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Sample records for copper phthalocyanine derivative

  1. Effect of annealing on bulk heterojunction organic solar cells based on copper phthalocyanine and perylene derivative

    KAUST Repository

    Kim, Inho

    2012-02-01

    We investigated the effects of annealing on device performances of bulk heterojunction organic solar cells based on copper phthalocyanine (CuPc) and N,N′-3,4,9,10-perylenetetracarboxylic diimide (PTCDI-C6). Blended films of CuPc and PTCDI-C6 with annealing at elevated temperature were characterized by measuring optical absorption, photoluminescence, and X-ray diffraction. Enhanced molecular ordering and increments in domain sizes of donor and acceptor for the blended films were observed, and their influences on device performances were discussed. Annealing led to substantial improvements in photocurrent owing to enhanced molecular ordering and formation of percolation pathways. © 2011 Elsevier B.V. All rights reserved.

  2. EPR study on copper- and vanadium complexes with substituted phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Shklyaev, A.A.; Selyutin, G.E.; Shakot' ko, N.I.; Mikhalenko, S.A. (Nauchno-Issledovatel' skij Inst. Organicheskikh Poluproduktov i Krasitelej, Moscow (USSR))

    1984-06-01

    The structure of binuclear associates of substituted vanadyl- and copper-phthalocyanines is investigated. The EPR study has shown that metal phthalocyanine protonation in acid media (CH/sub 2/Cl/sub 2/, Py, H/sub 2/SO/sub 4/, toluence, etc) is accompanied by destabilization of bonds of the central ion with a polycyclic ligand. Substituted copper- and vanadyl phthalocyanines form dimerized associates where M-M interatmic distance varies in a wide range from 4.1 to 12 A.

  3. Dielectric response of branched copper phthalocyanine

    Science.gov (United States)

    Hamam, Khalil J.; Al-Amar, Mohammad M.; Mezei, Gellert; Guda, Ramakrishna; Burns, Clement A.

    2017-09-01

    The dielectric constant of pressed pellets and thin films of branched copper phthalocyanine (CuPc) was investigated as a function of frequency from 0.1 kHz to 1 MHz and temperature from 20 °C to 100 °C. Surface morphology was studied using a scanning electron microscope. The high-frequency values of the dielectric constant of pellets and thin films are ~3.5 and ~5.8, respectively. The response was only weakly dependent on frequency and temperature. The branched structure of the CuPc molecules helped to cancel out the effects of low-frequency polarization mechanisms. A planar delocalized charge system with two-dimensional localization was found using time-resolved photoluminescence measurements.

  4. Effect of pyridine on infrared absorption spectra of copper phthalocyanine.

    Science.gov (United States)

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

    2008-02-01

    Infrared absorption spectra of copper phthalocyanine in KBr pellet and pyridine solution in 400-1625 and 2900-3200 cm(-1)regions are reported. In the IR spectra of solid sample, presence of weak bands, which are forbidden according to the selection rules of D4h point group, is explained on the basis of distortion in the copper phthalocyanine molecule caused by the crystal packing effects. Observation of a new band at 1511 cm(-1) and change in intensity of some other bands in pyridine are interpreted on the basis of coordination of the solvent molecule with the central copper ion.

  5. Interfacial Engineering of Perovskite Solar Cells by Employing a Hydrophobic Copper Phthalocyanine Derivative as Hole-Transporting Material with Improved Performance and Stability.

    Science.gov (United States)

    Jiang, Xiaoqing; Yu, Ze; Lai, Jianbo; Zhang, Yuchen; Hu, Maowei; Lei, Ning; Wang, Dongping; Yang, Xichuan; Sun, Licheng

    2017-04-22

    In high-performance perovskite solar cells (PSCs), hole-transporting materials (HTMs) play an important role in extracting and transporting the photo-generated holes from the perovskite absorber to the cathode, thus reducing unwanted recombination losses and enhancing the photovoltaic performance. Herein, solution-processable tetra-4-(bis(4-tert-butylphenyl)amino)phenoxy-substituted copper phthalocyanine (CuPc-OTPAtBu) was synthesized and explored as a HTM in PSCs. The optical, electrochemical, and thermal properties were fully characterized for this organic metal complex. The photovoltaic performance of PSCs employing this CuPc derivative as a HTM was further investigated, in combination with a mixed-ion perovskite as a light absorber and a low-cost vacuum-free carbon as cathode. The optimized devices [doped with 6 % (w/w) tetrafluoro-tetracyano-quinodimethane (F4TCNQ)] showed a decent power conversion efficiency of 15.0 %, with an open-circuit voltage of 1.01 V, a short-circuit current density of 21.9 mA cm-2 , and a fill factor of 0.68. Notably, the PSC devices studied also exhibited excellent long-term durability under ambient condition for 720 h, mainly owing to the introduction of the hydrophobic HTM interlayer, which prevents moisture penetration into the perovskite film. The present work emphasizes that solution-processable CuPc holds a great promise as a class of alternative HTMs that can be further explored for efficient and stable PSCs in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Transport properties of copper phthalocyanine based organic electronic divices

    OpenAIRE

    Opitz, Andreas

    2010-01-01

    Transport properties of copper phthalocyanine based organic electronic divices / W. Brütting ... - In: Cooperative phenomena in solids with electronic correlations / Ed. by: U. Eckern ... - Les Ulis : EDP Sciences, 2010. - S. 117-134. - (The European physical journal : special topics ; 180)

  7. 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.

  8. Modelling copper-phthalocyanine/cobalt-phthalocyanine chains: towards magnetic quantum metamaterials.

    Science.gov (United States)

    Wu, Wei

    2014-07-23

    The magnetic properties of a theoretically designed molecular chain structure CuCoPc2, in which copper-phthalocyanine (CuPc) and cobalt-phthalocyanine (CoPc) alternate, have been investigated across a range of chain structures. The computed exchange interaction for the α-phase CuCoPc2 is ∼ 5 K (ferromagnetic), in strong contrast to the anti-ferromagnetic interaction recently observed in CuPc and CoPc. The computed exchange interactions are strongly dependent on the stacking angle but weakly on the sliding angle, and peak at 20 K (ferromagnetic). These ferromagnetic interactions are expected to arise from direct exchange with the strong suppression of super-exchange interaction. These first-principles calculations show that π-conjugated molecules, such as phthalocyanine, could be used as building blocks for the design of magnetic materials. This therefore extends the concept of quantum metamaterials further into magnetism. The resulting new magnetic materials could find applications in the studies such as organic spintronics.

  9. Wisely Designed Phthalocyanine Derivative for Convenient Molecular Fabrication on a Substrate.

    Science.gov (United States)

    Harada, Wataru; Hirahara, Mana; Togashi, Takanari; Ishizaki, Manabu; Kurihara, Masato; Haga, Masa-Aki; Kanaizuka, Katsuhiko

    2018-01-30

    An axial-substituted silicon phthalocyanine derivative, SiPc(OR) 2 (R = C 4 H 9 ), that is soluble in organic solvent is conveniently synthesized. This silicon phthalocyanine derivative reacts with a hydroxyl group on a substrate and then with another phthalocyanine derivative under mild conditions. The accumulation number of the phthalocyanine molecules on the substrates is easily controlled by the immersion time. On the basis of AFM (atomic force microscopy) images, the surface of the phthalocyanine-modified glass substrate has uneven structures on the nanometer scale. ITO electrodes modified with the composition of the phthalocyanine derivative and PCBM show stable cathodic photocurrent generation upon light irradiation.

  10. 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.

  11. 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.

  12. Resonance Raman spectra of. cap alpha. -copper phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Bovill, A.J.; McConnell, A.A.; Nimmo, J.A.; Smith, W.E.

    1986-02-13

    Raman spectra of ..cap alpha..-copper phthalocyanine (..cap alpha..-CuPc) were recorded at room temperature and at 10 K with excitation wavelengths between 457 and 714 nm. Resonance enhancement was greatest for modes for which the largest displacements were on either the inner five-membered ring of the isoindole groups or the inner macrocycle and consequently assignment of the bands to modes of the entire molecule was possible by comparison with nickel octaethylporphyrin. Four out of five bands resonant in the Q band region and preresonant near the B band absorption region are totally symmetric modes. B band preresonance occurs more strongly with high-frequency modes. At low temperatures, multimode interactions are reduced and profiles were obtained which can be compared with solution profiles of porphyrins. Both Q/sub x/ and Q/sub y/ 0-0 scattering can be identified and a helper mode is evident. A term enhancement predominates, with B/sub 1g/ and B/sub 2g/ modes enhanced because of a Jahn-Teller distortion of the excited state. The resonance studies, together with electronic absorption spectra and published theoretical studies, confirm that the Q band in ..cap alpha..-CuPc is largely due to an allowed ..pi..-..pi..* transition associated mainly with the macrocycle and inner five-membered rings of the isoindole groups. 25 references, 5 figures, 2 tables.

  13. 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

  14. 40 CFR 721.9674 - Sulfonated-copper phthalocyanine salt of a triarylmethane dye (generic).

    Science.gov (United States)

    2010-07-01

    ... of a triarylmethane dye (generic). 721.9674 Section 721.9674 Protection of Environment ENVIRONMENTAL... triarylmethane dye (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as sulfonated-copper phthalocyanine salt of a triarylmethane dye...

  15. 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

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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...

  1. 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.

  2. Hybrid Solar Cell with TiO2 Film: BBOT Polymer and Copper Phthalocyanine as Sensitizer

    Directory of Open Access Journals (Sweden)

    Saptadip Saha

    2016-01-01

    Full Text Available An organic-inorganic hybrid solar cell was fabricated using Titanium dioxide (TiO2: 2,5-bis(5-tert-butyl-2-benzoxazolyl thiophene (BBOT film and Copper Phthalocyanine (CuPc as a sensitizer. BBOT was used in photodetector in other reported research works, but as per best of our knowledge, it was not implemented in solar cells till date. The blend of TiO2: BBOT blend was used to fabricate the film on ITO-coated glass and further a thin layer of CuPc was coated on the film. This was acted as photoanode and another ITO coated glass with a platinum coating was used as a counter electrode (cathode. An optimal blend of acetonitrile (solvent (50-100%, 1,3-dimethylimidazolium iodide (10-25%, iodine (2.5-10% and lithium iodide, pyridine derivative and thiocyanate was used as electrolytes in the hybrid solar cell. The different structural, optical and electrical characteristics were measured. The Hybrid solar cell showed a maximum conversion efficiency of 6.51%.

  3. Non-covalent interaction between Cu-phthalocyanine and methanato borondifluoride derivatives in two different medium

    Science.gov (United States)

    Pal, Chiranjit; Chaudhuri, Tandrima; Chattopdhyay, Subrata; Banerjee, Manas

    2017-04-01

    This study sort out chemical physics of non-covalent interaction between Copper phthalocyanine (CuPC) with Methanato borondifluoride derivatives (MBDF) in chloroform and ethanol. Formation of isosbestic points indicated stable ground state equilibrium between CuPC and MBDF, association ability were more pronounced in less polar chloroform. Interesting overall parallel orientation of MBDF over CuPC in gas phase geometries indicated that fluorine centre of MBDF lying just above the Cu-centre of CuPC. Thus strong interaction between Cu(II)- and F- centre could not be overruled and was also established by NBO calculation. TDDFT along with FMO features and heat of reaction values clearly designated the existence of π-π interaction and effect of solvent polarity on that interaction.

  4. 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.

  5. 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.

  6. 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.

  7. Graphene wrapped Copper Phthalocyanine nanotube: Enhanced photocatalytic activity for industrial waste water treatment

    Science.gov (United States)

    Mukherjee, Moumita; Ghorai, Uttam Kumar; Samanta, Madhupriya; Santra, Angshuman; Das, Gour P.; Chattopadhyay, Kalyan K.

    2017-10-01

    To improve the photocatalytic performance of metal phthalocyanine based catalyst, Copper Phthalocyanine (CuPc) functionalized reduced graphene oxide (RGO) nanocomposite has been synthesized through a simple chemical approach. The obtained product was characterized by X-ray diffraction technique (XRD), Fourier transform infrared (FTIR) spectroscopy, Ultraviolet-visible spectroscopy (UV-vis) and High resolution transmission electron microscopy (HRTEM). The photocatalytic activity of the RGO/CuPc nanocomposite was performed by the degradation of Rhodamine B (RhB) under visible light irradiation. The photocatalytic studies revealed that the RGO/CuPc nanocomposite exhibits much stronger catalytic behavior than the pristine CuPc nanotube. A plausible mechanism for the photodegradation of Rhodamine B (RhB) was suggested. The RGO wrapped CuPc nanotube composite materials offer great potential as active photocatalysts for degradation of organic pollutions in industrial waste water.

  8. Preparation, magnetic and electromagnetic properties of organic magnetic prepolymer containing copper phthalocyanine ring

    Energy Technology Data Exchange (ETDEWEB)

    Wei Junji; Xu Mingzhen; Zhang Jiandong; Zhao Rui [Research Branch of Functional Materials, Institute of Microelectronic and Solid State Electronic, High-Temperature Resistant Polymers and Composites Key Laboratory of Sichuan Province, University of Electronic Science and Technology of China, Chengdu 610054 (China); Liu Xiaobo, E-mail: liuxb@uestc.edu.cn [Research Branch of Functional Materials, Institute of Microelectronic and Solid State Electronic, High-Temperature Resistant Polymers and Composites Key Laboratory of Sichuan Province, University of Electronic Science and Technology of China, Chengdu 610054 (China)

    2012-09-15

    A novel kind of organic magnetic prepolymer containing copper phthalocyanine ring was prepared via the polymerization of ferrocenyl organic metal magnetic resin (FOMR) with cuprous chloride. The process of prepolymerization was monitored by Fourier transform infrared spectroscopy and ultraviolet-visible spectrophotometry. Magnetic behavior of the samples was studied by a vibrating sample magnetometer. The experimental results indicated that the organic magnetic prepolymer containing copper phthalocyanine ring showed ferromagnetic property and the magnetism of the samples can be finely tuned by controlling the condition of the reaction. The maximum saturation magnetization of the organic magnetic prepolymer containing copper phthalocyanine ring increased from 3.69 to 8.38 emu/g by increasing the reaction time. Meanwhile, the remnant magnetization increased from 1.06 to 2.36 emu/g. Measurement of electromagnetic parameters of the samples showed that complex permittivity and complex permeability also increased with increase in the reaction time. Among these, the imaginary part of permittivity increased from 0.22 to 0.38 at the frequency of 10.0 GHz. - Highlights: Black-Right-Pointing-Pointer A novel organic magnetic prepolymer was successfully prepared. Black-Right-Pointing-Pointer The saturation magnetization of samples increased with increase in the reaction time. Black-Right-Pointing-Pointer The complex permittivity of samples increased with increase in the reaction time. Black-Right-Pointing-Pointer The complex permeability of samples increased with increase in the reaction time. Black-Right-Pointing-Pointer The material is believed to be useful in electronic and biomedical fields.

  9. Copper phthalocyanine labelled magnetic microcapsules: preparation, and binding properties in vitro and in vivo for mutagens having planar molecular structure.

    Science.gov (United States)

    Povey, A C; O'Neill, I K

    1990-11-01

    Copper phthalocyanine tetrasulphonic acid (CPTS) functions were introduced into magnetic semi-permeable polyethyleneimine (PEI) microcapsules in order to create a recoverable scavenging system for trapping and biomonitoring, within the gastrointestinal cavity, of mutagens having a planar molecular structure. Stable ionic CPTS and covalent (thionylated CPTS, TCPTS) adducts to the microcapsule PEI were produced and shown to trap benzo[a]pyrene (B[a]P) in vitro in relation to the porphyrin/B[a]P ratio employed. 3-hydroxy B[a]P and B[a]P 3,6-dione from a crude B[a]P metabolite mixture, and a set of planar mutagens from crude opium/morphine pyrolysate mixtures could also be recovered in 7-86% yields after shaking with modified microcapsules followed by methanol/ammonia (50:1) desorption. Tetraols derived from B[a]P 7,8-diol-9,10 epoxide could also be recovered. Modified microcapsules were recovered magnetically from faeces of rats treated with [14C]B[a]P, and 45-51% of trapped radioactivity could be directly desorbed for HPLC assay compared with 30% for unmodified microscapsules. The relative extent of trapping by unmodified or CPTS- or TCPTS-modified microcapsules was different for various substrates, and it appears that the copper phthalocyanine tetrasulphonic acid moiety competes with another unidentified absorption/desorption structure in the microcapsules. These results show that selective and reversible trapping of carcinogens/mutagens having planar molecular structure can be achieved within the gastrointestinal tract.

  10. 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.

  11. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Sotthewes, K.; Heimbuch, R.; Zandvliet, H. J. W. [Physics of Interfaces and Nanomaterials, MESA" + Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE Enschede (Netherlands)

    2015-10-07

    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 bridge” configuration, where two benzopyrrole groups (lobes) are connected to a Au-induced nanowire, whereas the other two lobes are connected to the adjacent nanowire. Three types of lobe configurations are found: a bright lobe, a dim lobe, and a fuzzy lobe. The dim and fuzzy lobes exhibit a well-defined switching behavior between two discrete levels, while the bright lobe shows a broad oscillation band. The observed dynamic behavior is induced by electrons that are injected into the LUMO+1 orbital of the CuPc molecule. By precisely adjusting the tip-molecule distance, the switching frequency of the lobes can be tuned accurately.

  14. Tuning carrier mobility without spin transport degrading in copper-phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, S. W.; Wang, P.; Chen, B. B.; Zhou, Y. [National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University, 22 Hankou Road, Nanjing 210093 (China); Ding, H. F., E-mail: hfding@nju.edu.cn, E-mail: dwu@nju.edu.cn; Wu, D., E-mail: hfding@nju.edu.cn, E-mail: dwu@nju.edu.cn [National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University, 22 Hankou Road, Nanjing 210093 (China); Collaborative Innovation Center of Advanced Microstructures, Nanjing University, 22 Hankou Road, Nanjing 210093 (China)

    2015-07-27

    We demonstrate more than one order of magnitude of carrier mobility tuning for the copper-phthalocyanine (CuPc) without spin transport degrading in organic spin valve devices. Depending on the preparation conditions, organic spin valves with the CuPc film mobility of 5.78 × 10{sup −3} and 1.11 × 10{sup −4} cm{sup 2}/V s are obtained for polycrystalline and amorphous CuPc, respectively. Strikingly, the spin diffusion lengths are almost the same regardless of their mobilities that are ∼50 times different, which is in sharp contrast with previous prediction. These findings directly support that the spin relaxation in CuPc is dominated by the spin-orbit coupling.

  15. Marine sponge skeleton photosensitized by copper phthalocyanine: A catalyst for Rhodamine B degradation

    Directory of Open Access Journals (Sweden)

    Norman Małgorzata

    2016-01-01

    Full Text Available We present a combined approach to photo-assisted degradation processes, in which a catalyst, H2O2 and UV irradiation are used together to enhance the oxidation of Rhodamine B (RB. The heterogeneous photocatalyst was made by the process of adsorption of copper phthalocyanine tetrasulfonic acid (CuPC onto purified spongin-based Hippospongia communis marine sponge skeleton (HcS. The product obtained, CuPC-HcS, was investigated by a variety of spectroscopic (carbon-13 nuclear magnetic resonance 13C NMR, Fourier transform infrared spectroscopy FTIR, energy-dispersive X-ray spectroscopy EDS and microscopic techniques (scanning electron microscopy SEM, fluorescent and optical microscopy, as well as thermal analysis. The study confirms the stable combination of the adsorbent and adsorbate. For a 10 mg/L RB solution, the percentage degradation reached 95% using CuPC-HcS as a heterocatalyst. The mechanism of RB removal involves adsorption and photodegradation simultaneously.

  16. Energy level alignment at the methylammonium lead iodide/copper phthalocyanine interface

    Directory of Open Access Journals (Sweden)

    Shi Chen

    2014-08-01

    Full Text Available The energy level alignment at the CH3NH3PbI3/copper phthalocyanine (CuPc interface is investigated by X-ray photoelectron spectroscopy (XPS and ultraviolet photoelectron spectroscopy (UPS. XPS reveal a 0.3 eV downward band bending in the CuPc film. UPS validate this finding and further reveal negligible interfacial dipole formation – verifying the viability of vacuum level alignment. The highest occupied molecular orbital of CuPc is found to be closer to the Fermi level than the valance band maximum of CH3NH3PbI3, facilitating hole transfer from CH3NH3PbI3 to CuPc. However, subsequent hole extraction from CuPc may be impeded by the downward band bending in the CuPc layer.

  17. Low voltage copper phthalocyanine organic thin film transistors with a polymer layer as the gate insulator

    Energy Technology Data Exchange (ETDEWEB)

    Liu Xueqiang; Bi Weihong [College of Information Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zhang Tong, E-mail: liuxq003@sina.com [State Key Laboratory of Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, Changchun 130012 (China)

    2010-12-15

    Low voltage organic thin film transistors (OTFTs) were created using polymethyl-methacrylate-co g-lyciclyl-methacrylate (PMMA-GMA) as the gate dielectric. The OTFTs performed acceptably at supply voltages of about 10 V. From a densely packed copolymer brush, a leakage current as low as 2 x 10{sup -8} A/cm{sup 2} was obtained. From the measured capacitance-insulator frequency characteristics, a dielectric constant in the range 3.9-5.0 was obtained. By controlling the thickness of the gate dielectric, the threshold voltage was reduced from -3.5 to -2.0 V. The copper phthalocyanine (CuPc) based organic thin film transistor could be operated at low voltage and 1.2 x 10{sup -3} cm{sup 2}/(V{center_dot}s) mobility. (semiconductor devices)

  18. Quantum dot with zinc and copper substituted phthalocyanines.1. Energy transfer in solution and in-situ light absorption in Langmuir monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Bursa, B.; Biadasz, A.; Kędzierski, K.; Wróbel, D., E-mail: danuta.wrobel@put.poznan.pl

    2014-01-15

    The paper deals with spectroscopic characterization of a core/shell CdSe/ZnS quantum dot and phthalocyanines substituted with butyl and octakis(octyloxy) peripheral groups: zinc (II) and copper (II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine, zinc (II) and copper (II) 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine in chloroform as well as in a form of 2D Langmuir monolayers. The isotherms of surface pressure as a function of the mean area per molecule are examined and the in-situ absorption study of the Langmuir monolayer is also studied. The influence of the substituents attached to the phthalocyanine macroring and of the presence of the quantum dot on dye spectroscopic properties (absorption and fluorescence) is shown. Molecular arrangement of the molecular skeleton of the phthalocyanines on water substrate is evaluated. A comparison of the in-situ absorption of the phthalocyanine monolayers and electronic absorption spectra of the dyes in chloroform supports the existence of dye aggregates in the monolayer. Interaction between the phthalocyanine dyes and CdSe/ZnS quantum dot observed as dot fluorescence quenching is also discussed. -- Highlights: • Energy transfer from quantum dot to dyes. • Electronic spectra of quantum dot and phthalocyanines in chloroform and in-situ light absorption of Langmuir monolayers. • The system perfectly fits to the sunlight and is suitable for light conversion.

  19. Shelf-life time test of p- and n-channel organic thin film transistors using copper phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Nenon, Sebastien [Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), UPR CNRS 3118, Aix Marseille Universite, Campus Luminy, Case 913, 13288 Marseille Cedex 09 (France); Kanehira, Daiki; Yoshimoto, Noriyuki [Department of Materials Science and Engineering, Iwate University, 4-3-5 Ueda, Morioka 020-8551 (Japan); Fages, Frederic [Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), UPR CNRS 3118, Aix Marseille Universite, Campus Luminy, Case 913, 13288 Marseille Cedex 09 (France); Videlot-Ackermann, Christine, E-mail: videlot@cinam.univ-mrs.f [Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), UPR CNRS 3118, Aix Marseille Universite, Campus Luminy, Case 913, 13288 Marseille Cedex 09 (France)

    2010-07-30

    P- and n-type channel thin film transistors (OTFTs) were fabricated by using hexadecahydrogen copper phthalocyanine (H{sub 16}CuPc) and hexadecafluoro copper phthalocyanine (F{sub 16}CuPc) molecules, respectively. Top-contact and bottom-contact source-drain configurations were used for both semiconductors. Furthermore, the temperature and film thickness dependences on the mobility values were measured in the saturation regime of source-drain current. Unipolar mobilities in such single-layer OTFTs were correlated to thin film morphology by X-ray diffraction analysis and atomic force microscopy measurements. Shelf-life time tests of p-type and n-type OTFTs are detailed as OTFT configuration and substrate temperature dependence over a time period of 100 days.

  20. Spectroscopic investigation of different concentrations of the vapour deposited copper phthalocyanine as a "guest" in polyimide matrix.

    Science.gov (United States)

    Georgiev, Anton; Yordanov, Dancho; Dimov, Dean; Assa, Jacob; Spassova, Erinche; Danev, Gencho

    2015-04-05

    Nanocomposite layers 250 nm copper phthalocyanine/polyimide prepared by simultaneous vapour deposition of three different sources were studied. Different concentrations of copper phthalocyanine as a "guest" in polyimide matrix as a function of conditions of the preparation have been determined by FTIR (Fourier Transform Infrared) and UV-VIS (Ultraviolet-Visible) spectroscopies. The aim was to estimate the possibility of the spectroscopic methods for quantitative determination of the "guest" and compare with the quality of the polyimide thin films in relation to the "guest" concentration. The band at 1334 cm(-1) has been used for quantitative estimation of "guest" in polyimide matrix. The concentrations of the copper phthalocyanine less than 20% require curve fitting techniques with Fourier self deconvolution. The relationship between "guest" concentrations and degree of imidization, as well as the electronic UV-VIS spectra are discussed in relation to the composition, imidization degree and the two crystallographic modification of the embedded chromophore. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Phthalocyanine derivatives possessing 2-(morpholin-4-yl)ethoxy groups as potential agents for photodynamic therapy.

    Science.gov (United States)

    Kucinska, Malgorzata; Skupin-Mrugalska, Paulina; Szczolko, Wojciech; Sobotta, Lukasz; Sciepura, Mateusz; Tykarska, Ewa; Wierzchowski, Marcin; Teubert, Anna; Fedoruk-Wyszomirska, Agnieszka; Wyszko, Eliza; Gdaniec, Maria; Kaczmarek, Mariusz; Goslinski, Tomasz; Mielcarek, Jadwiga; Murias, Marek

    2015-03-12

    Three 2-(morpholin-4-yl)ethoxy substituted phthalocyanines were synthesized and characterized. Phthalocyanine derivatives revealed moderate to high quantum yields of singlet oxygen production depending on the solvent applied (e.g., in DMF ranging from 0.25 to 0.53). Their photosensitizing potential for photodynamic therapy was investigated in an in vitro model using cancer cell lines. Biological test results were found particularly encouraging for the zinc(II) phthalocyanine derivative possessing two 2-(morpholin-4-yl)ethoxy substituents in nonperipheral positions. Cells irradiated for 20 min at 2 mW/cm(2) revealed the lowest IC50 value at 0.25 μM for prostate cell line (PC3), whereas 1.47 μM was observed for human malignant melanoma (A375) cells. The cytotoxic activity in nonirradiated cells of novel phthalocyanine was found to be very low. Moreover, the cellular uptake, localization, cell cycle, apoptosis through an ELISA assay, and immunochemistry method were investigated in LNCaP cells. Our results showed that the tested photosensitizer possesses very interesting biological activity, depending on experimental conditions.

  2. Effect of film morphology on oxygen and water interaction with copper phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Nicholas [California State University, Long Beach (CSULB); Gredig, Thomas [California State University, Long Beach (CSULB); Ivanov, Ilia N [ORNL

    2016-01-01

    Copper phthalocyanine (CuPc) films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25 C, 150 C, and 250 C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. Mass loading by O2 was enhanced by a factor of 5 in films deposited at 250 C, possibly due to the ~200 C CuPc transition which allows higher O2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales > 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O2/H2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold, which is consistent with findings of other studies.

  3. Thermal Annealing Effect on Poly(3-hexylthiophene): Fullerene:Copper-Phthalocyanine Ternary Photoactive Layer

    Science.gov (United States)

    Derouiche, H.; Mohamed, A. B.

    2013-01-01

    We have fabricated poly(3-hexylthiophene) (P3HT)/copper phthalocyanine (CuPc)/fullerene (C60) ternary blend films. This photoactive layer is sandwiched between an indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT/PSS) photoanode and a bathocuproine (BCP)/aluminium photocathode. The thin films have been characterized by atomic force microscope (AFM) and ultraviolet/visible spectroscopy in order to study the influence of P3HT doping on the morphological and optical properties of the photoactive layer. We have also compared the I-V characteristics of three different organic solar cells: ITO/PEDOT:PSS/CuPc0.5:C600.5/BCP/Al and ITO/PEDOT:PSS/P3HT0.3:CuPc0.3:C600.4/BCP/Al with and without annealing. Both structures show good photovoltaic behaviour. Indeed, the incorporation of P3HT into CuPc:C60 thin film improves all the photovoltaic characteristics. We have also seen that thermal annealing significantly improves the optical absorption ability and stabilizes the organic solar cells making it more robust to chemical degradation. PMID:23766722

  4. Change spectroscopic studies and optimization electrical properties of PVP/PEO doped copper phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Ragab, H.M., E-mail: yara20092009@yahoo.com [Department of Physics, Faculty of Science, Al-Azhar University, Girls Branch, Cairo 11754 (Egypt); Basic Science Department, Faculty of Preparatory Year, Hail University (Saudi Arabia); Ahmad, F.; Radwan, Sh.N. [Department of Physics, Faculty of Science, Al-Azhar University, Girls Branch, Cairo 11754 (Egypt)

    2016-12-01

    Composite films of polyvinyl pyrrolidone and Polyethylene oxide (PVP/PEO) blend doped with 1, 4 and 12 wt% of copper Phthalocyanines (CuPc) were prepared by casting method. The samples were studied using different techniques. The X-ray (XRD) revealed average crystallite size and X-ray intensity decrease at 1 CuPc %; this implies to an increase on the degree of amorphousity, then increase at CuPc >1%. The change in both the intensity and position of some absorption peaks of the blend with CuPc content were observed in Fourier transform infrared (FTIR) spectroscopy suggest the complexation of polymer blend. The UV–Vis spectroscopy revealed that the optical band gap decreases as well as band tail width increases with increasing CuPc concentration. It may be reflect the role of CuPc in modifying the electronic structure of the polymeric matrix. The charge carrier concentration is responsible for conductivity improvement in electrolytes rather than the mobility.

  5. High-mobility solution-processed copper phthalocyanine-based organic field-effect transistors

    Energy Technology Data Exchange (ETDEWEB)

    Chaure, Nandu B [Department of Physics, University of Pune, Ganeshkhind, Pune 411007 (India); Cammidge, Andrew N; Chambrier, Isabelle; Cook, Michael J [School of Chemistry, University of East Anglia, Norwich, NR4 7TJ (United Kingdom); Cain, Markys G; Murphy, Craig E [National Physical Laboratory, Hampton Road, Teddington, Middlesex TW11 0LW (United Kingdom); Pal, Chandana; Ray, Asim K, E-mail: Asim.Ray@brunel.ac.uk [The Wolfson Centre for Materials Processing, Brunel University, Uxbridge, Middlesex UB8 3PH (United Kingdom)

    2011-03-15

    Solution-processed films of 1,4,8,11,15,18,22,25-octakis(hexyl) copper phthalocyanine (CuPc{sub 6}) were utilized as an active semiconducting layer in the fabrication of organic field-effect transistors (OFETs) in the bottom-gate configurations using chemical vapour deposited silicon dioxide (SiO{sub 2}) as gate dielectrics. The surface treatment of the gate dielectric with a self-assembled monolayer of octadecyltrichlorosilane (OTS) resulted in values of 4x10{sup -2} cm{sup 2} V{sup -1} s{sup -1} and 10{sup 6} for saturation mobility and on/off current ratio, respectively. This improvement was accompanied by a shift in the threshold voltage from 3 V for untreated devices to -2 V for OTS treated devices. The trap density at the interface between the gate dielectric and semiconductor decreased by about one order of magnitude after the surface treatment. The transistors with the OTS treated gate dielectrics were more stable over a 30-day period in air than untreated ones.

  6. Position-dependent performance of copper phthalocyanine based field-effect transistors by gold nanoparticles modification.

    Science.gov (United States)

    Luo, Xiao; Li, Yao; Lv, Wenli; Zhao, Feiyu; Sun, Lei; Peng, Yingquan; Wen, Zhanwei; Zhong, Junkang; Zhang, Jianping

    2015-01-21

    A facile fabrication and characteristics of copper phthalocyanine (CuPc)-based organic field-effect transistor (OFET) using the gold nanoparticles (Au NPs) modification is reported, thereby achieving highly improved performance. The effect of Au NPs located at three different positions, that is, at the SiO2/CuPc interface (device B), embedding in the middle of CuPc layer (device C), and on the top of CuPc layer (device D), is investigated, and the results show that device D has the best performance. Compared with the device without Au NPs (reference device A), device D displays an improvement of field-effect mobility (μ(sat)) from 1.65 × 10(-3) to 5.51 × 10(-3) cm(2) V(-1) s(-1), and threshold voltage decreases from -23.24 to -16.12 V. Therefore, a strategy for the performance improvement of the CuPc-based OFET with large field-effect mobility and saturation drain current is developed, on the basis of the concept of nanoscale Au modification. The model of an additional electron transport channel formation by FET operation at the Au NPs/CuPc interface is therefore proposed to explain the observed performance improvement. Optimum CuPc thickness is confirmed to be about 50 nm in the present study. The device-to-device uniformity and time stability are discussed for future application.

  7. High-mobility solution-processed copper phthalocyanine-based organic field-effect transistors

    Directory of Open Access Journals (Sweden)

    Nandu B Chaure, Andrew N Cammidge, Isabelle Chambrier, Michael J Cook, Markys G Cain, Craig E Murphy, Chandana Pal and Asim K Ray

    2011-01-01

    Full Text Available Solution-processed films of 1,4,8,11,15,18,22,25-octakis(hexyl copper phthalocyanine (CuPc6 were utilized as an active semiconducting layer in the fabrication of organic field-effect transistors (OFETs in the bottom-gate configurations using chemical vapour deposited silicon dioxide (SiO2 as gate dielectrics. The surface treatment of the gate dielectric with a self-assembled monolayer of octadecyltrichlorosilane (OTS resulted in values of 4×10−2 cm2 V−1 s−1 and 106 for saturation mobility and on/off current ratio, respectively. This improvement was accompanied by a shift in the threshold voltage from 3 V for untreated devices to -2 V for OTS treated devices. The trap density at the interface between the gate dielectric and semiconductor decreased by about one order of magnitude after the surface treatment. The transistors with the OTS treated gate dielectrics were more stable over a 30-day period in air than untreated ones.

  8. Thermal Annealing Effect on Poly(3-hexylthiophene: Fullerene:Copper-Phthalocyanine Ternary Photoactive Layer

    Directory of Open Access Journals (Sweden)

    H. Derouiche

    2013-01-01

    Full Text Available We have fabricated poly(3-hexylthiophene (P3HT/copper phthalocyanine (CuPc/fullerene (C60 ternary blend films. This photoactive layer is sandwiched between an indium tin oxide (ITO/poly(3,4-ethylenedioxythiophene:poly(styrene sulfonate (PEDOT/PSS photoanode and a bathocuproine (BCP/aluminium photocathode. The thin films have been characterized by atomic force microscope (AFM and ultraviolet/visible spectroscopy in order to study the influence of P3HT doping on the morphological and optical properties of the photoactive layer. We have also compared the characteristics of three different organic solar cells: ITO/PEDOT:PSS/CuPc0.5:C600.5/BCP/Al and ITO/PEDOT:PSS/P3HT0.3:CuPc0.3:C600.4/BCP/Al with and without annealing. Both structures show good photovoltaic behaviour. Indeed, the incorporation of P3HT into CuPc:C60 thin film improves all the photovoltaic characteristics. We have also seen that thermal annealing significantly improves the optical absorption ability and stabilizes the organic solar cells making it more robust to chemical degradation.

  9. Controllable preparation of copper phthalocyanine single crystal nano column and its chlorine gas sensing properties

    Directory of Open Access Journals (Sweden)

    Jianhong Zhao

    2016-09-01

    Full Text Available The unsubstituted copper phthalocyanine (CuPc single crystal nano columns were fabricated for the first time as chlorine (Cl2 gas sensors in this paper. The nano columns of CuPc have been prepared on different substrates via template-free physical vapor deposition (PVD approach. The growth mechanism of CuPc nano column on quartz was explored and the same condition used on other substrates including glass, sapphire (C-plane, M-plane, R-plane, Si and SiO2/Si came to a same conclusion, which confirmed that the aligned growth of CuPc nano column is not substrate-dependent. And then the CuPc nano column with special morphology was integrated as in-situ sensor device which exhibits high sensitivity and selectivity towards Cl2 at room temperature with a minimum detection limit as low as 0.08 ppm. The response of sensor was found to increase linearly (26∼659% with the increase for Cl2 within concentration range (0.08∼4.0ppm. These results clearly demonstrate the great potential of the nano column growth and device integration approach for sensor device.

  10. Humidity and illumination organic semiconductor copper phthalocyanine sensor for environmental monitoring.

    Science.gov (United States)

    Karimov, K S; Qazi, I; Khan, T A; Draper, P H; Khalid, F A; Mahroof-Tahir, M

    2008-06-01

    In this investigation properties of organic semiconductor copper phthalocyanine (CuPc) capacitive humidity and illumination sensors were studied. Organic thin film was deposited by vacuum evaporation on a glass substrate with silver surface-type electrodes to form the Ag/CuPc/Ag sensor. The capacitance of the samples was evaluated at room temperature in the relative humidity range of 35-92%. It was observed that capacitance of the Ag/CuPc/Ag sensor increases with increase in humidity. The ratio of the relative capacitance to relative humidity was about 200. It is assumed that in general the capacitive response of the sensor is associated with polarization due to absorption of water molecules and transfer of charges (electrons and holes). It was observed that under filament lamp illumination of up to 1,000 lx the capacitance of the Ag/CuPc/Ag photo capacitive detectors increased continuously by 20% as compared to dark condition. It is assumed that photo capacitive response of the sensor is associated with polarization due to transfer of photo-generated electrons and holes. An equivalent circuit of the Ag/CuPc/Ag capacitive humidity and illumination sensor was developed. Humidity and illumination dependent capacitance properties of this sensor make it attractive for use in humidity and illumination multi-meters. The sensor may be used in instruments for environmental monitoring of humidity and illumination.

  11. Change spectroscopic studies and optimization electrical properties of PVP/PEO doped copper phthalocyanines

    Science.gov (United States)

    Ragab, H. M.; Ahmad, F.; Radwan, Sh. N.

    2016-12-01

    Composite films of polyvinyl pyrrolidone and Polyethylene oxide (PVP/PEO) blend doped with 1, 4 and 12 wt% of copper Phthalocyanines (CuPc) were prepared by casting method. The samples were studied using different techniques. The X-ray (XRD) revealed average crystallite size and X-ray intensity decrease at 1 CuPc %; this implies to an increase on the degree of amorphousity, then increase at CuPc >1%. The change in both the intensity and position of some absorption peaks of the blend with CuPc content were observed in Fourier transform infrared (FTIR) spectroscopy suggest the complexation of polymer blend. The UV-Vis spectroscopy revealed that the optical band gap decreases as well as band tail width increases with increasing CuPc concentration. It may be reflect the role of CuPc in modifying the electronic structure of the polymeric matrix. The charge carrier concentration is responsible for conductivity improvement in electrolytes rather than the mobility.

  12. Phase modification of copper phthalocyanine semiconductor by converting powder to thin film

    Science.gov (United States)

    Ai, Xiaowei; Lin, Jiaxin; Chang, Yufang; Zhou, Lianqun; Zhang, Xianmin; Qin, Gaowu

    2018-01-01

    Thin films of copper phthalocyanine (CuPc) semiconductor were deposited on glass substrates by a thermal evaporation system using the CuPc powder in a high vacuum. The crystal structures of both the films and the powder were measured by the X-ray diffraction spectroscopy technique. It is observed that CuPc films only show one peak at 6.84°, indicating a high texture of α phase along (200) orientation. In comparison, CuPc powder shows a series of peaks, which are confirmed from the mixture of both α and β phases. The effects of substrate anneal temperature on the film structure, grain size and optical absorption property of CuPc films were also investigated. All the films are of α phase and the full width of half maximum for (200) diffraction peak becomes narrow with increasing the substrate temperatures. The average grain size calculated by the Scherrer's formula is 33.63 nm for the film without anneal, which is increased up to 58.29 nm for the film annealed at 200 °C. Scanning electron microscope was further measured to prove the growth of crystalline grain and to characterize the morphologies of CuPc films. Ultraviolet-visible absorption spectra were employed to study the structure effect on the optical properties of both CuPc films and powder. Fourier Transform infrared spectroscopy was used to identify the crystalline nature of both CuPc powder and film.

  13. 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.

  14. Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines

    Science.gov (United States)

    Demirbaş, Ümit; Akçay, Hakkı Türker; Koca, Atıf; Kantekin, Halit

    2017-08-01

    In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine (4) and its zinc(II) (5), copper(II) (6) and cobalt(II) (7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1H-NMR, UV-vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. CoIIPc went [CoIIPc-2]/[CoIPc-2]1-, [CoIPc-2]1-/[CoIPc-3]2-, [CoIPc-3]2-/[CoIPc-4]3- and [CoIIPc-2]/[CoIIPc-2]1+ reduction and oxidation processes respectively. Differently ZnIIPc only showed four ligand-based reductions and two ligand based oxidation processes.

  15. Chemical sensing of copper phthalocyanine sol-gel glass through organic vapors

    Energy Technology Data Exchange (ETDEWEB)

    Ridhi, R.; Gawri, Isha; Abbas, Saeed J.; Saini, G. S. S.; Tripathi, S. K. [Department of Physics, Center of Advanced Study in Physics, Panjab University, Chandigarh-160 014 (INDIA) Fax: +91-172-2783336; Tel.:+91-172-2544362 (India)

    2015-05-15

    The sensitivities of metallophthalocyanine to vapor phase electron donors has gained significance in many areas and disciplines due to their sensing properties and ease of operation. In the present study the interaction mechanism of organic vapors in Copper Phthalocyanine (CuPc) sol-gel glass has been studied. The interaction mechanism is affected by many factors like morphology, electrical or optical properties of film. CuPc sol-gel glass has been synthesized using chemical route sol-gel method. Its structural characterization was conducted using XRD and the amorphous nature of the silicate glass was observed with characteristic α polymorph phase of CuPc at around 6.64° with 13.30Å interplanar spacing. The size of the particle as determined using Debbye Scherre’s formula comes out around 15.5 nm. The presence of α phase of CuPc was confirmed using FTIR with the appearance of crystal parameter marker band at 787 cm-1. Apart from this A2u and Eu symmetry bands of CuPc have also been observed. The UV absorption spectrum of CuPc exhibits absorption peaks owing to π→ π* and n→ π* transitions. A blue shift in the prepared CuPc glass has been observed as compared to the dopant CuPc salt indicating increase of band gap. A split in B (Soret) band and Q band appears as observed with the help of Lorentzian fitting. CuPc sol gel glass has been exposed with chemical vapors of Methanol, Benzene and Bromine individually and the electrical measurements have been carried out. These measurements show the variation in conductivity and the interaction mechanism has been analyzed.

  16. Performance enhancement of organic thin-film transistors with improved copper phthalocyanine crystallization by inserting ultrathin pentacene buffer

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Wei; Yu, Junsheng, E-mail: jsyu@uestc.edu.cn; Yu, Xinge; Li, Yu; Zeng, Hongjuan

    2012-08-31

    Organic thin-film transistors (OTFTs) with high crystallization copper phthalocyanine (CuPc) active layers were fabricated by inserting an ultrathin pentacene buffer layer between the dielectric and CuPc layers. Comparing with the OTFTs without a pentacene buffer layer, the charge carrier mobility of the OTFT with a buffer layer presented a much higher value of {approx} 0.20 cm{sup 2}/V s. Meanwhile, by investigating the morphology of the CuPc active layer with an ultrathin pentacene buffer layer through scanning electron microscopy and X-ray diffraction, the high crystallization of the CuPc film with a larger grain size and less grain boundaries can be observed. As a result, the resistance of the conducting channel was decreased, leading to a performance improvement of the OTFTs. - Highlights: Black-Right-Pointing-Pointer Pentacene was inserted between dielectric and copper phthalocyanine (CuPc) films. Black-Right-Pointing-Pointer High performance devices were obtained. Black-Right-Pointing-Pointer Crystallization enhancement of CuPc was observed by scanning electron microscopy.

  17. Single crystal growth in spin-coated films of polymorphic phthalocyanine derivative under solvent vapor

    Energy Technology Data Exchange (ETDEWEB)

    Higashi, T.; Ohmori, M.; Ramananarivo, M. F.; Fujii, A., E-mail: afujii@opal.eei.eng.osaka-u.ac.jp; Ozaki, M. [Division of Electrical, Electronic, and Information Engineering, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan)

    2015-12-01

    The effects of solvent vapor on spin-coated films of a polymorphic phthalocyanine derivative were investigated. Growth of single crystal films via redissolving organic films under solvent vapor was revealed by in situ microscopic observations of the films. X-ray diffraction measurement of the films after exposing to solvent vapor revealed the phase transition of polymorphs under solvent vapor. The direction of crystal growth was clarified by measuring the crystal orientation in a grown monodomain film. The mechanism of crystal growth based on redissolving organic films under solvent vapor was discussed in terms of the different solubilities of the polymorphs.

  18. Photodynamic antimicrobial chemotherapy using zinc phthalocyanine derivatives in treatment of bacterial skin infection

    Science.gov (United States)

    Chen, Zhuo; Zhang, Yaxin; Wang, Dong; Li, Linsen; Zhou, Shanyong; Huang, Joy H.; Chen, Jincan; Hu, Ping; Huang, Mingdong

    2016-01-01

    Photodynamic antimicrobial chemotherapy (PACT) is an effective method for killing bacterial cells in view of the increasing problem of multiantibiotic resistance. We herein reported the PACT effect on bacteria involved in skin infections using a zinc phthalocyanine derivative, pentalysine β-carbonylphthalocyanine zinc (ZnPc-Lys). Compared with its anionic ZnPc counterpart, ZnPc-Lys showed an enhanced antibacterial efficacy in vitro and in an animal model of localized infection. Meanwhile, ZnPc-Lys was observed to significantly reduce the wound skin blood flow during wound healing, indicating an anti-inflammation activity. This study provides new insight on the mechanisms of PACT in bacterial skin infection.

  19. Near-IR absorbing phthalocyanine derivatives as materials for organic solar cells

    Science.gov (United States)

    Mayukh, Mayank

    2011-12-01

    Phthalocyanines (Pcs) are highly conjugated synthetic porphyrin analogs that exhibit high extinction coefficients and hole mobilities, and strong pi-pi interactions. We have developed a general method for the synthesis of peripherally functionalized Pc chromophores using 'click' chemistry, wherein an alkynyl substituted Pc is reacted with an azide, providing an elegant route to the creation of a library of numerous Pcs. We have also developed a simple route to the synthesis of tri- and tetravalent metal Pc derivatives such as titanyl phthalocyanine (TiO Pc) involving solvent-free conditions. Solvent-free conditions are environmentally friendly and industrially economical, and in the present context effectively eliminate the formation of non-metallated phthalocyanine (H 2Pc), a side product often seen in other routes that interferes with their purification. We have also prepared and characterized thin-films of some of these Pcs, TiOPcs in particular, wherein we have developed an easy route to various TiO Pc polymorphs exhibiting different near-IR sensitivities via spin-coating whose optical properties are reminiscent of Phase-I and Phase-II polymorphs of the unmodified TiOPc. Phase-II is particularly interesting as it is photoelectrically active in the near-IR region with a Q-band maximum at ca. 890 nm. We have also fabricated and characterized organic solar cells in both planar heterojunction (PHJ) and bulk heterojunction (BHJ) architectures based on one of these materials, which exhibited good near-IR photoactivity with the absorption spectrum extending up to 1 micrometer in the near-IR. The incident and absorbed photon to current efficiency (IPCE and APCE) spectra showed contributions from the TiOPc in the near-IR region with local maxima around 680 nm and 920 nm, corresponding to the Frenkel and the charge-transfer (CT) bands of the TiOPc, respectively.

  20. Synthesis, characterization and femtosecond nonlinear saturable absorption behavior of copper phthalocyanine nanocrystals doped-PMMA polymer thin films

    Science.gov (United States)

    Zongo, S.; Dhlamini, M. S.; Neethling, P. H.; Yao, A.; Maaza, M.; Sahraoui, B.

    2015-12-01

    In this work, we report the femtosecond nonlinear saturable absorption response of synthesized copper phthalocyanine nanocrystals (CPc-NCs)-doped PMMA polymer thin films. The samples were initially characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), UV-Vis and scanning electron microscopy (SEM) techniques. The crystalline phase and morphological analysis revealed nanocrystals of monoclinic structure with an average crystallite size between 31.38 nm and 42.5 nm. The femtosecond Z-scan study at 800 nm central wavelength indicated a saturable absorption behavior of which the mechanism is closely related to the surface plasmon resonance (SPR) of the particles. This nonlinear effect could potentially make the CPc-NCs useful in nonlinear optical devices.

  1. Structural approach to improve the response characteristics of copper phthalocyanine thin film-based NO{sub 2} gas sensor

    Energy Technology Data Exchange (ETDEWEB)

    Nagasawa, Tadashi; Murakami, Kenji; Watanabe, Kenzo

    1998-07-01

    In order to realize a high-sensitivity, low temperature operable NO{sub 2} gas sensor, thin films of {alpha}-form copper phthalocyanine ({alpha}-CuPc) have been deposited by vacuum sublimation. In this study, the authors have attempted to improve the gas-sensing characteristics through a modification of the film microstructure. Firstly, the gas sensitivity is remarkably increased by an insertion of higher-sensitive layer (vanadyl Pc film) between the {alpha}-CuPc film and the glass substrate in the low gas concentration range. Secondly, a reversibility in cycles of gas doping and dedoping is improved by film deposition on hydrofluoric acid-treated substrate. It is found from atomic force microscope analyses that this phenomenon may be closely related to a modification of the film microstructure.

  2. Axially substituted silicon(IV) phthalocyanine and its quaternized derivative as photosensitizers towards tumor cells and bacterial pathogens.

    Science.gov (United States)

    Ömeroğlu, İpek; Kaya, Esra Nur; Göksel, Meltem; Kussovski, Vesselin; Mantareva, Vanya; Durmuş, Mahmut

    2017-10-15

    Axially di-(alpha,alpha-diphenyl-4-pyridylmethoxy) silicon(IV) phthalocyanine (3) and its quaternized derivative (3Q) were synthesized and tested as photosensitizers against tumor and bacterial cells. These new phthalocyanines were characterized by elemental analysis, and different spectroscopic methods such as FT-IR, UV-Vis, MALDI-TOF and (1)H NMR. The photophysical properties such as absorption and fluorescence, and the photochemical properties such as singlet oxygen generation of both phthalocyanines were investigated in solutions. The obtained values were compared to the values obtained with unsubstituted silicon(IV) phthalocyanine dichloride (SiPcCl2). The addition of two di-(alpha,alpha-diphenyl-4-pyridylmethanol) groups as axial ligands showed an improvement of the photophysical and photochemical properties and an increasement of the singlet oxygen quantum yield (ΦΔ) from 0.15 to 0.33 was determined. The photodynamic efficacy of synthesized photosensitizers (3 and 3Q) were evaluated with promising photocytotoxicity (17% cell survival for 3 and 28% for 3Q) against the cervical cancer cell line (HeLa). The photodynamic inactivation of pathogenic bacterial strains Streptococcus mutans, Staphylococcus aureus, and Pseudomonas aeruginosa suggested a high susceptibility with quaternized derivative (3Q). The both Gram-positive bacterial strains were fully photoinactivated with 11μM 3Q and mild light dose 50J.cm(-2). In case of P. aeruginosa the effect was negligible for concentrations up to 22μM 3Q and light dose 100J.cm(-2). The results suggested that the novel axially substituted silicon(IV) phthalocyanines have promising characteristic as photosensitizer towards tumor cells. The quaternized derivative 3Q has high potential for photoinactivation of pathogenic bacterial species. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. 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.

  4. Micro-Raman spectroscopy and chemometrical analysis for the distinction of copper phthalocyanine polymorphs in paint layers.

    Science.gov (United States)

    Defeyt, C; Van Pevenage, J; Moens, L; Strivay, D; Vandenabeele, P

    2013-11-01

    In art analysis, copper phthalocyanine (CuPc) is often identified as an important pigment (PB15) in 20th century artworks. Raman spectroscopy is a very valuable technique for the detection of this pigment in paint systems. However, PB15 is used in different polymorphic forms and identification of the polymorph could retrieve information on the production process of the pigment at the moment. Raman spectroscopy, being a molecular spectroscopic method of analysis, is able to discriminate between polymorphs of crystals. However, in the case of PB15, spectral interpretation is not straightforward, and Raman data treatment requires some improvements concerning the PB15 polymorphic discrimination in paints. Here, Raman spectroscopy is combined with chemometrical analysis in order to develop a procedure allowing us to identify the PB15 crystalline structure in painted layers and in artworks. The results obtained by Linear Discriminant Analysis (LDA), using intensity ratios as variables, demonstrate the ability of this procedure to predict the crystalline structure of a PB15 pigment in unknown paint samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. An efficient copper phthalocyanine additive of perovskite precursor for improving the photovoltaic performance of planar perovskite solar cells

    Science.gov (United States)

    Wu, Shufang; Liu, Qingwei; Zheng, Ya; Li, Renjie; Peng, Tianyou

    2017-08-01

    Solution processable planar heterojunction perovskite solar cell has drawn much attention as a promising low-cost photovoltaic device, and much effort has been made to improve its power conversion efficiency by choosing appropriate additives for the perovskite precursor solution. Different to those additives reported, a soluble and thermal stable tert-butyl substituted copper phthalocyanine (CuPc(tBu)4) as additive is first introduced into the perovskite precursor solution of a planar perovskite solar cell that is fabricated via the one-step solution process. It is found that the pristine device without CuPc(tBu)4 additive exhibits a power conversion efficiency of 15.3%, while an extremely low concentration (4.4 × 10-3 mM) of CuPc(tBu)4 in the precursor solution leads to the corresponding device achieving an enhanced power conversion efficiency of 17.3%. CuPc(tBu)4 as an additive can improve the quality of perovskite layer with higher crystallinity and surface coverage, then resulting in enhanced light absorption and reduced charge recombination, and thus the better power conversion efficiency. The finding presented here provides a new choice for improving the quality of perovskite layer and the photovoltaic performance of the planar heterojunction perovskite solar cells.

  6. Orienting the Microstructure Evolution of Copper Phthalocyanine as an Anode Interlayer in Inverted Polymer Solar Cells for High Performance.

    Science.gov (United States)

    Li, Zhiqi; Liu, Chunyu; Zhang, Xinyuan; Li, Shujun; Zhang, Xulin; Guo, Jiaxin; Guo, Wenbin; Zhang, Liu; Ruan, Shengping

    2017-09-20

    Recent advances in the interfacial modification of inverted-type polymer solar cells (PSCs) have resulted from controlling the surface energy of the cathode-modified layer (TiO2 or ZnO) to enhance the short-circuit current (Jsc) or optimizing the contact morphology of the cathode (indium tin oxide or fluorine-doped tin oxide) and active layer to increase the fill factor. Herein, we report that the performance enhancement of PSCs is achieved by incorporating a donor macromolecule copper phthalocyanine (CuPc) as an anode modification layer. Using the approach based on orienting the microstructure evolution, uniformly dispersed island-shaped CuPc spot accumulations are built on the top of PTB7:PC71BM blend film, leading to an efficient spectral absorption and photogenerated exciton splitting. The best power conversion efficiency of PSCs is increased up to 9.726%. In addition to the enhanced light absorption, the tailored anode energy level alignment and optimized boundary morphology by incorporating the CuPc interlayer boost charge extraction efficiency and suppress the interfacial molecular recombination. These results demonstrate that surface morphology induction through molecular deposition is an effective method to improve the performance of PSCs, which reveals the potential implications of the interlayer between the organic active layer and the electrode buffer layer.

  7. Photodynamic antimicrobial chemotherapy using zinc phthalocyanine derivative for bacterial skin infection

    Science.gov (United States)

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

    2014-09-01

    Folliculitis, furunculosis and acne vulgaris are very common skin disorders of the hair follicles and are associated with large grease-producing (sebaceous) glands. Although the detailed mechanisms involved these skin disorders are not fully understood, it is believed that the bacteria Propionibacterium acnes and Staphylococcus aureus are the key pathogenic factors involved. Conventional treatments targeting the pathogenic factors include a variety of topical and oral medications such as antibiotics. The wide use of antibiotics leads to bacterial resistance, and hence there is a need for new alternatives in above bacterial skin treatment. Photodynamic antimicrobial chemotherapy (PACT) is based on an initial photosensitization of the infected area, followed by irradiation with visible light, producing singlet oxygen which is cytotoxic to bacteria. Herein we reported a zinc phthalocyanine derivative, pentalysine β-carbonylphthalocyanine zinc (ZnPc-(Lys)5) and its PACT effect for the bacteria involved in these skin infections. Our results demonstrated strong bactericidal effects of this photosensitizer on both strains of the bacteria, suggesting ZnPc-(Lys)5 as a promising antimicrobial photosensitizer for the treatment of infectious diseases caused by these bacteria.

  8. Cobalt-phthalocyanine-derived ultrafine Co3O4 nanoparticles as high-performance anode materials for lithium ion batteries

    Science.gov (United States)

    Wang, Heng-guo; Zhu, Yanjie; Yuan, Chenpei; Li, Yanhui; Duan, Qian

    2017-08-01

    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 Co3O4, Fe2O3, 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, Co3O4 nanoparticles were evaluated as anode materials for LIBs, which show high initial capacity (1132.9 mAh g-1 at 0.05 A g-1), improved cycling stability (585.6 mAh g-1 after 200 cycles at 0.05 A g-1), and good rate capability (238.1 mAh g-1 at 2 A g-1) due to the unique properties of the ultrafine Co3O4 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.

  9. Electronic Spectroscopy of Phthalocyanine and Porphyrin Derivatives in Superfluid Helium Nanodroplets.

    Science.gov (United States)

    Slenczka, Alkwin

    2017-07-25

    Phthalocyanine and porphyrin were among the first organic compounds investigated by means of electronic spectroscopy in superfluid helium nanodroplets. Superfluid helium nanodroplets serve as a very gentle host system for preparing cold and isolated molecules. The uniqueness of helium nanodroplets is with respect to the superfluid phase which warrants the vanishing viscosity and, thus, minimal perturbation of the dopant species at a temperature as low as 0.37 K. These are ideal conditions for the study of molecular spectra in order to analyze structures as well as dynamic processes. Besides the investigation of the dopant species itself, molecular spectroscopy in helium droplets provides information on the helium droplet and in particular on microsolvation. This article, as part of a special issue on phthalocyanines and porphyrins, reviews electronic spectroscopy of phthalocyanine and porphyrin compounds in superfluid helium nanodroplets. In addition to the wide variety of medical as well as technical and synthetical aspects, this article discusses electronic spectroscopy of phthalocyanines and porphyrins in helium droplets in order to learn about both the dopant and the helium environment.

  10. Fluorinated copper phthalocyanine nanowires for enhancing interfacial electron transport in organic solar cells.

    Science.gov (United States)

    Yoon, Seok Min; Lou, Sylvia J; Loser, Stephen; Smith, Jeremy; Chen, Lin X; Facchetti, Antonio; Marks, Tobin J; Marks, Tobin

    2012-12-12

    Zinc oxide is a promising candidate as an interfacial layer (IFL) in inverted organic photovoltaic (OPV) cells due to the n-type semiconducting properties as well as chemical and environmental stability. Such ZnO layers collect electrons at the transparent electrode, typically indium tin oxide (ITO). However, the significant resistivity of ZnO IFLs and an energetic mismatch between the ZnO and the ITO layers hinder optimum charge collection. Here we report that inserting nanoscopic copper hexadecafluorophthalocyanine (F(16)CuPc) layers, as thin films or nanowires, between the ITO anode and the ZnO IFL increases OPV performance by enhancing interfacial electron transport. In inverted P3HT:PC(61)BM cells, insertion of F(16)CuPc nanowires increases the short circuit current density (J(sc)) versus cells with only ZnO layers, yielding an enhanced power conversion efficiency (PCE) of ∼3.6% vs ∼3.0% for a control without the nanowire layer. Similar effects are observed for inverted PTB7:PC(71)BM cells where the PCE is increased from 8.1% to 8.6%. X-ray scattering, optical, and electrical measurements indicate that the performance enhancement is ascribable to both favorable alignment of the nanowire π-π stacking axes parallel to the photocurrent flow and to the increased interfacial layer-active layer contact area. These findings identify a promising strategy to enhance inverted OPV performance by inserting anisotropic nanostructures with π-π stacking aligned in the photocurrent flow direction.

  11. Phthalocyanine polymers

    Science.gov (United States)

    Achar, B. N.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1985-01-01

    A method of forming 4,4',4'',4''' -tetraamino phthalocyanines involves reducing 4,4',4'',4''' -tetranitro phthalocyanines, polymerizing the metal tetraamino phthalocyanines with a tetracarboxylic dianhydride (preferably aromatic) or copolymerizing with a tetracarboxylic dianhydride and a diamine (preferably also aromatic) to produce amic acids which are then dehydrocyclized to imides. Thermally and oxidatively stable polymers result which form tough, flexible films, varnishes, adhesives, and fibers.

  12. Macroscopically aligned molecular stacking structures in mesogenic phthalocyanine derivative films fabricated by heated spin-coating method

    Energy Technology Data Exchange (ETDEWEB)

    Higashi, Takuya; Fiderana Ramananarivo, Mihary; Ohmori, Masashi; Yoshida, Hiroyuki; Fujii, Akihiko, E-mail: afujii@opal.eei.eng.osaka-u.ac.jp; Ozaki, Masanori

    2015-11-02

    Spin-coated films of a mesogenic phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH{sub 2}), with macroscopic alignment of molecular stacking structure were obtained by processing in liquid-crystal phase of C6PcH{sub 2}. The column axis direction of the hexagonal columnar structure of C6PcH{sub 2} was determined by microscopic observation and polarized optical absorption measurement and was uniform in the millimeter-scale area. Highly ordered molecular stacking structure in the film, which is similar to the single crystal, was clarified by measurement of molecular tilting angle with respect to the column axis. The origin of the macroscopic molecular alignment during film formation was investigated by taking the process-temperature-dependent properties of the films into consideration. - Highlights: • We fabricated mesogenic phthalocyanine films by heated spin-coating method. • The maximum domain size was obtained by fabricating at mesogenic-phase temperature. • The optic axis direction in the film was uniform in the millimeter-scale area. • The crystalline structure in the film was similar to that of the single crystal. • The effects of mesogenic phase during the formation on the molecular alignment were presumed.

  13. 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.

  14. Helical self-assembly of optically active phthalocyanine derivatives: effect of Zn-O coordination bond on morphology and handedness of nanostructures.

    Science.gov (United States)

    Zhang, Congcong; Jing, Lu; Lin, Sha; Hao, Zijuan; Tian, Jing; Zhang, Xiaomei; Zhu, Peihua

    2013-11-11

    Two optically active phthalocyanine derivatives with eight peripheral chiral (S)-4'-(2-methylbutoxy)biphenyl moieties on the β-position of the phthalocyanine ring are synthesized. The circular dichroism (CD) spectra show signals in the Q absorption region for both compounds 1 and 2 in chloroform solution, indicating the effective chiral-information transfer from the peripheral chiral (S)-4'-(2-methylbutoxy)biphenyl side chains to the phthalocyanine chromophore at the molecular level. Their self-assembling properties are further investigated by using electronic absorption and Fourier transform infrared spectroscopy, transmission electronic microscopy, scanning electronic microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Experimental results reveal the effect of the metal-coordination bond on molecular packing models in these nanostructures, which in turn results in the self-assembled nanostructures with different morphologies, from nanosheets for 1 to helical nanofibers for 2. In addition, good semiconducting properties of the nanostructures fabricated from phthalocyanine derivatives 1 and 2 are revealed by current-voltage measurements. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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

  16. Effects of spin–orbit coupling and many-body correlations in STM transport through copper phthalocyanine

    Directory of Open Access Journals (Sweden)

    Benjamin Siegert

    2015-12-01

    Full Text Available The interplay of exchange correlations and spin–orbit interaction (SOI on the many-body spectrum of a copper phtalocyanine (CuPc molecule and their signatures in transport are investigated. We first derive a minimal model Hamiltonian in a basis of frontier orbitals that is able to reproduce experimentally observed singlet–triplet splittings. In a second step SOI effects are included perturbatively. Major consequences of the SOI are the splitting of former degenerate levels and a magnetic anisotropy, which can be captured by an effective low-energy spin Hamiltonian. We show that scanning tunneling microscopy-based magnetoconductance measurements can yield clear signatures of both these SOI-induced effects.

  17. Spectroscopic investigation on the interaction of copper porphyrazines and phthalocyanine with human telomeric G-quadruplex DNA.

    Science.gov (United States)

    Hassani, Leila; Hakimian, Fatemeh; Safaei, Elham

    2014-01-01

    The G-quadruplex DNA is a novel target for anticancer drug discovery and many scientific groups are investigating interaction of small molecules with G-quadruplex DNA to discover therapeutic agents for cancer. Here, interaction of a phthalocyanine (Cu(PcTs)) and two tetrapyridinoporphyrazines ([Cu(2,3-tmtppa)](4+) and [Cu(3,4-tmtppa)](4+)) with Na(+) and K(+) forms of human telomeric G-quadruplex DNA has been investigated by spectroscopic techniques. The results indicated that interaction of the cationic porphyrazines is remarkably stronger than the anionic phthalocyanine and they presumably bind to the G-quadruplex DNA through end-stacking. Fluorescent intercalator displacement assay implied the displacement ability of the complexes with thiazole orange. In addition, circular dichroism spectra of both quadruplex forms converge to the Na(+) isoform after binding to the porphyrazines. In conclusion, the porphyrazines as the complexes that bind to the G-quadruplex DNA, could be suitable candidates for further investigations about inhibition of telomerase enzyme. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Laboratory evaluation of borate:amine:copper derivatives In wood for fungal decay protection

    Science.gov (United States)

    George Chen

    2011-01-01

    This study aimed to evaluate borate:amine:copper derivatives in wood for fungal decay protection as well as the permanence of copper and boron in wood. Each of four derivatives of borate:amine:copper prevented fungal decay in wood. Disodium tetraborate decahydrate (borax):amine:copper derivatives with 0.61-0.63% retention after water leaching prevented decay by...

  19. Tetra-methyl substituted copper (II) phthalocyanine as a hole injection enhancer in organic light-emitting diodes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yu-Long; Xu, Jia-Ju; Lin, Yi-Wei; Chen, Qian; Shan, Hai-Quan; Xu, Zong-Xiang, E-mail: xu.zx@sustc.edu.cn, E-mail: val.roy@cityu.edu.hk [Department of Chemistry, South University of Science and Technology of China, Shenzhen, Guangdong, P. R. China, 518055 (China); Yan, Yan; Roy, V. A. L., E-mail: xu.zx@sustc.edu.cn, E-mail: val.roy@cityu.edu.hk [Department of Physics and Materials Science, City University of Hong Kong, Hong Kong SAR (Hong Kong)

    2015-10-15

    We have enhanced hole injection and lifetime in organic light-emitting diodes (OLEDs) by incorporating the isomeric metal phthalocyanine, CuMePc, as a hole injection enhancer. The OLED devices containing CuMePc as a hole injection layer (HIL) exhibited higher luminous efficiency and operational lifetime than those using a CuPc layer and without a HIL. The effect of CuMePc thickness on device performance was investigated. Atomic force microscope (AFM) studies revealed that the thin films were smooth and uniform because the mixture of CuMePc isomers depressed crystallization within the layer. This may have caused the observed enhanced hole injection, indicating that CuMePc is a promising HIL material for highly efficient OLEDs.

  20. Tetra-methyl substituted copper (II phthalocyanine as a hole injection enhancer in organic light-emitting diodes

    Directory of Open Access Journals (Sweden)

    Yu-Long Wang

    2015-10-01

    Full Text Available We have enhanced hole injection and lifetime in organic light-emitting diodes (OLEDs by incorporating the isomeric metal phthalocyanine, CuMePc, as a hole injection enhancer. The OLED devices containing CuMePc as a hole injection layer (HIL exhibited higher luminous efficiency and operational lifetime than those using a CuPc layer and without a HIL. The effect of CuMePc thickness on device performance was investigated. Atomic force microscope (AFM studies revealed that the thin films were smooth and uniform because the mixture of CuMePc isomers depressed crystallization within the layer. This may have caused the observed enhanced hole injection, indicating that CuMePc is a promising HIL material for highly efficient OLEDs.

  1. 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.

  2. Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of non-peripherally tetra-5-methyl-1,3,4-thiadiazole substituted copper(II) iron(II) and oxo-titanium (IV) phthalocyanines

    Science.gov (United States)

    Demirbaş, Ümit; Akyüz, Duygu; Akçay, Hakkı Türker; Barut, Burak; Koca, Atıf; Kantekin, Halit

    2017-09-01

    In this study novel substituted phthalonitrile (3) and non-peripherally tetra 5-Methyl-1,3,4-thiadiazole substituted copper(II) (4), iron(II) (5) and oxo-titanium (IV) (6) phthalocyanines were synthesized. These novel compounds were fully characterized by FT-IR, 1H NMR, UV-vis and MALDI-TOF mass spectroscopic techniques. Voltammetric and in situ spectroelectrochemical measurements were performed for metallo-phthalocyanines (4-6). TiIVOPc and FeIIPc showed metal-based and ligand-based electron transfer reactions while CuIIPc shows only ligand-based electron transfer reaction. Voltammetric measurements indicated that the complexes have reversible, diffusion controlled and one-electron redox reactions. The assignments of the redox processes and color of the electrogenerated species of the complexes were determined with in-situ spectroelectrochemical and electrocolorimetric measurements. These measurements showed that the complexes can be used as the electrochromic materials for various display technologies.

  3. Hydroxyethyl cellulose doped with copper(II) phthalocyanine-tetrasulfonic acid tetrasodium salt as an effective dual functional hole-blocking layer for polymer light-emitting diodes

    Science.gov (United States)

    Wu, Cheng-Liang; Chen, Yun

    2017-07-01

    We report a doping method to improve the performance of solution-processed polymer light-emitting diodes (PLEDs). Doping 12 wt% copper(II) phthalocyanine-tetrasulfonated acid tetrasodium salt (TS-CuPc) into hydroxyethyl cellulose (HEC) as a dual functional hole-blocking layer (df-HBL) of multilayer PLED (glass/ITO/PEDOT:PSS/HY-PPV/TS-CuPc-doped HEC/LiF/Al) significantly enhanced maximum luminance, maximum current and power efficiency over that without the df-HBL (10,319 cd/m2, 2.98 cd/A and 1.24 lm/W) to (29,205 cd/m2, 13.27 cd/A and 9.56 lm/W). CV measurements reveal that HEC possesses a powerful hole-blocking capability. Topography and conductivity AFM images show that doping TS-CuPc increases the interfacial contact area and interfacial conductivity, which can overcome the insulating nature of HEC and thus further facilitate electron injection. Enhancements in device performance are attributed to the improved carrier balance and recombination in the presence of df-HBL, confirmed in electron-only and hole-only devices. Moreover, apparently raised open-circuit voltages provide further evidence that enhanced electron injection is indeed realized by the df-HBL. This study demonstrates an effective approach to develop highly efficient PLEDs.

  4. X-ray Photoelectron Spectroscopy characterization of native and RCA-treated Si (111) substrates and their influence on surface chemistry of copper phthalocyanine thin films

    Energy Technology Data Exchange (ETDEWEB)

    Krzywiecki, M., E-mail: maciej.krzywiecki@polsl.p [Institute of Physics, Silesian University of Technology, 44-100 Gliwice (Poland); Grzadziel, L. [Institute of Physics, Silesian University of Technology, 44-100 Gliwice (Poland); Peisert, H.; Biswas, I.; Chasse, T. [Institute of Physical and Theoretical Chemistry, University of Tuebingen, D-72076 Tuebingen (Germany); Szuber, J. [Institute of Electronics, Silesian University of Technology, 44-100 Gliwice (Poland)

    2010-03-01

    In this paper native and RCA-treated n- and p-doped Si(111) substrates and ultra-thin 16-nm copper phthalocyanine (CuPc) layers deposited thereon were investigated using X-ray Photoemission Spectroscopy and Angle-Resolved X-ray Photoemission Spectroscopy. The oxide layer thickness was determined to be 1.3 nm on the RCA-treated substrates and 0.8 nm on the native ones. The analysis of substrate carbon contamination showed the existence of C-H, C-OH and COOH components on all substrates. The RCA clean removes more readily the carbon components with the OH group from the n-type Si and causes the segregation of the contaminants. The initial carbon species propagate in the evaporated CuPc layer up to a thickness of about 5 nm affecting the shape of the C1s peak. Additionally, the behavior of the binding energy difference between N1s and Si2p peaks upon the CuPc growth shows that there may occur various CuPc molecule adsorption modes on investigated Si substrates. It could be a useful information, from the technological point of view, especially for low dimensional electronic device preparation.

  5. Improvement of the photovoltaic parameters of perovskite solar cells using a reduced-graphene-oxide-modified titania layer and soluble copper phthalocyanine as a hole transporter.

    Science.gov (United States)

    Nouri, Esmaiel; Mohammadi, Mohammad Reza; Xu, Zong-Xiang; Dracopoulos, Vassilios; Lianos, Panagiotis

    2018-01-08

    Functional perovskite solar cells can be made by using a simple, inexpensive and stable soluble tetra-n-butyl-substituted copper phthalocyanine (CuBuPc) as a hole transporter. In the present study, TiO2/reduced graphene oxide (T/RGO) hybrids were synthesized via an in situ solvothermal process and used as electron acceptor/transport mediators in mesoscopic perovskite solar cells based on soluble CuBuPc as a hole transporter and on graphene oxide (GO) as a buffer layer. The impact of the RGO content on the optoelectronic properties of T/RGO hybrids and on the solar cell performance was studied, suggesting improved electron transport characteristics and photovoltaic parameters. An enhanced electron lifetime and recombination resistance led to an increase in the short circuit current density, open circuit voltage and fill factor. The device based on a T/RGO mesoporous layer with an optimal RGO content of 0.2 wt% showed 22% higher photoconversion efficiency and higher stability compared with pristine TiO2-based devices.

  6. Improved photoswitching response times of MoS2 field-effect transistors by stacking p-type copper phthalocyanine layer

    Science.gov (United States)

    Pak, Jinsu; Min, Misook; Cho, Kyungjune; Lien, Der-Hsien; Ahn, Geun Ho; Jang, Jingon; Yoo, Daekyoung; Chung, Seungjun; Javey, Ali; Lee, Takhee

    2016-10-01

    Photoswitching response times (rise and decay times) of a vertical organic and inorganic heterostructure with p-type copper phthalocyanine (CuPc) and n-type molybdenum disulfide (MoS2) semiconductors are investigated. By stacking a CuPc layer on MoS2 field effect transistors, better photodetection capability and fast photoswitching rise and decay phenomena are observed. Specifically, with a 2 nm-thick CuPc layer on the MoS2 channel, the photoswitching decay time decreases from 3.57 s to 0.18 s. The p-type CuPc layer, as a passivation layer, prevents the absorption of oxygen on the surface of the MoS2 channel layer, which results in a shortened photoswitching decay time because adsorbed oxygen destroys the balanced ratio of electrons and holes, leading to the interruption of recombination processes. The suggested heterostructure may deliver enhanced photodetection abilities and photoswitching characteristics for realizing ultra-thin and sensitive photodetectors.

  7. Introduction of dielectric phthalocyanine copper into nano-structure Fe{sub 3}O{sub 4} for excellent microwave absorption

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Shihua; Meng, Fanbin; Jia, Kun, E-mail: jiakun@uestc.edu.cn; Liu, Xiaobo, E-mail: liuxb@uestc.edu.cn

    2015-05-15

    Phthalocyanine copper/magnetite (CuPc/Fe{sub 3}O{sub 4}) magnetic nanohybrids were synthesized from CuPc and FeCl{sub 3}·6H{sub 2}O via a facile solvent-thermal route. The nanohybrids were monodispersed solid nanospheres and the diameter can be adjusted by polymerization degree of CuPc. Importantly, the as-prepared CuPc/Fe{sub 3}O{sub 4} nanohybrids showed excellent microwave absorption properties due to the introduction of dielectric CuPc. A reflection loss ≤−5 dB from 10.0 GHz to 18.0 GHz with multi-frequency microwave absorption was exhibited, and the maximum reflection loss reached to −32.96 dB at 14.50 GHz. Furthermore, the microwave absorption property can be tuned easily by varying polymerization degree of CuPc and the layer thickness of the samples, respectively. Thus, these results offered a promising strategy for the fabrication of absorbents for thin-thickness and strong-absorption microwave absorbing materials with working frequencies adjustable over a wide range. - Highlights: • The diameter can be adjusted by varying polymerization degree of CuPc. • CuPc/Fe{sub 3}O{sub 4} exhibits a reflection loss ≤−5 dB from 10.0 to 18.0 GHz. • The nanohybrids exhibit multi-frequency microwave absorption from 10.0 to 18.0 GHz. • The maximum reflection loss reaches to −32.96 dB at 14.50 GHz. • The microwave absorption can be tuned by varying polymerization degree of CuPc.

  8. Substituent effects on zinc phthalocyanine derivatives: a theoretical calculation and screening of sensitizer candidates for dye-sensitized solar cells.

    Science.gov (United States)

    Yang, Linlin; Guo, Lianshun; Chen, Qianqian; Sun, Huafei; Yan, Hui; Zeng, Qinghua; Zhang, Xianxi; Pan, Xu; Dai, Songyuan

    2012-09-01

    A series of unsymmetrical phthalocyanine sensitizer candidates with different donor and acceptor substituents, namely ZnPcBPh, ZnPcBOPh, ZnPcBtBu, ZnPcBN(Ph)₂, ZnPcBNHPh, ZnPcBNH₂, ZnPcBNHCH₃ and ZnPcBN(CH₃)₂, were designed and calculated using density functional theory (DFT) and time-dependent DFT calculations. The molecular orbital energy levels, the molecular orbital spatial distributions and the electronic absorption spectra of the ZnPcB series molecules were compared with those of TT7 and TT8 to reveal the substituent effects of different donor and acceptor groups on the phthalocyanine compounds and select good sesitizer candidates. The results show that some of these compounds have considerably smaller orbital energy gaps, red-shifted absorption bands and better charge-separated states, causing them to absorb photons in the lower energy region. Several new absorption bands emerge in the 400-600 nm region, which makes it possible for them to become panchromatic sensitizers. This characteristic is superior to the phthalocyanine sensitizers reported previously, including the current record holder, PcS6. The sensitizer candidates screened in the current work are very promising for providing good performance and might even challenge the photon-to-electricity conversion efficiency record of 4.6% for phthalocyanine sensitizers. Copyright © 2012 Elsevier Inc. All rights reserved.

  9. Phthalocyanine based metal containing porous carbon sheet

    Science.gov (United States)

    Honda, Z.; Sakaguchi, Y.; Tashiro, M.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

    2017-03-01

    Highly-ordered fused-ring poly copper phthalocyanine (PCuPc) was prepared using copper octacyanophthalocyanine as a building block, and two-dimensional (2D) square superlattices were directly observed by the transmission electron microscopy. Remarkably, we have found a formation of polymer network that consists of a 2D porous PCuPc sheet in which the centers of phthalocyanine units are alternately occupied by Cu atom and vacancy. Using this "half-filling" PCuPc, it must be possible to create alternating arrangements for transition metal centers, and therefore control the magnetic properties of the 2D carbon sheets.

  10. Potential Tuning of Nanoarchitectures Based on Phthalocyanine Nanopillars: Construction of Effective Photocurrent Generation Systems.

    Science.gov (United States)

    Kawaguchi, Takuya; Okamura, Shota; Togashi, Takanari; Harada, Wataru; Hirahara, Mana; Miyake, Ryosuke; Haga, Masa-aki; Ishida, Takao; Kurihara, Masato; Kanaizuka, Katsuhiko

    2015-09-02

    Nanopillars composed of a photoresponsive phthalocyanine derivative have been conveniently fabricated using a continuous silane coupling reaction on a substrate. The chemical potentials of phthalocyanine nanopillars (PNs) are precisely controlled by changing the number of phthalocyanine derivatives on the substrate. In addition, photocurrent generation efficiencies have been strongly influenced by the number of phthalocyanine derivatives. High photocurrent conversion cells in a solid state have been obtained by the combination of PNs and a fullerene derivative.

  11. Enhancement of the photovoltaic conversion efficiency of copper phthalocyanine thin film devices by incorporation of metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Stenzel, O.; Stendal, A.; Voigtsberger, K.; Von Borczyskowski, C. [Technical University of Chemnitz-Zwickau, Institute of Physics, Subdept. of Optical Spectroscopy and Molecular Physics, Chemnitz (Germany)

    1995-07-30

    ITO-copperphthalocyanine-indium sandwich structures have been prepared by thermal evaporation in high vacuum. Different types of metal nanoclusters have been incorporated at the ITO-copperphthalocyanine interface. Significant differences in the photovoltaic conversion efficiency of the sandwich samples have been established as a function of the excitation wavelength. Copper clusters have been found to increase the conversion efficiency by a factor of nearly three for solar illumination. The observed effects are discussed assuming resonant light absorption in the metal clusters as the responsible physical mechanism for enhancement

  12. 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.

  13. A phthalocyanine--fluorescein conjugate

    OpenAIRE

    ÜN, İlker; ZORLU, YUNUS; İBİŞOĞLU, Hanife; Dumoulin, Fabienne

    2013-01-01

    A phthalocyanine--fluorescein conjugate was designed and prepared. Its photophysical properties (electronic absorption and fluorescence) were determined and compared with those of an analogous derivative functionalized by a simple triazole without chromophore. It is likely to be used as a theranostic agent in photodynamic therapy.

  14. Control of olive oil adulteration with copper-chlorophyll derivatives.

    Science.gov (United States)

    Roca, María; Gallardo-Guerrero, Lourdes; Mínguez-Mosquera, María Isabel; Gandul Rojas, Beatriz

    2010-01-13

    The present work proposes an analytical method able to detect in an adulterated olive oil sample the addition of the copper complexes of chlorophylls (E 141i). The method consists of a pigment extraction in liquid phase and subsequent analysis by HPLC-DAD. The profile of chlorophyll pigments of an olive oil is determined essentially by its content in pheophytins (a and b), but in no case any copper derivative. Different samples of colorant E 141i have been analyzed, the natural coloring additives used to adulterate vegetable oils. The 99.59+/-0.52% of the chlorophyll pigments present in the different samples of E 141i colorant are not those of an olive oil (more than 75% are cupro-derivatives). Thus, the simple detection of one of the compounds in an olive oil indicates adulteration. The major chlorophyll derivative in all the E 141i colorants samples is Cu-pyropheophytin a and its limit of detection (LOD) defined at a signal-to-noise ratio of about 3 was 6.58 ng/g.

  15. Control of molecular packing structure of a derivative of vanadyl-phthalocyanine using pore wall of porous alumina and/or magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Takami, Seiichi [Advanced Device Materials Group, Advanced Electronic Materials Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)], E-mail: TAKAMI.Seiichi@nims.go.jp; Shirai, Yasuhiro; Wakayama, Yutaka; Chikyow, Toyohiro [Advanced Device Materials Group, Advanced Electronic Materials Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)

    2008-03-03

    We filled one-dimensional alumina pores with a molten derivative of vanadyl-phthalocyanine (VOPcHt) and evaluated the effect of the surface of pore wall on the molecular packing structure of VOPcHt. We also evaluated the effect of a magnetic field of 5.0 T on the packing structure of VOPcHt that was solidified on a flat substrate. X-ray diffraction measurements revealed that both the surface effect as well as the magnetic field controlled the packing structure of VOPcHt. When both the pore wall and the magnetic field existed, the surface effect was dominant in the control of the packing structure. These results provide practical methods to fabricate nanostructures of organic molecules with a controlled molecular packing structure.

  16. substituted copper and nickel phthalocyanines

    Indian Academy of Sciences (India)

    Administrator

    The characterization on them showed that they were optically active and had strong intermo- lecular forces in some ... bottomed flask equipped with an air condenser. The resulting solution was stirred and heated at 135°C ..... Scientific Program of Tianjin City (06TXT. JJC14200), the Jiangsu Province Science Foundation.

  17. Pathogenic adaptations to host-derived antibacterial copper

    Science.gov (United States)

    Chaturvedi, Kaveri S.; Henderson, Jeffrey P.

    2014-01-01

    Recent findings suggest that both host and pathogen manipulate copper content in infected host niches during infections. In this review, we summarize recent developments that implicate copper resistance as an important determinant of bacterial fitness at the host-pathogen interface. An essential mammalian nutrient, copper cycles between copper (I) (Cu+) in its reduced form and copper (II) (Cu2+) in its oxidized form under physiologic conditions. Cu+ is significantly more bactericidal than Cu2+ due to its ability to freely penetrate bacterial membranes and inactivate intracellular iron-sulfur clusters. Copper ions can also catalyze reactive oxygen species (ROS) generation, which may further contribute to their toxicity. Transporters, chaperones, redox proteins, receptors and transcription factors and even siderophores affect copper accumulation and distribution in both pathogenic microbes and their human hosts. This review will briefly cover evidence for copper as a mammalian antibacterial effector, the possible reasons for this toxicity, and pathogenic resistance mechanisms directed against it. PMID:24551598

  18. 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

  19. Phthalocyanine Tetraamine Epoxy-Curing Agents

    Science.gov (United States)

    Fohlen, G. M.; Achar, B. N.; Parker, J. A.

    1986-01-01

    Tough fire- and chemical-resistant epoxies produced by using metalphthalocyanine tetraamines (MPT's) of copper, cobalt, or nickel as curing agents. Synthesis of MPT's commercially realizable and gives pure compounds with almost 90-percent yield. Synthesis applicable for metals with atomic radii of about 1.35 angstroms, including Cu, Co, Ni, Zn, Fe, Pt, Al, and V. Possible to use metal phthalocyanines to cure epoxy resins in homogeneous reaction.

  20. Copper-promoted methylene C-H oxidation to a ketone derivative by O2

    DEFF Research Database (Denmark)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J.

    2017-01-01

    ) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO4). The co-ligand in this complex, N-(2′-pyridylcarbonyl)pyridine-2-carboximidate (bpca−), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water...

  1. Tetra methyl substituted Cu(II) phthalocyanine as alternative hole transporting material for organometal halide perovskite solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Sfyri, Georgia [FORTH/ICE-HT, PO Box 1414, 26504 Patras (Greece); Physics Department, University of Patras, 26500 Patras (Greece); Kumar, Challuri Vijay [FORTH/ICE-HT, PO Box 1414, 26504 Patras (Greece); Wang, Yu-Long [Department of Chemistry, South University of Science and Technology of China, ShenZhen 518055, GuangDong (China); Xu, Zong-Xiang, E-mail: xu.zx@sustc.edu.cn [Department of Chemistry, South University of Science and Technology of China, ShenZhen 518055, GuangDong (China); Krontiras, C.A. [Physics Department, University of Patras, 26500 Patras (Greece); Lianos, Panagiotis, E-mail: lianos@upatras.gr [FORTH/ICE-HT, PO Box 1414, 26504 Patras (Greece); Department of Chemical Engineering, University of Patras, 26500 Patras (Greece)

    2016-01-01

    Graphical abstract: - Highlights: • Tetra methyl substituted copper phthalocyanine as alternative hole transporting material. • Application to organometal halide perovskite solar cells. • Comparison with unsubstituted copper phtalocyanine. • Enhancement of Q band transitions due to more successful packaging. - Abstract: Copper phthalocyanine is a promising hole transporting material, which can be employed with solid state perovskite solar cells. Tetra methyl substituted copper phthalocyanine was presently studied as a hole transporting material and demonstrated improved performance with respect to unsubstituted copper phthalocyanine. This material shows a strong absorption in the Visible and Near IR part of the electromagnetic spectrum contributing to the absorption of photons. Its LUMO and HOMO level are favourably positioned for injecting electrons and scavenging holes. Methyl substitution facilitates closer molecular packing leading to a stronger extinction coefficient, stronger π–π interaction and higher charge carrier mobility.

  2. Derivation of Soil Ecological Criteria for Copper in Chinese Soils.

    Science.gov (United States)

    Wang, Xiaoqing; Wei, Dongpu; Ma, Yibing; McLaughlin, Mike J

    2015-01-01

    Considerable information on copper (Cu) ecotoxicity as affected by biological species and abiotic properties of soils has been collected from the last decade in the present study. The information on bioavailability/ecotoxicity, species sensitivity and differences in laboratory and field ecotoxicity of Cu in different soils was collated and integrated to derive soil ecological criteria for Cu in Chinese soils, which were expressed as predicted no effect concentrations (PNEC). First, all ecotoxicity data of Cu from bioassays based on Chinese soils were collected and screened with given criteria to compile a database. Second, the compiled data were corrected with leaching and aging factors to minimize the differences between laboratory and field conditions. Before Cu ecotoxicity data were entered into a species sensitivity distribution (SSD), they were normalized with Cu ecotoxicity predictive models to modify the effects of soil properties on Cu ecotoxicity. The PNEC value was set equal to the hazardous concentration for x% of the species (HCx), which could be calculated from the SSD curves, without an additional assessment factor. Finally, predictive models for HCx based on soil properties were developed. The soil properties had a significant effect on the magnitude of HCx, with HC5 varying from 13.1 mg/kg in acidic soils to 51.9 mg/kg in alkaline non-calcareous soils. The two-factor predictive models based on soil pH and cation exchange capacity could predict HCx with determination coefficients (R2) of 0.82-0.91. The three-factor predictive models--that took into account the effect of soil organic carbon--were more accurate than two-factor models, with R2 of 0.85-0.99. The predictive models obtained here could be used to calculate soil-specific criteria. All results obtained here could provide a scientific basis for revision of current Chinese soil environmental quality standards, and the approach adopted in this study could be used as a pragmatic framework for

  3. 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

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

    NARCIS (Netherlands)

    Uhlmann, C.; Swart, I.|info:eu-repo/dai/nl/304837652; 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

  5. Structure, transport and photoconductance of PbS quantum dot monolayers functionalized with a copper phthalocyanine derivative

    NARCIS (Netherlands)

    André, A.; Theurer, C.; Lauth, J.D.; Maiti, S.; Hodas, M.; Samadi Khoshkhoo, M.; Kinge, S; Meixner, A. J.; Schreiber, F.; Siebbeles, L.D.A.; Braun, K; Scheele, M.

    2017-01-01

    We simultaneously surface-functionalize PbS nanocrystals with Cu 4,4′,4′′,4′′′-tetraaminophthalocyanine and assemble this hybrid material into macroscopic monolayers. Electron microscopy and X-ray scattering reveal a granular mesocrystalline structure with strong coherence between the atomic

  6. Adsorption kinetic investigations of phthalocyanine derivatives self assembled monolayers (SAMs) on gold: Temperature influence on the SAM formation process and quality

    OpenAIRE

    Liličenko, Nadežda

    2015-01-01

    The ordered nano-structured surfaces, like self-assembled monolayers (SAMs) are of a great scientific interest, due to the low cost, simplicity, and versatility of this method. SAMs found numerous of applications in molecular electronics, biochemistry and optical devices. Phthalocyanine (Pc) complexes are of particular interest for the SAM preparation. These molecules exhibit fascinating physical properties and are chemically and thermally stable. Moreover their complex stru...

  7. Efficient Friedel-Crafts benzoylation of aniline derivatives with 4-fluorobenzoyl chloride using copper triflate in the synthesis of aminobenzophenones

    DEFF Research Database (Denmark)

    Tran, Phuong Hoang; Phung, Huy Quang; Hansen, Poul Erik

    2016-01-01

    An efficient pathway for the synthesis of the aminobenzophenone derivatives via Friedel–Crafts benzoylation using copper triflate as catalyst is proposed. New derivatives are synthesized. The copper triflate could be easily recovered and reused without loss of catalytic activity. Both the use of ...... of ionic liquids and microwave heating turned out to be fruitful....

  8. Efficient Friedel-Crafts benzoylation of aniline derivatives with 4-fluorobenzoyl chloride using copper triflate in the synthesis of aminobenzophenones

    DEFF Research Database (Denmark)

    Tran, Phuong Hoang; Phung, Huy Quang; Hansen, Poul Erik

    2016-01-01

    An efficient pathway for the synthesis of the aminobenzophenone derivatives via Friedel–Crafts benzoylation using copper triflate as catalyst is proposed. New derivatives are synthesized. The copper triflate could be easily recovered and reused without loss of catalytic activity. Both the use of ...

  9. 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

  10. 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.

  11. Copper(I) mediated cross-coupling of amino acid derived organozinc reagents with acid chlorides

    DEFF Research Database (Denmark)

    Hjelmgaard, Thomas; Tanner, David Ackland

    2006-01-01

    This paper describes the development of a straightforward experimental protocol for copper-mediated cross-coupling of amino acid derived beta-amido-alkylzinc iodides 1 and 3 with a range of acid chlorides. The present method uses CuCN center dot 2LiCl as the copper source and for organozinc reagent...... 1 the methodology appears to be limited to reaction with more stable acid chlorides, providing the desired products in moderate yields. When applied to organozinc reagent 3, however, the protocol is more general and provides the products in good yields in all but one of the cases tested....

  12. Thin films of tetrafluorosubstituted cobalt phthalocyanine: Structure and sensor properties

    Energy Technology Data Exchange (ETDEWEB)

    Klyamer, Darya D.; Sukhikh, Aleksandr S. [Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Pr. 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Pirogova Str. 2 (Russian Federation); Krasnov, Pavel O. [Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Pr. 3, Novosibirsk 630090 (Russian Federation); Gromilov, Sergey A. [Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Pr. 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Pirogova Str. 2 (Russian Federation); Morozova, Natalya B. [Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Pr. 3, Novosibirsk 630090 (Russian Federation); Basova, Tamara V., E-mail: basova@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Pr. 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Pirogova Str. 2 (Russian Federation)

    2016-05-30

    Highlights: • Thin films of tetrafluorosubstituted cobalt phthalocyanine were studied. • The effect of fluorine substituents to the films structure and properties was verified. • The sensor response of tetrafluorosubstituted phthalocyanine toward NH{sub 3} was studied. • The structure of analyte/phthalocyanine complex was analysed using DFT calculations. - Abstract: In this work, thin films of tetrafluorosubstituted cobalt phthalocyanine (CoPcF{sub 4}) were prepared by organic molecular beam deposition and their structure was studied using UV–vis, polarization dependent Raman spectroscopy, XRD and atomic force microscopy. Quantum chemical calculations (DFT) have been employed in order to determine the detailed assignment of the bands in the CoPcF{sub 4} IR and Raman spectra. The electrical sensor response of CoPcF{sub 4} films to ammonia vapours was investigated and compared with that of unsubstituted cobalt phthalocyanine films. In order to explain the difference in sensitivity of the unsubstituted and fluorinated phthalocyanines to ammonia, the nature and properties of chemical binding between CoPc derivatives and NH{sub 3} were described by quantum-chemical calculations utilizing DFT method. The effect of post-deposition annealing on surface morphology and gas sensing properties of CoPcF{sub 4} films was also studied.

  13. Copper removal from contaminated soils by soil washing process using camellian-derived saponin

    Science.gov (United States)

    Reyes, Arturo; Fernanda Campos, Maria; Videla, Álvaro; Letelier, María Victoria; Fuentes, Bárbara

    2015-04-01

    Antofagasta Region in North of Chile has been the main copper producer district in the world. As a consequence of a lack of mining closure regulation, a large number of abandon small-to-medium size metal-contaminated sites have been identified in the last survey performed by the Chilean Government. Therefore, more research development on sustainable reclamation technologies must be made in this extreme arid-dry zone. The objective of this study is to test the effectiveness of soil remediation by washing contaminated soil using camellian-derived saponin for the mobilization of copper. Soil samples were taken from an abandoned copper mine site located at 30 km North Antofagasta city. They were dried and sieved at 75 µm for physico-chemical characterization. A commercial saponin extracted from camellias seed was used as biosurfactant. The soil used contains 67.4 % sand, 26.3 % silt and 6.3 % clay. The soil is highly saline (electric conductivity, 61 mScm-1), with low organic matter content (0.41%), with pH 7.30, and a high copper concentration (2200 mg Kg-1 soil). According to the sequential extraction procedure of the whole soil, copper species are mainly as exchangeable fraction (608.2 mg Kg-1 soil) and reducible fraction (787.3 mg Kg-1 soil), whereas the oxidizable and residual fractions are around 205.7 and 598.8 mg Kg-1 soil, respectively. Soil particles under 75 µm contain higher copper concentrations (1242 mg Kg-1 soil) than the particle fraction over 75 µm (912 mg Kg-1 soil). All washing assays were conducted in triplicate using a standard batch technique with and without pH adjustment. The testing protocols includes evaluation of four solid to liquid ratio (0.5:50; 1.0:50; 2.0:50, and 5.0:50) and three saponin concentrations (0, 1, and 4 mg L-1). After shaking (24 h, 20±1 °C) and subsequently filtration (0.45 µm), the supernatants were analyzed for copper and pH. The removal efficiencies of copper by saponin solutions were calculated in according to the

  14. Synthesis, characterization and biological studies of copper(II) complexes with 2-aminobenzimidazole derivatives

    Science.gov (United States)

    Joseph, J.; Suman, A.; Nagashri, K.; Joseyphus, R. Selwin; Balakrishnan, Nisha

    2017-06-01

    Novel series of four copper(II) complexes with 2-aminobenzimidazole derivatives (obtained from the Knoevenagel condensate of acetylacetone (obtained from acetylacetone and halogen substituted benzaldehydes) and 2-aminobenzimidazole) were synthesized. They were structurally characterized using elemental analysis, molar conductance, FAB mass, FT- IR, 1H &13C-NMR, UV-Vis., and EPR techniques. On the basis of analytical and spectral studies, the distorted square planar geometry was assigned for all the complexes. The antibacterial screening of the ligands and their copper complexes indicated that all the complexes showed higher anti microbial activities than the free ligands. Superoxide dismutase and antioxidant activities of the copper complexes have also been performed. In the electrochemical technique, the shift in ΔEp, E1/2 and Ipc values were explored for the interaction of the complexes with CT-DNA. During the electrolysis process, the present ligand system stabilizes unusual oxidation state of copper in the complexes. It is believed that the copper complexes with curcumin analogs may enhance chemotherapeutic behavior.

  15. Formation of passivating layers by 1,2,4-triazole derivatives on copper in aqueous solutions

    Science.gov (United States)

    Kuznetsov, Yu. I.; Shikhaliev, Kh. S.; Agafonkina, M. O.; Andreeva, N. P.; Semiletov, A. M.; Chirkunov, A. A.; Potapov, A. Yu.; Solov'ev, V. E.

    2017-12-01

    Ellipsometry and electrochemical measurements are used to study the adsorption of some substituted 1,2,4-triazoles on copper and their effect on dissolution of copper in aqueous buffer solutions at pH 7.4. It is found that the adsorption of triazole compounds on copper is polymolecular at potential E = 0.0 V, in relation to a normal hydrogen electrode. The first layer is described by the Temkin equation with free adsorption energy (-Δ G a 0) = 55.2-76.3 kJ/mol and an energy heterogeneity factor that varies from 0.91 to 2.5. The maximum value of -Δ G a 0 is found for an acid and a hydrogen sulfide corrosion inhibitor that is a mixture of triazole derivatives. The same inhibitor is the one least sensitive to the energy heterogeneity of the surface of a copper electrode, due to its high chemical reactivity and ability to be adsorbed on different active sites. This inhibitor is likely chemisorbed on copper and forms an ultrathin coating in an aqueous solution that is vastly superior to similar coatings produced by the familiar corrosion inhibitors of triazole group compounds in protecting against atmospheric corrosion.

  16. A Fulleropyrrolidine-phthalocyanine dyad for photovoltaic applications

    NARCIS (Netherlands)

    Loi, M.A.; Denk, P.; Hoppe, H.; Neugebauer, H.; Meissner, D.; Winder, C.; Brabec, C.J.; Sariciftci, N.S.; Gouloumis, A.; Vázquez, P.; Torres, T.

    2003-01-01

    We report on photophysical properties of a novel dyad molecule having as antenna/donor a Zn-phthalocyanine derivative and as acceptor a C60 derivative covalently attached. We found evidences for long living photoinduced electron transfer in solid state. Photovoltaic action of thin film devices of

  17. Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: Controlling the catalytic selectivity of hydrocarbons

    NARCIS (Netherlands)

    Kas, Recep; Kortlever, R.; Milbrat, Alexander; Koper, M.T.M.; Mul, Guido; Baltrusaitis, Jonas

    2014-01-01

    The catalytic activity and hydrocarbon selectivity in electrochemical carbon dioxide (CO2) reduction on cuprous oxide (Cu2O) derived copper nanoparticles is discussed. Cuprous oxide films with [100], [110] and [111] orientation and variable thickness were electrodeposited by reduction of copper(II)

  18. Metal phthalocyanine polymers

    Science.gov (United States)

    Achar, B. N.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1984-01-01

    Metal 4, 4', 4", 4"'=tetracarboxylic phthalocyanines (MPTC) are prepared by reaction of trimellitic anhydride, a salt or hydroxide of the desired metal (or the metal in powdered form), urea and a catalyst. A purer form of MPTC is prepared than heretofore. These tetracarboxylic acids are then polymerized by heat to sheet polymers which have superior heat and oxidation resistance. The metal is preferably a divalent metal having an atomic radius close to 1.35A.

  19. Kinetic response study in chemiresistive gas sensor based on carbon nanotube surface functionalized with substituted phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Anshul Kumar; Saini, Rajan; Bedi, R. K.; Mahajan, Aman, E-mail: dramanmahajan@yahoo.co.in, E-mail: anshulsharma.phy@gmail.com [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India); Kumar, Pankaj [Department of Applied Sciences, I.K. Gujral Punjab Technical University, Kapurthala 144601 (India)

    2016-05-06

    A kind of hybrid material is prepared by functionalizing multi-wall carbon nanotubes (MWCNTs-COOH) with substituted copper phthalocyanine and the formation of CuPcOC{sub 8}/MWCNTs-COOH hybrid is confirmed by scanning electron microscopy and transmission electron microscopy. The results indicated that on the surface of nanotubes substituted CuPcOC{sub 8} derivatives has been successfully anchored through π-π stacking interaction. The gas sensing application of the fabricated hybrid material is tested upon exposure to different hazardous species, specifically NO{sub 2}, NO, Cl{sub 2} and NH{sub 3} at operating temperature of 150°C. It has been demonstrated that for Cl{sub 2} minimum detection limit of CuPcOC{sub 8}/MWCNTs-COOH hybrid is 100 ppb. The response of hybrid sensor is found to be increased with increase in the concentration of Cl{sub 2}.

  20. Chemical Conversions of Biomass-Derived Platform Chemicals over Copper-Silica Nanocomposite Catalysts.

    Science.gov (United States)

    Upare, Pravin P; Hwang, Young Kyu; Lee, Jong-Min; Hwang, Dong Won; Chang, Jong-San

    2015-07-20

    Biomass and biomass-derived carbohydrates have a high extent of functionality, unlike petroleum, which has limited functionality. In biorefinery applications, the development of methods to control the extent of functionality in final products intended for use as fuels and chemicals is a challenge. In the chemical industry, heterogeneous catalysis is an important tool for the defunctionalization of functionalized feedstocks and biomass-derived platform chemicals to produce value-added chemicals. Herein, we review the recent progress in this field, mainly of vapor phase chemical conversion of biomass-derived C4 -C6 carboxylic acids and esters using copper-silica nanocomposite catalysts. We also demonstrate that these nanocomposite catalysts very efficiently convert biomass-derived platform chemicals into cyclic compounds, such as lactones and hydrofurans, with high selectivities and yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. 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

  3. Spiro copper(II)-metallacycles derived from 5-arylaminomethylene-barbituric acids: Synthesis and structural characterization

    Science.gov (United States)

    Fırıncı, Erkan; Giziroglu, Emrah; Celepci, Duygu Barut; Söyleyici, Hakan Can; Aygün, Muhittin

    2017-06-01

    Schiff bases derived from 2,4,6-trioxohexahydroprimidine-5-carbaldehyde can behave as chelating ligands. 5-[(2,6-diisopropylphenylamino)-methylene]pyrimidine-2,4,6-trione (LB1) and 1,3-dimethyl-5-[(2-phenoxyphenylamino)-methylene]pyrimidine-2,4,6-trione (LB2) were used as ligand in the synthesis of novel mononuclear five-coordinated copper(II) complexes. The spectroscopic properties of the ligands were detected by FT-IR and NMR. The molecular structure of LB2 was determined by X-ray diffraction which crystallizes in the orthorhombic Pca21 space group. The complexes of Cu(LB1)2 (2) and Cu(LB2)2 (3) were characterized by elemental analysis, FT-IR and X-ray diffraction. The X-ray diffraction studies reveal 2 and 3 contain five-coordinated Cu(II) atom which is surrounded by two nitrogen and three oxygen atoms. The coordination geometry of complexes were examined using the Addison's model. The results show that complex 2 has distorted trigonal bipyramidal geometry, but complex 3 has distorted square pyramidal geometry. Also, the synthesized copper complexes can be regarded as spiro metallacycles in which copper is central spiro atom.

  4. Synthesis and Characterization of Novel Thiourea Derivatives and Their Nickel and Copper Complexes

    OpenAIRE

    Gün Binzet; Gülten Kavak; Nevzat Külcü; Süheyla Özbey; Ulrich Flörke; Hakan Arslan

    2013-01-01

    New benzoyl thiourea derivatives and their nickel and copper complexes were synthesized. The structure of the synthesized compounds were confirmed by elemental analysis, FT-IR, and 1H NMR techniques. Four of the synthesized compounds are analyzed by X-ray single crystal diffraction technique. Whereas N,N-dimethyl-N′-(4-fluorobenzoyl)thiourea, N,N-diethyl-N′-(4-fluorobenzoyl)thiourea, and N,N-di-n-butyl-N′-(4-fluorobenzoyl) thiourea crystallize in the monoclinic system, bis(N,N-di-n-propyl-N′-...

  5. 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

  6. 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...

  7. 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

  8. Metal (2) 4,4',4",4'" phthalocyanine tetraamines as curing agents for epoxy resins

    Science.gov (United States)

    Achar, B. N.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1985-01-01

    Metal, preferably divalent copper, cobalt or nickel, phthalocyanine tetraamines are used as curing agents for epoxides. The resulting copolymers have high thermal and chemical resistance and are homogeneous. They are useful as binders for laminates, e.g., graphite cloth laminate.

  9. Copper-promoted methylene C-H oxidation to a ketone derivative by O2.

    Science.gov (United States)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J

    2017-01-17

    The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O2 in air under ambient conditions when [Cu(dpeo)2](ClO4)2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO4). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca(-)), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca(-) are not recovered and [Cu(pic)2H2O] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O2 activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by H2O2 in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O2. The metastable copper complexes [Cu(dpeo)2](ClO4)2 and [Cu(bpca)(hidpe)](ClO4), along with [NiX2(dpeo)2] (X = Cl, Br), [Ni(dpeo)3](ClO4)2, [Co(dpeo)3](ClO4)3 and the mixed valence complex [Fe(III)Fe(dpeo-H)3(dpeo)3](PF6)4, have been structurally characterized.

  10. 21 CFR 73.3124 - Phthalocyanine green.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Phthalocyanine green. 73.3124 Section 73.3124 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3124 Phthalocyanine green. (a) Identity. The color additive is phthalocyanine green (CAS Reg. No. 1328-53-6), Colour Index No. 74260. (b) Uses...

  11. 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.

  12. Chiral copper(II) complex based on natural product rosin derivative as promising antitumour agent.

    Science.gov (United States)

    Fei, Bao-Li; Huang, Zhi-Xiang; Xu, Wu-Shuang; Li, Dong-Dong; Lu, Yang; Gao, Wei-Lin; Zhao, Yue; Zhang, Yu; Liu, Qing-Bo

    2016-07-01

    To evaluate the biological preference of chiral drug candidates for molecular target DNA, the synthesis and characterization of a chiral copper(II) complex (2) of a chiral ligand N,N'-(pyridin-2-ylmethylene) dehydroabietylamine (1) was carried out. The interactions of 1 and 2 with salmon sperm DNA were investigated by viscosity measurements, UV, fluorescence and circular dichroism (CD) spectroscopic techniques. Absorption spectral, emission spectral and viscosity analysis reveal that 1 and 2 interacted with DNA through intercalation and 2 exhibited a higher DNA binding ability. In the absence/presence of ascorbic acid, 1 and 2 cleaved supercoiled pBR322 DNA by single-strand and 2 displayed stronger DNA cleavage ability. In addition, in vitro cytotoxicity of 1 and 2 against HeLa, SiHa, HepG-2 and A431 cancer cell lines study show that they exhibited effective cytotoxicity against the tested cell lines, notably, 2 showed a superior cytotoxicity than the widely used drug cisplatin under identical conditions, indicating it has the potential to act as effective anticancer drug. Flow cytometry analysis indicates 2 produced death of HeLa cancer cells through an apoptotic pathway. Cell cycle analysis demonstrates that 2 mainly arrested HeLa cells at the S phase. The study represents the first step towards understanding the mode of the promising chiral rosin-derivative based copper complexes as chemotherapeutics. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Non-Ceruloplasmin Copper Distinguishes A Distinct Subtype of Alzheimer's Disease: A Study of EEG-Derived Brain Activity.

    Science.gov (United States)

    Tecchio, Franca; Vecchio, Fabrizio; Ventriglia, Mariacarla; Porcaro, Camillo; Miraglia, Francesca; Siotto, Mariacristina; Rossini, Paolo M; Rongioletti, Mauro; Squitti, Rosanna

    2016-01-01

    Meta-analyses show that percentages of non-Cp-Cu-copper that is not bound to ceruloplasmin (also known as 'free' copper)-in serum are higher in Alzheimer's disease (AD) patients. Genetic heterogeneity in AD patients stratified on the basis of non-Cp-Cu cut-off sustains the existence of a copper AD metabolic subtype. Non-Cp-Cu abnormalities correlated with alterations of electroencephalographic rhythms (EEG). We aimed to determine whether an EEG-derived brain cortical rhythm's heterogeneity between two AD groups stratified on the basis of a copper marker. We assessed levels of copper, ceruloplasmin, Non-Cp-Cu, and the APOE4 genotype in 67 AD patients and compared resting EEG-derived eLORETA cortical rhythms between AD groups stratified in terms of 'Normal' and 'High' non-Cp-Cu. The High non-Cp-Cu group experienced a lower power in all bands (0.2-48 Hz) in the parietal cortices (p=0.019) and a more limited alpha band (8-13 Hz) power in the sensory lobes (temporal, occipital, and parietal p>0.05 consistently) than the Normal non-Cp-Cu AD group. When corrected for MMSE, the non-Cp-Cu levels correlated with a reduction of high-frequency brain activity (from high alpha to gamma, 10.5-48 Hz). This neurophysiological heterogeneity in EEG-derived brain cortical rhythms between the two AD groups sustains a copper AD metabolic subtype; Non-Cp-Cu is a marker of this copper AD.

  14. Characterization of evaporated trivalent and tetravalent phthalocyanines thin films: different degree of organization

    Energy Technology Data Exchange (ETDEWEB)

    Del Cano, T. [Dpto. Fisica de la Materia Condensada, Universidad de Valladolid, Prado de la Magdalena s/n, 47011 Valladolid (Spain); Parra, V. [Dpto. Quimica Fisica y Quimica Inorganica, E.T.S. I.I, Universidad de Valladolid, C/ Paseo del Cauce s/n, 47011 Valladolid (Spain); Rodriguez-Mendez, M.L. [Dpto. Quimica Fisica y Quimica Inorganica, E.T.S. I.I, Universidad de Valladolid, C/ Paseo del Cauce s/n, 47011 Valladolid (Spain); Aroca, R.F. [Materials and Surface Science Group, University of Windsor, Windsor, Ont. (Canada); De Saja, J.A. [Dpto. Fisica de la Materia Condensada, Universidad de Valladolid, Prado de la Magdalena s/n, 47011 Valladolid (Spain)]. E-mail: sajasaez@fmc.uva.es

    2005-06-30

    Evaporated thin films of trivalent - chloroindiumphthalocyanine (ClInPc) and chlorogalliumphthalocyanine (ClGaPc) - and tetravalent phthalocyanines - vanadyl-phthalocyanine (VOPc) and titanylphthalocyanine (TiOPc) - have been characterized by means of electronic absorption and infrared spectroscopy (both in transmission and reflection-absorption modes). It was found that the ability of self-organization clearly differs between trivalent and tetravalent phthalocyanine derivatives. The results revealed that ClGaPc and ClInPc thin films result to be highly organized. On the other hand, the evaporation of tetravalent phthalocyanines powders forms amorphous thin films. However, further film treatments (thermal annealing and solvent exposure) lead to the phase transition from amorphous to {alpha}-form, and as a result, a high degree of molecular organization is induced.

  15. 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.

  16. Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper

    DEFF Research Database (Denmark)

    Bertheussen, Erlend; Verdaguer Casadevall, Arnau; Ravasio, Davide

    2016-01-01

    Oxide-derived copper (OD-Cu) electrodes exhibit unprecedented CO reduction performance towards liquid fuels, producing ethanol and acetate with >50 % Faradaic efficiency at −0.3 V (vs. RHE). By using static headspace-gas chromatography for liquid phase analysis, we identify acetaldehyde as a mino...

  17. Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper

    DEFF Research Database (Denmark)

    Bertheussen, Erlend; Verdaguer Casadevall, Arnau; Ravasio, Davide

    2016-01-01

    Oxide-derived copper (OD-Cu) electrodes exhibit unprecedented CO reduction performance towards liquid fuels, producing ethanol and acetate with >50 % Faradaic efficiency at −0.3 V (vs. RHE). By using static headspace-gas chromatography for liquid phase analysis, we identify acetaldehyde as a minor...

  18. Direct access to β-oxodiazo compounds by copper(II)-catalyzed oxidative rearrangement of stabilized vinyl diazo derivatives.

    Science.gov (United States)

    Barluenga, José; Lonzi, Giacomo; Riesgo, Lorena; Tomás, Miguel; López, Luis A

    2011-11-16

    The copper(II)-catalyzed reaction of alkenyldiazo compounds with iodosylbenzene leading to β-oxodiazo derivatives is reported. This process occurs via an unprecedented 1,2-shift of the diazoacetate function. A selection of the synthetic applications of a representative member of this new class of functionalized diazo derivatives in the regioselective synthesis of substituted 1,4-dicarbonyl compounds is also reported.

  19. Synthesis of Biologically Active Indenoisoquinoline Derivatives via a One-Pot Copper(II)-Catalyzed Tandem Reaction.

    Science.gov (United States)

    Huang, Chia-Yu; Kavala, Veerababurao; Kuo, Chun-Wei; Konala, Ashok; Yang, Tang-Hao; Yao, Ching-Fa

    2017-02-17

    A concise route for the synthesis of indenoisoquinoline derivatives from 2-iodobenzamide and 1,3-indanedione derivatives in the presence of copper(II) chloride and cesium carbonate in acetonitrile solvent is reported. A wide variety of 2-iodobenzamide derivatives and indandiones could be used to synthesize indenoisoquinoline derivatives and other fused indenoisoquinoline in moderate to good yields. This methodology was adapted for the one-step synthesis of a series of clinically active topoisomerase I inhibitors such as NSC 314622, LMP-400, LMP-776.

  20. Antibacterial, antibiofilm and antioxidant screening of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid

    Science.gov (United States)

    Bukonjić, Andriana M.; Tomović, Dušan Lj.; Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Radojević, Ivana D.; Maksimović, Jovana Z.; Vasić, Sava M.; Čomić, Ljiljana R.; Trifunović, Srećko R.; Radić, Gordana P.

    2017-01-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-propyl derivative of thiosalicylic acid was confirmed by X-ray structural study. The binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid crystallized in two polymorphic forms with main structural difference in the orientation of phenyl rings relative to corresponding carboxylate groups. The antibacterial activity was tested determining the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) by using microdilution method. The influence on bacterial biofilm formation was determined by tissue culture plate method. In general, the copper(II)-complexes manifested a selective and moderate activity. The most sensitive bacteria to the effects of Cu(II)-complexes was a clinical isolate of Pseudomonas aeruginosa. For this bacteria MIC and biofilm inhibitory concentration (BIC) values for all tested complexes were in the range or better than the positive control, doxycycline. Also, for the established biofilm of clinical isolate Staphylococcus aureus, BIC values for the copper(II)-complex with S-ethyl derivative of thiosalicylic acid,[Cu2(S-et-thiosal)4(H2O)2] (C3) and copper(II)-complex with S-butyl derivative of thiosalicylic acid, [Cu2(S-bu-thiosal)4(H2O)2] (C5) were in range or better than the positive control. All the complexes acted better against Gram-positive bacteria (Staphylococcus aureus and Staphylococcus aureus ATCC 25923) than Gram-negative bacteria (Proteus mirabilis ATCC 12453, Pseudomonas aeruginosa, and P. aeruginosa ATCC 27855). The complexes showed weak antioxidative properties tested by two methods (1,1-diphenyl-2-picrylhydrazyl (DPPH) and reducing power assay).

  1. 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...

  2. Phthalocyanine and azaphthalocyanines containing eugenol ...

    Indian Academy of Sciences (India)

    The crystal structures of two pyrazine compounds were also determined by the single crystal diffraction technique. This study showed that two phthalocyanines compounds (3a and 4a) could be potential lipase inhibitor agents due to greater hydrophobicity than other azaphtalocyanines. Compound 4a displayed lowest ...

  3. Nonperipheral Tetrakis(dibutylamino)phthalocyanines. New Types of 1,8,15,22-Tetrakis(substituted)phthalocyanine Isomers.

    Science.gov (United States)

    Chen, Yuxiang; Fang, Wenjuan; Wang, Kang; Liu, Wei; Jiang, Jianzhuang

    2016-09-19

    Cyclic tetramerization of 3-(dibutylamino)phthalonitrile in refluxing n-pentanol in the presence of magnesium pentanoate afforded the four regioisomer-containing nonperipheral 1,8-/11,15-/18,22-/25-tetrakis(dibutylamino)phthalocyaninato magnesium complexes with the 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomer Mg{Pc[α-N(C4H9)2]4-C4} (2). This, in combination with its much superior crystallinity over the remaining three isomers, renders the easy isolation of 2 only through two simple recrystallizations from THF and methanol. Treatment of 2 with trifluoroacetic acid induced the isolation of metal-free 1,8,15,22-tetrakis(dibutylamino)phthalocyanine, H2{Pc[α-N(C4H9)2]4-C4} (1), which further reacted with M(OAc)2·nH2O (M = Ni, Zn) in refluxing n-pentanol, giving the 1,8,15,22-tetrakis(dibutylamino)phthalocyaninato metal complexes M{Pc[α-N(C4H9)2]4-C4} (M = Ni (3), Zn (4)). The full series of four 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric compounds have been characterized by a series of spectroscopic methods and single-crystal X-ray diffraction analyses. Obviously, the present result provides a simple and effective pathway for the synthesis and isolation of novel 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric derivatives, providing one step forward toward completing bis(alkyl)amino-incorporated phthalocyanine species.

  4. Inhibition of copper amine oxidases by pyridine-derived aldoximes and ketoximes.

    Science.gov (United States)

    Mlícková, K; Sebela, M; Cibulka, R; Frébort, I; Pec, P; Liska, F; Tanizawa, K

    2001-01-01

    The reactions of pea diamine oxidase (PSAO) and 2-phenylethylamine oxidase from Arthrobacter globiformis (AGAO) with pyridine-derived oximes were studied. Pyridine carbaldoximes and alkyl pyridyl ketoximes act as strong non-competitive inhibitors of the enzymes. The inhibition constants K(i) of these compounds vary between 10(-4) and 10(-5) M, for AGAO and some of the studied oximes were found even micromolar K(i) values. The presence of pyridine moiety in the studied compounds has remarkable influence on the inhibition potency. Elementary oximes lacking the heterocyclic ring, i.e., aliphatic (acetone oxime), alicyclic (cyclohexanone oxime) and aromatic (benzaldoxime), are considerably weaker non-competitive inhibitors (K(i) similar to 10(-3) or 10(-2) M). The position of the pyridine ring substitution by -C(R)=NOH group does not play a significant role for the inhibition potency of the studied oxime compounds. If the pyridine nitrogen is quaternised (in hydroxyiminomethyl-1-methylpyridinium iodides), the compound looses its inhibitory properties. Extended length of alkyl substituents on the ketoxime group of alkyl pyridyl ketoximes increases the K(i) value. The enzyme-bound copper represents one of possible target sites for pyridine-derived oxime inhibitors. The addition of an alkyl pyridyl ketoxime or a pyridine carbaldoxime to a native PSAO sample perturbs the absorption spectrum of the enzyme (by an absorption increase in the region 300-400 nm) that is not observed in the spectrum of reacted PSAO apoenzyme. However, an additional formation of hydrogen bonds with amino acid side-chains at the active site should be considered, namely for 3- and 4-substituted pyridine derivatives.

  5. Selective determination of trace copper(II) by cathodic adsorptive stripping voltammetry with a naphthol-derivative Schiff's base.

    Science.gov (United States)

    Shamsipur, Mojtaba; Saeidi, Mahboubeh; Sharghi, Hashem; Naeimi, Hossein

    2003-01-01

    A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with a recently synthesized naphthol-derivative Schiff's base (2,2'-[1,2-ethanediylbis(nitriloethylidyne)]bis(1-naphthalene)) is presented. The method is based on adsorptive accumulation of the resulting copper-Schiff's base complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurement at the reduction current of adsorbed complex at -0.15 V (vs. Ag/AgCl). The optimal conditions for the stripping analysis of copper include pH 5.5 to 6.5, 8 microM Schiff's base and an accumulation potential of -0.05 V (vs. Ag/AgCI). The peak current is linearly proportional to the copper concentration over a range 2.3-50.8 ng ml(-1) with a limit of detection of 1.9 ng ml(-1). The accumulation time and RSD are 90 s and (3.2-3.5)%, respectively. The method was applied to the determination of copper in some analytical grade salts, tap water, human serum and sheep's liver.

  6. Derived reference doses for three compounds used in the photovoltaics industry: Copper indium diselenide, copper gallium diselenide, and cadmium telluride

    Energy Technology Data Exchange (ETDEWEB)

    Moskowitz, P.D.; Bernholc, N.; DePhillips, M.P.; Viren, J.

    1995-07-06

    Polycrystalline thin-film photovoltaic modules made from copper indium diselenide (CIS), copper gallium diselenide (CGS), and cadmium telluride (CdTe) arc nearing commercial development. A wide range of issues are being examined as these materials move from the laboratory to large-scale production facilities to ensure their commercial success. Issues of traditional interest include module efficiency, stability and cost. More recently, there is increased focus given to environmental, health and safety issues surrounding the commercialization of these same devices. An examination of the toxicological properties of these materials, and their chemical parents is fundamental to this discussion. Chemicals that can present large hazards to human health or the environment are regulated often more strictly than those that are less hazardous. Stricter control over how these materials are handled and disposed can increase the costs associated with the production and use of these modules dramatically. Similarly, public perception can be strongly influenced by the inherent biological hazard that these materials possess. Thus, this report: presents a brief background tutorial on how toxicological data are developed and used; overviews the toxicological data available for CIS, CGS and CdTe; develops ``reference doses`` for each of these compounds; compares the reference doses for these compounds with those of their parents; discusses the implications of these findings to photovoltaics industry.

  7. Hydrothermally derived water-dispersible mixed valence copper-chitosan nanocomposite as exceptionally potent antimicrobial agent

    Science.gov (United States)

    Basumallick, Srijita; Rajasekaran, Parthiban; Tetard, Laurene; Santra, Swadeshmukul

    2014-10-01

    We report, for the first time, a one-step hydrothermal (HT) process to design and synthesize water-dispersible chitosan nanoparticles loaded with mixed valence copper. Interestingly, this HT copper-chitosan biocompatible composite exhibits exceptionally high antimicrobial properties. A comprehensive characterization of the composite indicates that the hydrothermal process results in the formation of monodispersed nanoparticles with average size of 40 ± 10 nm. FT-IR and Raman spectroscopic studies unveiled that the hydrolysis of the glycoside bonds as the origin of the depolymerization of chitosan. Furthermore, X-Ray Photoelectron Spectroscopy measurements confirmed the presence of mixed valence copper states in the composite, while UV-Vis and FT-IR studies revealed the chemical interaction of copper with the chitosan matrix. Hence, the extensive spectroscopic data provide strong evidence that the chitosan structure was rearranged to capture copper oxide nanoparticles. Finally, HT copper-chitosan composite showed a complete killing effect when tested against both Gram negative ( E. coli) and Gram positive ( S. aureus) bacteria at metallic copper concentration of 100 μg/ml (1.57 mM). At the same concentration, neither pure chitosan nor copper elicited such antimicrobial efficacy. Thus, we show that HT process significantly enhances the synergistic antimicrobial effect of chitosan and copper in addition to increasing the water dispersibility.

  8. 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.

  9. Benzaldehyde Thiosemicarbazone Derived from Limonene Complexed with Copper Induced Mitochondrial Dysfunction in Leishmania amazonensis

    Science.gov (United States)

    Britta, Elizandra Aparecida; Barbosa Silva, Ana Paula; Ueda-Nakamura, Tânia; Dias-Filho, Benedito Prado; Silva, Cleuza Conceição; Sernaglia, Rosana Lázara; Nakamura, Celso Vataru

    2012-01-01

    Background Leishmaniasis is a major health problem that affects more than 12 million people. Treatment presents several problems, including high toxicity and many adverse effects, leading to the discontinuation of treatment and emergence of resistant strains. Methodology/Principal Findings We evaluated the in vitro antileishmanial activity of benzaldehyde thiosemicarbazone derived from limonene complexed with copper, termed BenzCo, against Leishmania amazonensis. BenzCo inhibited the growth of the promastigote and axenic amastigote forms, with IC50 concentrations of 3.8 and 9.5 µM, respectively, with 72 h of incubation. Intracellular amastigotes were inhibited by the compound, with an IC50 of 10.7 µM. BenzCo altered the shape, size, and ultrastructure of the parasites. Mitochondrial membrane depolarization was observed in protozoa treated with BenzCo but caused no alterations in the plasma membrane. Additionally, BenzCo induced lipoperoxidation and the production of mitochondrial superoxide anion radicals in promastigotes and axenic amastigotes of Leishmania amazonensis. Conclusion/Significance Our studies indicated that the antileishmania activity of BenzCo might be associated with mitochondrial dysfunction and oxidative damage, leading to parasite death. PMID:22870222

  10. Synthesis and Characterization of Novel Thiourea Derivatives and Their Nickel and Copper Complexes

    Directory of Open Access Journals (Sweden)

    Gün Binzet

    2013-01-01

    Full Text Available New benzoyl thiourea derivatives and their nickel and copper complexes were synthesized. The structure of the synthesized compounds were confirmed by elemental analysis, FT-IR, and 1H NMR techniques. Four of the synthesized compounds are analyzed by X-ray single crystal diffraction technique. Whereas N,N-dimethyl-N′-(4-fluorobenzoylthiourea, N,N-diethyl-N′-(4-fluorobenzoylthiourea, and N,N-di-n-butyl-N′-(4-fluorobenzoyl thiourea crystallize in the monoclinic system, bis(N,N-di-n-propyl-N′-(4-fluorobenzoylthioureato nickel(II complex crystallizes in the triclinic system. These ligand molecules form dimers through strong intermolecular hydrogen bonds such as N–H⋯S, C–H⋯O, and N–H⋯O. Moreover, there are different types of intramolecular interactions in the crystal structures. Bis(N,N-dimethyl-N′-(4-fluorobenzoylthioureato nickel(II complex has a nearly square-planar coordination. The distance of nickel atom from the best plane through the coordination sphere is 0.029 Å.

  11. Benzaldehyde thiosemicarbazone derived from limonene complexed with copper induced mitochondrial dysfunction in Leishmania amazonensis.

    Directory of Open Access Journals (Sweden)

    Elizandra Aparecida Britta

    Full Text Available BACKGROUND: Leishmaniasis is a major health problem that affects more than 12 million people. Treatment presents several problems, including high toxicity and many adverse effects, leading to the discontinuation of treatment and emergence of resistant strains. METHODOLOGY/PRINCIPAL FINDINGS: We evaluated the in vitro antileishmanial activity of benzaldehyde thiosemicarbazone derived from limonene complexed with copper, termed BenzCo, against Leishmania amazonensis. BenzCo inhibited the growth of the promastigote and axenic amastigote forms, with IC(50 concentrations of 3.8 and 9.5 µM, respectively, with 72 h of incubation. Intracellular amastigotes were inhibited by the compound, with an IC(50 of 10.7 µM. BenzCo altered the shape, size, and ultrastructure of the parasites. Mitochondrial membrane depolarization was observed in protozoa treated with BenzCo but caused no alterations in the plasma membrane. Additionally, BenzCo induced lipoperoxidation and the production of mitochondrial superoxide anion radicals in promastigotes and axenic amastigotes of Leishmania amazonensis. CONCLUSION/SIGNIFICANCE: Our studies indicated that the antileishmania activity of BenzCo might be associated with mitochondrial dysfunction and oxidative damage, leading to parasite death.

  12. Adsorption of copper (II) by using derived-farmyard and poultry manure biochars: Efficiency and mechanism

    Science.gov (United States)

    Batool, Saima; Idrees, Muhammad; Hussain, Qaiser; Kong, Jie

    2017-12-01

    Biochar (BC) has recently become an attractive adsorbent for the removal of toxic metals from aqueous media. In this study, the adsorption efficiency of BCs derived through farmyard and poultry manure (DBC-FYM, DBC-PM) for the removal of copper (Cu2+) from water was evaluated. The porosity, surface structure, internal morphology, thermal stability and functional groups of the DBCs were analyzed using different analytical techniques such as scanning electron microscopy (SEM), X-ray photon spectroscopy (XPS), thermogravimetric analyses (TGA) and fourier transmission infrared spectroscopy (FTIR). Kinetics and isothermal data were acquired by batch adsorption mode. The isothermal sorption data was well correlated (R2 > 0.98) with the Freundlich model describing multilayer sorption of Cu2+ on heterogeneous DBCs surface. The maximum Cu2+ sorption was estimated as 44.50 mg/g for DBC-FYM and 43.68 mg/g for DBC-PM. The sorption data followed the pseudo-second order kinetics, indicating the chemical interaction between Cu2+ and the negative charged surface of DBCs. The thermodynamic parameters indicated that the reaction was exothermic and spontaneous. Post-sorption analysis of the DBCs by XPS suggested the formation of CuO and carbonate dihydroxide. The outcomes of the present study indicated that DBCs could be valuable green sorbents for removing Cu2+ from contaminated aqueous media.

  13. Crystal structures of triazine-3-thione derivatives by reaction with copper and cobalt salts.

    Science.gov (United States)

    López-Torres, Elena; Mendiola, Maria Antonia; Pastor, César J

    2006-04-03

    The reaction of 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione L1H2OCH3 with copper(II) chloride leads to the formation of an organic molecule L2 containing two triazine rings linked by a new S-S bond. A binuclear copper(II) complex, 1, containing L1 is also isolated. The reaction of L1H2OCH3 with copper(I) chloride yields a hexanuclear cluster of copper(I), 2, in which the copper atoms form a distorted octahedron with the ligand L1 acting as an NS chelate and sulfur bridge, giving to the copper ion a trigonal geometry by one N and two S atoms. In any reaction of the disulfide L2 with metal salts, complexes containing this molecule are isolated. Reactions with copper(I) and copper(II) chloride and nickel(II) and cadmium(II) nitrate produce the S-S bond cleavage, giving complexes containing the triazine L1 behaving as the NS anion, which show spectroscopic characteristics identical with those formed by reaction with L1H2OCH3. However, the reaction with cobalt(II) nitrate gives a low-spin octahedral cobalt(III) complex, in which an asymmetric rupture of the disulfide L2 has been produced, giving an unexpected complex with a new ligand and keeping the S-S bond.

  14. Removal of Copper ions from aqueous solutions using polymer derivations of poly (styrene-alt-maleic anhydride

    Directory of Open Access Journals (Sweden)

    Naser Samadi

    2017-06-01

    Full Text Available In this study chelating resins have been considered to be suitable materials for the recovery of Copper (II ions in water treatments. Furthermore, these modified resins were reacted with 1,2-diaminoethane in the presence of ultrasonic irradiation for the preparation of a tridimensional chelating resin on the Nano scale for the recovery of Copper (II ions from aqueous solutions. This method which is used for removing and determining Copper (II ions using copolymers derived resins of poly (styrene-alternative-maleic anhydride (SMA and atomic absorption spectroscopy. The method is simple, sensitive, inexpensive and fast. The various parameters such as pH, contact time, concentrations of metal ions, mass of resin, and agitation speed were investigated on adsorption effect. The adsorption behavior of Copper (II ions were investigated by the synthesis of chelating resins at various pHs. The prepared resins showed a good tendency for removing the selected metal ions from aqueous solution, even at an acidic pH. Also, the prepared resins were examined for the removal of Copper (II ions from real samples such as industrial wastewater and were shown to be very efficient at adsorption in the cases of Copper (II ions. The pseudo-first-order, pseudo-second-order, and intra-particle diffusion kinetics equations were used for modeling of adsorption data and it was shown that pseudo-second-order kinetic equation could best describe the adsorption kinetics. The intra-particle diffusion study revealed that external diffusion might be involved in this case. The resins were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction analysis.

  15. Phthalocyanine Blends Improve Bulk Heterojunction Solar Cells

    Science.gov (United States)

    Varotto, Alessandro; Nam, Chang-Yong; Radivojevic, Ivana; Tomé, Joao; Cavaleiro, José A.S.; Black, Charles T.; Drain, Charles Michael

    2010-01-01

    A core phthalocyanine platform allows engineering the solubility properties the band gap; shifting the maximum absorption toward the red. A simple method to increase the efficiency of heterojunction solar cells uses a self-organized blend of the phthalocyanine chromophores fabricated by solution processing. PMID:20136126

  16. Inhibition of corrosion of copper in nitric acid solution by some arylmethylene cyanothioacetamide derivatives

    Science.gov (United States)

    Fouda, A. S.; Mohamed, A. K.; Mostafa, H. A.

    1998-01-01

    The inhibition of corrosion of copper in 2M HNO3 solution by some arylmethylene cyanothioacetamide derivatives was tested using polarization measurements. The results showed that these compounds act as mixed type inhibitors and inhibition efficiencies up to 90% can be obtained. The inhibition was assumed to occur via physical adsorption of the inhibitor molecules fitting a Frumkin isotherm. The influence of the substituent group on the inhibition efficiency of the inhibitor was explained in terms of the density of the electron cloud on the cyanothioacetamide moiety and the mode of adsorption. The increase in temperature was found to increase the corrosion in absence and in presence of inhibitors. Some thermodynamic functions were also computed and discussed. L'inhibition de la corrosion du cuivre dans des solutions 2M HNO3 par quelques dérivés d'arylméthylène cyanothioacétamides a été testée par des mesures de polarisation. Les résultats montrent que ces composés se comportent comme des inhibiteurs mixtes. Des efficacités d'inhibition jusqu'à 90 % peuvent être obtenues. L'inhibition est supposée se produire par l'adsorption des molécules d'inhibiteur suivant une isotherme de Frumkin. L'influence de groupe substituant sur l'efficacité de l'inhibiteur a été interprétée en terme de densité du nuage électronique sur la partie cyanothioacétamide et de mode d'adsorption. L'augmentation de la température augmente la corrosion en l'absence et en présence d'inhibiteur. Certaines fonctions thermodynamiques ont également été calculées et discutées.

  17. Synthesis, characterization and toxicity studies of pyridinecarboxaldehydes and L-tryptophan derived Schiff bases and corresponding copper (II) complexes

    Science.gov (United States)

    Malakyan, Margarita; Babayan, Nelly; Grigoryan, Ruzanna; Sarkisyan, Natalya; Tonoyan, Vahan; Tadevosyan, Davit; Matosyan, Vladimir; Aroutiounian, Rouben; Arakelyan, Arsen

    2016-01-01

    Schiff bases and their metal-complexes are versatile compounds exhibiting a broad range of biological activities and thus actively used in the drug development process. The aim of the present study was the synthesis and characterization of new Schiff bases and their copper (II) complexes, derived from L-tryptophan and isomeric (2-; 3-; 4-) pyridinecarboxaldehydes, as well as the assessment of their toxicity in vitro. The optimal conditions of the Schiff base synthesis resulting in up to 75-85% yield of target products were identified. The structure-activity relationship analysis indicated that the location of the carboxaldehyde group at 2-, 3- or 4-position with regard to nitrogen of the pyridine ring in aldehyde component of the L-tryptophan derivative Schiff bases and corresponding copper complexes essentially change the biological activity of the compounds. The carboxaldehyde group at 2- and 4-positions leads to the higher cytotoxic activity, than that of at 3-position, and the presence of the copper in the complexes increases the cytotoxicity. Based on toxicity classification data, the compounds with non-toxic profile were identified, which can be used as new entities in the drug development process using Schiff base scaffold. PMID:28344771

  18. 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.

  19. Copper(II)-selective membrane electrode based on a recently synthesized naphthol-derivative Schiff's base

    Energy Technology Data Exchange (ETDEWEB)

    Alizadeh, N.; Ershad, S. [Dept. of Chemistry, Tarbiat Moderres Univ., Tehran (Iran); Naeimi, H.; Sharghi, H. [Dept. of Chemistry, Shiraz Univ. (Iran); Shamsipur, M. [Dept. of Chemistry, Razi Univ., Kermanshah (Iran)

    1999-11-01

    A PVC membrane electrode for copper(II) ions based on a recently synthesized naphthol-derivative Schiff's base as membrane carrier was prepared. The sensor exhibits a Nernstian response for Cu{sup 2+} ions over a wide concentration range (5.0 x 10{sup -6}-5.0 x 10{sup -2} mol/L) with a detection limit of 3.1 x 10{sup -6} mol/L (0.2 {mu}g/mL). It has a very short response time of about 5 s and can be used for 3 months without any divergence in potential. The proposed electrode revealed good selectivities over a wide variety of other cations including alkali, alkaline earth, transition and heavy metal ions and could be used in a pH range of 4.0-7.0. It was successfully applied to the direct determination and potentiometric titration of copper ion. (orig.)

  20. An assessment of the application factor used to derive the saltwater acute ambient water quality copper criterion.

    Science.gov (United States)

    Arnold, W Ray; Cotsifas, Jeffrey S

    2008-04-01

    The basis for all US Environmental Protection Agency (USEPA) acute ambient water quality criteria is the chemical specific final acute value (FAV; an estimate of the concentration of the chemical corresponding to a cumulative probability of 0.05 of acute toxicity values for all genera with which acceptable acute tests have been conducted). The acute criterion for all chemicals is equal to the chemical's FAV divided by an application factor of 2. The intention of dividing the FAV by a factor of 2 is to convert the acute toxicity value to an incipient acute toxicity value, resulting in an acute criterion concentration that will protect against toxic effects to aquatic organisms. In the case of copper (Cu) in saltwater, the FAV is reduced from the normal 0.05 probability to equal to the genus mean acute value (GMAV; the geometric mean of copper effect concentration 50% [EC50] values) of the economically important marine bivalves of the genus Mytilus. Analyses to determine an application factor specific to Mytilus and copper were performed to assess the adequacy of the application factor of 2. An estimate of a dissolved copper application factor that is specific to and protective of Mytilus was determined using the results of sixty-four 48-h embryo survival and shell development copper toxicity tests of natural water samples collected from sites around the United States. A variety of point-estimate effects concentrations (EC1, EC5, EC10, EC20, and chronic values [ChV]) and statistical toxic-effect endpoints (no observed effect concentration [NOEC] and lowest observed effect concentration [LOEC]) were derived from the test results and compared. The most similar toxic effect endpoint estimates were EC1 approximately equal to NOEC, EC10 approximately equal to ChV, and EC20 approximately equal to LOEC. Probabilistic methods were used to determine a specific application factor with a high probability of providing protection. This analysis suggests that an application factor

  1. Antibacterial activity of agricultural waste derived wollastonite doped with copper for bone tissue engineering.

    Science.gov (United States)

    Azeena, S; Subhapradha, N; Selvamurugan, N; Narayan, S; Srinivasan, N; Murugesan, R; Chung, T W; Moorthi, A

    2017-02-01

    Bioactive ceramic materials with metal ions generation brought great attention in the class of biomaterials development and widely employed as a filler material for bone tissue regeneration. The present study aimed to fabricate calcium silicate based ceramic material doped with copper metal particles by sol-gel method. Rice straw of agricultural waste was utilized as a source material to synthesize wollastonite, then wollastonite was doped with copper to fabricate copper doped wollastonite (Cu-Ws) particles. The synthesized materials were subjected to physio-chemical characterization by TEM, DLS, FTIR, XRD and DSC analysis. It was found that the sizes of the WS particles was around 900nm, while adding copper the size was increased upto 1184nm and the addition of copper to the material sharpening the peak. The release of Cu ions was estimated by ICP analysis. The anti-bacterial potentiality of the particles suggested that better microbial growth inhibition against E. coli (Gram negative) and S. aureus (Gram positive) strains from ATCC, in which the growth inhibition was more significant against S. aureus. The biocompatibility in mouse Mesenchymal Stem cells (mMSC) showed the non-toxic effect up to 0.05mg/ml concentration while the increase in concentration was found to be toxic to the cells. So the particles may have better potential application with the challenging prevention of post implantation infection in the field of bone tissue engineering (BTE). Copyright © 2016. Published by Elsevier B.V.

  2. Hybrid copper complex-derived conductive patterns printed on polyimide substrates

    Science.gov (United States)

    Lee, Byoungyoon; Jeong, Sooncheol; Kim, Yoonhyun; Jeong, Inbum; Woo, Kyoohee; Moon, Jooho

    2012-06-01

    We synthesized new copper complexes that can be readily converted into highly conductive Cu film. Mechanochemical milling of copper (I) oxide suspended in formic acid resulted in the submicron-sized Cu formate together Cu nanoparticles. The submicrometer-sized Cu formates are reactive toward inter-particle sintering and metallic Cu seeds present in the Cu complexes assist their decomposition and the nucleation of Cu. The hybrid copper complex film printed on polyimide substrate is decomposed into dense and uniform Cu layer after annealing at 250 °C for 30 min under nitrogen atmosphere. The resulting Cu film exhibited a low resistivity of 8.2 μΩ·cm and good adhesion characteristics.

  3. 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.

  4. 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.

  5. Physico-chemical characterization and anti- microbial activity of copper(II complexes with 2-amino and 2-methylbenzimidazole derivatives

    Directory of Open Access Journals (Sweden)

    Podunavac-Kuzmanović Sanja O.

    2004-01-01

    Full Text Available Copper(II chloride, in warm ethanolic solution, reacted with 2-amino and 2-methylbenzimidazole derivatives to give complexes of the formula CuL2Cl2·nH2O, where L=1-benzyl-2-aminobenzimidazole 1-(4-methylbenzyl-2-aminobenzimidazole, 1-benzyl-2-methylbenzimidazole and 1-(4-methylbenzyl-2-methylbenzimidazole( n=1 or 2. The complexes were characterized by elemental analysis of the metal, molar conductivity magnetic susceptibility measurements and IR spectra. The molar conductivities of copper(IIcomplexes in dimethyl formamide (DMF corresponding to a 1:1 type of electrolyte indicate that in all the complexes one of the coordinated chloride ions has been replaced by DMF molecule. The room temperature effective magnetic moments and IR data of the complexes suggest that all Cu(II complexes have a tetrahedral configuration, which is realized by participation of the pyridine nitrogen of two organic ligand molecules and two chloride anions. The antimicrobial activity of the ligands and their complexes against Pseudomonas aeruginosa, Bacillus sp. Staphylococcus aureus, Sarcina lutea and Saccharomyces cerevisiae was investigated. The effect of copper complexation on the ligand antimicrobial activity is discussed.

  6. Synthesis, structural study and electrochemical properties of copper(II complexes derived from benzene- and p-toluenesulphonylhydrazones

    Directory of Open Access Journals (Sweden)

    A. REGUIG

    2003-02-01

    Full Text Available The synthesis and characterization of benzene- and p-toluenesulphonylhydrazones derived from salicylaldehyde and 2-hydroxy-1-naphthaldehyde and their Cu(II complexes are reported. The compounds were characterized on the basis of elemental analyses, electronic and IR spectra, magnetic moments, and conductance measurements. The electrochemical behavior of the Cu(II complexes was investigated in DMSO by cyclic voltammetry (CV, rotating disc electrode (RDE and coulometry. The oxidative polymerization of the copper complexes on a glassy carbon electrode was carried out in DMSO.

  7. Luminescence and physical properties of copper doped CdO derived nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Benhaliliba, M., E-mail: bmost_31@yahoo.fr [Physics Department, Sciences Faculty, Oran University of Sciences and Technology USTOMB, BP1505 Oran (Algeria); Benouis, C.E. [Physics Department, Sciences Faculty, Oran University of Sciences and Technology USTOMB, BP1505 Oran (Algeria); Tiburcio-Silver, A. [ITT-DIEE, Apdo, Postal 20, Metepec 3, 52176, Estado de Mexico (Mexico); Yakuphanoglu, F. [Firat University, Physics Department, Faculty of Sciences and Arts, 23119, Elazig (Turkey); Avila-Garcia, A.; Tavira, A. [Cinvestav-IPN, Departamento de Ingenieria Electrica-SEES, Apdo. postal 14-740, 07000 Mexico, D.F. (Mexico); Trujillo, R.R. [Centro de Investigacion en Dispositivos Semiconductores-BUAP 14 Sur y Av. San Claudio, C.U. Puebla, Pue. Mexico (Mexico); Mouffak, Z. [Department of Electrical and Computer Engineering California State University, Fresno, CA (United States)

    2012-10-15

    In this paper, we studied the photoluminescence (PL), the morphological, electrical and optical properties of pure and copper-doped cadmium oxide. CdO films were grown by a facile sol-gel spin coating process at 1200 rpm, and doped with copper at 2 and 3%. A (1 1 1)-oriented cubic structure with a lattice parameter of a=4.69 A was confirmed by X-ray diffraction. Copper was shown to improve the optical transmittance in the short wavelength range of the visible spectrum. The optical band gap of CdO ranged between 2.49 and 2.62 eV as a result of Cu content. At room temperature, resistance fell drastically with Cu doping levels. AFM analysis of samples exhibited nano-mounts and nanowires. Finally, PL results showed a strong blue-violet emission peak at 2.80 eV. Highlights: Black-Right-Pointing-Pointer Pure and copper doped CdO have been synthesized by a facile sol-gel route at fixed speed 1200 rpm. Black-Right-Pointing-Pointer Structural properties of pure and doped CdO were studied in details. Black-Right-Pointing-Pointer Transmittance in UV-vis and IR spectra were investigated. Optical band gaps were determined. Black-Right-Pointing-Pointer Atomic force microscope surface morphology has been analyzed and grain sizes and height were determined. Black-Right-Pointing-Pointer Room temperature resistance was measured. Pure and copper doped CdO photoluminescence has been achieved at ambient. Electrical measurement was complemented by Hall effect measurement in the aim to re-evaluate the resistivity and the carrier mobility.

  8. Synthesis and Characterization of Rare Earth Corrole-Phthalocyanine Heteroleptic Triple-Decker Complexes.

    Science.gov (United States)

    Lu, Guifen; Li, Jing; Yan, Sen; Zhu, Weihua; Ou, Zhongping; Kadish, Karl M

    2015-06-15

    We recently reported the first example of a europium triple-decker tetrapyrrole with mixed corrole and phthalocyanine macrocycles and have now extended the synthetic method to prepare a series of rare earth corrole-phthalocyanine heteroleptic triple-decker complexes, which are characterized by spectroscopic and electrochemical methods. The examined complexes are represented as M2[Pc(OC4H9)8]2[Cor(ClPh)3], where Pc = phthalocyanine, Cor = corrole, and M is Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), or Tb(III). The Y(III) derivative with OC4H9 Pc substituents was obtained in too low a yield to characterize, but for the purpose of comparison, Y2[Pc(OC5H11)8]2[Cor(ClPh)3] was synthesized and characterized in a similar manner. The molecular structure of Eu2[Pc(OC4H9)8]2[Cor(ClPh)3] was determined by single-crystal X-ray diffraction and showed the corrole to be the central macrocycle of the triple-decker unit with a phthalocyanine on each end. Each triple-decker complex undergoes up to eight reversible or quasireversible one-electron oxidations and reductions with E1/2 values being linearly related to the ionic radius of the central ions. The energy (E) of the main Q-band is also linearly related to the radius of the metal. Comparisons are made between the physicochemical properties of the newly synthesized mixed corrole-phthalocyanine complexes and previously characterized double- and triple-decker derivatives with phthalocyanine and/or porphyrin macrocycles.

  9. Gas sensing applications of phthalocyanine thin films

    Science.gov (United States)

    Starke, Thomas

    This thesis reports an investigation into the NO2 sensing properties of copper phthalocyanine (CuPc) thin films at room temperature in air. The gas sensing properties of the CuPc films were investigated using electrical conductivity and surface acoustic wave (SAW) sensing devices. Conductivity and SAW sensors were employed to detect changes of the film properties upon NO2 exposure in electrical conductivity and mass loading respectively. Initially, the response of electrical conductivity and SAW sensors incorporating an untreated layer of CuPc was investigated. Laser illumination of the films during the sensing experiments was found to have a significant effect on the mass loading response but little effect on the change in electrical conductivity. From these experiments it was suggested that NO2 adsorption on CuPc may be dominated by two different mechanisms, surface adsorption and bulk diffusion. It was also suggested that a reduction of one of these components would lead to a more controllable response. In order to minimise the effect of bulk diffusion, some of the CuPc films were doped with NO2 after deposition so filling the strongly bound bulk adsorption sites. In other devices, cooling of the CuPc layer in liquid nitrogen was used after deposition to change the surface structure in order to facilitate bulk diffusion. It was shown that these post-deposition treatment significantly changed the response characteristics of the CuPc film. Response kinetics of the experiments were analysed using the Langmuir and Elovich adsorption models, a method was suggested to determine the concentration of NO2 within the first few minutes of exposure using the value for the maximum rate of current change. A good correlation between this value and the concentration was found.

  10. Antimicrobial and anticancer photodynamic activity of a phthalocyanine photosensitizer with N-methyl morpholiniumethoxy substituents in non-peripheral positions.

    Science.gov (United States)

    Dlugaszewska, Jolanta; Szczolko, Wojciech; Koczorowski, Tomasz; Skupin-Mrugalska, Paulina; Teubert, Anna; Konopka, Krystyna; Kucinska, Malgorzata; Murias, Marek; Düzgüneş, Nejat; Mielcarek, Jadwiga; Goslinski, Tomasz

    2017-07-01

    Photodynamic therapy involves the use of a photosensitizer that is irradiated with visible light in the presence of oxygen, resulting in the formation of reactive oxygen species. A novel phthalocyanine derivative, the quaternary iodide salt of magnesium(II) phthalocyanine with N-methyl morpholiniumethoxy substituents, was synthesized, and characterized. The techniques used included mass spectrometry (MALDI TOF), UV-vis, NMR spectroscopy, and photocytotoxicity against bacteria, fungi and cancer cells. The phthalocyanine derivative possessed typical characteristics of compounds of the phthalocyanine family but the effect of quaternization was observed on the optical properties, especially in terms of absorption efficiency. The results of the photodynamic antimicrobial effect study demonstrated that cationic phthalocyanine possesses excellent photodynamic activity against planktonic cells of both Gram-positive and Gram-negative bacteria. The bactericidal effect was dose-dependent and all bacterial strains tested were killed to a significant degree by irradiated phthalocyanine at a concentration of 1×10(-4)M. There were no significant differences in the susceptibility of Gram-positive and Gram-negative bacteria to the applied photosensitizer. The photosensitivity of bacteria in the biofilm was lower than that in planktonic form. No correlation was found between the degree of biofilm formation and susceptibility to antimicrobial photodynamic inactivation. The anticancer activity of the novel phthalocyanine derivative was tested using A549 adenocarcinomic alveolar basal epithelial cells and the human oral squamous cell carcinoma cells derived from tongue (HSC3) or buccal mucosa (H413). No significant decrease in cell viability was observed under different conditions or with different formulations of the compound. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Enantiopure copper(II) complex of natural product rosin derivative: DNA binding, DNA cleavage and cytotoxicity.

    Science.gov (United States)

    Fei, Bao-Li; Yin, Bin; Li, Dong-Dong; Xu, Wu-Shuang; Lu, Yang

    2016-12-01

    To develop chiral anticancer drug candidates for molecular target DNA, the synthesis and characterization of a novel enantiomerically pure copper(II) complex [Cu 1 Cl 2 ] (2) of an optically pure ligand N-(pyridin-2-ylmethylene) dehydroabietylamine (1) was carried out. The coordination geometry of the copper center is a distorted square-planar arrangement. The interactions of 1 and 2 with salmon sperm DNA were investigated by viscosity measurements, UV, fluorescence and circular dichroism (CD) spectroscopic techniques. All the results reveal that 1 and 2 interacted with DNA through intercalation and 2 exhibited a higher DNA binding ability. Further, 1 and 2 could cleave supercoiled pBR322 DNA by single strand and 2 displayed stronger cleavage ability in the presence of ascorbic acid. In vitro cytotoxicity of 1 and 2 against HeLa, SiHa, HepG-2 and A431 cancer cell lines was studied using CCK-8 assay. The results indicate that 2 had a superior cytotoxicity than 1 and the widely used drug cisplatin under identical conditions. Flow cytometry analysis demonstrates 2 produced death of HeLa cancer cells through an apoptotic pathway. Cell cycle analysis shows that 2 mainly arrested HeLa cells at the S phase. A novel enantiomerically pure copper(II) complex [Cu 1 Cl 2 ] (2) of an optically pure ligand N-(pyridin-2-ylmethylene) dehydroabietylamine (1), based on natural product rosin has been synthesized. 2 has the potential to act as effective anticancer drug.

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

    Science.gov (United States)

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

    2006-09-07

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

  13. A new approach to ferrocene derived alkenes via copper-catalyzed olefination

    Directory of Open Access Journals (Sweden)

    Vasily M. Muzalevskiy

    2015-11-01

    Full Text Available A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ozcesmeci, Ibrahim [Technical University of Istanbul, Department of Chemistry, Istanbul (Turkey); Koca, Atif, E-mail: akoca@marmara.edu.tr [Marmara University, Department of Chemical Engineering, Faculty of Engineering, Istanbul (Turkey); Guel, Ahmet, E-mail: ahmetg@itu.edu.tr [Technical University of Istanbul, Department of Chemistry, Istanbul (Turkey)

    2011-05-30

    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{sub 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{sup II} and Mn{sup 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{sub 2}{sup -}-Co{sup II}Pc{sup -2}]{sup -} and [O{sub 2}{sup 2}-Co{sup II}Pc{sup -2}]{sup 2-}, MnPc forms {mu}-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.

  15. Synthesis and properties of a new nanomaterial based on copper octacarboxyphthalocyaninate

    Science.gov (United States)

    Golovashova, E. S.; Mengel', Ya. S.; Ageeva, T. A.; Kudrik, E. V.; Koifman, O. I.

    2017-12-01

    A new, highly ordered nanomaterial containing copper phthalocyaninate as the main structural unit is prepared via the interaction between copper 4,5-octacarboxyphthalocyaninate and aluminum nitrate nonahydrate in DMF. It is shown that the newly synthesized compound is an efficient catalyst for the oxidation of ascorbic acid by atmospheric oxygen.

  16. Copper(II) complexes with 2-pyridineformamide-derived thiosemicarbazones: Spectral studies and toxicity against Artemia salina

    Science.gov (United States)

    Ferraz, Karina O.; Wardell, Solange M. S. V.; Wardell, James L.; Louro, Sonia R. W.; Beraldo, Heloisa

    2009-07-01

    The copper(II) complexes [Cu(H2Am4DH)Cl 2] ( 1), [Cu(H2Am4Me)Cl 2] ( 2), [Cu(H2Am4Et)Cl 2] ( 3) and [Cu(2Am4Ph)Cl] ( 4) with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives were studied by means of infrared and EPR spectral techniques. The crystal structure of 4 was determined. The studied compounds proved to be toxic to Artemia salina, suggesting that they could present cytotoxic activity against solid tumors. Among the free thiosemicarbazones H2Am4Ph presented higher toxicity than all other compounds, which showed comparable effects. In the case of complexes 2 and 3 toxicity is probably attributable to the complex as an entity or to a synergistic effect involving the thiosemicarbazone and copper. H2Am4Ph and complexes 2 and 3 revealed to be the most promising compounds as potential antineoplasic agents.

  17. Photophysical, electrochemical, thermal and aggregation properties of new metal phthalocyanines

    Science.gov (United States)

    Jeong, Jaemyeng; Kumar, Rangaraju Satish; Mergu, Naveen; Son, Young-A.

    2017-11-01

    In this study, the synthesis of di(ethylene glycol) naphthalene substituted metal-phthalocyanines was reported. These novel phthalocyanines were characterized by elemental and spectroscopic analysis, including 1H NMR, FT-IR, UV-Vis spectral and MALDI-TOF mass data. The aggregation behavior of these phthalocyanines was examined in chloroform at different concentrations, and we confirmed that the phthalocyanines were non-aggregated. Further thermal stability, electrochemical, theoretical studies and metal sensing properties also investigated. In addition, we successfully prepared phthalocyanine (6d) blended polyurethane electrospun (ES) nanofibers.

  18. Conductivity modeling of gas sensors based on copper ...

    African Journals Online (AJOL)

    application, the use of chemical gas sensors constitutes a very attractive alternative [2]. Amongst all ... of our gas sensor device consists in a copper phthalocyanine (CuPc) thin films of 300 nm prepared by physical vapor ..... thin layer, modeling the law of conductivity evolution versus the concentration of the doping gas at ...

  19. Conductivity modeling of gas sensors based on copper ...

    African Journals Online (AJOL)

    The main objective of this work is to study the electronic conductivity of copper phthalocyanine (CuPc) thin films in presence of certain strong oxidizing gases involved in air pollution, particularly NO2, for use as gas sensor devices. To achieve this objective, the first part presents a study of the conductivity evolution of these ...

  20. 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.

  1. Peripherally and non-peripherally tetra-benzothiazole substituted metal-free zinc (II) and lead (II) phthalocyanines: Synthesis, characterization, and investigation of photophysical and photochemical properties

    Science.gov (United States)

    Demirbaş, Ümit; Göl, Cem; Barut, Burak; Bayrak, Rıza; Durmuş, Mahmut; Kantekin, Halit; Değirmencioğlu, İsmail

    2017-02-01

    In this study, novel phthalonitrile compounds bearing 2-methylbenzo[d]thiazol-5-yloxy groups (4 and 5) and their peripherally and non-peripherally tetra-substituted metal-free (6 and 7), zinc (II) (8 and 9), and lead (II) (10 and 11) phthalocyanine derivatives were synthesized and characterized for the first time. These novel compounds showed extremely good solubility in most common organic solvents. The novel phthalocyanine compounds presented excellent results from photophysical and photochemical examinations in DMF solution. Especially, the singlet oxygen quantum yield (ΦΔ) values of the substituted zinc (II) phthalocyanines indicate that these compounds have significant potential as photosensitizers in cancer treatment by the photodynamic therapy (PDT) technique. The fluorescence quenching behaviour of these novel phthalocyanine compounds by 1,4-benzoquinone (BQ) was also examined in DMF solution.

  2. 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.

  3. Catalytic and recyclability properties of phytogenic copper oxide nanoparticles derived from Aglaia elaeagnoidea flower extract

    Directory of Open Access Journals (Sweden)

    G. Manjari

    2017-07-01

    Full Text Available The phytogenic synthesis method to highly active, recoverable and recyclable heterogeneous copper oxide nanocatalyst and encapsulated within biomaterial that acts as a nontoxic and renewable source of reducing and stabilizing agent. The biosynthesized CuO NPs were characterized using UV–Vis absorption spectroscopy, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, energy dispersive X-ray spectroscopy (EDX, transmission electron microscopy (TEM and thermo gravimetric analysis-differential scanning calorimetry (TGA–DSC, techniques. The formation of CuO NPs with the size 20–45 nm range is shown in TEM image. Significantly, in aqueous phase CuO NPs have high catalytic activity for the reduction of Congo red (CR, methylene blue (MB and 4-nitrophenol (4-NP in the presence of the sodium borohydride (NaBH4 at room temperature. In addition, CuO NPs catalyst can be easily recovered by centrifugation and reused for 6 cycles with more than 90% conversion efficiency. CuO nanocatalyst, leaching after catalytic application was investigated by ICPAES (Inductively coupled plasma atomic emission spectroscopy. CuO NPs possess great prospects in reduction of pernicious dyes and nitro organic pollutants in water.

  4. Copper complexes containing thiosemicarbazones derived from 6-nitropiperonal: Antimicrobial and biophysical properties

    Science.gov (United States)

    Beckford, Floyd A.; Webb, Kelsey R.

    2017-08-01

    A series of four thiosemicarbazones from 6-nitropiperonal along with the corresponding copper complexes were synthesized. The biophysical characteristics of the complexes were investigated by the binding to DNA and human serum albumin. The binding to DNA is moderate; the binding constants run from (0.49-7.50) × 104 M- 1. In relation to HSA, the complexes interact strongly with binding constants on the order of 105 M- 1. The complexes also display antioxidant behavior as determined by the ability to scavenge diphenylpicrylhydrazyl (dpph) and nitric oxide radicals. The antimicrobial profiles of the compounds, tested against a panel of microbes including five of the ESKAPE pathogens (Staphylococcus aureus, MRSA, Escherichia coli, Klebsiella pneumoniae, MDR, Acinetobacter baumannii, Pseudomonas aeruginosa) and two yeasts (Candida albicans and Cryptococcus neoformans var. grubii), are also described. The compounds contain a core moiety that is similar to oxolinic acid, a quinolone antibiotic that targets DNA gyrase and topoisomerase (IV). The binding interaction between the complexes and these important antibacterial targets were studied by computational methods, chiefly docking studies. The calculated dissociation constants for the interaction with DNA gyrase B (from Staphylococcus aureus) range from 4.32 to 24.65 μM; the binding was much stronger to topoisomerase IV, with dissociation constants ranging from 0.37 to 1.27 μM.

  5. Photodynamic therapy of human malignant tumors: a comparative study between photohem and tetrasulfonated aluminum phthalocyanine

    Science.gov (United States)

    Stranadko, Eugeny P.; Skobelkin, Oleg K.; Litvin, Grigory D.; Astrakhankina, Tamara A.

    1996-01-01

    The analysis of the results of photodynamic therapy (PDT) for treating malignant neoplasms of the skin, mammary glands, tongue, oral mucous, lower lip, larynx, lungs, urinary bladder, rectum and other locations has been made. During 1992-1995 543 tumoral foci in 146 patients have been treated with PDT. All patients were previously treated with conventional techniques without effect or they were not treated due to contraindications either because of severe accompanying diseases or because of old age. A part of the patients had PDT because of recurrences or intradermal metastases in 1-2 years after surgical, radial or combined treatment. Two home-made preparations were used as photosensitizers: Photohem (hematoporphyrine derivative) and Photosense (aluminum sulfonated phthalocyanine). Light sources were: the argon pumped dye laser ('Innova-200,' 'Coherent') and home-made laser devices: copper-vapor laser-pumped dye laser ('Yakhroma-2,' Frjazino), gas-discharge unit 'Xenon' (wavelength 630 nm), gold-vapor laser (wavelength 627.8 nm) for Photohem; while for Photosense sessions we used solid-state laser on ittrium aluminate 'Poljus-1' (wavelength 670 mn). Up to now we have follow-up control data within 2 months and 3 years. Positive effect of PDT was seen in 92.4% of patients including complete regression of tumors in 62.3% and partial -- in 30.1%. Currently, this new perspective technique of treating malignant neoplasms is successfully being used in Russia; new photosensitizers and light sources for PDT and fluorescent tumour diagnostics are being developed as well.

  6. Copper-catalyzed domino synthesis of nitrogen heterocycle-fused benzoimidazole and 1,2,4-benzothiadiazine 1,1-dioxide derivatives.

    Science.gov (United States)

    Yang, Daoshan; An, Baojuan; Wei, Wei; Tian, Laijin; Huang, Ben; Wang, Hua

    2015-02-09

    A convenient copper-catalyzed domino method for the synthesis of nitrogen heterocycle-fused benzoimidazole and 1,2,4-benzothiadiazine 1,1-dioxides has been developed using readily available 2-bromo-N-phenylbenzenesulfonamides and benzimidazole derivatives as the starting materials. The domino process comprises an Ullmann-type N-arylation and intramolecular C-H amination. The inexpensive and efficient copper-catalyzed method should provide a new and useful strategy for for constructing novel, biologically interesting heterocycles containing benzoimidazole and 1,2,4-benzothiadiazine 1,1-dioxide motifs.

  7. Analysis of total copper, cadmium and lead in refuse-derived fuels (RDF): study on analytical errors using synthetic samples.

    Science.gov (United States)

    Skutan, Stefan; Aschenbrenner, Philipp

    2012-12-01

    Components with extraordinarily high analyte contents, for example copper metal from wires or plastics stabilized with heavy metal compounds, are presumed to be a crucial source of errors in refuse-derived fuel (RDF) analysis. In order to study the error generation of those 'analyte carrier components', synthetic samples spiked with defined amounts of carrier materials were mixed, milled in a high speed rotor mill to particle sizes <1 mm, <0.5 mm and <0.2 mm, respectively, and analyzed repeatedly. Copper (Cu) metal and brass were used as Cu carriers, three kinds of polyvinylchloride (PVC) materials as lead (Pb) and cadmium (Cd) carriers, and paper and polyethylene as bulk components. In most cases, samples <0.2 mm delivered good recovery rates (rec), and low or moderate relative standard deviations (rsd), i.e. metallic Cu 87-91% rec, 14-35% rsd, Cd from flexible PVC yellow 90-92% rec, 8-10% rsd and Pb from rigid PVC 92-96% rec, 3-4% rsd. Cu from brass was overestimated (138-150% rec, 13-42% rsd), Cd from flexible PVC grey underestimated (72-75% rec, 4-7% rsd) in <0.2 mm samples. Samples <0.5 mm and <1 mm spiked with Cu or brass produced errors of up to 220% rsd (<0.5 mm) and 370% rsd (<1 mm). In the case of Pb from rigid PVC, poor recoveries (54-75%) were observed in spite of moderate variations (rsd 11-29%). In conclusion, time-consuming milling to <0.2 mm can reduce variation to acceptable levels, even given the presence of analyte carrier materials. Yet, the sources of systematic errors observed (likely segregation effects) remain uncertain.

  8. Synthesis, characterization, MCD spectroscopy, and TD-DFT calculations of copper-metalated nonperipherally substituted octaoctyl derivatives of tetrabenzotriazaporphyrin, cis- and trans-tetrabenzodiazaporphyrin, tetrabenzomonoazaporphyrin, and tetrabenzoporphyrin.

    Science.gov (United States)

    Mack, John; Sosa-Vargas, Lydia; Coles, Simon J; Tizzard, Graham J; Chambrier, Isabelle; Cammidge, Andrew N; Cook, Michael J; Kobayashi, Nagao

    2012-12-03

    Synthesis of the title compounds has been achieved through refinement of a recently reported synthetic protocol whereby varying equivalents of MeMgBr are reacted with 1,4-dioctylphthalonitrile to produce mixtures favoring specific hybrid structures. The initially formed magnesium-metalated compounds are obtained as pure materials and include, for the first time, both isomers (cis and trans) of tetrabenzodiazaporphyrin. The compounds were demetalated to the metal-free analogues, which were then converted into the copper-metalated derivatives. The X-ray structure of the copper tetrabenzotriazaporphyrin derivative is reported. The metal-free and copper-metalated macrocycles exhibit columnar mesophase behavior, and it is found that the mesophase stability is unexpectedly reduced in the diazaporphyrin derivatives compared to the rest of the series. The results of time-dependent density functional theory calculations for the copper complexes are compared to the observed optical properties. Michl's perimeter model was used as a conceptual framework for analyzing the magnetic circular dichroism spectral data, which predicted and accounted for trends in the observed experimental spectra.

  9. Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts

    DEFF Research Database (Denmark)

    Verdaguer Casadevall, Arnau; Li, Christina W.; Johansson, Tobias Peter

    2015-01-01

    CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H-2 reduction of Cu2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Tem...

  10. Nickel(II) and copper(II) complexes with humic acid anions and their derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Ryabova, I.N. [Kazakh Academy of Science, Karaganda (Kazakhstan)

    2008-01-15

    Complexation of Ni(II) and Cu(II) in aqueous solutions with anions of humic acids, extracted from naturally oxidized coal, and with their hydroxymethyl derivatives is studied spectrophotometrically and potentiometrically. The complexation stoichiometry and the stability constants of the complexes are determined.

  11. Silicon(IV) Phthalocyanine-Decorated Cyclodextrin Vesicles as a Self-Assembled Phototherapeutic Agent against MRSA.

    Science.gov (United States)

    Galstyan, Anzhela; Kauscher, Ulrike; Block, Desiree; Ravoo, Bart Jan; Strassert, Cristian A

    2016-05-25

    The host-guest complexation of a tailored Si(IV) phthalocyanine with supramolecular β-cyclodextrin vesicles (CDV) was studied, revealing a reduced aggregation of the photoactive center upon binding to the CDV, even in aqueous environments. For this purpose, a photosensitizing unit axially decorated with one adamantyl group and one pyridinium moiety on the other side was obtained by two successive click reactions on a bis-azido-functionalized derivative of Si(IV) phthalocyanine. To evaluate its potential as a photosensitizer against antibiotic-resistant bacteria, comparative studies of the photophysical properties including absorption and emission spectroscopy, lifetimes as well as fluorescence and singlet oxygen quantum yields were determined for the Si(IV) phthalocyanine alone and upon self-assembly on the CDV surface. In vitro phototoxicity against the methicillin-resistant Staphylococcus aureus (MRSA) USA300 was evaluated, showing an almost complete inactivation.

  12. 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

  13. Langmuir Blodgett films of porphyrins and phthalocyanines

    CERN Document Server

    Portus, D

    2002-01-01

    Phthalocyanines and porphyrins have been studied for many years as bulk, thick and thin films. Their use in Langmuir and Langmuir-Blodgett films is governed by their peripheral substituents. These can enhance or reduce their ability to form 'quality' ultra-thin films. There are a number of potential and current applications for thin films of porphyrins and phthalocyanines, which include CD-R discs and gas-sensors. It is the latter that this PhD has focussed on. Ultra-thin films of phthalocyanines, porphyrins and a porphyrin/phthalocyanine hybrid dye were deposited onto glass microscope slides, gold-coated glass microscope slides and quartz crystals. These assemblies were then characterised using Ultraviolet-Visible spectroscopy, pressure-area isotherms, surface plasmon resonance and a quartz crystal microbalance to try and determine the nature of the molecules on the surface of the substrate. The thin films were exposed to chlorine gas and the change in their absorption spectrum and (in some cases) their surf...

  14. Effect of New Water-Soluble Dendritic Phthalocyanines on Human Colorectal and Liver Cancer Cell Lines

    Directory of Open Access Journals (Sweden)

    Ebru YABAŞ

    2017-08-01

    Full Text Available Human hepatocellular carcinoma (HepG2 cells and colorectal adenocarcinoma (DLD-1 cells were treated with the synthesized water soluble phthalocyanine derivatives to understand the effect of the compounds both on colorectal and liver cancer cells. The compounds inhibited cell proliferation and displayed cytotoxic effect on these cancer cell lines however; the effect of the compounds on healthy control fibroblast cell line was comparatively lower. The compounds can be employed for cancer treatment as anticancer agents.

  15. Self-diffusivity and interdiffusivity of molten aluminum-copper alloys under pressure, derived from molecular dynamics.

    Science.gov (United States)

    Rudd, Robert E; Cabot, William H; Caspersen, Kyle J; Greenough, Jeffrey A; Richards, David F; Streitz, Frederick H; Miller, Paul L

    2012-03-01

    We use molecular dynamics (MD) to simulate diffusion in molten aluminum-copper (AlCu) alloys. The self-diffusivities and Maxwell-Stefan diffusivities are calculated for AlCu mixtures using the Green-Kubo formulas at temperatures from 1000 to 4000 K and pressures from 0 to 25 GPa, along with additional points at higher temperatures and pressures. The diffusivities are corrected for finite-size effects. The Maxwell-Stefan diffusivity is compared to the diffusivity calculated from the self-diffusivities using a generalization of the Darken equation. We find that the effects of cross-correlation are small. Using the calculated self-diffusivities, we have assessed whether dilute hard-sphere and dilute Lennard-Jones models apply to the molten mixture. Neither of the two dilute gas diffusivities describes the diffusivity in molten Al and Cu. We report generalized analytic models for the self-diffusivities and interdiffusivity (mutual diffusivity) that fit the MD results well. The MD-derived transport coefficients are in good agreement with the available experimental data. We also report MD calculations of the viscosity and an analytic fit to those results. The ionic thermal conductivity is discussed briefly.

  16. Synthesis, spectroscopic characterization, X-ray study and in vitro cytotoxicity of 5-hydroxycoumarin derivatives and their copper complexes

    Science.gov (United States)

    Ostrowska, Kinga; Maciejewska, Dorota; Drzewiecka-Antonik, Aleksandra; Klepka, Marcin T.; Wolska, Anna; Dobrzycki, Łukasz; Sztokfisz, Alicja; Czajkowska, Agnieszka; Młynarczuk-Biały, Izabela

    2017-10-01

    We have synthesized a series of bromo derivatives of 5-hydroxycoumarin and two new Cu(II) complexes with 6-acetyl-8-bromo-5-hydroxy-4,7-dimethylcoumarin (L2) and 6-acetyl-3,8-dibromo-5-hydroxy-4,7-dimethylcoumarin (L3) ligands, designed as potential active compounds against human cancer cell lines. The elemental analysis, mass spectroscopy, NMR and infrared spectroscopy have been used for basic characterization of analyzed compounds. The X-ray crystal structure analysis for one representative organic compound, 3,6,8-tribromo-5-hydroxy-4,7-dimethylcoumarin (c) has been performed. It has shown that coumarin system is nearly planar and the Br⋯Br interaction is a very characteristic feature of the molecular association for organic ligands. The complexes, Cu(L2)2·3H2O and Cu(L3)(ClO4)·2.5H2O, have been found as four-coordinated and contain copper in the +2 oxidation state according to X-ray absorption spectroscopy. All the compounds have been screened in vitro for their cytotoxic activity against mouse fibroblast and human prostate cancer cells. The coordination products of brominated ligands have shown to be more active than the free ligands and demonstrate significant in-vitro cytotoxicity against human prostate cancer cells (DU145).

  17. A selective distance-based paper analytical device for copper(II) determination using a porphyrin derivative.

    Science.gov (United States)

    Pratiwi, Rimadani; Nguyen, Michael P; Ibrahim, Slamet; Yoshioka, Naoki; Henry, Charles S; Tjahjono, Daryono H

    2017-11-01

    Meso-tetrakis(1,2-dimethylpyrazolium-4-yl)porphyrin sulfonate (TDMPzP), a water-soluble porphyrin derivative, was synthesized and used as a colorimetric reagent for Cu(2+) detection on a microfluidic paper-based analytical device (µPAD) using distance-based quantification. TDMPzP showed a high selectivity for Cu(2+) detection in aqueous solutions. When Cu(2+) was added to the TDMPzP under acidic conditions, a color change from green to a pink was observed by the naked eye. Under optimized conditions, the application of this system to a distance-based μPAD exhibited good analytical response. The presence of common metal ions (Al(3+), Fe(3+), Mg(2+), Co(2+), Mn(2+), Zn(2+), Pb(2+), Cd(2+), Sn(2+), and Ni(2+)) did not interfere with Cu(2+) detection within reasonable tolerance ratios. The lowest concentration of copper that could be measured was 1mgL(-1) (1ppm) which meets the requirements for drinking water contamination regulations from the US Environmental Protection Agency (EPA) and World Health Organization (WHO) guidelines for drinking water. Real drinking water samples were analyzed to confirm the practical application of this system and the results showed good agreement with ICP-MS data. This distance-based µPAD based on TDMPzP for Cu(2+) detection is convenient and effective for real-time drinking water analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Cytotoxic activity, albumin and DNA binding of new copper(II) complexes with chalcone-derived thiosemicarbazones.

    Science.gov (United States)

    Da Silva, Jeferson G; Recio Despaigne, Angel A; Louro, Sonia R W; Bandeira, Cristiano C; Souza-Fagundes, Elaine M; Beraldo, Heloisa

    2013-07-01

    [Cu(HL)Cl2] complexes of chalcone-derived thiosemicarbazones were obtained with 3-phenyl-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCTPh), complex (1), 3-(4-chlorophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4ClPh), complex (2), 3-(4-bromophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4BrPh), complex (3), and 3-(4-nitrophenyl-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4NO2Ph), complex (4). 1-3 showed interaction with bovine serum albumin (BSA) and deoxyribonucleic acid from calf thymus (CT-DNA). The cytotoxic activities of the thiosemicarbazones and complexes (1-4) were tested against HL60 (wild type human promyelocytic leukemia), Jurkat (human immortalized line of T lymphocyte), MDA-MB 231 (human breast carcinoma) and HCT-116 (human colorectal carcinoma) tumor cell lineages. Upon coordination to copper(II) cytotoxicity significantly increased in Jurkat, MDA-MB 231 and HCT-116 cells. Unlike the free thiosemicarbazones, 1-4 induced DNA fragmentation in solid tumor cells indicating their pro-apoptotic potential. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  19. Near room temperature ferromagnetism of copper phthalocyanine thin films

    Energy Technology Data Exchange (ETDEWEB)

    Wang, XueYan, E-mail: xueyanadeline@163.com; Zheng, JianBang; Chen, Lei; Qiao, Kai; Xu, JiaWei; Cao, ChongDe

    2015-11-30

    Highlights: • The α-CuPc films without and with light Ni-doping were characterized by X-ray photoelectron spectroscopy to confirm the absence of other ferromagnetic impurities. • The α-CuPc film exhibited ferromagnetic hysteresis with saturation magnetization of ∼6.77 emu/cm{sup 3} and coercivity of ∼96 Oe at 280 K, while that of the Ni-doped α-CuPc film are ∼0.69 emu/cm{sup 3} and ∼113 Oe, respectively. • Through the density functional theory calculations, the origin of the ferromagnetism arise from Cu 3d states and N 2s2p electronic spin polarization, as well as p–d exchange coupling interactions, and spin-unbalanced electronic structure of C 2p induced by the π–π interactions. - Abstract: We reported near room temperature ferromagnetism of α-CuPc films without and with light Ni-doping. Two samples were characterized by X-ray photoelectron spectroscopy (XPS) to confirm the absence of other ferromagnetic impurities. The α-CuPc film exhibited ferromagnetic hysteresis with saturation magnetization of ∼6.77 emu/cm{sup 3} and coercivity of ∼96 Oe at 280 K, while that of the Ni-doped α-CuPc film are ∼0.69 emu/cm{sup 3} and ∼113 Oe, respectively. Through the density functional theory (DFT) calculations, the origin of the ferromagnetism arise from Cu 3d states and N 2s2p electronic spin polarization, as well as p-d exchange coupling interactions, and spin-unbalanced electronic structure of C 2p induced by the π–π interactions.

  20. Structure-Stability Relationships of Phthalocyanine Copper Complexes

    Directory of Open Access Journals (Sweden)

    G. P. Shaposhnikov

    2000-06-01

    Full Text Available The influence of NO2, Br, and COOH function substituents in various positions of Cu(IIPc on the reactivity of the latter concerning the dissociation of the metal - nitrogen bonds in proton donor solvents is discussed.

  1. Near room temperature ferromagnetism of copper phthalocyanine thin films

    Science.gov (United States)

    Wang, XueYan; Zheng, JianBang; Chen, Lei; Qiao, Kai; Xu, JiaWei; Cao, ChongDe

    2015-11-01

    We reported near room temperature ferromagnetism of α-CuPc films without and with light Ni-doping. Two samples were characterized by X-ray photoelectron spectroscopy (XPS) to confirm the absence of other ferromagnetic impurities. The α-CuPc film exhibited ferromagnetic hysteresis with saturation magnetization of ∼6.77 emu/cm3 and coercivity of ∼96 Oe at 280 K, while that of the Ni-doped α-CuPc film are ∼0.69 emu/cm3 and ∼113 Oe, respectively. Through the density functional theory (DFT) calculations, the origin of the ferromagnetism arise from Cu 3d states and N 2s2p electronic spin polarization, as well as p-d exchange coupling interactions, and spin-unbalanced electronic structure of C 2p induced by the π-π interactions.

  2. Antimicrobial Activity of Some Thiourea Derivatives and Their Nickel and Copper Complexes

    Directory of Open Access Journals (Sweden)

    Cevdet Akbay

    2009-01-01

    Full Text Available Five thiourea derivative ligands and their Ni2+ and Cu2+ complexes have been synthesized. The compounds were screened for their in vitro anti-bacterial activity using Gram-positive bacteria (two different standard strains of Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, Streptococcus pyogenes, Bacillus cereus and Gram-negative bacteria (Esherichia coli, Pseudomonas aeruginosa, Enterobacter cloacae, Proteus vulgaris, Enterobacter aerogenes and in vitro anti-yeast activity (Candida albicans, Candida krusei, Candida glabrata, Candida tropicalis, Candida parapsilosis. The minimum inhibitory concentration was determined for all ligands and their complexes. In vitro anti-yeast activity of both ligands and their metal complexes is greater than their in vitro anti-bacterial activity. The effect of the structure of the investigated compounds on the antimicrobial activity is discussed.

  3. Novel aminonaphthoquinone mannich bases derived from lawsone and their copper(II) complexes: synthesis, characterization and antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Neves, Amanda P.; Barbosa, Claudia C.; Greco, Sandro J.; Vargas, Maria D. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Inst. de Quimica; Visentin, Lorenzo C. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica; Pinheiro, Carlos B. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisica; Mangrich, Antonio S. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Centro Politecnico. Dept. de Quimica; Barbosa, Jussara P.; Costa, Gisela L. da [Instituto Oswaldo Cruz, Rio de Janeiro, RJ (Brazil)

    2009-07-01

    A series of novel Mannich bases (HL1-HL13) derived from 2-hydroxy-1,4-naphthoquinone (lawsone), substituted benzaldehydes [C{sub 6}H{sub 2}R{sup 1}R{sup 2}R{sup 3}C(O)H] and various primary amines (NH{sub 2}R{sup 4}, R{sup 4} = n-butyl, benzyl, allyl, 2-furfuryl), and their Cu{sup 2+} complexes, [Cu(L1){sub 2}]-[Cu(L13){sub 2}], have been synthesized and fully characterized by analytical and spectroscopic methods. The structures of complexes 1 (R{sup 1} R{sup 2} = R{sup 3} = H; R{sup 4} = Bu), 2 (R{sup 1} = R{sup 3} = H; R{sup 2} = NO{sub 2}; R{sup 4}= Bu) and 7 (R{sup 1} OH; R{sup 2} = R{sup 3} = H; R{sup 4}= Bu) were determined by single crystal X-ray diffraction studies. All complexes crystallize in centrosymmetric space groups, with a copper atom in the inversion centre. Two L. coordinate through the naphthalen-2-olate oxygen and secondary amine-N atoms, forming six membered chelate rings around the copper atom in a trans-N{sub 2}O{sub 2} environment; spectroscopic data confirm that the other complexes exhibit similar molecular arrangement. The antimicrobial activity of all compounds has been tested on seven different strains of bacteria: Bacillus cereus, Bacillus subtilis, Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae, Pseudomonas aeruginosa and Staphylococcus aureus. In general, Mannich bases were more active than complexes, HL11 (R{sup 1} = OH; R{sup 2} =H; R{sup 3} = Me; R{sup 4}= Bn) and HL13 (R{sup 1} = OH; R{sup 2} = H; R{sup 3} = Br; R{sup 4}= Bn) being the most potent inhibitors. The MIC for the most active compound HL11 against S. Coli was 20 {mu}mol L{sup -1} (8 {mu}g mL{sup -1}), better than Chloramphenicol (90 {mu}mol L{sup -1}) and well below most values reported for other naphthoquinones. (author)

  4. 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.

  5. 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.

  6. Photosensitizing activity of water- and lipid-soluble phthalocyanines on prokaryotic and eukaryotic microbial cells.

    Science.gov (United States)

    Bertoloni, G; Rossi, F; Valduga, G; Jori, G; Ali, H; van Lier, J E

    1992-01-01

    The photosensitizing activity of lipophilic zinc-phthalocyanine (Zn-Pc) and its water-soluble sulphonated derivative (Zn-PcS) towards Streptococcus faecium and Candida albicans was studied and correlated with the amount of cell-bound photosensitizer. With both micro-organisms Zn-PcS was more tightly bound in larger amounts than Zn-Pc in the protoplasts of the cytoplasmic membrane. As a consequence, the photoinduced damage in S. faecium initially involved membrane proteins, while DNA was modified only upon prolonged irradiation. For C. albicans only Zn-PcS showed a preferential affinity for the spheroplasts and the decrease in cell survival was not accompanied by detectable modifications of the electrophoretic pattern of membrane proteins. The photoinduced ultrastructural alteration of both micro-organisms suggests damage at membrane level. This would indicate the involvement of different targets in bacteria and yeast for phthalocyanine photosensitization.

  7. Copper Ion Attenuated the Antiproliferative Activity of Di-2-pyridylhydrazone Dithiocarbamate Derivative; However, There Was a Lack of Correlation between ROS Generation and Antiproliferative Activity

    Directory of Open Access Journals (Sweden)

    Tingting Wang

    2016-08-01

    Full Text Available The use of chelators for cancer treatment has been an alternative option. Dithiocarbamates have recently attracted considerable attention owning to their diverse biological activities; thus, the preparation of new dithiocarbamate derivatives with improved antitumor activity and selectivity as well as probing the underlying molecular mechanism are required. In this study, di-2-pyridylhydrazone dithiocarbamate S-propionic acid (DpdtpA and its copper complex were prepared and characterized, and its antiproliferative activity was evaluated. The proliferation inhibition assay showed that DpdtpA exhibited excellent antiproliferative effect in hepatocellular carcinoma (IC50 = 1.3 ± 0.3 μM for HepG2, and 2.5 ± 0.6 μM for Bel-7402. However, in the presence of copper ion, the antiproliferative activity of DpdtpA was dramatically attenuated (20–30 fold owing to the formation of copper chelate. A preliminarily mechanistic study revealed that reactive oxygen species (ROS generation mediated the antiproliferative activity of DpdtpA, and accordingly induced apoptosis, DNA cleavage, and autophagy. Surprisingly, the cytotoxicity of DpdtpA copper complex (DpdtpA–Cu was also involved in ROS generation; however, a paradoxical relation between cellular ROS level and cytotoxicity was observed. Further investigation indicated that DpdtpA could induce cell cycle arrest at the S phase; however, DpdtpA–Cu lacked this effect, which explained the difference in their antiproliferative activity.

  8. Third Derivative Spectrophotometric Method for Simultaneous Determination of Copper and Nickel Using 6-(2-Naphthyl)-2, 3-dihydro-1,2,4- triazine-3-thione

    OpenAIRE

    Maliheh Barazandeh Tehrani; Effat Souri

    2011-01-01

    A simple and sensitive derivative spectrophotometric method for simultaneous determination of nickel and copper using 6-(2- naphthyl)-2,3-dihydro-1,2,4-triazine-3-thione (NDTT) as a selective analytical reagent was developed. The complexes of metal ions with NDTT were formed immediately in basic media and extracted with chloroform. The zero-crossing measurement technique was found suitable for the direct measurement of the third-derivative value of Ni-NDTT and Cu-NDTT at 501 and 472 nm respec...

  9. 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.

  10. Application of mercapto ordered carbohydrate-derived porous carbons for trace detection of cadmium and copper ions in agricultural products.

    Science.gov (United States)

    Behbahani, Mohammad; Abolhasani, Jafar; Amini, Mostafa M; Sadeghi, Omid; Omidi, Fariborz; Bagheri, Akbar; Salarian, Mani

    2015-04-15

    In this paper, we have introduced nanoporous carbon modified with mercapto groups as a new solid-phase method for extraction of cadmium(II) and copper(II) ions. The modified nanoporous carbon sorbent was characterised by thermogravimetric analysis, differential thermal analysis, transmission electron microscopy, Fourier transform infrared spectrometry, X-ray diffraction, and nitrogen adsorption surface area (BET) measurements. Effects of pH value, flow rates, type, concentration and volume of the eluent, breakthrough volume, and effect of other ions were studied. The experimental results show that simultaneous trace cadmium(II) and copper(II) ions can be quantitatively preconcentrated at pH 6.0 with recoveries >97%. Under optimised conditions, limits of detection are 0.04 and 0.09 ng mL(-1) for the ions of cadmium and copper respectively, and the precision of the method for analysis of cadmium and copper ions (5.0 μg of each target ions, N=8) are 2.4% and 2.1%, respectively. The obtained capacities of mercapto-nanoporous carbon were found to be 145 and 95 mg g(-1) for cadmium and copper ions, respectively. The accuracy of the proposed procedure was verified by analysing standard reference material. Finally, the introduced sorbent was successfully applied for trace determination of cadmium and copper ions in food samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Derivation of ecological criteria for copper in land-applied biosolids and biosolid-amended agricultural soils.

    Science.gov (United States)

    Lu, Tao; Li, Jumei; Wang, Xiaoqing; Ma, Yibing; Smolders, Erik; Zhu, Nanwen

    2016-12-01

    The difference in availability between soil metals added via biosolids and soluble salts was not taken into account in deriving the current land-applied biosolids standards. In the present study, a biosolids availability factor (BAF) approach was adopted to investigate the ecological thresholds for copper (Cu) in land-applied biosolids and biosolid-amended agricultural soils. First, the soil property-specific values of HC5add (the added hazardous concentration for 5% of species) for Cu(2+) salt amended were collected with due attention to data for organisms and soils relevant to China. Second, a BAF representing the difference in availability between soil Cu added via biosolids and soluble salts was estimated based on long-term biosolid-amended soils, including soils from China. Third, biosolids Cu HC5input values (the input hazardous concentration for 5% of species of Cu from biosolids to soil) as a function of soil properties were derived using the BAF approach. The average potential availability of Cu in agricultural soils amended with biosolids accounted for 53% of that for the same soils spiked with same amount of soluble Cu salts and with a similar aging time. The cation exchange capacity was the main factor affecting the biosolids Cu HC5input values, while soil pH and organic carbon only explained 24.2 and 1.5% of the variation, respectively. The biosolids Cu HC5input values can be accurately predicted by regression models developed based on 2-3 soil properties with coefficients of determination (R(2)) of 0.889 and 0.945. Compared with model predicted biosolids Cu HC5input values, current standards (GB4284-84) are most likely to be less protective in acidic and neutral soil, but conservative in alkaline non-calcareous soil. Recommendations on ecological criteria for Cu in land-applied biosolids and biosolid-amended agriculture soils may be helpful to fill the gaps existing between science and regulations, and can be useful for Cu risk assessments in soils

  12. Phthalocyanine Conductors : New Trend for Crystal and Functionality Design

    OpenAIRE

    Inabe, Tamotsu; Ishikawa, Manabu; Asari, Takehiro; Hasegawa, Hiroyuki; Fujita, Akiko; Matsumura, Naoko; Naito, Toshio; Matsuda, Masaki; Tajima, Hiroyuki

    2006-01-01

    Conductors obtained from axially substituted phthalocyanine units are presented. In contrast to face-to-face one-dimensional stacking in conductors with planar phthalocyanins, various types of π−π stacking structures can be obtained owing to the slipped stacking.

  13. Third Derivative Spectrophotometric Method for Simultaneous Determination of Copper and Nickel Using 6-(2-Naphthyl-2, 3-dihydro-1,2,4- triazine-3-thione

    Directory of Open Access Journals (Sweden)

    Maliheh Barazandeh Tehrani

    2011-01-01

    Full Text Available A simple and sensitive derivative spectrophotometric method for simultaneous determination of nickel and copper using 6-(2- naphthyl-2,3-dihydro-1,2,4-triazine-3-thione (NDTT as a selective analytical reagent was developed. The complexes of metal ions with NDTT were formed immediately in basic media and extracted with chloroform. The zero-crossing measurement technique was found suitable for the direct measurement of the third-derivative value of Ni-NDTT and Cu-NDTT at 501 and 472 nm respectively. Beer’s law is obeyed in the concentration range 1-30 μg/mL for both cations with different ratios. The limit of detection was 0.26 μg/mL and 0.13 μg/mL for copper and nickel respectively. The within day and between day variations showed coefficient of variation (CV% values less than 2.80 and 2.97 for copper and nickel respectively. The error of the determination method did not exceed 6.50%. Analysis of alloy sample showed that this method can be successfully used for simultaneous determination of Cu and Ni in real samples.

  14. A biocompatible sol-gel derived titania coating for medical implants with antibacterial modification by copper integration.

    Science.gov (United States)

    Gollwitzer, Hans; Haenle, Maximilian; Mittelmeier, Wolfram; Heidenau, Frank; Harrasser, Norbert

    2018-02-19

    Implant-associated infections are dangerous complications and may cause dramatic illness with hematogeneous spread of bacteria and secondary infections. Since treatment of these infections remains most challenging and commonly requires implant removal, prevention is of utmost importance. In the present work a titania-sol was equipped with a copper salt resulting after calcination in a titania coating (TiO 2 ) with antibacterial properties combined with good cytocompatibility. In vitro tests with bacteria as well as tissue cells were carried out under corresponding conditions. Mouse fibroblasts and different staphylococcal strains were used for growth inhibition assays with serial dilutions of CuCl 2 . Cultivation on the surface of bare Ti6Al4V, TiO 2 -coated and copper-filled TiO 2 -coated Ti6Al4V samples was performed with both bacteria and tissue cells. Bacterial and cellular proliferation and mitochondrial activity were hereby determined. Coating of Ti6Al4V with pure TiO 2 significantly improved cytocompatibility compared to the uncoated alloy. In the growth inhibition assays, fibroblasts tolerated higher concentrations of copper ions than did bacteria. Nevertheless, copper integration reduced fibroblast proliferation and mitochondrial activity on the surface coating. On the other hand, integration of copper into the TiO 2 -coating significantly reduced adhesion of viable bacteria resulting in a promising combination of cytocompatibility and antibacterial properties. Additionally, significant bacterial growth inhibition by antibacterial amounts of copper was also demonstrated in the supernatant. In conclusion, the copper-loaded TiO 2 -coatings for medical implants may be a promising approach to reduce the rate of implant-associated infections.

  15. [Simultaneous determination of trace amounts of iron(II), copper(I) and cobalt(II) in aloe by second derivative peak area spectrophotometry].

    Science.gov (United States)

    Li, Hong-mei; Su, Li-hong; Chen, Rui-zhan

    2004-04-01

    A new method for simultaneous determination of iron(II), copper(I) and cobalt(II) was established by second derivative peak area spectrophotometry in chromogenic system of 1,10-phenanthroline. The method could avoid disturbing by some ions. The accuracy and sensitivity were improved. There is a linear relationship in the range of 0.0-8.5 microg x mL(-1) for Fe(II); of 0.0-7.3 microg x mL(-1) for Cu(I); and of 0.0-5.9 microg x mL(-1) for Co(II). The method has been applied to simultaneous determination of iron(II), copper(I) and cobalt(II) in aloe with satisfactory results. The average recovery is 98.6%-102% and the RSD is 0.1%-0.2%. There is no remarkable difference between these results and those of ICP-AES method.

  16. 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

  17. Dependence Properties of Sol-Gel Derived CuO@SiO2 Nanostructure to Diverse Concentrations of Copper Oxide

    Directory of Open Access Journals (Sweden)

    V. Homaunmir

    2013-01-01

    Full Text Available Various concentrations of copper oxide were embedded into silica matrix of xerogel forms using copper source Cu(NO32·3H2O. The xerogel samples were prepared by hydrolysis and condensation of tetraethyl orthosilicate (TEOS with determination of new molar ratios of the components by the sol-gel method. In this paper, three samples of copper oxide were doped into silica matrices using different concentrations. We obtained 10, 20, and 30 wt.% of copper oxide in silica matrices labeled as A, B, and C, respectively. The absorption and transmittance spectra of the gel matrices were treated at different concentrations by Uv-vis spectrophotometer. Quantities of water and transparency in the silica network change the spectral characteristics of Cu2+ ions in the host silica. Absorption spectra of the samples heated to higher concentration complete the conversion of Cu2+ ions to Cu+ ions. The effects of concentration of copper oxide were characterized by X-ray diffraction (XRD patterns, and the transmission electron microscope (TEM micrographs. Also, textural properties of samples were studied by surface area analysis (BET method at different concentrations.

  18. Ordered growth of vanadyl phthalocyanine (VOPc) on an iron phthalocyanine (FePc) monolayer.

    Science.gov (United States)

    Rochford, Luke A; Ramadan, Alexandra J; Woodruff, D Phil; Heutz, Sandrine; Jones, Tim S

    2015-11-28

    The growth and characterisation of a non-planar phthalocyanine (vanadyl phthalocyanine, VOPc) on a complete monolayer (ML) of a planar phthalocyanine (Iron(II) phthalocyanine, FePc) on an Au(111) surface, has been investigated using ultra-high vacuum (UHV) scanning tunnelling microscopy (STM) and low energy electron diffraction (LEED). The surface mesh of the initial FePc monolayer has been determined and shown to correspond to an incommensurate overlayer, not commensurate as previously reported. Ordered islands of VOPc, with (1 × 1) epitaxy, grow on the FePc layer at submonolayer coverages. The individual VOPc molecules occupy sites directly atop the underlying FePc molecules, indicating that significant intermolecular bonding must occur. It is proposed that this interaction implies that the V[double bond, length as m-dash]O points down into the surface, allowing a Fe-O bond to form. The detailed appearance of the STM images of the VOPc molecules is consistent with previous studies in other VOPc growth studies in which this molecular orientation has been proposed.

  19. 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

  20. Synthesis of Copper-Chelates Derived from Amino Acids and Evaluation of Their Efficacy as Copper Source and Growth Stimulator for Lactuca sativa in Nutrient Solution Culture.

    Science.gov (United States)

    Kaewchangwat, Narongpol; Dueansawang, Sattawat; Tumcharern, Gamolwan; Suttisintong, Khomson

    2017-11-15

    Five tetradentate ligands were synthesized from l-amino acids and utilized for the synthesis of Cu(II)-chelates 1-5. The efficacy of Cu(II)-chelates as copper (Cu) source and growth stimulator in hydroponic cultivation was evaluated with Lactuca sativa. Their stability test was performed at pH 4-10. The results suggested that Cu(II)-chelate 3 is the most pH tolerant complex. Levels of Cu, Zn, and Fe accumulated in plants supplied with Cu(II)-chelates were compared with those supplied with CuSO 4 at the same Cu concentration of 8.0 μM. The results showed that Cu(II)-chelate 3 significantly enhanced Cu, Zn, and Fe content in shoot by 35, 15, and 48%, respectively. Application of Cu(II)-chelate 3 also improved plant dry matter yield by 54%. According to the results, Cu(II)-chelate 3 demonstrated the highest stimulating effect on plant growth and plant mineral accumulation so that it can be used as an alternative to CuSO 4 for supplying Cu in nutrient solutions and enhancing the plant growth.

  1. Complexes cobalt(II, zinc(II and copper(II with some newly synthesized benzimidazole derivatives and their antibacterial activity

    Directory of Open Access Journals (Sweden)

    S. O. PODUNAVAC-KUZMANOVIC

    1999-05-01

    Full Text Available The preparation and properties of some complexes of cobalt(II, zinc(II and copper(II with several newly synthesized benzimidazole derivatives (L are reported. The complexes, of the general formula [MCl2L2] (M=Co(II, Zn(II and [CuCl2L(H2O], have a tetrahedral structure. The complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility measurements, IR and absorption electronic spectra. The antibacterial activitiy of the benzimidazoles and their complexes was evaluated against Erwinia carotovora subsp. carotovora and Erwinia amylovora. The complexes were found to be more toxic than the ligands.

  2. 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

  3. Semiconducting thin films of fluorinated and unsubstituted phthalocyanines for applications in organic field effect transistors

    Energy Technology Data Exchange (ETDEWEB)

    Brinkmann, Harry; Keil, Christopher; Schlettwein, Derck [Institute of Applied Physics, Justus-Liebig-University Giessen (Germany); Tsaryova, Olga; Woehrle, Dieter [Institute of Organic and Macromolecular Chemistry, University of Bremen (Germany)

    2010-07-01

    Perfluorinated phthalocyanines (F{sub 16}Pc) show n-type characteristics as active layers in organic field transistors while organic field transistors with unsubstituted phthalocyanines (Pc) exhibit p-type characteristics. The growth of F{sub 16}Pc and Pc films has been studied in OFETs on organic (polyimide, PMMA) and inorganic insulating layers (SiO{sub 2}) with different surface modifications (HMDS treatments). We report here about the dependence of the growth mode of the films and the field effect mobility on the used substrate for the copper complexes. The development of the electrical conduction was studied in-situ during film growth and the field effect mobility was determined for various film thicknesses in different regimes of the Stranski-Krastanov growth mechanism that led to the formation of ultrathin conductive layers in the monolayer range followed by reorganization towards island growth. Optical absorbance was measured in reflection or transmission in dependence of the used substrate to investigate details of the intermolecular coupling.

  4. Formation of highly toxic hydrogen cyanide upon ruby laser irradiation of the tattoo pigment phthalocyanine blue

    Science.gov (United States)

    Schreiver, Ines; Hutzler, Christoph; Laux, Peter; Berlien, Hans-Peter; Luch, Andreas

    2015-08-01

    Since laser treatment of tattoos is the favored method for the removing of no longer wanted permanent skin paintings, analytical, biokinetics and toxicological data on the fragmentation pattern of commonly used pigments are urgently required for health safety reasons. Applying dynamic headspace—gas chromatography with mass spectrometric detection (DHS—GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC—ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension. Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue. Further, for the first time we introduce pyrolysis-GC/MS as method suitable to simulate pigment fragmentation that may occur spontaneously or during laser removal of organic pigments in the living skin of tattooed people. According to the literature such regular tattoos hold up to 9 mg pigment/cm2 skin.

  5. 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.

  6. A novel ferrocenic copper(II) complex Salen-like, derived from 5-chloromethyl-2-hydroxyacetophenone and N-ferrocenmethylaniline: Design, spectral approach and solvent effect towards electrochemical behavior of Fc+/Fc redox couple

    OpenAIRE

    Ouennoughi, Yasmina; Karce, Houssam Eddine; Aggoun, Djouhra; Lanez, Touhami; Ruiz-Rosas, Ramiro; Bouzerafa, Brahim; Ourari, Ali; Morallon, Emilia

    2017-01-01

    This paper reports the synthesis, spectroscopic characterizations and electrochemical behavior of the obtained tetradentate copper (II)-Schiff base complex with its two wings as ferrocenylaniline moieties. This new ferrocenic derivative with two ferrocenylaniline entities surrounding the copper (II)-Salen complex (5) was synthesized by reacting N-ferrocenmethyl-N-phenyl-5-aminomethyl-2-hydroxyacetophenone (3) with one half equivalent of 1,2-diaminoethane in absolute ethanol. As for the interm...

  7. 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.

  8. Delivery of a hydrophobic phthalocyanine photosensitizer using PEGylated gold nanoparticle conjugates for the in vivo photodynamic therapy of amelanotic melanoma

    OpenAIRE

    Camerin, Monica; Moreno, Miguel; Marín, María J.; Schofield, Claire L; Chambrier, Isabelle; Cook, Michael J; Coppellotti, Olimpia; Jori, Giulio; Russell, David A.

    2016-01-01

    Photodynamic therapy (PDT) is a treatment of cancer whereby tumours are destroyed by reactive oxygen species generated upon photoactivation of a photosensitizer drug. Hydrophobic photosensitizers are known to be ideal for PDT; however, their hydrophobicity necessitates that they are typically administered using emulsions. Here, a delivery vehicle for photodynamic therapy based on the co-self-assembly of both a Zn(ii)-phthalocyanine derivative photosensitizer and a polyethylene glycol (PEG) de...

  9. Syntheses of Octasubstituted Metal Phthalocyanines for Nonlinear Optics

    Science.gov (United States)

    Guo, Huaisong; Townsend, Cheryl; Sanghadasa, Mohan; Amai, Robert L. S.; Clark, Ronald D.; Penn, Benjamin

    1998-01-01

    Many organic materials can be used as nonlinear optical media. Phthalocyanines are of special interest because they show an unusually large third order nonlinear response, they are thermally and photochemically stable and they can be formed into oriented thin films (Langmuir-Blodgett films). They also can be easily complexed by a large variety of metals, which place them at the interface between organics and organometallics, and allows for fine tuning of the macro cycle electronic properties by the coordinated metal and substituent groups. A series of 1,4,8,11,15,18,22,25-octaalkoxy metal-free and metal phthalocyanines and 2,3,9,10,16,17,23,24-octaalkoxy metal phthalocyanines has been synthesized. Their nonlinear optical properties have been measured. The physical properties of all the phthalocyanines synthesized in this work are subject to both acid and solvent effects.

  10. Photodynamic response of an endothelial hybridoma cell line using zinc(II) tetrasubstituted phthalocyanines

    Science.gov (United States)

    Cruse-Sawyer, Janet E.; Dixon, B.; Roberts, David J.; Griffiths, John; Brown, Stanley B.

    1995-03-01

    The EAhy 926 cell is a hybridoma line derived from human endothelium and A549/8 cells. They display stable endothelial characteristics and may provide an indication of how endothelial cells respond to photodynamic therapy. Cells were grown as monolayers, seeded at a density of 104 cells/35 mm dish, and then incubated with zinc (II) tetrasubstituted phthalocyanines (carboxylated, sulphonated, pyridinium or diethanolamine sulphonamide). After 24 hours, the cells were illuminated with laser light at 680 nm or 692 nm as appropriate. The response to each photosensitizer was evaluated using cell proliferation, clonogenicity, and release of tissue factor.

  11. Synthesis and photophysical studies of phthalocyanine-gold nanoparticle conjugates.

    Science.gov (United States)

    Nombona, Nolwazi; Antunes, Edith; Litwinski, Christian; Nyokong, Tebello

    2011-11-28

    This work reports on the synthesis, characterization and photophysical studies of phthalocyanine-gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.

  12. Automated synthesis of a 96 product-sized library of triazole derivatives using a solid phase supported copper catalyst.

    Science.gov (United States)

    Jlalia, Ibtissem; Beauvineau, Claire; Beauvière, Sophie; Onen, Esra; Aufort, Marie; Beauvineau, Aymeric; Khaba, Eihab; Herscovici, Jean; Meganem, Faouzi; Girard, Christian

    2010-04-28

    This article deal with the parallel synthesis of a 96 product-sized library using a polymer-based copper catalyst that we developed which can be easily separated from the products by simple filtration. This gave us the opportunity to use this catalyst in an automated chemical synthesis station (Chemspeed ASW-2000). Studies and results about the preparation of the catalyst, its use in different solvent systems, its recycling capabilities and its scope and limitations in the synthesis of this library will be addressed. The synthesis of the triazole library and the very good results obtained will finally be discussed.

  13. Synthesis, Crystal Structure, and Characterization of Ternary Copper(II Complex Derived from N-(salicylidene-L-valine

    Directory of Open Access Journals (Sweden)

    Sundaramurthy Santha Lakshmi

    2016-01-01

    Full Text Available Ternary Schiff base copper(II complex [CuL(tmpda] (where H2L is N-(salicylidene-L-valine; tmpda is N,N,N′,N′-tetramethyl-1,3-propanediamine has been characterized by UV-Vis., FTIR, and single crystal XRD. The crystal structure displays a distorted square pyramidal geometry in which Schiff base is bonded to the Cu(II ion via phenolate oxygen, imine nitrogen, and an oxygen atom of the carboxylate group through the basal plane and the chelating diamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, displays an axial and equatorial mode of binding via NN-donor atoms.

  14. Synthesis, characterization and structure of nickel and copper compounds containing ligands derived from keto-enehydrazines and their catalytic application for aerobic oxidation of alcohols.

    Science.gov (United States)

    Gaona, Miguel Ángel; Montilla, Francisco; Álvarez, Eleuterio; Galindo, Agustín

    2015-04-14

    Ligand precursors HL(R,Ph) (R = Me, Ph) were synthesised by condensation of acetylacetone and the corresponding N,N-substituted hydrazines and were characterised spectroscopically and structurally. Both in the solid state and in solution they behave as (Z)-keto-enehydrazines and this was confirmed by DFT calculations which showed that this form was the most stable of their possible tautomers. The reaction of HL(R,Ph) compounds with copper acetate and nickel acetate in EtOH afforded the corresponding complexes [M(L(R,Ph))2] (M = Cu, Ni; R = Me, Ph). The methyl-substituted derivatives were structurally characterised by X-ray methods. A four-coordinate environment around the metal centre, where the two L(Me,Ph) ligands act as bidentate N,O-chelators and lie in a pseudo-trans conformation, was found for both compounds. The dihedral angle between the two six-membered metallacycles M(L(Me,Ph)) was 0° for nickel, a typical square planar coordination, meanwhile it was 23° for copper, a square planar slightly distorted to pseudotetrahedral coordination. Copper complexes [Cu(L(R,Ph))2] were tested as catalysts, in combination with TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl radical), for the aerobic oxidation of 4-nitrobenzyl alcohol as the model reaction. An almost complete conversion to the corresponding aldehyde was observed after 1 h at 60 °C and 1 bar of dioxygen, in toluene as the solvent. Importantly, air at atmospheric pressure was also observed to be appropriate for the oxidation, although longer reaction times were required. After the optimization of the reaction conditions, the study was extended to other alcohol substrates and good catalytic activity was found for benzylic-type alcohols, while low yield was found for 1-octanol.

  15. Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine.

    Science.gov (United States)

    Barreto, Wagner J; Barreto, Sônia R G; Ando, Rômulo A; Santos, Paulo S; DiMauro, Eduardo; Jorge, Thiago

    2008-12-15

    The anionic complexes [Cu(L(1-))3](1-), L(-)=dopasemiquinone or L-dopasemiquinone, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the nuCC+nuCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g=2.0005 and g=2.0923, and for Cu(II) with g=2.008 and g=2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease.

  16. Copper(II) complexes with 4-hydroxyacetophenone-derived acylhydrazones: Synthesis, characterization, DNA binding and cleavage properties

    Science.gov (United States)

    Gup, Ramazan; Gökçe, Cansu; Aktürk, Selçuk

    2015-01-01

    Two new Cu(II) complexes of Schiff base-hydrazone ligands, hydroxy-N‧-[(1Z)-1-(4-hydroxyphenyl)ethylidene]benzohydrazide [H3L1] and ethyl 2-(4-(1-(2-(4-(2-ethoxy-2-oxoethoxy)benzoyl)hydrazono)ethyl)phenoxy)acetate (HL2) have been synthesized and then characterized by microcopy and spectral studies. X-ray powder diffraction illustrates that [Cu(L2)2] complex is crystalline in nature whereas [Cu(H2L1)2]·2H2O has an amorphous structure. Binding of the copper complexes with Calf thymus DNA (CT-DNA) has been investigated by UV-visible spectra, exhibiting non-covalent binding to CT-DNA. DNA cleavage experiments have been also investigated by agarose gel electrophoresis in the presence and absence of an oxidative agent (H2O2). The effect of complex concentration on the DNA cleavage reaction has been also studied. Both copper complexes show nuclease activity, which significantly depends on concentrations of the complexes, in the presence of H2O2 through oxidative mechanism whereas they slightly cleavage DNA in the absence an oxidative agent.

  17. Spin doping using transition metal phthalocyanine molecules

    Science.gov (United States)

    Atxabal, A.; Ribeiro, M.; Parui, S.; Urreta, L.; Sagasta, E.; Sun, X.; Llopis, R.; Casanova, F.; Hueso, L. E.

    2016-12-01

    Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale.

  18. 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.

  19. 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.

  20. 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

  1. Biphenyl derived oxovanadium(IV) and copper(II) salen-type complexes--structure and redox tuning.

    Science.gov (United States)

    Plitt, Patrick; Pritzkow, Hans; Oeser, Thomas; Kraemer, Roland

    2005-05-01

    A series of vanadyl(IV) salen (N,N'-bis(salicylidene)ethylenediaminato)-type complexes (1-4) bearing phenyl or 2-hydroxyphenyl moieties have been prepared and characterized by means of mass spectrometry, infra-red, electron paramagnetic resonance (EPR), UV/Vis spectroscopy, cyclovoltammetry and X-ray crystallography. Their structures have been compared to their copper(II) analogs 5-8. Hydrogen intralinkages have been observed in the crystal structure of 5. The pendant hydroxy groups fine-tune the redox properties of the complexes. The catalytic activity in the oxygenation of ethyl phenyl sulfide to the corresponding sulfoxide was investigated. Results indicate that complex 1 bearing hydroxyphenyl subunits and a phenylene bridge is the most selective under these reaction conditions, with the smallest amount of the over-oxidized product, sulfone.

  2. Copper(II) complexes derived from di-2-pyridyl ketone- N4-phenyl-3-semicarbazone: Synthesis and spectral studies

    Science.gov (United States)

    Reena, T. A.; Kurup, M. R. Prathapachandra

    2010-08-01

    Five copper(II) complexes [CuLCl] 2·CuCl 2·4H 2O ( 1), [CuLOAc] ( 2), [CuLNO 3] 2 ( 3), [CuLN 3] ( 4) and [CuLNCS]·3/2H 2O ( 5) of di-2-pyridyl ketone- N4-phenyl-3-semicarbazone (HL) were synthesized and characterized by elemental analyses and electronic, infrared and EPR spectral techniques. In all these complexes the semicarbazone undergoes deprotonation and coordinates through enolate oxygen, azomethine and pyridyl nitrogen atoms. All the complexes are EPR active due to the presence of an unpaired electron. EPR spectra of all the complexes in DMF at 77 K suggest axial symmetry and the presence of half field signals for the complexes 1 and 3 indicates dimeric structures.

  3. ANTINFLAMMATORY ACTIVITY OF AN N, N'-DISALICYLIDENEMETHYLENDIAMINE-DERIVED SCHIFF BIS BASE AND ITS COPPER(II) COMPLEX.

    Science.gov (United States)

    Tântaru, Gladiola; Nechifor, M; Apostu, M; Vieriu, Mădălina; Panainte, Alina Diana; Bibire, Nela

    2015-01-01

    The cooper(II) complex combination of N, N'-disalicylidenemethylenediamine and the Schiff bis base were investigated for anti-inflammatory activity. In vivo, the anti-inflammatory activity of the metallic complex in comparison with the activity of the Schiff bis base was tested by the method of Winter and co-workers using the Levy technique. Our study on the anti-inflammatory activity of a new Schiff bis base and its complex cooper(II) combination showed that the Schiff bis bases exhibited significant anti-inflammatory action in acute experimental inflammation when compared to the control group. The copper cation from the complex combination enhanced the anti-inflammatory effect of the Schiff bis base, the effect being stronger at doses of 10 mg/kg cooper(II) complex. The Schiff bis base and its cooper(II) complex had an anti-inflammatory effect comparable to that of indomethacin.

  4. Highly efficient photodynamic therapy colloidal system based on chloroaluminum phthalocyanine/pluronic micelles.

    Science.gov (United States)

    Py-Daniel, Karen R; Namban, Joy S; de Andrade, Laise R; de Souza, Paulo E N; Paterno, Leonardo G; Azevedo, Ricardo B; Soler, Maria A G

    2016-06-01

    Phthalocyanine derivatives comprise the second generation of photosensitizer molecules employed in photodynamic therapy (PDT) and have attracted much attention due to their outstanding photosensitizing performance. Most phthalocyanines are hydrophobic compounds that require association to drug delivery systems for clinical use. In this study, formulations of Pluronic F127 micelles incorporated with chloroaluminum phthalocyanine, or else F127/AlClPc, were produced at optimized conditions aiming at efficient and biocompatible PDT colloidal systems. Absorption/emission spectroscopies, as well as dynamic light scattering were performed to evaluate the optimum conditions for the F127 micelle formation and AlClPc incorporation. The micelles formation was attained with F127 concentrations ranging from 50 to 150mgmL(-1). At these conditions, AlClPc photosensitizer molecules were encapsulated into the hydrophobic micelle core and, therefore, readily solubilized in physiological medium (PBS pH 7.2). Encapsulation efficiency of about 90% resulted from different AlClPc concentrations. Identification of singlet oxygen production by irradiated F127/AlClPc formulations indicated good applicability for PDT. In vitro tests conducted with A549 human lung carcinoma cell line incubated with the F127/AlClPc formulations, at different AlClPc loadings, followed by only 18min of light irradiation (660nm LED, fluence of 25.3J/cm(2)), showed a cellular damage as high as 90% for rather low dosages of AlClPc (0.1-5.0μgmL(-1)). Further, no cytotoxicity occurred on non-irradiated cells. These findings suggest those F127/AlClPc formulations are highly promising for PDT applications, since they are easily prepared and the incubation and irradiation times are significantly shortened. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Iron Oxide-Supported Copper Oxide Nanoparticles (Nanocat-Fe-CuO): Magnetically Recyclable Catalysts for the Synthesis of Pyrazole Derivatives, 4-Methoxyaniline, and Ullmann-type Condensation Reactions

    Science.gov (United States)

    An efficient and benign protocol is reported for the synthesis of 4-methoxyaniline, medicinally important pyrazole derivatives, and Ullmann-type condensation reaction using magnetically separable and reusable magnetite-supported copper (nanocat-Fe-CuO) nanoparticles under mild co...

  6. Pharmaceutical development, composition and quantitative analysis of phthalocyanine as the photosensitizer for cancer photodynamic therapy.

    Science.gov (United States)

    Jiang, Zhou; Shao, Jingwei; Yang, Tingting; Wang, Jian; Jia, Lee

    2014-01-01

    Phthalocyanine (Pc) and its related derivatives are a class of functional materials that are easily activated by the light at a special wavelength. As such photosensitizer, Pc has been applied to photodynamic therapy (PDT), in addition to its broad applications in many fields, for both malignant and benign diseases. One of our long-term research focuses is to develop Pc for cancer therapy. Herein we briefly review mechanisms of action of Pc used for photodynamic therapy, its pharmaceutical development and molecular modification to enhance its drugability and improve its intracellular localization. We also describe the current status of the Pc derivatives under clinical investigation, and analyze the methods used for quantitative analysis of those Pc derivatives. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Third-order nonlinear optical properties of metal dithiolene- and phthalocyanine-doped sol-gel materials

    Science.gov (United States)

    Gall, Gavin J.; King, Terence A.; Oliver, Stephen N.; Capozzi, Carol A.; Seddon, Angela B.; Hill, Callum A. S.; Underhill, Allan E.

    1994-10-01

    Recent studies on metal dithiolene complexes in solution and PMMA have shown this range of materials to exhibit high third-order nonlinear optical coefficients, (Chi) 3, and excellent figures of merit. Phthalocyanine dyes have been shown to exhibit optical limiting due to the nonlinear effect of reverse saturable absorption. We report here on the third-order nonlinear optical characterization of several metal dithiolene and phthalocyanine compounds doped in sol-gel derived materials. These hosts provide a physically and chemically stable environment for the nonlinear compounds, and offer the potential of high levels of doping. The dithiolene and phthalocyanine compounds were incorporated into partially densified sol-gel silica glass (xerogels) by the post-doping technique, and into the hybrid organic-inorganic materials at the sol-stage. To obtain optical quality surfaces on the porous xerogel, a unique polishing technique has been developed. Picosecond and nanosecond pulsed laser studies of nonlinear refraction and absorption are presented, together with laser damage and micro-hardness measurements. For the dithiolenes, concentrations of the order of 1018 molecules/cm3 for both the hybrid material and the xerogel were studied using the degenerate four wave mixing (DFWM) technique. (Chi) 3 values up to 1.4 X 10-19 m2/V2 (equivalent to 1.0 X 10-11 esu) were observed in the sol-gel host.

  8. 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.

  9. Copper transport.

    Science.gov (United States)

    Linder, M C; Wooten, L; Cerveza, P; Cotton, S; Shulze, R; Lomeli, N

    1998-05-01

    In adult humans, the net absorption of dietary copper is approximately 1 mg/d. Dietary copper joins some 4-5 mg of endogenous copper flowing into the gastrointestinal tract through various digestive juices. Most of this copper returns to the circulation and to the tissues (including liver) that formed them. Much lower amounts of copper flow into and out of other major parts of the body (including heart, skeletal muscle, and brain). Newly absorbed copper is transported to body tissues in two phases, borne primarily by plasma protein carriers (albumin, transcuprein, and ceruloplasmin). In the first phase, copper goes from the intestine to the liver and kidney; in the second phase, copper usually goes from the liver (and perhaps also the kidney) to other organs. Ceruloplasmin plays a role in this second phase. Alternatively, liver copper can also exit via the bile, and in a form that is less easily reabsorbed. Copper is also present in and transported by other body fluids, including those bathing the brain and central nervous system and surrounding the fetus in the amniotic sac. Ceruloplasmin is present in these fluids and may also be involved in copper transport there. The concentrations of copper and ceruloplasmin in milk vary with lactational stage. Parallel changes occur in ceruloplasmin messenger RNA expression in the mammary gland (as determined in pigs). Copper in milk ceruloplasmin appears to be particularly available for absorption, at least in rats.

  10. pH-Responsive Dimeric Zinc(II) Phthalocyanine in Mesoporous Silica Nanoparticles as an Activatable Nanophotosensitizing System for Photodynamic Therapy.

    Science.gov (United States)

    Wong, Roy C H; Chow, Sun Y S; Zhao, Shirui; Fong, Wing-Ping; Ng, Dennis K P; Lo, Pui-Chi

    2017-07-19

    An acid-cleavable acetal-linked zinc(II) phthalocyanine dimer with an azido terminal group (cPc) was prepared and conjugated to alkyne-modified mesoporous silica nanoparticles via copper(I)-catalyzed alkyne-azide cycloaddition reaction. For comparison, an amine-linked analogue (nPc) was also prepared as a non-acid-cleavable counterpart. These dimeric phthalocyanines were significantly self-quenched due to the close proximity of the phthalocyanine units inside the mesopores, resulting in much weaker fluorescence emission and singlet oxygen generation, both in N,N-dimethylformamide and in phosphate-buffered saline (PBS), compared with the free molecular counterparts. Under acidic conditions in PBS, the cPc-encapsulated nanosystem was activated in terms of fluorescence emission and singlet oxygen production. After internalization into human colon adenocarcinoma HT29 cells, it exhibited much higher intracellular fluorescence and photocytotoxicity compared to the nanosystem entrapped with nPc. The activation of this nanosystem was also demonstrated in tumor-bearing nude mice. The intratumoral fluorescence intensity increased gradually over 24 h, while for the nPc counterpart the fluorescence remained very weak. The results suggest that this nanosystem serves as a promising activatable nanophotosensitizing agent for photodynamic therapy.

  11. Tunable charge transfer properties in metal-phthalocyanine heterojunctions.

    Science.gov (United States)

    Siles, P F; Hahn, T; Salvan, G; Knupfer, M; Zhu, F; Zahn, D R T; Schmidt, O G

    2016-04-28

    Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.

  12. Copper hypersensitivity

    DEFF Research Database (Denmark)

    Fage, Simon W; Faurschou, Annesofie; Thyssen, Jacob P

    2014-01-01

    hypersensitivity, a database search of PubMed was performed with the following terms: copper, dermatitis, allergic contact dermatitis, contact hypersensitivity, contact sensitization, contact allergy, patch test, dental, IUD, epidemiology, clinical, and experimental. Human exposure to copper is relatively common...

  13. Structure-matched Phthalocyanine Ion Pair as a Red-emitting Fluorescent Optical Probe for the Analysis of Sodium Dodecylbenzenesulfonate with High Specificity and Sensitivity.

    Science.gov (United States)

    Yu, Fei; Guo, Menglin; Deng, Yabin; Lu, Yin; Chen, Lin; Huang, Ping; Li, Donghui

    2016-01-01

    We have found that a positively charged cationic copper phthalocyanine, Alcian blue (Alcian blue 8GX), can efficiently quench the fluorescence of an oppositely charged red fluorescent phthalocyanine compound with a matched molecular structure, tetrasulfonated aluminum phthalocyanine (AlS4Pc), because of the formation of an ion pair complex (AlS4Pc-Alcian blue 8GX) that exhibits almost no fluorescence. An investigation was carried out on the fluorescence recovery of AlS4Pc-Alcian blue 8GX caused by a series of anionic surfactants containing a sulfonic group (sodium dodecylbenzenesulfonate (SDBS), sodium lauryl sulfate (SLS), and sodium dodecyl sulfate (SDS)). The results showed that SDBS exhibited a significant response, and the highest sensitivity among the surfactants. Due to its high efficiency of fluorescence quenching and the high level of fluorescence recovery, direct observes can even be performed by the naked eye. The results revealed that the Alcian blue 8GX-AlS4Pc ion-pair complex fluorescent probe only responded to SDBS in the low-concentration range. Based on the new founding, this study proposed a novel principle and method of fluorescence enhancement to specifically measure the concentration of SDBS, thereby achieving a highly sensitive and highly specific determination of SDBS. Under the optimal conditions, the fluorescence intensity (I(f)) of the system and the concentration of SDBS in the range of 1 × 10(-7) - 1 × 10(-5) mol/dm(3) exhibited a good linear relationship. This method is highly sensitive, and the operation is simple and rapid. It had been applied for the quantitative analysis of SDBS in environmental water, while achieving satisfactory results compared with those of the standard method. This study developed a new application of the fluorescent phthalocyanine compounds used as molecular probes in analytical sciences.

  14. Synthesis, characterization and antifungal activity of a series of manganese(II) and copper(II) complexes with ligands derived from reduced N,N'-O-phenylenebis(salicylideneimine).

    Science.gov (United States)

    Belaid, Sabrina; Landreau, Anne; Djebbar, Safia; Benali-Baitich, Ouassini; Bouet, Gilles; Bouchara, Jean-Philippe

    2008-01-01

    A series of manganese(II) and copper(II) complexes with reduced Schiff bases derived from o-phenylenediamine has been prepared and characterized by elemental analysis, TG measurements, ESR, magnetic measurements, FTIR, UV-Visible spectra and conductivity. These complexes were found to be [MnL(H2O)n] and [CuL](H2O)n species with n=0-2. Their antifungal activity was evaluated on different human fungi including yeasts of the Candida genus (C. albicans, C. glabrata, C. tropicalis and C. parapsilopsis) some opportunistic moulds belonging to the Aspergillus (A. fumigatus, A. terreus and A. flavus), Scedosporium genus (S. apiospermum and S. prolificans) and some dermatophytes (M. gypseum, M. persicolor, T. mentagrophytes, M. canis and T. tonsurans). The manganese complexes showed a significant growth inhibition of the dermatophytes tested and fungi of the genus Scedosporium. This is very interesting as these fungi are usually poorly susceptible to current antifungal including Amphotericin B and Itraconazole chosen as reference in this study.

  15. Excited-State Deactivation of Branched Phthalocyanine Compounds.

    Science.gov (United States)

    Zhu, Huaning; Li, Yang; Chen, Jun; Zhou, Meng; Niu, Yingli; Zhang, Xinxing; Guo, Qianjin; Wang, Shuangqing; Yang, Guoqiang; Xia, Andong

    2015-12-21

    The excited-state relaxation dynamics and chromophore interactions in two phthalocyanine compounds (bis- and trisphthalocyanines) are studied by using steady-state and femtosecond transient absorption spectral measurements, where the excited-state energy-transfer mechanism is explored. By exciting phthalocyanine compounds to their second electronically excited states and probing the subsequent relaxation dynamics, a multitude of deactivation pathways are identified. The transient absorption spectra show the relaxation pathway from the exciton state to excimer state and then back to the ground state in bisphthalocyanine (bis-Pc). In trisphthalocyanine (tris-Pc), the monomeric and dimeric subunits are excited and the excitation energy transfers from the monomeric vibrationally hot S1 state to the exciton state of a pre-associated dimer, with subsequent relaxation to the ground state through the excimer state. The theoretical calculations and steady-state spectra also show a face-to-face conformation in bis-Pc, whereas in tris-Pc, two of the three phthalocyanine branches form a pre-associated face-to-face dimeric conformation with the third one acting as a monomeric unit; this is consistent with the results of the transient absorption experiments from the perspective of molecular structure. The detailed structure-property relationships in phthalocyanine compounds is useful for exploring the function of molecular aggregates in energy migration of natural photosynthesis systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Encapsulation of phthalocyanine supramolecular stacks into virus-like particles

    NARCIS (Netherlands)

    Brasch, M.; de la Escosura, Andrés; Ma, Y.; Uetrecht, Charlotte; Heck, Albert J.R.; Torres, Tomás; Cornelissen, Jeroen Johannes Lambertus Maria

    2011-01-01

    We report herein the encapsulation of a water-soluble phthalocyanine (Pc) into virus-like particles (VLPs) of two different sizes, depending on the conditions. At neutral pH, the cooperative encapsulation/templated assembly of the particles induces the formation of Pc stacks instead of Pc dimers,

  17. Porphyrin-phthalocyanine nanorods (P-PcNR) formed by ...

    African Journals Online (AJOL)

    ... tetra {2,(3)-(2-mercaptopyridine) phthalocyaninato}(MTSPyPc). The transmission electron microscope (TEM) images of the colloid suspension of the aggregate confirmed formation of nanorods while their electron spectra showed that the molecules formed J-aggregation. Keywords: Porphyrin, Phthalocyanine, Nanorods, ...

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

    Indian Academy of Sciences (India)

    Administrator

    which have been an active focus of intense research for the development of efficient light-to-energy con- version devices. Moreover, phthalocyanine mole- cules have unique properties in terms of light absorption in the far visible region of the solar spec- trum (λ = 690 nm) with molecular extinction coeffi- cients (ε) higher than ...

  20. Axially Ligated Phthalocyanine Conductors with Magnetic Moments

    Directory of Open Access Journals (Sweden)

    Tamotsu Inabe

    2017-04-01

    Full Text Available This mini-review describes electrical conductivity, magnetic properties, and magnetotransport properties of one-dimensional partially oxidized salts composed of axially ligated phthalocyanines, TPP[M(Pc(CN2]2 (TPP = tetraphenylphosphonium, Pc = phthalocyaninato, with M of Fe (d5, S = 1/2 and Cr (d3, S = 3/2. These salts are isomorphous, and π–π interactions in the crystal, that becomes the origin of the charge carriers, are nearly the same. Both the Fe and Cr salts show carrier localization and charge disproportionation which is enhanced by the interaction between local magnetic moments and conduction π-electrons (π–d interaction. However, the magnetic properties are slightly different between them. M = Fe has been found to show unique anisotropic magnetic properties and antiferromagnetic short-range magnetic order between the d-spins. On the other hand, for M = Cr, its magnetic moment is isotropic. Temperature dependence of the magnetic susceptibility shows typical Curie–Weiss behavior with negative Weiss temperature, but the exchange interaction is complicated. Both M = Fe and M = Cr show large negative magnetoresistance, reflecting the difference in the anisotropy. The magnetoresistance ratio (MR is larger in the Fe system than in the Cr system in the low magnetic field range, but MR in the Cr system exceeds that in the Fe system when the magnetic field becomes higher than 15 T. We discuss the mechanism of the giant negative magnetoresistance with reference to the d–d, π–d, and π–π interactions.

  1. Silicon phthalocyanine 4 phototoxicity in Trichophyton rubrum.

    Science.gov (United States)

    Lam, Minh; Dimaano, Matthew L; Oyetakin-White, Patricia; Retuerto, Mauricio A; Chandra, Jyotsna; Mukherjee, Pranab K; Ghannoum, Mahmoud A; Cooper, Kevin D; Baron, Elma D

    2014-06-01

    Trichophyton rubrum is the leading pathogen that causes long-lasting skin and nail dermatophyte infections. Currently, topical treatment consists of terbinafine for the skin and ciclopirox for the nails, whereas systemic agents, such as oral terbinafine and itraconazole, are also prescribed. These systemic drugs have severe side effects, including liver toxicity. Topical therapies, however, are sometimes ineffective. This led us to investigate alternative treatment options, such as photodynamic therapy (PDT). Although PDT is traditionally recognized as a therapeutic option for treating a wide range of medical conditions, including age-related macular degeneration and malignant cancers, its antimicrobial properties have also received considerable attention. However, the mechanism(s) underlying the susceptibility of dermatophytic fungi to PDT is relatively unknown. As a noninvasive treatment, PDT uses a photosensitizing drug and light, which, in the presence of oxygen, results in cellular destruction. In this study, we investigated the mechanism of cytotoxicity of PDT in vitro using the silicon phthalocyanine (Pc) 4 [SiPc(OSi(CH3)2(CH2)3N(CH3)2)(OH)] in T. rubrum. Confocal microscopy revealed that Pc 4 binds to cytoplasmic organelles, and upon irradiation, reactive oxygen species (ROS) are generated. The impairment of fungal metabolic activities as measured by an XTT (2,3-bis[2-methoxy-4-nitro-5-sulfophenyl]-2H-tetrazolium-5-carboxyanilide inner salt) assay indicated that 1.0 μM Pc 4 followed by 670 to 675 nm light at 2.0 J/cm(2) reduced the overall cell survival rate, which was substantiated by a dry weight assay. In addition, we found that this therapeutic approach is effective against terbinafine-sensitive (24602) and terbinafine-resistant (MRL666) strains. These data suggest that Pc 4-PDT may have utility as a treatment for dermatophytosis. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

  2. Luminescent copper(ı) (pseudo)halide complexes with neocuproine and a novel bulky tris (aminomethyl) phosphine derived from 2-piperazinopyridine

    Energy Technology Data Exchange (ETDEWEB)

    Starosta, Radosław, E-mail: radoslaw.starosta@chem.uni.wroc.pl; Komarnicka, Urszula K.; Puchalska, Małgorzata

    2013-11-15

    A novel bulky phosphine derived from 2-piperazinopyridine P(CH{sub 2}N(CH{sub 2}CH{sub 2}){sub 2}N-2-py){sub 3} (1) and its chalcogenide derivatives (oxide, sulfide and selenide) have been synthesized and characterized by elemental analysis, NMR spectroscopy and mass spectrometry. Next, two new copper(I) iodide or isothiocyanate complexes with 1 and 2,9-dimethyl-1,10-phenanthroline (dmp): [CuI(dmp)(1)] (1I) and [CuNCS(dmp)(1)] (1T), have been also synthesized and characterized by elemental analysis and studied by NMR, UV–vis, IR and luminescence spectroscopies. The X-ray structure of the complex 1T·1.81(CH{sub 3}COCH{sub 3}) was determined. The coordination geometry around the Cu(I) center is pseudo-tetrahedral with distortions resulting mostly from the molecular packing in the crystal cell. Both complexes exhibit orange photoluminescence in the solid state, which is much stronger for 1I than for 1T. The luminescence spectra of both complexes at room and 77 K temperatures show relatively large bands with a typical batochromic shift accompanying the lowering of the temperature. On the basis of TDDFT calculations we interpreted these bands as of (MX,MPR{sub 3})LCT type resulting mainly from the transitions from the copper–iodine (or isothiocyanate) bonds and a small admixture of copper–phosphine bonds to antibonding orbitals of dmp diimine. Highlights: • A novel tris(aminomethyl)phosphine is obtained from 2-piperazinopyridine • Two new CuI and CuNCS complexes with dmp and a novel phosphine are presented. • An X-ray structure of one of the complexes is characterized. • Solid-state UV–vis and luminescence spectra of the complexes are discussed. • Main absorbance and luminescence bands are of (MX,MPR{sub 3})LCT type.

  3. Mononuclear nickel (II) and copper (II) coordination complexes supported by bispicen ligand derivatives: Experimental and computational studies

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Nirupama; Niklas, Jens; Poluektov, Oleg; Van Heuvelen, Katherine M.; Mukherjee, Anusree

    2017-01-01

    The synthesis, characterization and density functional theory calculations of mononuclear Ni and Cu complexes supported by the N,N’-Dimethyl-N,N’-bis-(pyridine-2-ylmethyl)-1,2-diaminoethane ligand and its derivatives are reported. The complexes were characterized by X-ray crystallography as well as by UV-visible absorption spectroscopy and EPR spectroscopy. The solid state structure of these coordination complexes revealed that the geometry of the complex depended on the identity of the metal center. Solution phase characterization data are in accord with the solid phase structure, indicating minimal structural changes in solution. Optical spectroscopy revealed that all of the complexes exhibit color owing to d-d transition bands in the visible region. Magnetic parameters obtained from EPR spectroscopy with other structural data suggest that the Ni(II) complexes are in pseudo-octahedral geometry and Cu(II) complexes are in a distorted square pyramidal geometry. In order to understand in detail how ligand sterics and electronics affect complex topology detailed computational studies were performed. The series of complexes reported in this article will add significant value in the field of coordination chemistry as Ni(II) and Cu(II) complexes supported by tetradentate pyridyl based ligands are rather scarce.

  4. Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18 O Labeling.

    Science.gov (United States)

    Lum, Yanwei; Ager, Joel W

    2018-01-08

    Oxide-derived (OD) Cu catalysts have high selectivity towards the formation of multi-carbon products (C2 /C3 ) for aqueous electrochemical CO2 reduction (CO2 R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing 18 O-enriched OD Cu catalysts and testing them for CO2 R. These catalysts maintain a high selectivity towards C2 /C3 products (ca. 60 %) for up to 5 h in 0.1 m KHCO3 at -1.0 V vs. RHE. However, secondary-ion mass spectrometry measurements show that only a small fraction (CO2 R. Furthermore, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sergeeva, Alena S., E-mail: alenasergeeva@mail.ru [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation); Fraunhofer Institute for Cell Therapy and Immunology, Branch Bioanalytics and Bioprocesses (Fraunhofer IZI-BB), Muehlenberg 13, 14476 Potsdam (Germany); Volkova, Elena K., E-mail: ekvolkova87@rambler.ru [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation); Bratashov, Daniil N., E-mail: dn2010@gmail.com [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation); Shishkin, Mikhail I., E-mail: shishkin1mikhail@gmail.com [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation); Atkin, Vsevolod S., E-mail: ceba91@list.ru [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation); Markin, Aleksey V., E-mail: markinav@mail.ru [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation); Skaptsov, Aleksandr A., E-mail: skaptsov@yandex.ru [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation); Volodkin, Dmitry V., E-mail: dmitry.volodkin@izi-bb.fraunhofer.de [Fraunhofer Institute for Cell Therapy and Immunology, Branch Bioanalytics and Bioprocesses (Fraunhofer IZI-BB), Muehlenberg 13, 14476 Potsdam (Germany); Gorin, Dmitry A., E-mail: gorinda@mail.ru [Saratov State University, Astrakhanskaya 83, 410012 Saratov (Russian Federation)

    2015-05-29

    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.

  6. Synthesis of an ABCD-Type Phthalocyanine by Intramolecular Cyclization Reaction.

    Science.gov (United States)

    Chow, Sun Y S; Ng, Dennis K P

    2016-07-01

    Unsymmetrical phthalocyanines with a low symmetry can exhibit unique and intriguing properties that can facilitate their applications in certain disciplines. The synthesis of these compounds, however, has posed a great difficulty. A novel and unprecedented approach for phthalocyanine synthesis is reported that involves intramolecular cyclization of prelinked tetrakisphthalonitriles. By using this strategy, the first ABCD-type phthalocyanine has been prepared in 7.2% yield.

  7. Peptides derived from the copper-binding region of lysyl oxidase exhibit antiangiogeneic properties by inhibiting enzyme activity: an in vitro study.

    Science.gov (United States)

    Mohankumar, Arun; Renganathan, Bhuvanasundar; Karunakaran, Coral; Chidambaram, Subbulakshmi; Konerirajapuram Natarajan, Sulochana

    2014-11-01

    Despite the rigorous research on abnormal angiogenesis, there is a persistent need for the development of new and efficient therapies against angiogenesis-related diseases. The role of Lysyl oxidase (LOX) in angiogenesis and cancer has been established in prior studies. Copper is known to induce the synthesis of LOX, and hence regulates its activity. Hypoxia-induced metastasis is dependent on LOX expression and activity. It has been believed that the inhibition of LOX would be a therapeutic strategy to inhibit angiogenesis. To explore this, we designed peptides (M peptides) from the copper-binding region of LOX and hypothesized them to modulate LOX. The peptides were characterized, and their copper-binding ability was confirmed by mass spectrometry. The M peptides were found to reduce the levels of intracellular copper when the cells were co-treated with copper. The peptides showed promising effect on aortic LOX, recombinant human LOX and LOX produced by human umbilical vein endothelial cells (HUVECs). The study also explores the effect of these peptides on copper and hypoxia-stimulated angiogenic response in HUVECs. It was found that the M peptides inhibited copper/hypoxia-induced LOX activity and inhibited stimulated HUVEC tube formation and migration. This clearly indicated the potential of M peptides in inhibiting angiogenesis, highlighting their role in the formulation of drugs for the same. Copyright © 2014 European Peptide Society and John Wiley & Sons, Ltd.

  8. Giant Paramagnetism of Copper Nanoparticles in Nanocomposites Cu@C

    Science.gov (United States)

    Sharoyan, Eduard; Mirzakhanyan, Armen; Gyulasaryan, Harutyun; Manukyan, Aram; Estiphanos, Medhanie; Goff, Michael; Bernal, Oscar; Kocharian, Armen

    The copper nanoparticles in nanocomposites Cu@C, encapsulated in graphitized carbon shell was obtained by the solid-phase pyrolysis method of polycrystalline phthalocyanine (CuPc, Pc =C32N8H16) . The average sizes of the nanoparticles are in the range of 2-6 nm. Magnetic measurements were carried out by vibrational magnetometer in the temperature range 10-300 K. At low temperatures (Science, in the frames of the research project SCS-13-1C090. The work at California State University was supported by the National Science Foundation-Partnerships for Research and Education in Materials under Grant DMR-1523588.

  9. Noncovalent binding of xanthene and phthalocyanine dyes with graphene sheets: the effect of the molecular structure revealed by a photophysical study.

    Science.gov (United States)

    Zhang, Xian-Fu; Liu, Su-Ping; Shao, Xiao-Na

    2013-09-01

    The fluorescence and absorption properties of several xanthene and phthalocyanine dyes were measured in the presence and absence of chemically derived graphene (CDG) sheets. The interaction of pyronine Y (PYY) with graphene sheets was compared with that of rhodamine 6G (R6G) to reveal the effect of the molecular structure. Although the presence of the perpendicular benzene moiety in a R6G or phthalocyanine molecule does cause the difficulty for forming dye-CDG complex and make CDG less efficient in quenching the fluorescence intensity and shortening the fluorescence lifetime, it does not affect the band position of charge transfer absorption, suggesting that no molecular shape change occurred in a dye molecule caused by the interaction with CDG sheets. The spectroscopic and thermodynamic data indicated that the dye-CDG binding is of charge transfer nature, while the dynamic fluorescence quenching is due to photoinduced energy and electron transfer. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Copper (II)

    African Journals Online (AJOL)

    CLEMENT O BEWAJI

    ABSTRACT: A Schiff base was prepared from the reaction of 2 - amino - 3 – methylbutanoic acid and 2, 4 - pentanedione. The reaction of the prepared Schiff base with ethanolic solution of copper (II) chloride formed diaquo bis( N – 2 – amino – 3 - methylbutyl - 2, 4 - pentanedionato) copper (II) complex. The Schiff base is ...

  11. Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water.

    Science.gov (United States)

    Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M; Gnecco, Enrico

    2014-07-21

    The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

  12. 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

  13. Solution-Processable Silicon Phthalocyanines in Electroluminescent and Photovoltaic Devices.

    Science.gov (United States)

    Zysman-Colman, Eli; Ghosh, Sanjay S; Xie, Guohua; Varghese, Shinto; Chowdhury, Mithun; Sharma, Nidhi; Cordes, David B; Slawin, Alexandra M Z; Samuel, Ifor D W

    2016-04-13

    Phthalocyanines and their main group and metal complexes are important classes of organic semiconductor materials but are usually highly insoluble and so frequently need to be processed by vacuum deposition in devices. We report two highly soluble silicon phthalocyanine (SiPc) diester compounds and demonstrate their potential as organic semiconductor materials. Near-infrared (λ(EL) = 698-709 nm) solution-processed organic light-emitting diodes (OLEDs) were fabricated and exhibited external quantum efficiencies (EQEs) of up to 1.4%. Binary bulk heterojunction solar cells employing P3HT or PTB7 as the donor and the SiPc as the acceptor provided power conversion efficiencies (PCE) of up to 2.7% under simulated solar illumination. Our results show that soluble SiPcs are promising materials for organic electronics.

  14. Conductance switching of a phthalocyanine molecule on an insulating surface

    Science.gov (United States)

    Dou, Kun Peng; Kaun, Chao-Cheng

    2017-08-01

    We study the electron transport through the double-barrier junction consisted of the phthalocyanine molecule adsorbed on a NaCl bilayer on a metal substrate and the STM tip from first principles. The hydrogen tautomerization reaction happened in the molecule changes the spatial extensions of the molecular π orbitals under the tip, leading to junction conductance switching. Shifting the molecule to locate on different ions also varies the conductance. The transport channels of the tautomers on different adsorbed sites are identified.

  15. Metal phthalocyanine intermediates for the preparation of polymers

    Science.gov (United States)

    Achar, B. N.; Fohlen, G. M.; Parker, J. A.

    1985-01-01

    Metal 4, 4', 4"",-tetracarboxylic phthalocyanines (MPTC) are prepared by reaction of trimellitic anhydride, a salt or hydroxide of the desired metal (or the metal in powdered form), urea and a catalyst. A purer form of MPTC is prepared than heretofore. These tetracarboxylic acids are then polymerized by heat to sheet polymers which have superior heat and oxidation resistance. The metal is preferably a divalent metal having an atomic radius close to 1.35A.

  16. 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

  17. 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 : phthalocyanine s * phenol * chlorophenols Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 5.252, year: 2009

  18. Magnetic anisotropy of metal functionalized phthalocyanine 2D networks

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Guojun [Department of Physics, Xiangtan University, Hunan 411105 (China); Zhang, Yun [Department of Physics and Information Technology, Baoji University of Arts and Sciences, Baoji 721016 (China); Xiao, Huaping, E-mail: hpxiao@xtu.edu.cn [Department of Physics, Xiangtan University, Hunan 411105 (China); Cao, Juexian, E-mail: jxcao@xtu.edu.cn [Department of Physics, Xiangtan University, Hunan 411105 (China)

    2016-06-15

    The magnetic anisotropy of metal including Cr, Mn, Fe, Co, Mo, Tc, Ru, Rh, W, Re, Os, Ir atoms functionalized phthalocyanine networks have been investigated with first-principles calculations. The magnetic moments can be expressed as 8-n μ{sub B} with n the electronic number of outmost d shell in the transition metals. The huge magnetocrystalline anisotropy energy (MAE) is obtained by torque method. Especially, the MAE of Re functionalized phthalocyanine network is about 20 meV with an easy axis perpendicular to the plane of phthalocyanine network. The MAE is further manipulated by applying the external biaxial strain. It is found that the MAE is linear increasing with the external strain in the range of −2% to 2%. Our results indicate an effective approach to modulate the MAE for practical application. - Graphical abstract: The charge density redistribution (ρ{sub MPc}-ρ{sub M}-ρ{sub Pc}) and spin density of the CoPc molecule, from top- and side-views. Purple and green isosurfaces indicate charge depletion and accumulation, respectively. Display Omitted.

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. 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

  4. 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...

  5. Improved antimicrobial therapy with cationic tetra- and octa-substituted phthalocyanines

    Science.gov (United States)

    Angelov, I.; Mantareva, V.; Kussovski, V.; Woehrle, D.; Borisova, E.; Avramov, L.

    2008-12-01

    Photodynamic therapy (PDT) today is an innovative and not yet widespread light-drug initiated treatment that is based on the photoactive compound irradiated with proper light to produce oxygen species that are toxic to the pathogenic biological objects- bacteria, viruses, tumor cells. The obstacles that limited the efficacy of PDT concern to the selectivity and multi-drug resistance prolong time for cellular release and side effects of skin photosensitivity for commercial porphyrin originated photosensitizers (PS). Now there are very intensive investigations for introducing in practice a new, with a least side effects PSs for PDT. The usefulness of the more extended macromolecules structured with proper substituents refers not only to the improved optical properties like far-red and with intensive absorption and emission capacity, but mainly to the ability for selective delivery and adhesion to the target cells, such as bacteria or other pathogens. The present study focuses on the charge effect of photodynamic agent on the uptake capacity toward gram-negative bacteria cells and their further photoinactivation. The multi-drug resistant microorganism Aeromanas hydrophilla, which is causing diseases to fishes and humans, is treated. The new octa-cationic phthalocyanines are designed to compare PDT efficacy to the efficacy of tetra-substituted derivatives with the same functional peripheral substituents. The higher cellular accumulation to the bacteria cells as a result of the high number of positive charges of photosensitizer, leading to the better adhesion to the cellular membranes and improved photoinactivation of bacteria causing superficial and intraorgan infections. These results set a base of a rationale design of covalently octa-substituted phthalocyanines with positive charge for a successful treatment of microorganisms.

  6. Experimental and theoretical studies on the corrosion inhibition of copper by two indazole derivatives in 3.0% NaCl solution.

    Science.gov (United States)

    Qiang, Yujie; Zhang, Shengtao; Xu, Shenying; Li, Wenpo

    2016-06-15

    Corrosion experiments and theoretical calculations were performed to investigate the inhibition mechanism of indazole (IA) and 5-aminoindazole (AIA) for copper in NaCl solution. The results obtained from weight loss and electrochemical experiments are in good agreement, and reveal that these compounds are high-efficiency inhibitors with inhibition efficiency order: AIA>IA, which was further confirmed by field emission scanning electronic microscope (FESEM) observation. Besides, the quantum chemical calculations and molecular dynamics (MD) simulation showed that both studied inhibitors are adsorbed strongly on the copper surface in parallel mode. The adsorption of these molecules on copper substrate was found to obey Langmuir isotherm. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Two Spectrophotometric Assays for Dopamine Derivatives in Pharmaceutical Products and in Biological Samples of Schizophrenic Patients Using Copper Tetramine Complex and Tri-iodide Reagent

    Directory of Open Access Journals (Sweden)

    F. A. Nour El-Dien

    2005-01-01

    Full Text Available Two simple, rapid, and sensitive spectrophotometric methods are proposed for the determination of levodopa (LD. The first method is based on coupling of 4-aminoantipyrine (4-AAP with one of the dopamine derivatives (LD, CD to give a new ligand that reacts with copper tetramine complex to give intensely colored chelates. The colored products are quantified spectrophotometrically at 525 and 520 nm for LD and CD, respectively. The optimization of the experimental conditions is described. The method has been used for the determination of 19.7–69.0 and 18.1–54.3μg mL−1 of LD and CD, respectively. The accuracy of the method is achieved by the values of recovery (100±0.2% and the precision is supported by the low standard deviation (SD =0.17–0.59 and relative standard deviation (CV =0.4%–1.54% values. The second method is based on the formation of ion-pair iodinated inner sphere or outer sphere colored complexes between the LD and triiodide ions at pH 5 and room temperature (23±3°C. This method has been used for the determination of LD within the concentration range 39.44–78.88μg mL−1 with SD =0.22–0.24 and recovery percent =100±0.3%. The sensitivity of the two methods is indicated by Sandell's sensitivity of 0.014–0.019 g cm−2. The results of the two methods are compared with those of the official method. The interference of common drug additives, degradation products, and excipients was also studied. The proposed methods were applied successfully to the determination of the LD-CD synthetic mixture and Levocare drug. The determination of LD in urine of some schizophrenic patients was applied with good precision and accuracy. The reliability of the methods was established by parallel determinations against the official British pharmacopoeia method.

  8. Two Spectrophotometric Assays for Dopamine Derivatives in Pharmaceutical Products and in Biological Samples of Schizophrenic Patients Using Copper Tetramine Complex and Triiodide Reagent

    Science.gov (United States)

    2005-01-01

    Two simple, rapid, and sensitive spectrophotometric methods are proposed for the determination of levodopa (LD). The first method is based on coupling of 4-aminoantipyrine (4-AAP) with one of the dopamine derivatives (LD, CD) to give a new ligand that reacts with copper tetramine complex to give intensely colored chelates. The colored products are quantified spectrophotometrically at 525 and 520 nm for LD and CD, respectively. The optimization of the experimental conditions is described. The method has been used for the determination of 19.7–69.0 and 18.1–54.3 μg mL−1 of LD and CD, respectively. The accuracy of the method is achieved by the values of recovery (100 ± 0.2%) and the precision is supported by the low standard deviation (SD = 0.17–0.59) and relative standard deviation (CV = 0.4%–1.54%) values. The second method is based on the formation of ion-pair iodinated inner sphere or outer sphere colored complexes between the LD and triiodide ions at pH 5 and room temperature (23 ± 3°C). This method has been used for the determination of LD within the concentration range 39.44–78.88 μg mL−1 with SD = 0.22–0.24 and recovery percent = 100 ± 0.3%. The sensitivity of the two methods is indicated by Sandell's sensitivity of 0.014–0.019 g cm−2. The results of the two methods are compared with those of the official method. The interference of common drug additives, degradation products, and excipients was also studied. The proposed methods were applied successfully to the determination of the LD-CD synthetic mixture and Levocare drug. The determination of LD in urine of some schizophrenic patients was applied with good precision and accuracy. The reliability of the methods was established by parallel determinations against the official British pharmacopoeia method. PMID:15689633

  9. Cu@C nanoporous composites containing little copper oxides derived from dimethyl imidazole modified MOF199 as electrocatalysts for hydrogen evolution reaction

    Science.gov (United States)

    Wei, Xuedong; Li, Na; Zhang, Xianming

    2017-12-01

    It remains a huge challenge to develop non precious electrocatalysts with high activity to substitute commercial Pt catalysts for hydrogen evolution reactions (HER). Here, the C-Cu-DI and C-Cu materials with the copper based nanoporous carbon structures were synthesized by carbonizing MOF199 and DI-MOF199. The composite structure and HER electrocatalytic properties of the C-Cu-DI and C-Cu materials are studied. The results show that C-Cu-DI and C-Cu samples exhibit good catalytic activity. And C-Cu-DI sample through the addition of Dimethyl imidazole(DI) in the DI-MOF199 precursor has higher electrocatalytic activity than the C-Cu sample. The superior catalytic activity is attributed to the special composite structure of nanoscale deposition particles on the framework with plenty of nano pores and nano copper and few copper oxidation particles distributed or wrapped into the amorphous porous carbon phase. The nano copper and few copper oxidation particles in the C-Cu and C-Cu-DI catalysts maybe provide the more effective catalytic activity sites. The C-Cu-DI composite with large size spherical hollow deposition particles has higher conductivity, better BET surface area and reasonable micro-meso-macro porous distribution, so the overpotentials at the current density of 1 mA cm-2 and 10 mA cm-2 are respectively 270 mV and 390 mV vs. RHE. Although the HER activity has a big gap with commercial platinum catalyst, this study can provide an important experimental exploration for the design of copper based non noble metal/nano porous carbon composite HER electrocatalyst.

  10. Copper Test

    Science.gov (United States)

    ... Tests G6PD Gamma-Glutamyl Transferase (GGT) Gastrin Gastrointestinal Pathogens Panel Genetic Tests for Targeted Cancer Therapy Glucose ... hepatic). Copper is found in many foods including nuts, chocolate, mushrooms, shellfish, whole grains, dried fruits, and ...

  11. Copper Test

    Science.gov (United States)

    ... Pregnancy hCG Tumor Marker HDL Cholesterol Heavy Metals Helicobacter pylori Testing Hematocrit Hemoglobin Hemoglobin A1c Hemoglobinopathy Evaluation ... or trying to get more copper in my diet? In most cases, a regular diet satisfies the ...

  12. Peroxynitrite Chemistry Derived from Nitric Oxide Reaction with a Cu(II)-OOH Species and a new Copper Mediated NO Reductive Coupling Reaction

    Science.gov (United States)

    Kim, Sunghee; Siegler, Maxime A.; Karlin, Kenneth D.

    2014-01-01

    New peroxynitrite-copper chemistry ensues via addition of nitric oxide (•NO(g)) to a CuII-hydroperoxo species. In characterizing the system, the ligand-Cu(I) complex was shown to effect •NO(g) reductive coupling, a new reaction type. Biological implications are discussed. PMID:24322625

  13. Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(II)-OOH species and a copper mediated NO reductive coupling reaction.

    Science.gov (United States)

    Kim, Sunghee; Siegler, Maxime A; Karlin, Kenneth D

    2014-03-18

    New peroxynitrite-copper chemistry ensues via addition of nitric oxide (˙NO(g)) to a Cu(II)-hydroperoxo species. In characterizing the system, the ligand-Cu(i) complex was shown to effect a seldom observed ˙NO(g) reductive coupling reaction. Biological implications are discussed.

  14. Structurally diverse copper complexes bearing NNO-tridentate Schiff-base derivatives as efficient catalysts for copolymerization of carbon dioxide and cyclohexene oxide.

    Science.gov (United States)

    Tsai, Chen-Yen; Huang, Bor-Hunn; Hsiao, Mon-Wei; Lin, Chu-Chieh; Ko, Bao-Tsan

    2014-05-19

    Structurally diverse copper acetate complexes based on NNO-tridentate Schiff-base ligands were synthesized and characterized as mono-, di-, and trinuclear complexes with respect to varied ancillary ligands. Treatment of the ligand precursors (L(1)-H = 2-(1-((2-(dimethylamino)ethyl)imino)ethyl)-4-methylphenol, L(2)-H = 4-chloro-2-(1-((2-(dimethylamino)ethyl)imino)ethyl)phenol, and L(3)-H = 2-(1-((2-(dimethylamino)ethyl)imino)ethyl)-5-methylphenol) with Cu(OAc)2·H2O (1 equiv) in refluxing ethanol afforded five-coordinate mono- or bimetallic copper complexes ([(L(1))Cu(OAc)(H2O)] (1); [(L(2))Cu(OAc)(H2O)] (2); [(L(3))2Cu2(OAc)2] (3)) in high yields. Dinuclear copper acetate analogue [(L(1))2Cu2(OAc)2] (4) resulted from treatment of L(1)-H as the ligand precursor in refluxing anhydrous MeOH with equimolar proportions of metal acetate salt under a dry nitrogen atmosphere. However, a trinuclear complex, [(L(4))2Cu3(OAc)4] (5), was obtained on utilizing 2-(1-((2-(dimethylamino)ethyl)imino)ethyl)-5-methoxyphenol (L(4)-H) as the proligand under the same synthetic route of 1-3; this complex was also synthesized in the reaction of L(4)-H and copper(II) acetate monohydrate in the ratio of 2:3, giving a quantitative yield. All complexes are active catalysts for copolymerization of cyclohexene oxide (CHO) and CO2 without cocatalysts. In particular, dinuclear Cu complex 3 performed satisfactorily to produce polycarbonates with controllable molecular weights and high carbonate linkages. These copper complexes are the first examples that are effective for both CO2/CHO copolymerization and formation of polymers in a controlled fashion.

  15. Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N⁴-methyl-3-thiosemicarbazone: crystal structure of a novel sulfur bridged copper(II) box-dimer.

    Science.gov (United States)

    Jayakumar, K; Sithambaresan, M; Aiswarya, N; Kurup, M R Prathapachandra

    2015-03-15

    Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ=0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g||>g⊥>2.0023 and the g values in frozen DMF are consistent with the d(x2-y2) ground state. The thermal stabilities of some of the complexes were also determined. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N4-methyl-3-thiosemicarbazone: Crystal structure of a novel sulfur bridged copper(II) box-dimer

    Science.gov (United States)

    Jayakumar, K.; Sithambaresan, M.; Aiswarya, N.; Kurup, M. R. Prathapachandra

    2015-03-01

    Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N4-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ = 0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)sbnd I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g|| > g⊥ > 2.0023 and the g values in frozen DMF are consistent with the dx2-y2 ground state. The thermal stabilities of some of the complexes were also determined.

  17. Simultaneous determination of nickel and copper by H-point standard addition method-first-order derivative spectrophotometry in plant samples after separation and preconcentration on modified natural clinoptilolite as a new sorbent.

    Science.gov (United States)

    Roohparvar, Rasool; Taher, Mohammad Ali; Mohadesi, Alireza

    2008-01-01

    For the simultaneous determination of nickel(ll) and copper(ll) in plant samples, a rapid and accurate method was developed. In this method, solid-phase extraction (SPE) and first-order derivative spectrophotometry (FDS) are combined, and the result is coupled with the H-point standard addition method (HPSAM). Compared with normal spectrophotometry, derivative spectrophotometry offers the advantages of increased selectivity and sensitivity. As there is no need for carrying out any pretreatment of the sample, the spectrophotometry method is easy, but because of a high detection limit, it is not so practical. In order to decrease the detection limit, it is suggested to combine spectrophotometry with a preconcentration method such as SPE. In the present work, after separation and preconcentration of Ni(ll) and Cu(ll) on modified clinoptilolite zeolite that is loaded with 2-[1-(2-hydroxy-5-sulforphenyl)-3-phenyl-5-formaza-no]-benzoic acid monosodium salt (zincon) as a selective chromogenic reagent, FDS-HPSAM, which is a simple and selective spectrophotometric method, has been applied for simultaneous determination of these ions. With optimum conditions, the detection limit in original solutions is 0.7 and 0.5 ng/mL, respectively, for nickel and copper. The linear concentration ranges in the proposed method for nickel and copper ions in original solutions are 1.1 to 3.0 x 10(3) and 0.9 to 2.0 x 10(3) ng/mL, respectively. The recommended procedure is applied to successful determination of Cu(ll) and Ni(ll) in standard and real samples.

  18. One-step preparation of a water-soluble carbon nanohorn/phthalocyanine hybrid for dual-modality photothermal and photodynamic therapy.

    Science.gov (United States)

    Jiang, Bang-Ping; Hu, Lan-Fang; Shen, Xing-Can; Ji, Shi-Chen; Shi, Zujin; Liu, Chan-Juan; Zhang, Li; Liang, Hong

    2014-10-22

    The biomedical applications of carbon nanomaterials, especially integrating noninvasive photothermal therapy (PTT) and photodynamic therapy (PDT), into a single system have enormous potential in cancer therapy. Herein, we present a novel and facile one-step method for the preparation of water-soluble single-walled carbon nanohorns (SWNHs) and metal phthalocyanines (MPc) hybrid for PTT and PDT. The hydrophilic MPc, tetrasulfonic acid tetrasodium salt copper phthalocyanine (TSCuPc), is coated on the surface of SWNHs via noncovalent π-π interaction using the sonication method. In this PTT/PDT nanosystem, SWNHs acts as a photosensitizer carrier and PTT agent, while TSCuPc acts as a hydrophilic and PDT agent. The EPR results demonstrated that the generated reactive oxygen species (ROS) not only from the photoinduced electron transfer process from TSCuPc to SWNHs but also from SWNHs without exciting TSCuPc to its excited state. The test of photothermal conversion proved that not only do SWNHs contribute to the photothermal therapy (PTT) effect, TSCuPc probably also contributes to that when it coats on the surface of SWNHs upon exposure to a 650-nm laser. More importantly, the results of in vitro cell viability revealed a significantly enhanced anticancer efficacy of combined noninvasive PTT/PDT, indicating that the SWNHs-TSCuPc nanohybrid is a hopeful candidate material for developing an efficient and biocompatible nanoplatform for biomedical application.

  19. 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.

  20. The complex nature of phthalocyanine/gold interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lindner, Susi, E-mail: s.wintz@ifw-dresden.de [IFW Dresden, P.O. Box 270116, D-01171 Dresden (Germany); Treske, Uwe; Knupfer, Martin [IFW Dresden, P.O. Box 270116, D-01171 Dresden (Germany)

    2013-02-15

    We compare the electronic properties of the interface between Au(1 0 0) and cobalt phthalocyanine (CoPc), fluorinated F{sub 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{sub 16}CoPc to gold, there is a local charge transfer to the central Co ion, which as a result is reduced to Co(I).

  1. An ultrafast study of Zinc Phthalocyanine in DMSO

    CSIR Research Space (South Africa)

    Ombinda-Lemboumba, Saturnin

    2010-10-01

    Full Text Available continuum. The pump-probe technique used in this study is described and experimental results obtained are discussed. 1. Introduction Zinc phthalocyanine (ZnPc) is a promising photodynamic therapy (PDT) photosensitiser which has a relatively long... conversion from S1 to S0. In addition we were able to resolve a mono-exponential fast process with a time constant of 2.7 ? 0.5 ps at 630 nm. This was attributed to solvation dynamics. 3. References [1] A. Ogunsipe, J. Chen, and T. Nyokong...

  2. Antioxidant, DNA binding and nuclease activities of heteroleptic copper(II) complexes derived from 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols and diimines

    Science.gov (United States)

    Ravichandran, J.; Gurumoorthy, P.; Imran Musthafa, M. A.; Kalilur Rahiman, A.

    2014-12-01

    A series of heteroleptic copper(II) complexes of the type [CuL1-4(diimine)](ClO4)2 (1-8) [L1-4 = 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols, and diimine = 2,2‧-bipyridyl (bpy) or 1,10-phenanthroline (phen)], have been synthesized and characterized by spectroscopic methods. The IR spectra of complexes indicate the presence of uncoordinated perchlorate anions and the electronic spectra revealed the square pyramidal geometry with N4O coordination environment around copper(II) nuclei. Electrochemical studies of the mononuclear complexes evidenced one-electron irreversible reduction wave in the cathodic region. The EPR spectra of complexes with g|| (2.206-2.214) and A|| (154-172 × 10-4 cm-1) values support the square-based CuN3O coordination chromophore and the presence of unpaired electron localized in dx-y ground state. Antioxidant studies against DPPH revealed effective radical scavenging properties of the synthesized complexes. Binding studies suggest that the heteroleptic copper(II) complexes interact with calf thymus DNA (CT-DNA) through minor-groove and electrostatic interaction, and all the complexes display pronounced nuclease activity against supercoiled pBR322 DNA.

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

    CERN Document Server

    Ito, Y

    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.

  4. Raman and Luminescent Spectra of Sulfonated Zn Phthalocyanine Enhanced by Gold Nanoparticles

    Science.gov (United States)

    Kavelin, V.; Fesenko, O.; Dubyna, H.; Vidal, C.; Klar, T. A.; Hrelescu, C.; Dolgov, L.

    2017-03-01

    Sulfonated Zn phthalocyanine, as a prospective photosensitizer in the photodynamic therapy of tumors, is investigated by means of Raman, infrared, and fluorescence spectroscopies. Conventional and surface-enhanced spectra from this photosensitizer are obtained and compared. Gold nano-islands attached to silica cores (Au-SiO2) are proposed as nanostructures providing plasmonically enhanced signals. Pronounced enhancement of Raman and infrared spectral bands from sulfonated Zn phthalocyanine allows their more convenient assignment with vibrational modes of sulfonated Zn phthalocyanine. In comparison to Raman and IR, the fluorescence is less enhanced by Au-SiO2 particles.

  5. Titanium and Ruthenium Phthalocyanines for NO2 Sensors: A Mini-Review

    Directory of Open Access Journals (Sweden)

    Valerio Rossi Albertini

    2009-07-01

    Full Text Available This review presents studies devoted to the description and comprehension of phenomena connected with the sensing behaviour towards NO2 of films of two phthalocyanines, titanium bis-phthalocyanine and ruthenium phthalocyanine. Spectroscopic, conductometric, and morphological features recorded during exposure to the gas are explained and the mechanisms of gas-molecule interaction are also elucidated. The review also shows how X-ray reflectivity can be a useful tool for monitoring morphological parameters such as thickness and roughness that are demonstrated to be sensitive variables for monitoring the exposure of thin films of sensor materials to NO2 gas.

  6. Fully protected glycosylated zinc (II) phthalocyanine shows high uptake and photodynamic cytotoxicity in MCF-7 cancer cells.

    Science.gov (United States)

    Kimani, Stanley G; Shmigol, Tatiana A; Hammond, Samantha; Phillips, James B; Bruce, James I; MacRobert, Alexander J; Malakhov, Mikhail V; Golding, Jon P

    2013-01-01

    Phthalocyanine photosensitizers are effective in anticancer photodynamic therapy (PDT) but suffer from limited solubility, limited cellular uptake and limited selectivity for cancer cells. To improve these characteristics, we synthesized isopropylidene-protected and partially deprotected tetra β-glycosylated zinc (II) phthalocyanines and compared their uptake and accumulation kinetics, subcellular localization, in vitro photocytotoxicity and reactive oxygen species generation with those of disulfonated aluminum phthalocyanine. In MCF-7 cancer cells, one of the compounds, zinc phthalocyanine {4}, demonstrated 10-fold higher uptake, 5-fold greater PDT-induced cellular reactive oxygen species concentration and 2-fold greater phototoxicity than equimolar (9 μm) disulfonated aluminum phthalocyanine. Thus, isopropylidene-protected β-glycosylation of phthalocyanines provides a simple method of improving the efficacy of PDT. © 2012 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

  7. A novel Schiff base derived from the gabapentin drug and copper (II) complex: Synthesis, characterization, interaction with DNA/protein and cytotoxic activity.

    Science.gov (United States)

    Shokohi-Pour, Zahra; Chiniforoshan, Hossein; Momtazi-Borojeni, Amir Abbas; Notash, Behrouz

    2016-09-01

    A novel Schiff base [C20H23NO3], has been prepared and characterized using FT-IR, UV-vis, (1)H NMR spectroscopy, elemental analysis and X-ray crystallography. A copper (II) complex [Cu(C20H22NO3)2]·H2O has also been synthesized and characterized. The new ligand and complex thus obtained were investigated by their interaction with calf thymus DNA and BSA using electronic absorption spectroscopy, fluorescence spectroscopy, and thermal denaturation. The intrinsic binding constants Kb of the ligand and Cu (II) complex, with CT-DNA obtained from UV-vis absorption studies were 1.53×10(4)M(-1) and 3.71×10(5)M(-1), respectively. Moreover the addition of the two compounds to CT-DNA (1:2) led to an increase of the melting temperature of DNA up to around 2.61°C for the ligand and 3.99°C for the Cu (II) complex. The ligand and Cu (II) complex bind to CT-DNA via a partial intercalative, as shown by the experimental data. In addition, the albumin interactions of the two compounds were studied by fluorescence quenching spectra, the results indicating that the binding mechanism is a static quenching process. The in vitro cytotoxicity of the two compounds on three different cancer cell lines was evaluated by MTT assay. The results showed that the copper complex exerted enhanced cytotoxicity compared with the Schiff base ligand; thereby, this complex clearly implies a positive synergistic effect. Furthermore, the copper complex showed a high, selective, and dose-dependent cytotoxicity against cancer cell lines. Copyright © 2016. Published by Elsevier B.V.

  8. Highly positive-charged zinc(II) phthalocyanine as non-aggregated and efficient antifungal photosensitizer.

    Science.gov (United States)

    Li, Xing-Shu; Guo, Jun; Zhuang, Jing-Jing; Zheng, Bi-Yuan; Ke, Mei-Rong; Huang, Jian-Dong

    2015-06-01

    A new tetra-α-substituted zinc(II) phthalocyanine containing dodeca-amino groups (compound 4) and its quaternized analogue (compound 5) have been prepared and evaluated for their photoactivities against Candida albicans. Compared with the dodeca-amino phthalocyanine 4, the dodeca-cationic phthalocyanine 5 exhibits a higher photodynamic inactivation against C. albicans with an IC90 value down to 1.46 μM, which can be attributed to its non-aggregated nature in aqueous environments and more efficient cellular uptake. More interestingly, 5 shows a higher photodynamic inactivation on C. albicans due to its stronger affinity to C. albicans cells than mammalian cells. These results suggest that the highly positive-charged phthalocyanine 5 is a potential non-aggregated antifungal photosensitizer, which shows some selectivity toward the fungus. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Nonlinear optical response of tetra and mono substituted zinc phthalocyanine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fashina, Adedayo; Nyokong, Tebello, E-mail: t.nyokong@ru.ac.za

    2015-11-15

    The nonlinear absorption properties of 6 mono-substituted and 3 symmetric zinc phthalocyanine complexes have been studied in dimethylsulfoxide (DMSO) using 10 ns pulses at 532 nm. The non linear absorption of the complexes has been studied using the Z-scan technique. The study showed that both the singlet and triplet excited states contribute to the non linear absorption behavior. The nonlinear third-order susceptibility and second-order hyperpolarizability values of the complexes are reported. It was observed that two of the symmetric phthalocyanine complexes (5-α substituted with aminophenoxy and 9-β substituted with carboxyphenoxy) showed better and promising optical nonlinearity when compared to the other complexes studied. - Highlights: • Nonlinear absorption properties of zinc phthalocyanine are reported • Singlet and triplet excited states contribute to the non linear absorption. • Symmetrically tetra substituted phthalocyanines showed better optical nonlinearity.

  10. In vivo fluorescence kinetics and localisation of aluminium phthalocyanine disulphonate in an autologous tumour model

    NARCIS (Netherlands)

    Witjes, MJH; Speelman, OC; Nikkels, PGJ; Nooren, CAAM; Nauta, JM; vanderHolt, B; vanLeengoed, HLLM; Roodenburg, JLN

    Sulphonated phthalocyanines are studied as photosensitisers for photodynamic therapy of cancer. Their strong fluorescence and tumour-localising properties make them also potentially useful for detection of cancer by fluorescence. For this purpose, we have studied the fluorescence kinetics and

  11. 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.

  12. 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.

  13. ABAB Phthalocyanines: Scaffolds for Building Unprecedented Donor–π–Acceptor Chromophores

    Science.gov (United States)

    Fazio, Ettore; Jaramillo‐García, Javier; Medel, María; Urbani, Maxence; Grätzel, Michael

    2016-01-01

    Abstract Unique donor–π–acceptor phthalocyanines have been synthesized through the asymmetric functionalization of an ABAB phthalocyanine, crosswise functionalized with two iodine atoms through Pd‐catalyzed cross‐coupling reactions with adequate electron‐donor and electron‐acceptor moieties. These push–pull molecules have been optically and electrochemically characterized, and their ability to perform as chromophores for dye‐sensitized solar cells has been tested. PMID:28168157

  14. Copper Isotope Constraints on the Genesis of the Keweenaw Peninsula Native Copper District, Michigan, USA

    Directory of Open Access Journals (Sweden)

    Theodore J. Bornhorst

    2017-09-01

    Full Text Available The Keweenaw Peninsula native copper district of Michigan, USA is the largest concentration of native copper in the world. The copper isotopic composition of native copper was measured from stratabound and vein deposits, hosted by multiple rift-filling basalt-dominated stratigraphic horizons over 110 km of strike length. The δ65Cu of the native copper has an overall mean of +0.28‰ and a range of −0.32‰ to +0.80‰ (excluding one anomalous value. The data appear to be normally distributed and unimodal with no substantial differences between the native copper isotopic composition from the wide spread of deposits studied here. This suggests a common regional and relatively uniform process of derivation and precipitation of the copper in these deposits. Several published studies indicate that the ore-forming hydrothermal fluids carried copper as Cu1+, which is reduced to Cu0 during the precipitation of native copper. The δ65Cu of copper in the ore-forming fluids is thereby constrained to +0.80‰ or higher in order to yield the measured native copper values by reductive precipitation. The currently accepted hypothesis for the genesis of native copper relies on the leaching of copper from the rift-filling basalt-dominated stratigraphic section at a depth below the deposits during burial metamorphism. Oxidative dissolution of copper from magmatic source rocks with magmatic δ65Cu of 0‰ ± 0.3‰ is needed to obtain the copper isotopic composition of the metamorphogenic ore-forming hydrothermal fluids. In order to accommodate oxidative dissolution of copper from the rift-filling basalt source rocks, the copper needs to have been sited in native copper. Magmatic native copper in basalt is likely stable when the magma is low in sulfur. Low sulfur is predicted by the lack of sulfide minerals in the ore deposits and in the rift-filling basalt-dominated section, which are source rocks, the same rocks through which the ore fluids moved upwards, and

  15. Synthesis, spectral characterization and biological evaluation of copper(II) and nickel(II) complexes with thiosemicarbazones derived from a bidentate Schiff base

    Science.gov (United States)

    Chandra, Sulekh; Bargujar, Savita; Nirwal, Rita; Yadav, Neesha

    2013-04-01

    Complexes of copper(II) and nickel(II) of general composition M(L)2X2, have been synthesized with the ligand 1-Tetralone thiosemicarbazone (where L = 1-Tetralone thiosemicarbazone and X=Cl,1/2SO42-). The molar conductance of the complexes in fresh solution of DMSO lies in the range of 10-20 Ω-1 cm2 mol-1 indicating their non-electrolytic behavior. Thus, the complexes may be formulated as [M(L2)X2]. Ligand was characterized by mass, NMR, IR and single crystallographic studies. All the complexes were characterized by elemental analyses, magnetic moments, IR, electronic and EPR spectral studies. The IR spectral data of ligand indicated the involvement of sulfur and azomethine nitrogen in coordination to the central metal ion. The copper(II) and nickel(II) complexes were found to have magnetic moments1.93-1.96 BM and 2.91-2.94 BM corresponding to one and two unpaired electrons respectively. On the basis of molar conductance, EPR, electronic and infrared spectral studies, a tetragonal geometry has been assigned for Cu(II) chloride complex and trigonal bipyramidal to Cu(II) sulfate complex but an octahedral geometry for Ni(II) complexes. Newly synthesized ligand and its Cu(II) and Ni(II) complexes have also been screened against different bacterial and fungal species.

  16. Spectroscopic properties of some mixed ligand copper(II) complexes of N-(2-aminoethyl)-1,2-ethanediamine and ethanediamine and its alkylated derivatives

    Science.gov (United States)

    Sastry, B. A.; Chary, K. S.; Subramanian, R.; Ponticelli, G.; Puggioni, G.

    1992-04-01

    IR, EPR and electronic spectral studies have been made on a series of complexes with general formula [M(dien)L](BØ 4) 2nH 2O (M = Cu(II), Zn(II), Cd(II), dien = N-(2-aminoethyl)-1,2-ethanediamine, L = ethanediamine (en), Me 4en, Et 2en, Me = methyl, Et = ethyl, BØ 4 = tetraphenylborate, n = 0 or 2] taking copper(II) as a magnetic probe in polycrystalline and solution forms to obtain stereochemical information. A five-coordinate square-based pyramidal (SBP) geometry with CuN 3N' 2 moiety having moderately covalent metal-ligand σ-bonds is found to exist in unalkylated mixed ligand complexes. Among alkylated complexes [Cu/Cd(dien)(Me 4en)](BØ 4) 2 is found to possess two species having tetrahedral and SBP with trigonal bipyramidal distortion geometries unlike the other alkylated complexes which have indicated the presence of one species having SBP coordination geometry with varying degrees of trigonal bipyramidal distortions and metal-ligand σ-bond strengths. EPR studies in dilute dmf and pyridine solutions of copper(II) complexes indicated the presence of solute-solvent interaction.

  17. Palladium Nanoparticles Immobilized on Individual Calcium Carbonate Plates Derived from Mussel Shell Waste: An Ecofriendly Catalyst for the Copper-Free Sonogashira Coupling Reaction.

    Science.gov (United States)

    Saetan, Trin; Lertvachirapaiboon, Chutiparn; Ekgasit, Sanong; Sukwattanasinitt, Mongkol; Wacharasindhu, Sumrit

    2017-09-05

    The conversion of waste into high-value materials is considered an important sustainability strategy in modern chemical industries. A large volume of shell waste is generated globally from mussel cultivation. In this work, mussel shell waste (Perna viridis) is transformed into individual calcium carbonate plates (ICCPs) and is applied as a support for a heterogeneous catalyst. Palladium nanoparticles (3-6 nm) are deposited with an even dispersion on the ICCP surface, as demonstrated by X-ray diffraction and scanning electron microscopy. Using this system, Sonogashira cross-coupling reactions between aryl iodides and terminal acetylenes were accomplished in high yields with the use of 1 % Pd/ICCP in the presence of potassium carbonate without the use of any copper metal or external ligand. The Pd/ICCP catalyst could also be reused up to three times and activity over 90 % was maintained with negligible Pd-metal leaching. This work demonstrates that mussel shell waste can be used as an inexpensive and effective support for metal catalysts in coupling reactions, as demonstrated by the successful performance of the Pd-catalyzed, copper-free Sonogashira cross-coupling process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Experimental and theoretical investigations of copper (I/II) complexes with triazine-pyrazole derivatives as ligands and their in situ C-N bond cleavage

    Science.gov (United States)

    Wang, Ji-Xiao; Wang, Che; Wang, Xuan; Wang, Xin-Yu; Xing, Yong-Heng; Sun, Qiao

    2015-05-01

    Two copper complexes, Cu(SCN)(Mpz∗T-(EtO)2) (1) (Mpz∗T-(EtO)2 = L3) and CuCl(H2O)(Mpz∗T-O2) (2) (Mpz∗T-O2 = L4) were synthesized by the reaction of 2,4,6-tri(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (L1) or 2,4,6-tri(1H-pyrazol-1-yl)-1,3,5-triazine (L2) with CuCl2·2H2O in anhydrous ethanol and methanol, respectively. The complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, single crystal X-ray diffraction and X-ray powder diffraction. The structural characterizations and quantum mechanical calculations of the two complexes were analyzed in detail. It was found that an in site reaction occurred during the synthesis process of complexes 1 and 2, likely due to catalytic property of copper ions which leads to the C-N bond cleavage to generate new organic species, namely, Mpz∗T-(EtO)2 (L3) and Mpz∗T-O2 (L4).

  19. Canine Models for Copper Homeostasis Disorders.

    Science.gov (United States)

    Wu, Xiaoyan; Leegwater, Peter A J; Fieten, Hille

    2016-02-04

    Copper is an essential trace nutrient metal involved in a multitude of cellular processes. Hereditary defects in copper metabolism result in disorders with a severe clinical course such as Wilson disease and Menkes disease. In Wilson disease, copper accumulation leads to liver cirrhosis and neurological impairments. A lack in genotype-phenotype correlation in Wilson disease points toward the influence of environmental factors or modifying genes. In a number of Non-Wilsonian forms of copper metabolism, the underlying genetic defects remain elusive. Several pure bred dog populations are affected with copper-associated hepatitis showing similarities to human copper metabolism disorders. Gene-mapping studies in these populations offer the opportunity to discover new genes involved in copper metabolism. Furthermore, due to the relatively large body size and long life-span of dogs they are excellent models for development of new treatment strategies. One example is the recent use of canine organoids for disease modeling and gene therapy of copper storage disease. This review addresses the opportunities offered by canine genetics for discovery of genes involved in copper metabolism disorders. Further, possibilities for the use of dogs in development of new treatment modalities for copper storage disorders, including gene repair in patient-derived hepatic organoids, are highlighted.

  20. Canine Models for Copper Homeostasis Disorders

    Directory of Open Access Journals (Sweden)

    Xiaoyan Wu

    2016-02-01

    Full Text Available Copper is an essential trace nutrient metal involved in a multitude of cellular processes. Hereditary defects in copper metabolism result in disorders with a severe clinical course such as Wilson disease and Menkes disease. In Wilson disease, copper accumulation leads to liver cirrhosis and neurological impairments. A lack in genotype-phenotype correlation in Wilson disease points toward the influence of environmental factors or modifying genes. In a number of Non-Wilsonian forms of copper metabolism, the underlying genetic defects remain elusive. Several pure bred dog populations are affected with copper-associated hepatitis showing similarities to human copper metabolism disorders. Gene-mapping studies in these populations offer the opportunity to discover new genes involved in copper metabolism. Furthermore, due to the relatively large body size and long life-span of dogs they are excellent models for development of new treatment strategies. One example is the recent use of canine organoids for disease modeling and gene therapy of copper storage disease. This review addresses the opportunities offered by canine genetics for discovery of genes involved in copper metabolism disorders. Further, possibilities for the use of dogs in development of new treatment modalities for copper storage disorders, including gene repair in patient-derived hepatic organoids, are highlighted.

  1. Fluorination of phthalocyanine substituents: Improved photoproperties and enhanced photodynamic efficacy after optimal micellar formulations.

    Science.gov (United States)

    Pucelik, Barbara; Gürol, Ilke; Ahsen, Vefa; Dumoulin, Fabienne; Dąbrowski, Janusz M

    2016-11-29

    A fluorinated phthalocyanine and its non-fluorinated analogue were selected to evaluate the potential enhancement of fluorination on photophysical, photochemical and redox properties as well as on biological activity in cellular and animal models. Due to the pharmacological relevance, the affinity of these phthalocyanines towards biological membranes (logPow) as well as their primary interaction with human serum albumin (HSA) or low-density lipoprotein (LDL) were determined. Water-dispersible drug formulation of phthalocyanines via Pluronic(®)-based triblock copolymer micelles was prepared to avoid self-aggregation effects and to improve their delivery. The obtained results demonstrate that phthalocyanines incorporation into tunable-polymeric micelles significantly enhanced their cellular uptake and their photocytotoxicity. The improved biodistribution and photodynamic efficacy of the phthalocyanines-triblock copolymer conjugates was also confirmed in vivo in CT26 bearing BALB/c mice. PDT with both compounds led to tumor growth inhibition in all treated animals. Fluorinated phthalocyanine 2 turned out to be the most effective anticancer agent as the tumors of 20% of mice treated regressed completely and did not appear for over one year after treatment. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  2. Copper catalysed synthesis of indolylquinazolinone alkaloid ...

    Indian Academy of Sciences (India)

    We describe the total synthesis of indolylquinazolinone alkaloid bouchardatine and some of the quinazolinone derivatives. The aerobic oxidation induced by copper(I) bromide, followed by Vilsmeier-Haack formylation gives the natural product bouchardatine alkaloid in good yield.

  3. Iron (II) and copper (II) phthalocyanine-catalyzed synthesis of 2-nitro ...

    Indian Academy of Sciences (India)

    Meanwhile, major reaction parameters such as concentrations of catalyst and NaOH, reaction temperature and oxygen pressure have been investigated. Through optimization of the reaction parameters, the highest yield of NMSBA and conversion of NMST (up to 53%, 89.3%, respectively) were achieved with oxygen (2.0 ...

  4. and copper(II) phthalocyanine-catalyzed synthesis of 2-nitro-4 ...

    Indian Academy of Sciences (India)

    CHENG HUANG

    2017-09-22

    Sep 22, 2017 ... reacted for 8 h. The reaction solution was diluted with the solvent to a certain volume to be quantitatively analyzed the. NMST conversion and NMSBA yield by high-performance liquid chromatography (HPLC). 2.3 Analytical methods. The concentration of NMST and NMSBA was analyzed by. HPLC (Dionex ...

  5. Photodynamic therapy potential of thiol-stabilized CdTe quantum dot-group 3A phthalocyanine conjugates (QD-Pc)

    Science.gov (United States)

    Tekdaş, Duygu Aydın; Durmuş, Mahmut; Yanık, Hülya; Ahsen, Vefa

    Thiol stabilized CdTe quantum dot (QD) nanoparticles were synthesized in aqueous phase and were used as energy donors to tetra-triethyleneoxythia substituted aluminum, gallium and indium phthalocyanines through fluorescence resonance energy transfer (FRET). Energy transfer occurred from the QDs to phthalocyanines upon photoexcitation of the QDs. An enhancement in efficiency of energy transfer with the nature of the carboxylic thiol stabilizer on the QDs was observed. As a result of the nanoparticle and the phthalocyanine mixing, the photoluminescence efficiency of the phthalocyanine moieties in the mixtures does not strictly follow the quantum yields of the bare phthalocyanines. The photochemistry study of phthalocyanines in the presence of the QDs revealed high singlet oxygen quantum yield, hence the possibility of using QDs in combination with phthalocyanines as photosensitizers in photodynamic therapy of cancer. The fluorescence of the CdTe quantum dots-phthalocyanine conjugates (QDs-Pc) were effectively quenched by addition of 1,4-benzoquinone.

  6. Copper metallothioneins.

    Science.gov (United States)

    Calvo, Jenifer; Jung, Hunmin; Meloni, Gabriele

    2017-04-01

    Metallothioneins (MTs) are a class of low molecular weight and cysteine-rich metal binding proteins present in all the branches of the tree of life. MTs efficiently bind with high affinity several essential and toxic divalent and monovalent transition metals by forming characteristic polynuclear metal-thiolate clusters within their structure. MTs fulfil multiple biological functions related to their metal binding properties, with essential roles in both Zn(II) and Cu(I) homeostasis as well as metal detoxification. Depending on the organism considered, the primary sequence, and the specific physiological and metabolic status, Cu(I)-bound MT isoforms have been isolated, and their chemistry and biology characterized. Besides the recognized role in the biochemistry of divalent metals, it is becoming evident that unique biological functions in selectively controlling copper levels, its reactivity as well as copper-mediated biochemical processes have evolved in some members of the MT superfamily. Selected examples are reviewed to highlight the peculiar chemical properties and biological functions of copper MTs. © 2016 IUBMB Life, 69(4):236-245, 2017. © 2017 International Union of Biochemistry and Molecular Biology.

  7. Synthesis of Two Potentially Heptadentate (N4O3 Schiff-base Ligands Derived from Condensation of Tris(3-aminopropyl-amine and Salicylaldehyde or 4-Hydroxysalicylaldehyde. Nickel(II and Copper(II Complexes of the Former Ligand

    Directory of Open Access Journals (Sweden)

    R. V. Parish

    2002-02-01

    Full Text Available Two potentially heptadentate (N4O3 tripodal Schiff-base ligands: tris(3-(salicylideneiminopropylamine (H3L1 and tris(3-(4’-hydroxysalicylideneimino-propylamine (H3L2 have been prepared and characterized by various spectroscopic methods (IR, FAB-MS, NMR. They are derived from the condensation reactions of tris(3-aminopropylamine (tpt, with 3 equivalents of either salicylaldehyde or the ringsubstituted salicylaldehyde, 4-hydroxysalicylaldehyde. The nickel(II and copper(II complexes of H3L1 were obtained from the its reactions Ni(II and Cu(II salts in absolute methanol. These complexes were studied by IR and FAB-Mass spectrometry.

  8. Vibrational spectroscopic analysis of aluminum phthalocyanine chloride. experimental and DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Soliman, I.M., E-mail: solidhima@gmail.com [Physics Department, Faculty of Science, Ain Shams University, Abbasia, Cairo (Egypt); El-Nahass, M.M. [Physics Department, Faculty of Education, Ain Shams University, Roxy, Cairo (Egypt); Eid, Kh.M. [Physics Department, Faculty of Education, Ain Shams University, Roxy, Cairo (Egypt); Physics department, Bukairiayh for Sciences & Arts, Quassim University, Quassim (Saudi Arabia); Ammar, H.Y. [Physics Department, Faculty of Arts and science, Najran University, Najran (Saudi Arabia)

    2016-06-15

    In this work, we report a combined experimental and theoretical study of aluminum phthalocyanine chloride (AlPcCl). The FT-IR and Raman spectra of AlPcCl were recorded and analyzed. The density functional theory (DFT) computations have been performed at B3LYP/6-31g and B3LYP/6-311g to derive equilibrium geometry, vibrational wavenumbers, intensity and NLO properties. All the observed vibrational bands have been discussed and assigned to normal mode or to combinations on the basis of our DFT calculations as a primary source of attribution and also by comparison with the previous results for similar compounds. The natural bond orbital (NBO) calculations were performed to study the atomic charge distribution of the investigated compound. The calculated results showed that dipole moment of the investigated compound was 4.68 Debye and HOMO-LUMO energy gap was 2.14 eV. The lowering of frontier orbital gap appears to be the cause of its enhanced charge transfer interaction.

  9. The carbonate radical anion-induced covalent aggregation of human copper, zinc superoxide dismutase, and alpha-synuclein: intermediacy of tryptophan- and tyrosine-derived oxidation products.

    Science.gov (United States)

    Zhang, Hao; Andrekopoulos, Christopher; Joseph, Joy; Crow, John; Kalyanaraman, B

    2004-06-01

    In this review, we describe the free radical mechanism of covalent aggregation of human copper, zinc superoxide dismutase (hSOD1). Bicarbonate anion (HCO3-) enhances the covalent aggregation of hSOD1 mediated by the SOD1 peroxidase-dependent formation of carbonate radical anion (CO3*-), a potent and selective oxidant. This species presumably diffuses out the active site of hSOD1 and reacts with tryptophan residue located on the surface of hSOD1. The oxidative degradation of tryptophan to kynurenine and N-formyl kynurenine results in the covalent crosslinking and aggregation of hSOD1. Implications of oxidant-mediated aggregation of hSOD1 in the increased cytotoxicity of motor neurons in amyotrophic lateral sclerosis are discussed.

  10. Synthesis, Characterization, Crystal Structure and Antimicrobial Activity of Copper(II Complexes with the Schiff Base Derived from 2-Hydroxy-4-Methoxybenzaldehyde

    Directory of Open Access Journals (Sweden)

    Elena Pahonțu

    2015-04-01

    Full Text Available A novel Schiff base, ethyl 4-[(E-(2-hydroxy-4-methoxyphenylmethylene-amino]benzoate (HL, was prepared and structurally characterized on the basis of elemental analyses, 1H NMR, 13C NMR, UV-Vis and IR spectral data. Six new copper(II complexes, [Cu(L(NO3(H2O2] (1, [Cu(L2] (2, [Cu(L(OAc] (3, [Cu2 (L2Cl2(H2O4] (4, [Cu(L(ClO4(H2O] (5 and [Cu2(L2S(ClO4(H2O]ClO4·H2O (6 have been synthesized. The characterization of the newly formed compounds was done by IR, UV-Vis, EPR, FAB mass spectroscopy, elemental and thermal analysis, magnetic susceptibility measurements and molar electric conductivity. The crystal structures of Schiff base and the complex [Cu2(L2S(ClO4(H2O]ClO4·H2O (6 have been determined by single crystal X-ray diffraction studies. Both copper atoms display a distorted octahedral coordination type [O4NS]. This coordination is ensured by three phenol oxygen, two of which being related to the µ-oxo-bridge, the nitrogen atoms of the azomethine group and the sulfur atoms that come from the polydentate ligand. The in vitro antimicrobial activity against Escherichia coli ATCC 25922, Salmonella enteritidis, Staphylococcus aureus ATCC 25923, Enterococcus and Candida albicans strains was studied and compared with that of free ligand. The complexes 1, 2, 5 showed a better antimicrobial activity than the Schiff base against the tested microorganisms.

  11. Sensing Properties of Cobalt-Phthalocyanine-Based Multipurpose Sensor

    Science.gov (United States)

    Wahab, Fazal; Sayyad, M. H.; Khan, Dil Nawaz; Tahir, Muhammad; Aziz, Fakhra; Khan, Rashid; Karimov, Kh. S.

    2017-04-01

    Cobalt phthalocyanine (CoPc), an organic semiconductor, has been introduced as an active sensing layer in a surface-type multipurpose sensor owing to its stability, low fabrication cost, and multifunctional sensitivity. The capacitance of the sensor was recorded to increase 26.7-fold for a change in relative humidity (RH) from 0% to 92.3%, 12.6-fold for a change in illumination from 11.5 lx to 23,000 lx, and 5.2-fold for a change in temperature from 27°C to 187°C. The morphology of the active thin film of the sensor was analyzed by atomic force microscopy, revealing a rough surface favorable for moisture absorption and light harvesting. The CoPc film was amorphous in nature according to x-ray diffraction analysis. By virtue of its response to humidity, light, and temperature, this represents an attractive approach for cost-effective environmental sensing applications.

  12. Copper and Copper Proteins in Parkinson's Disease

    OpenAIRE

    Sergio Montes; Susana Rivera-Mancia; Araceli Diaz-Ruiz; Luis Tristan-Lopez; Camilo Rios

    2014-01-01

    Copper is a transition metal that has been linked to pathological and beneficial effects in neurodegenerative diseases. In Parkinson’s disease, free copper is related to increased oxidative stress, alpha-synuclein oligomerization, and Lewy body formation. Decreased copper along with increased iron has been found in substantia nigra and caudate nucleus of Parkinson’s disease patients. Copper influences iron content in the brain through ferroxidase ceruloplasmin activity; therefore decreased pr...

  13. 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)

  14. Essential role of copper-zinc superoxide dismutase for ischemia-induced neovascularization via modulation of bone marrow-derived endothelial progenitor cells.

    Science.gov (United States)

    Groleau, Jessika; Dussault, Sylvie; Haddad, Paola; Turgeon, Julie; Ménard, Catherine; Chan, John S; Rivard, Alain

    2010-11-01

    To investigate the effect of oxidative stress on ischemia-induced neovascularization in copper-zinc (CuZn) superoxide dismutase (SOD)-deficient mice. In the vascular wall, CuZnSOD is essential for protecting against excessive oxidative stress and maintaining endothelial function. However, its specific role for the development of new vessels in response to ischemia is unknown. After surgically induced hind limb ischemia, CuZnSOD-deficient mice showed impaired neovascularization, as assessed by blood flow recuperation (laser Doppler) and capillary density in the ischemic muscles. This was associated with increased levels of oxidative stress in ischemic tissues and peripheral blood, together with reduced plasmatic NO production. CuZnSOD-deficient mice demonstrated an important reduction in the number of endothelial progenitor cells (EPCs) in the bone marrow and spleen. Moreover, EPCs isolated from CuZnSOD-deficient mice showed increased oxidative stress levels, decreased NO production, and a reduced ability to migrate and integrate into capillary-like networks. Importantly, the functional activities of CuZnSOD-deficient EPCs were rescued after treatment with the SOD-mimetic Tempol (a membrane-permeable radical scavenger) or the NO donor sodium nitroprusside (SNP). Moreover, the neovascularization defect in CuZnSOD-deficient mice could be rescued by wild-type (but not CuZnSOD-deficient) EPC supplementation. Protection against oxidative stress by CuZnSOD may be essential for EPC function and reparative neovascularization after ischemia.

  15. A new ternary copper(II) complex derived from 2-(2'-pyridyl)benzimidazole and glycylglycine: synthesis, characterization, DNA binding and cleavage, antioxidation and HSA interaction.

    Science.gov (United States)

    Fu, Xia-Bing; Lin, Zi-Hua; Liu, Hai-Feng; Le, Xue-Yi

    2014-03-25

    A new ternary copper(II)-dipeptide complex [Cu(glygly)(HPB)(Cl)]⋅2H2O (glygly=glycylglycine anion, HPB=2-(2'-pyridyl)benzimidazole) has been synthesized and characterized. The DNA interaction of the complex was studied by spectroscopic methods, viscosity, and electrophoresis measurements. The antioxidant activity was also investigated using the pyrogallol autoxidation assay. Besides, the interaction of the complex with human serum albumin (HSA) in vitro was examined by multispectroscopic techniques. The complex partially intercalated to CT-DNA with a high binding constant (Kb=7.28×10(5) M(-1)), and cleaved pBR322 DNA efficiently via an oxidative mechanism in the presence of Vc, with the HO· and O2(-) as the active species, and the SOD as a promoter. Furthermore, the complex shows a considerable SOD-like activity with the IC50 value of 3.8386 μM. The complex exhibits desired binding affinity to HSA, in which hydrogen bond or vander Waals force played a major role. The alterations of HSA secondary structure induced by the complex were confirmed by UV-visible, CD, synchronous fluorescence and 3D fluorescence spectroscopy. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. A new ternary copper(II) complex derived from 2-(2";-pyridyl)benzimidazole and glycylglycine: Synthesis, characterization, DNA binding and cleavage, antioxidation and HSA interaction

    Science.gov (United States)

    Fu, Xia-Bing; Lin, Zi-Hua; Liu, Hai-Feng; Le, Xue-Yi

    2014-03-01

    A new ternary copper(II)-dipeptide complex [Cu(glygly)(HPB)(Cl)]ṡ2H2O (glygly = glycylglycine anion, HPB = 2-(2";-pyridyl)benzimidazole) has been synthesized and characterized. The DNA interaction of the complex was studied by spectroscopic methods, viscosity, and electrophoresis measurements. The antioxidant activity was also investigated using the pyrogallol autoxidation assay. Besides, the interaction of the complex with human serum albumin (HSA) in vitro was examined by multispectroscopic techniques. The complex partially intercalated to CT-DNA with a high binding constant (Kb = 7.28 × 105 M-1), and cleaved pBR322 DNA efficiently via an oxidative mechanism in the presence of Vc, with the HO· and O2-rad as the active species, and the SOD as a promoter. Furthermore, the complex shows a considerable SOD-like activity with the IC50 value of 3.8386 μM. The complex exhibits desired binding affinity to HSA, in which hydrogen bond or vander Waals force played a major role. The alterations of HSA secondary structure induced by the complex were confirmed by UV-visible, CD, synchronous fluorescence and 3D fluorescence spectroscopy.

  17. Synthesis, DNA interaction and anticancer activity of copper(II) complexes with 4'-phenyl-2,2':6',2″-terpyridine derivatives.

    Science.gov (United States)

    Liang, Jie-Wen; Wang, Yi; Du, Ke-Jie; Li, Guan-Ying; Guan, Rui-Lin; Ji, Liang-Nian; Chao, Hui

    2014-12-01

    Three novel copper(II) complexes CuL(1)Cl2 (1) (L(1)=4'-(3-methoxyphenyl)-2,2':6'- 2″-terpyridine), CuL(2)Cl2 (2) (L(2)=4'-(4-methoxyphenyl)-2,2':6'-2″-terpyridine) and CuL(3)Cl2 (3) (L(3)=4'-(3,5-dimethoxyphenyl)-2,2':6'-2″-terpyridine) have been synthesized and characterized. Absorption spectral titration experiments, ethidium bromide displacement assays, and cyclic voltammetric experiments were carried out and the results suggested that these complexes bound to DNA through an intercalative mode. Moreover, these complexes were found to cleave pBR322 DNA efficiently in the presence of glutathione (GSH), and exhibited good anticancer activity against HeLa, Hep-G2 and BEL-7402 cell lines. Nuclear chromatin cleavage was also observed by acridine orange/ethidium bromide (AO/EB) staining assays and comet assays. These results demonstrated that these three Cu(II) complexes caused DNA damage and induced the apoptosis of HeLa cells. Mechanistic investigations revealed the participation of reactive oxygen species which can be trapped by reactive oxygen species (ROS) radical scavengers and ROS sensors. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. Photodynamic activity of BAM-SiPc, an unsymmetrical bisamino silicon(IV) phthalocyanine, in tumour-bearing nude mice.

    Science.gov (United States)

    Leung, S C H; Lo, P-C; Ng, D K P; Liu, W-K; Fung, K-P; Fong, W-P

    2008-05-01

    Ever since the discovery of photodynamic therapy, there has been a continuous search for more potent photosensitizers. Towards that end, we have synthesized a number of novel phthalocyanine derivatives. The unsymmetrical bisamino silicon(IV) phthalocyanine BAM-SiPc is one of the most potent compounds. In in vitro cell culture, it exhibits high phototoxicity against a number of cancer cell lines. In the present investigation, the in vivo effect of BAM-SiPc was studied in the tumour-bearing nude mice model. The biodistribution of BAM-SiPc was followed to evaluate its tumour selectivity and rate of clearance. The tumour volume in the hepatocarcinoma HepG2- and the colorectal adenocarcinoma HT29-bearing nude mice was measured after photodynamic therapy. The level of intrinsic toxicity induced was also investigated. Finally, the metabolism of BAM-SiPc in the 'normal' WRL68 liver cells and the hepatocarcinoma HepG2 cells was compared. The results not only showed significant tumour regression of HepG2 and growth inhibition of HT29 in the tumour-bearing nude mice, but also no apparent hepatic or cardiac injury with the protocol used. Histological analyses showed that apoptosis was induced in the solid tumour. BAM-SiPc could be metabolized by WRL68 liver cells but not by the hepatocarcinoma HepG2 cells. Unfortunately, BAM-SiPc did not show any specific targeting towards the tumour tissue. The efficiency of BAM-SiPc in inhibiting tumour growth makes it a good candidate for further evaluation. Enhancement of its uptake in tumour tissue by conjugation with biomolecules is currently under investigation.

  19. Molecular responses of mouse macrophages to copper and copper oxide nanoparticles inferred from proteomic analyses.

    Science.gov (United States)

    Triboulet, Sarah; Aude-Garcia, Catherine; Carrière, Marie; Diemer, Hélène; Proamer, Fabienne; Habert, Aurélie; Chevallet, Mireille; Collin-Faure, Véronique; Strub, Jean-Marc; Hanau, Daniel; Van Dorsselaer, Alain; Herlin-Boime, Nathalie; Rabilloud, Thierry

    2013-11-01

    The molecular responses of macrophages to copper-based nanoparticles have been investigated via a combination of proteomic and biochemical approaches, using the RAW264.7 cell line as a model. Both metallic copper and copper oxide nanoparticles have been tested, with copper ion and zirconium oxide nanoparticles used as controls. Proteomic analysis highlighted changes in proteins implicated in oxidative stress responses (superoxide dismutases and peroxiredoxins), glutathione biosynthesis, the actomyosin cytoskeleton, and mitochondrial proteins (especially oxidative phosphorylation complex subunits). Validation studies employing functional analyses showed that the increases in glutathione biosynthesis and in mitochondrial complexes observed in the proteomic screen were critical to cell survival upon stress with copper-based nanoparticles; pharmacological inhibition of these two pathways enhanced cell vulnerability to copper-based nanoparticles, but not to copper ions. Furthermore, functional analyses using primary macrophages derived from bone marrow showed a decrease in reduced glutathione levels, a decrease in the mitochondrial transmembrane potential, and inhibition of phagocytosis and of lipopolysaccharide-induced nitric oxide production. However, only a fraction of these effects could be obtained with copper ions. In conclusion, this study showed that macrophage functions are significantly altered by copper-based nanoparticles. Also highlighted are the cellular pathways modulated by cells for survival and the exemplified cross-toxicities that can occur between copper-based nanoparticles and pharmacological agents.

  20. Molecular Responses of Mouse Macrophages to Copper and Copper Oxide Nanoparticles Inferred from Proteomic Analyses*

    Science.gov (United States)

    Triboulet, Sarah; Aude-Garcia, Catherine; Carrière, Marie; Diemer, Hélène; Proamer, Fabienne; Habert, Aurélie; Chevallet, Mireille; Collin-Faure, Véronique; Strub, Jean-Marc; Hanau, Daniel; Van Dorsselaer, Alain; Herlin-Boime, Nathalie; Rabilloud, Thierry

    2013-01-01

    The molecular responses of macrophages to copper-based nanoparticles have been investigated via a combination of proteomic and biochemical approaches, using the RAW264.7 cell line as a model. Both metallic copper and copper oxide nanoparticles have been tested, with copper ion and zirconium oxide nanoparticles used as controls. Proteomic analysis highlighted changes in proteins implicated in oxidative stress responses (superoxide dismutases and peroxiredoxins), glutathione biosynthesis, the actomyosin cytoskeleton, and mitochondrial proteins (especially oxidative phosphorylation complex subunits). Validation studies employing functional analyses showed that the increases in glutathione biosynthesis and in mitochondrial complexes observed in the proteomic screen were critical to cell survival upon stress with copper-based nanoparticles; pharmacological inhibition of these two pathways enhanced cell vulnerability to copper-based nanoparticles, but not to copper ions. Furthermore, functional analyses using primary macrophages derived from bone marrow showed a decrease in reduced glutathione levels, a decrease in the mitochondrial transmembrane potential, and inhibition of phagocytosis and of lipopolysaccharide-induced nitric oxide production. However, only a fraction of these effects could be obtained with copper ions. In conclusion, this study showed that macrophage functions are significantly altered by copper-based nanoparticles. Also highlighted are the cellular pathways modulated by cells for survival and the exemplified cross-toxicities that can occur between copper-based nanoparticles and pharmacological agents. PMID:23882024

  1. Virus inactivation under the photodynamic effect of phthalocyanine zinc(II) complexes.

    Science.gov (United States)

    Remichkova, Mimi; Mukova, Luchia; Nikolaeva-Glomb, Lubomira; Nikolova, Nadya; Doumanova, Lubka; Mantareva, Vanya; Angelov, Ivan; Kussovski, Veselin; Galabov, Angel S

    2017-03-01

    Various metal phthalocyanines have been studied for their capacity for photodynamic effects on viruses. Two newly synthesized water-soluble phthalocyanine Zn(II) complexes with different charges, cationic methylpyridyloxy-substituted Zn(II)- phthalocyanine (ZnPcMe) and anionic sulfophenoxy-substituted Zn(II)-phthalocyanine (ZnPcS), were used for photoinactivation of two DNA-containing enveloped viruses (herpes simplex virus type 1 and vaccinia virus), two RNA-containing enveloped viruses (bovine viral diarrhea virus and Newcastle disease virus) and two nude viruses (the enterovirus Coxsackie B1, a RNA-containing virus, and human adenovirus 5, a DNA virus). These two differently charged phthalocyanine complexes showed an identical marked virucidal effect against herpes simplex virus type 1, which was one and the same at an irradiation lasting 5 or 20 min (Δlog=3.0 and 4.0, respectively). Towards vaccinia virus this effect was lower, Δlog=1.8 under the effect of ZnPcMe and 2.0 for ZnPcS. Bovine viral diarrhea virus manifested a moderate sensitivity to ZnPcMe (Δlog=1.8) and a pronounced one to ZnPcS at 5- and 20-min irradiation (Δlog=5.8 and 5.3, respectively). The complexes were unable to inactivate Newcastle disease virus, Coxsackievirus B1 and human adenovirus type 5.

  2. Effects of orientation at the phthalocyanine-CdSe interface on the electron transfer characteristics.

    Science.gov (United States)

    Golovanov, V V; Nazarchuk, B V; Golovanova, V V; Tkachenko, N V; Rantala, T T

    2017-04-19

    A phthalocyanine molecule adsorbed on the (101[combining macron]0) surface of wurtzite CdSe is theoretically modeled by the DFT method. We have found that a linker does not affect substantially the redox properties of phthalocyanine, while saturation of the macrocycle with peripheral substituent groups causes a downward shift in the energy position of its frontier orbitals that can hinder electron injection to the CdSe surface. Tilting of the phthalocyanine molecule relative to the surface also leads to the lowering of its molecular electronic levels relative to the bands of CdSe. At a tilting angle of 30°, the LUMO level of the dye appears to be lower than the conduction band minimum of cadmium selenide, which makes the electron transfer to its hybridized surface unfavorable. By contrast, the HOMO level of the phenylbutyric acid linker provides a suitable intermediate channel for the hole transfer from the valence band of CdSe to the phthalocyanine that points to the possible acceptor behavior of the phthalocyanine molecule in its hybrids with CdSe nanostructures.

  3. Multinuclear Phthalocyanine-Fused Molecular Nanoarrays: Synthesis, Spectroscopy, and Semiconducting Property.

    Science.gov (United States)

    Shang, Hong; Xue, Zheng; Wang, Kang; Liu, Huibiao; Jiang, Jianzhuang

    2017-06-27

    The post-cyclization strategy rather than the conventional ante-cyclotetramerization method was employed for the synthesis of multinuclear phthalocyanine-fused molecular nanoarrays. Reaction of 2,3,9,10,16,17-hexakis(2,6-dimethylphenoxy)-23,24-diaminophthalocyaninato zinc(II) with 2,7-di-tert-butylpyrene-4,5-dione, 2,7-di-tert-butylpyrene-4,5,9,10-tetraone, and hexaketocyclohexane in refluxing acetic acid afforded the corresponding mono-, bi-, and trinuclear phthalocyanine-fused zinc complexes (Pz-pyrene){Zn[Pc(OC8 H9 )6 ]} (1), (Pz2 -pyrene){Zn[Pc(OC8 H9 )6 ]}2 (2), {(HAT){Zn[Pc(OC8 H9 )6 ]}3 } (3) in 46, 13, and 25 % yield, respectively, which extend the scope of multinuclear phthalocyanine-fused nanoarrays with different molecular skeletons. The self-assembly behavior of trinuclear phthalocyanine 3 in THF/CH3 CN was investigated by electronic absorption spectroscopy and SEM, and the fabricated nanorods showed interesting semiconducting properties, which suggest good application potential of these multinuclear phthalocyanine-fused molecular nanoarrays. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Fluorescent Phthalocyanine Assembly Distinguishes Chiral Isomers of Different Types of Amino Acids and Sugars.

    Science.gov (United States)

    Jiang, Yuying; Liu, Chenxi; Wang, Xiqian; Wang, Tianyu; Jiang, Jianzhuang

    2017-07-25

    The functions of some natural supramolecular architectures, such as ribosomes, are dependent on the recognition of different types of chiral biomolecules. However, the recognition of different types of chiral molecules (multiobject chiral recognition), such as amino acids and sugars, by independent and identically artificial supramolecular assembly, was rarely achieved. In this article, simple amphiphilic achiral phthalocyanine was found to form supramolecular chiral assemblies with charged water-soluble polymers upon host-guest interactions at the air/water interface. Among these systems, one identical phthalocyanine/poly(l-lysine) assembly not only can distinguish enantiomers of different amino acids but also can recognize several epimers of monose. The chiral recognitions were achieved by comparing either the steady-state fluorescence intensity or fluorescence quenching rate of phthalocyanine/poly(l-lysine) assemblies, before and after interaction with different small chiral molecules. It was demonstrated that the interactions between poly(l-lysine) and different small chiral molecules could change the aggregation of phthalocyanines. And the sensitivity of fluorescence and the excellent multiobject chiral recognition properties of the phthalocyanine/poly(l-lysine) assembly are dependent on the subtle molecular packing mode and the cooperation of different noncovalent interactions.

  5. Elaboration of ammonia gas sensors based on electrodeposited polypyrrole--cobalt phthalocyanine hybrid films.

    Science.gov (United States)

    Patois, Tilia; Sanchez, Jean-Baptiste; Berger, Franck; Fievet, Patrick; Segut, Olivier; Moutarlier, Virginie; Bouvet, Marcel; Lakard, Boris

    2013-12-15

    The electrochemical incorporation of a sulfonated cobalt phthalocyanine (sCoPc) in conducting polypyrrole (PPy) was done, in the presence or absence of LiClO4, in order to use the resulting hybrid material for the sensing of ammonia. After electrochemical deposition, the morphological features and structural properties of polypyrrole/phthalocyanine hybrid films were investigated and compared to those of polypyrrole films. A gas sensor consisting in platinum microelectrodes arrays was fabricated using silicon microtechnologies, and the polypyrrole and polypyrrole/phthalocyanine films were electrochemically deposited on the platinum microelectrodes arrays of this gas sensor. When exposed to ammonia, polymer-based gas sensors exhibited a decrease in conductance due to the electron exchange between ammonia and sensitive polymer-based layer. The characteristics of the gas sensors (response time, response amplitude, reversibility) were studied for ammonia concentrations varying from 1 ppm to 100 ppm. Polypyrrole/phthalocyanine films exhibited a high sensitivity and low detection limit to ammonia as well as a fast and reproducible response at room temperature. The response to ammonia exposition of polypyrrole films was found to be strongly enhanced thanks to the incorporation of the phthalocyanine in the polypyrrole matrix. © 2013 Elsevier B.V. All rights reserved.

  6. Enhancement of oxygen reduction activity of nanoshell carbons by introducing nitrogen atoms from metal phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Ozaki, Jun-ichi, E-mail: jozaki@cee.gunma-u.ac.j [Department of Chemical and Environmental Engineering, Graduate School of Engineering, Gunma University, 1-5-1, Tenjin-cho, Kiryu, Gunma 376-8515 (Japan); Tanifuji, Shin-ichi; Furuichi, Atsuya; Yabutsuka, Katsutoshi [Department of Chemical and Environmental Engineering, Graduate School of Engineering, Gunma University, 1-5-1, Tenjin-cho, Kiryu, Gunma 376-8515 (Japan)

    2010-02-15

    Nanoshell carbon is a type of catalytically grown nanocarbon with a hollow, round, shell-like structure, with a diameter in the range of approximately 20-50 nm. It has been shown to possess the electrocatalytic activity for oxygen reduction reaction (ORR) and is also expected to be a non-Pt catalyst for polymer electrolyte fuel cells. This paper reports the synergetic enhancement of the ORR activity of nanoshell carbons caused by the coexistence of nitrogen atoms. The nanoshell carbons were prepared by the carbonization of furan resin in the presence of acetylacetonates (AAs) and of phthalocyanines (Pcs), which contained Fe, Co, and Ni. The Pc-derived nanoshells (MP-T series; M = Co or Fe, T = carbonization temperature) showed higher ORR activities than the AA-derived nanoshells (MA-T series; M = Co or Fe, T = carbonization temperature) when the same metal elements were employed. An XPS study revealed that nitrogen species were introduced to the surface of the nanoshells when Pcs were used as the nanoshell-forming catalysts, and that no metal species remained on the nanoshells. Principally, the ORR activity of the carbons was governed by the presence of the nanoshells and further enhancement could be achieved by the introduction of nitrogen atoms. 0.78 V of OCV and 0.21 W cm{sup -2} of the maximum power density were observed for a fuel cell whose MEA consisted of 3CoP1000 cathode and a commercial Pt/C anode, when it was operated at 80 deg. C under a pressurized condition of 0.35 MPa.

  7. Antwerp Copper Plates

    DEFF Research Database (Denmark)

    Wadum, Jørgen

    1999-01-01

    In addition to presenting a short history of copper paintings, topics detail artists’ materials and techniques, as well as aspects of the copper industry, including mining, preparation and trade routes.......In addition to presenting a short history of copper paintings, topics detail artists’ materials and techniques, as well as aspects of the copper industry, including mining, preparation and trade routes....

  8. Synthesis, characterization and electrochemical studies of heterometallic manganese(IV)-zinc(II) and manganese(IV)-copper(II) complexes derived from bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone

    Science.gov (United States)

    Koch, Angira; Phukan, Arnab; Chanu, Oinam B.; Kumar, A.; Lal, R. A.

    2014-02-01

    Five manganese(IV) complexes [Mn(L)(bpy)] (1) and heterobimetallic complexes [MMn(L)Cl2(H2O)4]·1.5H2O (M = ZnII(2), CuII(3)) and [MnM(L)(bpy)Cl2] (M = ZnII(4), CuII(5)] have been synthesized from bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone (H4L) in methanol medium. The composition of the complexes have been established based on the data obtained from analytical, thermoanalytical and mass spectral studies. The structures of the complexes have been discussed in the light of molar conductance, magnetic moment, electronic, EPR, IR, FT-IR spectroscopic studies and transmission electron microscopies. The molar conductance values of these complexes in DMSO suggest their non-electrolytic nature. The μeff value for the complexes (1), (2) and (4) fall in the range 3.82-4.12 BM characteristic of the presence of the manganese(IV) in them. The complex (3) has μeff value of 3.70 BM at RT indicating considerable antiferromagnetic interaction between Mn(IV) and Cu(II). The μeff value of 4.72 BM for complex (5) is slightly lower than 4.90 BM for S = 2 ground state. In the complex (1) to (3), the ligand is coordinated to the metal centres as tetradentate ligand while in the complexes (4) and (5) as hexadentate ligand. Manganese(IV) has distorted octahedral stereochemistry in all complexes. Copper(II) has distorted octahedral and square planar stereochemistry in complexes (3) and (5) while zinc has distorted octahedral and tetrahedral stereochemistry, respectively. EPR studies of the complexes are also reported. The electron transfer reactions of the complexes have also been investigated by cyclic voltammetry.

  9. Copper and copper proteins in Parkinson's disease.

    Science.gov (United States)

    Montes, Sergio; Rivera-Mancia, Susana; Diaz-Ruiz, Araceli; Tristan-Lopez, Luis; Rios, Camilo

    2014-01-01

    Copper is a transition metal that has been linked to pathological and beneficial effects in neurodegenerative diseases. In Parkinson's disease, free copper is related to increased oxidative stress, alpha-synuclein oligomerization, and Lewy body formation. Decreased copper along with increased iron has been found in substantia nigra and caudate nucleus of Parkinson's disease patients. Copper influences iron content in the brain through ferroxidase ceruloplasmin activity; therefore decreased protein-bound copper in brain may enhance iron accumulation and the associated oxidative stress. The function of other copper-binding proteins such as Cu/Zn-SOD and metallothioneins is also beneficial to prevent neurodegeneration. Copper may regulate neurotransmission since it is released after neuronal stimulus and the metal is able to modulate the function of NMDA and GABA A receptors. Some of the proteins involved in copper transport are the transporters CTR1, ATP7A, and ATP7B and the chaperone ATOX1. There is limited information about the role of those biomolecules in the pathophysiology of Parkinson's disease; for instance, it is known that CTR1 is decreased in substantia nigra pars compacta in Parkinson's disease and that a mutation in ATP7B could be associated with Parkinson's disease. Regarding copper-related therapies, copper supplementation can represent a plausible alternative, while copper chelation may even aggravate the pathology.

  10. Copper and Copper Proteins in Parkinson's Disease

    Science.gov (United States)

    Rivera-Mancia, Susana; Diaz-Ruiz, Araceli; Tristan-Lopez, Luis; Rios, Camilo

    2014-01-01

    Copper is a transition metal that has been linked to pathological and beneficial effects in neurodegenerative diseases. In Parkinson's disease, free copper is related to increased oxidative stress, alpha-synuclein oligomerization, and Lewy body formation. Decreased copper along with increased iron has been found in substantia nigra and caudate nucleus of Parkinson's disease patients. Copper influences iron content in the brain through ferroxidase ceruloplasmin activity; therefore decreased protein-bound copper in brain may enhance iron accumulation and the associated oxidative stress. The function of other copper-binding proteins such as Cu/Zn-SOD and metallothioneins is also beneficial to prevent neurodegeneration. Copper may regulate neurotransmission since it is released after neuronal stimulus and the metal is able to modulate the function of NMDA and GABA A receptors. Some of the proteins involved in copper transport are the transporters CTR1, ATP7A, and ATP7B and the chaperone ATOX1. There is limited information about the role of those biomolecules in the pathophysiology of Parkinson's disease; for instance, it is known that CTR1 is decreased in substantia nigra pars compacta in Parkinson's disease and that a mutation in ATP7B could be associated with Parkinson's disease. Regarding copper-related therapies, copper supplementation can represent a plausible alternative, while copper chelation may even aggravate the pathology. PMID:24672633

  11. [Copper and copper alloys. Technology updates].

    Science.gov (United States)

    Loconsolo, V; Crespi, M

    2012-01-01

    The correlations between copper and copper alloys and human health have been the subject of some recent and extensive scientific researches. The voluntary risks evaluation, which anticipated the EU REACH Directive application, has shown that copper is a "safe" product for human health and for environment. In addition, it could be of great help thanks to its antibacterial properties. Copper tube can contribute in a relevant way to the prevention of water systems pollution by Legionella. Also the spreading of nosocomial infections is significantly contrasted by the use of copper and copper alloys for the production of articles intended for being frequently touched by people. The Environmental Protection Agency of the United States has in fact "registered" as antibacterial over 350 of copper alloys.

  12. Assessing the potential of group 13 and 14 metal/metalloid phthalocyanines as hole transport layers in organic light emitting diodes

    Energy Technology Data Exchange (ETDEWEB)

    Plint, Trevor; Lessard, Benoît H. [Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario M5S 3E5 (Canada); Bender, Timothy P. [Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario M5S 3E5 (Canada); Department of Materials Science and Engineering, University of Toronto, 184 College Street, Toronto, Ontario M5S 3E4 (Canada); Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada)

    2016-04-14

    In this study, we have assessed the potential application of group 13 and 14 metal and metalloid phthalocyanines ((X){sub 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){sub n}-MPc)(50 nm)/Alq{sub 3} (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/m{sup 2} 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 (Cl{sub 2}-SiPc, Cl{sub 2}-GePc, and Cl{sub 2}-SnPc, respectively) showed poor performance compared to Cl-AlPc, having peak luminances of only 38 ± 4 cd/m{sup 2} (12 V), 23 ± 1 cd/m{sup 2} (8.5 V), and 59 ± 5 cd/m{sup 2} (13.5 V), respectively. However, by performing a simple axial substitution of the chloride groups of Cl{sub 2}-SiPc with pentafluorophenoxy groups, the resulting bis(pentafluorophenoxy) silicon phthalocyanine (F{sub 10}-SiPc) containing OLED had a peak luminance of 5141 ± 941 cd/m{sup 2} (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.

  13. Nonlinear optical and optical limiting properties of polymeric carboxyl phthalocyanine coordinated with rare earth atom

    Science.gov (United States)

    Zhao, Peng; Wang, Zonghua; Chen, Jishi; Zhou, Yu; Zhang, Fushi

    2017-04-01

    The nonlinear optical properties of the polymeric carboxyl phthalocyanine with lanthanum (LaPPc.COOH), holmium (HoPPc.COOH) and ytterbium (YbPPc.COOH) as centric atom, were investigated by the Z-scan method using a picosecond 532 nm laser. The synthesized phthalocyanines had steric polymeric structure and dissolved well in aqueous solution. The nonlinear optical response of them was attributed to the reverse saturable absorption and self-focus refraction. The nonlinear absorption properties decreased with the centric atoms changing from La, Ho to Yb. The largest second-order hyperpolarizability and optical limiting response threshold of LaPPc.COOH were 3.89 × 10-29 esu and 0.32 J/cm2, respectively. The reverse saturable absorption was explained by a three level mode of singlet excited state under the picosecond irradiation. The result indicates the steric structure presented additive stability of these polymeric phthalocyanines for their application as potential optical limiting materials.

  14. Hollow silica nanoparticles loaded with hydrophobic phthalocyanine for near-infrared photodynamic and photothermal combination therapy.

    Science.gov (United States)

    Peng, Juanjuan; Zhao, Lingzhi; Zhu, Xingjun; Sun, Yun; Feng, Wei; Gao, Yanhong; Wang, Liya; Li, Fuyou

    2013-10-01

    Owing to the convenience and minimal invasiveness, phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), is emerging as a powerful technique for cancer treatment. To date, however, few examples of combination PDT and PTT have been reported. Phthalocyanine (Pc) is a class of traditional photosensitizer for PDT, but its bioapplication is limited by high hydrophobicity. In this present study, hollow silica nanospheres (HSNs) were employed to endow the hydrophobic phthalocyanine with water-dispersity, and the as-prepared hollow silica nanoparticles loaded with hydrophobic phthalocyanine (Pc@HSNs) exhibits highly efficient dual PDT and PTT effects. In vitro and in vivo experimental results clearly indicated that the dual phototherapeutic effect of Pc@HSNs can kill cancer cells or eradicate tumor tissues. This multifunctional nanomedicine may be useful for PTT/PDT treatment of cancer. © 2013 Published by Elsevier Ltd.

  15. Au nanorods modulated NIR fluorescence and singlet oxygen generation of water soluble dendritic zinc phthalocyanine.

    Science.gov (United States)

    Zhou, Xuefei; He, Xiaohong; Wei, Shiliang; Jia, Kun; Liu, Xiaobo

    2016-11-15

    A novel cyano-terminated zinc phthalocyanine (ZnPc-CN) exhibiting visible near infrared (vis-NIR) emitting around 690nm in N,N-dimethylformamide (DMF) solvent has been synthesized. Furthermore, the peripheral cyano groups of newly synthesized zinc phthalocyanine were hydrolyzed in strong basic solution, leading to water soluble carboxylated zinc phthalocyanine (ZnPc-COOH) with completely quenched fluorescence in aqueous solution. Interestingly, we found that the NIR fluorescence of aqueous ZnPc-COOH was dramatically recovered in the presence of gold nanorods (Au NR), which was due to the alternation of ZnPc-COOH molecules self-assembling via electrostatic interaction between cetyltrimethylammonium bromide (CTAB) on the surface of Au NR and peripheral carboxyl of ZnPc-COOH. In addition, ZnPc-COOH/Au NR conjugates demonstrated an improved singlet oxygen generation, which could be served as potential bioimaging probe and photosensitizer for photodynamic therapy. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. 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.

  17. Dendrimer Phthalocyanine Theranostics for Flourescence Imaging and Photodynamic Therapy of Atheromatous Plagues

    DEFF Research Database (Denmark)

    Ficker, Mario

    the formation of singlet oxygen and enabled photodynamic therapy. In vivo studies in mice and rabbit models showed that the dendrimer phthalocyanine formulations could target the macrophage-rich plaque areas, which are the most vulnerable and dangerous plaques. No localization of the compound in the healthy...... therapy. For this purpose, a dendrimer nanoparticle system was developed that showed promising cytotoxicity and immunogenicity. These dendrimers were capable of solvating lipophilic phthalocyanines, which are second-generation photosensitizers. The dendrimer phthalocyanine conjugates had light emission...... endothelium was found, which is a necessity in order to successfully treat a patient without injuring healthy tissue. The high uorescence intensity and the selective targeting of the plaques enabled in vivo 2D-NIRF imaging using an angioplasty rabbit model. Photodynamic therapy studies were successfully...

  18. Azide-derivatized gold nanosphere "clicked" to indium and zinc phthalocyanines for improved nonlinear optical limiting

    Science.gov (United States)

    Bankole, Owolabi M.; Nyokong, Tebello

    2017-05-01

    We report on the conjugation of azide-derivatized gold nanoparticles (AuNPs) to alkyne moieties of ZnPc and InPc via azide-alkyne Huisgen cycloaddition reaction to form phthalocyanines-AuNPs (MPc-AuNPs) conjugates. The detailed structural characterizations of the composites were in good agreement with the expected results. The nonlinear absorption coefficients and other nonlinear optical limiting parameters were almost two times larger for the conjugates compared to free phthalocyanines. We established direct relationship between improved photophysical characterizations and enhanced nonlinear effects of reverse saturable absorption mechanisms favoured by excited triplet absorption of the phthalocyanines in the presence of AuNPs. The combination of InPc with AuNPs resulted in the lowest limiting intensity value of 0.06 J/cm2, hence the best performance in terms of optical limiting.

  19. Characterization of phthalocyanine functionalized quantum dots by dynamic light scattering, laser Doppler, and capillary electrophoresis.

    Science.gov (United States)

    Ramírez-García, Gonzalo; Oluwole, David O; Nxele, Siphesihle Robin; d'Orlyé, Fanny; Nyokong, Tebello; Bedioui, Fethi; Varenne, Anne

    2017-02-01

    In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy. Graphical Abstract Schematic illustration of the phthalocyanine capped QDs nanoconjugates and the capillary electrophoresis methods applied for size and ζ-potential characterization.

  20. Helical fibrous nanostructures self-assembled from metal-free phthalocyanine with peripheral chiral menthol units.

    Science.gov (United States)

    Lv, Wei; Wu, Xingcui; Bian, Yongzhong; Jiang, Jianzhuang; Zhang, Xiaomei

    2009-10-19

    (D)- and (L)-enantiomers of a novel metal-free 2(3),9(10),16(17),23(24)-tetrakis(2-isopropyl-5-methylcyclohexoxyl)phthalocyanine (1) with four chiral menthol units attached at the peripheral positions of a phthalocyanine ligand have been synthesized, and characterized. Neither the (D)-1 nor the (L)-1 enantiomer display a circular dichroism (CD) signal in the Soret and Q absorption region of the phthalocyanine ligand, indicating the lack of effective chiral information transfer from the chiral menthol tails to the phthalocyanine chromophore at the molecular level. Their self-assembly properties were systematically studied by CD spectroscopy, transmission electron microscopy, scanning electron microscopy, and atom force microscopy technique. Although four constitutional stereoisomers of each enantiomer were synthesized, because the four chiral menthol substituents are randomly located at peripheral positions of the phthalocyanine ring, cooperation of intermolecular pi-pi interactions between the phthalocyanine rings with chiral discrimination of the chiral side chains of the (D)-1 and the (L)-1 enantiomer induces the formation of one-dimensional helices with left- and right-handed helical molecular arrangement, respectively, according to the CD spectroscopic results. This reveals the effective chiral information transfer from the chiral menthol tails to the phthalocyanine chromophore at the supermolecular level. The formed one-dimensional helices twist around each other to maximize the van der Waals interaction, leading to the formation of highly ordered fibrous nanostructures with both right- and left-handed helicity according to the staggering angles between the neighboring phthalocyanine molecules, indicating the hierarchical formation of these fibrous nanostructures. Careful inspection of these nanofibers indicates the majority of nanofibers with right- and left-handed helicity formed from (D)-1 and (L)-1 enantiomer, respectively, with the ratio of approximately

  1. 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.

  2. Mixed configuration ground state in iron(II) phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Fernández-Rodríguez, Javier; Toby, Brian; van Veenendaal, Michel

    2015-06-01

    We calculate the angular dependence of the x-ray linear and circular dichroism at the L2,3 edges of α-Fe(II) Phthalocyanine (FePc) thin films using a ligand-field model with full configuration interaction. We find the best agreement with the experimental spectra for a mixed ground state of 3E (a2 e3b1 ) and 3B (a1 e4b1 ) g 1g g 2g 2g 1g g 2g with the two configurations coupled by the spin-orbit interaction. The 3Eg(b) and 3B2g states have easy-axis and easy-plane anisotropies, respectively. Our model accounts for an easy-plane magnetic anisotropy and the measured magnitudes of the in-plane orbital and spin moments. The proximity in energy of the two configurations allows a switching of the magnetic anisotropy from easy plane to easy axis with a small change in the crystal field, as recently observed for FePc adsorbed on an oxidized Cu surface. We also discuss the possibility of a quintet ground state (5A1g is 250 meV above the ground state) with planar anisotropy by manipulation of the Fe-C bond length by depositing the complex on a substrate that is subjected to a mechanical strain.

  3. 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.

  4. Adsorption studies of a microporous phthalocyanine network polymer.

    Science.gov (United States)

    Maffei, A Verena; Budd, Peter M; McKeown, Neil B

    2006-04-25

    The adsorption/desorption of N2 at 77 K and the adsorption from aqueous solution at 298 K of four organic probe molecules of different sizes (phenol, 4-nitrophenol, orange II, naphthol green B) were studied for a phthalocyanine network polymer of intrinsic microporosity (PIM) and for an activated carbon (Darco 20-40 mesh). N2 sorption analysis gave similar surface areas for the PIM and the carbon (610 and 545 m2 g(-1), respectively) but showed differences in pore size distribution, the PIM being essentially microporous (pore size < 2 nm), with a high proportion of ultramicropores (<0.7 nm), while the carbon had a broader pore size distribution, extending into the mesopore region. The carbon acted as an adsorbent for all the organic probe molecules studied, while the PIM was more selective, adsorbing the smaller molecules but rejecting the large dye naphthol green B. The PIM offers selectivity combined with a well-defined chemical structure incorporating catalytic sites.

  5. A novel copper complex supported on magnetic reduced graphene oxide: an efficient and green nanocatalyst for the synthesis of 1-amidoalkyl-2-naphthol derivatives

    Science.gov (United States)

    Kooti, M.; Karimi, M.; Nasiri, E.

    2018-02-01

    A new Cu(II) complex supported on magnetic reduced graphene oxide was prepared and characterized by various techniques, such as FT-IR, XRD, SEM, EDX, TEM, TGA, BET, ICP, and VSM. The synthesized nanocomposite, which has size distribution of 25-30 nm, was employed as catalyst in one-pot synthesis of 1-amidoalkyl-2-naphthols via three-component condensation reaction of amides, aromatic aldehydes, and 2-naphthol, under solvent-free conditions. The introduced catalysis procedure for the synthesis of 1-amidoalkyl-2-naphthol derivatives offers several advantages namely, short reaction times, high yields, facile recyclability, and cost effectiveness. [Figure not available: see fulltext.

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

    Science.gov (United States)

    Oshima, Tatsuya; Oshima, Chinatsu; Baba, Yoshinari

    2015-05-15

    Affinity extraction based on the interaction between a target molecule and a specific affinity ligand offers a novel separation system for biomolecules in an aqueous two-phase system, however, most of affinity ligands are expensive. In the present study, metal affinity extraction of histidine (His) derivatives using a complex between Cu(II) and a commercially available chelating ligand was studied in a poly(ethylene glycol) (PEG)/Li2SO4 ATPS. Alizarin complexone (3-[N,N-bis(carboxymethyl)amino methyl]-1,2-dihydroxy anthraquinone, AC) was selected as the chelating ligand because of the good extractability of Cu(II) into the upper PEG-rich phase. On the basis of coordinate bonding with Cu(II), the extraction of His in the presence of the Cu(II)-AC complex under neutral condition was 73%, which was much higher than that under Cu(II) free condition (13%). Among a series of divalent transition metal ions (Cu(II), Ni(II), Co(II), and Zn(II)), Cu(II) was the most effective for the extraction of His. Derivatives of His were selectively extracted in the presence of many other amino acids because of the specificity of the interaction between Cu(II) and imidazole group of His. Extracted His was quantitatively stripped from the Cu(II)-AC complex using competitive complexation with agents such as iminodiacetic acid and imidazole. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Lead and copper immobilization in a shooting range soil using soybean stover- and pine needle-derived biochars: Chemical, microbial and spectroscopic assessments

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, Mahtab [Korea Biochar Research Center & Department of Biological Environment, Kangwon National University, Chuncheon 200-701 (Korea, Republic of); Soil Sciences Department, College of Food and Agricultural Sciences, King Saud University, PO Box 2460, Riyadh 11451 (Saudi Arabia); Ok, Yong Sik; Rajapaksha, Anushka Upamali; Lim, Jung Eun [Korea Biochar Research Center & Department of Biological Environment, Kangwon National University, Chuncheon 200-701 (Korea, Republic of); Kim, Byung-Yong; Ahn, Jae-Hyung [Agricultural Microbiology Division, National Academy of Agricultural Science, Rural Development Administration, Wanju 565-851 (Korea, Republic of); Lee, Young Han [Division of Plant Environment Research, Gyeongsangnam-do Agricultural Research and Extension Service, Jinju 660-360 (Korea, Republic of); Al-Wabel, Mohammad I [Soil Sciences Department, College of Food and Agricultural Sciences, King Saud University, PO Box 2460, Riyadh 11451 (Saudi Arabia); Lee, Sung-Eun, E-mail: selpest@knu.ac.kr [School of Applied Biosciences, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Lee, Sang Soo, E-mail: sslee97@kangwon.ac.kr [Korea Biochar Research Center & Department of Biological Environment, Kangwon National University, Chuncheon 200-701 (Korea, Republic of)

    2016-01-15

    Highlights: • Biochar immobilizes Pb and Cu in a contaminated shooting range soil. • Soybean stover-biochar is an efficient metal immobilizer than pine needle-biochar. • Biochar produced at 700 °C showed significant potential of sequestering C in soil. • Biochar showed less impact on the bacterial community than feedstock biomass. - Abstract: Biochar (BC) could be a potential candidate for the remediation of metal contaminated soil. Mechanistic understandings are needed for the appropriate selection of BC and investigating molecular microbial ecological interactions. The soybean stover-derived BCs were more effective in immobilizing Pb (88%) and Cu (87%) than the pine needle-derived BCs in a contaminated shooting range soil. The sequential chemical extractions indicated that BCs stimulated the geochemical transformation of metal species. Spectroscopic investigations using scanning electron microscopic elemental dot mapping and extended X-ray absorption fine structure spectroscopic measurements showed that Pb in the BCs amended soils was immobilized by the formation of stable chloropyromorphite. Soil organic C and microbial activity were also enhanced by BC. The non-labile C fraction in the soil amended with BCs produced at 700 °C was increased. Biochars showed less impact on the bacterial community than feedstock biomass as promulgated by the pyrosequencing of 16S rRNA gene. The feedstock type (namely soybean stover and pine needles) was the main factor influencing the BCs efficacy on metals’ (im) mobilization and bacterial health in soils.

  8. Enhanced photodynamic leishmanicidal activity of hydrophobic zinc phthalocyanine within archaeolipids containing liposomes

    Science.gov (United States)

    Perez, Ana Paula; Casasco, Agustina; Schilrreff, Priscila; Defain Tesoriero, Maria Victoria; Duempelmann, Luc; Altube, Maria Julia; Higa, Leticia; Morilla, Maria Jose; Petray, Patricia; Romero, Eder L

    2014-01-01

    In this work, the in vitro anti-Leishmania activity of photodynamic liposomes made of soybean phosphatidylcholine, sodium cholate, total polar archaeolipids (TPAs) extracted from the hyperhalophile archaea Halorubrum tebenquichense and the photosensitizer zinc phthalocyanine (ZnPcAL) was compared to that of ultradeformable photodynamic liposomes lacking TPAs (ZnPcUDLs). We found that while ZnPcUDLs and ZnPcALs (130 nm mean diameter and −35 mV zeta potential) were innocuous against promastigotes, a low concentration (0.01 μM ZnPc and 7.6 μM phospholipids) of ZnPcALs irradiated at a very low-energy density (0.2 J/cm2) eliminated L. braziliensis amastigotes from J774 macrophages, without reducing the viability of the host cells. In such conditions, ZnPcALs were harmless for J774 macrophages, HaCaT keratinocytes, and bone marrow-derived dendritic cells. Therefore, topical photodynamic treatment would not likely affect skin-associated lymphoid tissue. ZnPcALs were extensively captured by macrophages, but ZnPcUDLs were not, leading to 2.5-fold increased intracellular delivery of ZnPc than with ZnPcUDLs. Despite mediating low levels of reactive oxygen species, the higher delivery of ZnPc and the multiple (caveolin- and clathrin-dependent plus phagocytic) intracellular pathway followed by ZnPc would have been the reason for the higher antiamastigote activity of ZnPcALs. The leishmanicidal activity of photodynamic liposomal ZnPc was improved by TPA-containing liposomes. PMID:25045264

  9. Phthalocyanine Doped Metal Oxide Nanoparticles on Multiwalled Carbon Nanotubes Platform for the detection of Dopamine

    Science.gov (United States)

    Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Fayemi, Omolola E.; Olasunkanmi, Lukman O.; Ebenso, Eno E.

    2017-03-01

    The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ.

  10. Effects of central metal on electronic structure, magnetic properties, infrared and Raman spectra of double-decker phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Oku, Takeo

    2016-09-01

    Graphical abstract: - Highlights: • Electron density distributions were delocalized on the phthalocyanine rings. • The chemical shift was separated by the nuclear quadrupole interaction based on the EFG and η. • The magnetic parameters were dependent on the perturbation of the crystal field. • The vibration modes were shifted by the asymmetrical structure. - Abstract: The effects of the central metal in double-decker metal phthalocyanine on the electronic structure, magnetic properties, and infrared and Raman spectra of the complex were investigated. Electron density distributions were delocalized on the phthalocyanine rings. The narrow energy gap and infrared peaks observed in the ultra-violet–visible–near infrared spectra of the systems were attributed to phthalocyanine ring–ring interactions the between overlapping π-orbitals on each ring. The chemical shift behavior of the phthalocyanine rings was separated by the deformation of their structure owing to nuclear magnetic interaction of the nuclear quadrupole interaction as determined by the electronic field gradient and asymmetric parameters. The magnetic parameters of principle g-tensors were dependent on the perturbation of the crystal field by the hybridization of the d-spin in the central metal conjugated with nitrogen ligands. In the case of the vanadyl system, the IR vibration modes were shifted by the soft vibration mode for resolving the symmetrical structure. Inactive Raman vibration modes arose from no-polarization on the phthalocyanine rings. Double-decker metal phthalocyanines have great advantages for the control of the magnetic mechanism for quantum spin entanglement in the relaxation process.

  11. Analytical approaches for clarification of DNA-double decker phthalocyanine binding mechanism: As an alternative anticancer chemotherapeutic.

    Science.gov (United States)

    Bağda, Esra; Yabaş, Ebru; Bağda, Efkan

    2017-02-05

    In the present study a novel water soluble double-decker phthalocyanine was synthesized and calf thymus DNA interaction of the synthesized double-decker phthalocyanine was investigated. 5-(3-pyridyl)-1,3,4-oxadiazole substituted phthalonitrile 1 was prepared by a nucleophilic displacement reaction of 4-nitrophthalonitrile with 5-(3-pyridyl)-1,3,4-oxadiazole-2-thiol. Lutetium(III) double-decker phthalocyanine 2 was prepared by cyclotetramerization of compound 1. Water soluble lutetium(III) double-decker phthalocyanine 3 was prepared with quaternarization of compound 2. The synthesized double-decker phthalocyanine and calf thymus DNA interaction was investigated with UV-vis titrimetric methods, gel electrophoresis, and viscosity measurements. The fluorometric ethidium bromide replacement assay was conducted to clarify the binding mode of water soluble double-decker phthalocyanine. The thermodynamic parameters for interaction, K, ΔG(0), ΔH(0) and ΔS(0) were calculated between the temperature ranges of 25°C-75°C. To the best of our knowledge, this is the first study about a double-decker phthalocyanine and DNA interaction. Copyright © 2016. Published by Elsevier B.V.

  12. Copper(II Complexes with Ligands Derived from 4-Amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one: Synthesis and Biological Activity

    Directory of Open Access Journals (Sweden)

    Raluca Cernat

    2006-11-01

    Full Text Available The synthesis of Cu(II complexes derived from Schiff base ligands obtainedby the condensation of 2-hydroxybenzaldehyde or terephtalic aldehyde with 4-amino-antipyrine (4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one is presented. The newlyprepared compounds were characterized by 1H-NMR, UV-VIS, IR and ESRspectroscopy. The determination of the antimicrobial activity of the ligands and of thecomplexes was carried out on samples of Escherichia coli, Klebsiella pneumoniae,Acinetobacter boumanii, Pseudomonas aeruginosa, Staphylococcus aureus and Candidasp. The qualitative and quantitative antimicrobial activity test results proved that all theprepared complexes are very active, especially against samples of Ps. aeruginosa, A.Boumanii, E. coli and S. aureus.

  13. Phototoxic effects of free phthalocyanine and phthalocyanine conjugated to gold nanoparticles for targeted photodynamic therapy of melanoma cancer

    Science.gov (United States)

    Manoto, Sello L.; Oluwole, David O.; Malabi, Rudzani; Maphanga, Charles; Ombinda-Lemboumba, Saturnin; Nyokong, Tebello; Mthunzi-Kufa, Patience

    2017-02-01

    Photodynamic therapy (PDT) has emerged as an effective treatment modality for various malignant neoplasia and diseases. In PDT, the photochemical interaction of photosensitizer (PS), light and molecular oxygen produces singlet oxygen which can lead to tumour cell apoptosis, necrosis or autophagy. The success of PDT is limited by the hydrophobic characteristic of the PS which hinders treatment administration and efficiency. To circumvent this limitation, PS can be incorporated in nanostructured drug delivery systems such as gold nanoparticles (AuNPs). In this study, we investigated the effectiveness of free zinc monocarboxyphenoxy phthalocyanine (ZnMCPPc) and ZnMCPPc conjugated to AuNPs. Commercially purchased melanoma cancer cells cultured as cell monolayers were used in this study. Changes in cellular response were evaluated using cellular morphology, viability, proliferation and cytotoxicity. Untreated cells showed no changes in cellular morphology, proliferation and cytotoxicity. However, photoactivated free ZnMCPPc and ZnMCPPc conjugated to AuNPs showed changes in cellular morphology and a dose dependent decrease in cellular viability and proliferation as well as an increase in cell membrane. ZnMCPPc conjugated to AuNPs showed an improved efficiency in PDT as compared to free ZnMCPPc, which might be as a result of the vehicle effect of AuNPs. Both PSs used in this study were effective in inducing cell death with ZnMCPPc conjugated to AuNPs showing great potential as an effective PS for PDT.

  14. Heat-Treated Metal Phthalocyanine Complex as an Oxygen Reduction Catalyst for Non-Aqueous Electrolyte Li/air Batteries

    Science.gov (United States)

    2011-01-01

    e lec tac ta Heat-treated metal phthalocyanine complex as an oxygen reduction catalyst for non-aqueous electrolyte Li/air batteries Sheng S. Zhang...Oxygen reduction Electrocatalysis Metal phthalocyanine complex Air electrode Li/air battery a b s t r a c t In this work we study heat-treated FeCu... phthalocyanine (FeCuPc) complexes as the catalyst for oxygen reduction in non-aqueous electrolyte Li/air cells by supporting the catalyst on a high

  15. Circular dichroism spectroscopic investigation of double-decker phthalocyanine with G-Quadruplex as promising telomerase inhibitor

    Science.gov (United States)

    Baǧda, Efkan; Baǧda, Esra; Yabaş, Ebru

    2017-01-01

    In the present study, interaction of a double-decker phthalocyanine with two G-quadruplex DNA, Tel 21 and cMYC, was investigated. To the best of our knowledge, this is the first study about G-quadruplex-double decker phthalocyanine interaction. The spectrophotometric titration method was used for binding constant calculations. From the binding constants, it can be said that double-decker phthalocyanine more likely to bind Tel 21 rather than cMYC. The conformational changes upon binding were monitored via circular dichroism spectroscopy. The ethidium bromide replacement assay was investigated spectrofluorometrically.

  16. Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato(-) Anions and Indium(III) Phthalocyanine Bromide Radical Anions.

    OpenAIRE

    Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2017-01-01

    Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu4 N(+) )2 [M(III) (HFl-O(-) )(Pc(.3-) )](.-) (Br(-) )⋅1.5 C6 H4 Cl2 [M=Al (1), Ga (2); HFl-O(-) =fluoren-9-olato(-) anion; Pc=phthalocyanine] and (Bu4 N(+) ) [In(III) Br(Pc(.3-) )](.-) ⋅0.875 C6 H4 Cl2 ⋅0.125 C6 H14 (3). The salts were found to contain Pc(.3-) radical anions with negatively charged ...

  17. Aquatic Life Criteria - Copper

    Science.gov (United States)

    Documents pertain to Aquatic Life Ambient Water Quality criteria for Copper (2007 Freshwater, 2016 Estuarine/marine). These documents contain the safe levels of Copper in water that should protect to the majority of species.

  18. Oligolysine-conjugated zinc(II) phthalocyanines as efficient photosensitizers for antimicrobial photodynamic therapy.

    Science.gov (United States)

    Ke, Mei-Rong; Eastel, Jennifer Mary; Ngai, Karry L K; Cheung, Yuk-Yam; Chan, Paul K S; Hui, Mamie; Ng, Dennis K P; Lo, Pui-Chi

    2014-07-01

    A series of zinc(II) phthalocyanines conjugated with an oligolysine chain (n=2, 4, and 8) were synthesized and characterized by using various spectroscopic methods. As shown by using UV/Vis and fluorescence spectroscopic methods, these compounds were nonaggregated in N,N-dimethylformamide, and gave a weak fluorescence emission and high singlet oxygen quantum yield (Φ(Δ) =0.86-0.89) as a result of their di-α-substitution. They became slightly aggregated in water with 0.05 % Cremophor EL, but they could still generate singlet oxygen effectively. The antimicrobial photodynamic activities of these compounds were then examined against various bacterial strains, including the Gram-positive methicillin-sensitive Staphylococcus aureus ATCC 25923 and methicillin-resistant Staphylococcus aureus ATCC BAA-43, and the Gram-negative Escherichia coli ATCC 35218 and Pseudomonas aeruginosa ATCC 27853. Generally, the dyes were much more potent toward the Gram-positive bacteria. Only 15 to 90 nM of these photosensitizers was required to induce a 4 log reduction in the cell viability of the strains. For Escherichia coli, the photocytotoxicity increased with the length of the oligolysine chain. The octalysine derivative showed the highest potency with a 4 log reduction concentration of 0.8 μM. Pseudomonas aeruginosa was most resistant to the photodynamic treatment. The potency of the tetralysine derivative toward a series of clinical strains of Staphylococcus aureus was also examined and found to be comparable with that toward the nonclinical counterparts. Moreover, the efficacy of these compounds in photodynamic inactivation of viruses was also examined. They were highly photocytotoxic against the enveloped viruses influenza A virus (H1N1) and herpes simplex virus type 1 (HSV1), but exhibited no significant cytotoxicity against the nonenveloped viruses adenovirus type 3 (Ad3) or coxsackievirus (Cox B1). The octalysine derivative also showed the highest potency with

  19. Characterizing the functional dynamics of zinc phthalocyanine from femtoseconds to nanoseconds

    NARCIS (Netherlands)

    Savolainen, Janne; van der Linden, Dennis; Dijkhuizen, Niels; Herek, Jennifer Lynn

    2008-01-01

    A promising photosensitizer, zinc phthalocyanine, is investigated by means of steady-state and time-resolved pump-probe spectroscopies. Spectrally resolved pump-probe data are recorded on time scales ranging from femtoseconds to nanoseconds. Global analysis yields the excited-state absorption

  20. STM and STS investigation of ultrathin tin phthalocyanine layers adsorbed on HOPG(0001) and Au(111)

    DEFF Research Database (Denmark)

    Walzer, Karsten; Hietschold, M.

    2001-01-01

    The initial adsorption of tin phthalocyanine (SnPc) on graphite and gold surfaces was studied by low-temperature UHV-STM. At submonolayer coverages on highly oriented pyrolytic graphite (HOPG), SnPc forms substrate-defined molecular chains, while SnPc monolayers reveal dense packed structures...

  1. Nanoparticles improve biological functions of phthalocyanine photosensitizers used for photodynamic therapy.

    Science.gov (United States)

    Jia, Xiao; Jia, Lee

    2012-10-01

    Photodynamic therapy (PDT) is a new technology using photodynamic effect for disease diagnosis and treatment. It is a two-step technique involving the uptake of a photosensitizer by cancer tissue followed by light irradiation that excites the photosensitizer to produce highly reactive oxygen species, the latter execute apoptosis of cancerous cells. As a second-generation of photosensitizers, phthalocyanine demonstrates higher absorption in the 650-800 nm range and short tissue accumulation compared to their first generation. However, many potent phthalocyanine photosensitizers are hydrophobic and poorly water-soluble, which limit their therapeutic applications. As a result, advanced delivery systems and different strategies are called for to improve the effectiveness of PDT. Facts have proved that using nanoparticles as carries of photosensitizers is a very promising route. Nanoparticles have the potentials to increase photosensitizers' aqueous solubility, bioavailability and stability, and deliver photosensitizers to the target tissues. This article reviewed the commonly-used nanoparticles, including colloid gold, quantum dots, paramagnetic nanoparticles, silica-based materials, polymer-based nanoparticles, as potential delivery systems for phthalocyanine photosensitizers, and summarized the improved biological functions of phthalocyanine photosensitizers in PDT.

  2. Evidence of a Chiral Superstructure in the Discotic Mesophase of an Optically Active Phthalocyanine

    NARCIS (Netherlands)

    Nostrum, Cornelus F. van; Bosman, Anton W.; Gelinck, Gerwin H.; Picken, Stephen J.; Schouten, Pieter G.; Warman, John M.; Schouten, Arend-Jan; Nolte, Roeland J.M.

    1993-01-01

    In the liquid crystalline phase of optically active phthalocyanine (S)-1 the columns are helically distorted, as has been shown by circular dichroism experiments on a Langmuir-Blodgett film of (S)-1 and by small angle X-ray diffraction studies, and confirmed by time-resolved microwave conductivity

  3. Spectroscopic insights on imidazole substituted phthalocyanine photosensitizers: fluorescence properties, triplet state and singlet oxygen generation.

    Science.gov (United States)

    Zhang, Xian-Fu; Lin, Yong; Guo, Wenfeng; Zhu, Jingzhong

    2014-12-10

    Imidazole substituted metal phthalocyanine (Pc) complexes were synthesized. UV-vis absorption, steady state and time-resolved fluorescence, as well as laser flash photolysis were used to measure the photophysical and photosensitizing properties. All the imidazole-phthalocyanine conjugates show high ΦT (quantum yield of excited triplet formation), high ΦΔ (singlet oxygen formation yield, >0.50) and good fluorescence properties (quantum yield Φf>0.20 and lifetime τf>3.0 ns). Compared to the unsubstituted Pc, both α- and β-imidazole substitutions result in the remarkable decrease in Φf and τf, but the α-substitution is stronger. The imidazole substitution, on the other hand, causes the increase of ΦT, τT, and ΦΔ values. Magnesium phthalocyanine (MgPc) is more susceptible to the substitution than zinc phthalocyanine (ZnPc). The mechanism responsible for the result is suggested based on the involvement of intramolecular photoinduced electron transfer. The high ΦΔ and appropriate fluorescence properties make the Pcs good candidate for PDT photosensitizers. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Photophysical and magnetic properties of magnetic silica gel-supported silicon phthalocyanine complexes.

    Science.gov (United States)

    Ozawa, Kazutaka; Ishii, Kazuyuki

    2009-02-21

    Enhanced S(1)--> T(1) intersystem crossing of silicon phthalocyanine (SiPc) owing to iron oxide nanoparticles and intense MCD signal of diamagnetic SiPc have been experimentally shown by using SiPcs supported on magnetic silica gel, in which the iron oxide nanoparticles were effectively dispersed.

  5. 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

  6. 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

  7. 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

  8. 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

  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. 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.

  11. Influence of Axial and Peripheral Ligands on the Electronic Structure of Titanium Phthalocyanines

    NARCIS (Netherlands)

    Pickup, David F.; Zegkinoglou, Ioannis; Ballesteros, Beatriz; Ganivet, Carolina R.; Garcia-Lastra, J. M.; Cook, Peter L.; Johnson, Phillip S.; Rogero, Celia; de Groot, Frank|info:eu-repo/dai/nl/08747610X; Rubio, Angel; de la Torre, Gema; Enrique Ortega, J.; Himpsel, F. J.

    2013-01-01

    To discover how molecular changes affect the electronic structure of dye molecules for solar cells, we have investigated four titanium phthalocyanines customized by axial and peripheral ligands (monodentate oxo versus bidentate catechol and tert-butyl versus tert-butylphenoxy, respectively). X-ray

  12. 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

  13. Porphyrin- or phthalocyanine-bridged silsesquioxane nanoparticles for two-photon photodynamic therapy or photoacoustic imaging.

    Science.gov (United States)

    Mauriello-Jimenez, Chiara; Henry, Maxime; Aggad, Dina; Raehm, Laurence; Cattoën, Xavier; Wong Chi Man, Michel; Charnay, Clarence; Alpugan, Serkan; Ahsen, Vefa; Tarakci, Deniz Kutlu; Maillard, Philippe; Maynadier, Marie; Garcia, Marcel; Dumoulin, Fabienne; Gary-Bobo, Magali; Coll, Jean-Luc; Josserand, Véronique; Durand, Jean-Olivier

    2017-11-09

    Porphyrin- or phthalocyanine-bridged silsesquioxane nanoparticles (BSPOR and BSPHT) were prepared. Their endocytosis in MCF-7 cancer cells was shown with two-photon excited fluorescence (TPEF) imaging. With two-photon excited photodynamic therapy (TPE-PDT), BSPOR was more phototoxic than BSPHT, which in contrast displayed a very high signal for photoacoustic imaging in mice.

  14. Delivery of a hydrophobic phthalocyanine photosensitizer using PEGylated gold nanoparticle conjugates for the in vivo photodynamic therapy of amelanotic melanoma.

    Science.gov (United States)

    Camerin, Monica; Moreno, Miguel; Marín, María J; Schofield, Claire L; Chambrier, Isabelle; Cook, Michael J; Coppellotti, Olimpia; Jori, Giulio; Russell, David A

    2016-05-11

    Photodynamic therapy (PDT) is a treatment of cancer whereby tumours are destroyed by reactive oxygen species generated upon photoactivation of a photosensitizer drug. Hydrophobic photosensitizers are known to be ideal for PDT; however, their hydrophobicity necessitates that they are typically administered using emulsions. Here, a delivery vehicle for photodynamic therapy based on the co-self-assembly of both a Zn(ii)-phthalocyanine derivative photosensitizer and a polyethylene glycol (PEG) derivative onto gold nanoparticles is reported. The PEG on the particle surface ensured that the conjugates were water soluble and enhanced their retention in the serum, improving the efficiency of PDT in vivo. The pharmacokinetic behaviour of the nanoparticle conjugates following intravenous injection into C57/BL6 mice bearing a subcutaneous transplanted B78H1 amelanotic melanoma showed a significant increase of retention of the nanoparticles in the tumour. PDT tumour destruction was achieved 3 h following injection of the nanoparticle conjugates leading to a remarkable 40% of the treated mice showing no tumour regrowth and complete survival. These results highlight that dual functionalised nanoparticles exhibit significant potential in PDT of cancer especially for difficult to treat cancers such as amelanotic melanoma.

  15. Layered composites of PEDOT/PSS/nanoparticles and PEDOT/PSS/phthalocyanines as electron mediators for sensors and biosensors

    Directory of Open Access Journals (Sweden)

    Celia García-Hernández

    2016-12-01

    Full Text Available The sensing properties of electrodes chemically modified with PEDOT/PSS towards catechol and hydroquinone sensing have been successfully improved by combining layers of PEDOT/PSS with layers of a secondary electrocatalytic material such as gold nanoparticles (PEDOT/PSS/AuNPs, copper phthalocyanine (PEDOT/PSS/CuPc or lutetium bisphthalocyanine (PEDOT/PSS/LuPc2. Layered composites exhibit synergistic effects that strongly enhance the electrocatalytic activity as indicated by the increase in intensity and the shift of the redox peaks to lower potentials. A remarkable improvement has been achieved using PEDOT/PSS/LuPc2, which exhibits excellent electrocatalytic activity towards the oxidation of catechol. The kinetic studies demonstrated diffusion-controlled processes at the electrode surfaces. The kinetic parameters such as Tafel slopes and charge transfer coefficient (α confirm the improved electrocatalytic activity of the layered electron mediators. The peak currents increased linearly with concentration of catechol and hydroquinone over the range of 1.5 × 10−4 to 4.0 × 10−6 mol·L−1 with a limit of detection on the scale of μmol·L−1. The layered composite hybrid systems were also found to be excellent electron mediators in biosensors containing tyrosinase and laccase, and they combine the recognition and biocatalytic properties of biomolecules with the unique catalytic features of composite materials. The observed increase in the intensity of the responses allowed detection limits of 1 × 10−7 mol·L−1 to be attained.

  16. Copper-tantalum alloy

    Science.gov (United States)

    Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

    1986-07-15

    A tantalum-copper alloy can be made by preparing a consumable electrode consisting of an elongated copper billet containing at least two spaced apart tantalum rods extending longitudinally the length of the billet. The electrode is placed in a dc arc furnace and melted under conditions which co-melt the copper and tantalum to form the alloy.

  17. The in vivo efficacy of phthalocyanine-nanoparticle conjugates for the photodynamic therapy of amelanotic melanoma.

    Science.gov (United States)

    Camerin, Monica; Magaraggia, Michela; Soncin, Marina; Jori, Giulio; Moreno, Miguel; Chambrier, Isabelle; Cook, Michael J; Russell, David A

    2010-07-01

    The efficiency of a Zn(II)-phthalocyanine disulphide (C11Pc), a compound with both phthalocyanine units bearing seven hexyl chains and a sulphur terminated C11 chain, as a photodynamic therapy (PDT) agent was investigated in C57 mice bearing a sub-cutaneously transplanted amelanotic melanoma. The phthalocyanine was intravenously injected at a dose of 1.5 micromol/kg body weight either free or bound to gold nanoparticles, using a Cremophor emulsion as a delivery vehicle. Biodistribution studies at selected post-injection times showed that the nanoparticle-associated C11Pc was recovered in significantly larger amounts from all the examined tissues and the serum and yielded a greater selectivity of tumour targeting: thus, the ratio between the amount of phthalocyanine recovered from the amelanotic melanoma and the skin (peritumoural tissue) increased from 2.3 to 5.5 from the free to the gold nanoparticle-bound C11Pc at 24 h after injection. PDT studies with the C11Pc-loaded amelanotic melanoma showed a markedly more significant response of the tumour in the mice that had received the nanoparticle-bound photosensitiser; the PDT effect was especially extensive if the irradiation was performed at 3h after C11Pc injection when large phthalocyanine amounts were still present in the serum. This suggests that the PDT promoted by C11Pc predominantly acts via vascular damage at least in this specific animal model. This hypothesis was fully confirmed by electron microscopy observations of tumour specimens obtained at different times after the end of PDT, showing an extensive damage of the blood capillaries and the endothelial cells. Copyright 2010 Elsevier Ltd. All rights reserved.

  18. Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato-Anions and Indium(III) Phthalocyanine Bromide Radical Anions.

    Science.gov (United States)

    Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2017-04-18

    Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu 4 N + ) 2 [M III (HFl-O - )(Pc .3- )] .- (Br - )⋅1.5 C 6 H 4 Cl 2 [M=Al (1), Ga (2); HFl-O - =fluoren-9-olato - anion; Pc=phthalocyanine] and (Bu 4 N + ) [In III Br(Pc .3- )] .- ⋅0.875 C 6 H 4 Cl 2 ⋅0.125 C 6 H 14 (3). The salts were found to contain Pc .3- radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc .3- in the near-IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl-O - anions in 1 and 2 with short Al-O and Ga-O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C-O bonds [1.402(3) and 1.391(11) Å in 1 and 2, respectively] in the HFl-O - anions are longer than the same bond in the fluorenone ketyl (1.27-1.31 Å). Salts 1-3 show effective magnetic moments of 1.72, 1.66, and 1.79 μ B at 300 K, respectively, owing to the presence of unpaired S=1/2 spins on Pc .3- . These spins are coupled antiferromagnetically with Weiss temperatures of -22, -14, and -30 K for 1-3, respectively. Coupling can occur in the corrugated two-dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J/k B =-0.9 and -1.1 K, respectively, and in the π-stacking {[In III Br(Pc .3- )] .- } 2 dimers of 3 with an exchange interaction of J/k B =-10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc .3- . It was found that increasing the size of the central metal atom strongly broadened these EPR signals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Intermolecular interaction of nickel (ii) phthalocyanine tetrasulfonic acid tetrasodium salt with bovine serum albumin: A multi-technique study.

    Science.gov (United States)

    Dezhampanah, Hamid; Firouzi, Roghaye; Hasani, Leila

    2017-02-01

    The interaction of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt with bovine serum albumin (BSA) has been investigated by combination of fluorescence, UV-vis absorption, Fourier transform infrared (FT-IR), and circular dichorism (CD) spectroscopies as well as through molecular docking. Fluorescence quenching and absorption spectra were investigated as a mean for estimating the binding parameters. Analysis of fluorescence quenching data at different temperatures was performed in order to specify the thermodynamics parameters for interactions of phthalocyanine complex with BSA. According to experimental data it was suggested that phthalocyanine had a significant binding affinity to BSA and the process was entropy driven. Based on the results of molecular docking it was indicated that the main active binding site for this phthalocyanine complex is site I in subdomain IIA of BSA. The results provide useful information for understanding the binding mechanism of anticancer drug-albumin and gives insight into the biological activity and metabolism of the drug in blood.

  20. Characterization of conjugates of NaYF4:Yb,Er,Gd upconversion nanoparticle with aluminium phthalocyanines

    Science.gov (United States)

    Watkins, Zane; Uddin, Imran; Britton, Jonathan; Nyokong, Tebello

    2017-02-01

    NaYF4:Er/Yb/Gd upconversion nanoparticles (UCNP) capped with amino groups were covalently attached to chloro aluminium tetrasulphonated phthalocyanine (ClAlTSPc) and chloro aluminium tetracarboxy phthalocyanine (ClAlTCPc). The conjugates were characterized using different techniques such as infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). There was a decrease in the intensity of fluorescence emission spectra of the UCNPs at 658 nm in the presence of the phthalocyanines. This decrease indicates an energy transfer between the donor UCNP and conjugated accepting phthalocyanine (Pc), due to Förster resonance energy transfer (FRET). FRET efficiencies of 18% and 21% for ClAlTSPc and ClAlTCPc, respectively, were obtained. Oxygen generation by ClAlTSPc following FRET was proved.

  1. Synthesis of new polymorphs of {mu}-oxo-metal(III) phthalocyanine dimers and their photoconductive properties; {mu}-okiso-kinzoku(III) futaroshianinni ryotai no shinki kessho hentai no tansaku to denshi shashin kankotai to shiteno tokusei hyoka

    Energy Technology Data Exchange (ETDEWEB)

    Yamasaki, Y.; Kuroda, K.; Takaki, K. [Orient Chemical Industries Ltd., Osaka (Japan). I-2Group, R and D Department

    1997-12-10

    The titled {mu}-oxo-metal(III) phthalocyanine dimers were prepared and investigated their polymorphs through X-ray diffraction analysis. It was found that {mu}-oxo-aluminum phthalocyanine dimer and {mu}-oxo-gallium phthalocyanine dimer have several polymorphs, but one of the target compounds, that is {mu}-oxo-indium phthalocyanine dimer, could not be synthesized because chloroindium phthalocyanine was easily hydrolyzed through acid-pasting treatment procedure to give metal-free phthalocyanine. The characterization of these compounds by the several chemical analytical methods was satisfied for the target molecules and the FD-Mass analysis distinguished clearly between the hydroxymetal phthalocyanine and the corresponding phthalocyanine dimer. We also studied their photoconductive properties on the bilayer photoreceptor consisted of the above phthalocyanine dimer as the charge generating material. It was found that the specific polymorphs of {mu}-oxo-metal(III) phthalocyanine dimers have good photoconductive properties: the APL-II(the II type of {mu}-oxo-Al(III) phthalocyanine dimer discussed in this article) has a good spectral response of the photosensitivity in the shorter wavelength, and the GPL-G (the G type of {mu}-oxo-Ga(III) phthalocyanine dimer discussed in this article) has a fairly high photosensitivity in the wavelength region of laser diode light wavelength, compared with the common phthalocyanine photoreceptors. 14 refs., 9 figs., 3 tabs.

  2. Scientific Opinion on dietary reference values for copper

    DEFF Research Database (Denmark)

    Sjödin, Anders Mikael

    2015-01-01

    Following a request from the European Commission, the EFSA Panel on Dietetic Products, Nutrition and Allergies (NDA) derived Dietary Reference Values (DRVs) for copper. Owing to the absence of appropriate biomarkers of copper status and the limitations of available balance studies, the Panel was ...

  3. Mechanistic studies of copper(II)-mediated oxidation of vic-dioxime ...

    Indian Academy of Sciences (India)

    plexes of 1,10-phenanthroline derived furoxans were isolated by oxidation of the corresponding copper(II) ... and nitrogen oxides, manganese dioxide, lead tetraace- ... of complex 3 fur- ther supports the reduction of copper(II) to copper(I) during the oxidative transformation of vic-dioxime to furoxan. 3. Mechanistic studies.

  4. High-potential perfluorinated phthalocyanine-fullerene dyads for generation of high-energy charge-separated states: formation and photoinduced electron-transfer studies.

    Science.gov (United States)

    Das, Sushanta K; Mahler, Andrew; Wilson, Angela K; D'Souza, Francis

    2014-08-25

    High oxidation potential perfluorinated zinc phthalocyanines (ZnF(n)Pcs) are synthesised and their spectroscopic, redox, and light-induced electron-transfer properties investigated systematically by forming donor-acceptor dyads through metal-ligand axial coordination of fullerene (C60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine- (Py) and phenylimidazole-functionalised fullerene (C60Im) derivatives to the zinc centre of the F(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) M(-1); nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6-31G* method. The HOMO and LUMO levels are located on the Pc and C60 entities, respectively; this suggests the formation of ZnF(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-C60Py(.-) (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C60 dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge-separated states. The energy of the charge-separated state for dyads composed of ZnF(n)Pc is higher than that of normal ZnPc-C60 dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar-energy harvesting and optoelectronic device building applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. Sporicidal efficacy of thermal-sprayed copper alloy coating.

    Science.gov (United States)

    Shafaghi, Romina; Mostaghimi, Javad; Pershin, Valerian; Ringuette, Maurice

    2017-05-01

    Approximately 200 000 Canadians acquire healthcare-associated bacterial infections each year and several-fold more acquire food-borne bacterial illnesses. Bacterial spores are particularly problematic because they can survive on surfaces for several months. Owing to its sporicidal activity, copper alloy sheet metal is sometimes used in hospital settings, but its widespread use is limited by cost and incompatibility with complex furniture and instrument designs and topographies. A potential alternative is the use of thermal spray technology to coat surfaces with copper alloys. We compared the sporicidal activity of thermally sprayed copper alloy on stainless steel with that of copper alloy sheet metal against Bacillus subtilis spores. Spores remained intact for at least 1 week on uncoated stainless steel, whereas spore fragmentation was initiated within 2 h of exposure to either copper surface. Less than 15% of spores were viable 2 h after exposure to either copper surface, as compared with stainless steel. By day 7, only degraded spores and petal-like nanoflowers were present on the copper surfaces. Nanoflowers, which are laminar arrangements of thin crystal sheets composed of carbon - copper phosphate, appeared to be derived from the degraded spores. Altogether, these results indicate that a thermal-sprayed copper alloy coating on stainless steel provides sporicidal activity similar to that afforded by copper alloy sheet metal.

  7. Hybrid ZnO/phthalocyanine photovoltaic device with highly resistive ZnO intermediate layer.

    Science.gov (United States)

    Izaki, Masanobu; Chizaki, Ryo; Saito, Takamasa; Murata, Kazufumi; Sasano, Junji; Shinagawa, Tsutomu

    2013-10-09

    We report a hybrid photovoltaic device composed of a 3.3 eV bandgap zinc oxide (ZnO) semiconductor and metal-free phthalocyanine layers and the effects of the insertion of the highly resistive ZnO buffer layer on the electrical characteristics of the rectification feature and photovoltaic performance. The hybrid photovoltaic devices have been constructed by electrodeposition of the 300 nm thick ZnO layer in a simple zinc nitrate aqueous solution followed by vacuum evaporation of 50-400 nm thick-phthalocyanine layers. The ZnO layers with the resistivity of 1.8 × 10(3) and 1 × 10(8) Ω cm were prepared by adjusting the cathodic current density and were installed into the hybrid photovoltaic devices as the n-type and buffer layer, respectively. The phthalocyanine layers with the characteristic monoclinic lattice showed a characteristic optical absorption feature regardless of the thickness, but the preferred orientation changed depending on the thickness. The ZnO buffer-free hybrid 50 nm thick phthalocyanine/n-ZnO photovoltaic device showed a rectification feature but possessed a poor photovoltaic performance with a conversion efficiency of 7.5 × 10(-7) %, open circuit voltage of 0.041 V, and short circuit current density of 8.0 × 10(-5) mA cm(-2). The insertion of the ZnO buffer layer between the n-ZnO and phthalocyanine layers induced improvements in both the rectification feature and photovoltaic performance. The excellent rectification feature with a rectification ratio of 3188 and ideally factor of 1.29 was obtained for the hybrid 200 nm thick phthalocyanine/ZnO buffer/n-ZnO photovoltaic device, and the hybrid photovoltaic device possessed an improved photovoltaic performance with the conversion efficiency of 0.0016%, open circuit voltage of 0.31 V, and short circuit current density of 0.015 mA cm(-2).

  8. Recovery of the bulk-like electronic structure of manganese phthalocyanine beyond the first monolayer on Bi2Te3

    Science.gov (United States)

    Hewitt, A. S.; Boltersdorf, J.; Maggard, P. A.; Dougherty, D. B.

    2017-08-01

    The evolution of electronic structure of manganese phthalocyanine on Bi2Te3 shows a transition to a bulk-like aspect abruptly after completion of the first layer. This allows the inference that, in the first layer, there is charge transfer and electronic hybridization involving the occupied Mn-derived d orbitals of the molecule into the conduction band of the substrate. The charge transfer coupling is seen using angle-resolved ultraviolet photoelectron spectroscopy by monitoring the evolution of work function and band structure with increasing molecular film thickness. The electronic structure in the second layer is more bulk-like as indicated by the reappearance of well-known low energy d orbitals that were depopulated in the first layer. Scanning tunneling microscopy shows that the transition to bulk like behavior is also reflected in film structure as a transition from a unique disordered monolayer to a locally ordered and dense second layer. These observations are relevant to ongoing efforts to control topological insulator interfaces especially for spintronics applications.

  9. Self-assembly of individually addressable complexes of C60 and phthalocyanines on a metal surface: Structural and electronic investigations

    Energy Technology Data Exchange (ETDEWEB)

    Samuely, Tomas [University of Basel (Switzerland); Liu, Shi-Xia; Haas, Marco; Decurtins, Silvio [University of Bern (Switzerland); Jung, Thomas [Paul-Scherrer-Institute (Switzerland); Stoehr, Meike [University of Groningen (Netherlands)

    2011-07-01

    A complex phase behavior was found for a specific phthalocyanine (Pc) derivative adsorbed on either Au(111) or Ag(111). The Pc molecule is symmetrically substituted with eight peripheral di-(tert-butyl)phenoxy (DTPO) groups. The pronounced ability of the DTPO groups to rotate, allows the molecule to adopt different conformations and hence to arrange itself in different ordered patterns. In particular, when all DTPO substituents are arranged above the plane of the Pc core (a bowl-like structure is formed), the interaction of the Pc core with the metal substrate is enabled. Moreover, for such an assembly the hosting properties for the adsorption of C{sub 60} were investigated. The C{sub 60} molecules adsorb at two clearly distinguishable positions on the predeposited Pc layer: they are in contact either with the metal substrate in between two adjacent Pc molecules or with the Pc core. For the latter case, the C{sub 60} is located directly above the pi-conjugated Pc core. Hence, the presented system combines the three following features: (i) the direct electronic interaction between donor and acceptor moieties, (ii) the formation by self-assembly, and (iii) thermal stability. Thereby, the direct investigation of a single donor-acceptor complex is enabled.

  10. Handling of Copper and Copper Oxide Nanoparticles by Astrocytes.

    Science.gov (United States)

    Bulcke, Felix; Dringen, Ralf

    2016-02-01

    Copper is an essential trace element for many important cellular functions. However, excess of copper can impair cellular functions by copper-induced oxidative stress. In brain, astrocytes are considered to play a prominent role in the copper homeostasis. In this short review we summarise the current knowledge on the molecular mechanisms which are involved in the handling of copper by astrocytes. Cultured astrocytes efficiently take up copper ions predominantly by the copper transporter Ctr1 and the divalent metal transporter DMT1. In addition, copper oxide nanoparticles are rapidly accumulated by astrocytes via endocytosis. Cultured astrocytes tolerate moderate increases in intracellular copper contents very well. However, if a given threshold of cellular copper content is exceeded after exposure to copper, accelerated production of reactive oxygen species and compromised cell viability are observed. Upon exposure to sub-toxic concentrations of copper ions or copper oxide nanoparticles, astrocytes increase their copper storage capacity by upregulating the cellular contents of glutathione and metallothioneins. In addition, cultured astrocytes have the capacity to export copper ions which is likely to involve the copper ATPase 7A. The ability of astrocytes to efficiently accumulate, store and export copper ions suggests that astrocytes have a key role in the distribution of copper in brain. Impairment of this astrocytic function may be involved in diseases which are connected with disturbances in brain copper metabolism.

  11. Electrolytic recovery of dilute copper from a mixed industrial effluent of high strength COD

    Energy Technology Data Exchange (ETDEWEB)

    Chellammal, S., E-mail: chellas_p@yahoo.co.in [Offshore Platform and Marine Electrochemistry Centre, CECRI Unit, New Harbour Area, Tuticorin 628 004, Tamil Nadu (India); Raghu, S.; Kalaiselvi, P.; Subramanian, G. [Offshore Platform and Marine Electrochemistry Centre, CECRI Unit, New Harbour Area, Tuticorin 628 004, Tamil Nadu (India)

    2010-08-15

    In this study, the electrochemical treatment has been investigated in the real acidic effluent of copper-phthalocyanine dye manufacturing plant. Galvanostatic batch electrolyses have been carried out in an undivided cell using stainless steel as cathode, dimensionally stable anode (DSA) and graphite as anodes at different current densities and temperatures. The influence of these variables on current efficiency, cell voltage, energy consumption and deposit quality was reported. Under optimized conditions, the maximum copper recovery of 98% and COD removal efficiency of 87.3% with the energy consumption of about 11.23 kWh/kg of Cu and 6.08 kWh/kg of COD, respectively at 30 deg. C were achieved in the acidic raw effluent using 2D parallel-plate cathode. While in 3D stainless steel turning cathode reactor, 99.5% of copper can efficiently be recovered from dilute solution with an acceptable current efficiency of about 56.8% with minimum energy consumption of 2.37 kWh/kg of Cu. The experimental results suggested that the efficiency of copper removal is hindered by the presence of organic species in the mixed industrial effluent.

  12. Biogenic nanoparticles: copper, copper oxides, copper sulphides, complex copper nanostructures and their applications.

    Science.gov (United States)

    Rubilar, Olga; Rai, Mahendra; Tortella, Gonzalo; Diez, Maria Cristina; Seabra, Amedea B; Durán, Nelson

    2013-09-01

    Copper nanoparticles have been the focus of intensive study due to their potential applications in diverse fields including biomedicine, electronics, and optics. Copper-based nanostructured materials have been used in conductive films, lubrification, nanofluids, catalysis, and also as potent antimicrobial agent. The biogenic synthesis of metallic nanostructured nanoparticles is considered to be a green and eco-friendly technology since neither harmful chemicals nor high temperatures are involved in the process. The present review discusses the synthesis of copper nanostructured nanoparticles by bacteria, fungi, and plant extracts, showing that biogenic synthesis is an economically feasible, simple and non-polluting process. Applications for biogenic copper nanoparticles are also discussed.

  13. Novel axially carborane-cage substituted silicon phthalocyanine photosensitizer; synthesis, characterization and photophysicochemical properties.

    Science.gov (United States)

    Atmaca, Göknur Yaşa; Dizman, Cemil; Eren, Tarık; Erdoğmuş, Ali

    2015-02-25

    The novel axially dicarborane substituted silicon (IV) (SiPc-DC) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl)2 (SiPc) with o-Carborane monool. The compound was characterized by mass spectrometry, UV-Vis, FT-IR, (1)H and (11)B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen (ΦΔ) and photodegradation quantum yield (Φd)) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies (ΦΔ=0.41, 0.39). Copyright © 2014 Elsevier B.V. All rights reserved.

  14. 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...

  15. Review Article: Structures of phthalocyanine molecules on surfaces studied by STM

    Directory of Open Access Journals (Sweden)

    Yongfeng Wang

    2012-12-01

    Full Text Available This review mainly focuses on progress recently achieved in the growth of phthalocyanine molecules on single-crystal surfaces of sub-monolayer up to few-monolayer thin films studied by scanning tunneling microscopy in our groups. On metallic surfaces such as Au(111, Ag(111 and Cu(111, molecular superstructures are determined by combining directional intermolecular interactions caused by symmetry reduction, molecule-substrate interactions and indirect long-range interactions due to quantum interference of surface state electrons. On semiconducting TiO2 surface, molecular assembling structures are dictated by the strong molecule-substrate interaction. However, on insulating NaCl film, molecule-molecule interaction dominates over the molecule-NaCl coupling, leading to molecular growth behavior. Knowledge obtained from these studies would help people better understand the physicochemical properties of the phthalocyanine molecules at surfaces so that their new applications could be further explored and uncovered in the future.

  16. Phthalocyanine-Biomolecule Conjugated Photosensitizers for Targeted Photodynamic Therapy and Imaging.

    Science.gov (United States)

    Iqbal, Zafar; Chen, Jincan; Chen, Zhuo; Huang, Mingdong

    2015-01-01

    Photodynamic therapy (PDT) is now in clinical practice in many European and American countries as a minimally invasive therapeutic technique to treat oncologic malignancies and other nononcologic conditions. Phthalocyanines (Pcs) are gathering importance as effective photosensitizers in targeted PDT and imaging of tumors. The possibility of modification around the Pc macrocycle led the researchers to the synthesis of a diversity of photosensitizers with varied cell specificity, cellular internalization and localization, photodynamic cytotoxicity and excretion. Cellular targeting is the primary aspect of an ideal photosensitizer for targeting PDT. Therefore, Pcs have been structurally modified with a variety of biomolecules capable of recognizing the specific lesions. This review emphasizes the photocytotoxicity and the cellular uptakes of phthalocyanine photosensitizers conjugated with biomolecules including carbohydrates, nucleotides and protein constituents such as amino acids and peptides. In addition, the role of the Pc-biomolecule conjugates in imaging and antimicrobial chemotherapy has been discussed.

  17. 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.

  18. Template Effect of the Graphene Moiré Lattice on Phthalocyanine Assembly

    Directory of Open Access Journals (Sweden)

    Nicolas Néel

    2017-05-01

    Full Text Available Superstructures of metal-free phthalocyanine (2H-Pc molecules on graphene-covered Ir(111 have been explored by scanning tunnelling microscopy. Depending on the sub-monolayer coverage different molecular assemblies form at the surface. They reflect the transition from a graphene template effect on the 2H-Pc arrangement to molecular superstructures that are mainly governed by the intermolecular coupling.

  19. Template Effect of the Graphene Moiré Lattice on Phthalocyanine Assembly.

    Science.gov (United States)

    Néel, Nicolas; Kröger, Jörg

    2017-05-03

    Superstructures of metal-free phthalocyanine (2H-Pc) molecules on graphene-covered Ir(111) have been explored by scanning tunnelling microscopy. Depending on the sub-monolayer coverage different molecular assemblies form at the surface. They reflect the transition from a graphene template effect on the 2H-Pc arrangement to molecular superstructures that are mainly governed by the intermolecular coupling.

  20. Electrocatalytic oxidation of Epinephrine and Norepinephrine at metal oxide doped phthalocyanine/MWCNT composite sensor

    OpenAIRE

    Mphuthi, Ntsoaki G.; Abolanle S. Adekunle; Ebenso, Eno E.

    2016-01-01

    Glassy carbon electrode (GCE) was modified with metal oxides (MO?=?Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, and the electrocatalytic properties were studied. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using FTIR, Raman and SEM techniques. The electrodes were characterized using cyclic voltammetry (CV) technique. The electrocatalytic behaviour of the electrode towards epinephrine (EP) and norepinephri...

  1. 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

  2. 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

  3. 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

  4. Lattice expansion of highly oriented 2D phthalocyanine covalent organic framework films.

    Science.gov (United States)

    Spitler, Eric L; Colson, John W; Uribe-Romo, Fernando J; Woll, Arthur R; Giovino, Marissa R; Saldivar, Abraham; Dichtel, William R

    2012-03-12

    Expanding into application: covalent organic framework (COF) films are ideally suited for vertical charge transport and serve as precursors of ordered heterojunctions. Their pores, however, were previously too small to accommodate continuous networks of complementary electron acceptors. Four phthalocyanine COFs with increased pore size well into the mesoporous regime are now described. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Copper-containing zeolite catalysts

    Science.gov (United States)

    Price, Geoffrey L.; Kanazirev, Vladislav

    1996-01-01

    A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl.sub.2, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

  6. In vivo photodynamic inactivation of Candida albicans using chloro-aluminum phthalocyanine.

    Science.gov (United States)

    Carmello, J C; Alves, F; Ribeiro, Apd; Basso, F G; de Souza Costa, C A; Tedesco, A C; Primo, F L; Mima, E G; Pavarina, A C

    2016-07-01

    This study evaluated the photoinactivation of Candida albicans in a murine model of oral candidiasis using chloro-aluminum phthalocyanine (ClAlP) encapsulated in cationic nanoemulsions (NE) and chloro-aluminum phthalocyanine (ClAlP) diluted in DMSO (DMSO) as photosensitizer (PS). Seventy-five 6-week-old female Swiss mice were immunosuppressed and inoculated with C. albicans to induce oral candidiasis. PDT was performed on the tongue by the application of the photosensitizers and LED light (100 J cm(-2) -660 nm). Twenty-four hours and 7 days after treatments, microbiological evaluation was carried out by recovering C. albicans from the tongue of animals (CFU ml(-1) ). Then, mice were sacrificed and the tongues were surgically removed for histological and biomolecular analysis of pro- and anti-inflammatory cytokines. Data were analyzed by ANOVA followed by Tukey's post hoc test. ClAlP-NE-mediated PDT reduced 2.26 log10 of C. albicans recovered from the tongue when compared with the control group (P-L-) (P phthalocyanine entrapped in cationic nanoemulsions was effective in reducing C. albicans recovered from the oral lesions of immunocompromised mice. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  7. 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.

  8. Phthalocyanine/chitosan-TiO{sub 2} photocatalysts: Characterization and photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Hamdi, A. [University of Sfax-Faculty of Science-LCI-Sfax-Tunisia (Tunisia); Boufi, S. [University of Sfax-Faculty of Science-LMSE-Sfax-Tunisia (Tunisia); Bouattour, S., E-mail: soraa.boufi@yahoo.com [University of Sfax-Faculty of Science-LCI-Sfax-Tunisia (Tunisia)

    2015-06-01

    Graphical abstract: - Highlights: • Hybrid chitosan–phthalocyanine-TiO{sub 2} photocatalyst are elaborated at room temperature without any calcination treatment. • After immersion in water, the alkoxide groups underwent hydrolysis and the (TiO{sub 6}) octahedra started to join together. • The enhanced activity of the hybrid catalyst is attributed to the cooperative role of the three components of the photocatalyst. - Abstract: Chitosan (CS) was used as a template to prepare a hybrid chitosan–phthalocyanine-TiO{sub 2} (PC/CS-TiO{sub 2}) photocatalyst at room temperature without any calcination treatment. The as-prepared hybrid photocatalyst (PC/CS-TiO{sub 2}) was characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and UV–vis diffuse reflectance spectroscopy (DRS). The results of the photodegradation of aniline, used as a model pollutant, revealed that the hybrid photocatalyst (PC/CS-TiO{sub 2}) exhibited a photocatalytic activity under visible-light irradiation. The enhanced activity of the hybrid catalyst is attributed to the cooperative role of the three components of the photocatalyst; chitosan as a template for the immobilization crystalline TiO{sub 2} nanoparticles, phthalocyanine that promote the light absorption in the visible range and TiO{sub 2} acting as an acceptor of electrons generated by the photons absorption to produce superoxide radicals.

  9. Aqueous speciation and electrochemical properties of a water-soluble manganese phthalocyanine complex.

    Science.gov (United States)

    Blakemore, James D; Hull, Jonathan F; Crabtree, Robert H; Brudvig, Gary W

    2012-07-07

    The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide : pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d(4)S = 2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pK(a) values is obtained by fitting the data to a standard pK(a) model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pK(a) values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts.

  10. Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

    Science.gov (United States)

    Blakemore, James D.; Hull, Jonathan F.

    2012-01-01

    The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

  11. 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.

  12. 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.

  13. Analysis of photoluminescence decay kinetics of aluminum phthalocyanine nanoparticles interacting with immune cells

    Directory of Open Access Journals (Sweden)

    F. G. Bystrov

    2016-01-01

    Full Text Available This work is dedicated to the study of the photoluminescence kinetics of aluminum phthalocyanine nanoparticles in colloidal solutions at different pH and in the interaction with immune cells (macrophages. For measurements we used a registration system based on Hamamatsu streak camera (C10627-13 Hamamatsu Photonics with picosecond temporal resolution (15 ps, conjugated with the fiberoptic spectrometer and picosecond laser pumping. The changes in fluorescence decay kinetics as additional lifetime components of fluorescence were found during the experiment. The number of components and duration of lifetimes changed while interacting with cells and depends on pH. At pH 2 the presence of two fluorescence lifetimes was recorded: the first one was 5 ns, which corresponded to the molecular form in solution, and 1.5 ns, which corresponded to bound state of phthalocyanine molecules. Due to the absence of other possible objects for bounding in the solution except of the nanoparticles we can suggest with a high degree of accuracy that the bounding occurs with the very these nanoparticles. Analysis of the fluorescence lifetimes of aluminum phthalocyanine nanoparticles in macrophages indicated the presence of two components: 9 ns and 4.5 ns. A model of surface molecules transitions from parallel to perpendicular position, regarding to the plane of the crystal nanoparticle was proposed.

  14. In vitro photodynamic effect by phthalocyanine in A549 cell line

    Science.gov (United States)

    Nevrelova, Pavla; Kolarova, Hana; Bajgar, Robert; Strnad, Miroslav

    2007-03-01

    Photodynamic therapy (PDT) utilizes a combination of sensitizer, visible light and molecular oxygen to generate singlet oxygen and reactive oxygen species (ROS) such as hydrogen peroxide, hydroxyl radical and superoxid anion. Photochemical reactions lead to damage and destruction of cancer cells. The most suitable and effective source of radiation used in PDT is a laser. For this study, a semiconductor laser with output power of 50 mW and 675 nm was selected. In this paper we report a generation of ROS using chloroaluminium disulphonated phthalocyanine (ClAlPcS II) in A549 bronchogenic carcinoma cell line after PDT in vitro. Phthalocyanines, belonging to a new generation of substances for PDT, exhibit effective tissue penetration because of their proper light absorption region, chemical stability and photodynamic stability. The fluorescence measurement with molecular probes, CM-H IIDCFDA and Amplex Red, was performed for detection of ROS generation and hydrogen peroxide release from cells. Our results demonstrated, that irradiation of cells by laser dose of 10 J.cm -2 induces higher rates of fluorescence in cells loaded with phthalocyanine compared to 20 J.cm -2. Furthermore, the production of ROS increases up to sensitizer concentration of 10 μM. The highest ROS generation was observed at laser dose of 10 J.cm -2 and 10 μM ClAlPcS II. The rates of fluorescence for hydrogen peroxid measurements were almost identical with all chosen concentrations at laser doses of 10 and 20 J.cm -2.

  15. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    -[()-2-octanyloxy]-substituted copper and nickel phthalocyanines · Fang-Di Cong ... Synthesis and anti-inflammatory activity of 3-indolyl pyridine derivatives through one-pot multi component reaction · Prakasam Thirumurugan S Mahalaxmi ...

  16. Improved Electroformed Structural Copper and Copper Alloys

    Science.gov (United States)

    Malone, G. A.; Hudson, W.; Babcock, B.; Edwards, R.

    1998-01-01

    Electroforming offers a superior means for fabricating internally cooled heat exchangers and structures subjected to thermal environments. Copper is deposited from many such applications because of the good thermal conductivity. It suffers from mediocre yield strength as a structural material and loses mechanical strength at intermediate temperatures. Mechanical properties similar to those of electroformed nickel are desired. Phase 1 examined innovative means to improve deposited copper structural performance. Yield strengths as high as 483 MPa (70 ksi) were obtained with useful ductility while retaining a high level of purity essential to good thermal conductivity. Phase 2 represents a program to explore new additive combinations in copper electrolytes to produce a more fine, equiaxed grain which can be thermally stabilized by other techniques such as alloying in modest degrees and dispersion strengthening. Evaluation of new technology - such as the codeposition of fullerness (diamond-like) particles were made to enhance thermal conductivity in low alloys. A test fire quality tube-bundle engine was fabricated using these copper property improvement concepts to show the superiority of the new coppers and fabrications methods over competitive technologies such as brazing and plasma deposition.

  17. 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

  18. Copper (II) Complex

    African Journals Online (AJOL)

    CLEMENT O BEWAJI

    ABSTRACT: N – histidyl – 2, 4 – pentanedione Schiff base was prepared from the reaction of histidine and 2, 4 - pentandione. The reaction of methanolic solution of N – histidyl – 2, 4 – pentanedione Schiff base with ethanolic solution of copper (II) chloride gave diaquo bis( N – histidyl - 2, 4 - pentanedionato) copper (II) ...

  19. Copper Pyrimidine based MOFs

    Indian Academy of Sciences (India)

    Figure S17. Self assembly of the tecton [CuI(pdz)Cl] can occur through two paths that causes the occurrence of supramolecular isomers. .... The pdz ligands bridge a pair of copper atoms in a chain through coordinate bonds. In addition ...... The weight loss thereafter corresponds to degradation of copper halide framework.

  20. Copper and silver halates

    CERN Document Server

    Woolley, EM; Salomon, M

    2013-01-01

    Copper and Silver Halates is the third in a series of four volumes on inorganic metal halates. This volume presents critical evaluations and compilations for halate solubilities of the Group II metals. The solubility data included in this volume are those for the five compounds, copper chlorate and iodate, and silver chlorate, bromate and iodate.

  1. Triblock copolymers encapsulated poly (aryl benzyl ether) dendrimer zinc(II) phthalocyanine nanoparticles for enhancement in vitro photodynamic efficacy.

    Science.gov (United States)

    Huang, Yide; Yu, Huizhen; Lv, Huafei; Zhang, Hong; Ma, Dongdong; Yang, Hongqin; Xie, Shusen; Peng, Yiru

    2016-12-01

    A novel series of nanoparticles formed via an electrostatic interaction between the periphery of negatively charged 1-2 generation aryl benzyl ether dendrimer zinc (II) phthalocyanines and positively charged poly(L-lysin) segment of triblock copolymer, poly(L-lysin)-block-poly(ethylene glycol)-block-poly(L-lysin), was developed for the use as an effective photosensitizers in photodynamic therapy. The dynamic light scattering, atomic force microscopy showed that two nanoparticles has a relevant size of 80-150nm. The photophysical properties and singlet oxygen quantum yields of free dendrimer phthalocyanines and nanoparticles exhibited generation dependence. The intracellular uptake of dendrimer phthalocyanines in Hela cells was significantly elevated as they were incorporated into the micelles, but was inversely correlated with the generation of dendrimer phthalocyanines. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles induced efficient cell death. Using a mitochondrial-sepcific dye rhodamine 123 (Rh123), our fluorescence microscopic result indicated that nanoparticles localized to the mitochondria. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Sequential energy and charge transfer processes in mixed host-guest complexes of subphthalocyanine, porphyrin and phthalocyanine chromophores.

    Science.gov (United States)

    Menting, Roel; Ng, Dennis K P; Röder, Beate; Ermilov, Eugeny A

    2012-11-14

    Porphyrins, phthalocyanines and subphthalocyanines are three attractive classes of chromophores with intriguing properties making them suitable for the design of artificial photosynthetic systems. The assembly of these components by a supramolecular approach is of particular interest as it provides a facile means to build multi-chromophoric arrays with various architectures and tuneable photophysical properties. In this paper, we show the formation of mixed host-guest supramolecular complexes that consist of a β-cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a series of silicon(IV) phthalocyanines substituted axially with two β-cyclodextrins via different spacers. We found that the three components form supramolecular complexes held by host-guest interactions in aqueous solution. Upon excitation of the subphthalocyanine part of the complex, the excitation energy is delivered to the phthalocyanine unit via excitation energy transfer and the porphyrin chromophore acts as an energy transfer bridge enabling this process. It was shown that photo-induced charge transfer also takes place. A sequential electron transfer process from the porphyrin unit to the phthalocyanine moiety and subsequently from the subphthalocyanine moiety to the porphyrin unit takes place, and the probability of this process is controlled by the linker between β-cyclodextrin and phthalocyanine. The lifetime of the charge-separated state was found to be 1.7 ns by transient absorption spectroscopy.

  3. PHOTOTOXIC EFFECT OF ALUMINIUM-CHLORINE AND ALUMINIUM-HYDROXIDE PHTHALOCYANINES ON LEISHMANIA (L.) AMAZONENSIS.

    Science.gov (United States)

    Nesi-Reis, V; Navasconi, T R; Lera-Nosone, D S S L; Oliveira, E L; Barbosa, P M; Caetano, W; Silveira, T G V; Aristides, S M A; Hioka, N; Lonardoni, M V C

    2017-12-21

    This study investigated the activity of photosensitive phthalocyanines on promastigotes and amastigotes of Leishmania (L.) amazonensis. Aluminum phthalocyanine chloride (AlPcCl), Aluminum phthalocyanine hydroxide (AlPcOH) and zinc phthalocyanine (PcZn) were tested in the presence (matte red LED, potency of 2.5-2.3 μW for 30 minutes) and absence of light against L. amazonensis promastigotes and the parasite viability was evaluated after 24, 48 and 72 h. The amastigote forms were treated with AlPcCl and AlPcOH, following the same lighting protocols described for the promastigote forms, being evaluated after 24 h. Cytotoxicity to human erythrocytes and peritoneal macrophages was also evaluated. The results showed that AlPcCl and AlPcOH in the presence of light have antileishmania activity, with leishmanistatic effects on promastigotes and amastigotes of L. amazonensis, without causing cytotoxicity to peritoneal macrophages and erythrocytes. The concentrations that inhibited 50% of the promastigote forms after 24 h of light exposure were 0.21 ± 0.08 μM for AlPcCl and 0.23 ± 0.06 μM for AlPcOH. In 48 h and 72 h after the treatment, the IC 50 of AlPcCl was 0.13 ± 0.02 and 0.12 ± 0.03 μM and for AlPcOH was 0.14 ± 0.01 μM and 0.11 ± 0.01 μM, respectively. PcZn showed no activity on promastigotes of L. amazonensis. This study showed a substantial photodynamic activity of the phthalocyanines AlPcCl and AlPcOH against intracellular amastigotes forms of L. amazonensis after irradiation, presenting IC 50 values of 0.62 ± 0.06 μM and 0.92 ± 0.12 μM, respectively. These results support the possibility of using photodynamic therapy for the treatment of cutaneous leishmaniasis. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Bioaccessibility and Solubility of Copper in Copper-Treated Lumber

    Science.gov (United States)

    Micronized copper (MC)-treated lumber is a recent replacement for Chromated Copper Arsenate (CCA) and Ammonium Copper (AC)-treated lumbers; though little is known about the potential risk of copper (Cu) exposure from incidental ingestion of MC-treated wood. The bioaccessibility o...

  5. Posttranslational regulation of copper transporters

    NARCIS (Netherlands)

    van den Berghe, P.V.E.

    2009-01-01

    The transition metal copper is an essential cofactor for many redox-active enzymes, but excessive copper can generate toxic reactive oxygen species. Copper homeostasis is maintained by highly conserved proteins, to balance copper uptake, distribution and export on the systemic and cellular level.

  6. Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor

    Directory of Open Access Journals (Sweden)

    Carlos J. Lucio-Ortiz

    2013-09-01

    Full Text Available Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD, scanning electronic microscope (SEM, and N2 physisorption isotherms were also determined. The Ni/Al2O3 sample reveled agglomerated (1 μm of nanoparticles of Ni (30–80 nm however, NiO particles were also identified, probably for the low temperature during the H2 reduction treatment (350 °C, the Cu/Al2O3 sample presented agglomerates (1–1.5 μm of nanoparticles (70–150 nm, but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH3ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption.

  7. Design of a Gd-DOTA-phthalocyanine conjugate combining MRI contrast imaging and photosensitization properties as a potential molecular theranostic.

    Science.gov (United States)

    Aydın Tekdaş, Duygu; Garifullin, Ruslan; Şentürk, Berna; Zorlu, Yunus; Gundogdu, Umut; Atalar, Ergin; Tekinay, Ayse B; Chernonosov, Alexander A; Yerli, Yusuf; Dumoulin, Fabienne; Guler, Mustafa O; Ahsen, Vefa; Gürek, Ayşe Gül

    2014-01-01

    The design and synthesis of a phthalocyanine--Gd-DOTA conjugate is presented to open the way to novel molecular theranostics, combining the properties of MRI contrast imaging with photodynamic therapy. The rational design of the conjugate integrates isomeric purity of the phthalocyanine core substitution, suitable biocompatibility with the use of polyoxo water-solubilizing substituents, and a convergent synthetic strategy ended by the use of click chemistry to graft the Gd-DOTA moiety to the phthalocyanine. Photophysical and photochemical properties, contrast imaging experiments and preliminary in vitro investigations proved that such a combination is relevant and lead to a new type of potential theranostic agent. © 2014 The American Society of Photobiology.

  8. Microwave-assisted synthesis, characterization and spectral properties of non-peripherally tetra-substituted phthalocyanines containing eugenol moieties

    Science.gov (United States)

    Kantar, Cihan; Şahin, Zarife Sibel; Büyükgüngör, Orhan; Şaşmaz, Selami

    2015-06-01

    The microwave-assisted synthesis and characterization of novel non-peripherally eugenol substituted metallophthalocyanines (M: Co(II), Ni(II), Cu(II), Zn(II)) have been reported for the first time in this study. All the new compounds were characterized by a combination of FT-IR, 1H NMR, 13C NMR, and UV/vis spectroscopy techniques. The crystal structure of compound (1) was also determined by the single crystal diffraction technique. Newly synthesized eugenol substituted phthalocyanines have more redshift Q bands (about 17-18 nm) than previously reported eugenol substituted phthalocyanines. Zinc(II)phthalocyanine (1d) has an extra absorption band at 746 nm that calling "X band" at UV/vis spectrum.

  9. A density functional theory investigation of charge mobility in titanyl-phthalocyanines and their tailored peripherally substituted complexes

    CERN Document Server

    De Lile, Jeffrey R

    2016-01-01

    Titanyl-phthalocyanines catalytic ability towards oxygen reduction is demonstrated in experimental literature. Our recent theoretical simulations revealed electronic structure origin of catalytic ability in peripherally and axially substituted triplet and singlet titanyl-phthalocyanines. However, the origin of high electron transfer ability to spontaneously reduce peroxide in chlorine substituted singlet complex and triplet state Ti(II)Pc complexes remain elusive. Thus, we performed density functional theory calculations to study Ti(IV)Pc and their tailored peripheral substituted complexes as representative compounds of titanyl-phthalocyanines for charge mobilities, reorganization energies and electronic couplings. In addition, oxo(phthalocyaninato)titanium(IV) (TiOPc) convex and concave compounds were investigated to benchmark the method. Based on the results, Reorganization energies of triplet state Ti(II)Pc and their tailored peripheral substituted complexes are compared with Ti(IV)Pc singlet complexes in ...

  10. Crystal Structure of Ruthenium Phthalocyanine with Diaxial Monoatomic Ligand: Bis(TriphenylphosphineIminium Dichloro(Phthalocyaninato(2-Ruthenium(III

    Directory of Open Access Journals (Sweden)

    Derrick Ethelbhert Yu

    2013-01-01

    Full Text Available Axially-ligated iron phthalocyanines have been found to be good molecular conductors with giant negative magnetoresistance (GNMR which originates from a strong intramolecular π-d interaction between the metal and phthalocyanine. Ab initio theoretical calculations showed that substitution of ruthenium into the phthalocyanine complex would result in a significant increase in the π-d interaction of the system, potentially intensifying GNMR. This paper presents the crystal preparation and X-ray structural characterization of bis(triphenylphosphineiminium dichloro(phthalocyaninato(2-ruthenium(III, PNP [RuIII(Pc2−Cl2]. It is observed that [RuIII(Pc2−Cl2] system has a symmetric planar RuPc unit with perpendicular axial ligands which results in a unidirectional and uniform solid-state arrangement, suitable for π-d interaction-based molecular conductors with potentially exceptional GNMR.

  11. Fabricating Copper Nanotubes by Electrodeposition

    Science.gov (United States)

    Yang, E. H.; Ramsey, Christopher; Bae, Youngsam; Choi, Daniel

    2009-01-01

    Copper tubes having diameters between about 100 and about 200 nm have been fabricated by electrodeposition of copper into the pores of alumina nanopore membranes. Copper nanotubes are under consideration as alternatives to copper nanorods and nanowires for applications involving thermal and/or electrical contacts, wherein the greater specific areas of nanotubes could afford lower effective thermal and/or electrical resistivities. Heretofore, copper nanorods and nanowires have been fabricated by a combination of electrodeposition and a conventional expensive lithographic process. The present electrodeposition-based process for fabricating copper nanotubes costs less and enables production of copper nanotubes at greater rate.

  12. Synthesis, characterization, and X-ray crystal structures of cyclam derivatives. 5. Copper(II) binding studies of a pyridine-strapped 5,12-dioxocyclam-based macrobicycle.

    Science.gov (United States)

    Meyer, Michel; Frémond, Laurent; Espinosa, Enrique; Guilard, Roger; Ou, Zhongping; Kadish, Karl M

    2004-09-06

    The copper(II) binding properties of the macrobicyclic diamide 1,9,12,18,22-pentaazatricyclo[7.6.6.1(3,7)]docosa-3,5,7(22)-triene-13,19-dione (L1) have been fully investigated by spectroscopic (IR, UV-vis, EPR, MALDI-TOF MS), X-ray diffraction, potentiometric, electrochemical, and spectroelectrochemical methods. This constrained receptor possesses a hemispherical cavity created by cross-bridging the 1 and 8 positions of trans-dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,12-dione, L2) with a 2,6-pyridyl strap. Treatment of L1 with a copper salt in methanol produces a red complex of [Cu(L1H(-1))]+ formula in which the copper atom is embedded in a 13-membered ring and coordinated by both amines as well as the pyridine and one deprotonated amide nitrogen atoms. Infrared spectroscopy provides evidence for protonation of the carbonyl oxygen atom belonging to the copper-bound amide of [Cu(L1H(-1))]+ under strongly acidic conditions. The resulting conversion of the amidate into an iminol group highlights the inert character of the corresponding complexes, which do not dissociate at low pH values. In contrast, both secondary amides of L1 deprotonate in the presence of a weak base, thus affording a blue pentacoordinated [Cu(L1H(-2))] compound where the copper atom sits in the center of the 14-membered dioxocyclam fragment. In aqueous solution, both complexes undergo a pH-driven (pK(a) = 8.73(2)) molecular reorganization, which is reminiscent of a glider motion. The copper(II) cation switches rapidly and reversibly from a four-coordinate flattened tetrahedral arrangement of the donor atoms in the red species to a five-coordinate environment in the blue species, which is intermediate between a square pyramid and a trigonal bipyramid. Conversion of the red to the blue form was also demonstrated to occur upon reduction of [Cu(L1H(-1))]+ by cyclic voltammetry (E(pc) = -0.64 V/SCE in CH(3)CN).

  13. 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.

  14. Heterobridged dinuclear, tetranuclear, dinuclear-based 1-d, and heptanuclear-based 1-D complexes of copper(II) derived from a dinucleating ligand: syntheses, structures, magnetochemistry, spectroscopy, and catecholase activity.

    Science.gov (United States)

    Majumder, Samit; Sarkar, Sohini; Sasmal, Sujit; Sañudo, E Carolina; Mohanta, Sasankasekhar

    2011-08-15

    The work in this paper presents syntheses, characterization, crystal structures, variable-temperature/field magnetic properties, catecholase activity, and electrospray ionization mass spectroscopic (ESI-MS positive) study of five copper(II) complexes of composition [Cu(II)(2)L(μ(1,1)-NO(3))(H(2)O)(NO(3))](NO(3)) (1), [{Cu(II)(2)L(μ-OH)(H(2)O)}(μ-ClO(4))](n)(ClO(4))(n) (2), [{Cu(II)(2)L(NCS)(2)}(μ(1,3)-NCS)](n) (3), [{Cu(II)(2)L(μ(1,1)-N(3))(ClO(4))}(2)(μ(1,3)-N(3))(2)] (4), and [{Cu(II)(2)L(μ-OH)}{Cu(II)(2)L(μ(1,1)-N(3))}{Cu(II)(μ(1,1)-N(3))(4)(dmf)}{Cu(II)(2)(μ(1,1)-N(3))(2)(N(3))(4)}](n)·ndmf (5), derived from a new compartmental ligand 2,6-bis[N-(2-pyridylethyl)formidoyl]-4-ethylphenol, which is the 1:2 condensation product of 4-ethyl-2,6-diformylphenol and 2-(2-aminoethyl)pyridine. The title compounds are either of the following nuclearities/topologies: dinuclear (1), dinuclear-based one-dimensional (2 and 3), tetranuclear (4), and heptanuclear-based one-dimensional (5). The bridging moieties in 1-5 are as follows: μ-phenoxo-μ(1,1)-nitrate (1), μ-phenoxo-μ-hydroxo and μ-perchlorate (2), μ-phenoxo and μ(1,3)-thiocyanate (3), μ-phenoxo-μ(1,1)-azide and μ(1,3)-azide (4), μ-phenoxo-μ-hydroxo, μ-phenoxo-μ(1,1)-azide, and μ(1,1)-azide (5). All the five compounds exhibit overall antiferromagnetic interaction. The J values in 1-4 have been determined (-135 cm(-1) for 1, -298 cm(-1) for 2, -105 cm(-1) for 3, -119.5 cm(-1) for 4). The pairwise interactions in 5 have been evaluated qualitatively to result in S(T) = 3/2 spin ground state, which has been verified by magnetization experiment. Utilizing 3,5-di-tert-butyl catechol (3,5-DTBCH(2)) as the substrate, catecholase activity of all the five complexes have been checked. While 1 and 3 are inactive, complexes 2, 4, and 5 show catecholase activity with turn over numbers 39 h(-1) (for 2), 40 h(-1) (for 4), and 48 h(-1) (for 5) in dmf and 167 h(-1) (for 2) and 215 h(-1) (for 4) in acetonitrile

  15. 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.

  16. Synthesis, characterization and investigation of the spectroscopic properties of novel peripherally 2,3,5-trimethylphenoxy substituted Cu and Co phthalocyanines, the computational and experimental studies of the 4-(2,3,5-trimethylphenoxyphthalonitrile

    Directory of Open Access Journals (Sweden)

    Nesuhi Akdemir

    2016-11-01

    Full Text Available 4-(2,3,5-trimethylphenoxyphthalonitrile (3 was firstly prepared via aromatic nucleophilic substitution reaction and characterized by FT-IR, mass spectrometry, 1H and 13C NMR techniques. The molecular structure of the compound (3 was optimized using Density Functional Theory (DFT/B3LYP method with 6-311G(d,p basis set in the ground state. The molecular geometric parameters which were obtained by X-ray single crystal diffraction method and the spectral results were compared with computed bond lengths and angles, vibrational frequencies and 1H, 13C NMR chemical shifts values of the compound (3. Also, Cu(II and Co(II phthalocyanines were synthesized by the treatment of dinitrile derivative with anhydrous CuCl2 or CoCl2 under N2 atmosphere in dry n-pentanol at 140oC. The new compounds have been determined by elemental analysis, FT-IR and electronic absorption. The UV-Vis spectra of the Cu(II and Co(II phthalocyanines were recorded with different concentration in THF and also with different solvents as DMF, DMSO, DCM, CHCl3, toluene.

  17. Sliding Friction of Copper

    National Research Council Canada - National Science Library

    Liu, Tung

    1963-01-01

    .... With less clean surfaces, the coefficient of friction obtained was about 0.4. Since the degree of cleanliness cannot be controlled quantitatively, the friction - load curve of sliding copper pairs in air exhibits a bifurcation characteristic...

  18. Temporal aspects of copper homeostasis and its crosstalk with hormones

    Directory of Open Access Journals (Sweden)

    Lola ePeñarrubia

    2015-04-01

    Full Text Available To cope with the dual nature of copper as being essential and toxic for cells, plants temporarily adapt the expression of copper homeostasis components to assure its delivery to cuproproteins while avoiding the interference of potential oxidative damage derived from both copper uptake and photosynthetic reactions during light hours. The circadian clock participates in the temporal organization of coordination of plant nutrition adapting metabolic responses to the daily oscillations. This timely control improves plant fitness and reproduction and holds biotechnological potential to drive increased crop yields. Hormonal pathways, including those of abscisic acid, gibberellins, ethylene, auxins, and jasmonates are also under direct clock and light control, both in mono and dicotyledons. In this review, we focus on copper transport in Arabidopsis thaliana and Oryza sativa and the presumable role of hormones in metal homeostasis matching nutrient availability to growth requirements and preventing metal toxicity. The presence of putative hormone-dependent regulatory elements in the promoters of copper transporters genes suggests hormonal regulation to match special copper requirements during plant development. Spatial and temporal processes that can be affected by hormones include the regulation of copper uptake into roots, intracellular trafficking and compartmentalisation, and long-distance transport to developing vegetative and reproductive tissues. In turn, hormone biosynthesis and signalling are also influenced by copper availability, which suggests reciprocal regulation subjected to temporal control by the central oscillator of the circadian clock. This transcriptional regulatory network, coordinates environmental and hormonal signalling with developmental pathways to allow enhanced micronutrient acquisition efficiency.

  19. Structural and electronic properties of copper-doped chalcogenide glasses

    Science.gov (United States)

    Guzman, David M.; Strachan, Alejandro

    2017-10-01

    Using ab initio molecular dynamics based on density functional theory, we study the atomic and electronic structure, and transport properties of copper-doped germanium-based chalcogenide glasses. These mixed ionic-electronic conductor materials exhibit resistance or threshold switching under external electric field depending on slight variations of chemical composition. Understanding the origin of the transport character is essential for the functionalization of glassy chalcogenides for nanoelectronics applications. To this end, we generated atomic structures for GeX3 and GeX6 (X = S, Se, Te) at different copper concentrations and characterized the atomic origin of electronic states responsible for transport and the tendency of copper clustering as a function of metal concentration. Our results show that copper dissolution energies explain the tendency of copper to agglomerate in telluride glasses, consistent with filamentary conduction. In contrast, copper is less prone to cluster in sulfides and selenides leading to hysteresisless threshold switching where the nature of transport is dominated by electronic midgap defects derived from polar chalcogen bonds and copper atoms. Simulated I -V curves show that at least 35% by weight of copper is required to achieve the current demands of threshold-based devices for memory applications.

  20. Through-space electronic communication of zinc phthalocyanine with substituted [60]Fullerene bearing O2Nxaza-crown macrocyclic ligands

    Science.gov (United States)

    Ghanbari, Bahram; Shahhoseini, Leila; Mahlooji, Niloofar; Gholamnezhad, Parisa; Taheri Rizi, Zahra

    2017-01-01

    Two new macrocyclic ligands containing 17- and 19-membered O2N3-donor aza-crowns anchored to [60]Fullerene were synthesized and characterized by employing HPLC, electrospray ionization mass (ESI-MS), 1H and 13C NMR, UV-vis, IR spectroscopies, as well as powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA) in solid state. TGA measurements revealed that upon linking each of these macrocycle rings to [60]Fullerene, the decomposition point measured for [60]Fullerene moiety was increased, indicating on the promoted stability of [60]Fullerene backbone during binding to these macrocyclic ligands. Moreover, the ground state non-covalent interactions of [60]Fullerene derivatives of O2Nx (x = 2, and 3) aza-crown macrocyclic ligands namely, L1-L4 with zinc phthalocyanine (ZnPc) were also investigated by UV-vis absorption, steady state and time resolved fluorescence spectrophotometry in N-methyl-2-pyrrolidone (NMP). The calculation of Stern-Volmer constants (KSV) indicated on existence of an efficient quenching mechanism comprising of the excited singlet state of ZnPc in the presence of L1-L4. The observation of an appropriate correlation between decrease in fluorescence intensity and lifetime parameters led us to propose the occurrence of a static mechanism for the fluorescence quenching of ZnPc in the presence of L1-L3. The binding constants (KBH) of L1-L4/ZnPc were also determined applying the fluorescence quenching experiments. Meanwhile, the incompatibility of both KSV and KBH values found for L4 was also described in terms of structural features using DFT calculations using the B3LYP functional and 6-31G* basis set.

  1. Copper Phenoxyl Complexes

    OpenAIRE

    Butsch, Katharina

    2010-01-01

    The work described in the following was inspired by radical copper enzymes such as Galactose Oxidase (GO). GO catalyses the two-electron oxidation of terminal alcohols to the corresponding aldehydes using air oxygen. Transfer of two electrons is possible, since GO contains two magnetically coupled one-electron redox centres: a tyrosylate ligand from the apo-protein, which exists either in the tyrosylate or the tyrosyl radical form and is bound to a copper ion possessing two stable oxidation s...

  2. Evaluation of biocidal efficacy of copper alloy coatings in comparison with solid metal surfaces: generation of organic copper phosphate nanoflowers.

    Science.gov (United States)

    Gutierrez, H; Portman, T; Pershin, V; Ringuette, M

    2013-03-01

    To analyse the biocidal efficacy of thermal sprayed copper surfaces. Copper alloy sheet metals containing >60% copper have been shown to exhibit potent biocidal activity. Surface biocidal activity was assessed by epifluorescence microscopy. After 2-h exposure at 20 °C in phosphate-buffered saline (PBS), contact killing of Gram-negative Escherichia coli and Gram-positive Staphylococcus epidermidis by brass sheet metal and phosphor bronze was 3-4-times higher than that by stainless steel. SEM observations revealed that the surface membranes of both bacterial strains were slightly more irregular when exposed to brass sheet metal than stainless steel. However, when exposed to phosphor bronze coating, E. coli were 3-4 times larger with irregular membrane morphology. In addition, the majority of the cells were associated with spherical carbon-copper-phosphate crystalline nanostructures characteristic of nanoflowers. The membranes of many of the S. epidermidis exhibited blebbing, and a small subset was also associated with nanoflowers. Our data indicate that increasing the surface roughness of copper alloys had a pronounced impact on the membrane integrity of Gram-positive and, to a lesser degree, Gram-negative bacteria. In the presence of PBS, carbon-copper-phosphate-containing nanoflowers were formed, likely nucleated by components derived from killed bacteria. The intimate association of the bacteria with the nanoflowers and phosphor bronze coating likely contributed to their nonreversible adhesion. Thermal spraying of copper alloys provides a strategy for the rapid coating of three-dimensional organic and inorganic surfaces with biocidal copper alloys. Our study demonstrates that the macroscale surface roughness generated by the thermal spray process enhances the biocidal activity of copper alloys compared with the nanoscale surface roughness of copper sheet metals. Moreover, the coating surface topography provides conditions for the rapid formation of organic copper

  3. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  4. Methylsulfonyl Zn phthalocyanine: A polyvalent and powerful hydrophobic photosensitizer with a wide spectrum of photodynamic applications.

    Science.gov (United States)

    İşci, Ümit; Beyreis, Marlena; Tortik, Nicole; Topal, Sevinc Z; Glueck, Michael; Ahsen, Vefa; Dumoulin, Fabienne; Kiesslich, Tobias; Plaetzer, Kristjan

    2016-03-01

    The biomedical photodynamic principle is based on the light-induced and photosensitizer-mediated killing of unwanted or harmful cells by overproduction of reactive oxygen species. Motivated by the success of photodynamic therapy (PDT) against several types of tumors, further applications of this approach are constantly identified which require the design and synthesis of novel photosensitizers with specifically tailored properties for a particular clinical application. Hydrophobic photosensitizers are currently gaining attention and hence a tetramethylsulfonyl Zn(II) phthalocyanine (2) was designed with respect to the desired photoproperties. The photodynamic potential of 2 was assessed by the determination of its photophysical and photochemical properties, and by a large range of biological tests including its phototoxicity against cancer cells and Gram(+) bacteria. Unsubstituted ZnPc was used as a reference compound for comparison purposes. Phthalocyanine 2 has a better oxygen generation and is more photostable than ZnPc. 2 is a polyvalent and powerful hydrophobic photosensitizer with a wide spectrum of photodynamic applications against cancer (tested on A431 cells) and for Gram(+) PDI. Against Staphylococcus aureus, a maximum photokilling efficiency of more than 6 log10 steps was induced by a 5μM concentration of 2, outperforming the 3 log10 criterion for an antimicrobial effect (according to the recommendation of the American Society for Microbiology) by more than three orders of magnitude. Phthalocyanine 2 has attractive photophysical and -chemical characteristics. Initial evaluation of its application in anti-tumor PDT and PDI suggest potential for further pre-clinical and clinical development of this compound. Copyright © 2015 Elsevier B.V. All rights reserved.

  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. Fluorescence investigation of the detachment of aluminum phthalocyanine molecules from aluminum phthalocyanine nanoparticles in monocytes/macrophages and skin cells and their localization in monocytes/macrophages.

    Science.gov (United States)

    Breymayer, Jasmin; Rück, Angelika; Ryabova, Anastasiya V; Loschenov, Victor B; Steiner, Rudolf W

    2014-09-01

    Nanoparticles made from aluminum phthalocyanine (AlPc) are non-fluorescent in the nanoparticle form. Once AlPc molecules become detached from the particle, fluorescence occurs. Preliminary work showed the benefit of using aluminum phthalocyanine nanoparticles (nAlPc) for the rating of the rejection risk of skin autografts in mice by measuring fluorescence intensities of detached AlPc. Skin autografts showing a high fluorescence intensity were finally rejected suggesting an inflammatory process. In contrast, autografts with normal autofluorescence were accepted. This work was focused on the mechanism of this finding. The aim is detecting inflammatory processes and the potential use of nAlPc for PDT as a new treatment modality. The effect of the lipopolysaccharide-stimulated monocyte/macrophage murine cell line J774A.1 on the monomerization of internalized nAlPc was tested. Further, we investigated the influence of J774A.1 cells and the normal skin cell lines L-929 or HaCaT on the dissolution of nAlPc by laser scanning microscopy and flow cytometry. Localization of AlPc molecules after uptake and dissolution of nanoparticles by the cells was surveyed. In co-culture models composed of J774A.1 and HaCaT/L-929 cells, the AlPc fluorescence intensity in J774A.1 cells is 1.38/1.89 fold higher, respectively. According to localization measurements in J774A.1 cells it can be assumed that nAlPc is taken up via endocytosis and remains in endosomes and/or lysosomes dissolving there. Detached molecules of AlPc cause rapture of the endosomal and/or lysosomal membrane after irradiation to become quite uniformly distributed in the cytoplasm. Evidence for monocytes/macrophages being the origin of the measured AlPc fluorescence in rejected skin autografts was confirmed. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Anisotropic charge transport properties in boron sub phthalocyanine chloride thin films

    Science.gov (United States)

    Kalia, Sameer; Mahajan, Aman; Ghansyam, C. G.; Debnath, A. K.; Saxsena, Vibha; Aswal, D. K.; Bedi, R. K.

    2017-03-01

    Anisotropic charge transport properties in organic semiconducting thin films of Boron Sub Phthalocyanine Chloride (Sub-Pc) have been studied by admittance spectroscopy applying a bias voltage parallel and perpendicular to the substrate. Sub-Pc long ordered structures confined in different directions induce anisotropic carrier mobility in films. The film with a thickness of 11 nm exhibited carrier mobilities three orders higher along the substrate than perpendicular to it. Furthermore, AFM, Kelvin Probe, and UV-Vis spectroscopic studies corroborated the established mobility-structure relationship.

  8. Nanostructuring on zinc phthalocyanine thin films for single-junction organic solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Chaudhary, Dhirendra K.; Kumar, Lokendra, E-mail: lokendrakr@allduniv.ac.in [Department of Physics, University of Allahabad, Allahabad-211 002 (India)

    2016-05-23

    Vertically aligned and random oriented crystalline molecular nanorods of organic semiconducting Zinc Phthalocyanine (ZnPc) have been grown on ITO coated glass substrate using solvent volatilization method. Interesting changes in surface morphology were observed under different solvent treatment. Vertically aligned nanorods of ZnPc thin film were observed in the films treated with acetone, where as the random oriented nanorods were observed in the films treated with chloroform. The X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) have been used for characterization of nanostructures. The optical properties of the nanorods have been investigated by UV-Vis. absorption spectroscopy.

  9. Photovoltaic properties of cadmium selenide–titanyl phthalocyanine planar heterojunction devices

    Energy Technology Data Exchange (ETDEWEB)

    Szostak, J.; Jarosz, G.; Signerski, R., E-mail: ryszard@mif.pg.gda.pl

    2015-07-29

    Graphical abstract: - Highlights: • CdSe/TiOPc cells harvest light practically in the whole visible range. • Two mechanism of photogeneration of charge carriers are distinguished. • Monomolecular recombination of free charge carriers is predominant. • Relatively high fill factor under monochromatic illumination was obtained. • Thickness optimization is required for the improvement of current density. - Abstract: Photovoltaic phenomenon taking place in cadmium selenide (CdSe)/titanyl phthalocyanine (TiOPc) planar heterojunction devices is described. Mechanisms of free charge carrier generation and their recombination in the dark and under illumination are analyzed, chosen photovoltaic parameters are presented.

  10. Rhenium-phthalocyanine molecular nanojunction with high magnetic anisotropy and high spin filtering efficiency

    Energy Technology Data Exchange (ETDEWEB)

    Li, J. [State Key Laboratory of Surface Physics, Key Laboratory of Computational Physical Sciences, and Department of Physics, Fudan University, Shanghai 200433 (China); Institute of Nanomaterial and Nanostructure, Changsha University of Science and Technology, Changsha 410114 (China); Hu, J. [School of Physical Science and Technology, Soochow University, Suzhou, Jiangsu 215006 (China); Wang, H. [State Key Laboratory of Surface Physics, Key Laboratory of Computational Physical Sciences, and Department of Physics, Fudan University, Shanghai 200433 (China); Wu, R. Q., E-mail: wur@uci.edu [State Key Laboratory of Surface Physics, Key Laboratory of Computational Physical Sciences, and Department of Physics, Fudan University, Shanghai 200433 (China); Department of Physics and Astronomy, University of California, Irvine, California 92697-4575 (United States)

    2015-07-20

    Using the density functional and non-equilibrium Green's function approaches, we studied the magnetic anisotropy and spin-filtering properties of various transition metal-Phthalocyanine molecular junctions across two Au electrodes. Our important finding is that the Au-RePc-Au junction has both large spin filtering efficiency (>80%) and large magnetic anisotropy energy, which makes it suitable for device applications. To provide insights for the further experimental work, we discussed the correlation between the transport property, magnetic anisotropy, and wave function features of the RePc molecule, and we also illustrated the possibility of controlling its magnetic state.

  11. Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

    OpenAIRE

    Blakemore, James D.; Hull, Jonathan F.; Crabtree, Robert H.; Brudvig, Gary W.

    2012-01-01

    The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH...

  12. Fabrication of nickel phthalocyanine free-standing film on ionic liquid surface and photoelectrical response

    Science.gov (United States)

    Xiao, Yan; Zhang, Miao-Rong; Li, Jia-Jia; Pan, Ge-Bo

    2017-11-01

    In this study, we report for the preparation of nickel phthalocyanine (NiPc) free-standing films on ionic liquid (IL) surface by a physical vapor deposition method. Different from on the solid substrate, the as-obtained film is α phase and with a 2D network structure. In addition, the good transferability of the film make it can be easily transferred onto any substrate for further device applications. The device based on these films shows good photoelectrical property, high stability and high photosensitivity.

  13. Electrical Properties of Zn-Phthalocyanine and Poly (3-hexylthiophene Doped Nematic Liquid Crystal

    Directory of Open Access Journals (Sweden)

    Y. Karakuş

    2011-01-01

    Full Text Available An E7 coded nematic liquid crystal was doped with zinc phthalocyanine and poly (3-hexylthiophene. A variety of properties including relaxation time, absorption coefficient, and critical frequency of this doped system were investigated using impedance spectroscopy. The doped systems displayed increased absorption coefficients in the range 0.22–0.55 and relaxation times from 5.05×10−7 s to 3.59×10−6 s with a decrease in the critical frequency from 3.54 MHz to 2.048 MHz.

  14. 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.

  15. Spin filtering in transition-metal phthalocyanine molecules from first principles

    Science.gov (United States)

    Niu, Li; Wang, Huan; Bai, Lina; Rong, Ximing; Liu, Xiaojie; Li, Hua; Yin, Haitao

    2017-08-01

    Using first-principles calculations based on density functional theory and the nonequilibrium Green's function formalism, we studied the spin transport through metal-phthalocyanine (MPc, M=Ni, Fe, Co, Mn, Cr) molecules connected to aurum nanowire electrodes. We found that the MnPc, FePc, and CrPc molecular devices exhibit a perfect spin filtering effect compared to CoPc and NiPc. Moreover, negative differential resistance appears in FePc molecular devices. The transmission coefficients at different bias voltages were further presented to understand this phenomenon. These results would be useful in designing devices for future nanotechnology.

  16. 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

    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......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...

  17. Influence of axial and peripheral ligands on the electronic structure of titanium phthalocyanines

    DEFF Research Database (Denmark)

    Pickup, David F.; García Lastra, Juan Maria; Rogero, Celia

    2013-01-01

    To discover how molecular changes affect the electronic structure of dye molecules for solar cells, we have investigated four titanium phthalocyanines customized by axial and peripheral ligands (monodentate oxo versus bidentate catechol and tert-butyl versus tert-butylphenoxy, respectively). X......-ray absorption spectroscopy and photoelectron spectroscopy were combined with density functional theory (DFT) and crystal-field multiplet calculations to characterize the Ti 3d and N 2p valence electrons that form the frontier orbitals. When a monodentate oxo axial ligand was replaced by a bidentate catechol...... time-dependent density functional theory (TDDFT) and compared to experiment. © 2013 American Chemical Society....

  18. Theoretical study of band alignment in nano-porous ZnO interacting with substituted Phthalocyanines

    OpenAIRE

    Wahnón Benarroch, Perla; Palacios Clemente, Pablo

    2011-01-01

    The aim of this work is the theoretical study of the band alignment between the two components of a hybrid organic-inorganic solar-cell. The working organic molecules are metal tetra-sulphonated phthalocyanines (M-Pc) and the inorganic material is nano-porous ZnO growth in the 001 direction. The theoretical calculations are being made using the density functional theory (DFT) using a GGA functional with the SIESTA code, which projects electron wave functions and density onto a real space grid...

  19. Iron phthalocyanine modified mesoporous titania nanoparticles for photocatalytic activity and CO2 capture applications.

    Science.gov (United States)

    Ramacharyulu, P V R K; Muhammad, Raeesh; Praveen Kumar, J; Prasad, G K; Mohanty, Paritosh

    2015-10-21

    An iron(II)phthalocyanine (Fepc) modified mesoporous titania (Fepc-TiO2) nanocatalyst with a specific surface area of 215 m(2) g(-1) has been synthesized by a hydrothermal method. Fepc-TiO2 degrades one of the highly toxic chemical warfare agents, sulfur mustard (SM), photocatalytically under sunlight with an exposure time of as low as 70 min. Furthermore, the mesoporous Fepc-TiO2 also captured 2.1 mmol g(-1) of CO2 at 273 K and 1 atm.

  20. 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.

  1. Trigonal Based Copper Sites - A Natural Situation?

    OpenAIRE

    Coyle, Joanne Lyssa

    2000-01-01

    This thesis is concerned with the synthesis and characterisation of copper model compounds which are of interest in a biological context. These model compounds fall into two main classes; iminopodands and azacryptands. The iminopodands are derived from the condensation of tris(2- aminoethy1)amine (tren) or tris(3-aminoisopropy1)amine (trpn) and a range of aromatic aldehydes. The compounds invariably co-ordinated Cu(1) and the structural consequences of the flexibility are examined and systema...

  2. A first archetype of boron dipyrromethene-phthalocyanine pentad dye: design, synthesis, and photophysical and photochemical properties.

    Science.gov (United States)

    Göl, Cem; Malkoç, Mustafa; Yeşilot, Serkan; Durmuş, Mahmut

    2014-05-28

    A novel type of phthalocyanine pentad containing four boron dipyrromethene (BODIPY) units at peripheral positions of the phthalocyanine framework has been designed and synthesized for the first time. The Sonogashira coupling reaction between 4,4'-difluoro-8-(4-ethynyl)-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (Ethynyl-BODIPY) and 2(3),9(10),16(17),23(24)-tetrakis(iodo) zinc(ii) phthalocyanine (Iodo-Pc) has been used for the synthesis of the target compound. The BODIPY-phthalocyanine pentad dye (BODIPY-Pc) has been fully characterized by (1)H NMR, MALDI-TOF mass, FT-IR and UV-Vis spectroscopic techniques and elemental analysis as well. The photoinduced energy transfer process for this dye system was explored in tetrahydrofuran solution. The singlet oxygen generation capability and photodegradation behaviours of this BODIPY-Pc pentad dye were also investigated in DMSO for the determination of the usability of this new type of dye system as a photosensitizer in PDT applications.

  3. Slow Structural Rearrangement of a Side-Chain Phthalocyanine Methacrylate Polymer at the Air-Water Interface

    NARCIS (Netherlands)

    Nostrum, C.F. van; Nolte, R.J.M.; Devillers, M.A.C.; Oostergetel, G.T.; Teerenstra, M.N.; Schouten, A.J.

    1993-01-01

    A polymethacrylate with dodecoxy-substituted phthalocyanine units in the side chains has been used to form Langmuir-Blodgett monolayers at the air-water interface. The monolayers are highly crystalline. They expand slowly even when a constant surface pressure is applied. The structural change

  4. A cell-selective glutathione-responsive tris(phthalocyanine) as a smart photosensitiser for targeted photodynamic therapy.

    Science.gov (United States)

    Chow, Sun Y S; Zhao, Shirui; Lo, Pui-Chi; Ng, Dennis K P

    2017-08-29

    A biotin-conjugated disulfide-linked tris(phthalocyanine) has been synthesised and characterised. As shown by electronic absorption and steady-state fluorescence spectroscopy methods, the compound remains non-aggregated in N,N-dimethylformamide, but is significantly aggregated in phosphate buffered saline with 1% Cremophor EL. The reduction in fluorescence intensity and singlet oxygen generation efficiency as compared with the monomeric counterpart suggests that the tris(phthalocyanine) exhibits an excellent self-quenching effect, particularly in an aqueous medium. Upon interaction with glutathione, both the fluorescence emission and singlet oxygen production can be restored as a result of the cleavage of the disulfide linkages, thereby releasing the phthalocyanine units and reducing their aggregation and self-quenching effects. With a biotin moiety, this tris(phthalocyanine) is preferentially taken up by the biotin-receptor-positive HeLa cells and activated by the intracellular glutathione, resulting in fluorescence recovery and photocytotoxicity with an IC50 value of 0.68 μM. This compound can therefore act as a dual functional photosensitiser.

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

    Science.gov (United States)

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

    2016-12-15

    Iron(II) phthalocyanine was immobilized onto amidoximated polyacrylonitrile fiber to construct a bioinspired catalytic system for oxidizing organic dyes by H2O2 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-vis 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 H2O2 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 OO bond. This feature also enables the catalyst to only degrade the dyes adjacent to the catalytic active centers and enhances the efficient utilization of H2O2. In addition, this catalyst could effectively catalyze the mineralization of organic dyes and can be easily recycled without any loss of activity. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. 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.

  7. Energy transfer, excited-state deactivation, and exciplex formation in artificial caroteno-phthalocyanine light-harvesting antennas

    NARCIS (Netherlands)

    Berera, R.; van Stokkum, I.H.M.; Kodis, G.; Keirstead, A.E.; Pillai, S.; Herrero, C.; Palacios, R.E.; Vengris, M.; van Grondelle, R.; Gust, D.; Moore, T.A.; Moore, A.L.; Kennis, J.T.M.

    2007-01-01

    We present results from transient absorption spectroscopy on a series of artificial light-harvesting dyads made up of a zinc phthalocyanine (Pc) covalently linked to carotenoids with 9, 10, or 11 conjugated carbon-carbon double bonds, referred to as dyads 1, 2, and 3, respectively. We assessed the

  8. Combination of hyperthermia and photodynamic therapy on mesenchymal stem cell line treated with chloroaluminum phthalocyanine magnetic-nanoemulsion

    Science.gov (United States)

    de Paula, Leonardo B.; Primo, Fernando L.; Pinto, Marcelo R.; Morais, Paulo C.; Tedesco, Antonio C.

    2015-04-01

    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 (0.15×1013 or 1.50×1013 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 0.15×1013 or 1.50×1013 magnetic particle/mL, respectively. Finally, an average reduction in cell viability of about 66% was found while combining the hyperthermia and photodynamic therapy treatments.

  9. Crystal fields of porphyrins and phthalocyanines from polarization-dependent 2p-to-3d multiplets

    DEFF Research Database (Denmark)

    Johnson, Phillip S.; García Lastra, Juan Maria; Kennedy, Colton K.

    2014-01-01

    Polarization-dependent X-ray absorption spectroscopy is combined with density functional calculations and atomic multiplet calculations to determine the crystal field parameters 10Dq, Ds, and Dt of transition metal phthalocyanines and octaethylporphyrins (Mn, Fe, Co, Ni). The polarization depende...... for optimizing electron-hole separation in dye-sensitized solar cells....

  10. 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.

  11. Electrical conduction in composites containing copper core-copper ...

    Indian Academy of Sciences (India)

    Composites of nanometre-sized copper core-copper oxide shell with diameters in the range 6.1 to 7.3 nm dispersed in a silica gel were synthesised by a technique comprising reduction followed by oxidation of a suitably chosen precursor gel. The hot pressed gel powders mixed with nanometre-sized copper particles ...

  12. Nanostructures of an amphiphilic zinc phthalocyanine polymer conjugate for photodynamic therapy of psoriasis.

    Science.gov (United States)

    Jin, Yiguang; Zhang, Xiaohan; Zhang, Baolei; Kang, Hongxiang; Du, Lina; Li, Miao

    2015-04-01

    Psoriasis is a chronic inflammatory skin disease affecting 2-5% of the population worldwide and it severely affects patient quality of life. In this study, an amphiphilic zinc phthalocyanine polymer conjugate (ZPB) was synthesized, in which zinc phthalocyanine (ZnPc) was conjugated with the poly(ethylene glycol) (PEG) chain of Brij 58. ZPB showed two maximum UV-vis absorption wavelengths, 348 nm and 678 nm. A monomolecular micelle of ZPB formed in water with a mean size of 25 nm and zeta potential of -15 mV. The nanostructures aggregated into cloudy precipitates, which were easily dispersed. The nanostructure showed the shell-core structure with the ZnPc segments as the core and the PEG chains as the shell. The anti-psoriasis effect of the ZPB nanostructure was explored using a guinea pig psoriasis model. After comparing the anti-psoriasis effects of saline, light alone, ZPB alone, and the combination of light and ZPB, the combination of light and ZPB showed the best photodynamic therapy of psoriasis based on the light excitation of the photosensitizer ZPB and the psoriasis was nearly cured according to the histopathological investigation. The ZPB nanostructure is a promising anti-psoriasis nanomedicine based on photodynamic therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Enhanced electrochemical sensing of thiols based on cobalt phthalocyanine immobilized on nitrogen-doped graphene.

    Science.gov (United States)

    Xu, Huiying; Xiao, Jingjing; Liu, Baohong; Griveau, Sophie; Bedioui, Fethi

    2015-04-15

    A hybrid nanocomposite based on cobalt phthalocyanine (CoPc) immobilized on nitrogen-doped graphene (N-G) (N-G/CoPc) has been developed to modify glassy carbon electrode (GCE) for the sensitive detection of thiols. The nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Cyclic voltammetric studies showed that cobalt phthalocyanine and nitrogen doped graphene have a synergic effect and significantly enhance the electrocatalytic activity of the modified electrode towards thiols oxidation compared with electrodes modified with solely CoPc or N-G. The electrochemical oxidation responses were studied and the reaction mechanisms were discussed. The sensors exhibited a wide linear response range from 1μΜ to 16mM and a low detection limit of 1μΜ for the determination of l-cysteine, reduced l-glutathione and 2-mercaptoethanesulfonic acid in alkaline aqueous solution. The proposed N-G/CoPc hybrids contribute to the construction of rapid, convenient and low-cost electrochemical sensors for sensitive detection of thiols. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy

    Science.gov (United States)

    2015-01-01

    The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)8. NiPc(OBu)8 is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν10 (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. PMID:24841906

  15. Characterization of crystal polymorphs of the organic semiconductor non-peripheral octa-hexyl phthalocyanine

    Science.gov (United States)

    Yoneya, Makoto; Miyamoto, Ayano; Shimizu, Yo; Ohmori, Masashi; Fujii, Akihiko; Ozaki, Masanori

    2017-08-01

    The carrier-transport and thermodynamic properties of two crystal polymorphs, i.e., bulk and needle polymorphs, of non-peripheral octa-hexyl substituted phthalocyanine were investigated using density functional theory calculations and molecular dynamics simulations. The calculated results show that the bulk and needle polymorphs have hole mobilities of the same order of magnitude and that the hole mobility of the bulk polymorph was approximately twice that of the needle polymorph. For ideal one-dimensional transport along π stacking columns, the difference in mobility between the two polymorphs was larger by a factor of approximately 8. Therefore, we can expect the bulk polymorph to have 2 (or 8) times higher mobility than the values for the needle polymorph. These results predict that the bulk polymorph has the potential to show higher device performance than the needle polymorph. We also obtained the results that imply that a needle-polymorph-like phase with uniform (monoclinic) phthalocyanine-core tilting (instead of the alternative tilting of the needle polymorph) could be a new polymorph in this crystal system.

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

    Science.gov (United States)

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

    2017-08-18

    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 assisted by 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-electronics devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Optimally tuned functionals improving the description of optical and electronic properties of the phthalocyanine molecule.

    Science.gov (United States)

    Pereira, Tamires Lima; Leal, Luciano Almeida; da Cunha, Wiliam Ferreira; Timóteo de Sousa Júnior, Rafael; Ribeiro Junior, Luiz Antonio; Antonio da Silva Filho, Demétrio

    2017-03-01

    By means of Density functional theory and time-dependent density functional theory calculations, we present a comprehensive investigation on the influence of different functional schemes on electronic and optical properties of the phthalocyanine molecule. By carrying out our own tuning on the OT-LC-BLYP/6-31G(d,p) functional, we show that such a procedure is fundamental to accurately match experimental results. We compare our results to several others available in the literature, including the B3LYP/6-31+G(d,p) set, which is commonly portrayed as the best combination in order to obtain a good description of the band gap. The results obtained here present not only significant improvement of the optical properties from the conventional BLYP, but we can also objectively report an improvement of our tuned functional when compared to the current benchmark of the literature as far as optical properties are concerned. Particularly, by means of this approach, it was possible to achieve a good agreement between the theoretical and experimental optical gap as well as of the positioning of the main peaks in the absorption spectrum. Our results thus suggest that correcting the long-range term on exchange term of the Coulomb operator, by means of a tuning procedure, is a good option to accurately describe properties of the phthalocyanine molecule.

  18. Aluminum-chloride-phthalocyanine encapsulated in liposomes: activity against naturally occurring dog breast cancer cells.

    Science.gov (United States)

    Rocha, Martha S T; Lucci, Carolina M; Longo, João Paulo F; Galera, Paula D; Simioni, Andreza R; Lacava, Zulmira G M; Tedesco, Antônio C; Azevedo, Ricardo B

    2012-04-01

    Breast tumors represent the most common malignant tumors. Current treatments for humans and pets rely on tumor excision and adjuvant chemotherapy, which may affect both cancer cells and normal cells. Photodynamic therapy (PDT) is an approved treatment modality for a variety of cancers and was recently recommended as a first-line treatment for non-melanoma skin cancers for humans. The main purpose of the present study was to determine the efficacy of PDT using aluminum-chloride-phthalocyanine that is encapsulated in liposomes and LED as a light source to kill naturally occurring female dog breast cancer in vitro. The cytotoxicity behavior of the encapsulated photosensitizer in the dark and under irradiation using the 670 nm laser were investigated using classical trypan blue and MTT cell viability tests, acridine orange and ethidium bromide staining to label organelles, and cell morphology. Cell morphology was evaluated using light and electron microscopy. Our results demonstrate a reduced cell viability that is associated with morphologic alterations. The neoplasic cell destruction was predominantly mediated via a necrotic process, which was assayed using acridine orange and ethidium bromide staining. These findings were confirmed using light and electronic microscopy. The photosensitizer or laser irradiation alone did not induce cytotoxicity or morphological alterations, indicating the safety and efficacy of PDT with chloro-aluminum-phthalocyanine that was encapsulated in liposomes for the treatment of breast cancer cells in vitro.

  19. Enhancement of Nitrite Oxidation by Heat-Treated Cobalt Phthalocyanine Supported on High Area Carbon

    Energy Technology Data Exchange (ETDEWEB)

    Baik, Bong Yong; Kim, Sung Hyun [Konkuk University, Seoul (Korea, Republic of); Kwag, Gwang Hoon [Kumho Chemical Laboratories, Daejeon (Korea, Republic of)

    2006-02-15

    We have shown that the higher catalytic activity of heat-treated CoPc toward the nitrite oxidation comes from both Co-N{sub x} structure and highly dispersed cobalt metal ion characteristics. This result can be compared with FePc case in which the Fe-N{sub x} structure existed even after heat-treatment at 1000 .deg. C. However, almost entire CoPc molecules were converted to metallic Co. Therefore, the best electrocatalyst could be prepared by any means to give Co-N{sub x} characteristics and high degree of dispersion of Co metal atoms. Our ongoing effort is to develop efficient electrocatalysts and sensors for nitrite detection. Nitrite is one of the major components of wastewater from nuclear power production and involved in the corrosion and bacterial process known as the nitrogen cycle. It also plays important physiological roles in the form of NO, for example, as an intra- and intercellular messenger, a neurotransmitter, and an immune system mediator. The detection of nitrite, therefore, is important from an environmental and biological point of view. We have been utilizing transition-metal (particularly Fe and Co) phthalocyanines and porphyrins for this purpose as they often display catalytic activities toward many important electrochemical reactions such as oxygen reduction and CO oxidation. We found that iron phthalocyanine (FePc) is a very effective catalyst for nitrite reduction, undergoing structural changes on the surface as a function of the redox state.

  20. Preparation of Organic Zn-Phthalocyanine-Based Semiconducting Materials and Their Optical and Electrochemical Characterization

    Directory of Open Access Journals (Sweden)

    Amira Hajri

    2013-01-01

    Full Text Available In order to increase the species of organic semiconductors, new Zn-phthalocyanines-based organic materials were synthesized and characterized. The new compounds have been characterized by 1H and 13C using NMR, FTIR, and UV-Vis. The absorption, fluorescence, and electrochemical properties were also studied. Green photoluminescence was observed in dilute solutions. In solid thin films, π-π* interactions influenced the optical properties, and redshifted photoluminescence spectra were obtained; red emissions for ZnPAL (647 nm and ZnPTr (655 nm were found. By cyclic voltammetry, the electrochemical band gap was estimated to be 1.94 and 1.17 eV for ZnPAl and ZnPTr, respectively. Single-layer diode devices of an indium tin oxide/Zn-phthalocyanine/aluminum configuration were fabricated and showed relatively low turn-on voltages (3.3 V for ZnPAl and 3 V for ZnPTr.