn)(C-aeaps)](2+) (aeaps, for aminoethylaminopropylsulfide), has been reacted with iodomethane, and the S-methyl thionium derivative has...... been isolated. The crystal structure of the resulting [Co(tacn)(C-aeaps-SCH(3))]Br(3) x 3 H(2)O at 122 K has been determined by X-ray diffraction techniques to verify the structure. The crystal structure determination shows that the carbon-cobalt bond length is even shorter (2.001(4) A) than in [Co......(tacn)(C-aeaps)](2+) participates in bonding to cobalt(III), having implications for the transformation between the carbon- and sulfur-bound forms of the aeaps ligand....

  8. An important rule for realizing metal → half-metal → semiconductor transition in single-molecule junctions

    Science.gov (United States)

    Zeng, Jing; Chen, Ke-Qiu; Long, Mengqiu

    2017-06-01

    Recently, Zhong et al (2015 Nano Lett. 15 8091) found that two additional hydrogen atoms can be adsorbed to the opposite aza-bridging nitrogen atoms of the manganese phthalocyanine (MnPc) macrocycle when exposed to H2. Thus the symmetry of the MnPc molecule is changed from 4-fold to 2-fold. Motivated by this recent experiment, we theoretically investigate a MnPc-based single-molecule junction in this work and propose a simple and reliable way to realize the transition of its electronic properties. On the basis of spin-polarized density-functional theory calculations combined with the Keldysh nonequilibrium Green’s technique, we find that the gradual hydrogenation in MnPc molecules gives rise to the changes of the hardness of the electron density and spin-selective orbital decoupling, which eventually leads to the realization of the first ever metal  →  half-metal  →  semiconductor transition behavior in single-molecule junctions. Analysis of molecular projected self-consistent Hamiltonian, Mulliken population, and local density of states also reveals an important rule for realizing this transition behavior. Our research confirms that the hydrogenation of MnPc molecules can realize various molecular functionalities in unitary material background.

  9. An important rule for realizing metal → half-metal → semiconductor transition in single-molecule junctions

    International Nuclear Information System (INIS)

    Zeng, Jing; Chen, Ke-Qiu; Long, Mengqiu

    2017-01-01

    Recently, Zhong et al (2015 Nano Lett . 15 8091) found that two additional hydrogen atoms can be adsorbed to the opposite aza-bridging nitrogen atoms of the manganese phthalocyanine (MnPc) macrocycle when exposed to H 2 . Thus the symmetry of the MnPc molecule is changed from 4-fold to 2-fold. Motivated by this recent experiment, we theoretically investigate a MnPc-based single-molecule junction in this work and propose a simple and reliable way to realize the transition of its electronic properties. On the basis of spin-polarized density-functional theory calculations combined with the Keldysh nonequilibrium Green’s technique, we find that the gradual hydrogenation in MnPc molecules gives rise to the changes of the hardness of the electron density and spin-selective orbital decoupling, which eventually leads to the realization of the first ever metal  →  half-metal  →  semiconductor transition behavior in single-molecule junctions. Analysis of molecular projected self-consistent Hamiltonian, Mulliken population, and local density of states also reveals an important rule for realizing this transition behavior. Our research confirms that the hydrogenation of MnPc molecules can realize various molecular functionalities in unitary material background. (paper)

  10. Total body irradiation with a reconditioned cobalt teletherapy unit.

    Science.gov (United States)

    Evans, Michael D C; Larouche, Renée-Xavière; Olivares, Marina; Léger, Pierre; Larkin, Joe; Freeman, Carolyn R; Podgorsak, Ervin B

    2006-01-01

    While the current trend in radiotherapy is to replace cobalt teletherapy units with more versatile and technologically advanced linear accelerators, there remain some useful applications for older cobalt units. The expansion of our radiotherapy department involved the decommissioning of an isocentric cobalt teletherapy unit and the replacement of a column-mounted 4-MV LINAC that has been used for total body irradiation (TBI). To continue offering TBI treatments, we converted the decommissioned cobalt unit into a dedicated fixed-field total body irradiator and installed it in an existing medium-energy LINAC bunker. This article describes the logistical and dosimetric aspects of bringing a reconditioned cobalt teletherapy unit into clinical service as a total body irradiator.

  11. Potential for cobalt recovery from lateritic ores in Europe

    Science.gov (United States)

    Herrington, R.

    2012-04-01

    Cobalt is one of the 'critical metals' identified under the EU Raw Materials Initiative. Annually the global mine production of cobalt is around 55,000 tonnes,with Europe's industries consuming around 30% of that figure. Currently Europe produces around 27 tonnes of cobalt from mines in Finland although new capacity is planned. Co-bearing nickel laterite ores being mined in Greece, Macedonia and Kosovo where the cobalt is currently not being recovered (ores have typical analyses of 0.055% Co and >1% Ni,). These ores are currently treated directly in pyrometallurgical plants to recover the contained nickel and this process means there is no separate cobalt product produced. Hydrometallurgical treatment of mineralogically suitable laterite ores can recover the cobalt; for example Cuba recovers 3,500 tonnes of cobalt from its laterite mining operations, which are of a similar scale to the current European operations. Implementation of hydrometallurgical techniques is in its infancy in Europe with one deposit in Turkey planning to use atmospheric heap leaching to recover nickel and copper from oxide-dominated ores. More widespread implementation of these methods to mineralogically suitable ore types could unlock the highly significant undeveloped resources (with metal contents >0.04% Co and >1% Ni), which have been defined throughout the Balkans eastwards into Turkey. At a conservative estimate, this region has the potential to supply up to 30% of the EU cobalt requirements.

  12. Effect of pentacene/Ag anode buffer and UV-ozone treatment on durability of small-molecule organic solar cells

    International Nuclear Information System (INIS)

    Inagaki, S; Sueoka, S; Harafuji, K

    2017-01-01

    Three surface modifications of indium tin oxide (ITO) are experimentally investigated to improve the performance of small-molecule organic solar cells (OSCs) with an ITO/anode buffer layer (ABL)/copper phthalocyanine (CuPc)/fullerene/bathocuproine/Ag structure. An ultrathin Ag ABL and ultraviolet (UV)-ozone treatment of ITO independently improve the durability of OSCs against illumination stress. The thin pentacene ABL provides good ohmic contact between the ITO and the CuPc layer, thereby producing a large short-circuit current. The combined use of the abovementioned three modifications collectively achieves both better initial performance and durability against illumination stress. (paper)

  13. Effect of pentacene/Ag anode buffer and UV-ozone treatment on durability of small-molecule organic solar cells

    Science.gov (United States)

    Inagaki, S.; Sueoka, S.; Harafuji, K.

    2017-06-01

    Three surface modifications of indium tin oxide (ITO) are experimentally investigated to improve the performance of small-molecule organic solar cells (OSCs) with an ITO/anode buffer layer (ABL)/copper phthalocyanine (CuPc)/fullerene/bathocuproine/Ag structure. An ultrathin Ag ABL and ultraviolet (UV)-ozone treatment of ITO independently improve the durability of OSCs against illumination stress. The thin pentacene ABL provides good ohmic contact between the ITO and the CuPc layer, thereby producing a large short-circuit current. The combined use of the abovementioned three modifications collectively achieves both better initial performance and durability against illumination stress.

  14. Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

    International Nuclear Information System (INIS)

    Viana, A.S.; Leupold, S.; Montforts, F.-P.; Abrantes, L.M.

    2005-01-01

    A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 x 10 -10 mol cm -2 and a thickness of 13 A, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water

  15. Organic phthalocyanine films with high mobilities for efficient field-effect transistor switches

    Czech Academy of Sciences Publication Activity Database

    Schauer, F.; Zhivkov, I.; Nešpůrek, Stanislav

    266-269, 1-3 (2000), s. 999-1003 ISSN 0022-3093. [International Conference on Amorphous and Microcrystalline Semiconductors /18./. Snowbird, 23.08.1999-27.08.1999] R&D Projects: GA MŠk OC 518.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : phthalocyanine * charge mobility * field-effect transistor Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.269, year: 2000

  16. Temperature dependent viscosity of cobalt ferrite / ethylene glycol ferrofluids

    Science.gov (United States)

    Kharat, Prashant B.; Somvanshi, Sandeep B.; Kounsalye, Jitendra S.; Deshmukh, Suraj S.; Khirade, Pankaj P.; Jadhav, K. M.

    2018-04-01

    In the present work, cobalt ferrite / ethylene glycol ferrofluid is prepared in 0 to 1 (in the step of 0.2) volume fraction of cobalt ferrite nanoparticles synthesized by co-precipitation method. The XRD results confirmed the formation of single phase spinel structure. The Raman spectra have been deconvoluted into individual Lorentzian peaks. Cobalt ferrite has cubic spinel structure with Fd3m space group. FT-IR spectra consist of two major absorption bands, first at about 586 cm-1 (υ1) and second at about 392 cm-1 (υ2). These absorption bands confirm the formation of spinel-structured cobalt ferrite. Brookfield DV-III viscometer and programmable temperature-controlled bath was used to study the relationship between viscosity and temperature. Viscosity behavior with respect to temperature has been studied and it is revealed that the viscosity of cobalt ferrite / ethylene glycol ferrofluids increases with an increase in volume fraction of cobalt ferrite. The viscosity of the present ferrofluid was found to decrease with increase in temperature.

  17. Synthesis of cobalt boride nanoparticles using radio frequency thermal plasma

    International Nuclear Information System (INIS)

    Lapitan, Jr. Lorico DS.; Ying Ying Chen; Seesoek Choe; Watanabe, Takayuki

    2012-01-01

    Nano size cobalt boride particles were synthesized from vapor phase using a 30 kw-4 MHz radio frequency (RF) thermal plasma. Cobalt and boron powder mixtures used as precursors in different composition and feed rate were evaporated immediately in the high temperature plasma and cobalt boride nanoparticles were produced through the quenching process. The x-ray diffractometry (XRD) patterns of cobalt boride nanoparticles prepared from the feed powder ratio of 1:2 and 1:3 for Co: B showed peaks that are associated with the Co 2 B and CoB crystal phases of cobalt boride. The XRD analysis revealed that increasing the powder feed rate results in a higher mass fraction and a larger crystalline diameter of cobalt boride nanoparticles. The images obtained by field emission scanning electron microscopy (FE-SEM) revealed that cobalt boride nanoparticles have a spherical morphology. The crystallite size of the particles estimated with XRD was found to be 18-22 nm. (author)

  18. Study to use graded cobalt adjuster in 540 MWe PHWR

    International Nuclear Information System (INIS)

    Raj, Manish; Fernando, M.P.S.; Pradhan, A.S.; Kumar, A.N.

    2007-01-01

    Full text: There are 17 adjusters in 540 MWe PHWR, which are essentially provided for xenon override function. They also provide flux flattening being in the central region of the reactor core. The present design of adjusters consists of stainless steel tube. The adjuster rods are grouped into 8 banks for movement. Since adjusters are normally fully inserted during reactor operation, they are best suited for production of cobalt 60. The nickel-plated cobalt in the form of either slugs or pellet are used for the design of cobalt pencils. The number of pencils can be varied to optimize the reactivity load and cobalt 60 production requirement. The worth and activity of cobalt adjusters have been worked out considering different pin configuration for the adjuster assembly. To start with we have assumed all adjusters throughout its length are of the same configuration. The flux depression factors within the cobalt pencils have been considered in the estimations of the specific and total cobalt 60 activities. The option of using graded cobalt adjusters, where different pin configuration along the length is considered for better flux flattening

  19. Intracellular photoinduced oxidative stress by zinc phthalocyanine photosensitization: a study of the early events in real time using confocal microscopy

    Science.gov (United States)

    Alexandratou, Eleni; Yova, Dido; Handris, Panagiotis; Kletsas, Dimitris; Loukas, Spyros

    2003-10-01

    Oxidative stress has been implicated in several biological and pathological aspects. Reactive oxygen species (ROS) have been proposed to act as signal transduction molecules activating reactions leading to cell rescue or to cell apoptosis/necrosis. In the present study, oxidative stress was induced by photosensitization of zinc phthalocyanine (ZnPc) in human fibroblasts using a photodynamic dose that did not lead to apoptosis or necrosis. The induction of oxidative stress was performed at the microscope stage in preassigned time. The cascade of phenomena evoked was studied in real time and at the single cell level using confocal laser scanning microscopy. Using specific vital fluorescent probes, alterations induced by oxidative stress in mitochondria membrane potential, in intracellular pH and in calcium concentration were recorded. Image processing and analysis techniques were used to quantify the observed changes. Subcellular localization of the photosensitizer was studied in order to determine the primary and immediate ROS target. It was found that ZnPc is mainly localized in the mitochondria region.

  20. Radiation synthesis and characterization of zinc phthalocyanine composite based on 2-hydroxyethyl methacrylate/methyl methacrylate copolymer

    International Nuclear Information System (INIS)

    Abdel Ghaffar, A.M.; Youssef, Tamer E.; Mohamed, Hanan H.

    2016-01-01

    The synthesis and characterization of new 2-hydroxyethyl methacrylate-co-methyl methacrylate/zinc phthalocyanine composite Poly(HEMA/MMA/ZnPc) is described for the first time in this study. The aim of this research is to present possibility of radiation synthesis of the newly zinc phthalocyanine composites as potential candidates for wide range of applications. Gel (%) and swelling for Poly(hydroxyethyl methacrylate) Poly(HEMA) and the based Poly(hydroxyethyl methacrylate/methyl methacrylate) copolymer Poly(HEMA/MMA) with different composition 100/0, 95/5, 90/10 and 80/20 wt % were evaluated. It was found that Poly(HEMA/MMA) copolymer with composition 95/5 wt % characterized by its high swelling property at pH 7.4. The prepared composites I and II Poly(HEMA/MMA/ZnPc) with composition (95/5/1 wt%) and (95/5/1.5 wt%) respectively have been characterized by FTIR and TGA. The effect of gamma irradiation on the chemical properties of composite I was described. It is observed that the Zinc phthalocyanine with low concentration 1 wt % enhance chemical, thermal properties and stabilization against gamma radiation of the prepared composite I. - Highlights: • The preparation of Poly(HEMA/MMA/ZnPc) by radiation forming modified composites. • The low concentration of ZcPc (1 or 1.5 wt %) lead to form outstanding properties. • These composites are a potential candidate for wide range of applications.

  1. Radiation synthesis and characterization of zinc phthalocyanine composite based on 2-hydroxyethyl methacrylate/methyl methacrylate copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Abdel Ghaffar, A.M., E-mail: am_abdelghaffar@yahoo.com [Radiation Research of Polymer Chemistry Department, Industrial Irradiation Division, National Center for Radiation Research and Technology, Atomic Energy Authority P.O. Box 29, Nasr City, Cairo (Egypt); Youssef, Tamer E. [Applied Organic Chemistry Department, Chemical Industries Research Division, National Research Center, Dokki, Cairo, 12622 (Egypt); Chemical and Materials Engineering Department, Faculty of Engineering, King Abdulaziz University, P.O. Box 80204, Jeddah, 21589 (Saudi Arabia); Mohamed, Hanan H. [Chemistry Department, Faculty of Science, Helwan University, Ain Helwan, Cairo (Egypt)

    2016-08-01

    The synthesis and characterization of new 2-hydroxyethyl methacrylate-co-methyl methacrylate/zinc phthalocyanine composite Poly(HEMA/MMA/ZnPc) is described for the first time in this study. The aim of this research is to present possibility of radiation synthesis of the newly zinc phthalocyanine composites as potential candidates for wide range of applications. Gel (%) and swelling for Poly(hydroxyethyl methacrylate) Poly(HEMA) and the based Poly(hydroxyethyl methacrylate/methyl methacrylate) copolymer Poly(HEMA/MMA) with different composition 100/0, 95/5, 90/10 and 80/20 wt % were evaluated. It was found that Poly(HEMA/MMA) copolymer with composition 95/5 wt % characterized by its high swelling property at pH 7.4. The prepared composites I and II Poly(HEMA/MMA/ZnPc) with composition (95/5/1 wt%) and (95/5/1.5 wt%) respectively have been characterized by FTIR and TGA. The effect of gamma irradiation on the chemical properties of composite I was described. It is observed that the Zinc phthalocyanine with low concentration 1 wt % enhance chemical, thermal properties and stabilization against gamma radiation of the prepared composite I. - Highlights: • The preparation of Poly(HEMA/MMA/ZnPc) by radiation forming modified composites. • The low concentration of ZcPc (1 or 1.5 wt %) lead to form outstanding properties. • These composites are a potential candidate for wide range of applications.

  2. Investigations on bioaccumulation of cobalt by fish eggs

    International Nuclear Information System (INIS)

    Harms, U.; Behringer, H.; Kunze, J.

    1978-01-01

    In ionized form cobalt is taken up by fish eggs directly from the water. Accumulation takes place on the chorion where the metal ions are reversibly bound to functional groups of the protein of the envelope of the egg or of the mycosa. To a small extent there occurs a transport of metal ions into the interior of the egg. It could not be clarified within the scope of the studies performed if this process is to be attributed to diffusion. Binding of the cobalt ions to the chorion leads, within hours, to a nearly uncharged final state, an apparent equilibrium, whose position is determined by the cobalt ion concentration of the breeding medium. Foreign ions (electrolytes like Ca 2+ ) lead to reduced uptake of cobalt ions, because they compete with the latter for binding places in the egg's envelope. Complex-forming substances (cysteine) result in lower absorption rates, too, the concentration of available cobalt ions in the water being reduced. (orig.) [de

  3. Bis(tri-n-hexylsilyl oxide) silicon phthalocyanine: a unique additive in ternary bulk heterojunction organic photovoltaic devices.

    Science.gov (United States)

    Lessard, Benoît H; Dang, Jeremy D; Grant, Trevor M; Gao, Dong; Seferos, Dwight S; Bender, Timothy P

    2014-09-10

    Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS)2-SiPc) as an additive in a P3HT:PC61BM cascade ternary bulk heterojunction organic photovoltaic (BHJ OPV) device results in an increase in the short circuit current (J(SC)) and efficiency (η(eff)) of up to 25% and 20%, respectively. The previous studies have attributed the increase in performance to the presence of (3HS)2-SiPc at the BHJ interface. In this study, we explored the molecular characteristics of (3HS)2-SiPc which makes it so effective in increasing the OPV device J(SC) and η(eff. Initially, we synthesized phthalocyanine-based additives using different core elements such as germanium and boron instead of silicon, each having similar frontier orbital energies compared to (3HS)2-SiPc and tested their effect on BHJ OPV device performance. We observed that addition of bis(tri-n-hexylsilyl oxide) germanium phthalocyanine ((3HS)2-GePc) or tri-n-hexylsilyl oxide boron subphthalocyanine (3HS-BsubPc) resulted in a nonstatistically significant increase in JSC and η(eff). Secondly, we kept the silicon phthalocyanine core and substituted the tri-n-hexylsilyl solubilizing groups with pentadecyl phenoxy groups and tested the resulting dye in a BHJ OPV. While an increase in JSC and η(eff) was observed at low (PDP)2-SiPc loadings, the increase was not as significant as (3HS)2-SiPc; therefore, (3HS)2-SiPc is a unique additive. During our study, we observed that (3HS)2-SiPc had an extraordinary tendency to crystallize compared to the other compounds in this study and our general experience. On the basis of this observation, we have offered a hypothesis that when (3HS)2-SiPc migrates to the P3HT:PC61BM interface the reason for its unique performance is not solely due to its frontier orbital energies but also might be due to a high driving force for crystallization.

  4. Measurement for cobalt target activity and its axial distribution

    International Nuclear Information System (INIS)

    Li Xingyuan; Chen Zigen.

    1985-01-01

    Cobalt target activity and its axial distribution are measured in process of producing radioactive isotopes 60 Co by irradiation in HFETR. Cobalt target activity is obtained with measured data at 3.60 m and 4.60 m, relative axial distribution of cobalt target activity is obtained with one at 30 cm, and axial distribution of cobalt target activity(or specific activity) is obtained with both of data. The difference between this specific activity and measured result for 60 Co teletherapy sources in the end is less than +- 5%

  5. 21 CFR 73.3110a - Chromium-cobalt-aluminum oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium-cobalt-aluminum oxide. 73.3110a Section... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110a Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide (Pigment Blue 36) (CAS Reg. No...

  6. Characterization and Catalytic Activity of Montmorillonite K10-Supported Cobalt Catalysts

    International Nuclear Information System (INIS)

    Gobara, H.M.; Ghattas, M.S.; Henien, S.A.

    2010-01-01

    Montmorillonite K10-supported cobalt catalysts were prepared by wet impregnation method. The samples were analyzed by XRD, TPR, FTTR and BET characterization techniques. [Three phases of cobalt species were identified namely, cobalt oxide (Co 3 O 4 ), cobalt silicate (Co 2 S 1 O 4 ) and cobalt aluminate (CoAl 2 O 4 ). These species were most probably existing within the inter lamellar spaces of the meso porous montmorillonite K10 support]. The two bands observed at 1385 and 760 cm 1 were characteristic of metal species rather than the support, being mostly of Co - O bond vibration. The hysteresis loop, pore size distribution, pore volume and BET surface area were greatly affected by cobalt loading. The catalyst containing 18 wt% cobalt was the most selective sample for ethylene production from ethanol dehydration.

  7. Photovoltaic behaviour of titanyl phthalocyanine thin films and titania bilayer films

    Czech Academy of Sciences Publication Activity Database

    Drabik, M.; Zachary, A. M.; Choi, Y.; Hanuš, J.; Toušek, J.; Toušková, J.; Cimrová, Věra; Slavinská, D.; Biederman, H.; Hanley, L.

    2008-01-01

    Roč. 268, č. 1 (2008), s. 57-60 ISSN 1022-1360. [Microsymposium on Advanced Polymer Materials for Photonics and Electronics /47./. Prague, 15.07.2007-19.07.2007] R&D Projects: GA MŠk(CZ) 1M06031 Grant - others:National Science Foundation(US) CHE0241425; GA MŠk(CZ) 1P05ME754 Institutional research plan: CEZ:AV0Z40500505 Keywords : conjugated polymers * photovoltaics * phthalocyanine * thin films * titania Subject RIV: BM - Solid Matter Physics ; Magnetism

  8. Preparation of thin phthalocyanine layers and their structural and absorption properties

    Czech Academy of Sciences Publication Activity Database

    Kment, Štěpán; Klusoň, Petr; Drobek, M.; Kužel, R.; Gregora, Ivan; Kohout, Michal; Hubička, Zdeněk

    2009-01-01

    Roč. 517, č. 17 (2009), s. 5274-5279 ISSN 0040-6090 R&D Projects: GA AV ČR KAN301370701; GA MŠk(CZ) 1M06002; GA AV ČR KAN400720701; GA ČR(CZ) GD203/08/H032 Institutional research plan: CEZ:AV0Z10100522; CEZ:AV0Z40720504 Keywords : vacuum sublimation * phthalocyanine s * sensors * thin fims Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.727, year: 2009

  9. Radiation induced ligand loss from cobalt complexes

    International Nuclear Information System (INIS)

    Funston, A. M.; McFadyen, W.D.; Tregloan, P.A.

    2000-01-01

    Full text: Due to the rapid nature of ligand dissociation from cobalt(II) complexes the study of the rate of ligand dissociation necessitates the use of a technique such as pulse radiolysis. This allows the rapid reduction of the corresponding cobalt(III) complex by a reducing radical, such as the aquated electron, to form the cobalt(II) complex. However, to date, no systematic study of either the mechanism of reduction or the influence of the electronic structure on the rate of ligand dissociation has been carried out. In order to understand these processes more fully the mechanism of reduction of a range of related cobalt(III) complexes by the aquated electron and the subsequent rate of ligand dissociation from the resulting cobalt(II) complexes is being investigated. It has been found that a number of processes are observed following the initial rapid reaction of the cobalt(III) complex with the aquated electron. Ultimately ligand loss is observed. Depending upon the complex, the initial processes observed may include the formation of coordinated radicals and electron transfer within the complex. For complexes containing aromatic ligands such as 2,2'-bipyridine, 1,10-phenanthroline and dipyrido[3,2-a:2',3'-c]phenazine the formation of a coordinated radical is observed as the initial reduction step. The kinetics of ligand dissociation of these complexes has been determined. The loss of monodentate ligands is fast and has been indistinguishable from the reduction processes when aromatic ligands are also present in the complex. However, for diamine chelates and diimine chelates spectra of the transient species can be resolved

  10. The cobalt-60 container scanner

    International Nuclear Information System (INIS)

    Jigang, A.; Liye, Z.; Yisi, L.; Haifeng, W.; Zhifang, W.; Liqiang, W.; Yuanshi, Z.; Xincheng, X.; Furong, L.; Baozeng, G.; Chunfa, S.

    1997-01-01

    The Institute of Nuclear Energy Technology (INET) has successfully designed and constructed a container (cargo) scanner, which uses cobalt-60 of 100-300 Ci as radiation source. The following performances of the Cobalt-60 container scanner have been achieved at INET: a) IQI (Image Quality Indicator) - 2.5% behind 100 mm of steel; b) CI (Contrast Indicator) - 0.7% behind 100 mm of steel; c) SP (Steel Penetration) - 240 mm of steel; d) Maximum Dose per Scanning - 0.02mGy; e) Throughput - twenty 40-foot containers per hour. These performances are equal or similar to those of the accelerator scanners. Besides these nice enough inspection properties, the Cobalt-60 scanner possesses many other special features which are better than accelerator scanners: a) cheap price - it will be only or two tenths of the accelerator scanner's; b) low radiation intensity - the radiation protection problem is much easier to solve and a lot of money can be saved on the radiation shielding building; c) much smaller area for installation and operation; d) simple operation and convenient maintenance; e) high reliability and stability. The Cobalt-60 container (or cargo) scanner is satisfied for boundary customs, seaports, airports and railway stations etc. Because of the nice special features said above, it is more suitable to be applied widely. Its high properties and low price will make it have much better application prospects

  11. Molecular structure effects in photodegradation of phenol and its chlorinated derivatives with phthalocyanines

    Czech Academy of Sciences Publication Activity Database

    Klusoň, P.; Drobek, M.; Krejčíková, S.; Krýsa, J.; Kalaji, A.; Cajthaml, Tomáš; Rakušan, J.

    2008-01-01

    Roč. 80, 3-4 (2008), s. 321-326 ISSN 0926-3373 R&D Projects: GA AV ČR KAN400720701 Grant - others:CZ(CZ) GD203/03/H140; Mšk(CZ) IM4531433201 Program:GD Institutional research plan: CEZ:AV0Z50200510 Keywords : phthalocyanines * phenol * chlorophenols Subject RIV: EE - Microbiology, Virology Impact factor: 4.853, year: 2008

  12. Highly selective cobalt-catalyzed hydrovinylation of styrene

    NARCIS (Netherlands)

    Grutters, M.M.P.; Müller, C.; Vogt, D.

    2006-01-01

    The hydrovinylation reaction is a codimerization of a 1,3-diene or vinyl arene and ethene with great potential for fine chemicals and pharmaceuticals. For the first time, enantioselective cobalt-catalyzed hydrovinylations of styrene were achieved with a cobalt-based system bearing a chiral

  13. Cobalt Blues The Story of Leonard Grimmett, the Man Behind the First Cobalt-60 Unit in the United States

    CERN Document Server

    Almond, Peter R

    2013-01-01

    For the latter half of the 20th century, cobalt-60 units were the mainstay of radiation treatments for cancer. Cobalt Blues describes the development of the first cobalt-60 unit in the United States and the man behind it, Leonard Grimmett. Conceptually conceived before World War II, it only became possible because of the development of nuclear reactors during the war. Although Grimmett conceived of and published his ideas first, the Canadians built the first units because of the capability of their reactor to produce more suitable cobalt-60 sources. This book tells the story of how Grimmett and others came together at the time that the U S Atomic Energy Agency was pushing the use of radioactivity in medicine. Due to his sudden death, very little information about Grimmett was known until recently, when various documents have come to light, allowing the full story to be told.

  14. Synergistic enhancement of supercapacitance upon integration of nickel (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine with SWCNT-phenylamine

    CSIR Research Space (South Africa)

    Agboola, BO

    2010-06-01

    Full Text Available Supercapacitive behaviour of a novel functional material, nickel (II) octa [(3,5-biscarboxylate)-phenoxy] phthalocyanine (NiOBCPPc) upon covalent integration with phenylamine functionalized single-walled carbon nanotubes (SWCNT...

  15. Changes in the Spectral Features of Zinc Phthalocyanine Induced by Nitrogen Dioxide Gas in Solution and in Solid Polymer Nanofiber Media.

    Science.gov (United States)

    Zugle, Ruphino; Tetteh, Samuel

    2017-03-01

    The changes in the spectral features of zinc phthalocyanine in the visible domain as a result of its interaction with nitrogen dioxide gas were assessed in this work. This was done both in solution and when the phthalocyanine was incorporated into a solid polystyrene polymer nanofiber matrix. The spectral changes were found to be spontaneous and marked in both cases suggesting a rapid response criterion for the detection of the gas. In particular, the functionalised nano-fabric material could serve as a practical fire alarm system as it rapidly detects the nitrogen dioxide gas generated during burning.

  16. ELECTROCATALYTIC ACTIVITY FOR O2 REDUCTION OF UNSUBSTITUTED AND PERCHLORINATED IRON PHTHALOCYANINES ADSORBED ON AMINO-TERMINATED MULTIWALLED CARBON NANOTUBES DEPOSITED ON GLASSY CARBON ELECTRODES

    OpenAIRE

    CAÑETE, PAULINA; SILVA, J. FRANCISCO; ZAGAL, JOSÉ H

    2014-01-01

    Amino-functionalized multiwalled carbon nanotubes (MWCNT-NH2) were modified with Fe phthalocyanine (FePc) and perchlorinated Fe phthalocyanine (16(Cl)FePc) and deposited on glassy carbon electrodes (GCE). The electrocatalytic activity of these hybrid electrodes was examined for the reduction of molecular oxygen in alkaline media (0.2 M NaOH) using stationary and rotating disk electrodes. Electrodes containing 16(Cl)FePc are more active than those containing FePc. Electrodes containing CNTs ar...

  17. Sputtering on cobalt with noble gas ions

    International Nuclear Information System (INIS)

    Sarholt-Kristensen, L.; Johansen, A.; Johnson, E.

    1983-01-01

    Single crystals of cobalt have been bombarded with 80 keV Ar + ions and with 80 keV and 200 keV Xe + ions in the [0001] direction of the hcp phase and the [111] direction of the fcc phase. The sputtering yield has been measured as function of target temperature (20 0 C-500 0 C), showing a reduction in sputtering yield for 80 keV Ar + ions and 200 keV Xe + ions, when the crystal structure changes from hcp to fcc. In contrast to this, bombardment with 80 keV Xe + ions results in an increase in sputtering yield as the phase transition is passed. Sputtering yields for [111] nickel are in agreement with the sputtering yields for fcc cobalt indicating normal behaviour of the fcc cobalt phase. The higher sputtering yield of [0001] cobalt for certain combinations of ion mass and energy may then be ascribed to disorder induced partly by martensitic phase transformation, partly by radiation damage. (orig.)

  18. Trigonal Prismatic Tris-pyridineoximate Transition Metal Complexes: A Cobalt(II) Compound with High Magnetic Anisotropy.

    Science.gov (United States)

    Pavlov, Alexander A; Savkina, Svetlana A; Belov, Alexander S; Nelyubina, Yulia V; Efimov, Nikolay N; Voloshin, Yan Z; Novikov, Valentin V

    2017-06-19

    High magnetic anisotropy is a key property of paramagnetic shift tags, which are mostly studied by NMR spectroscopy, and of single molecule magnets, for which magnetometry is usually used. We successfully employed both these methods in analyzing magnetic properties of a series of transition metal complexes, the so-called clathrochelates. A cobalt complex was found to be both a promising paramagnetic shift tag and a single molecule magnet because of it having large axial magnetic susceptibility tensor anisotropy at room temperature (22.5 × 10 -32 m 3 mol -1 ) and a high effective barrier to magnetization reversal (up to 70.5 cm -1 ). The origin of this large magnetic anisotropy is a negative value of zero-field splitting energy that reaches -86 cm -1 according to magnetometry and NMR measurements.

  19. Asymmetric Response toward Molecular Fluorination in Binary Copper–Phthalocyanine/Pentacene Assemblies

    DEFF Research Database (Denmark)

    de Oteyza, D. G.; García Lastra, Juan Maria; Goiri, E.

    2014-01-01

    We report a didactic and simple example of the subtleness in the balance of intermolecular and molecule–substrate interactions and its effect on molecular self-assembly. The study is performed on two closely related molecular blends of copper phthalocyanines and pentacene, in each of which one of...... intermolecular interactions and a larger corrugation in the molecule–substrate interaction potential, results in a disordered layer. However, the difference between the two blend’s structures vanishes when substrates with less corrugated interaction potentials are used....

  20. Energy-level alignment at interfaces between manganese phthalocyanine and C60

    Directory of Open Access Journals (Sweden)

    Daniel Waas

    2017-04-01

    Full Text Available We have used photoelectron spectroscopy to determine the energy-level alignment at organic heterojunctions made of manganese phthalocyanine (MnPc and the fullerene C60. We show that this energy-level alignment depends upon the preparation sequence, which is explained by different molecular orientations. Moreover, our results demonstrate that MnPc/C60 interfaces are hardly suited for application in organic photovoltaic devices, since the energy difference of the two lowest unoccupied molecular orbitals (LUMOs is rather small.

  1. Manipulating the dipole layer of polar organic molecules on metal surfaces via different charge-transfer channels

    Science.gov (United States)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Wang, Chin-Yung; Pi, Tun-Wen; Ishii, Hisao; Tang, S.-J.

    The key properties of organic films such as energy level alignment (ELA), work functions, and injection barriers are closely linked to this dipole layer. Using angle resolved photoemission spectroscopy (ARPES), we systemically investigate the coverage-dependent work functions and spectra line shapes of occupied molecular orbital states of a polar molecule, chloroaluminium phthalocyanine (ClAlPc), grown on Ag(111) to show that the orientations of the first ClAlPc layer can be manipulated via the molecule deposition rate and post annealing, causing ELA at organic-metal interface to differ for about 0.3 eV between Cl-up and Cl-down configuration. Moreover, by comparing the experimental results with the calculations based on both gas-phase model and realistic model of ClAlPc on Ag(111) , we evidence that the different orientations of ClAlPc dipole layers lead to different charge-transfer channels between ClAlPc and Ag, a key factor that controls the ELA at organic-metal interface.

  2. Phthalocyanine-nanocarbon ensembles: From discrete molecular and supramolecular systems to hybrid nanomaterials

    OpenAIRE

    Bottari, Giovanni; De La Torre, Gema; Torres, Tomas

    2015-01-01

    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Accounts of Chemical Research, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ar5004384 Conspectus Phthalocyanines (Pcs) are macrocyclic and aromatic compounds that present unique electronic features such as high molar absorption coefficients, rich redox chemistry, and...

  3. Interaction of selected gases with zinc phthalocyanine thin films: theoretical and experimental studies

    Czech Academy of Sciences Publication Activity Database

    Šebera, Jakub; Fitl, P.; Vlček, J.; Vrňata, M.; Fendrych, František; Kopeček, Jaromír; Kratochvílová, Irena

    2013-01-01

    Roč. 64, č. 1 (2013), "10202-p1"-"10202-p6" ISSN 1286-0042 R&D Projects: GA TA ČR TA01011165; GA ČR(CZ) GAP304/10/1951; GA ČR(CZ) GAP108/11/1298 Institutional support: RVO:68378271 Keywords : Zinc phthalocyanine * charge transport * sensor * DFT Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.789, year: 2013

  4. Ab initio electronic structure and correlations in pristine and potassium-doped molecular crystals of copper phthalocyanine

    NARCIS (Netherlands)

    Giovannetti, G.; Brocks, G.; van den Brink, J.

    2008-01-01

    We investigate the effect that potassium intercalation has on the electronic structure of copper phthalocyanine (CuPc) molecular crystals by means of ab initio density functional calculations. Pristine CuPc (in its alpha and beta structures) is found to be an insulator containing local magnetic

  5. A laboratory and field evaluation of the mobility of cobalt-60/EDTA

    International Nuclear Information System (INIS)

    Jones, T.L.; Gee, G.W.; Kirkham, R.R.; Swanson, J.L.

    1983-01-01

    We have observed a time and soil type dependence in the ability of the organic complexant EDTA to keep cobalt-60 in solution. Test results indicate that short-term adsorption tests lasting 5 days or less can be misleading. In short-term tests using cobalt-60/EDTA and soil from the Hanford site, low sorption in batch tests and high mobility in column tests were observed. During long-term batch test using cobalt-60/EDTA, the percentage of cobalt remaining in solution decreased from 90% after 7 days to less than 10% after 500 days. In laboratory and field column tests where low water flow rates allowed long contact time, virtually no cobalt movement was observed even though in the field test tritium was transported over 4 meters. Long-term batch tests using cobalt-60/EDTA and soil from Savannah River burial grounds showed that cobalt remainin in solution dropped to 30% of the total cobalt added after 5 days and to less than 1% after 15 days. Batch tests using soil from Oak Ridge burial grounds were less dramatic showing cobalt in solution decreasing from 90% after 5 days to 70% after 35 days. The cobalt-60/EDTA complex appears to be dissociating and leaving uncomplexed cobalt which is readily sorbed. The dissociation seems to be rather complete in Hanford and Savannah River soil but limited in the Oak Ridge soil. The implication to waste management is that the potential for transport of cobalt by EDTA may not be as serious at all burial sites as once thought

  6. EXAFS Determination of the Structure of Cobalt in Carbon-Supported Cobalt and Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Bouwens, S.M.A.M.; Veen, J.A.R. van; Beer, V.H.J. de; Prins, R.

    1991-01-01

    The structure of the cobalt present in carbon-supported Co and Co-Mo sulfide catalysts was studied by means of X-ray absorption spectroscopy at the Co K-edge and by X-ray photoelectron spectroscopy (XPS). Thiophene hydrodesulfurization activities were used to measure the catalytic properties of

  7. A spot test for detection of cobalt release - early experience and findings

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Menné, Torkil; Johansen, Jeanne D

    2010-01-01

    It is often difficult to establish clinical relevance of metal exposure in cobalt-allergic patients. Dermatologists and patients may incorrectly assume that many metallic items release cobalt at levels that may cause cobalt dermatitis. Cobalt-allergic patients may be unaware that they are exposed...

  8. Spins of adsorbed molecules investigated by the detection of Kondo resonance

    Science.gov (United States)

    Komeda, Tadahiro

    2014-12-01

    Surface magnetism has been one of the platforms to explore the magnetism in low dimensions. It is also a key component for the development of quantum information processes, which utilizes the spin degree of freedom. The Kondo resonance is a phenomenon that is caused by an interaction between an isolated spin and conduction electrons. First observed in the 1930s as an anomalous increase in the low-temperature resistance of metals embedded with magnetic atoms, the Kondo physics mainly studied the effects of bulk magnetic impurities in the resistivity. In the last 15 years it has undergone a revival by a scanning tunneling microscope (STM) which enables the measurement of the Kondo resonance at surfaces using an atomic scale point contact. The detection of the Kondo resonance can be a powerful tool to explore surface magnetism. In this article, I review recent studies of the surface spin of adsorbed molecules by the detection of the Kondo resonance. Researches on metal phthalocyanine (MPc) and porphyrin molecules will be examined. In addition, the Kondo resonance for double-decker lanthanoide Pc molecules will be discussed. Some of the double-decker Pc molecules show single-molecule magnet (SMM) behavior, which attracts attention as a material for electronic devices. For both classes, the ligand plays a crucial role in determining the parameters of the Kondo resonance, such as the Kondo temperature and the change of the shape from peak to Fano-dip. In addition, the spin in delocalized molecular orbital forms the Kondo resonance, which shows significant differences from the Kondo resonance formed by the metal spins. Since molecular orbital can be tuned in a flexible manner by the design of the molecule, the Kondo resonance formed by delocalized molecular orbital might expand the knowledge of this field.

  9. Inter-molecule interaction for magnetic property of vanadyl tetrakis(thiadiazole) porphyrazine film on Au(1 1 1)

    Science.gov (United States)

    Hou, Jie; Wang, Yu; Eguchi, Keitaro; Nanjo, Chihiro; Takaoka, Tsuyoshi; Sainoo, Yasuyuki; Awaga, Kunio; Komeda, Tadahiro

    2018-05-01

    We report scanning tunneling microscope (STM) observation of vanadyl tetrakis(thiadiazole) porphyrazine (VOTTDPz) molecules, which is a family molecule of phthalocyanine (Pc) but without Csbnd H termination in the perimeter, deposited on Au(1 1 1) surface. Well-ordered film corresponding to 4 × 4 superstructure with respect to Au(1 1 1) surface is formed, in which the centers of the molecules are separated by 1.12 nm, which is much smaller than that observed for a VOPc molecule on Au(1 1 1), due to the absence of Csbnd H termination. At the same time, the azimuthal angles of neighboring molecules rotate with each other by 30°. A contrast variation of bright and dark molecules is observed, which are interpreted as O-up and O-down molecules, respectively, based on the density functional theory simulation. Spin-polarized local density of states calculation shows spin-polarized V 3d state, which is delocalized over the ring. Spin detection is executed by measuring Kondo resonance in the tunneling spectroscopy near the Fermi level, which is caused by the interaction of an isolated spin and conduction electron of the substrate. We detected asymmetric and weak Kondo peak for out-of-plane outer magnetic field of 0 T, which becomes strong and symmetric peak at 5 T, which is understood by the shift of the spin center of the Kondo resonance from V 3d to delocalized π state in ring with the magnetic field.

  10. Incentives and opportunities for reducing the cobalt content in reactor core components

    International Nuclear Information System (INIS)

    Ocken, H.

    1985-01-01

    Cobalt in core components contributes to radiation field buildup on out-of-core surfaces. Core components containing cobalt-base alloys and cobalt as an impurity are identified. The use of cobalt-free wear-resistant alloys and construction materials with lower impurity levels of cobalt is disused. It is argued that such measures are cost effective. Lower radiation fields and disposal costs will offset higher raw material costs. Component performance will not be affected. (author)

  11. Removal of Cobalt Ion by Adsorbing Colloidal Flotation

    Energy Technology Data Exchange (ETDEWEB)

    Jung, In Ha; Lee, Jung Won [Korea Atomic Energy Research Institute, Taejon (Korea)

    1998-09-30

    Simulated waste liquid containing 50 ppm cobalt ion was treated by adsorbing colloidal flotation using Fe(III) or Al(III) as flocculant and a sodium lauryl sulfate as a collector. Parameters such as pH, surfactant concentration, Fe(III) or Al(III) concentration, gas flow rate, etc., were considered. The flotation with Fe(III) showed 99.8% removal efficiency of cobalt on the conditions of initial cobalt ion concentration 50 ppm, pH 9.5, gas flow rate 70 ml/min, and flotation time 30 min. When the waste solution was treated with 35% H{sub 2}O{sub 2} prior to adsorbing colloidal flotation, the optimal pH for removing cobalt shifted to weak alkaline range and flotation could be applied in wider range of pH as compared to non-use of H{sub 2}O{sub 2}. Additional use of 20 ppm Al(III) after precipitation of 50 ppm Co(II) with 50 ppm Fe(III) made the optimal pH range for preferable flotation wider. Foreign ions such as, NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, Na{sup +}, Ca{sup 2+} were adopted and their effects were observed, Of which sulfate ion was found to be detrimental to removal of cobalt ion by flotation. Coprecipitation of Co ion with Fe(III) and Al(III) resulted in better removal efficiency of cobalt ion in the presence of sulfate ion. (author). 14 refs., 13 figs.

  12. Heating analysis of cobalt adjusters in reactor core

    International Nuclear Information System (INIS)

    Mei Qiliang; Li Kang; Fu Yaru

    2011-01-01

    In order to produce 60 Co source for industry and medicine applications in CANDU-6 reactor, the stainless steel adjusters were replaced with the cobalt adjusters. The cobalt rod will generate the heat when it is irradiated by neutron and γ ray. In addition, 59 Co will be activated and become 60 Co, the ray released due to 60 Co decay will be absorbed by adjusters, and then the adjusters will also generate the heat. So the heating rate of adjusters to be changed during normal operation must be studied, which will be provided as the input data for analyzing the temperature field of cobalt adjusters and the relative heat load of moderator. MCNP code was used to simulate whole core geometric configuration in detail, including reactor fuel, control rod, adjuster, coolant and moderator, and to analyze the heating rate of the stainless steel adjusters and the cobalt adjusters. The maximum heating rate of different cobalt adjuster based on above results will be provided for the steady thermal hydraulic and accident analysis, and make sure that the reactor is safe on the thermal hydraulic. (authors)

  13. Optical limiting properties of optically active phthalocyanine derivatives

    Science.gov (United States)

    Wang, Peng; Zhang, Shuang; Wu, Peiji; Ye, Cheng; Liu, Hongwei; Xi, Fu

    2001-06-01

    The optical limiting properties of four optically active phthalocyanine derivatives in chloroform solutions and epoxy resin thin plates were measured at 532 nm with 10 ns pulses. The excited state absorption cross-section σex and refractive-index cross-section σr were determined with the Z-scan technique. These chromophores possess larger σex than the ground state absorption cross-section σ0, indicating that they are the potential materials for reverse saturable absorption (RSA). The negative σr values of these chromophores add to the thermal contribution, producing a larger defocusing effect, which may be helpful in further enhancing their optical limiting performance. The optical limiting responses of the thin plate samples are stronger than those of the chloroform solutions.

  14. The effect of gaseous ammonia on cobalt perrhenate

    International Nuclear Information System (INIS)

    Maslov, L.P.; Men'shikov, O.D.; Borisov, V.V.; Sorokin, S.I.; Krutovertsev, S.A.; Kharkevich, S.I.; Ivanova, O.M.

    1994-01-01

    The influence of humid air ammonia mixture on crystal pentahydrate of cobalt(2) perrhenate has been studied by the methods of PES, IR spectroscopy thermal analysis and electrophysical measurements. It is shown that with an increase in ammonia content in gaseous phase cobalt perrhenate successively transforms into diaquodiammine-, tetrammine- and μ-dioxo-bis-(tetrammine) derivatives of cobalt. Reversibility of dioxocomplex formation and a correlation between the change in electrophysical properties of crystal sample and change in ammonia content in gaseous phase are pointed out. 16 refs.; 4 figs.; 1 tab

  15. Nitrogen induced ferromagnetism in Cobalt doped BaTiO3

    Directory of Open Access Journals (Sweden)

    Chandrima Mitra

    2012-09-01

    Full Text Available The electronic structure and magnetism of Cobalt doped BaTiO3 (BaTi1−xCoxO3 is investigated. Substitutional Nitrogen on an Oxygen site is found to play an important role in inducing net magnetic moments in the system. The presence of a Nitrogen atom as nearest neighbour to a Cobalt atom is crucial in producing spin splitting of both the Nitrogen and Cobalt states thereby introducing a net local magnetic moment. The introduction of Nitrogen is further found to enhance ferromagnetic interactions between Cobalt atoms.

  16. Analysis of radioactive cobalt

    International Nuclear Information System (INIS)

    1977-01-01

    This is a manual published by Science and Technology Agency, Japan, which prescribes on the analysis method for radioactive cobalt which is a typical indexing nuclide among the radioactive nuclides released from nuclear facilities. Since the released cobalt is mainly discharged to coastal region together with waste water, this manual is written for samples of sea water, sea bottom sediments and marine organisms. Radioactive cobalt includes the nuclides of 57 co, 58 Co, 60 Co, etc., the manual deals with them as a whole as 60 Co of long half life. Though 60 Co analysis has become feasible comparatively simply due to scintillation or semi-conductor spectrometry, trace 60 Co analysis is performed quantitatively by co-precipitation or collection into alumina and scintillation spectrometry. However, specific collecting operation and γ-γ coincidence measurement have been required so far. This manual employs 60 Co collection by means of ion-exchange method and measurement with low background GM counting system, to analyze quantitatively and rapidly low level 60 Co. It is primarily established as the standard analyzing method for the survey by local autonomous bodies. It is divided into 4 chapters including introduction sea water, marine organisms, and sea bottom sediments. List of required reagents is added in appendix. (Wakatsuki, Y.)

  17. Nano cobalt oxides for photocatalytic hydrogen production

    KAUST Repository

    Mangrulkar, Priti A.

    2012-07-01

    Nano structured metal oxides including TiO 2, Co 3O 4 and Fe 3O 4 have been synthesized and evaluated for their photocatalytic activity for hydrogen generation. The photocatalytic activity of nano cobalt oxide was then compared with two other nano structured metal oxides namely TiO 2 and Fe 3O 4. The synthesized nano cobalt oxide was characterized thoroughly with respect to EDX and TEM. The yield of hydrogen was observed to be 900, 2000 and 8275 mmol h -1 g -1 of photocatalyst for TiO 2, Co 3O 4 and Fe 3O 4 respectively under visible light. It was observed that the hydrogen yield in case of nano cobalt oxide was more than twice to that of TiO 2 and the hydrogen yield of nano Fe 3O 4 was nearly four times as compared to nano Co 3O 4. The influence of various operating parameters in hydrogen generation by nano cobalt oxide was then studied in detail. Copyright © 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  18. Synthesis and characterization of cobalt-manganese oxides

    International Nuclear Information System (INIS)

    Valencia, J.; Arias, N.P.; Giraldo, O.; Rosales-Rivera, A.

    2012-01-01

    Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn 4+ to Mn 3+ . VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.

  19. Total quality management of cobalt-60 sources

    International Nuclear Information System (INIS)

    Malkoske, G.R.

    1999-01-01

    Total Quality Management of Cobalt-60 sources by a supplier requires a life cycle approach to source management. This covers various aspects, including design, manufacturing, installation, field inspection, source surveillance and return of cobalt-60 sources at the end of their useful life. The Total Quality Management approach demonstrates a strong industry commitment to the beneficial use of gamma technology for industrial irradiation applications in both developed nations and in those nations who are developing their infrastructure and techniques for the beneficial use of this technology. MDS Nordion continues to demonstrate its support and commitment to the industry by developing and implementing state-of-the-art standards for the safe use of cobalt-60 sources

  20. Solubility of cobalt in primary circuit solutions

    International Nuclear Information System (INIS)

    Lambert, I.; Joyer, F.

    1992-01-01

    The solubility of cobalt ferrite (CoFe 2 O 4 ) was measured in PWR primary circuit conditions, in the temperature range 250-350 deg C, and the results were compared with the ones obtained on magnetite and nickel ferrite. As in the former cases, it was found that, in the prevailing primary circuit conditions, the solubility of the cobalt ferrite was minimum at temperatures around 300 deg C, for cobalt as well as for iron. The equilibrium iron concentration is significantly lower than in the case of magnetite. The results are discussed in relation with the POTHY code, based only on thermodynamic laws and data, used for the prediction of the primary circuit chemistry

  1. Cobalt source calibration

    International Nuclear Information System (INIS)

    Rizvi, H.M.

    1999-01-01

    The data obtained from these tests determine the dose rate of the two cobalt sources in SRTC. Building 774-A houses one of these sources while the other resides in room C-067 of Building 773-A. The data from this experiment shows the following: (1) The dose rate of the No.2 cobalt source in Building 774-A measured 1.073 x 10 5 rad/h (June 17, 1999). The dose rate of the Shepherd Model 109 Gamma cobalt source in Building 773-A measured 9.27 x 10 5 rad/h (June 25, 1999). These rates come from placing the graduated cylinder containing the dosimeter solution in the center of the irradiation chamber. (2) Two calibration tests in the 774-A source placed the graduated cylinder with the dosimeter solution approximately 1.5 inches off center in the axial direction. This movement of the sample reduced the measured dose rate 0.92% from 1.083 x 10 5 rad/h to 1.073 x 10 5 rad/h. and (3) A similar test in the cobalt source in 773-A placed the graduated cylinder approximately 2.0 inches off center in the axial direction. This change in position reduced the measured dose rate by 10.34% from 1.036 x 10 6 to 9.27 x 10 5 . This testing used chemical dosimetry to measure the dose rate of a radioactive source. In this method, one determines the dose by the chemical change that takes place in the dosimeter. For this calibration experiment, the author used a Fricke (ferrous ammonium sulfate) dosimeter. This solution works well for dose rates to 10 7 rad/h. During irradiation of the Fricke dosimeter solution the Fe 2+ ions ionize to Fe 3+ . When this occurs, the solution acquires a slightly darker tint (not visible to the human eye). To determine the magnitude of the change in Fe ions, one places the solution in an UV-VIS Spectrophotometer. The UV-VIS Spectrophotometer measures the absorbency of the solution. Dividing the absorbency by the total time (in minutes) of exposure yields the dose rate

  2. Evaluation of antibacterial properties of novel phthalocyanines against Escherichia coli - comparison of analytical methods

    Czech Academy of Sciences Publication Activity Database

    Mikula, Přemysl; Kalhotka, L.; Jančula, Daniel; Zezulka, Štěpán; Kořínková, R.; Černý, J.; Maršálek, Blahoslav; Toman, Petr

    2014-01-01

    Roč. 138, Sep 2014 (2014), s. 230-239 ISSN 1011-1344 R&D Projects: GA TA ČR TA01010356; GA MPO FR-TI3/196; GA ČR(CZ) GAP205/10/2280 Institutional support: RVO:67985939 ; RVO:61389013 Keywords : phthalocyanine s * photosensitizers * antibacterial effect Subject RIV: EF - Botanics; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 2.960, year: 2014

  3. Piezoelectric properties and thermal stabilities of cobalt-modified potassium bismuth titanate

    International Nuclear Information System (INIS)

    Guo, Zhen-Lei; Wang, Chun-Ming; Zhao, Tian-Long; Yu, Si-Long; Cao, Zhao-Peng

    2013-01-01

    The cobalt-modified potassium bismuth titanate (K 0.5 Bi 4.5 Ti 4 O 15 , KBT) piezoelectric ceramics have been prepared using conventional solid–state reaction. X-ray diffraction analysis revealed that the cobalt-modified KBT ceramics have a pure four-layer (m = 4) Aurivillius-type structure. The dielectric, ferroelectric, and piezoelectric properties of cobalt-modified KBT ceramics were investigated in detail. The piezoelectric activities of KBT ceramics were significantly improved by the cobalt modification. The reasons for piezoelectric activities enhancement with cobalt modification were given. The piezoelectric coefficient d 33 and Curie temperature T c for the 5 mol% cobalt-modified KBT ceramics (KBT-Co5) were found to be 28 pC/N and 575 °C, respectively. The DC resistivity, frequency constants (N p and N t ), and electromechanical properties at elevated temperature were investigated, indicating the cobalt-modified KBT piezoelectric ceramics possess stable piezoelectric properties up to 500 °C. The results show the cobalt-modified KBT ceramics are potential materials for high temperature piezoelectric applications. - Highlights: • We examine the piezoelectric properties of the cobalt-modified K 0.5 Bi 4.5 Ti 4 O 15 . • A high level of piezoelectric activities (d 33 = 28 pC/N) are obtained. • High Curie temperature (T c = 575 °C) is acquired for the optimal composition. • The Co-modified K 0.5 Bi 4.5 Ti 4 O 15 is promising as high temperature materials

  4. Flexible heterostructures based on metal phthalocyanines thin films obtained by MAPLE

    International Nuclear Information System (INIS)

    Socol, M.; Preda, N.; Rasoga, O.; Breazu, C.; Stavarache, I.; Stanculescu, F.; Socol, G.; Gherendi, F.; Grumezescu, V.; Popescu-Pelin, G.; Girtan, M.; Stefan, N.

    2016-01-01

    Highlights: • Organic heterostructures prepared by MAPLE having a large absorbtion domain. • Photogeneration process is evidenced in the structure with ZnPc:TPyP mixed layer. • An increase in current value is observed in the structure with MgPc:TPyP mixed layer. - Abstract: Heterostructures based on zinc phthalocyanine (ZnPc), magnesium phthalocyanine (MgPc) and 5,10,15,20-tetra(4-pyrydil)21H,23H-porphine (TPyP) were deposited on ITO flexible substrates by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. Organic heterostructures containing (TPyP/ZnPc(MgPc)) stacked or (ZnPc(MgPc):TPyP) mixed layers were characterized by X-ray diffraction-XRD, photoluminescence-PL, UV–vis and FTIR spectroscopy. No chemical decomposition of the initial materials was observed. The investigated structures present a large spectral absorption in the visible range making them suitable for organic photovoltaics applications (OPV). Scanning electron microscopy-SEM and atomic force microscopy-AFM revealed morphologies typical for the films prepared by MAPLE. The current–voltage characteristics of the investigated structures, measured in dark and under light, present an improvement in the current value (∼3 order of magnitude larger) for the structure based on the mixed layer (Al/MgPc:TPyP/ITO) in comparison with the stacked layer (Al/MgPc//TPyP/ITO). A photogeneration process was evidenced in the case of structures Al/ZnPc:TPyP/ITO with mixed layers.

  5. Flexible heterostructures based on metal phthalocyanines thin films obtained by MAPLE

    Energy Technology Data Exchange (ETDEWEB)

    Socol, M., E-mail: cela@infim.ro [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); Preda, N.; Rasoga, O. [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); Breazu, C. [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); University of Bucharest, Faculty of Physics, 405 Atomistilor Street, PO Box MG-11, 077125 Bucharest-Magurele (Romania); Stavarache, I. [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); Stanculescu, F. [University of Bucharest, Faculty of Physics, 405 Atomistilor Street, PO Box MG-11, 077125 Bucharest-Magurele (Romania); Socol, G.; Gherendi, F.; Grumezescu, V.; Popescu-Pelin, G. [National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Street, PO Box MG-36, 077125 Bucharest-Magurele (Romania); Girtan, M. [Laboratoire de Photonique d’Angers, Université d’Angers, 2, Bd. Lavoisier, 49045 Angers (France); Stefan, N. [National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Street, PO Box MG-36, 077125 Bucharest-Magurele (Romania)

    2016-06-30

    Highlights: • Organic heterostructures prepared by MAPLE having a large absorbtion domain. • Photogeneration process is evidenced in the structure with ZnPc:TPyP mixed layer. • An increase in current value is observed in the structure with MgPc:TPyP mixed layer. - Abstract: Heterostructures based on zinc phthalocyanine (ZnPc), magnesium phthalocyanine (MgPc) and 5,10,15,20-tetra(4-pyrydil)21H,23H-porphine (TPyP) were deposited on ITO flexible substrates by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. Organic heterostructures containing (TPyP/ZnPc(MgPc)) stacked or (ZnPc(MgPc):TPyP) mixed layers were characterized by X-ray diffraction-XRD, photoluminescence-PL, UV–vis and FTIR spectroscopy. No chemical decomposition of the initial materials was observed. The investigated structures present a large spectral absorption in the visible range making them suitable for organic photovoltaics applications (OPV). Scanning electron microscopy-SEM and atomic force microscopy-AFM revealed morphologies typical for the films prepared by MAPLE. The current–voltage characteristics of the investigated structures, measured in dark and under light, present an improvement in the current value (∼3 order of magnitude larger) for the structure based on the mixed layer (Al/MgPc:TPyP/ITO) in comparison with the stacked layer (Al/MgPc//TPyP/ITO). A photogeneration process was evidenced in the case of structures Al/ZnPc:TPyP/ITO with mixed layers.

  6. Physical and photophysical properties of mixed double- and triple-decker sandwiches of porphyrins and phthalocyanines

    International Nuclear Information System (INIS)

    Salabert, Isabelle

    1995-01-01

    The study of electron transfer and charge recombination processes in various oligomers of porphyrins and phthalocyanines is reported. Our objective is to determine the nature of processes which compete with electron transfer in such Systems. The first part of this thesis is devoted to the study of mixed double- and triple-decker sandwich compounds of porphyrins and phthalocyanines of cerium and praseodymium. The charge transfer reaction and geminated recombination from excited complexes in solution and in sublimated film are investigated by time-resolved absorption spectroscopy with femtosecond time scale resolution. These results show the influence of the magnetic nature of the metal ion and of the relative position of the chromophores in the complex on the photophysical processes. The physical and photophysical properties of complexes formed by pairing in solution porphyrins and porphyrazines bearing oppositely charged substituent are reported in the second part. The formation of mixed aggregates of high order (2 to 5) is observed and their nature are spectrally characterized. The photoproducts issued from these complexes are extremely stable. (author) [fr

  7. The cobalt radioactive isotopes in environment; Les isotopes radioactifs du cobalt dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2007-07-01

    For the year 1993 the total activity released in cobalt is 69 GBq for the whole of nuclear power plants. The part of activity in cobalt for La Hague in 1993 is 8 GBq of {sup 58}Co and 2 GBq of {sup 60}Co. The radioactive isotopes released by nuclear power plants or the reprocessing plant of La Hague under liquid effluents are shared by half between {sup 58}Co and {sup 60}Co. The exposure to sealed sources is the most important risk for the cobalt. The risk of acute exposure can associate a local irradiation of several decades of grays inducing a radiological burns, deep burn to treat in surgery by resection or graft even amputation. A global irradiation of organism for several grays induces an acute irradiation syndrome, often serious. At long term the stochastic effects are represented by leukemia and radio-induced cancers. The increase of probability of their occurrence is 1% by sievert. We must remind that the natural spontaneous probability is 25%. (N.C.)

  8. Separation of cobalt from synthetic intermediate and decontamination radioactive wastes using polyurethane foam

    International Nuclear Information System (INIS)

    Rao, S.V.S.; Lal, K.B.; Narasimhan, S.V.; Ahmed, J.

    1997-01-01

    Studies have been carried out on the removal of radioactive cobalt ( 60 Co) from synthetic intermediate level waste (ILW) and decontamination waste using neat polyurethane (PU) foam as well as n-tributyl phosphate-polyurethane (TBP-PU) foam. The radioactive cobalt has been extracted on the PU foam as cobalt thiocyanate from the ILW. Maximum removal of cobalt has been observed when the concentration of thiocyanate in the solution is about 0.4 M. Cobalt can be separated from decontamination waste containing ethylenediaminetetraacetic acid (EDTA) and iron(II). The extent of extraction of cobalt is slow and the separation of iron and cobalt is better with the neat PU foam compared to the TBP-PU foam. The presence of iron in the decontamination waste facilitates the extraction of cobalt thiocyanate on the PU foam. Column studies have been carried out in order to extend these studies to the plant scale. The capacities of the PU foams for cobalt have been determined. The effect of density and the surface area of PU foam have been investigated. Fourier Transform Infrared (FT-IR) spectral studies have been conducted to find out the interaction between PU foam and cobalt thiocyanate species

  9. Crystal structures of salicylideneguanylhydrazinium chloride and its copper(II) and cobalt(III) chloride complexes

    International Nuclear Information System (INIS)

    Chumakov, Yu. M.; Tsapkov, V. I.; Bocelli, G.; Antosyak, B. Ya.; Shova, S. G.; Gulea, A. P.

    2006-01-01

    The crystal structures of salicylideneguanylhydrazinium chloride hydrate hemiethanol solvate (I), salicylideneguanylhydrazinium trichloroaquacuprate(II) (II), and bis(salicylideneguanylhydrazino)cobalt(III) chloride trihydrate (III) are determined using X-ray diffraction. The structures of compounds I, II, and III are solved by direct methods and refined using the least-squares procedure in the anisotropic approximation for the non-hydrogen atoms to the final factors R = 0.0597, 0.0212, and 0.0283, respectively. In the structure of compound I, the monoprotonated molecules and chlorine ions linked by hydrogen bonds form layers aligned parallel to the (010) plane. In the structure of compound II, the salicylaldehyde guanylhydrazone cations and polymer chains consisting of trichloroaquacuprate(II) anions are joined by an extended three-dimensional network of hydrogen bonds. In the structure of compound III, the [Co(LH) 2 ] + cations, chloride ions, and molecules of crystallization water are linked together by a similar network

  10. Characterization of a Cobalt-Tungsten Interconnect

    DEFF Research Database (Denmark)

    Harthøj, Anders; Holt, Tobias; Caspersen, Michael

    2012-01-01

    is to act both as a diffusion barrier for chromium and provide better protection against high temperature oxidation than a pure cobalt coating. This work presents a characterization of a cobalt-tungsten alloy coating electrodeposited on the ferritic steel Crofer 22 H which subsequently was oxidized in air......A ferritic steel interconnect for a solid oxide fuel cell must be coated in order to prevent chromium evaporation from the steel substrate. The Technical University of Denmark and Topsoe Fuel Cell have developed an interconnect coating based on a cobalt-tungsten alloy. The purpose of the coating...... for 300 h at 800 °C. The coating was characterized with Glow Discharge Optical Spectroscopy (GDOES), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The oxidation properties were evaluated by measuring weight change of coated samples of Crofer 22 H and Crofer 22 APU as a function...

  11. Association between cobalt allergy and dermatitis caused by leather articles

    DEFF Research Database (Denmark)

    Bregnbak, David; Thyssen, Jacob P; Zachariae, Claus

    2015-01-01

    BACKGROUND: Cobalt is a strong skin sensitizer and a prevalent contact allergen. Recent studies have recognized exposure to leather articles as a potential cause of cobalt allergy. OBJECTIVES: To examine the association between contact allergy to cobalt and a history of dermatitis resulting from...... exposure to leather. METHODS: A questionnaire case-control study was performed: the case group consisted of 183 dermatitis patients with a positive patch test reaction to cobalt chloride and a negative patch test reaction to potassium dichromate; the control group consisted of 621 dermatitis patients who...... did not react to either cobalt or chromium in patch testing. Comparisons were made by use of a χ(2) -test, Fisher's exact, and the Mann-Whitney test. Logistic regression analyses were used to test for associations while taking confounding factors into consideration. RESULTS: Leather was observed...

  12. Multiwalled Carbon Nanotubes Decorated with Cobalt Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    D. G. Larrude

    2012-01-01

    Full Text Available Multiwalled carbon nanotubes (MWCNTs synthesized by spray pyrolysis were decorated with cobalt oxide nanoparticles using a simple synthesis route. This wet chemistry method yielded nanoparticles randomly anchored to the surface of the nanotubes by decomposition of cobalt nitrate hexahydrate diluted in acetone. Electron microscopy analysis indicated that dispersed particles were formed on the MWCNTs walls. The average size increased with the increasing concentration of cobalt nitrate in acetone in the precursor mixture. TEM images indicated that nanoparticles were strongly attached to the tube walls. The Raman spectroscopy results suggested that the MWCNT structure was slightly damaged after the nanoparticle growth.

  13. Transport properties of cobalt at low temperatures

    DEFF Research Database (Denmark)

    Radharkishna, P.; Nielsen, Mourits

    1965-01-01

    Measurements are made of electrical resistivity, absolute thermoelectric power, and thermal conductivity of polycrystalline cobalt between 1.2 and 6 K; results are discussed on basis of inter-electronic scattering.......Measurements are made of electrical resistivity, absolute thermoelectric power, and thermal conductivity of polycrystalline cobalt between 1.2 and 6 K; results are discussed on basis of inter-electronic scattering....

  14. Absorption Spectroscopy, Molecular Dynamics Calculations, and Multivariate Curve Resolution on the Phthalocyanine Aggregation

    Energy Technology Data Exchange (ETDEWEB)

    Ajloo, Davood; Ghadamgahi, Maryam; Shaheri, Freshte; Zarei, Kobra [Damghan Univ., Damghan (Iran, Islamic Republic of)

    2014-05-15

    Co(II)-tetrasulfonated phthalocyanine (CoTSP) is known to be aggregated to dimer at high concentration levels in water. A study on the aggregation of CoTSP using multivariate curve resolution analysis of the visible absorbance spectra over a concentration range of 30, 40 and 50 μM in the presence of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile (AN) and ethanol (EtOH) in the concentration range of 0 to 3.57 M is conducted. A hard modeling-based multivariate curve resolution method was applied to determine the dissociation constants of the CoTSP aggregates at various temperatures ranging from 25, 45 and 65 .deg. C and in the presence of various co-solvents. Dissociation constant for aggregation was increased and then decrease by temperature and concentration of phthalocyanine, respectively. Utilizing the vant Hoff relation, the enthalpy and entropy of the dissociation equilibriums were calculated. For the dissociation of both aggregates, the enthalpy and entropy changes were positive and negative, respectively. Molecular dynamics simulation of cosolvent effect on CoTSP aggregation was done to confirm spectroscopy results. Results of radial distribution function (RDF), root mean square deviation (RMSD) and distance curves confirmed more effect of polar solvent to decrease monomer formation.

  15. Absorption Spectroscopy, Molecular Dynamics Calculations, and Multivariate Curve Resolution on the Phthalocyanine Aggregation

    International Nuclear Information System (INIS)

    Ajloo, Davood; Ghadamgahi, Maryam; Shaheri, Freshte; Zarei, Kobra

    2014-01-01

    Co(II)-tetrasulfonated phthalocyanine (CoTSP) is known to be aggregated to dimer at high concentration levels in water. A study on the aggregation of CoTSP using multivariate curve resolution analysis of the visible absorbance spectra over a concentration range of 30, 40 and 50 μM in the presence of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile (AN) and ethanol (EtOH) in the concentration range of 0 to 3.57 M is conducted. A hard modeling-based multivariate curve resolution method was applied to determine the dissociation constants of the CoTSP aggregates at various temperatures ranging from 25, 45 and 65 .deg. C and in the presence of various co-solvents. Dissociation constant for aggregation was increased and then decrease by temperature and concentration of phthalocyanine, respectively. Utilizing the vant Hoff relation, the enthalpy and entropy of the dissociation equilibriums were calculated. For the dissociation of both aggregates, the enthalpy and entropy changes were positive and negative, respectively. Molecular dynamics simulation of cosolvent effect on CoTSP aggregation was done to confirm spectroscopy results. Results of radial distribution function (RDF), root mean square deviation (RMSD) and distance curves confirmed more effect of polar solvent to decrease monomer formation

  16. Synchrotron-based measurements of the electronic structure of the organic semiconductor copper phthalocyanine

    International Nuclear Information System (INIS)

    Downes, J.E.

    2004-01-01

    Full text: Copper phthalocyanine (CuPc) is a prototypical molecular organic semiconductor that is currently used in the construction of many organic electronic devices such as organic light emitting diodes (OLEDs). Although the material is currently being used, and despite many experimental and theoretical studies, it's detailed electronic structure is still not completely understood. This is likely due to two key factors. Firstly, the interaction of the Cu 3d and phthalocyanine ligand 2p electrons leads to the formation of a complex arrangement of localized and delocalized states near the Fermi level. Secondly, thin films of the material are subject to damage by the photon beam used to make measurements of their electronic structure. Using the synchrotron-based techniques of soft x-ray emission spectroscopy (XES) and x-ray photoemission spectroscopy (XPS), we have measured the detailed electronic structure of in-situ grown thin film samples of CuPc. Beam damage was minimized by continuous translation of the sample during data acquisition. The results obtained differ significantly from previous XES and ultraviolet photoemission measurements, but are in excellent agreement with recent density functional calculations. The reasons for these discrepancies will be explained, and their implications for future measurements on similar materials will be explored

  17. Capacitance measurements and AC conductivity of Nickel Phthalocyanine films

    International Nuclear Information System (INIS)

    Darwish, S.

    2005-01-01

    A C dark Current measurements of nickel phthalocyanine thin films using ohmic gold electrodes are investigated in the frequency range 30-10 Hz and within the temperature range 295-385 K. The A C conductivity as D Ac is found to vary as within the index s < 1, indicating a dominant hopping process at low temperatures. From the temperature dependence of A C conductivity, free carrier conduction with mean activation energy of 0.31 eV is observed at higher temperatures. Capacitance and loss tangent are found to be decreased with increasing frequency and increase with increasing temperature. Such characteristics are found to be in good qualitative agreement with existing equivalent circuit model assuming ohmic contacts

  18. A spot test for detection of cobalt release – early experience and findings

    DEFF Research Database (Denmark)

    Thyssen, Jacob P.; Menné, Torkil; Johansen, Jeanne D.

    2010-01-01

    Background: It is often difficult to establish clinical relevance of metal exposure in cobalt-allergic patients. Dermatologists and patients may incorrectly assume that many metallic items release cobalt at levels that may cause cobalt dermatitis. Cobalt-allergic patients may be unaware that they...

  19. Assessment of cobalt levels in wastewater, soil and vegetable ...

    African Journals Online (AJOL)

    User

    Key words: Cobalt level, Kubanni River, soil, vegetable, wastewater. INTRODUCTION. Cobalt is ... metals released into the environment from a variety of anthropogenic activities ..... Heavy Metal Stress in Plants, 2nd Edition,. Springer,. United.

  20. Synthesis and phosphatase activity of a Cobalt(II) phenanthroline ...

    Indian Academy of Sciences (India)

    MAMONI GARAI

    2017-09-19

    Sep 19, 2017 ... Synthesis and phosphatase activity of a Cobalt(II) phenanthroline complex. MAMONI GARAIa ... tion, cobalt complexes have gained importance because of their application as ... 2.3 Physical measurements. Infrared spectrum ...

  1. Correlation between morphology and magnetic properties of electrochemically produced cobalt powder particles

    Directory of Open Access Journals (Sweden)

    Maksimović Vesna M.

    2015-01-01

    Full Text Available Cobalt 3D powder particles were successfully prepared by the galvanostatic electrodeposition. Electrodeposited cobalt powder were characterized by X-ray diffraction (XRD, scanning electron microscope (SEM, Energy Dispersive Spectroscopy (EDS analysis and SQUID magnetometry. It has been shown that morphology, structure and magnetic properties of cobalt particles are closely associated and can be easily controlled by adjusting process parameters of electrodeposition. Morphology of cobalt powder particles is strongly affected by hydrogen evolution reaction as a parallel reaction to cobalt electrodeposition. Depending on the applied current density, the two types of powder particles were formed: dendrites at lower and spongy-like particles at higher current densities. Morphologies and structures of powder particles are correlated with their magnetic properties, and compared with those of the bulk cobalt. In comparison with the properties of bulk cobalt, the obtained 3D structures exhibited a decreased saturation magnetization (MS, but an enhanced coercivity (HC which is explained by their peculiar morphology. [Projekat Ministarstva nauke Republike Srbije, br. III 45012

  2. Novel Topical Photodynamic Therapy of Prostate Carcinoma Using Hydroxy-aluminum Phthalocyanine Entrapped in Liposomes

    Czech Academy of Sciences Publication Activity Database

    Sutoris, K.; Rakušan, J.; Karásková, M.; Mattová, J.; Beneš, J.; Nekvasil, Miloš; Ježek, Petr; Zadinová, M.; Poučková, P.; Větvička, D.

    2013-01-01

    Roč. 33, č. 4 (2013), s. 1563-1568 ISSN 0250-7005 R&D Projects: GA MPO(CZ) 2A-1TP1/026; GA MŠk(CZ) OE09026; GA TA ČR(CZ) TA01010781 Institutional support: RVO:67985823 Keywords : PC prostate carcinomas * LNCaP * liposomes * hydroxy-aluminum phthalocyanine * photodynamic therapy Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 1.872, year: 2013

  3. Synthesis and characterization of cobalt-manganese oxides

    Energy Technology Data Exchange (ETDEWEB)

    Valencia, J. [Laboratorio de Magnetismo y Materiales Avanzados, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis 55455-0153 (United States); Arias, N.P. [Laboratorio de Materiales Nanoestructurados y Funcionales, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Departamento de Ingenieria Electrica, Electronica y Computacion, Facultad de Ingenieria y Arquitectura, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Giraldo, O. [Laboratorio de Materiales Nanoestructurados y Funcionales, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Rosales-Rivera, A., E-mail: arosalesr@unal.edu.co [Laboratorio de Magnetismo y Materiales Avanzados, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia)

    2012-08-15

    Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn{sup 4+} to Mn{sup 3+}. VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.

  4. Estimation of cobalt release from feed water heater tubes of BWRs

    International Nuclear Information System (INIS)

    Uchida, S.; Kitamura, M.; Ozawa, Y.

    1983-01-01

    To evaluate the release source of cobalt from heater tubes of the feed water line, release rate measurements were carried out by detecting 60 Co released from irradiated stainless steel in contact with neutral water at an oxygen concentration of 20 ppb. The dependences of cobalt release rate on temperature, flow velocity and exposure time were studied after 670 hours of release experiments, and an empirical equation (which is presented) was obtained in the temperature range from 150 to 240 deg C. A decrease in the cobalt release rate above 250 deg C was considered due to the formation of a protective oxide layer. From these data, the amount of cobalt released from individual feed water heaters was evaluated. It was demonstrated that low cobalt containing stainless steel was economically applied only in the higher temperature region of the heater (20% of the total surface) to reduce cobalt feed rate into the reactor (to approx. 1/2). (author)

  5. A novel method to synthesize cobalt oxide (Co3O4) nanowires from cobalt (Co) nanobowls

    DEFF Research Database (Denmark)

    Srivastava, Akhilesh Kumar; Madhavi, S.; Ramanujan, R.V.

    2010-01-01

    A novel method suitable for the synthesis of the cobalt oxide (Co3O4) nanowires at targeted regions is presented in this report. Cobalt (Co) nanobowls synthesized by colloidal crystal directed assembly were transformed into Co3O4 nanowires by a simple heat treatment process. Co nanobowls exhibited...... a two phase (h.c.p. + f.c.c.) microstructure while single phase microstructure was observed for Co3O4 nanowires. Ferromagnetic Co nanobowls showed a dependence of coercivity on bowl size while Co3O4 exhibited weak ferromagnetic behavior....

  6. A review of cobalt adsorption on transition metal oxides

    International Nuclear Information System (INIS)

    Walker, S.M.

    1987-04-01

    This report reviews studies of cobalt adsorption on transition metal oxides, in the context of corrosion product and radioactivity transport in PWR primary circuits. In general, uptake of cobalt increases with pH, with temperature and with decreasing ionic strength. Very little data are available under PWR primary circuit conditions, but the limited data available suggest that cobalt uptake by the zirconium oxide corrosion product layer on fuel pins may be significant compared to that deposited on fuel crud. If fuel crud levels can be reduced in future by coolant chemistry control then uptake by the zirconia will assume a greater relative role. It is planned to use an autoclave to study uptake of cobalt on oxidised Zircaloy surfaces at temperatures up to 593K under PWR primary circuit chemistry conditions. (author)

  7. Ion exchange of Cobalt and Cadmium in Zeolite X

    International Nuclear Information System (INIS)

    Nava M, I.

    1994-01-01

    The growing development in the industry has an important contribution to the environmental damage, where the natural effluents are each day more contaminated by toxic elements, such as: mercury, chromium, lead and cadmium. So as to separate such elements it has sorbent must have enough stability, and have a sharp capacity of sorption. In this work it was studied the sorption behavior of cobalt and on the other hand, cadmium in aqueous solutions, which along with sodic form of the Zeolite X, undergoes a phenomenon of ionic interchange. Such interchange was verify to different concentration of cadmium, cobalt and hydronium ion. The content of cobalt and sodium in the interchanged samples was detected through the neutronic activation analysis. The results disclose a higher selectivity for cadmium than cobalt. (Author)

  8. The Application of Moessbauer Emission Spectroscopy to Industrial Cobalt Based Fischer-Tropsch Catalysts

    International Nuclear Information System (INIS)

    Loosdrecht, J. van de; Berge, P. J. van; Craje, M. W. J.; Kraan, A. M. van der

    2002-01-01

    The application of Moessbauer emission spectroscopy to study cobalt based Fischer-Tropsch catalysts for the gas-to-liquids process was investigated. It was shown that Moessbauer emission spectroscopy could be used to study the oxidation of cobalt as a deactivation mechanism of high loading cobalt based Fischer-Tropsch catalysts. Oxidation was observed under conditions that are in contradiction with the bulk cobalt phase thermodynamics. This can be explained by oxidation of small cobalt crystallites or by surface oxidation. The formation of re-reducible Co 3+ species was observed as well as the formation of irreducible Co 3+ and Co 2+ species that interact strongly with the alumina support. The formation of the different cobalt species depends on the oxidation conditions. Iron was used as a probe nuclide to investigate the cobalt catalyst preparation procedure. A high-pressure Moessbauer emission spectroscopy cell was designed and constructed, which creates the opportunity to study cobalt based Fischer-Tropsch catalysts under realistic synthesis conditions.

  9. Plasma sprayed samarium--cobalt permanent magnets

    International Nuclear Information System (INIS)

    Willson, M.C.; Janowiecki, R.J.

    1975-01-01

    Samarium--cobalt permanent magnets were fabricated by arc plasma spraying. This process involves the injection of relatively coarse powder particles into a high-temperature gas for melting and spraying onto a substrate. The technique is being investigated as an economical method for fabricating cobalt--rare earth magnets for advanced traveling wave tubes and cross-field amplifiers. Plasma spraying permits deposition of material at high rates over large areas with optional direct bonding to the substrate, and offers the ability to fabricate magnets in a variety of shapes and sizes. Isotropic magnets were produced with high coercivity and good reproducibility in magnetic properties. Post-spray thermal treatments were used to enhance the magnetic properties of sprayed deposits. Samarium--cobalt magnets, sprayed from samarium-rich powder and subjected to post-spray heat treatment, displayed energy products in excess of 9 million gauss-oersteds and coercive forces of approximately 6000 oersteds. Bar magnet arrays were constructed by depositing magnets on ceramic substrates. (auth)

  10. The cobalt radioactive isotopes in environment

    International Nuclear Information System (INIS)

    2007-01-01

    For the year 1993 the total activity released in cobalt is 69 GBq for the whole of nuclear power plants. The part of activity in cobalt for La Hague in 1993 is 8 GBq of 58 Co and 2 GBq of 60 Co. The radioactive isotopes released by nuclear power plants or the reprocessing plant of La Hague under liquid effluents are shared by half between 58 Co and 60 Co. The exposure to sealed sources is the most important risk for the cobalt. The risk of acute exposure can associate a local irradiation of several decades of grays inducing a radiological burns, deep burn to treat in surgery by resection or graft even amputation. A global irradiation of organism for several grays induces an acute irradiation syndrome, often serious. At long term the stochastic effects are represented by leukemia and radio-induced cancers. The increase of probability of their occurrence is 1% by sievert. We must remind that the natural spontaneous probability is 25%. (N.C.)

  11. Phthalocyanine-loaded graphene nanoplatform for imaging-guided combinatorial phototherapy

    Directory of Open Access Journals (Sweden)

    Taratula O

    2015-03-01

    Full Text Available Olena Taratula,1 Mehulkumar Patel,2 Canan Schumann,1 Michael A Naleway,1 Addison J Pang,1 Huixin He,2 Oleh Taratula1 1Department of Pharmaceutical Sciences, College of Pharmacy, Oregon State University, Portland, OR, USA; 2Department of Chemistry, Rutgers University-Newark, Newark, NJ, USA Abstract: We report a novel cancer-targeted nanomedicine platform for imaging and prospect for future treatment of unresected ovarian cancer tumors by intraoperative multimodal phototherapy. To develop the required theranostic system, novel low-oxygen graphene nanosheets were chemically modified with polypropylenimine dendrimers loaded with phthalocyanine (Pc as a photosensitizer. Such a molecular design prevents fluorescence quenching of the Pc by graphene nanosheets, providing the possibility of fluorescence imaging. Furthermore, the developed nanoplatform was conjugated with poly(ethylene glycol, to improve biocompatibility, and with luteinizing hormone-releasing hormone (LHRH peptide, for tumor-targeted delivery. Notably, a low-power near-infrared (NIR irradiation of single wavelength was used for both heat generation by the graphene nanosheets (photothermal therapy [PTT] and for reactive oxygen species (ROS-production by Pc (photodynamic therapy [PDT]. The combinatorial phototherapy resulted in an enhanced destruction of ovarian cancer cells, with a killing efficacy of 90%–95% at low Pc and low-oxygen graphene dosages, presumably conferring cytotoxicity to the synergistic effects of generated ROS and mild hyperthermia. An animal study confirmed that Pc loaded into the nanoplatform can be employed as a NIR fluorescence agent for imaging-guided drug delivery. Hence, the newly developed Pc-graphene nanoplatform has the significant potential as an effective NIR theranostic probe for imaging and combinatorial phototherapy. Keywords: graphene nanosheets, phthalocyanine, photothermal therapy, photodynamic therapy, theranostic 

  12. Calculation support for industrial production of cobalt-60 at Leningrad NPP

    International Nuclear Information System (INIS)

    Artemov, Vladimir; Elshin, Alexander; Ivanov, Alexander; Gorbunov, Evgeny; Ikonnikov, Roman; Pimenov, Alexander

    2008-01-01

    Cobalt-60 is industrially produced at the Leningrad NPP by irradiation of cobalt-59 in special-purpose facilities loaded into the RBMK reactor core (all 4 units). The paper describes calculation methods used to determine the current activity of cobalt in irradiation assemblies for their timely unloading. The described peculiarities of core calculation model account for continuous refueling, overloading of irradiation assemblies and individual thermohydraulics in each channel under variation of reactor power. Fuel burnup in the core is calculated with a time step of about 24 hours. The resulting values for cobalt activity and uncertainties are presented in the paper as well. Deviation of calculated cobalt activity from measured activity is within the experimental accuracy of 10% (at confidence probability of 0.95). (authors)

  13. Sorption behavior of cobalt on manganese dioxide, smectite and their mixture

    International Nuclear Information System (INIS)

    Ohnuki, T.; Kozai, N.

    1995-01-01

    The sorption behavior of cobalt on manganese dioxide, the clay mineral smectite and mixtures of the two was studied by batch type sorption/desorption experiments at neutral pH. Sorption behavior was examined by sequential extraction, in which the sorbents were contacted first with a 1 M CH 3 COONH 4 solution and then with a hydroxylamine solution (NH 2 OH of 1 M with 25 weight % CH 3 COOH). More than 70% of the sorbed cobalt was desorbed from smectite with a 1 M CH 3 COONH 4 solution: about 15% of the cobalt remained on the smectite after treatment with the hydroxylamine solution. Less than 1% of the remaining cobalt was desorbed from manganese dioxide with a 1 M CH 3 COONH 4 solution; with the hydroxylamine solution, all was desorbed. In mixtures of MnO 2 and smectite that were formulated to sorb equal amounts of cobalt regardless of the MnO 2 /smectite ratio in the mixture, less than 5% of the sorbed cobalt was desorbed by treatment with 1 M CH 3 COONH 4 . The fraction of the cobalt desorbed by treatment with the hydroxylamine solution increased with increased MnO 2 in the mixtures. The fraction of the cobalt sorbed on MnO 2 in the mixture was estimated from the desorption experiments. The results showed that higher fractions were sorbed onto MnO 2 than were estimated by the weighted averages of distribution coefficients for MnO 2 and smectite. Therefore, in minerals of the mixture, manganese dioxide is a more important component than smectite for the sorption of cobalt. (orig.)

  14. Synthesis of Ruthenium(III Phthalocyanine with Di-axial Bromo Ligands - A Promising Molecular Conductor with Giant Negative Magnetoresistance

    Directory of Open Access Journals (Sweden)

    Mario A.V. Gamboa

    2015-01-01

    Full Text Available The electron transport of Phthalocyanines (Pc with central metal and di-axial ligands (such as FeIII(PcL2; where L = CN, Cl, Br originates from its intermolecular Pc π-π orbital overlap while its giant negative magnetoresistance (GNMR arises from its intramolecular Pc-π(HOMO and Fe-d (s=1/2 interaction. However, the π-d interaction tends to localize itinerant electrons resulting in the decrease in the conductivity of the FeIII(PcL2 series compared to the non-magnetic CoIII(PcL2 where π-d interaction is absent. More so, the axial ligand field energy of the FeIII(PcL2 system is found to have the ability to proportionally modulate the π-d interaction. In reference thereof, theoretical calculations point that isostructural RuIII(PcBr2 would provide the best balance of π-d orbital energy interplay. That is, RuIII(PcBr2 is expected to be a molecule with high electrical conductivity and GNMR which would make it an ideal magnetic molecular conductor. This paper reports on the synthesis of RuIII(PcBr2.

  15. Enhanced fluorescence of tetrasulfonated zinc phthalocyanine by graphene quantum dots and its application in molecular sensing/imaging.

    Science.gov (United States)

    Wang, Jian; Zhang, Yanjun; Ye, Jiqing; Jiang, Zhou

    2017-06-01

    When excited at 435 nm, tetra-sulfonate zinc phthalocyanine (ZnPcS 4 ) emitted dual fluorescence at 495 and 702 nm. The abnormal fluorescence at 495 nm was experimentally studied and analyzed in detail for the first time. The abnormal fluorescence at 495 nm was deduced to originate from triplet-triplet (T-T) energy transfer of excited phthalocyanine ( 3 *ZnPcS 4 ). Furthermore, graphene quantum dots (GQDs) enhanced the 495 nm fluorescence quantum yield (Q) of ZnPcS 4 . The fluorescence properties of ZnPcS 4 -GQDs conjugate were retained in a cellular environment. Based on the fluorescence of ZnPcS 4 -GQDs conjugate, we designed and prepared an Apt29/thrombin/Apt15 sandwich thrombin sensor with high specificity and affinity. This cost-saving, simple operational sensing strategy can be extended to use in sensing/imaging of other biomolecules. Copyright © 2016 John Wiley & Sons, Ltd.

  16. Concentration of radioactive cobalt by seaweeds in the food chain

    International Nuclear Information System (INIS)

    Nakahara, Motokazu; Koyanagi, Taku; Saiki, Masamichi

    1976-01-01

    On the pathway of radioactive substances in marine environments, seaweeds play an important role because of their higher concentration factors for many radionuclides and because they constitute a link of food chain in the sea. In the present work, uptake, distribution and excretion of radioactive cobalt were studied on several kinds of seaweeds by radioisotope tracer experiments under laboratory conditions and concentration factors were calculated. The concentration factors were also estimated from the results of stable cobalt determination by activation analysis or atomic absorption spectrometry on seaweeds and seawater, and compared with the results of tracer expts. The seaweeds showed the species specificity for the concentration of stable and radioactive cobalt with diverse values of concentration factors and biological half-lives. The transfer of radioactive cobalt in the food chain from contaminated seaweeds to mollusca was examined by feeding abalones, Haliotis discus, with four kinds of seaweed labelled with 60 Co and observing retention. Absorption rate for radioactive cobalt by abalones calculated at two days after feeding showed diverse values depending upon the species of seaweed, as follows: 47% through Laminaria japonica and Ulva pertusa, 31% through Undaria pinnatifida and 26 through Eisenia bicyclis, respectively. From the results, it was assumed that the accumulation of radioactive cobalt by mollusca is affected by the species of seaweeds as food. A very high concentration of ingested radioactive cobalt in the midgut gland was seen on the autoradiograph of abalone samples. (auth.)

  17. Concentration of radioactive cobalt by seaweeds in the food chain

    International Nuclear Information System (INIS)

    Nakahara, M.; Koyanagi, T.; Saiki, M.

    1975-01-01

    On the pathway of radioactive substances in marine environments, seaweeds play an important role because of their higher concentration factors for many radionuclides and because they constitute a link in the food chain. In the present work, uptake, distribution and excretion of radioactive cobalt were studied on several kinds of seaweeds by radioisotope tracer experiments under laboratory conditions and concentration factors were calculated. The concentration factors were also estimated from the results of stable cobalt determination by activation analysis or atomic absorption spectrometry on seaweeds and seawater, and compared with the results of tracer experiments. The seaweeds showed the species specificity for the concentration of stable and radioactive cobalt with diverse values of concentration factors and biological half-lives. The transfer of radioactive cobalt in the food chain from contaminated seaweeds to mollusca was examined by feeding abalones, Haliotis discus, with four kinds of seaweed labelled with 60 Co and observing retention. Absorption rate for radioactive cobalt by abalones calculated at two days after feeding showed diverse values depending upon the species of seaweed, as follows: 47% through Laminaria japonica and Ulva pertusa, 31% through Undaria pinnatifida and 26% through Eisenia bicyclis, respectively. From the results, it was assumed that the accumulation of radioactive cobalt by mollusca is affected by the species of seaweeds as food. A very high concentration of ingested radioactive cobalt in the midgut gland was seen on the autoradiograph of abalone samples. (author)

  18. Electron and Cooper-pair transport across a single magnetic molecule explored with a scanning tunneling microscope

    Science.gov (United States)

    Brand, J.; Gozdzik, S.; Néel, N.; Lado, J. L.; Fernández-Rossier, J.; Kröger, J.

    2018-05-01

    A scanning tunneling microscope is used to explore the evolution of electron and Cooper-pair transport across single Mn-phthalocyanine molecules adsorbed on Pb(111) from tunneling to contact ranges. Normal-metal as well as superconducting tips give rise to a gradual transition of the Bardeen-Cooper-Schrieffer energy gap in the tunneling range into a zero-energy resonance close to and at contact. Supporting transport calculations show that in the normal-metal-superconductor junctions this resonance reflects the merging of in-gap Yu-Shiba-Rusinov states as well as the onset of Andreev reflection. For the superconductor-superconductor contacts, the zero-energy resonance is rationalized in terms of a finite Josephson current that is carried by phase-dependent Andreev and Yu-Shiba-Rusinov levels.

  19. PENYERAPAN COBALT-60 DARI AIR OLEH TANAMAN KIAPU (Pistia stratiotes L.)

    OpenAIRE

    Lailatul Nuzzulul Safitri; Poppy Intan Tjahaja; Ida Bagus Made Suryatika

    2015-01-01

    Has conducted research Cobalt-60 radionuclide uptake by plants kiapu (Pistia stratiotes L.) found in many waters. The purpose of the study was to determine the value of the transfer factor on plant kiapu to Cobalt-60 in water. The study was conducted by growing plants on media kiapu gutter water in pots with the height 35 cm and diameter 11,5 cm containing Cobalt-60. The amount of Cobalt - 60 is absorbed and accumulated by the plant parts, i.e. roots and leaves, was observed by measuring the ...

  20. The structural evolution and diffusion during the chemical transformation from cobalt to cobalt phosphide nanoparticles

    KAUST Repository

    Ha, Don-Hyung

    2011-01-01

    We report the structural evolution and the diffusion processes which occur during the phase transformation of nanoparticles (NPs), ε-Co to Co 2P to CoP, from a reaction with tri-n-octylphosphine (TOP). Extended X-ray absorption fine structure (EXAFS) investigations were used to elucidate the changes in the local structure of cobalt atoms which occur as the chemical transformation progresses. The lack of long-range order, spread in interatomic distances, and overall increase in mean-square disorder compared with bulk structure reveal the decrease in the NP\\'s structural order compared with bulk structure, which contributes to their deviation from bulk-like behavior. Results from EXAFS show both the Co2P and CoP phases contain excess Co. Results from EXAFS, transmission electron microscopy, X-ray diffraction, and density functional theory calculations reveal that the inward diffusion of phosphorus is more favorable at the beginning of the transformation from ε-Co to Co2P by forming an amorphous Co-P shell, while retaining a crystalline cobalt core. When the major phase of the sample turns to Co 2P, the diffusion processes reverse and cobalt atom out-diffusion is favored, leaving a hollow void, characteristic of the nanoscale Kirkendall effect. For the transformation from Co2P to CoP theory predicts an outward diffusion of cobalt while the anion lattice remains intact. In real samples, however, the Co-rich nanoparticles continue Kirkendall hollowing. Knowledge about the transformation method and structural properties provides a means to tailor the synthesis and composition of the NPs to facilitate their use in applications. © 2011 The Royal Society of Chemistry.

  1. Development of hierarchically porous cobalt oxide for enhanced photo-oxidation of indoor pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, J. P., E-mail: chengjp@zju.edu.cn [Zhejiang University, State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering (China); Shereef, Anas; Gray, Kimberly A., E-mail: k-gray@northwestern.edu [Northwestern University, Center for Catalysis and Surface Science (United States); Wu, Jinsong [Northwestern University, Department of Materials Science and Engineering (United States)

    2015-03-15

    Porous cobalt oxide was successfully prepared by precipitation of cobalt hydroxide followed by low temperature thermal decomposition. The morphologies of the resultant oxides remained as the corresponding hydroxides, although the morphology of cobalt hydroxides was greatly influenced by the precursor salts. The cobalt oxides with average crystal size less than 20 nm were characterized by X-ray diffraction, scanning electron microscope, BET surface area, and XPS analysis. The photocatalytic activities of the various cobalt oxides morphologies were investigated by comparing the photo-degradation of acetaldehyde under simulated solar illumination. Relative to their low order structures and reference titania samples, the hierarchical nanostructures of cobalt oxide showed excellent abilities to rapidly degrade acetaldehyde, a model air pollutant. This was attributed to the unique nature of these hierarchical cobalt oxide nanoassemblies, which contained many catalytically active reaction sites and open pores.

  2. Study of ozone gas formed in the industrial radiation process with cobalt-60 and its impact on the environment

    International Nuclear Information System (INIS)

    Uzueli, Daniel Henrique

    2013-01-01

    The radiation processing is present in various products such as foods, medical disposable, electrical cables, gems, among others. This process aims to improve the properties, sterilize or sanitize irradiated products. In industrial irradiators facilities, electromagnetic radiation (gamma and X-rays) or electrons before they interact with the products in processing, there are a layer of air. To interact with this air layer, it causes radiolytic effects on the molecules present in the ambient atmosphere, and the main interaction are with the oxygen molecules that have their bonds broken, separating them into two highly reactive atoms that recombine with the other molecule of oxygen to form ozone gas. In this work it was studied the formation, decay and dispersion of ozone in industrial gamma irradiators facilities that use cobalt-60 as a source of radiation. The monitoring of ozone concentration was performed by optical absorption method in a commercial monitor. (author)

  3. Study of charge transfer processes in porphyrins- and phthalocyanins-based materials: from the liquid phase to the solid state

    International Nuclear Information System (INIS)

    Fournier, Thierry

    1994-01-01

    In order to efficiently conceive and build supramolecular materials for molecular electronics and optoelectronics, one need to have access to a large data base on the interactions between the elementary pieces of the material. Such a data base can be established only through the study of model Systems and model media. Oligomers of porphyrins and phthalocyanines constitute models of choice: due to the chemical versatility of the compounds, their physical and photophysical properties can be adjusted to produce a targeted function. The first part of this thesis is concerned with double- and triple-Decker mixed porphyrin and Phthalocyanines sandwich compounds of cerium. Then we study the photophysical properties of complexes formed by pairing in solution porphyrins and phthalocyanines bearing oppositely charged substituents. The charge transfer reactions and geminated recombinations are investigated by time-resolved absorption spectroscopy (from the femto- to millisecond time scales) for excited complexes either in solution, or confined in sol-gel matrices or in Langmuir-Blodgett films. The results obtained in the various media are compared and analysed by the Marcus theory. They allow to show that, for strongly coupled complexes, the solvent does not play any key role in the forward and backward electron transfer. We conclude this work by introducing a few targeted projects based on of the photophysical properties of these complexes, namely photodynamic therapy of cancers, nonlinear optics and the generation of photovoltage. (author) [fr

  4. Substoichiometric cobalt oxide monolayer on Ir(100)-(1 x 1)

    International Nuclear Information System (INIS)

    Gubo, M; Ebensperger, C; Meyer, W; Hammer, L; Heinz, K

    2009-01-01

    A substoichiometric monolayer of cobalt oxide has been prepared by deposition and oxidation of slightly less than one monolayer of cobalt on the unreconstructed surface of Ir(100). The ultrathin film was investigated by scanning tunnelling microscopy (STM) and quantitative low-energy electron diffraction (LEED). The cobalt species of the film reside in or near hollow positions of the substrate with, however, unoccupied sites (vacancies) in a 3 x 3 arrangement. In the so-formed 3 x 3 supercell the oxide's oxygen species are both threefold and fourfold coordinated to cobalt, forming pyramids with a triangular and square cobalt basis, respectively. These pyramids are the building blocks of the oxide. Due to the reduced coordination as compared to the sixfold one in the bulk of rock-salt-type CoO, the Co-O bond lengths are smaller than in the latter. For the threefold coordination they compare very well with the bond length in oxygen terminated CoO(111) films investigated recently. The substoichiometric 3 x 3 oxide monolayer phase transforms to a stoichiometric c(10 x 2)-periodic oxide monolayer under oxygen exposure, in which, however, cobalt and oxygen species are in (111) orientation and so form a CoO(111) layer.

  5. Assessing the potential of group 13 and 14 metal/metalloid phthalocyanines as hole transport layers in organic light emitting diodes

    Science.gov (United States)

    Plint, Trevor; Lessard, Benoît H.; Bender, Timothy P.

    2016-04-01

    In this study, we have assessed the potential application of group 13 and 14 metal and metalloid phthalocyanines ((X)n-MPcs) and their axially substituted derivatives as hole-transporting layers in organic light emitting diodes (OLEDs). OLEDs studied herein have the generic structure of glass/ITO/(N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB) or (X)n-MPc)(50 nm)/Alq3 (60 nm)/LiF (1 nm)/Al (80 nm), where X is an axial substituent group. OLEDs using chloro aluminum phthalocyanine (Cl-AlPc) showed good peak luminance values of 2620 ± 113 cd/m2 at 11 V. To our knowledge, Cl-AlPc has not previously been shown to work as a hole transport material (HTL) in OLEDs. Conversely, the di-chlorides of silicon, germanium, and tin phthalocyanine (Cl2-SiPc, Cl2-GePc, and Cl2-SnPc, respectively) showed poor performance compared to Cl-AlPc, having peak luminances of only 38 ± 4 cd/m2 (12 V), 23 ± 1 cd/m2 (8.5 V), and 59 ± 5 cd/m2 (13.5 V), respectively. However, by performing a simple axial substitution of the chloride groups of Cl2-SiPc with pentafluorophenoxy groups, the resulting bis(pentafluorophenoxy) silicon phthalocyanine (F10-SiPc) containing OLED had a peak luminance of 5141 ± 941 cd/m2 (10 V), a two order of magnitude increase over its chlorinated precursor. This material showed OLED characteristics approaching those of a baseline OLED based on the well-studied triarylamine NPB. Attempts to attach the pentafluorophenoxy axial group to both SnPc and GePc were hindered by synthetic difficulties and low thermal stability, respectively. In light of the performance improvements observed by simple axial substitution of SiPc in OLEDs, the use of axially substituted MPcs in organic electronic devices remains of continuing interest to us and potentially the field in general.

  6. Testing of cobalt-free alloys for valve applications using a special test loop

    International Nuclear Information System (INIS)

    Benhamou, C.

    1992-01-01

    Considering that use of cobalt alloys should be avoided as far as possible in PWR components, a programme aimed at establishing the performance of cobalt-free alloys has been performed for valve applications, where cobalt alloys are mainly used. Referring to past work, two types of cobalt-free alloys were selected: Ni-Cr-B-Si and Ni-Cr-Fe alloys. Cobalt-free valves' behaviour has been evaluated comparatively with cobalt valves by implementation of a programme in a special PWR test loop. At the issue of the loop test programme, which included endurance, thermal shock and erosion tests, cobalt-free alloys candidate to replace cobalt alloys are proposed in relation with valve type (globe valve and swing check valve). The following was established: (i) Colmonoy 4-26 (Ni-Cr-B-Si alloy) and Cenium Z20 (Ni-Cr-Fe alloy) deposited by plasma arc process were found suitable for use in 3inch swing check valves; (ii) for integral parts acting as guide rings, Nitronic 60 and Cesium Z20/698 were tested successfully; (iii) for small-bore components such as 2inch globe valves, no solution can yet be proposed; introduction of cobalt-free alloys is dependent on the development of automatic advanced arc surfacing techniques applied to small-bore components

  7. Neutron diffraction studies on cobalt substituted BiFeO3

    Science.gov (United States)

    Ray, J.; Biswal, A. K.; Acharya, S.; Babu, P. D.; Siruguri, V.; Vishwakarma, P. N.

    2013-02-01

    A dilute concentration of single phase Cobalt substituted Bismuth ferrite, BiFe1-XCoXO3; (x=0, 0.02) is prepared by sol-gel auto combustion method. Room temperature neutron diffraction patterns show no change in the crystal and magnetic structure upon cobalt doping. The calculation of magnetic moments shows 3.848 μB for Fe+ and 2.85 μB for Co3+. The cobalt is found to be in intermediate spin state.

  8. Characterization of Langmuir and Langmuir–Blodgett films of an octasubstituted zinc phthalocyanine

    International Nuclear Information System (INIS)

    Torrent-Burgués, J.; Cea, P.; Giner, I.; Guaus, E.

    2014-01-01

    In this work we report the fabrication of Langmuir and Langmuir–Blodgett (LB) films of a substituted ZnPc (octakis(oxyoctyl)phthalocyanine of zinc), and their characterization by means of several techniques. These characterization techniques include surface pressure (π-A) and surface potential (ΔV-A) isotherms as well as UV–vis Reflection spectroscopy and Brewster Angle Microscopy (BAM) for the films at the air–water interface together with UV–vis absorption and IR spectroscopies and Atomic Force Microscopy (AFM) for the LB films. The π-A and ΔV-A isotherms and BAM images indicate a phase transition at a surface pressure of ca. 9 mN/m and a multilayer formation at surface pressures around 19–20 mN/m; at a surface pressure around 27 mN/m a disordered collapse of the film occurs. In addition, AFM images of LB films at π = 10 mN/m and π = 20 mN/m show a monomolecular and a multilayered film, respectively. The comparison of the UV–vis spectrum of ZnPc in solution, the reflection spectra of the Langmuir films and UV–vis spectra of LB films reveals a significant reduction in the Q band intensity for the films, indicative of an organization of ZnPc in the Langmuir and LB films versus the random distribution in solution. The UV–vis Reflection spectra are also consistent with multilayer formation at surface pressures around 19–20 mN/m. The relative intensities of the IR spectrum bands change from the KBr pellet to the LB film which is also attributable to orientation effects in the film. Cyclic voltammetric experiments of LB films incorporating the ZnPc derivative show peaks that can be correlated with redox processes occurring in the phthalocyanine ring. A small but significant influence of the surface pressure and the number of deposited layers in the electrochemical behaviour is observed. The electrochemical response of cast films exhibits some differences with respect to that of LB films which have been attributed to their different molecular

  9. Characterization of Langmuir and Langmuir–Blodgett films of an octasubstituted zinc phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Torrent-Burgués, J. [Department of Chemical Engineering, Universitat Politècnica de Catalunya (UPC), C/Colom 1, 08222 Terrassa, Barcelona (Spain); Institut de Bioenginyeria de Catalunya (IBEC), 08028 Barcelona (Spain); Cea, P. [Departamento de Química Orgánica y Química Física, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Instituto de Nanociencia de Aragón (INA) y Laboratorio de Microscopias Avanzadas (LMA), Edificio i+d, Campus Rio Ebro, Universidad de Zaragoza, C/Mariano Esquillor, s/n, 50017 Zaragoza (Spain); Giner, I. [Departamento de Química Orgánica y Química Física, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Guaus, E. [Department of Chemical Engineering, Universitat Politècnica de Catalunya (UPC), C/Colom 1, 08222 Terrassa, Barcelona (Spain)

    2014-04-01

    In this work we report the fabrication of Langmuir and Langmuir–Blodgett (LB) films of a substituted ZnPc (octakis(oxyoctyl)phthalocyanine of zinc), and their characterization by means of several techniques. These characterization techniques include surface pressure (π-A) and surface potential (ΔV-A) isotherms as well as UV–vis Reflection spectroscopy and Brewster Angle Microscopy (BAM) for the films at the air–water interface together with UV–vis absorption and IR spectroscopies and Atomic Force Microscopy (AFM) for the LB films. The π-A and ΔV-A isotherms and BAM images indicate a phase transition at a surface pressure of ca. 9 mN/m and a multilayer formation at surface pressures around 19–20 mN/m; at a surface pressure around 27 mN/m a disordered collapse of the film occurs. In addition, AFM images of LB films at π = 10 mN/m and π = 20 mN/m show a monomolecular and a multilayered film, respectively. The comparison of the UV–vis spectrum of ZnPc in solution, the reflection spectra of the Langmuir films and UV–vis spectra of LB films reveals a significant reduction in the Q band intensity for the films, indicative of an organization of ZnPc in the Langmuir and LB films versus the random distribution in solution. The UV–vis Reflection spectra are also consistent with multilayer formation at surface pressures around 19–20 mN/m. The relative intensities of the IR spectrum bands change from the KBr pellet to the LB film which is also attributable to orientation effects in the film. Cyclic voltammetric experiments of LB films incorporating the ZnPc derivative show peaks that can be correlated with redox processes occurring in the phthalocyanine ring. A small but significant influence of the surface pressure and the number of deposited layers in the electrochemical behaviour is observed. The electrochemical response of cast films exhibits some differences with respect to that of LB films which have been attributed to their different molecular

  10. Microscopic study of carrier transport in the organic semiconductor zinc-phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Duarte, Joao Piroto [ESTeSC, Polytechnic Institute of Coimbra, 3040-854 Coimbra (Portugal); CEMDRX, Physics Department, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal); Alberto, Helena Vieira; Vilao, Rui Cesar; Gil, Joao M.; Weidinger, Alois; Campos, Nuno Ayres de [CEMDRX, Physics Department, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal)

    2010-04-15

    Nominally undoped zinc-phthalocyanine (ZnPc) was investigated using Muon Spin Rotation ({mu}SR) to probe microscopic carrier transport properties. The study focused on the relaxation of the positive muon's polarisation produced by spin-flip scattering with charge carriers. An energy of 71(8) meV was found for the temperature activation of carrier jumps, a value that does not match the activation energies known in ZnPc from electrical measurements, and that was attributed to a fast transport component in this material. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. Characterization of manganese tetraarylthiosubstituted phthalocyanines self assembled monolayers

    International Nuclear Information System (INIS)

    Matemadombo, Fungisai; Durmus, Mahmut; Togo, Chamunorwa; Limson, Janice; Nyokong, Tebello

    2009-01-01

    Manganese tetraarylthiosubstituted phthalocyanines (complexes 1-5) have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. SAM characteristics reported in this work are: ion barrier factor (∼1); interfacial capacitance (303-539 μF cm -2 ) and surface coverage (1.06 x 10 -10 -2.80 x 10 -10 mol cm -2 ). Atomic force microscopy was employed in characterizing a SAM. SAMs of complexes 1-5 were employed to detect L-cysteine (with limit of detection ranging from 2.83 x 10 -7 to 3.14 x 10 -7 M at potentials of 0.68-0.75 V vs. Ag|AgCl) and nitrite (limit of detection ranging from 1.78 x 10 -7 to 3.02 x 10 -7 M at potentials of 0.69-0.76 V vs. Ag|AgCl).

  12. Construction of an apparatus for nuclear orientation measurements at low temperatures. Application to neodymium-cobalt alloy; Realisation d'un appareil pour des mesures d'orientation nucleaire a basse temperature. Application a l'alliage neodyme-cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Mayer, E [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1965-10-01

    We describe experiments along which has been studied the anisotropy of {gamma} radiations emitted by oriented nuclei. We have used the great hyperfine fields acting on nuclei in ferromagnetic metals so as to produce alignment at low temperature. By irradiation we obtained a few cobalt 60 nuclei in our samples which were then cooled down to 0,01 K. The anisotropic rate of the 1,33 MeV {gamma} radiation was measured in function of the sample temperature, using as thermometer the anisotropy of {gamma} radiation emitted by cobalt 60 nuclei in a cobalt single crystal. Cobalt 60 was lined up in a cobalt nickel alloy (40% Ni). The hyperfine field at the cobalt was measured compared to the effective field in metallic cobalt: Heff(Co Ni)/Heff(Co metal) = 0.71 {+-} 0.12. These results are in good agreement with specific heat measurements made previously. Cobalt 60 has been polarised in a neodymium-cobalt alloy (NdCo{sub 5}). The field at the cobalt in NdCo{sub 5} has been measured compared to the field in metallic cobalt and taking the non-saturation into account we found 165000 oersteds < Heff(NdCo{sub 5}) < 220000 oersteds. (author) [French] Nous decrivons des experiences au cours desquelles nous avons etudie l'anisotropie de rayonnements {gamma} emis par des noyaux orientes. Nous avons utilise les grands champs hyperfins agissant sur las noyaux dans les metaux ferromagnetiques pour produire l'alignement a basse temperature. Par irradiation nous avons obtenu quelques noyaux de cobalt 60 dans nos echantillons qui furent ensuite refroidis a 0,01 K. Le degre d'anisotropie du rayonnement {gamma} de 1,33 MeV fut mesure en fonction de la temperature de l'echantillon en utilisant l'anisotropie du rayonnement {gamma} de noyaux de cobalt 60 dans un monocristal de cobalt metallique utilise comme thermometre. Le cobalt 60 a ete aligne dans un alliage de cobalt-nickel (40% Ni). Le champ hyperfin au niveau du cobalt a ete mesure par rapport au champ effectif dans le cobalt metallique

  13. Bioactivity and mechanical behaviour of cobalt oxide-doped ...

    Indian Academy of Sciences (India)

    tive base glass and cobalt oxide-doped glass were prepared by the addition of cobalt oxide (0, ... and 1 N HCl at 37. ◦. C as compared with the ... SO2−. 4. Cl. −. Simulated body fluid. 142.0. 5.0. 1.5. 2.5. 4.2. 1.0. 0.5. 147.8. Human blood plasma ...

  14. Cobalt production in RAPS-1

    International Nuclear Information System (INIS)

    Krishnan, P.D.; Purandare, H.D.

    1978-01-01

    At present in RAPS-1 radioisotope Co 60 is produced by irradiating Co 59 in the adjusters which perform the function of regulation of reactivity, power and xenon override. But the manrem expenditure of the crew handling the charge and discharge of the adjusters is going to be prohibitively high. It is therefore proposed to irradiate Co 59 in the fuel channel positions. The physics optimisation study for such irradiation is presented. The burnup penalty and loss of power are estimated to produce the required quantity of Co 60 after optimising the number of cobalt pencils in a bundle and the positions of the cobalt producing channels in the reactor core. (author)

  15. Nickel and cobalt bimetallic hydroxide catalysts for urea electro-oxidation

    International Nuclear Information System (INIS)

    Yan Wei; Wang Dan; Botte, Gerardine G.

    2012-01-01

    Nickel–Cobalt bimetallic hydroxide electrocatalysts, synthesized through a one-step electrodeposition method, were evaluated for the oxidation of urea in alkaline conditions with the intention of reducing the oxidation overpotential for this reaction. The Nickel–Cobalt bimetallic hydroxide catalysts were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Raman spectroscopy, cyclic voltammetry (CV), and polarization techniques. A significant reduction in the overpotential (150 mV) of the reaction was observed with the Nickel–Cobalt bimetallic hydroxide electrode (ca. 43% Co content) when compared to a nickel hydroxide electrode. The decrease of the urea oxidation potential on the Nickel–Cobalt bimetallic hydroxide electrodes reveals great potential for future applications of urea electro-oxidation, including wastewater remediation, hydrogen production, sensors, and fuel cells.

  16. Effect of diblock copolymer properties on the photophysical properties of dendrimer silicon phthalocyanine nanoconjugates

    Science.gov (United States)

    Chen, Kuizhi; Pan, Sujuan; Zhuang, Xuemei; Lv, Hafei; Que, Shoulin; Xie, Shusen; Yang, Hongqin; Peng, Yiru

    2016-07-01

    1-2 generation poly(benzyl aryl ether) dendrimer silicon phthalocyanines with axially disubstituted cyano terminal functionalities (G n -DSiPc(CN)4 n , (G n = n-generation dendrimer, n = 1-2)) were synthesized. Their structures were characterized by elemental analysis, IR, 1H NMR, and ESI-MS. Polymeric nanoparticles (G n -DSiPc(CN)4 n /m) were formed through encapsulating G n -DSiPc(CN)4 n into three monomethoxyl poly(ethylene glycol)-poly(ɛ-caprolactone) diblock copolymers (MPEG-PCL) with different hydrophilic/hydrophobic proportion, respectively. The effect of dendritic generation and the hydrophilic/hydrophobic proportion of diblock copolymers on the UV/Vis and fluorescence spectra of G n -DSiPc(CN)4 n and G n -DSiPc(CN)4 n /m were studied. The photophysical properties of polymeric nanoparticles exhibited dendritic generation and hydrophilic/hydrophobic proportion dependence. The fluorescence intensities and lifetimes of G n -DSiPc(CN)4 n /m were lower than the corresponding free dendrimer phthalocyanines. G n -DSiPc(CN)4 n encapsulated into MPEG-PCL with hydrophilic/hydrophobic molecular weight ratio 2000:4000 exhibited excellent photophysical property. The mean diameter of MPEG2000-PCL2000 micelles was about 70 nm, which decreased when loaded with G n -DSiPc(CN)4 n .

  17. The use of chloroaluminium phthalocyanine tetrasulfonate (AlPcTS) for time-delayed fluorescence imaging

    International Nuclear Information System (INIS)

    Gundy, Sarah; Putten, Wil van der; Shearer, Andy; Buckton, Daniel; Ryder, Alan G; Ball, Michael

    2004-01-01

    Phthalocyanine derivatives are currently under investigation for use in photodynamic therapy, which is a promising cancer treatment. These materials, which display preferential uptake in cancerous cells, also exhibit high fluorescence yields and can be used for tumour detection. Problems with steady-state fluorescence techniques such as excitation scatter and background autofluorescence can be eliminated by using time-resolved imaging techniques without the need for filters. A tissue phantom was assembled to test a constructed time-gated imaging system by drilling 36 wells of varying diameter and depth (10 mm to 1 mm) into a block of polymethyl methacrylate (PMMA). The system was used to record images of chloroaluminium phthalocyanine tetrasulfonate (AlPcTS) at differing concentrations in neat aqueous solvent and cell suspensions within the wells. A mixture of Intralipid (to mimic tissue scatter) and Evan's blue (to mimic tissue absorption) of depths ranging from 1 mm to 10 mm was placed on top of the PMMA block. The ensuing images were analysed using signal-to-noise ratios and contrast-detail curves. The results indicate that the time-gated imaging system can prevent background excitation scatter from distorting the fluorescence signal from a longer-lived photosensitizer without the need for filters

  18. Inhibition of the radiolytic hydrogen production in the nuclear waste of 'bitumen coated' type: study of the interaction between hydrogen and cobalt hydroxo-sulphide

    International Nuclear Information System (INIS)

    Pichon, C.

    2006-11-01

    In the nuclear field in France, the bitumen is mainly used for the conditioning of the radioactive muds generated by the fuel reprocessing. However, the self-irradiation of the bitumen induces a production of hydrogen which generates safety problems. The comparison of various storage sites showed that the presence of cobalt hydroxo sulphide limited such a production. Consequently, this compound was regarded as an 'inhibitor of radiolytic hydrogen production'. However, the origin of this phenomenon was not clearly identified. In order to propose an explanation to this inhibition phenomenon, model organic molecules were used to represent the components of the bitumen. Irradiations were carried out by protons to simulate the alpha radiolysis. The organic molecules irradiations by a proton beam showed that cobalt hydroxo sulphide CoSOH, does not act as a hydrogenation catalyst of unsaturated hydrocarbons, nor as a radicals scavenger, but consists of a trap of hydrogen. Experiments of hydrogen trapping at ambient temperature were carried out according to two techniques: gravimetry and manometry. The solid was characterized before and after interaction with hydrogen (infrared and Raman spectroscopies, X-ray diffraction). The initial solid was composed of amorphous cobalt hydroxo sulphide and a minor phase of cobalt hydroxide. The gravimetry and manometry experiments showed that the maximum of hydrogen trapping capacity is equal to 0.59 ± 0.18 mole of hydrogen per mole of cobalt. After interaction with hydrogen, the Co(OH) 2 phase disappeared and a new solid phase appeared corresponding to Co 9 S 8 . These observations, as well as the analysis of the gas phase, made it possible to conclude with the following reaction (1): 9 CoSOH + 11/2 H 2 = Co 9 S 8 + 9 H 2 O + H 2 S (1). Gravimetry experiments at temperatures between 50 and 210 C revealed the desorption of water but not of hydrogen sulphide. The absence of hydrogen sulphide in gaseous phase and the Co(OH) 2 phase

  19. Hydrogen evolution catalyzed by cobalt diimine-dioxime complexes.

    Science.gov (United States)

    Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent

    2015-05-19

    Mimicking photosynthesis and producing solar fuels is an appealing way to store the huge amount of renewable energy from the sun in a durable and sustainable way. Hydrogen production through water splitting has been set as a first-ranking target for artificial photosynthesis. Pursuing that goal requires the development of efficient and stable catalytic systems, only based on earth abundant elements, for the reduction of protons from water to molecular hydrogen. Cobalt complexes based on glyoxime ligands, called cobaloximes, emerged 10 years ago as a first generation of such catalysts. They are now widely utilized for the construction of photocatalytic systems for hydrogen evolution. In this Account, we describe our contribution to the development of a second generation of catalysts, cobalt diimine-dioxime complexes. While displaying similar catalytic activities as cobaloximes, these catalysts prove more stable against hydrolysis under strongly acidic conditions thanks to the tetradentate nature of the diimine-dioxime ligand. Importantly, H2 evolution proceeds via proton-coupled electron transfer steps involving the oxime bridge as a protonation site, reproducing the mechanism at play in the active sites of hydrogenase enzymes. This feature allows H2 to be evolved at modest overpotentials, that is, close to the thermodynamic equilibrium over a wide range of acid-base conditions in nonaqueous solutions. Derivatization of the diimine-dioxime ligand at the hydrocarbon chain linking the two imine functions enables the covalent grafting of the complex onto electrode surfaces in a more convenient manner than for the parent bis-bidentate cobaloximes. Accordingly, we attached diimine-dioxime cobalt catalysts onto carbon nanotubes and demonstrated the catalytic activity of the resulting molecular-based electrode for hydrogen evolution from aqueous acetate buffer. The stability of immobilized catalysts was found to be orders of magnitude higher than that of catalysts in the

  20. Sintered cobalt-rare earth intermetallic product

    International Nuclear Information System (INIS)

    Benz, M.C.

    1975-01-01

    A process is described for preparing novel sintered cobalt--rare earth intermetallic products which can be magnetized to form permanent magnets having stable improved magnetic properties. A cobalt--rare earth metal alloy is formed having a composition which at sintering temperature falls outside the composition covered by the single Co 5 R intermetallic phase on the rare earth richer side. The alloy contains a major amount of the Co 5 R intermetallic phase and a second solid CoR phase which is richer in rare earth metal content than the Co 5 R phase. The specific cobalt and rare earth metal content of the alloy is substantially the same as that desired in the sintered product. The alloy, in particulate form, is pressed into compacts and sintered to the desired density. The sintered product is comprised of a major amount of the Co 5 R solid intermetallic phase and up to about 35 percent of the product of the second solid CoR intermetallic phase which is richer in rare earth metal content than the Co 5 R phase