WorldWideScience

Sample records for metal-free phthalocyanine molecules

  1. Copper phthalocyanine and metal free phthalocyanine bulk heterojunction photodetector

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-15

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

  2. Copper phthalocyanine and metal free phthalocyanine bulk heterojunction photodetector

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  3. 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.

  4. 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.

  5. 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.

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

    Science.gov (United States)

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

    2014-12-01

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

  7. Electrodes Modification Based on Metal-Free Phthalocyanine: Example of Electrochemical Sensors for the Detection of Acetic Acid

    Directory of Open Access Journals (Sweden)

    Amadou L. Ndiaye

    2015-01-01

    Full Text Available Electroanalytical properties of tetra-tert-butyl phthalocyanine (PcH2-tBu modified electrodes are studied by cyclic voltammetry (CV. The modified electrodes are obtained by CV deposition techniques on gold (Au and glassy carbon (C screen-printed electrodes (SPEs and used for the electrochemical detection of acetic acid (AA. Based on the CV experiments, the electrodeposition mechanism is detailed. The modified PcH2-tBu electrodes reveal one oxidation and one reduction peak within the potential window of the working electrodes. In the presence of the analyte (acetic acid, the modified electrodes show sensitivity in the range of 10 mM to 400 mM. For the PcH2-tBu modified Au electrode, a limit of detection (LOD of 5.89 mM (based on the +0.06 V peak was obtained while for the PcH2-tBu modified C electrode a LOD of 17.76 mM (based on the +0.07 V peak was achieved. A signal decay of 17%, based on 20 experiments, is obtained when gold is used as working electrode. If carbon is used as working electrode a value of 7% is attained. A signal decay is observed after more than 50 cycles of experiments and is more pronounced when higher concentrations of acetic acid are used. A mechanism of sensing is proposed at the end.

  8. Structural Design Principle of Small-Molecule Organic Semiconductors for Metal-Free, Visible-Light-Promoted Photocatalysis.

    Science.gov (United States)

    Wang, Lei; Huang, Wei; Li, Run; Gehrig, Dominik; Blom, Paul W M; Landfester, Katharina; Zhang, Kai A I

    2016-08-08

    Herein, we report on the structural design principle of small-molecule organic semiconductors as metal-free, pure organic and visible light-active photocatalysts. Two series of electron-donor and acceptor-type organic semiconductor molecules were synthesized to meet crucial requirements, such as 1) absorption range in the visible region, 2) sufficient photoredox potential, and 3) long lifetime of photogenerated excitons. The photocatalytic activity was demonstrated in the intermolecular C-H functionalization of electron-rich heteroaromates with malonate derivatives. A mechanistic study of the light-induced electron transport between the organic photocatalyst, substrate, and the sacrificial agent are described. With their tunable absorption range and defined energy-band structure, the small-molecule organic semiconductors could offer a new class of metal-free and visible light-active photocatalysts for chemical reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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

  10. 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

  11. 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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    Science.gov (United States)

    Umari, P; Fabris, S

    2012-05-07

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

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

    International Nuclear Information System (INIS)

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

    2006-01-01

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

  16. 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.

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

    Science.gov (United States)

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

    2016-03-01

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

  18. 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

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

    Directory of Open Access Journals (Sweden)

    Jing Zhou

    2016-03-01

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

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

    Science.gov (United States)

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

    2018-01-17

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

  1. 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

  2. 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)

  3. Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

    Science.gov (United States)

    Yang, Yang

    2010-12-23

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-15

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

  5. Room temperature ferromagnetism in a phthalocyanine based carbon material

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  6. Room temperature ferromagnetism in a phthalocyanine based carbon material

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-02-07

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

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

    Science.gov (United States)

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

    2017-12-04

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

  9. 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.

  10. 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.

  11. Tuning CNT Properties for Metal-Free Environmental Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Raquel P. Rocha

    2016-06-01

    Full Text Available The application of carbon nanotubes (CNTs as metal-free catalysts is a novel approach for heterogeneous liquid phase catalytic systems. Textural and chemical modifications by liquid/gas phase or mechanical treatments, as well as solid state reactions, were successfully applied to obtain carbon nanotubes with different surface functionalities. Oxygen, nitrogen, and sulfur are the most common heteroatoms introduced on the carbon surface. This short-review highlights different routes used to develop metal-free carbon nanotube catalysts with enhanced properties for Advanced Oxidation Processes.

  12. 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.

  13. Metal-Free Approaches to Sterically-Hindered Bonds

    Science.gov (United States)

    Dunham, Veronica Vin-yi

    Developing methods to perform cross coupling reactions by means of catalysis is highly desirable in chemistry. Many industries in today's society, such as the petroleum, agriculture, pharmaceutical, electronics, and polymer industry, use catalysis to some extent whether it is to make molecules that offer crop protection or toward the synthesis of the active ingredient of a medication. It is noteworthy that over 90% of chemicals are made through catalytic processes and that the catalyst market reached $17 billion in 2014, which demonstrates the demand for such methods. While transition metal catalysts have advantages such as low catalyst loading, broad reactivity, and that they have been well studied, some disadvantages are that they can be relatively expensive and sometimes air sensitive which can make them challenging to use. Organocatalysis, specifically noncovalent catalysis operating through hydrogen bond donating interactions, offers an environmentally-friendly alternative to transition metal catalysis. Our lab utilizes organocatalysis as a strategy to synthesize challenging, sterically-hindered bonds. Nitrimines have been identified as powerful coupling partners for the sustainable construction of new sterically congested carbon-carbon and carbon-heteroatom bonds. Using urea catalysis, a metal-free method to synthesize previously inaccessible enamines has been developed. Conventional routes to synthesize enamines as important building blocks toward target molecules generally require Lewis/Bronsted acids or expensive transition metals; however, these methods are often unsuccessful when stericallyhindered substrates are used. To address this synthetic challenge, it was hypothesized that hydrogen bonding interactions between a urea organocatalyst and nitrimine would generate a reactive species suited for the effective carbon-nitrogen coupling with amines to give the desired enamine products. This reaction provides high yields (up to 99%) of enamines using a

  14. 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.

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  16. 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.

  17. Molecular mechanics calculations on cobalt phthalocyanine dimers

    NARCIS (Netherlands)

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

    1995-01-01

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

  18. Transition-Metal-Free Biomolecule-Based Flexible Asymmetric Supercapacitors.

    Science.gov (United States)

    Yang, Yun; Wang, Hua; Hao, Rui; Guo, Lin

    2016-09-01

    A transition-metal-free asymmetric supercapacitor (ASC) is successfully fabricated based on an earth-abundant biomass derived redox-active biomolecule, named lawsone. Such an ASC exhibits comparable or even higher energy densities than most of the recently reported transition-metal-based ASCs, and this green ASC generation from renewable resources is promising for addressing current issues of electronic hazard processing, high cost, and unsustainability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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

  20. 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

  1. 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.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  3. Electronic transport properties of (fluorinated) metal phthalocyanine

    KAUST Repository

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

    2015-01-01

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

  4. 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.

  5. Long-range corrected DFT calculations of charge-transfer integrals in model metal-free phthalocyanine complexes

    Czech Academy of Sciences Publication Activity Database

    Mikolajczyk, M. M.; Zalesny, R.; Czyznikowska, Z.; Toman, Petr; Leszczynski, J.; Bartkowiak, W.

    2011-01-01

    Roč. 17, č. 9 (2011), s. 2143-2149 ISSN 1610-2940 R&D Projects: GA ČR(CZ) GAP205/10/2280; GA MŠk MEB051010 Institutional research plan: CEZ:AV0Z40500505 Keywords : charge-transfer integral * density functional theory * long-range corrected functionals Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.797, year: 2011

  6. Recent Studies in Phthalocyanine Chemistry.

    Science.gov (United States)

    1986-07-01

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

  7. 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...

  8. Hydrogen evolution by a metal-free electrocatalyst

    KAUST Repository

    Zheng, Yao

    2014-04-28

    Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics. © 2014 Macmillan Publishers Limited. All rights reserved.

  9. 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.

  10. 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

  11. 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

  12. Double C-H activation of ethane by metal-free SO2*+ radical cations.

    Science.gov (United States)

    de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

    2010-06-01

    The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

  13. 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

  14. 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

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

    Science.gov (United States)

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

    2008-07-31

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

  16. 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.

  17. Recent Advances in Metal-Free Quinoline Synthesis

    Directory of Open Access Journals (Sweden)

    Ginelle A. Ramann

    2016-07-01

    Full Text Available The quinoline ring system is one of the most ubiquitous heterocycles in the fields of medicinal and industrial chemistry, forming the scaffold for compounds of great significance. These include anti-inflammatory and antitumor agents, the antimalarial drugs quinine and chloroquine, and organic light-emitting diodes. Quinolines were first synthesized in 1879, and since then a multitude of synthetic routes have been developed. Many of these methods, such as the Skraup, Doebner–Von Miller, and Friedlander quinoline syntheses, are well-known but suffer from inefficiency, harsh reaction conditions, and toxic reagents. This review focuses on recent transition metal-free processes toward these important heterocycles, including both novel routes and modifications to established methods. For example, variations on the Skraup method include microwave irradiation, ionic liquid media, and novel annulation partners, all of which have shown increased reaction efficiency and improved yield of the heteroring-unsubstituted quinoline products. Similarly, modifications to other synthetic routes have been implemented, with the quinoline products displaying a wide variety of substitution patterns.

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

    Science.gov (United States)

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

    2018-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-10-15

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  1. Al- or Si-decorated graphene oxide: A favorable metal-free catalyst for the N2O reduction

    International Nuclear Information System (INIS)

    Esrafili, Mehdi D.; Sharifi, Fahimeh; Nematollahi, Parisa

    2016-01-01

    Highlights: • The reduction of N 2 O by CO molecule is investigated over Al- and Si-decorated graphene oxides (Al-/Si-GO). • The N 2 O decomposition process can take place with a negligible activation energy over both surfaces. • Al-GO and Si-GO can be used as an efficient metal-free catalyst for the reduction of N 2 O molecule at ambient conditions. - Abstract: The structural and catalytic properties of Al- or Si-decorated graphene oxide (Al-/Si-GO) are studied by means of density functional theory calculations. The relatively large adsorption energy together with the small Al−O or Si−O binding distances indicate that the epoxy groups over the GO surface can strongly stabilize the single Al or Si atom. Hence, Al-GO and Si-GO are stable enough to be utilized in catalytic reduction of N 2 O by CO molecule. It is found that the adsorption and decomposition of N 2 O molecule over Si-GO is more favorable than over Al-GO, due to its larger adsorption energy (E ads ) and charge transfer (q CT ) values. On the other hand, the CO molecule is physically adsorbed over both surfaces, with relatively small E ads and q CT values. Therefore, at the presence of N 2 O and CO molecules as the reaction gas, the Al or Si atom of the surface should be dominantly covered by N 2 O molecule. Our results indicate that the N 2 O decomposition process can take place with a negligible activation energy over Al-/Si-GO surface, where the N 2 molecule can be easily released from the surface. Then, the activated oxygen atom (O ads ) which remains over the surface reacts with the CO molecule to form the CO 2 molecule via the reaction O ads + CO → CO 2 . Based on the calculated activation energies, it is suggested that both Al-GO and Si-GO can be used as an efficient metal-free catalyst for the reduction of N 2 O molecule at ambient conditions.

  2. Adsorption energy of iron-phthalocyanine on crystal surfaces

    International Nuclear Information System (INIS)

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

    2013-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Irina V. Martynenko

    2016-07-01

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

  4. Synthesis of metal free ultrathin graphitic carbon nitride sheet for photocatalytic dye degradation of Rhodamine B under visible light irradiation

    Science.gov (United States)

    Rahman, Shakeelur; Momin, Bilal; Higgins M., W.; Annapure, Uday S.; Jha, Neetu

    2018-04-01

    In recent times, low cost and metal free photocatalyts driven under visible light have attracted a lot of interest. One such photo catalyst researched extensively is bulk graphitic carbon nitride sheets. But the low surface area and weak mobility of photo generated electrons limits its photocatalytic performance in the visible light spectrum. Here we present the facile synthesis of ultrathin graphitic carbon nitride using a cost effective melamine precursor and its application in highly efficient photocatalytic dye degradation of Rhodamine B molecules. Compared to bulk graphitic carbon nitride, the synthesized ultrathin graphitic carbon nitride shows an increase in surface area, a a decrease in optical band gap and effective photogenerated charge separation which facilitates the harvest of visible light irradiation. Due to these optimal properties of ultrathin graphitic carbon nitride, it shows excellent photocatalytic activity with photocatalytic degradation of about 95% rhodamine B molecules in 1 hour.

  5. NUCLEOSYNTHESIS AND EVOLUTION OF MASSIVE METAL-FREE STARS

    International Nuclear Information System (INIS)

    Heger, Alexander; Woosley, S. E.

    2010-01-01

    The evolution and explosion of metal-free stars with masses 10-100 M sun are followed, and their nucleosynthetic yields, light curves, and remnant masses determined. Such stars would have been the first to form after the big bang and may have left a distinctive imprint on the composition of the early universe. When the supernova yields are integrated over a Salpeter initial mass function (IMF), the resulting elemental abundance pattern is qualitatively solar, but with marked deficiencies of odd-Z elements with 7 ≤ Z ≤ 13. Neglecting the contribution of the neutrino wind from the neutron stars that they form, no appreciable abundances are made for elements heavier than germanium. The computed pattern compares favorably with what has been observed in metal-deficient stars with [Z] ∼ sun ; where 1 B = 1 Bethe = 10 51 erg) for a Salpeter IMF, and may have played a role in reionizing the universe. Neglecting rotation, most of the stars end their lives as blue supergiants and form supernovae with distinctive light curves resembling SN 1987A, but some produce primary nitrogen due to dredge-up and become red supergiants. These make brighter supernovae like typical Type IIp's. For the lower mass supernovae considered, the distribution of remnant masses clusters around typical modern neutron star masses, but above 20-30 M sun , with the value depending on explosion energy, black holes are copiously formed by fallback, with a maximum hole mass of ∼40 M sun . A novel automated fitting algorithm is developed for determining optimal combinations of explosion energy, mixing, and IMF in the large model database to agree with specified data sets. The model is applied to the low-metallicity sample of Cayrel et al. and the two ultra-iron-poor stars HE0107-5240 and HE1327-2326. Best agreement with these very low metallicity stars is achieved with very little mixing, and none of the metal-deficient data sets considered show the need for a high-energy explosion component. In

  6. Al- or Si-decorated graphene oxide: A favorable metal-free catalyst for the N2O reduction

    Science.gov (United States)

    Esrafili, Mehdi D.; Sharifi, Fahimeh; Nematollahi, Parisa

    2016-11-01

    The structural and catalytic properties of Al- or Si-decorated graphene oxide (Al-/Si-GO) are studied by means of density functional theory calculations. The relatively large adsorption energy together with the small Alsbnd O or Sisbnd O binding distances indicate that the epoxy groups over the GO surface can strongly stabilize the single Al or Si atom. Hence, Al-GO and Si-GO are stable enough to be utilized in catalytic reduction of N2O by CO molecule. It is found that the adsorption and decomposition of N2O molecule over Si-GO is more favorable than over Al-GO, due to its larger adsorption energy (Eads) and charge transfer (qCT) values. On the other hand, the CO molecule is physically adsorbed over both surfaces, with relatively small Eads and qCT values. Therefore, at the presence of N2O and CO molecules as the reaction gas, the Al or Si atom of the surface should be dominantly covered by N2O molecule. Our results indicate that the N2O decomposition process can take place with a negligible activation energy over Al-/Si-GO surface, where the N2 molecule can be easily released from the surface. Then, the activated oxygen atom (Oads) which remains over the surface reacts with the CO molecule to form the CO2 molecule via the reaction Oads + CO → CO2. Based on the calculated activation energies, it is suggested that both Al-GO and Si-GO can be used as an efficient metal-free catalyst for the reduction of N2O molecule at ambient conditions.

  7. 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.

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

    International Nuclear Information System (INIS)

    Riechers, Ricarda Eva Friederike Elisabeth

    2011-01-01

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

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

    Science.gov (United States)

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

    2018-05-01

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

  10. 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.

  11. Metal-free indoline dye sensitized solar cells based on nanocrystalline Zn{sub 2}SnO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Lihua [Institute of New Energy Technology and Nano-Materials, Fuzhou University, Fuzhou, Fujian 350002 (China); Jiang, Lilong; Wei, Mingding [Institute of New Energy Technology and Nano-Materials, Fuzhou University, Fuzhou, Fujian 350002 (China); National Engineering Research Center for Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 (China)

    2010-02-15

    Zn{sub 2}SnO{sub 4} nanocrystals were synthesized and first used as the electrode materials for the metal-free indoline dyes sensitized solar cells (DSSCs). The highest efficiency of 3.08% was achieved for a D131 DSSC. This might be attributed to the fact that the D131 dye has a greater positive oxidation potential, which can lead to rapid dye regeneration, avoiding the geminate charge recombination between oxidized dye molecules and injected electrons in the Zn{sub 2}SnO{sub 4} film. The efficiency can be improved significantly using a mixture solution of D131 and N719 dyes for which an efficiency of 3.6% was obtained. (author)

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-28

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

  14. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

  16. 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.

  17. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2016-12-30

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by {sup 1}H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  18. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-01-01

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1 H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  19. Phthalocyanines as sensitizers for photodynamic water disinfection

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-07-01

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

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

    Science.gov (United States)

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

    2016-10-01

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

  1. A metal-free organic-inorganic aqueous flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Huskinson, B; Marshak, MP; Suh, C; Er, S; Gerhardt, MR; Galvin, CJ; Chen, XD; Aspuru-Guzik, A; Gordon, RG; Aziz, MJ

    2014-01-08

    As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox-active metals

  2. Allotropic Carbon Nanoforms as Advanced Metal-Free Catalysts or as Supports

    Directory of Open Access Journals (Sweden)

    Hermenegildo Garcia

    2014-01-01

    Full Text Available This perspective paper summarizes the use of three nanostructured carbon allotropes as metal-free catalysts (“carbocatalysts” or as supports of metal nanoparticles. After an introductory section commenting the interest of developing metal-free catalysts and main features of carbon nanoforms, the main body of this paper is focused on exemplifying the opportunities that carbon nanotubes, graphene, and diamond nanoparticles offer to develop advanced catalysts having active sites based on carbon in the absence of transition metals or as large area supports with special morphology and unique properties. The final section provides my personal view on future developments in this field.

  3. 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.

  4. Soluble substituted phthalocyanines for OFET applications

    Czech Academy of Sciences Publication Activity Database

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

    2008-01-01

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

  5. Soluble phthalocyanines - new materials for optoelectronics

    Czech Academy of Sciences Publication Activity Database

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

    2005-01-01

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

  6. A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides.

    Science.gov (United States)

    Xia, Zhonghua; Zhu, Qiang

    2013-08-16

    A transition-metal-free carboxyamidation process, using aryl diazonium tetrafluoroborates and isocyanides under mild conditions, has been developed. This novel conversion was initiated by a base and solvent induced aryl radical, followed by radical addition to isocyanide and single electron transfer (SET) oxidation, affording the corresponding arylcarboxyamide upon hydration of the nitrilium intermediate.

  7. Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

    KAUST Repository

    Ye, Min

    2016-10-01

    A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

  8. Thermodynamic driving force effects in the oxygen reduction catalyzed by a metal-free porphyrin

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Samec, Zdeněk

    2012-01-01

    Roč. 82, SI (2012), s. 457-462 ISSN 0013-4686 R&D Projects: GA ČR GAP208/11/0697 Institutional research plan: CEZ:AV0Z40400503 Keywords : oxygen reduction * metal-free porphyrin * electrocatalysis Subject RIV: CG - Electrochemistry Impact factor: 3.777, year: 2012

  9. Competitive inhibition of a metal-free porphyrin oxygen-reduction catalyst by water

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Záliš, Stanislav; Samec, Zdeněk

    2012-01-01

    Roč. 48, č. 34 (2012), s. 4094-4096 ISSN 1359-7345 R&D Projects: GA ČR GAP208/11/0697 Institutional research plan: CEZ:AV0Z40400503 Keywords : metal -free porphyrin * competitive inhibition * liquid-liquid interfaces Subject RIV: CG - Electrochemistry Impact factor: 6.378, year: 2012

  10. Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

    KAUST Repository

    Ye, Min; Wen, Yuelu; Li, Huifang; Fu, Yejuan; Wang, Qinghao

    2016-01-01

    A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

  11. A metal-free general procedure for oxidation of secondary amines to nitrones.

    Science.gov (United States)

    Gella, Carolina; Ferrer, Eric; Alibés, Ramon; Busqué, Félíx; de March, Pedro; Figueredo, Marta; Font, Josep

    2009-08-21

    An efficient and metal-free protocol for direct oxidation of secondary amines to nitrones has been developed, using Oxone in a biphasic basic medium as the sole oxidant. The method is general and tolerant with other functional groups or existing stereogenic centers, providing rapid access to enantiomerically pure compounds in good yields.

  12. Metal-Free N-Arylation of Secondary Amides at Room Temperature

    OpenAIRE

    Tinnis, Fredrik; Stridfeldt, Elin; Lundberg, Helena; Adolfsson, Hans; Olofsson, Berit

    2015-01-01

    The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.

  13. Metal-free TEMPO-promoted C(sp³)-H amination to afford multisubstituted benzimidazoles.

    Science.gov (United States)

    Xue, Ding; Long, Ya-Qiu

    2014-05-16

    An efficient TEMPO-air/cat. TEMPO-O2 oxidative protocol was developed to synthesize multisubstituted or fused tetracyclic benzimidazoles via a metal-free oxidative C-N coupling between the sp(3) C-H and free N-H of readily available N(1)-benzyl/alkyl-1,2-phenylenediamines.

  14. Base-oxidant promoted metal-free N-demethylation of arylamines

    Indian Academy of Sciences (India)

    A metal-free oxidative N-demethylation of arylamines with triethylamine as a base and tert-butyl hydroperoxide (TBHP) as oxidant is reported in this paper. The reaction is general, practical, inexpensive, non-toxic, and the method followed is environmentally benign, with moderate to good yields.

  15. 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.

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

    KAUST Repository

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

    2017-01-01

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

  17. 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.

  18. An effective zinc phthalocyanine derivative for photodynamic antimicrobial chemotherapy

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  20. 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.

  1. 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.

  2. Separation of copper-64 from copper phthalocyanine

    International Nuclear Information System (INIS)

    Battaglin, R.I.M.

    1979-01-01

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

  3. Sulphonated Phthalocyanines as Effective Oxidation Photocatalysts

    Czech Academy of Sciences Publication Activity Database

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

    2008-01-01

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

  4. Direct Growth of Graphene on Silicon by Metal-Free Chemical Vapor Deposition

    Science.gov (United States)

    Tai, Lixuan; Zhu, Daming; Liu, Xing; Yang, Tieying; Wang, Lei; Wang, Rui; Jiang, Sheng; Chen, Zhenhua; Xu, Zhongmin; Li, Xiaolong

    2018-06-01

    The metal-free synthesis of graphene on single-crystal silicon substrates, the most common commercial semiconductor, is of paramount significance for many technological applications. In this work, we report the growth of graphene directly on an upside-down placed, single-crystal silicon substrate using metal-free, ambient-pressure chemical vapor deposition. By controlling the growth temperature, in-plane propagation, edge-propagation, and core-propagation, the process of graphene growth on silicon can be identified. This process produces atomically flat monolayer or bilayer graphene domains, concave bilayer graphene domains, and bulging few-layer graphene domains. This work would be a significant step toward the synthesis of large-area and layer-controlled, high-quality graphene on single-crystal silicon substrates. [Figure not available: see fulltext.

  5. An ultrafast study of Zinc Phthalocyanine in DMSO

    CSIR Research Space (South Africa)

    Ombinda-Lemboumba, Saturnin

    2010-10-01

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

  6. Hole Mobility of Molecular β-Copper Phthalocyanine Crystal

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  7. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-12-01

    Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  8. Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

    Science.gov (United States)

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

    2016-10-01

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

  9. Synthesis of phthalocyanine doped sol-gel materials

    Science.gov (United States)

    Dunn, Bruce

    1993-01-01

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

  10. Nitroxyl Modified Tobacco Mosaic Virus as a Metal-Free High-Relaxivity MRI and EPR Active Superoxide Sensor.

    Science.gov (United States)

    Dharmarwardana, Madushani; Martins, André F; Chen, Zhuo; Palacios, Philip M; Nowak, Chance M; Welch, Raymond P; Li, Shaobo; Luzuriaga, Michael A; Bleris, Leonidas; Pierce, Brad S; Sherry, A Dean; Gassensmith, Jeremiah J

    2018-05-29

    Superoxide overproduction is known to occur in multiple disease states requiring critical care; yet, noninvasive detection of superoxide in deep tissue remains a challenge. Herein, we report a metal-free magnetic resonance imaging (MRI) and electron paramagnetic resonance (EPR) active contrast agent prepared by "click conjugating" paramagnetic organic radical contrast agents (ORCAs) to the surface of tobacco mosaic virus (TMV). While ORCAs are known to be reduced in vivo to an MRI/EPR silent state, their oxidation is facilitated specifically by reactive oxygen species-in particular, superoxide-and are largely unaffected by peroxides and molecular oxygen. Unfortunately, single molecule ORCAs typically offer weak MRI contrast. In contrast, our data confirm that the macromolecular ORCA-TMV conjugates show marked enhancement for T 1 contrast at low field (<3.0 T) and T 2 contrast at high field (9.4 T). Additionally, we demonstrated that the unique topology of TMV allows for a "quenchless fluorescent" bimodal probe for concurrent fluorescence and MRI/EPR imaging, which was made possible by exploiting the unique inner and outer surface of the TMV nanoparticle. Finally, we show TMV-ORCAs do not respond to normal cellular respiration, minimizing the likelihood for background, yet still respond to enzymatically produced superoxide in complicated biological fluids like serum.

  11. 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

  12. Conjugated Molecules for the Smart Filtering of Intense Radiations

    Directory of Open Access Journals (Sweden)

    Danilo Dini

    2003-04-01

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

  13. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    high temperatures and long reaction times. To address this issue, we have developed several new families of carbon- and boron-based ligands, which are even better donors. The corresponding metal complexes (particularly gold, rhodium, iridium, and ruthenium) of all these species will be tested in the Markovnikov and anti-Markovnikov hydroamination of alkynes, allenes, and also alkenes with ammonia and hydrazine. We will also develop metal-free catalytic processes for the functionalization of ammonia and hydrazine. By possessing both a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble and can mimic the chemical behavior of transition metals. Our preliminary results demonstrate that specially designed carbenes can split the N–H bond of ammonia by an initial nucleophilic activation that prevents the formation of Lewis acid-base adducts, which is the major hurdle for the transition metal catalyzed functionalization of NH3. The use of purely organic compounds as catalysts will eliminate the major drawbacks of transition-metal-catalysis technology, which are the excessive cost of metal complexes (metal + ligands) and in many cases the toxicity of the metal.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  15. 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.

  16. 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

  17. From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

    Science.gov (United States)

    Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

    2017-07-01

    Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-03-15

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

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  20. 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.

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

    Science.gov (United States)

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

    2015-03-01

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

  2. High-power spallation target using a heavy liquid metal free surface flow

    International Nuclear Information System (INIS)

    Litfin, K.; Fetzer, J.R.; Batta, A.; Class, A.G.; Wetzel, Th.

    2015-01-01

    A prototype of a heavy liquid metal free surface target as proposed for the multi-purpose hybrid research reactor for high-tech applications in Mol, Belgium, has been set up and experimentally investigated at the Karlsruhe Liquid Metal Laboratory. A stable operation was demonstrated in a wide range of operating conditions and the surface shape was detected and compared with numerical pre-calculations employing Star-CD. Results show a very good agreement of experiment and numerical predictions which is an essential input for other windowless target designs like the META:LIC target for the European Spallation Source. (author)

  3. Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles.

    Science.gov (United States)

    Lambert, Kyle M; Bobbitt, James M; Eldirany, Sherif A; Kissane, Liam E; Sheridan, Rose K; Stempel, Zachary D; Sternberg, Francis H; Bailey, William F

    2016-04-04

    Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98% isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Visible-Light-Promoted Metal-Free Aerobic Oxidation of Primary Amines to Acids and Lactones.

    Science.gov (United States)

    Cheng, Xiaokai; Yang, Bo; Hu, Xingen; Xu, Qing; Lu, Zhan

    2016-12-05

    A unique metal-free aerobic oxidation of primary amines via visible light photocatalytic double carbon-carbon bonds cleavage and multi carbon-hydrogen bonds oxidation was observed. Aerobic oxidation of primary amines could be controlled to afford acids by using dioxane with 18 W CFL, and lactones by using DMF with 8 W green LEDs, respectively. A plausible mechanism was proposed based on control experiments. This observation showed direct evidences for the fragmentation in the aerobic oxidation of aliphatic primary amines. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Photoemission from valence bands of transition metal-phthalocyanines

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  6. 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.

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

    Directory of Open Access Journals (Sweden)

    Piotr Olszowski

    2017-01-01

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

  8. 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.

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

    Science.gov (United States)

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

    2016-03-07

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

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

    Science.gov (United States)

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

    2017-11-16

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

  11. Effects of Computer-Aided Manufacturing Technology on Precision of Clinical Metal-Free Restorations

    Directory of Open Access Journals (Sweden)

    Ki-Hong Lee

    2015-01-01

    Full Text Available Purpose. The purpose of this study was to investigate the marginal fit of metal-free crowns made by three different computer-aided design/computer-aided manufacturing (CAD/CAM systems. Materials and Methods. The maxillary left first premolar of a dentiform was prepared for all-ceramic crown restoration. Thirty all-ceramic premolar crowns were made, ten each manufactured by the Lava system, Cercon, and Cerec. Ten metal ceramic gold (MCG crowns served as control. The marginal gap of each sample was measured under a stereoscopic microscope at 75x magnification after cementation. One-way ANOVA and the Duncan’s post hoc test were used for data analysis at the significance level of 0.05. Results. The mean (standard deviation marginal gaps were 70.5 (34.4 μm for the MCG crowns, 87.2 (22.8 μm for Lava, 58.5 (17.6 μm for Cercon, and 72.3 (30.8 μm for Cerec. There were no significant differences in the marginal fit among the groups except that the Cercon crowns had significantly smaller marginal gaps than the Lava crowns (P<0.001.  Conclusions. Within the limitation of this study, all the metal-free restorations made by the digital CAD/CAM systems had clinically acceptable marginal accuracy.

  12. Challenges in reconstructing an isolated anterior tooth with a metal-free crown

    Directory of Open Access Journals (Sweden)

    Max Doria Costa

    2013-01-01

    Full Text Available Introduction: Currently, new esthetic treatments are available to the dentist due to the advent of ceramic-ceramic prostheses. A new option has become part of daily clinical practice, with the promise of esthetic optimization through the elimination of metal in prosthetic crowns. The translucence of these new systems allows the transmission of light through the tooth structure, minimizing gingival darkness and producing a vibrant and natural appearance. Case Report: The patient, 30 years old, female, showed with a fractured tooth crown at the cervical level in the right lateral incisive. It was observed that the tooth had prior adequate endodontic treatment. A metal-free restorative system was selected. A plaster model was obtained for subsequent tooth preparative scanning and manufacture of ceramic framework. After receiving the framework, adjustments were made and the color choice of covering ceramic, following the protocol of choice for a chroma suboptimal aiming further characterization. After the ceramics application, adjustments in shape, texture, and occlusion were made. The crown was characterized by exterior paint, getting a favorable result, restoring esthetics and function. Discussion : The metal-free systems are a viable alternative to the restorative treatment when esthetics is desired, allowing a natural and harmonious smile, combined with the reliability of the restorative material.

  13. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene

    Science.gov (United States)

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O.; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik

    2016-10-01

    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

  14. Effects of Computer-Aided Manufacturing Technology on Precision of Clinical Metal-Free Restorations.

    Science.gov (United States)

    Lee, Ki-Hong; Yeo, In-Sung; Wu, Benjamin M; Yang, Jae-Ho; Han, Jung-Suk; Kim, Sung-Hun; Yi, Yang-Jin; Kwon, Taek-Ka

    2015-01-01

    The purpose of this study was to investigate the marginal fit of metal-free crowns made by three different computer-aided design/computer-aided manufacturing (CAD/CAM) systems. The maxillary left first premolar of a dentiform was prepared for all-ceramic crown restoration. Thirty all-ceramic premolar crowns were made, ten each manufactured by the Lava system, Cercon, and Cerec. Ten metal ceramic gold (MCG) crowns served as control. The marginal gap of each sample was measured under a stereoscopic microscope at 75x magnification after cementation. One-way ANOVA and the Duncan's post hoc test were used for data analysis at the significance level of 0.05. The mean (standard deviation) marginal gaps were 70.5 (34.4) μm for the MCG crowns, 87.2 (22.8) μm for Lava, 58.5 (17.6) μm for Cercon, and 72.3 (30.8) μm for Cerec. There were no significant differences in the marginal fit among the groups except that the Cercon crowns had significantly smaller marginal gaps than the Lava crowns (P < 0.001). Within the limitation of this study, all the metal-free restorations made by the digital CAD/CAM systems had clinically acceptable marginal accuracy.

  15. Injectable dextran hydrogels fabricated by metal-free click chemistry for cartilage tissue engineering.

    Science.gov (United States)

    Wang, Xiaoyu; Li, Zihan; Shi, Ting; Zhao, Peng; An, Kangkang; Lin, Chao; Liu, Hongwei

    2017-04-01

    Injectable dextran-based hydrogels were prepared for the first time by bioorthogonal click chemistry for cartilage tissue engineering. Click-crosslinked injectable hydrogels based on cyto-compatible dextran (Mw=10kDa) were successfully fabricated under physiological conditions by metal-free alkyne-azide cycloaddition (click) reaction between azadibenzocyclooctyne-modified dextran (Dex-ADIBO) and azide-modified dextran (Dex-N 3 ). Gelation time of these dextran hydrogels could be regulated in the range of approximately 1.1 to 10.2min, depending on the polymer concentrations (5% or 10%) and ADIBO substitution degree (DS, 5 or 10) of Dex-ADIBO. Rheological analysis indicated that the dextran hydrogels were elastic and had storage moduli from 2.1 to 6.0kPa with increasing DS of ADIBO from 5 to 10. The in vitro tests revealed that the dextran hydrogel crosslinked from Dex-ADIBO DS 10 and Dex-N 3 DS 10 at a polymer concentration of 10% could support high viability of individual rabbit chondrocytes and the chondrocyte spheroids encapsulated in the hydrogel over 21days. Individual chondrocytes and chondrocyte spheroids in the hydrogel could produce cartilage matrices such as collagen and glycosaminoglycans. However, the chondrocyte spheroids produced a higher content of matrices than individual chondrocytes. This study indicates that metal-free click chemistry is effective to produce injectable dextran hydrogels for cartilage tissue engineering. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Fluorine-doped carbon nanotubes as an efficient metal-free catalyst for destruction of organic pollutants in catalytic ozonation.

    Science.gov (United States)

    Wang, Jing; Chen, Shuo; Quan, Xie; Yu, Hongtao

    2018-01-01

    Metal-free carbon materials have been presented to be potential alternatives to metal-based catalysts for heterogeneous catalytic ozonation, yet the catalytic performance still needs to be enhanced. Doping carbon with non-metallic heteroatoms (e.g., N, B, and F) could alter the electronic structure and electrochemical properties of original carbon materials, has been considered to be an effective method for improving the catalytic activity of carbon materials. Herein, fluorine-doped carbon nanotubes (F-CNTs) were synthesized via a facile method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The as-synthesized F-CNTs exhibited notably enhanced catalytic activity towards catalytic ozonation for the degradation of organic pollutants. The oxalic acid removal efficiency of optimized F-CNTs was approximately two times as much as that of pristine CNTs, and even exceeded those of four conventional metal-based catalysts (ZnO, Al 2 O 3 , Fe 2 O 3 , and MnO 2 ). The XPS and Raman studies confirmed that the covalent CF bonds were formed at the sp 3 C sites instead of sp 2 C sites on CNTs, not only resulting in high positive charge density of C atoms adjacent to F atoms, but remaining the delocalized π-system with intact carbon structure of F-CNTs, which then favored the conversion of ozone molecules (O 3 ) into reactive oxygen species (ROS) and contributed to the high oxalic acid removal efficiency. Furthermore, electron spin resonance (ESR) studies revealed that superoxide radicals (O 2 - ) and singlet oxygen ( 1 O 2 ) might be the dominant ROS that responsible for the degradation of oxalic acid in these catalytic systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Cytocompatible in situ forming chitosan/hyaluronan hydrogels via a metal-free click chemistry for soft tissue engineering.

    Science.gov (United States)

    Fan, Ming; Ma, Ye; Mao, Jiahui; Zhang, Ziwei; Tan, Huaping

    2015-07-01

    Injectable hydrogels are important cell scaffolding materials for tissue engineering and regenerative medicine. Here, we report a new class of biocompatible and biodegradable polysaccharide hydrogels derived from chitosan and hyaluronan via a metal-free click chemistry, without the addition of copper catalyst. For the metal-free click reaction, chitosan and hyaluronan were modified with oxanorbornadiene (OB) and 11-azido-3,6,9-trioxaundecan-1-amine (AA), respectively. The gelation is attributed to the triazole ring formation between OB and azido groups of polysaccharide derivatives. The molecular structures were verified by FT-IR spectroscopy and elemental analysis, giving substitution degrees of 58% and 47% for chitosan-OB and hyaluronan-AA, respectively. The in vitro gelation, morphologies, equilibrium swelling, compressive modulus and degradation of the composite hydrogels were examined. The potential of the metal-free hydrogel as a cell scaffold was demonstrated by encapsulation of human adipose-derived stem cells (ASCs) within the gel matrix in vitro. Cell culture showed that this metal-free hydrogel could support survival and proliferation of ASCs. A preliminary in vivo study demonstrated the usefulness of the hydrogel as an injectable scaffold for adipose tissue engineering. These characteristics provide a potential opportunity to use the metal-free click chemistry in preparation of biocompatible hydrogels for soft tissue engineering applications. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kroeger, Ingo

    2011-05-20

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

  19. Transglutaminase-Catalyzed Bioconjugation Using One-Pot Metal-Free Bioorthogonal Chemistry.

    Science.gov (United States)

    Rachel, Natalie M; Toulouse, Jacynthe L; Pelletier, Joelle N

    2017-10-18

    General approaches for controlled protein modification are increasingly sought-after in the arena of chemical biology. Here, using bioorthogonal reactions, we present combinatorial chemoenzymatic strategies to effectuate protein labeling. A total of three metal-free conjugations were simultaneously or sequentially incorporated in a one-pot format with microbial transglutaminase (MTG) to effectuate protein labeling. MTG offers the particularity of conjugating residues within a protein sequence rather than at its extremities, providing a route to labeling the native protein. The reactions are rapid and circumvent the incompatibility posed by metal catalysts. We identify the tetrazine ligation as most-reactive for this purpose, as demonstrated by the fluorescent labeling of two proteins. The Staudinger ligation and strain-promoted azide-alkyne cycloaddition are alternatives. Owing to the breadth of labels that MTG can use as a substrate, our results demonstrate the versatility of this system, with the researcher being able to combine specific protein substrates with a variety of labels.

  20. Transition-Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Hua Zhang

    2009-12-01

    Full Text Available A highly efficient transition-metal-free catalytic system Br2/NaNO2/H2O has been developed for a robust and economic acid-free aerobic oxidation of sulfides. It is noteworthy that the sulfide function reacts under mild conditions without over-oxidation to sulfone. The role of NaNO2as an efficient NO equivalent for the activation of molecular oxygen was identified. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields by molecular oxygen. The present catalytic system utilizes cheap and readily available agents as the catalysts, exhibits high selectivity for sulfoxide products and releases only innocuous water as the by-products.

  1. Metal-free hybrids of graphitic carbon nitride and nanodiamonds for photoelectrochemical and photocatalytic applications.

    Science.gov (United States)

    Zhou, Li; Zhang, Huayang; Guo, Xiaochen; Sun, Hongqi; Liu, Shaomin; Tade, Moses O; Wang, Shaobin

    2017-05-01

    Graphitic carbon nitride (g-C 3 N 4 ) has been considered as a metal-free, cost-effective, eco-friendly and efficient catalyst for various photoelectrochemical applications. However, compared to conventional metal-based photocatalysts, its photocatalytic activity is still low because of the low mobility of carriers restricted by the polymer nature. Herein, a series of hybrids of g-C 3 N 4 (GCN) and nanodiamonds (NDs) were synthesized using a solvothermal method. The photoelectrochemical performance and photocatalytic efficiency of the GCN/NDs were investigated by means of the generation of photocurrent and photodegradation of methylene blue (MB) solutions under UV-visible light irradiations. In this study, the sample of GCN/ND-33% derived from 0.1g GCN and 0.05g NDs displayed the highest photocatalytic activity and the strongest photocurrent density. The mechanism of enhanced photoelectrochemical and photocatalytic performances was also discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Metal free structural colours via disordered nanostructures with nm resolution and full CYMK colour spectrum

    KAUST Repository

    Bonifazi, Marcella; Mazzone, Valerio; Fratalocchi, Andrea

    2017-01-01

    Structural colours represents a research area of great interest, due to a wide field of application ranging from micro-security to biomimetic materials. At present metallic substrate are heavily employed and only a partial spectra of colours can be realised. We propose a novel, metal-free technology that exploits the complex scattering from a disordered three-dimensional dielectric material on a silicon substrate. We reproduce experimentally the full spectrum of CMYK colours, including variations in intensity. Our resolution lies in the nm range, limited only by the electron beam lithography fabrication process. We demonstrate that this technique is extremely robust, suitable for flexible and reusable substrates. Full of these notable proprieties these nano-structures fits perfectly with the requirements of a real-world technology.

  3. Metal free structural colours via disordered nanostructures with nm resolution and full CYMK colour spectrum

    KAUST Repository

    Bonifazi, Marcella

    2017-02-28

    Structural colours represents a research area of great interest, due to a wide field of application ranging from micro-security to biomimetic materials. At present metallic substrate are heavily employed and only a partial spectra of colours can be realised. We propose a novel, metal-free technology that exploits the complex scattering from a disordered three-dimensional dielectric material on a silicon substrate. We reproduce experimentally the full spectrum of CMYK colours, including variations in intensity. Our resolution lies in the nm range, limited only by the electron beam lithography fabrication process. We demonstrate that this technique is extremely robust, suitable for flexible and reusable substrates. Full of these notable proprieties these nano-structures fits perfectly with the requirements of a real-world technology.

  4. 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

  5. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-10-08

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

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  8. Individual Magnetic Molecules on Ultrathin Insulating Surfaces

    Science.gov (United States)

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

    2012-02-01

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

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

    Science.gov (United States)

    Komeda, Tadahiro; Katoh, Keiichi; Yamashita, Masahiro

    2014-05-01

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

  10. Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts.

    Science.gov (United States)

    Hari, Durga Prasad; Schroll, Peter; König, Burkhard

    2012-02-15

    Visible light along with 1 mol % eosin Y catalyzes the direct C-H bond arylation of heteroarenes with aryl diazonium salts by a photoredox process. We have investigated the scope of the reaction for several aryl diazonium salts and heteroarenes. The general and easy procedure provides a transition-metal-free alternative for the formation of aryl-heteroaryl bonds.

  11. A new method to synthesize sulfur-doped graphene as effective metal-free electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhai, Chunyang; Sun, Mingjuan [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Zhu, Mingshan, E-mail: mingshanzhu@yahoo.com [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Song, Shaoqing [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China); Jiang, Shujuan, E-mail: sjjiang@ecit.edu.cn [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China)

    2017-06-15

    Highlights: • S doped graphene was facile synthesized by one-pot solvothermal method. • DMSO acted as S source as well as reaction solvent. • S-RGO worked as an efficient metal-free electrocatalyst for ORR. • S-RGO acted as a promising candidate instead of Pt-based catalyst. - Abstract: The exploration of a metal-free catalyst with highly efficient yet low-cost for the oxygen-reduction reaction (ORR) is under wide spread investigation. In this paper, by using dimethyl sulfoxide (DMSO) as S source as well as solvent, we report a new, low-cost, and facile solvothermal route to synthesize S-doped reduced graphene oxide (S-RGO). The existence of S element in the framework of RGO was solidly confirmed by energy-dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). The as-synthesized S-RGO can be worked as an efficient metal-free electrocatalyst for ORR. Moreover, compared to commercial Pt/C electrocatalyst, the S-RGO displays superior resistance to crossover effect and stability by evaluating the addition of methanol and CO poisoning experiment. This result not only shows S-RGO as a promising candidate instead of Pt-based catalyst for ORR, but also provides a new approach for the preparation of metal-free electrocatalyst in future.

  12. Metal-free one-pot synthesis of 2-substituted and 2,3-disubstituted morpholines from aziridines

    Directory of Open Access Journals (Sweden)

    Hongnan Sun

    2015-04-01

    Full Text Available The metal-free synthesis of 2-substituted and 2,3-disubstituted morpholines through a one-pot strategy is described. A simple and inexpensive ammonium persulfate salt enables the reaction of aziridines with halogenated alcohols to proceed via an SN2-type ring opening followed by cyclization of the resulting haloalkoxy amine.

  13. Synthesis of 2-Alkenylquinoline by Reductive Olefination of Quinoline N-Oxide under Metal-Free Conditions.

    Science.gov (United States)

    Xia, Hong; Liu, Yuanhong; Zhao, Peng; Gou, Shaohua; Wang, Jun

    2016-04-15

    Synthesis of 2-alkenylquinoline by reductive olefination of quinoline N-oxide under metal-free conditions is disclosed. Practically, the reaction could be performed with quinoline as starting material via a one-pot, two-step process. A possible mechanism is proposed that involves a sequential 1,3-dipolar cycloaddition and acid-assisted ring opening followed by a dehydration process.

  14. Synthesis of amino ester-embedded benzimidazoles: a one-pot sequential protocol under metal-free neutral conditions.

    Science.gov (United States)

    Roy, Priyabrata; Bodhak, Chandan; Pramanik, Animesh

    2017-02-01

    A one-pot three-component protocol has been developed for the synthesis of amino ester-embedded benzimidazoles under metal-free neutral conditions. Sequentially, the methodology involves coupling of an amino ester with 1-fluoro-2-nitrobenzene, reduction of the coupled nitroarene by sodium dithionite, and cyclization of the corresponding diamine with an aldehyde.

  15. 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.

  16. An Amorphous Noble-Metal-Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions.

    Science.gov (United States)

    Lv, Chade; Yan, Chunshuang; Chen, Gang; Ding, Yu; Sun, Jingxue; Zhou, Yansong; Yu, Guihua

    2018-02-23

    N 2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as a potential approach to achieve NH 3 production, which still heavily relies on the Haber-Bosch process at the cost of huge energy and massive production of CO 2 . A noble-metal-free Bi 4 V 2 O 11 /CeO 2 hybrid with an amorphous phase (BVC-A) is used as the cathode for electrocatalytic NRR. The amorphous Bi 4 V 2 O 11 contains significant defects, which play a role as active sites. The CeO 2 not only serves as a trigger to induce the amorphous structure, but also establishes band alignment with Bi 4 V 2 O 11 for rapid interfacial charge transfer. Remarkably, BVC-A shows outstanding electrocatalytic NRR performance with high average yield (NH 3 : 23.21 μg h -1  mg -1 cat. , Faradaic efficiency: 10.16 %) under ambient conditions, which is superior to the Bi 4 V 2 O 11 /CeO 2 hybrid with crystalline phase (BVC-C) counterpart. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

    Science.gov (United States)

    Yuan, Heyang; He, Zhen

    2017-07-01

    Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

    Science.gov (United States)

    Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

    2016-12-01

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  19. Bicarbonate-induced activation of H₂O₂ for metal-free oxidative desulfurization.

    Science.gov (United States)

    Bokare, Alok D; Choi, Wonyong

    2016-03-05

    Efficient oxidative desulfurization (ODS) of model oil containing dibenzothiophene (DBT) and aromatic thiophenic derivatives has been achieved at room temperature using hydrogen peroxide activation by inorganic bicarbonate (HCO3(-)). Using in-situ formation of peroxymonocarbonate as oxidant, the transformation of main model substrate DBT to corresponding DBT-sulfone was easily accomplished in biphasic reaction conditions. In the presence of water-acetonitrile polar phase, increasing the water content upto 50% decreased the extraction capacity more than 3 times, but ∼ 90% DBT oxidation was still achieved. The oxidizing capacity of bicarbonate catalyst was maintained during repeated ODS cycles, but DBT removal efficiency was critically dependent on the extraction capacity of the polar phase. Under heterogeneous reaction conditions, bicarbonate-modified ion-exchange resin achieved similar ODS activity compared to the homogeneous catalytic system. Additionally, the efficient formation of peroxymonocarbonate using gaseous CO2 precursor in alkaline conditions was also utilized for DBT oxidation. The present study proposes the NaHCO3/H2O2 catalytic system as an efficient and cheap metal-free alternative for the oxidative removal of aromatic sulfur compounds from fuel oil. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Synthesis of Stacked-Cup Carbon Nanotubes in a Metal Free Low Temperature System

    Science.gov (United States)

    Kimura, Yuki; Nuth, Joseph A.; Johnson, Natasha M.; Farmer, Kevin D.; Roberts, Kenneth P.; Hussaini, Syed R.

    2011-01-01

    Stacked-cup carbon nanotubes were formed by either Fischer-Tropsch type or Haber Bosch type reactions in a metal free system. Graphite particles were used as the catalyst. The samples were heated at 600 C in a gas mixture of CO 75 Torr, N2 75 Torr and H2 550 Torr for three days. Trans mission electron microscope analysis of the catalyst surface at the completion of the experiment recognized the growth of nanotubes. They were 10-50 nm in diameter and approximately 1 micrometer in length. They had a hollow channel of 5-20 nm in the center. The nanotubes may have grown on graphite surfaces by the CO disproportionation reaction and the surface tension of the carbon nucleus may have determined the diameter. Although, generally, the diameter of a carbon nanotube depends on the size of the cataly1ic particles, the diameter of the nanotubes on graphite particles was independent of the particle size and significantly confined within a narrow range compared with that produced using catalytic amorphous iron-silicate nanoparticles. Therefore, they must have an unknown formation process that is different than the generally accepted mechanism.

  1. Structural Stability and Performance of Noble Metal-Free SnO2-Based Gas Sensors

    Directory of Open Access Journals (Sweden)

    Antonio Tricoli

    2012-05-01

    Full Text Available The structural stability of pure SnO2 nanoparticles and highly sensitive SnO2-SiO2 nanocomposites (0–15 SiO2 wt% has been investigated for conditions relevant to their utilization as chemoresistive gas sensors. Thermal stabilization by SiO2 co-synthesis has been investigated at up to 600 °C determining regimes of crystal size stability as a function of SiO2-content. For operation up to 400 °C, thermally stable crystal sizes of ca. 24 and 11 nm were identified for SnO2 nanoparticles and 1.4 wt% SnO2-SiO2 nanocomposites, respectively. The effect of crystal growth during operation (TO = 320 °C on the sensor response to ethanol has been reported, revealing possible long-term destabilization mechanisms. In particular, crystal growth and sintering-neck formation were discussed with respect to their potential to change the sensor response and calibration. Furthermore, the effect of SiO2 cosynthesis on the cross-sensitivity to humidity of these noble metal-free SnO2-based gas sensors was assessed.

  2. Metal-Free Aqueous Flow Battery with Novel Ultrafiltered Lignin as Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Mukhopadhyay, Alolika [Department of Mechanical and Industrial Engineering, Northeastern University, 360 Huntington Avenue, 334 Snell Engineering, Boston, Massachusetts 02115, United States; Hamel, Jonathan [Department of Mechanical and Industrial Engineering, Northeastern University, 360 Huntington Avenue, 334 Snell Engineering, Boston, Massachusetts 02115, United States; Katahira, Rui [National Renewable Energy Laboratory, Denver West Parkway, Golden, Colorado 80401, United States; Zhu, Hongli [Department of Mechanical and Industrial Engineering, Northeastern University, 360 Huntington Avenue, 334 Snell Engineering, Boston, Massachusetts 02115, United States

    2018-03-05

    As the number of generation sources from intermittent renewable technologies on the electric grid increases, the need for large-scale energy storage devices is becoming essential to ensure grid stability. Flow batteries offer numerous advantages over conventional sealed batteries for grid storage. In this work, for the first time, we investigated lignin, the second most abundant wood derived biopolymer, as an anolyte for the aqueous flow battery. Lignosulfonate, a water-soluble derivative of lignin, is environmentally benign, low cost and abundant as it is obtained from the byproduct of paper and biofuel manufacturing. The lignosulfonate utilizes the redox chemistry of quinone to store energy and undergoes a reversible redox reaction. Here, we paired lignosulfonate with Br2/Br-, and the full cell runs efficiently with high power density. Also, the large and complex molecular structure of lignin considerably reduces the electrolytic crossover, which ensures very high capacity retention. The flowcell was able to achieve current densities of up to 20 mA/cm2 and charge polarization resistance of 15 ohm cm2. This technology presents a unique opportunity for a low-cost, metal-free flow battery capable of large-scale sustainable energy storage.

  3. Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

    Science.gov (United States)

    Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

    2018-01-01

    Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

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

    Science.gov (United States)

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

    2018-03-01

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

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

    Directory of Open Access Journals (Sweden)

    Eiza Shimizu

    2016-01-01

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

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

    DEFF Research Database (Denmark)

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

    2009-01-01

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    Science.gov (United States)

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

    2010-06-01

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

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

    International Nuclear Information System (INIS)

    Lee, Sang Uck

    2013-01-01

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

  10. Ethanol tolerant precious metal free cathode catalyst for alkaline direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Grimmer, Ilena; Zorn, Paul; Weinberger, Stephan; Grimmer, Christoph; Pichler, Birgit; Cermenek, Bernd; Gebetsroither, Florian; Schenk, Alexander; Mautner, Franz-Andreas

    2017-01-01

    Highlights: • Selective ORR catalysts are presented for alkaline direct ethanol fuel cells. • Perovskite based cathode catalysts show high tolerance toward ethanol. • A membrane-free alkaline direct ethanol fuel cell is presented. - Abstract: La 0.7 Sr 0.3 (Fe 0.2 Co 0.8 )O 3 and La 0.7 Sr 0.3 MnO 3 −based cathode catalysts are synthesized by the sol-gel method. These perovskite cathode catalysts are tested in half cell configuration and compared to MnO 2 as reference material in alkaline direct ethanol fuel cells (ADEFCs). The best performing cathode is tested in single cell setup using a standard carbon supported Pt 0.4 Ru 0.2 based anode. A backside Luggin capillary is used in order to register the anode potential during all measurements. Characteristic processes of the electrodes are investigated using electrochemical impedance spectroscopy. Physical characterizations of the perovskite based cathode catalysts are performed with a scanning electron microscope (SEM) and by X-ray diffraction showing phase pure materials. In half cell setup, La 0.7 Sr 0.3 MnO 3 shows the highest tolerance toward ethanol with a performance of 614 mA cm −2 at 0.65 V vs. RHE in 6 M KOH and 1 M EtOH at RT. This catalyst outperforms the state-of-the-art precious metal-free MnO 2 catalyst in presence of ethanol. In fuel cell setup, the peak power density is 27.6 mW cm −2 at a cell voltage of 0.345 V and a cathode potential of 0.873 V vs. RHE.

  11. Determination of the side-reaction coefficient of desferrioxamine B in trace-metal-free seawater

    Directory of Open Access Journals (Sweden)

    Johan Schijf

    2016-07-01

    Full Text Available Electrochemical techniques like adsorptive cathodic stripping voltammetry with competitive ligand equilibration (ACSV-CLE can determine total concentrations of marine organic ligands and their conditional binding constants for specific metals, but cannot identify them. Individual organic ligands, isolated from microbial cultures or biosynthesized through genomics, can be structurally characterized via NMR and tandem MS analysis, but this is tedious and time-consuming. A complementary approach is to compare known properties of natural ligands, particularly their conditional binding constants, with those of model organic ligands, measured under suitable conditions. Such comparisons cannot be meaningfully interpreted unless the side-reaction coefficient (SRC of the model ligand in seawater is thoroughly evaluated.We conducted series of potentiometric titrations, in non-coordinating medium at seawater ionic strength (0.7 M NaClO4 over a range of metal:ligand molar ratios, to study complexation of the siderophore desferrioxamine B (DFOB with Mg and Ca, for which it has the highest affinity among the major seasalt cations. From similar titrations of acetohydroxamic acid in the absence and presence of methanesulfonate (mesylate, it was determined that Mg and Ca binding to this common DFOB counter-ion is not strong enough to interfere with the DFOB titrations. Stability constants were measured for all DFOB complexes with Mg and Ca including, for the first time, the bidentate complexes. No evidence was found for Mg and Ca coordination with the DFOB terminal amine. From the improved DFOB speciation, we calculated five SRCs for each of the five (deprotonated forms of DFOB in trace-metal-free seawater, yet we also present a more convenient definition of a single SRC that allows adjustment of all DFOB stability constants to seawater conditions, no matter which of these forms is selected as the 'component' (reference species. An example of Cd speciation in

  12. Active and passive control of zinc phthalocyanine photodynamics

    NARCIS (Netherlands)

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

    2013-01-01

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

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

    Indian Academy of Sciences (India)

    Administrator

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

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

    Czech Academy of Sciences Publication Activity Database

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

    2009-01-01

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

  15. 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

  16. 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

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

  18. 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

  19. Fabrication and characterization of tetracyanoquinodimethane/phthalocyanine solar cells

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  20. Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

    Directory of Open Access Journals (Sweden)

    Liang Ma

    2017-02-01

    Full Text Available Surface-initiated atom transfer radical polymerization (SI-ATRP is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal.

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

    KAUST Repository

    Zhao, Junpeng

    2013-01-01

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

  2. Structural and biophysical properties of metal-free pathogenic SOD1 mutants A4V and G93A

    Energy Technology Data Exchange (ETDEWEB)

    Galaleldeen, Ahmad; Strange, Richard W.; Whitson, Lisa J.; Antonyuk, Svetlana V.; Narayana, Narendra; Taylor, Alexander B.; Schuermann, Jonathan P.; Holloway, Stephen P.; Hasnain, S.Samar; Hart, P. John; (Texas-HSC); (Liverpool)

    2010-07-19

    Amyotrophic lateral sclerosis (ALS) is a fatal, progressive neurodegenerative disease characterized by the destruction of motor neurons in the spinal cord and brain. A subset of ALS cases are linked to dominant mutations in copper-zinc superoxide dismutase (SOD1). The pathogenic SOD1 variants A4V and G93A have been the foci of multiple studies aimed at understanding the molecular basis for SOD1-linked ALS. The A4V variant is responsible for the majority of familial ALS cases in North America, causing rapidly progressing paralysis once symptoms begin and the G93A SOD1 variant is overexpressed in often studied murine models of the disease. Here we report the three-dimensional structures of metal-free A4V and of metal-bound and metal-free G93A SOD1. In the metal-free structures, the metal-binding loop elements are observed to be severely disordered, suggesting that these variants may share mechanisms of aggregation proposed previously for other pathogenic SOD1 proteins.

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

    Science.gov (United States)

    Chow, Yun Sang

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

  4. Influence of gamma ray irradiation and annealing temperature on the optical constants and spectral dispersion parameters of metal-free and zinc tetraphenylporphyrin thin films: A comparative study.

    Science.gov (United States)

    Zeyada, H M; Makhlouf, M M; El-Nahass, M M

    2015-09-05

    In this work, we report on the effect of γ-ray irradiation and annealing temperature on the optical properties of metal-free tetraphenylporphyrin, H2TPP, and zinc tetraphenylporphyrin, ZnTPP, thin films. Thin films of H2TPP and ZnTPP were successfully prepared by the thermal evaporation technique. The optical properties of H2TPP and ZnTPP films were investigated using spectrophotometric measurements of the transmittance and reflectance at normal incidence of light in the wavelength range from 200 to 2500 nm. The absorption spectra of H2TPP showed four absorption bands, namely the Q, B, N and M bands. The effect of inserting Zn atom into the cavity of porphyrin macrocycle in ZnTPP molecule distorted the Q and B bands, reduced the width of absorption region and influenced the optical constants and dispersion parameters. In all conditions, the type of electron transition is indirect allowed transition. Anomalous dispersion is observed in the absorption region but normal dispersion occurs in the transparent region of spectra. We adopted multi-oscillator model and the single oscillator model to interpret the anomalous and normal dispersion, respectively. We have found that the annealing temperature has mostly the opposite effect of γ-ray irradiation on absorption and dispersion characteristics of these films. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Thermal- and pH-Dependent Size Variable Radical Nanoparticles and Its Water Proton Relaxivity for Metal-Free MRI Functional Contrast Agents.

    Science.gov (United States)

    Morishita, Kosuke; Murayama, Shuhei; Araki, Takeru; Aoki, Ichio; Karasawa, Satoru

    2016-09-16

    For development of the metal-free MRI contrast agents, we prepared the supra-molecular organic radical, TEMPO-UBD, carrying TEMPO radical, as well as the urea, alkyl group, and phenyl ring, which demonstrate self-assembly behaviors using noncovalent bonds in an aqueous solution. In addition, TEMPO-UBD has the tertiary amine and the oligoethylene glycol chains (OEGs) for the function of pH and thermal responsiveness. By dynamic light scattering and transmission electron microscopy imaging, the resulting self-assembly was seen to form the spherical nanoparticles 10-150 nm in size. On heating, interestingly, the nanoparticles showed a lower critical solution temperature (LCST) behavior having two-step variation. This double-LCST behavior is the first such example among the supra-molecules. To evaluate of the ability as MRI contrast agents, the values of proton ((1)H) longitudinal relaxivity (r1) were determined using MRI apparatus. In conditions below and above CAC at pH 7.0, the distinguishable r1 values were estimated to be 0.17 and 0.21 mM(-1) s(1), indicating the suppression of fast tumbling motion of TEMPO moiety in a nanoparticle. Furthermore, r1 values became larger in the order of pH 7.0 > 9.0 > 5.0. Those thermal and pH dependencies indicated the possibility of metal-fee MRI functional contrast agents in the future.

  6. The molecular, electronic structures and vibrational spectra of metal-free, N,N'-dideuterio and magnesium tetra-2,3-pyridino-porphyrazines: Density functional calculations.

    Science.gov (United States)

    Liu, Zhongqiang; Zhang, Xianxi; Zhang, Yuexing; Li, Renjie; Jiang, Jianzhuang

    2006-10-01

    A theoretical investigation of the fully optimized geometries and electronic structures of the metal-free (TPdPzH(2)), N,N'-dideuterio (TPdPzD(2)), and magnesium (TPdPzMg) tetra-2,3-pyridino-porphyrazine has been conducted based on density functional theory. The optimized geometries at density functional theory level for these compounds are reported here for the first time. A comparison between the different molecules for the geometry, molecular orbital, and atomic charge is made. The substituent effect of the N atoms on the molecular structures of these compounds is discussed. The IR and Raman spectra for these three compounds have also been calculated at density functional B3LYP level using the 6-31G(d) basis set. Detailed assignments of the NH, NM, and pyridine ring vibrational bands in the IR and Raman spectra have been made based on assistance of animated pictures. The simulated IR spectra of TPdPzH(2) are compared with the experimental absorption spectra, and very good consistency has been found. The isotope effect on the IR and Raman spectra is also discussed.

  7. Ambipolar carrier transport properties and molecular packing structure of octahexyl-substituted copper phthalocyanine

    Science.gov (United States)

    Watanabe, Ken; Watanabe, Koichi; Tohnai, Norimitsu; Itani, Hiromichi; Shimizu, Yo; Fujii, Akihiko; Ozaki, Masanori

    2018-04-01

    The charge carrier mobility of a solution-processable low-molecular-weight organic semiconductor material, i.e., 1,4,8,11,15,18,22,25-octahexylphthalocyanine copper complex (C6PcCu), was investigated by the time-of-flight technique. The anomalous ambipolar carrier mobility was discussed from the viewpoint of the molecular packing structure, which was clarified by single-crystal X-ray structure analysis. In the comparison between the molecular packing structures of C6PcCu and its metal-free-type homologue, it was found that the difference in carrier mobility originates from the rotation of the molecule, which is caused by the steric hindrance due to the introduction of a center metal and the interpenetration of the nonperipheral alkyl chains.

  8. Experimental and numerical investigation of liquid-metal free-surface flows in spallation targets

    Energy Technology Data Exchange (ETDEWEB)

    Batta, A., E-mail: batta@kit.edu [Karlsruhe Institute of Technology, Germany Hermann-von-Helmholtz-PLATZ 1, 76344 Eggenstein-Leopoldshafen (Germany); Class, A.G.; Litfin, K.; Wetzel, Th. [Karlsruhe Institute of Technology, Germany Hermann-von-Helmholtz-PLATZ 1, 76344 Eggenstein-Leopoldshafen (Germany); Moreau, V.; Massidda, L. [CRS4 Centre for Advanced Studies, Research and Development in Sardinia, Polaris, Edificio 1, 09010 Pula, CA (Italy); Thomas, S.; Lakehal, D. [ASCOMP GmbH Zurich, Zurich (Switzerland); Angeli, D.; Losi, G. [DIEF – Department of Engineering “Enzo Ferrari”, University of Modena and Reggio Emilia, via Vignolese 905, 41125 Modena (Italy); Mooney, K.G. [University of Massachusetts Amherst, Department of Mechanical and Industrial Engineering, Amherst (United States); Van Tichelen, K. [SCK-CEN, Belgian Nuclear Research Centre, Boeretang 200, 2400 Mol (Belgium)

    2015-08-15

    Highlights: • Experimental study of free surface for lead bismuth eutectic target. • Numerical investigation of free surface of a liquid metal target. • Advanced free surface modelling. - Abstract: Accelerator Driven Systems (ADS) are extensively investigated for the transmutation of high-level nuclear waste within many worldwide research programs. The first advanced design of an ADS system is currently developed in SCK• CEN, Mol, Belgium: the Multi-purpose hYbrid Research Reactor for High-tech Applications (MYRRHA). Many European research programs support the design of MYRRHA. In the framework of the Euratom project ‘Thermal Hydraulics of Innovative nuclear Systems (THINS)’ a liquid-metal free-surface experiment is performed at the Karlsruhe Liquid Metal Laboratory (KALLA) of Karlsruhe Institute of Technology (KIT). The experiment investigates a full-scale model of the concentric free-surface spallation target of MYRRHA using Lead Bismuth Eutectic (LBE) as coolant. In parallel, numerical free surface models are developed and tested which are reviewed in the article. A volume-of-fluid method, a moving mesh model, a free surface model combining the Level-Set method with Large-Eddy Simulation model and a smoothed-particle hydrodynamics approach are investigated. Verification of the tested models is based on the experimental results obtained within the THINS project and on previous water experiments performed at the University Catholic de Louvain (UCL) within the Euratom project ‘EUROpean Research Programme for the TRANSmutation of High Level Nuclear Waste in Accelerator Driven System (EUROTRANS)’. The design of the target enables a high fluid velocity and a stable surface at the beam entry. The purpose of this paper is to present an overview of both experimental and numerical results obtained for free surface target characterization. Without entering in technical details, the status, the major achievements and lessons for the future with respect to

  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. A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

    Science.gov (United States)

    Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

    2017-11-01

    The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

  11. Green Synthesis of InP/ZnS Core/Shell Quantum Dots for Application in Heavy-Metal-Free Light-Emitting Diodes

    OpenAIRE

    Kuo, Tsung-Rong; Hung, Shih-Ting; Lin, Yen-Ting; Chou, Tzu-Lin; Kuo, Ming-Cheng; Kuo, Ya-Pei; Chen, Chia-Chun

    2017-01-01

    Quantum dot light-emitting diodes (QD-LEDs) have been considered as potential display technologies with the characterizations of high color purity, flexibility, transparency, and cost efficiency. For the practical applications, the development of heavy-metal-free QD-LEDs from environment-friendly materials is the most important issue to reduce the impacts on human health and environmental pollution. In this work, heavy-metal-free InP/ZnS core/shell QDs with different fluorescence were prepare...

  12. Dynamical propagation of nanosecond pulses in Naphthalocyanines and Phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-30

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

  13. Fracture resistance of metal-free composite crowns-effects of fiber reinforcement, thermal cycling, and cementation technique.

    Science.gov (United States)

    Lehmann, Franziska; Eickemeyer, Grit; Rammelsberg, Peter

    2004-09-01

    The improved mechanical properties of contemporary composites have resulted in their extensive use for the restoration of posterior teeth. However, the influence of fiber reinforcement, cementation technique, and physical stress on the fracture resistance of metal-free crowns is unknown. This in vitro study evaluated the effect of fiber reinforcement, physical stress, and cementation methods on the fracture resistance of posterior metal-free Sinfony crowns. Ninety-six extracted human third molars received a standardized tooth preparation: 0.5-mm chamfer preparation and occlusal reduction of 1.3 to 1.5 mm. Sinfony (nonreinforced crowns, n=48) and Sinfony-Vectris (reinforced crowns, n=48) crowns restoring original tooth contour were prepared. Twenty-four specimens of each crown type were cemented, using either glass ionomer cement (GIC) or resin cement. Thirty-two crowns (one third) were stored in humidity for 48 hours. Another third was exposed to 10,000 thermal cycles (TC) between 5 degrees C and 55 degrees C. The remaining third was treated with thermal cycling and mechanical loading (TCML), consisting of 1.2 million axial loads of 50 N. The artificial crowns were then vertically loaded with a steel sphere until failure occurred. Significant differences in fracture resistance (N) between experimental groups were assessed by nonparametric Mann-Whitney U-test (alpha=.05). Fifty percent of the Sinfony and Sinfony-Vectris crowns cemented with glass ionomer cement loosened after thermal cycling. Thermal cycling resulted in a significant reduction in the mean fracture resistance for Sinfony crowns cemented with GIC, from 2037 N to 1282 N (P=.004). Additional fatigue produced no further effects. Fiber reinforcement significantly increased fracture resistance, from 1555 N to 2326 N (P=.001). The minimal fracture resistance was above 600 N for all combinations of material, cement and loading. Fracture resistance of metal-free Sinfony crowns was significantly increased by

  14. Synthesis and spectral properties of europium phthalocyanine complexes

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  15. 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

  16. Electronic and gas sensing properties of soluble phthalocyanines

    Czech Academy of Sciences Publication Activity Database

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

    2009-01-01

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

  17. Base-promoted isomerization of CF3-containing allylic alcohols to the corresponding saturated ketones under metal-free conditions

    Directory of Open Access Journals (Sweden)

    Yoko Hamada

    2017-08-01

    Full Text Available Following to the computational expectation, our previously reported intriguing 1,3-proton shift of 4,4,4-trifluorobut-2-yn-1-ols was successfully extended to the 4,4,4-trifluorobut-2-en-1-ol system under metal-free conditions to afford the corresponding saturated ketones in high to excellent chemical yields using such a convenient and easy-to-handle base as DBU at the toluene refluxing temperature, and utilization of the corresponding optically active substrates unambiguously demonstrated that this transformation proceeded in a highly stereoselective fashion.

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

    Science.gov (United States)

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

    2012-03-25

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

  19. 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.

  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. 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

  3. 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

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

    Science.gov (United States)

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

    2008-12-11

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

  6. Functionalized Graphitic Carbon Nitride for Metal-free, Flexible and Rewritable Nonvolatile Memory Device via Direct Laser-Writing

    Science.gov (United States)

    Zhao, Fei; Cheng, Huhu; Hu, Yue; Song, Long; Zhang, Zhipan; Jiang, Lan; Qu, Liangti

    2014-01-01

    Graphitic carbon nitride nanosheet (g-C3N4-NS) has layered structure similar with graphene nanosheet and presents unusual physicochemical properties due to the s-triazine fragments. But their electronic and electrochemical applications are limited by the relatively poor conductivity. The current work provides the first example that atomically thick g-C3N4-NSs are the ideal candidate as the active insulator layer with tunable conductivity for achieving the high performance memory devices with electrical bistability. Unlike in conventional memory diodes, the g-C3N4-NSs based devices combined with graphene layer electrodes are flexible, metal-free and low cost. The functionalized g-C3N4-NSs exhibit desirable dispersibility and dielectricity which support the all-solution fabrication and high performance of the memory diodes. Moreover, the flexible memory diodes are conveniently fabricated through the fast laser writing process on graphene oxide/g-C3N4-NSs/graphene oxide thin film. The obtained devices not only have the nonvolatile electrical bistability with great retention and endurance, but also show the rewritable memory effect with a reliable ON/OFF ratio of up to 105, which is the highest among all the metal-free flexible memory diodes reported so far, and even higher than those of metal-containing devices. PMID:25073687

  7. Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

    Science.gov (United States)

    Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

    2017-12-01

    Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Design of new metal-free dyes for dye-sensitized solar cells: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Xiong; Zhou, Le; Li, Yawei [Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871 (China); Sun, Qiang, E-mail: sunqiang@pku.edu.cn [Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871 (China); Center for Applied Physics and Technology, Peking University, Beijing 100871 (China); Jena, Puru [Department of Physics, Virginia Commonwealth University, Richmond, VA 23284 (United States)

    2012-08-06

    Five new metal-free dyes with acceptor–π–donor (A–π–D) structure are studied using first-principles calculation based on density functional theory. Benzothiadiazole (BTD) and triphenylamine (TPA) were chosen, respectively, as an acceptor and a donor with 4-(dicyanomethylene)-2-methyl-6-(4-dimethylamino-styryl)-4H-pyran (DCM) as a π linker. The linker was further modified by -CH=CH- resulting in a red-shift with improved absorption spectra caused by the smaller energy gap and the increased orbital hybridization. The designed dyes are found to exhibit wide absorption spectra, high molar extinction coefficients, desirable orbital distributions, and good energy levels alignment, and hence can have potential applications in dye-sensitized solar cells. -- Highlights: ► New metal-free dyes with A–π–D architecture. ► With wide absorption spectra and high molar extinction coefficients. ► With desirable orbital distribution and good energy levels alignment.

  9. Functionalized Graphitic Carbon Nitride for Metal-free, Flexible and Rewritable Nonvolatile Memory Device via Direct Laser-Writing

    Science.gov (United States)

    Zhao, Fei; Cheng, Huhu; Hu, Yue; Song, Long; Zhang, Zhipan; Jiang, Lan; Qu, Liangti

    2014-07-01

    Graphitic carbon nitride nanosheet (g-C3N4-NS) has layered structure similar with graphene nanosheet and presents unusual physicochemical properties due to the s-triazine fragments. But their electronic and electrochemical applications are limited by the relatively poor conductivity. The current work provides the first example that atomically thick g-C3N4-NSs are the ideal candidate as the active insulator layer with tunable conductivity for achieving the high performance memory devices with electrical bistability. Unlike in conventional memory diodes, the g-C3N4-NSs based devices combined with graphene layer electrodes are flexible, metal-free and low cost. The functionalized g-C3N4-NSs exhibit desirable dispersibility and dielectricity which support the all-solution fabrication and high performance of the memory diodes. Moreover, the flexible memory diodes are conveniently fabricated through the fast laser writing process on graphene oxide/g-C3N4-NSs/graphene oxide thin film. The obtained devices not only have the nonvolatile electrical bistability with great retention and endurance, but also show the rewritable memory effect with a reliable ON/OFF ratio of up to 105, which is the highest among all the metal-free flexible memory diodes reported so far, and even higher than those of metal-containing devices.

  10. Fabrication of field-effect transistor utilizing oriented thin film of octahexyl-substituted phthalocyanine and its electrical anisotropy based on columnar structure

    Science.gov (United States)

    Ohmori, Masashi; Nakatani, Mitsuhiro; Kajii, Hirotake; Miyamoto, Ayano; Yoneya, Makoto; Fujii, Akihiko; Ozaki, Masanori

    2018-03-01

    Field-effect transistors with molecularly oriented thin films of metal-free non-peripherally octahexyl-substituted phthalocyanine (C6PcH2), which characteristically form a columnar structure, have been fabricated, and the electrical anisotropy of C6PcH2 has been investigated. The molecularly oriented thin films of C6PcH2 were prepared by the bar-coating technique, and the uniform orientation in a large area and the surface roughness at a molecular level were observed by polarized spectroscopy and atomic force microscopy, respectively. The field effect mobilities parallel and perpendicular to the column axis of C6PcH2 were estimated to be (1.54 ± 0.24) × 10-2 and (2.10 ± 0.23) × 10-3 cm2 V-1 s-1, respectively. The electrical anisotropy based on the columnar structure has been discussed by taking the simulated results obtained by density functional theory calculation into consideration.

  11. Negative differential resistance in nickel octabutoxy phthalocyanine and nickel octabutoxy phthalocyanine/graphene oxide ultrathin films

    Science.gov (United States)

    Sarkar, Arup; Suresh, K. A.

    2018-04-01

    We find negative differential resistance (NDR) at room temperature in ultrathin films of nickel (II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine [NiPc(OBu)8] deposited on highly ordered pyrolytic graphite (HOPG) substrate [NiPc(OBu)8/HOPG] and NiPc(OBu)8 on graphene oxide (GO) deposited on HOPG [NiPc(OBu)8/GO/HOPG]. For the NiPc(OBu)8/HOPG system, NiPc(OBu)8 was transferred four times onto HOPG by the Langmuir-Blodgett (LB) technique. We have prepared a stable Langmuir monolayer of amphiphilic GO at the air-water interface and transferred it onto HOPG by the LB technique. Further, the monolayer of NiPc(OBu)8 was transferred four times for good coverage on GO to obtain the NiPc(OBu)8/GO/HOPG system. The current-voltage characteristics were carried out using a current sensing atomic force microscope (CSAFM) with a platinum (Pt) tip that forms Pt/NiPc(OBu)8/HOPG and Pt/NiPc(OBu)8/GO/HOPG junctions. The CSAFM, UV-visible spectroscopy, and cyclic voltammetry studies show that the NDR effect occurs due to molecular resonant tunneling. In the Pt/NiPc(OBu)8/GO/HOPG junction, we find that due to the presence of GO, the features of NDR become more prominent. Also, GO causes a shift in NDR voltage towards a lower value in the negative bias direction. We attribute this behavior to the role of GO in injecting holes into the NiPc(OBu)8 film.

  12. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

    Science.gov (United States)

    Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

    2017-12-01

    In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Chloro-benquinone Modified on Graphene Oxide as Metal-free Catalyst: Strong Promotion of Hydroxyl Radical and Generation of Ultra-Small Graphene Oxide

    Science.gov (United States)

    Zhao, He; Wang, Juehua; Zhang, Di; Dai, Qin; Han, Qingzhen; Du, Penghui; Liu, Chenming; Xie, Yongbing; Zhang, Yi; Cao, Hongbin; Fan, Zhuangjun

    2017-03-01

    Carbon-based metal-free catalyst has attracted more and more attention. It is a big challenge to improve catalytic activity of metal-free catalyst for decomposition of H2O2 to produce hydroxyl radical (HO•). Here, we report chloro-benquinone (TCBQ) modified on graphene oxide (GO) as metal-free catalyst for strong promotion of HO•. By the incorporation of GO, the HO• production by H2O2 and TCBQ is significantly promoted. Based on density functional theory, TCBQ modified GO (GO-TCBQ) is more prone to be nucleophilic attacked by H2O2 to yield HO• via electron transfer acceleration. Furthermore, the generated HO• can cut GO nanosheets into uniform ultra-small graphene oxide (USGO) through the cleavage of epoxy and C-C bonds. Interestingly, the damaged GO and in situ formed GO fragments can further enhance decomposition of H2O2 to produce HO•. Different from other catalytic processes, the GO-TCBQ metal-free catalysis process can be enhanced by GO itself, producing more HO•, and uniform USGO also can be generated. Thus, the metal free catalysis will be considered a fabrication method for uniform USGO, and may be extended to other fields including detoxifying organic pollutants and the application as disinfectants.

  14. Metal-Free, Site-Selective Peptide Modification by Conversion of "Customizable" Units into β-Substituted Dehydroamino Acids.

    Science.gov (United States)

    Saavedra, Carlos J; Hernández, Dácil; Boto, Alicia

    2018-01-12

    Our site-selective modification of serine or threonine units in peptides allows the generation of β-substituted dehydroamino acids, which increase peptide resistance to hydrolysis and may improve their biological properties. Both the terminal and internal positions can be modified, and different customizable units can be activated separately. Remarkably, high Z selectivity is achieved, even at internal positions. The conversion involves a one-pot oxidative radical scission/phosphorylation process by using the low-toxicity (diacetoxyiodo)benzene/iodine system as the scission reagent. The resulting α-amino phosphonates undergo a Horner-Wadsworth-Emmons reaction to produce the dehydroamino acid derivatives (in a Z/E ratio of usually >98:2) under mild and metal-free conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    Science.gov (United States)

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  16. A "catalyst switch" Strategy for the sequential metal-free polymerization of epoxides and cyclic Esters/Carbonate

    KAUST Repository

    Zhao, Junpeng

    2014-06-24

    A "catalyst switch" strategy was used to synthesize well-defined polyether-polyester/polycarbonate block copolymers. Epoxides (ethylene oxide and/or 1,2-butylene oxide) were first polymerized from a monoalcohol in the presence of a strong phosphazene base promoter (t-BuP4). Then an excess of diphenyl phosphate (DPP) was introduced, followed by the addition and polymerization of a cyclic ester (ε-caprolactone or δ-valerolactone) or a cyclic carbonate (trimethylene carbonate), where DPP acted as both the neutralizer of phosphazenium alkoxide (polyether chain end) and the activator of cyclic ester/carbonate. This work has provided a one-pot sequential polymerization method for the metal-free synthesis of block copolymers from monomers which are suited for different types of organic catalysts. © 2014 American Chemical Society.

  17. Carbon based magnetism an overview of the magnetism of metal free carbon-based compounds and materials

    CERN Document Server

    Makarova, Tatiana

    2006-01-01

    Magnetism is one of the most intriguing phenomena observed in nature. Magnetism is relevant to physics and geology, biology and chemistry. Traditional magnets, an ubiquitous part of many everyday gadgets, are made of heavy iron- or nickel based materials. Recently there have been reports on the observation of magnetism in carbon, a very light and biocompatible element. Metal-free carbon structures exhibiting magnetic ordering represent a new class of materials and open a novel field of research that could lead to many new technologies. · The most complete, detailed, and accurate Guide in the magnetism of carbon · Dynamically written by the leading experts · Deals with recent scientific highlights · Gathers together chemists and physicists, theoreticians and experimentalists · Unified treatment rather than a series of individually authored papers · Description of genuine organic molecular ferromagnets · Unique description of new carbon materials with Curie temperatures well above ambient.

  18. A "catalyst switch" Strategy for the sequential metal-free polymerization of epoxides and cyclic Esters/Carbonate

    KAUST Repository

    Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

    2014-01-01

    A "catalyst switch" strategy was used to synthesize well-defined polyether-polyester/polycarbonate block copolymers. Epoxides (ethylene oxide and/or 1,2-butylene oxide) were first polymerized from a monoalcohol in the presence of a strong phosphazene base promoter (t-BuP4). Then an excess of diphenyl phosphate (DPP) was introduced, followed by the addition and polymerization of a cyclic ester (ε-caprolactone or δ-valerolactone) or a cyclic carbonate (trimethylene carbonate), where DPP acted as both the neutralizer of phosphazenium alkoxide (polyether chain end) and the activator of cyclic ester/carbonate. This work has provided a one-pot sequential polymerization method for the metal-free synthesis of block copolymers from monomers which are suited for different types of organic catalysts. © 2014 American Chemical Society.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  20. The complex nature of phthalocyanine/gold interfaces

    International Nuclear Information System (INIS)

    Lindner, Susi; Treske, Uwe; Knupfer, Martin

    2013-01-01

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

  1. 3D graphene preparation via covalent amide functionalization for efficient metal-free electrocatalysis in oxygen reduction

    Science.gov (United States)

    Ahmed, Mohammad Shamsuddin; Kim, Young-Bae

    2017-02-01

    3D and porous reduced graphene oxide (rGO) catalysts have been prepared with sp3-hybridized 1,4-diaminobutane (sp3-DABu, rGO-sp3-rGO) and sp2-hybridized 1,4-diaminobenzene (sp2-DABe, rGO-sp2-rGO) through a covalent amidation and have employed as a metal-free electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. Both compounds have used as a junction between functionalized rGO layers to improve electrical conductivity and impart electrocatalytic activity to the ORR resulting from the interlayer charge transfer. The successful amidation and the subsequent reduction in the process of catalyst preparation have confirmed by X-ray photoelectron spectroscopy. A hierarchical porous structure is also confirmed by surface morphological analysis. Specific surface area and thermal stability have increased after successful the amidation by sp3-DABu. The investigated ORR mechanism reveals that both functionalized rGO is better ORR active than nonfunctionalized rGO due to pyridinic-like N content and rGO-sp3-rGO is better ORR active than rGO-sp2-rGO due to higher pyridinic-like N content and π-electron interaction-free interlayer charge transfer. Thus, the rGO-sp3-rGO has proven as an efficient metal-free electrocatalyst with better electrocatalytic activity, stability, and tolerance to the crossover effect than the commercially available Pt/C for ORR.

  2. Metal-free spin and spin-gapless semiconducting heterobilayers: monolayer boron carbonitrides on hexagonal boron nitride.

    Science.gov (United States)

    Pan, Hongzhe; Zhang, Hongyu; Sun, Yuanyuan; Ding, Yingchun; Chen, Jie; Du, Youwei; Tang, Nujiang

    2017-06-07

    The interfaces between monolayer boron carbonitrides and hexagonal boron nitride (h-BN) play an important role in their practical applications. Herein, we respectively investigate the structural and electronic properties of two metal-free heterobilayers constructed by vertically stacking two-dimensional (2D) spintronic materials (B 4 CN 3 and B 3 CN 4 ) on a h-BN monolayer from the viewpoints of lattice match and lattice mismatch models using density functional calculations. It is found that both B 4 CN 3 and B 3 CN 4 monolayers can be stably adsorbed on the h-BN monolayer due to the van der Waals interactions. Intriguingly, we demonstrate that the bipolar magnetic semiconductor (BMS) behavior of the B 4 CN 3 layer and the spin gapless semiconductor (SGS) property of the B 3 CN 4 layer can be well preserved in the B 4 CN 3 /BN and B 3 CN 4 /BN heterobilayers, respectively. The magnetic moments and spintronic properties of the two systems originate mainly from the 2p z electrons of the carbon atoms in the B 4 CN 3 and B 3 CN 4 layers. Furthermore, the BMS behavior of the B 4 CN 3 /BN bilayer is very robust while the electronic property of the B 3 CN 4 /BN bilayer is sensitive to interlayer couplings. These theoretical results are helpful both in understanding the interlayer coupling between B 4 CN 3 or B 3 CN 4 and h-BN monolayers and in providing a possibility of fabricating 2D composite B 4 CN 3 /BN and B 3 CN 4 /BN metal-free spintronic materials theoretically.

  3. Two-Dimensional Metal-Free Organic Multiferroic Material for Design of Multifunctional Integrated Circuits.

    Science.gov (United States)

    Tu, Zhengyuan; Wu, Menghao; Zeng, Xiao Cheng

    2017-05-04

    Coexistence of ferromagnetism and ferroelectricity in a single 2D material is highly desirable for integration of multifunctional units in 2D material-based circuits. We report theoretical evidence of C 6 N 8 H organic network as being the first 2D organic multiferroic material with coexisting ferromagnetic and ferroelectric properties. The ferroelectricity stems from multimode proton-transfer within the 2D C 6 N 8 H network, in which a long-range proton-transfer mode is enabled by the facilitation of oxygen molecule when the network is exposed to the air. Such oxygen-assisted ferroelectricity also leads to a high Curie temperature and coupling between ferroelectricity and ferromagnetism. We also find that hydrogenation and carbon doping can transform the 2D g-C 3 N 4 network from an insulator to an n-type/p-type magnetic semiconductor with modest bandgap. Akin to the dopant induced n/p channels in silicon wafer, a variety of dopant created functional units can be integrated into the g-C 3 N 4 wafer by design for nanoelectronic applications.

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

    International Nuclear Information System (INIS)

    Ito, Y.; Suzuki, T.

    2000-01-01

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

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

    Science.gov (United States)

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

    2018-02-01

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

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

    OpenAIRE

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

    2012-01-01

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

  7. Vibrational spectra of charge transfer complexes of lead phthalocyanine

    International Nuclear Information System (INIS)

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

    2005-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-01-01

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

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

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

    Science.gov (United States)

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

    2018-06-01

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

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  12. 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.

  13. Permanent antistatic phthalocyanine/epoxy nanocomposites – Influence of crosslinking agent, solvent and processing temperature

    NARCIS (Netherlands)

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

    2010-01-01

    Cross-linked epoxy matrices containing small amounts of semi-conductive phthalocyanine (Phthalcon) nanoparticles were prepared using different crosslinking agents and processing temperatures. A starting mixture containing an optimum dispersion of these nanoparticles and with an almost equal and

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

    Science.gov (United States)

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

    2018-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-15

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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  18. 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.

  19. Molecule nanoweaver

    Science.gov (United States)

    Gerald, II; Rex, E [Brookfield, IL; Klingler, Robert J [Glenview, IL; Rathke, Jerome W [Homer Glen, IL; Diaz, Rocio [Chicago, IL; Vukovic, Lela [Westchester, IL

    2009-03-10

    A method, apparatus, and system for constructing uniform macroscopic films with tailored geometric assemblies of molecules on the nanometer scale. The method, apparatus, and system include providing starting molecules of selected character, applying one or more force fields to the molecules to cause them to order and condense with NMR spectra and images being used to monitor progress in creating the desired geometrical assembly and functionality of molecules that comprise the films.

  20. Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

    KAUST Repository

    Chen, Yin; Lin, Bin; Yu, Weili; Yang, Yong; Bashir, Shahid M.; Wang, Hong; Takanabe, Kazuhiro; Idriss, Hicham; Basset, Jean-Marie

    2015-01-01

    A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3N4) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site

  1. Sequential polymerization of ethylene oxide, ε-caprolactone and l-lactide: A one-pot metal-free route to tri- and pentablock terpolymers

    KAUST Repository

    Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

    2014-01-01

    Metal-free polymerization of ethylene oxide (EO) catalyzed by a relatively mild phosphazene base (t-BuP2) was proven feasible, which enabled the one-pot sequential polymerization of EO, ε-caprolactone, and l-lactide. Using either 3-phenyl-1-propanol

  2. One-pot synthesis of spiropyrroloquinoline-isoindolinone and their aza-analogs via the Ugi-4CR/metal-free intramolecular bis-annulation process.

    Science.gov (United States)

    Ghandi, Mehdi; Zarezadeh, Nahid; Abbasi, Alireza

    2015-08-14

    This presentation discloses a one-pot synthesis of a series of spiropyrroloquinoline isoindolinone and spiropyrroloquinoline aza-isoindolinone scaffolds. The reaction proceeds by the combination of a Ugi four-component reaction (4CR) and two intramolecular cyclizations under metal-free conditions. The proof of the structures relies on analytical investigation and X-ray crystallography.

  3. Mechanistic model of the oxygen reduction catalyzed by a metal-free porphyrin in one- and two-phase liquid systems

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Záliš, Stanislav; Samec, Zdeněk

    2013-01-01

    Roč. 110, NOV 2013 (2013), s. 816-821 ISSN 0013-4686 R&D Projects: GA ČR GAP208/11/0697 Institutional support: RVO:61388955 Keywords : oxygen reduction * metal -free porphyrin * catalysis Subject RIV: CG - Electrochemistry Impact factor: 4.086, year: 2013

  4. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

    Science.gov (United States)

    Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

    2014-09-14

    An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

  5. 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.

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

    OpenAIRE

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

    2016-01-01

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

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

    Czech Academy of Sciences Publication Activity Database

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

    2013-01-01

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

  8. Direct fabrication of metal-free hollow graphene balls with a self-supporting structure as efficient cathode catalysts of fuel cell

    International Nuclear Information System (INIS)

    Lu, Yanqi; Liu, Mingda; Nie, Huagui; Gu, Cancan; Liu, Ming; Yang, Zhi; Yang, Keqin; Chen, Xi’an; Huang, Shaoming

    2016-01-01

    Despite the good progress in developing carbon catalysts for oxygen reduction reaction (ORR), the current metal-free carbon catalysts are still far from satisfactory for large-scale applications of fuel cell. Developing hollow graphene balls with a self-supporting structure is considered to be an ideal method to inhibit graphene stacking and improve their catalytic performance. Herein, we fabricated metal-free hollow graphene balls with a self-supporting structure, through using a new strategy that involves direct metal-free catalytic growth from assembly of SiO_2 spheres. To our knowledge, although much researches involving the synthesis of graphene balls have been reported, investigations into the direct metal-free catalytic growth of hollow graphene balls are rare. Furthermore, the electrocatalytic performance shows that the resulting hollow graphene balls have significantly high catalytic activity. More importantly, such catalysts also possess much improved stability and better methanol tolerance in alkaline media during the ORR compared with commercial Pt/C catalysts. The outstanding performances coupled with an easy and inexpensive preparing method indicated the great potential of the hollow graphene balls with a self-supporting structure in large-scale applications of fuel cell.Graphical AbstractHollow graphene balls with a self-supporting structure have been successfully fabricated, through using a new strategy that involves direct metal-free catalytic growth from 3D assembly of SiO_2 spheres. The hollow graphene balls can exhibit a high catalytic activity, long-term stability, and an excellent methanol tolerance for the oxygen reduction reaction

  9. Direct fabrication of metal-free hollow graphene balls with a self-supporting structure as efficient cathode catalysts of fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yanqi; Liu, Mingda; Nie, Huagui, E-mail: huaguinie@126.com; Gu, Cancan; Liu, Ming; Yang, Zhi, E-mail: yang201079@126.com; Yang, Keqin; Chen, Xi’an; Huang, Shaoming, E-mail: smhuang@wzu.edu.cn [Wenzhou University, Nanomaterials and Chemistry Key Laboratory (China)

    2016-06-15

    Despite the good progress in developing carbon catalysts for oxygen reduction reaction (ORR), the current metal-free carbon catalysts are still far from satisfactory for large-scale applications of fuel cell. Developing hollow graphene balls with a self-supporting structure is considered to be an ideal method to inhibit graphene stacking and improve their catalytic performance. Herein, we fabricated metal-free hollow graphene balls with a self-supporting structure, through using a new strategy that involves direct metal-free catalytic growth from assembly of SiO{sub 2} spheres. To our knowledge, although much researches involving the synthesis of graphene balls have been reported, investigations into the direct metal-free catalytic growth of hollow graphene balls are rare. Furthermore, the electrocatalytic performance shows that the resulting hollow graphene balls have significantly high catalytic activity. More importantly, such catalysts also possess much improved stability and better methanol tolerance in alkaline media during the ORR compared with commercial Pt/C catalysts. The outstanding performances coupled with an easy and inexpensive preparing method indicated the great potential of the hollow graphene balls with a self-supporting structure in large-scale applications of fuel cell.Graphical AbstractHollow graphene balls with a self-supporting structure have been successfully fabricated, through using a new strategy that involves direct metal-free catalytic growth from 3D assembly of SiO{sub 2} spheres. The hollow graphene balls can exhibit a high catalytic activity, long-term stability, and an excellent methanol tolerance for the oxygen reduction reaction.

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

    Science.gov (United States)

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

    2017-10-31

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

  11. An Efficient Metal-Free Hydrophilic Carbon as a Counter Electrode for Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Mojgan Kouhnavard

    2016-01-01

    Full Text Available This study presents a new cost-effective metal-free counter electrode (CE for dye-sensitized solar cells (DSSCs. CE was prepared by doctor blading a hydrophilic carbon (HC particle on a fluorine-doped tin oxide substrate. Thereafter, HC CE was characterized using X-ray diffraction, profilometry, four-point probe testing, and cyclic voltammetry. A 2 µm thick HC CE revealed a comparable catalytic activity to that of the Pt electrode under the same experimental conditions. DSSC based on HC CE was analyzed and showed Jsc of 6.87 mA/cm2 close to that of DSSC with Pt CE (7.0 mA/cm2. More importantly, DSSC based on HC CE yielded a power conversion efficiency (η of 2.93% under AM 1.5 irradiation (100 mW/cm2, which was comparable to that of DSSC based on standard Pt CE. These findings suggest that HC CE could be a promising CE for low-cost DSSCs.

  12. Metal-Free Alternating Copolymerization of CO2with Epoxides: Fulfilling “Green” Synthesis and Activity

    KAUST Repository

    Zhang, Dongyue

    2016-08-16

    Polycarbonates were successfully synthesized for the first time through the anionic copolymerization of epoxides with CO2, under metal-free conditions. Using an approach based on the activation of epoxides by Lewis acids and of CO, by appropriate cations, well-defined alternating copolymers made of CO, and propylene oxide (PO) or cyclohexene oxide (CHO) were indeed obtained. Triethyl borane was the Lewis acid chosen to activate the epoxides, and onium halides or onium alkoxides involving either ammonium, phosphonium, or phosphazenium cations were selected to initiate the copolymerization. In the case of PO, the carbonate content of the poly(propylene carbonate) formed was in the range of 92-99% and turnover numbers (TON) were close to 500; in the case of CHO perfectly alternating poly(cyclohexene carbonate) were obtained and TON values were close to 4000. The advantages of such a copolymerization system are manifold: (i) no need for multistep catalyst/ligand synthesis as in previous works; (ii) no transition metal involved in the copolymer synthesis and therefore no coloration of the samples isolated; and (iii) no necessity for postsynthesis purification.

  13. Metal-free aqueous redox capacitor via proton rocking-chair system in an organic-based couple

    Science.gov (United States)

    Tomai, Takaaki; Mitani, Satoshi; Komatsu, Daiki; Kawaguchi, Yuji; Honma, Itaru

    2014-01-01

    Safe and inexpensive energy storage devices with long cycle lifetimes and high power and energy densities are mandatory for the development of electrical power grids that connect with renewable energy sources. In this study, we demonstrated metal-free aqueous redox capacitors using couples comprising low-molecular-weight organic compounds. In addition to the electric double layer formation, proton insertion/extraction reactions between a couple consisting of inexpensive quinones/hydroquinones contributed to the energy storage. This energy storage mechanism, in which protons are shuttled back and forth between two electrodes upon charge and discharge, can be regarded as a proton rocking-chair system. The fabricated capacitor showed a large capacity (>20 Wh/kg), even in the applied potential range between 0–1 V, and high power capability (>5 A/g). The support of the organic compounds in nanoporous carbon facilitated the efficient use of the organic compounds with a lifetime of thousands of cycles. PMID:24395117

  14. Simultaneous reduction and nitrogen functionalization of graphene oxide using lemon for metal-free oxygen reduction reaction

    Science.gov (United States)

    Begum, Halima; Ahmed, Mohammad Shamsuddin; Cho, Sung; Jeon, Seungwon

    2017-12-01

    Inspire by the vision of finding a simple and green method for simultaneous reduction and nitrogen (N)-functionalization of graphene oxide (GO), a N-rich reduced graphene oxide (rGO) has been synthesized through a facile and ecofriendly hydrothermal strategy while most of the existing methods are involving with multiple steps and highly toxic reducing agents that are harmful to human health and environment. In this paper, the simultaneous reduction and N-functionalization of GO using as available lemon juice (denoted as Lem-rGO) for metal-free electrocatalysis towards oxygen reduction reaction (ORR) is described. The proposed method is based on the reduction of GO using of the reducing and the N-precursor capability of ascorbic acid and citric acid as well as the nitrogenous compounds, respectively, that containing in lemon juice. The resultant Lem-rGO has higher reduction degree, higher specific surface area and better crystalline nature with N-incorporation than that of well investigated ascorbic acid and citric acid treated rGO. As a result, it shows better ORR electrocatalytic activity in respect to the improved onset potential, electron transfer rate and kinetics than those typical rGO catalysts. Moreover, it shows a significant tolerance to the anodic fuels and durability than the Pt/C during ORR.

  15. SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

    Science.gov (United States)

    Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

    2014-09-01

    The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Capacitance measurements and AC conductivity of Nickel Phthalocyanine films

    International Nuclear Information System (INIS)

    Darwish, S.

    2005-01-01

    A C dark Current measurements of nickel phthalocyanine thin films using ohmic gold electrodes are investigated in the frequency range 30-10 Hz and within the temperature range 295-385 K. The A C conductivity as D Ac is found to vary as within the index s < 1, indicating a dominant hopping process at low temperatures. From the temperature dependence of A C conductivity, free carrier conduction with mean activation energy of 0.31 eV is observed at higher temperatures. Capacitance and loss tangent are found to be decreased with increasing frequency and increase with increasing temperature. Such characteristics are found to be in good qualitative agreement with existing equivalent circuit model assuming ohmic contacts

  17. Optical limiting properties of optically active phthalocyanine derivatives

    Science.gov (United States)

    Wang, Peng; Zhang, Shuang; Wu, Peiji; Ye, Cheng; Liu, Hongwei; Xi, Fu

    2001-06-01

    The optical limiting properties of four optically active phthalocyanine derivatives in chloroform solutions and epoxy resin thin plates were measured at 532 nm with 10 ns pulses. The excited state absorption cross-section σex and refractive-index cross-section σr were determined with the Z-scan technique. These chromophores possess larger σex than the ground state absorption cross-section σ0, indicating that they are the potential materials for reverse saturable absorption (RSA). The negative σr values of these chromophores add to the thermal contribution, producing a larger defocusing effect, which may be helpful in further enhancing their optical limiting performance. The optical limiting responses of the thin plate samples are stronger than those of the chloroform solutions.

  18. Enhanced photodynamic efficacy of zinc phthalocyanine by conjugating to heptalysine.

    Science.gov (United States)

    Li, Linsen; Luo, Zhipu; Chen, Zhuo; Chen, Jincan; Zhou, Shanyong; Xu, Peng; Hu, Ping; Wang, Jundong; Chen, Naisheng; Huang, Jinling; Huang, Mingdong

    2012-11-21

    Zinc phthalocyanine (ZnPc) is a promising photosensitizer for photodynamic therapy, but faces some challenges: ZnPc is insoluble in water and thus requires either special formulation of ZnPc by, e.g., liposome or Cremophor EL, or chemical modification of Pc ring to enhance its bioavailability and photodynamic efficacy. Here, we conjugated monosubstituted ZnPc-COOH with a series of oligolysine moieties with different numbers of lysine residues (ZnPc-(Lys)(n) (n = 1, 3, 5, 7, 9) to improve the water solubility of the ZnPc conjugates. We measured the photosensitizing efficacies and the cellular uptakes of this series of conjugates on a normal and a cancerous cell line. In addition, we developed a sensitive in situ method to distinguish the difference in photodynamic efficacy among conjugates. Our results showed that ZnPc-(Lys)(7) has the highest photodynamic efficacy compared to the other conjugates investigated.

  19. Sensing of volatile organic compounds by copper phthalocyanine thin films

    Science.gov (United States)

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

    2017-02-01

    Thin films of copper phthalocyanine have been deposited by thermal evaporation technique. We have subsequently exposed these films to the vapours of methanol, ethanol and propanol. Optical absorption, infrared spectra and electrical conductivities of these films before and after exposure to chemical vapours have been recorded in order to study their sensing mechanisms towards organic vapours. These films exhibit maximum sensing response to methanol while low sensitivities of the films towards ethanol and propanol have been observed. The changes in sensitivities have been correlated with presence of carbon groups in the chemical vapours. The effect of different types of electrodes on response-recovery times of the thin film with organic vapours has been studied and compared. The electrodes gap distance affects the sensitivity as well as response-recovery time values of the thin films.

  20. Characterization of manganese tetraarylthiosubstituted phthalocyanines self assembled monolayers

    International Nuclear Information System (INIS)

    Matemadombo, Fungisai; Durmus, Mahmut; Togo, Chamunorwa; Limson, Janice; Nyokong, Tebello

    2009-01-01

    Manganese tetraarylthiosubstituted phthalocyanines (complexes 1-5) have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. SAM characteristics reported in this work are: ion barrier factor (∼1); interfacial capacitance (303-539 μF cm -2 ) and surface coverage (1.06 x 10 -10 -2.80 x 10 -10 mol cm -2 ). Atomic force microscopy was employed in characterizing a SAM. SAMs of complexes 1-5 were employed to detect L-cysteine (with limit of detection ranging from 2.83 x 10 -7 to 3.14 x 10 -7 M at potentials of 0.68-0.75 V vs. Ag|AgCl) and nitrite (limit of detection ranging from 1.78 x 10 -7 to 3.02 x 10 -7 M at potentials of 0.69-0.76 V vs. Ag|AgCl).

  1. Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2017-03-31

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu{sup 3+} doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface

  2. Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu"3"+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-06-30

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

  4. Molecule Matters

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 14; Issue 4. Molecule Matters – van der Waals Molecules - History and Some Perspectives on Intermolecular Forces. E Arunan. Feature Article Volume 14 Issue 4 April 2009 pp 346-356 ...

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

    Directory of Open Access Journals (Sweden)

    Benoît H. Lessard

    2016-07-01

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

  6. Metal-free ALS variants of dimeric human Cu,Zn-superoxide dismutase have enhanced populations of monomeric species.

    Directory of Open Access Journals (Sweden)

    Anna-Karin E Svensson

    2010-04-01

    Full Text Available Amino acid replacements at dozens of positions in the dimeric protein human, Cu,Zn superoxide dismutase (SOD1 can cause amyotrophic lateral sclerosis (ALS. Although it has long been hypothesized that these mutations might enhance the populations of marginally-stable aggregation-prone species responsible for cellular toxicity, there has been little quantitative evidence to support this notion. Perturbations of the folding free energy landscapes of metal-free versions of five ALS-inducing variants, A4V, L38V, G93A, L106V and S134N SOD1, were determined with a global analysis of kinetic and thermodynamic folding data for dimeric and stable monomeric versions of these variants. Utilizing this global analysis approach, the perturbations on the global stability in response to mutation can be partitioned between the monomer folding and association steps, and the effects of mutation on the populations of the folded and unfolded monomeric states can be determined. The 2- to 10-fold increase in the population of the folded monomeric state for A4V, L38V and L106V and the 80- to 480-fold increase in the population of the unfolded monomeric states for all but S134N would dramatically increase their propensity for aggregation through high-order nucleation reactions. The wild-type-like populations of these states for the metal-binding region S134N variant suggest that even wild-type SOD1 may also be prone to aggregation in the absence of metals.

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

    Science.gov (United States)

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

    2016-03-01

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

  8. Superior performance of borocarbonitrides, BxCyNz , as stable, low-cost metal-free electrocatalysts for the hydrogen evolution reaction

    Science.gov (United States)

    Chakraborty, Himanshu; Chhetri, Manjeet; Maitra, Somak; Waghmare, Umesh; Rao, C. N. R.

    We report superior hydrogen evolution activity of metal-free borocarbonitride (BCN) catalysts. The highly positive onset potential (-56 mV vs. RHE) and the current density of 10 mAcm2 at an overpotential of 70 mV exhibited by a carbon-rich BCN with the composition BC7N2 demonstrates the extraordinary electrocatalytic activity at par with Pt. Theoretical studies throw light on the cause of high activity of this composition. The high activity and good stability of BCN's surpass the characteristics of other metal-free catalysts reported in recent literature. an Energy Frontier Research Centre funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0012575.

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

    Science.gov (United States)

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

    2018-05-01

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

  10. Self-floating graphitic carbon nitride/zinc phthalocyanine nanofibers for photocatalytic degradation of contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tiefeng; Ni, Dongjing; Chen, Xia; Wu, Fei; Ge, Pengfei; Lu, Wangyang, E-mail: luwy@zstu.edu.cn; Hu, Hongguang; Zhu, ZheXin; Chen, Wenxing, E-mail: wxchen@zstu.edu.cn

    2016-11-05

    Highlights: • A facile synthetic strategy to prepare visible-light responsive electrospun nanofibers. • Self-floating nanofiber photocatalyts for the effective utilization of solar. • Possible degradation pathway of RhB and CBZ under visible light and solar irradiation. • Present a method for removing highly hazardous contaminants. - Abstract: The effective elimination of micropollutants by an environmentally friendly method has received extensive attention recently. In this study, a photocatalyst based on polyacrylonitrile (PAN)-supported graphitic carbon nitride coupled with zinc phthalocyanine nanofibers (g-C{sub 3}N{sub 4}/ZnTcPc/PAN nanofibers) was successfully prepared, where g-C{sub 3}N{sub 4}/ZnTcPc was introduced as the catalytic entity and the PAN nanofibers were employed as support to overcome the defects of easy aggregation and difficult recycling. Herein, rhodamine B (RhB), 4-chlorophenol and carbamazepine (CBZ) were selected as the model pollutants. Compared with the typical hydroxyl radical-dominated catalytic system, g-C{sub 3}N{sub 4}/ZnTcPc/PAN nanofibers displayed the targeted adsorption and degradation of contaminants under visible light or solar irradiation in the presence of high additive concentrations. According to the results of the radical scavenging techniques and the electron paramagnetic resonance technology, the degradation of target substrates was achieved by the attack of active species, including photogenerated hole, singlet oxygen, superoxide radicals and hydroxyl radicals. Based on the results of ultra-performance liquid chromatography and mass spectrometry, the role of free radicals on the photocatalytic degradation intermediates was identified and the final photocatalytic degradation products of both RhB and CBZ were some biodegradable small molecules.

  11. Sequential polymerization of ethylene oxide, ε-caprolactone and l-lactide: A one-pot metal-free route to tri- and pentablock terpolymers

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    Metal-free polymerization of ethylene oxide (EO) catalyzed by a relatively mild phosphazene base (t-BuP2) was proven feasible, which enabled the one-pot sequential polymerization of EO, ε-caprolactone, and l-lactide. Using either 3-phenyl-1-propanol or water as an initiator, the corresponding triblock or pentablock terpolymers were easily prepared. © 2014 the Partner Organisations.

  12. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  13. Transition metal-free oxidation of benzylic alcohols to carbonyl compounds by hydrogen peroxide in the presence of acidic silica gel

    Directory of Open Access Journals (Sweden)

    Hossein Ghafuri

    2015-01-01

    Full Text Available Oxidation of alcohols to carbonyl compounds has become an important issue in the process industry as well as many other applications. In this method, various benzylic alcohols were successfully converted to corresponding aldehydes and ketones under transition metal-free condition using hydrogen peroxide in the presence of some amount of catalytic acidic silica gel. Silica gel is inexpensive and available. One of the most important features of this method is its short reaction time.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-15

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

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

    Directory of Open Access Journals (Sweden)

    K. Dermentzis

    2013-01-01

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    International Nuclear Information System (INIS)

    Huc, Vincent

    1999-01-01

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-15

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

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  1. 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.

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

    International Nuclear Information System (INIS)

    Jin Ling; Chen Dajun

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-15

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

  4. Green Synthesis of InP/ZnS Core/Shell Quantum Dots for Application in Heavy-Metal-Free Light-Emitting Diodes.

    Science.gov (United States)

    Kuo, Tsung-Rong; Hung, Shih-Ting; Lin, Yen-Ting; Chou, Tzu-Lin; Kuo, Ming-Cheng; Kuo, Ya-Pei; Chen, Chia-Chun

    2017-09-19

    Quantum dot light-emitting diodes (QD-LEDs) have been considered as potential display technologies with the characterizations of high color purity, flexibility, transparency, and cost efficiency. For the practical applications, the development of heavy-metal-free QD-LEDs from environment-friendly materials is the most important issue to reduce the impacts on human health and environmental pollution. In this work, heavy-metal-free InP/ZnS core/shell QDs with different fluorescence were prepared by green synthesis method with low cost, safe, and environment-friendly precursors. The InP/ZnS core/shell QDs with maximum fluorescence peak at ~ 530 nm, superior fluorescence quantum yield of 60.1%, and full width at half maximum of 55 nm were applied as an emission layer to fabricate multilayered QD-LEDs. The multilayered InP/ZnS core/shell QD-LEDs showed the turn-on voltage at ~ 5 V, the highest luminance (160 cd/m 2 ) at 12 V, and the external quantum efficiency of 0.223% at 6.7 V. Overall, the multilayered InP/ZnS core/shell QD-LEDs reveal potential to be the heavy-metal-free QD-LEDs for future display applications.

  5. Green Synthesis of InP/ZnS Core/Shell Quantum Dots for Application in Heavy-Metal-Free Light-Emitting Diodes

    Science.gov (United States)

    Kuo, Tsung-Rong; Hung, Shih-Ting; Lin, Yen-Ting; Chou, Tzu-Lin; Kuo, Ming-Cheng; Kuo, Ya-Pei; Chen, Chia-Chun

    2017-09-01

    Quantum dot light-emitting diodes (QD-LEDs) have been considered as potential display technologies with the characterizations of high color purity, flexibility, transparency, and cost efficiency. For the practical applications, the development of heavy-metal-free QD-LEDs from environment-friendly materials is the most important issue to reduce the impacts on human health and environmental pollution. In this work, heavy-metal-free InP/ZnS core/shell QDs with different fluorescence were prepared by green synthesis method with low cost, safe, and environment-friendly precursors. The InP/ZnS core/shell QDs with maximum fluorescence peak at 530 nm, superior fluorescence quantum yield of 60.1%, and full width at half maximum of 55 nm were applied as an emission layer to fabricate multilayered QD-LEDs. The multilayered InP/ZnS core/shell QD-LEDs showed the turn-on voltage at 5 V, the highest luminance (160 cd/m2) at 12 V, and the external quantum efficiency of 0.223% at 6.7 V. Overall, the multilayered InP/ZnS core/shell QD-LEDs reveal potential to be the heavy-metal-free QD-LEDs for future display applications.

  6. Atkins' molecules

    CERN Document Server

    Atkins, Peters

    2003-01-01

    Originally published in 2003, this is the second edition of a title that was called 'the most beautiful chemistry book ever written'. In it, we see the molecules responsible for the experiences of our everyday life - including fabrics, drugs, plastics, explosives, detergents, fragrances, tastes, and sex. With engaging prose Peter Atkins gives a non-technical account of an incredible range of aspects of the world around us, showing unexpected connections, and giving an insight into how this amazing world can be understood in terms of the atoms and molecules from which it is built. The second edition includes dozens of extra molecules, graphical presentation, and an even more accessible and enthralling account of the molecules themselves.

  7. Interstellar Molecules

    Science.gov (United States)

    Solomon, Philip M.

    1973-01-01

    Radioastronomy reveals that clouds between the stars, once believed to consist of simple atoms, contain molecules as complex as seven atoms and may be the most massive objects in our Galaxy. (Author/DF)

  8. Potassium-intercalated H2Pc films : Alkali-induced electronic and geometrical modifications

    NARCIS (Netherlands)

    Nilson, K.; Ahlund, J.; Shariati, M. -N.; Schiessling, J.; Palmgren, P.; Brena, B.; Gothelid, E.; Hennies, F.; Huismans, Y.; Evangelista, F.; Rudolf, P.; Gothelid, M.; Martensson, N.; Puglia, C.; Åhlund, J.; Göthelid, E.; Göthelid, M.; Mårtensson, N.

    2012-01-01

    X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-04-01

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

  10. 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.

  11. 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.

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

    International Nuclear Information System (INIS)

    Kuznetsova, J O; Makarov, V I

    2016-01-01

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

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

    Science.gov (United States)

    Orellana, Walter

    2012-07-01

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

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-01-15

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

  16. Tissue Distribution Of Chloroaluminium Sulfonated Phthalocyanine In Dogs

    Science.gov (United States)

    M. M.; H. C.; Newman

    1989-06-01

    Chloroaluminum sulfonated phthalocyanine (A1PCS) was administered intravenously to clinically normal dogs, and A1PCS levels were determined in tissues using a sensitive assay. A1PCS accumulated to high levels in liver, spleen, bone marrow, kidney, and lung. These tissue levels confirm previous determinations in mice and rats. Only a small amount of dye was retained in skin and very small amounts in muscle and brain. A1PCS was cleared from the blood within 24 h, and excreted primarily by urine. Serum clearance was faster in males than in females. There were also significant tissue distribution differences between the genders, particularly during the first 12 h. The low levels of A1PCS in skin suggest that cutaneous photosensitivity and toxic skin reactions using this photosensitizer in photodynamic therapy of cancer may be eliminated. The difference in tissue distribution between genders is not only intriguing, but indicates that the optimal time window for treatment of various tissue sites may vary by gender.

  17. 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.

  18. Energy transfer and electron transfer in dimers and polymers of porphyrin and phthalocyanines: from the liquid phase to Langmuir-Blodgett films

    International Nuclear Information System (INIS)

    Lipskier, Jean-Francois

    1991-01-01

    The understanding of phenomena of photo-induced transfer of energy and of electron between chromophores belonging to a same supra-molecular entity is necessary for the design and fabrication of molecule devices performing the conversion of a light signal into electric signal or chemical potential. As porphyrin oligomers and phthalocyanine oligomers are examples of interest for the systematic study of parameters governing these processes, the first part of this research thesis addresses the study of dimers and trimers bound by covalent bridges. The second part addresses the study of physical-chemical properties of complexes bound by the Van der Waals interaction as well as by the Coulomb attraction. An extension to Langmuir-Blodgett films is proposed, and the properties of complexes organised in thin films according to this methodology are compared with those of their homologues in solution [fr

  19. Adhesion molecules

    CERN Document Server

    Preedy, Victor R

    2016-01-01

    This book covers the structure and classification of adhesion molecules in relation to signaling pathways and gene expression. It discusses immunohistochemical localization, neutrophil migration, and junctional, functional, and inflammatory adhesion molecules in pathologies such as leukocyte decompression sickness and ischemia reperfusion injury. Highlighting the medical applications of current research, chapters cover diabetes, obesity, and metabolic syndrome; hypoxia; kidney disease; smoking, atrial fibrillation, and heart disease, the brain and dementia; and tumor proliferation. Finally, it looks at molecular imaging and bioinformatics, high-throughput technologies, and chemotherapy.

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

    International Nuclear Information System (INIS)

    Setiawan, Duyeh

    2000-01-01

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

  1. Molecule Matters

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 16; Issue 12. Molecule Matters - Dinitrogen. A G Samuelson J Jabadurai. Volume 16 Issue 12 ... Author Affiliations. A G Samuelson1 J Jabadurai1. Department of Inroganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India.

  2. Molecule Matters

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 11; Issue 9. Molecule Matters - A Chromium Compound with a Quintuple Bond. K C Kumara Swamy. Feature Article Volume 11 Issue 9 September 2006 pp 72-75. Fulltext. Click here to view fulltext PDF. Permanent link:

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-15

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

  5. Metal-Free 2D/2D Phosphorene/g-C3 N4 Van der Waals Heterojunction for Highly Enhanced Visible-Light Photocatalytic H2 Production.

    Science.gov (United States)

    Ran, Jingrun; Guo, Weiwei; Wang, Hailong; Zhu, Bicheng; Yu, Jiaguo; Qiao, Shi-Zhang

    2018-04-30

    The generation of green hydrogen (H 2 ) energy using sunlight is of great significance to solve the worldwide energy and environmental issues. Particularly, photocatalytic H 2 production is a highly promising strategy for solar-to-H 2 conversion. Recently, various heterostructured photocatalysts with high efficiency and good stability have been fabricated. Among them, 2D/2D van der Waals (VDW) heterojunctions have received tremendous attention, since this architecture can promote the interfacial charge separation and transfer and provide massive reactive centers. On the other hand, currently, most photocatalysts are composed of metal elements with high cost, limited reserves, and hazardous environmental impact. Hence, the development of metal-free photocatalysts is desirable. Here, a novel 2D/2D VDW heterostructure of metal-free phosphorene/graphitic carbon nitride (g-C 3 N 4 ) is fabricated. The phosphorene/g-C 3 N 4 nanocomposite shows an enhanced visible-light photocatalytic H 2 production activity of 571 µmol h -1 g -1 in 18 v% lactic acid aqueous solution. This improved performance arises from the intimate electronic coupling at the 2D/2D interface, corroborated by the advanced characterizations techniques, e.g., synchrotron-based X-ray absorption near-edge structure, and theoretical calculations. This work not only reports a new metal-free phosphorene/g-C 3 N 4 photocatalyst but also sheds lights on the design and fabrication of 2D/2D VDW heterojunction for applications in catalysis, electronics, and optoelectronics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2015-08-19

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

  7. Intracellular photoinduced oxidative stress by zinc phthalocyanine photosensitization: a study of the early events in real time using confocal microscopy

    Science.gov (United States)

    Alexandratou, Eleni; Yova, Dido; Handris, Panagiotis; Kletsas, Dimitris; Loukas, Spyros

    2003-10-01

    Oxidative stress has been implicated in several biological and pathological aspects. Reactive oxygen species (ROS) have been proposed to act as signal transduction molecules activating reactions leading to cell rescue or to cell apoptosis/necrosis. In the present study, oxidative stress was induced by photosensitization of zinc phthalocyanine (ZnPc) in human fibroblasts using a photodynamic dose that did not lead to apoptosis or necrosis. The induction of oxidative stress was performed at the microscope stage in preassigned time. The cascade of phenomena evoked was studied in real time and at the single cell level using confocal laser scanning microscopy. Using specific vital fluorescent probes, alterations induced by oxidative stress in mitochondria membrane potential, in intracellular pH and in calcium concentration were recorded. Image processing and analysis techniques were used to quantify the observed changes. Subcellular localization of the photosensitizer was studied in order to determine the primary and immediate ROS target. It was found that ZnPc is mainly localized in the mitochondria region.

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

    Science.gov (United States)

    Jiang, Xue; Jiang, Zhou; Zhao, Jijun

    2017-12-01

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

  9. Synthesis of Ruthenium(III Phthalocyanine with Di-axial Bromo Ligands - A Promising Molecular Conductor with Giant Negative Magnetoresistance

    Directory of Open Access Journals (Sweden)

    Mario A.V. Gamboa

    2015-01-01

    Full Text Available The electron transport of Phthalocyanines (Pc with central metal and di-axial ligands (such as FeIII(PcL2; where L = CN, Cl, Br originates from its intermolecular Pc π-π orbital overlap while its giant negative magnetoresistance (GNMR arises from its intramolecular Pc-π(HOMO and Fe-d (s=1/2 interaction. However, the π-d interaction tends to localize itinerant electrons resulting in the decrease in the conductivity of the FeIII(PcL2 series compared to the non-magnetic CoIII(PcL2 where π-d interaction is absent. More so, the axial ligand field energy of the FeIII(PcL2 system is found to have the ability to proportionally modulate the π-d interaction. In reference thereof, theoretical calculations point that isostructural RuIII(PcBr2 would provide the best balance of π-d orbital energy interplay. That is, RuIII(PcBr2 is expected to be a molecule with high electrical conductivity and GNMR which would make it an ideal magnetic molecular conductor. This paper reports on the synthesis of RuIII(PcBr2.

  10. Aerobic Transition-Metal-Free Synthesis of 2,3-Diarylindoles and 5-Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jin; Moon, Hye Ran; Kim, Su Yeon; Kim, Jae Nyoung [Chonnam National Un iversity, Gwangju (Korea, Republic of)

    2016-01-15

    2,3-diarylindoles and 5-aryluracils were synthesized by ONSH pathway under transition-metal-free conditions in good to moderate yields using molecular oxygen as an oxidant. As 2,3-diarylindoles have been found in many biologically important compounds, the synthesis of this scaffold has received much attention. Most frequently, 2,3-diarylindoles have been prepared via palladium-catalyzed arylations of 2-arylindole with bromoarenes. During our recent transition metal-catalyzed arylations of indoles and uracils, we were interested in the arylation in the absence of an expensive transition metal catalyst.

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

    Science.gov (United States)

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

    2009-10-16

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

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

    NARCIS (Netherlands)

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

    2008-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Charles Biral Silva

    2017-12-01

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

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  15. 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.

  16. 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.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  18. 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

  19. 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

  20. 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

  1. 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

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

    Czech Academy of Sciences Publication Activity Database

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

    2010-01-01

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

  3. 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

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

    International Nuclear Information System (INIS)

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

    1981-01-01

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

  5. Effect of mixed-sulfonated aluminium phthalocyanine on human skin fibroblasts for photodynamic therapy

    CSIR Research Space (South Africa)

    Ndhundhuma, IM

    2008-08-01

    Full Text Available of the study was to evaluate the effect of mixed-sulfonated aluminium phthalocyanine (AlPcSmix) used as photosensitizers for PDT, determined by changes in cell morphology and cell viability of human skin fibroblasts (WS1). Methods. Cells incubated with 5, 10...

  6. Structural templating in a nonplanar phthalocyanine using single crystal copper iodide

    OpenAIRE

    Rochford, L. A. (Luke A.); Ramadan, Alexandra J.; Keeble, Dean S.; Ryan, Mary P.; Heutz, Sandrine; Jones, T. S. (Tim S.)

    2015-01-01

    Solution-grown copper iodide crystals are used as substrates for the templated growth of the nonplanar vanadyl phthalocyanine using organic molecular beam deposition. Structural characterization reveals a single molecular orientation produced by the (111) Miller plane of the copper iodide crystals. These fundamental measurements show the importance of morphology and structure in templating interactions for organic electronics applications.

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

    NARCIS (Netherlands)

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

    2003-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-07-01

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

  9. gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors.

    Science.gov (United States)

    Hu, Mingyou; Ni, Chuanfa; Li, Lingchun; Han, Yongxin; Hu, Jinbo

    2015-11-18

    A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.

  10. TiN nanoparticles on CNT-graphene hybrid support as noble-metal-free counter electrode for quantum-dot-sensitized solar cells.

    Science.gov (United States)

    Youn, Duck Hyun; Seol, Minsu; Kim, Jae Young; Jang, Ji-Wook; Choi, Youngwoo; Yong, Kijung; Lee, Jae Sung

    2013-02-01

    The development of an efficient noble-metal-free counter electrode is crucial for possible applications of quantum-dot-sensitized solar cells (QDSSCs). Herein, we present TiN nanoparticles on a carbon nanotube (CNT)-graphene hybrid support as a noble-metal-free counter electrode for QDSSCs employing a polysulfide electrolyte. The resulting TiN/CNT-graphene possesses an extremely high surface roughness, a good metal-support interaction, and less aggregation relative to unsupported TiN; it also has superior solar power conversion efficiency (4.13 %) when applying a metal mask, which is much higher than that of the state-of-the-art Au electrode (3.35 %). Based on electrochemical impedance spectroscopy measurements, the enhancement is ascribed to a synergistic effect between TiN nanoparticles and the CNT-graphene hybrid, the roles of which are to provide active sites for the reduction of polysulfide ions and electron pathways to TiN nanoparticles, respectively. The combination of graphene and CNTs leads to a favorable morphology that prevents stacking of graphene or bundling of CNTs, which maximizes the contact of the support with TiN nanoparticles and improves electron-transfer capability relative to either carbon material alone. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Metal-Free Poly-Cycloaddition of Activated Azide and Alkynes toward Multifunctional Polytriazoles: Aggregation-Induced Emission, Explosive Detection, Fluorescent Patterning, and Light Refraction.

    Science.gov (United States)

    Wu, Yongwei; He, Benzhao; Quan, Changyun; Zheng, Chao; Deng, Haiqin; Hu, Rongrong; Zhao, Zujin; Huang, Fei; Qin, Anjun; Tang, Ben Zhong

    2017-09-01

    The metal-free click polymerization (MFCP) of activated alkynes and azides or activated azide and alkynes have been developed into powerful techniques for the construction of polytriazoles without the obsession of metallic catalyst residues problem. However, the MFCP of activated azides and alkynes is rarely applied in preparation of functional polytriazoles. In this paper, soluble multifunctional polytriazoles (PIa and PIb) with high weight-average molecular weights (M w up to 32 000) are prepared via the developed metal-free poly-cycloaddition of activated azide and alkynes in high yields (up to 90%). The resultant PIa and PIb are thermally stable, and show aggregation-induced emission characteristics, enabling their aggregates to detect explosives with superamplification effect. Moreover, thanks to their containing aromatic rings and polar moieties, PIa and PIb exhibit high refractive indices. In addition, they can also be cross-linked upon UV irradiation to generate 2D fluorescent patterning due to their remaining azide groups and containing ester groups. Thus, these multifunctional polytriazoles are potentially applicable in the optoelectronic and sensing fields. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A Metal-Free Regioselective Multicomponent Approach for the Synthesis of Free Radical Scavenging Pyrimido-Fused Indazoles and Their Fluorescence Studies

    Directory of Open Access Journals (Sweden)

    Jeyakannu Palaniraja

    2016-11-01

    Full Text Available This study deals with a new and efficient metal-free regioselective synthesis of pyrimido-fused indazoles with nitrogen ring junction motifs. We have developed a metal-free domino type reaction between 3-aminoindazole, aryl aldehydes and aceotophenones in the presence of KOH/DMF that leads to pyrimido[1,2-b]indazole analogues. Response Surface Methodology (RSM coupled with a Box-Behnken design (BBD were utilized for exploring the effect of base used (A, temperature of reaction (B and (C, reaction time. This approach can allow access to a variety of pyrimidoindazole fluorophores and related compounds. The compound N,N-dimethyl-4-(2-phenylpyrimido[1,2-b]indazol-4-ylaniline (4e displays the maximum fluorescence intensity at 518 nm and shows a fluorescence quantum yield of 0.068. The synthesized pyramido-fused indazoles have been evaluated for their free radical scavenging activity and compound 4f showed good antioxidant activity.

  13. Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

    Science.gov (United States)

    Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

    2017-10-01

    The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  15. Noncovalent functionalization of pristine CVD single-walled carbon nanotubes with 3d metal(II) phthalocyanines by adsorption from the gas phase

    Science.gov (United States)

    Basiuk, Vladimir A.; Flores-Sánchez, Laura J.; Meza-Laguna, Victor; Flores-Flores, José Ocotlán; Bucio-Galindo, Lauro; Puente-Lee, Iván; Basiuk, Elena V.

    2018-04-01

    Noncovalent hybrids of carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of growing research effort focused on the development of new efficient organic photovoltaic cells, heterogeneous catalysts, lithium batteries, gas sensors, field effect transistors, among other possible applications. The main advantage of using unsubstituted Pcs is their very moderate cost and easy commercial availability. Unfortunately, the deposition of unsubstituted Pcs onto CNT sidewalls via the traditional liquid-phase strategy proves to be very problematic due to an extremely poor solubility of Pcs. At the same time, unsubstituted free-base H2Pc ligand and many of its transition metal complexes exhibit high thermal stability and volatility under reduced pressure, which allows for their physical vapor deposition onto solid surfaces. In the present work, we demonstrated the possibility of simple, fast, efficient and environmentally friendly noncovalent functionalization of single-walled CNTs (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me = Co, Ni, Cu and Zn. The functionalization can be performed at 400-500 °C under moderate vacuum, and takes about 2-3 h only. The nanohybrids obtained were characterized by means of Fourier-transform infrared, Raman, UV-vis and energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), scanning and transmission electron microscopy. TGA suggested that Pc weight content is 30%, 17% and 35% for NiPc, CuPc and ZnPc, respectively (CoPc exhibited anomalous behavior), which is close to the estimates from EDS spectra of 24-39%, 27-36% and 27-44% for CoPc, CuPc and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Pc hybrids, as compared to that of pristine nanotubes, was interpreted as very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the patterns of HOMO and LUMO distribution

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

    Science.gov (United States)

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

    2011-06-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-15

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

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

    International Nuclear Information System (INIS)

    Dhenaut, Christophe

    1995-01-01

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

  19. Nitrogen and sulfur co-doped graphene/carbon nanotube as metal-free electrocatalyst for oxygen evolution reaction: the enhanced performance by sulfur doping

    International Nuclear Information System (INIS)

    Zhao, Jujiao; Liu, Yanming; Quan, Xie; Chen, Shuo; Zhao, Huimin; Yu, Hongtao

    2016-01-01

    Highlights: • Metal-free 3D architecture N,S co-doped GR/CNT is prepared by a one-step method. • N,S co-doped GR/CNT exhibits good activity and stability for OER. • S doping is indicated beneficial for OER performance of metal-free catalysts. • The catalytic kinetics is highly correlated with the content of C-S-C structure. • 3D architecture composed of GR and CNT also contributes to the OER activity. - Abstract: Highly active metal-free electrocatalysts consisting of earth-abundant elements for oxygen evolution reaction (OER) are extremely desired for renewable energy technologies. Here we prepare the nitrogen and sulfur co-doped graphene/carbon nanotube (NS-GR/CNT) with 3D architecture by one-step hydrothermal method, which presents good performance for OER. The as-prepared NS-GR/CNT exhibits more negative onset potential and lower Tafel slope (0.56 V, 103 mV decade"−"1 vs. S.C.E. in 0.1 M KOH) compared to single N doped graphene/carbon nanotube (0.65 V, 285 mV decade"−"1), which indicates S doping can significantly enhance the OER performance. The X-ray photoelectron spectroscopy reveals that the thiophene-like S (C-S-C) is the dominant S species in all the S doped samples. NS-GR/CNT with C-S-C content of 0.26% has the Tafel slope of 151 mV decade"−"1 while the value for NS-GR/CNT with C-S-C content of 1.09% is 103 mV decade"−"1. The decreased Tafel slope demonstrates the catalytic kinetics are highly correlated with the content of C-S-C. Density functional theory calculations suggest that C-S-C may improve the catalytic kinetics by facilitating the adsorption of the OH"− intermediate. Besides, the 3D architecture composed of graphene and CNTs also contributes to the good performance and chronoamperometric measurement demonstrates the good durability of NS-GR/CNTs.

  20. Molecule Matters van der Waals Molecules

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 14; Issue 12. Molecule Matters van der Waals Molecules - Noble Gas Clusters are London Molecules! E Arunan. Feature Article Volume 14 Issue 12 December 2009 pp 1210-1222 ...

  1. OSU-6: A Highly Efficient, Metal-Free, Heterogeneous Catalyst for the Click Synthesis of 5-Benzyl and 5-Aryl-1H-tetrazoles

    Directory of Open Access Journals (Sweden)

    Baskar Nammalwar

    2015-12-01

    Full Text Available OSU-6, an MCM-41 type hexagonal mesoporous silica with mild Brönsted acid properties, has been used as an efficient, metal-free, heterogeneous catalyst for the click synthesis of 5-benzyl and 5-aryl-1H-tetrazoles from nitriles in DMF at 90 °C. This catalyst offers advantages including ease of operation, milder conditions, high yields, and reusability. Studies are presented that demonstrate the robust nature of the catalyst under the optimized reaction conditions. OSU-6 promotes the 1,3-dipolar addition of azides to nitriles without significant degradation or clogging of the nanoporous structure. The catalyst can be reused up to five times without a significant reduction in yield, and it does not require treatment with acid between reactions.

  2. Highly efficient transition metal-free coupling of acid chlorides with terminal alkynes in [bmim]Br: A rapid route to access ynones using MgCl2

    Directory of Open Access Journals (Sweden)

    Mohammad Navid Soltani Rad

    2018-03-01

    Full Text Available A simple, mild, highly efficient and transition metal-free protocol for synthesis of ynones in an ionic liquid is described. In this approach, the coupling reaction of different acid chlorides with terminal alkynes was efficiently carried out using 0.05 mol% MgCl2 in the presence of triethylamine in [bmim]Br at room temperature to afford the corresponding ynones in good to excellent yields. This method is highly efficient for various acid chlorides and alkynes including aliphatic, aromatic, and heteroaromatic substrates bearing different functional groups. The influence of some parameters in this reaction including type of ionic liquid, base and catalyst has been discussed.

  3. Nitrogen-doped micropore-dominant carbon derived from waste pine cone as a promising metal-free electrocatalyst for aqueous zinc/air batteries

    Science.gov (United States)

    Lei, Xiaoke; Wang, Mengran; Lai, Yanqing; Hu, Langtao; Wang, Hao; Fang, Zhao; Li, Jie; Fang, Jing

    2017-10-01

    The exploitation for highly effective and low-cost metal-free catalysts with facile and environmental friendly method for oxygen reduction reaction is still a great challenge. To find an effective method for catalyst synthesis, in this manuscript, waste biomass pine cone is employed as raw material and nitrogen-doped micropore-dominant carbon material with excellent ORR catalytic activity is successfully synthesized. The as-prepared N-doped micropore-dominant carbon possesses a high surface area of 1556 m2 g-1. In addition, this carbon electrocatalyst loaded electrode exhibits a high discharge voltage 1.07 V at the current density of 50 mA cm-2, which can be ascribed to the rich micropores and high content of pyridinic N of the prepared carbon, indicative of great potential in the application of zinc/air batteries.

  4. Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

    KAUST Repository

    Chen, Yin

    2015-11-02

    The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

  5. Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

    KAUST Repository

    Chen, Yin; Lin, Bin; Wang, Hong; Yang, Yong; Zhu, Haibo; Yu, Weili; Basset, Jean-Marie

    2015-01-01

    The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

  6. Investigation of electronic band structure and charge transfer mechanism of oxidized three-dimensional graphene as metal-free anodes material for dye sensitized solar cell application

    Science.gov (United States)

    Loeblein, Manuela; Bruno, Annalisa; Loh, G. C.; Bolker, Asaf; Saguy, Cecile; Antila, Liisa; Tsang, Siu Hon; Teo, Edwin Hang Tong

    2017-10-01

    Dye-sensitized solar cells (DSSCs) offer an optimal trade-off between conversion-efficiency and low-cost fabrication. However, since all its electrodes need to fulfill stringent work-function requirements, its materials have remained unchanged since DSSC's first report early-90s. Here we describe a new material, oxidized-three-dimensional-graphene (o-3D-C), with a band gap of 0.2 eV and suitable electronic band-structure as alternative metal-free material for DSSCs-anodes. o-3D-C/dye-complex has a strong chemical bonding via carboxylic-group chemisorption with full saturation after 12 sec at capacity of ∼450 mg/g (600x faster and 7x higher than optimized metal surfaces). Furthermore, fluorescence quenching of life-time by 28-35% was measured demonstrating charge-transfer from dye to o-3D-C.

  7. One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a "catalyst switch" strategy

    KAUST Repository

    Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

    2014-01-01

    A "catalyst switch" strategy has been used to sequentially polymerize four different heterocyclic monomers. In the first step, epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator in the presence of a strong phosphazene base promoter (t-BuP4). Then, an excess of diphenyl phosphate (DPP) was introduced, followed by addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). DPP acted as both neutralizer of the phosphazenium alkoxide (polyether chain end) and activator of the cyclic carbonate/ester. Using this method, linear- and star-tetrablock quarterpolymers were prepared in one pot. This work is emphasizing the strength of the previously developed catalyst switch strategy for the facile metal-free synthesis of complex macromolecular architectures. © 2014 Wiley Periodicals, Inc.

  8. One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a "catalyst switch" strategy

    KAUST Repository

    Zhao, Junpeng

    2014-08-06

    A "catalyst switch" strategy has been used to sequentially polymerize four different heterocyclic monomers. In the first step, epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator in the presence of a strong phosphazene base promoter (t-BuP4). Then, an excess of diphenyl phosphate (DPP) was introduced, followed by addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). DPP acted as both neutralizer of the phosphazenium alkoxide (polyether chain end) and activator of the cyclic carbonate/ester. Using this method, linear- and star-tetrablock quarterpolymers were prepared in one pot. This work is emphasizing the strength of the previously developed catalyst switch strategy for the facile metal-free synthesis of complex macromolecular architectures. © 2014 Wiley Periodicals, Inc.

  9. Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

    KAUST Repository

    Chen, Yin

    2015-06-12

    A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3N4) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g-C3N4. This catalyst family (with less than 0.1 wt% of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt% platinum as co-catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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

  11. Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst

    International Nuclear Information System (INIS)

    Yan, Kai; Chen, Aicheng

    2013-01-01

    Biomass-derived platform intermediate furfural and levulinic acid were efficiently hydrogenated to the value-added furfuryl alcohol and promising biofuel γ-valerolactone, respectively, using a noble-metal-free Cu–Cr catalyst, which was facilely and successfully synthesized by a modified co-precipitation method using the cheap metal nitrates. In the first hydrogenation of furfural, 95% yield of furfuryl alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the hydrogenation of levulinic acid, 90% yield of γ-valerolactone was highly selectively produced at 97.8% conversion. Besides, the physical properties of the resulting Cu–Cr catalysts were studied by XRD (X-ray diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray photoelectron spectroscopy) to reveal their influence on the catalytic performance. Subsequently, different reaction parameters were studied and it was found that Cu 2+ /Cr 3+ ratios (0.5, 1 and 2), reaction temperature (120–220 °C) and hydrogen pressure (35–70 bar) presented important influence on the catalytic activities. In the end, the stability of the Cu–Cr catalysts was also studied. - Highlights: • A noble-metal-free Cu–Cr catalyst was successfully synthesized using metal nitrates. • Cu–Cr catalysts were highly selective hydrogenation of biomass-derived furfural to FA. • Cu–Cr catalysts were efficient for hydrogenation of biomass-derived LA to biofuel GVL. • The physical properties of the resulting Cu–Cr catalysts were systematically studied. • Reaction parameters and stability in the hydrogenation of furfural were studied in details

  12. Clinical performance of provisional screw-retained metal-free acrylic restorations in an immediate loading implant protocol: a 242 consecutive patients' report.

    Science.gov (United States)

    Suarez-Feito, Jose-María; Sicilia, Alberto; Angulo, Jorge; Banerji, Subir; Cuesta, Isabel; Millar, Brian

    2010-12-01

    To evaluate the clinical performance of provisional screw-retained metal-free acrylic restorations in an immediate loading implant protocol. Two hundred and forty-two consecutive patients were selected retrospectively, who received 1011 implants and 311 immediate provisional screw-retained implant restorations (2-4 h after implant surgery). The patients were monitored for a period of 2-3 months, until they were referred for a final restoration. The primary variables recorded include the survival time and the appearance of fractures in the provisional restoration, and the independent variables included age, sex, dental arch, type of restoration, type of attachment and components used, as well as cantilevers and opposing dentition. A survival analysis (Kaplan-Meier) and a Cox regression analysis were performed. Twenty-three restorations in 20 patients (8.26%, 95% CI 4.8-11.7) showed at least one fracture (7.39%). More than half of the new fractures (52%, 12 cases) occurred in the first 4 weeks. The cumulative survival probability observed was greater in mandible (P=0.05) and non-cantilever restorations (P=0.001), and in those opposed by full restorations or natural teeth (P=0.001). With an opposing implant-supported prosthesis, the risk of fracture was multiplied by 4.7, and the use of cantilevers as well as the location of the restoration in the maxilla multiply the risk by 3.4-3.5. Immediate provisional screw-retained metal-free implant-supported restorations can be considered a reliable restoration (92.6% remain intact) for the healing period of 3 months. © 2010 John Wiley & Sons A/S.

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

    Directory of Open Access Journals (Sweden)

    Michael J. Brett

    2012-08-01

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

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

    Science.gov (United States)

    Poldi, G.; Caglio, S.

    2013-06-01

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

  16. 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.

  17. Photochemical oxygen reduction by zinc phthalocyanine and silver/gold nanoparticle incorporated silica thin films

    Energy Technology Data Exchange (ETDEWEB)

    Pal, Manas; Ganesan, Vellaichamy, E-mail: velganesh@yahoo.com; Azad, Uday Pratap

    2012-12-15

    Silver or gold nanoparticles are synthesized using a borohydride reduction method and are anchored simultaneously into/onto the mercaptopropyl functionalized silica. Later, zinc phthalocyanine is adsorbed onto the above materials. Thin films of these materials are prepared by coating an aqueous colloidal suspension of the respective material onto glass plates. Visible light irradiation of these films in oxygen saturated, stirred aqueous solutions effectively reduces oxygen to hydrogen peroxide. The photocatalytic reduction of oxygen is explained on the basis of the semiconducting properties of the silica films. The back electron transfer reaction is largely prevented by means of a sacrificial electron donor, triethanolamine. - Highlights: Black-Right-Pointing-Pointer Zinc phthalocyanine adsorbed silica materials were prepared. Black-Right-Pointing-Pointer Thin films of these materials photocatalytically reduce oxygen. Black-Right-Pointing-Pointer The photocatalysis is explained based on semiconductor properties of the materials. Black-Right-Pointing-Pointer Metal nanoparticles increase the photocatalytic efficiency of the materials.

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

    International Nuclear Information System (INIS)

    Ozcesmeci, Ibrahim; Koca, Atif; Guel, Ahmet

    2011-01-01

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

  19. Phthalocyanine-nanocarbon ensembles: From discrete molecular and supramolecular systems to hybrid nanomaterials

    OpenAIRE

    Bottari, Giovanni; De La Torre, Gema; Torres, Tomas

    2015-01-01

    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Accounts of Chemical Research, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ar5004384 Conspectus Phthalocyanines (Pcs) are macrocyclic and aromatic compounds that present unique electronic features such as high molar absorption coefficients, rich redox chemistry, and...

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

    International Nuclear Information System (INIS)

    Sugimoto, Hiroshi; Higashi, Teruaki; Mori, Masayasu

    1982-01-01

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

  1. 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.

  2. Interaction of tricyclic drugs with copper phthalocyanine dye immobilized on magnetic carriers

    Czech Academy of Sciences Publication Activity Database

    Šafaříková, Miroslava; Šafařík, Ivo

    3(Suppl.2), - (2002), s. 188-191 ISSN 1473-2262. [International Conference on the Scientific and Clinical Applications of Magnetic Carriers /4./. Tallahassee, 09.05.2002-11.05.2002] R&D Projects: GA MŠk OC 523.80; GA AV ČR IBS6087204 Institutional research plan: CEZ:AV0Z6087904 Keywords : magnetic * tricyclic drugs * phthalocyanine Subject RIV: CE - Biochemistry

  3. Molecular structure effects in photodegradation of phenol and its chlorinated derivatives with phthalocyanines

    Czech Academy of Sciences Publication Activity Database

    Klusoň, P.; Drobek, M.; Krejčíková, S.; Krýsa, J.; Kalaji, A.; Cajthaml, Tomáš; Rakušan, J.

    2008-01-01

    Roč. 80, 3-4 (2008), s. 321-326 ISSN 0926-3373 R&D Projects: GA AV ČR KAN400720701 Grant - others:CZ(CZ) GD203/03/H140; Mšk(CZ) IM4531433201 Program:GD Institutional research plan: CEZ:AV0Z50200510 Keywords : phthalocyanines * phenol * chlorophenols Subject RIV: EE - Microbiology, Virology Impact factor: 4.853, year: 2008

  4. 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.

  5. 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

  6. 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

  7. 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

  8. Organic phthalocyanine films with high mobilities for efficient field-effect transistor switches

    Czech Academy of Sciences Publication Activity Database

    Schauer, F.; Zhivkov, I.; Nešpůrek, Stanislav

    266-269, 1-3 (2000), s. 999-1003 ISSN 0022-3093. [International Conference on Amorphous and Microcrystalline Semiconductors /18./. Snowbird, 23.08.1999-27.08.1999] R&D Projects: GA MŠk OC 518.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : phthalocyanine * charge mobility * field-effect transistor Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.269, year: 2000

  9. 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.

  10. Comparison of chemical changes during photooxidation of polypropylene film and filament containing phthalocyanine pigment

    International Nuclear Information System (INIS)

    Ahmadi, Z.; Haghighat Kish, M.; Kotak, R.; Katbab, A. A.

    2008-01-01

    Photooxidation as an important process, which significantly affects the service life of the polypropylene products, has been the subject of much theoretical and experimental study. Pigments used often change the light stabilities of polypropylene. Out-door applications of pigmented polypropylene are now increasingly developed in products such as artificial grass. The aim of this work is to examine the effect of photo-oxidation on the structure of isotactic polypropylene (iPP) in film and filament forms, where phthalocyanine pigment is used. For production of films and filaments, iPP granules with MFI 25 g/10 min were used, with and without phthalocyanine pigment. Samples were exposed to xenon lamp for various time lengths. The extent of the changes in chemical and structural parameters was examined by differential scanning calorimetry, Fourier transform infrared spectroscopy and wide angle x-ray diffraction. The results show that carbonyl and hydroperoxide indices increase during the exposure to the radiation. The changes in melting points of the samples were not significant after irradiation process. The effects of phthalocyanine pigment in the photooxidation of film and filament were different. Crystalline fractions of the non-pigmented filament samples decreased during the irradiation time while increased in film samples. Build up of hydroperoxide and carbonyl group in filament was higher than in film samples; that could be due to the differences in structural parameters. Crystallinity variations during photooxidation are related to the nucleation effect of the pigment, chemical crystallization and phase transformation

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

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

    Science.gov (United States)

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

    2015-11-01

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

  13. 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.

  14. 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.

  15. The effect of NO2 on spectroscopic and structural properties of evaporated ruthenium phthalocyanine dimer

    International Nuclear Information System (INIS)

    Alagna, Lucilla; Capobianchi, Aldo; Paoletti, Anna Maria; Pennesi, Giovanna; Rossi, Gentilina; Casaletto, Maria Pia; Generosi, Amanda; Paci, Barbara; Albertini, Valerio Rossi

    2006-01-01

    The chemical interaction between NO 2 gas and dimeric ruthenium phthalocyanine (RuPc) 2 (Pc = phthalocyanine ligand) films has been investigated by different techniques: UV-Visible spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and Extended X-ray Absorption Fine Structure (EXAFS). The optical spectra in the Q band region (700-500 nm) registered 'in situ' enabled to follow the evolution of the process in real time indicating that a two steps reaction, showing two clear isosbestic points, occurs. The first phase was essentially characterised by: (a) the rapid disappearance of the 608 and 420 nm shoulders; (b) the intensity decrease of the main absorption peak and (c) the appearance of a new adsorption band centred around 510 nm. In the second step the remarkable feature is a further lowering of the main peak with the simultaneous decrease of the new 510 nm absorption. These spectral changes suggested that a chemical reaction occurred between NO 2 and ruthenium phthalocyanine with the formation of a radical species due to the macrocycle oxidation. The kinetics indicates that the adsorption of gas by the evaporated (RuPc) 2 film is a complex process involving more than one independent mechanism. XPS and EXAFS spectra collected before and after gas exposure showed that the central metals (Ru) were also involved in the oxidation process. The reversibility of the process has been also tested by treating the films at different temperatures, the original optical spectrum being not completely recovered

  16. 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

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

    KAUST Repository

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

    2010-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Fahrendorf, Sarah

    2013-01-24

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

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

    International Nuclear Information System (INIS)

    Fahrendorf, Sarah

    2013-01-01

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

  20. Making the invisible visible: improved electrospray ion formation of metalloporphyrins/-phthalocyanines by attachment of the formate anion (HCOO(-)).

    Science.gov (United States)

    Hitzenberger, Jakob Felix; Dammann, Claudia; Lang, Nina; Lungerich, Dominik; García-Iglesias, Miguel; Bottari, Giovanni; Torres, Tomás; Jux, Norbert; Drewello, Thomas

    2016-02-21

    A protocol is developed for the coordination of the formate anion (HCOO(-)) to neutral metalloporphyrins (Pors) and -phthalocyanines (Pcs) containing divalent metals as a means to improve their ion formation in electrospray ionization (ESI). This method is particularly useful when the oxidation of the neutral metallomacrocycle fails. While focusing on Zn(II)Pors and Zn(II)Pcs, we show that formate is also readily attached to Mn(II), Mg(II) and Co(II)Pcs. However, for the Co(II)Pc secondary reactions can be observed. Upon collision-induced dissociation (CID), Zn(II)Por/Pc·formate supramolecular complexes can undergo the loss of CO2 in combination with transfer of a hydride anion (H(-)) to the zinc metal center. Further dissociation leads to electron transfer and hydrogen atom loss, generating a route to the radical anion of the Zn(II)Por/Pc without the need for electrochemical reduction, although the Zn(II)Por/Pc may have a too low electron affinity to allow electron transfer directly from the formate anion. In addition to single Por molecules, multi Por arrays were successfully analyzed by this method. In this case, multiple addition of formate occurs, giving rise to multiply charged species. In these multi Por arrays, complexation of the formate anion occurs by two surrounding Por units (sandwich). Therefore, the maximum attainment of formate anions in these arrays corresponds to the number of such sandwich complexes rather than the number of porphyrin moieties. The same bonding motif leads to dimers of the composition [(Zn(II)Por/Pc)2·HCOO](-). In these, the formate anion can act as a structural probe, allowing the distinction of isomeric ions with the formate bridging two macrocycles or being attached to a dimer of directly connected macrocycles.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  3. Giant magnetoresistance through a single molecule.

    Science.gov (United States)

    Schmaus, Stefan; Bagrets, Alexei; Nahas, Yasmine; Yamada, Toyo K; Bork, Annika; Bowen, Martin; Beaurepaire, Eric; Evers, Ferdinand; Wulfhekel, Wulf

    2011-03-01

    Magnetoresistance is a change in the resistance of a material system caused by an applied magnetic field. Giant magnetoresistance occurs in structures containing ferromagnetic contacts separated by a metallic non-magnetic spacer, and is now the basis of read heads for hard drives and for new forms of random access memory. Using an insulator (for example, a molecular thin film) rather than a metal as the spacer gives rise to tunnelling magnetoresistance, which typically produces a larger change in resistance for a given magnetic field strength, but also yields higher resistances, which are a disadvantage for real device operation. Here, we demonstrate giant magnetoresistance across a single, non-magnetic hydrogen phthalocyanine molecule contacted by the ferromagnetic tip of a scanning tunnelling microscope. We measure the magnetoresistance to be 60% and the conductance to be 0.26G(0), where G(0) is the quantum of conductance. Theoretical analysis identifies spin-dependent hybridization of molecular and electrode orbitals as the cause of the large magnetoresistance.

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

    Directory of Open Access Journals (Sweden)

    David Klar

    2013-05-01

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

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  6. 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.

  7. Molecule Matters van der Waals Molecules

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 15; Issue 7. Molecule Matters van der Waals Molecules - Rg•••HF Complexes are Debye Molecules! E Arunan. Feature Article Volume 15 Issue 7 July 2010 pp 667-674. Fulltext. Click here to view fulltext PDF. Permanent link:

  8. Synthesis and spectral properties of axially substituted zirconium(IV) and hafnium(IV) water soluble phthalocyanines in solutions

    International Nuclear Information System (INIS)

    Gerasymchuk, Y.S.; Volkov, S.V.; Chernii, V.Ya.; Tomachynski, L.A.; Radzki, St.

    2004-01-01

    Methods of synthesis of novel water soluble axially substituted Zr(IV) and Hf(IV) phthalocyanines with gallic, 5-sulfosalicyllic, oxalic acids, and methyl ester of gallic acid as axial ligands coordinated to the central atom metal of phthalocyanine are presented. The absorption spectra of complex solutions in various solvents were characterized. The dependence of the spectral red shift from Reichardt's empirical polarity parameter is described. The deviation from the linearity of Beer-Bouguer-Lambert law was investigated for the range of concentration 5x10 -6 to 10x10 -5 M. Fluorescent properties of axially substituted phthalocyaninato metal complexes in DMSO solutions were investigated

  9. Noble-metal-free NiO@Ni-ZnO/reduced graphene oxide/CdS heterostructure for efficient photocatalytic hydrogen generation

    Science.gov (United States)

    Chen, Fayun; Zhang, Laijun; Wang, Xuewen; Zhang, Rongbin

    2017-11-01

    Noble-metal-free semiconductor materials are widely used for photocatalytic hydrogen generation because of their low cost. ZnO-based heterostructures with synergistic effects exhibit an effective photocatalytic activity. In this work, NiO@Ni-ZnO/reduced graphene oxide (rGO)/CdS heterostructures are synthesized by a multi-step method. rGO nanosheets and CdS nanoparticles were introduced into the heterostructures via a redox reaction and light-assisted growth, respectively. A novel Ni-induced electrochemical growth method was developed to prepare ZnO rods from Zn powder. NiO@Ni-ZnO/rGO/CdS heterostructures with a wide visible-light absorption range exhibited highly photocatalytic hydrogen generation rates under UV-vis and visible light irradiation. The enhanced photocatalytic activity is attributed to the Ni nanoparticles that act as cocatalysts for capturing photoexcited electrons and the improved synergistic effect between ZnO and CdS due to the rGO nanosheets acting as photoexcited carrier transport channels.

  10. DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster

    Directory of Open Access Journals (Sweden)

    Corneliu I. Oprea

    2013-01-01

    Full Text Available We report results of density functional theory (DFT calculations of a metal-free dye, 5-(4-sulfophenylazosalicylic acid disodium salt, known as Mordant Yellow 10 (MY-10, used as sensitizer for TiO2 dye-sensitized solar cells (DSSCs. Given the need to better understand the behavior of the dyes adsorbed on the TiO2 nanoparticle, we studied various single and double deprotonated forms of the dye bound to a TiO2 cluster, taking advantage of the presence of the carboxyl, hydroxyl, and sulfonic groups as possible anchors. We discuss various binding configurations to the TiO2 substrate and the charge transfer from the pigment to the oxide by means of DFT calculations. In agreement with other reports, we find that the carboxyl group tends to bind in bidentate bridging configurations. The salicylate uses both the carboxyl and hydroxyl substituent groups for either a tridentate binding to adjacent Ti(IV ions or a bidentate Ti-O binding together with an O-H-O binding, due to the rotation of the carboxyl group out of the plane of the dye. The sulfonic group prefers a tridentate binding. We analyze the propensity for electron transfer of the various dyes and find that for MY-10, as a function of the anchor group, the DSSC performance decreases in the order hydroxyl + carboxyl > carboxyl > sulfonate.

  11. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    Science.gov (United States)

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-02-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  12. Power generation in microbial fuel cells using platinum group metal-free cathode catalyst: Effect of the catalyst loading on performance and costs.

    Science.gov (United States)

    Santoro, Carlo; Kodali, Mounika; Herrera, Sergio; Serov, Alexey; Ieropoulos, Ioannis; Atanassov, Plamen

    2018-02-28

    Platinum group metal-free (PGM-free) catalyst with different loadings was investigated in air breathing electrodes microbial fuel cells (MFCs). Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating ring disk electrode (RRDE) setup with different catalyst loadings. The results showed that higher loading led to an increased in the half wave potential and the limiting current and to a further decrease in the peroxide production. The electrons transferred also slightly increased with the catalyst loading up to the value of ≈3.75. This variation probably indicates that the catalyst investigated follow a 2x2e - transfer mechanism. The catalyst was integrated within activated carbon pellet-like air-breathing cathode in eight different loadings varying between 0.1 mgcm -2 and 10 mgcm -2 . Performance were enhanced gradually with the increase in catalyst content. Power densities varied between 90 ± 9 μWcm -2 and 262 ± 4 μWcm -2 with catalyst loading of 0.1 mgcm -2 and 10 mgcm -2 respectively. Cost assessments related to the catalyst performance are presented. An increase in catalyst utilization led to an increase in power generated with a substantial increase in the whole costs. Also a decrease in performance due to cathode/catalyst deterioration over time led to a further increase in the costs.

  13. WS2 as an Effective Noble-Metal Free Cocatalyst Modified TiSi2 for Enhanced Photocatalytic Hydrogen Evolution under Visible Light Irradiation

    Directory of Open Access Journals (Sweden)

    Dongmei Chu

    2016-09-01

    Full Text Available A noble-metal free photocatalyst consisting of WS2 and TiSi2 being used for hydrogen evolution under visible light irradiation, has been successfully prepared by in-situ formation of WS2 on the surface of TiSi2 in a thermal reaction. The obtained samples were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray spectrometry (EDX, transmission electron microscopy (TEM, and X-ray photoelectron spectroscopy (XPS. The results demonstrate that WS2 moiety has been successfully deposited on the surface of TiSi2 and some kind of chemical bonds, such as Ti-S-W and Si-S-W, might have formed on the interface of the TiSi2 and WS2 components. Optical and photoelectrochemical investigations reveal that WS2/TiSi2 composite possesses lower hydrogen evolution potential and enhanced photogenerated charge separation and transfer efficiency. Under 6 h of visible light (λ > 420 nm irradiation, the total amount of hydrogen evolved from the optimal WS2/TiSi2 catalyst is 596.4 μmol·g−1, which is around 1.5 times higher than that of pure TiSi2 under the same reaction conditions. This study shows a paradigm of developing the effective, scalable and inexpensive system for photocatalytic hydrogen generation.

  14. Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

    Science.gov (United States)

    Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

    2014-11-21

    Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

  15. Monolayer CS as a metal-free photocatalyst with high carrier mobility and tunable band structure: a first-principles study

    Science.gov (United States)

    Yang, Xiao-Le; Ye, Xiao-Juan; Liu, Chun-Sheng; Yan, Xiao-Hong

    2018-02-01

    Producing hydrogen fuel using suitable photocatalysts from water splitting is a feasible method to harvest solar energy. A desired photocatalyst is expected to have suitable band gap, moderate band edge position, and high carrier mobility. By employing first-principles calculations, we explore a α-CS monolayer as a metal-free efficient photocatalyst. The α-CS monolayer shows good energetic, dynamic, and thermal stabilities and is insoluble in water, suggesting its experimental practicability. Monolayer and bilayer α-CS present not only appropriate band gaps for visible and ultraviolet light absorption but also moderate band alignments with water redox potentials in pH neutral water. Remarkably, the α-CS monolayer exhibits high (up to 8453.19 cm2 V-1s-1 for hole) and anisotropic carrier mobility, which is favorable to the migration and separation of photogenerated carriers. In addition, monolayer α-CS experiences an interesting semiconductor-metal transition by applying uniaxial strain and external electric field. Moreover, α-CS under certain strain and electric field is still dynamically stable with the absence of imaginary frequencies. Furthermore, we demonstrate that the graphite (0 0 1) surface is a potential substrate for the α-CS growth with the intrinsic properties of α-CS maintaining. Therefore, our results could pave the way for the application of α-CS as a promising photocatalyst.

  16. Nitrogen and sulfur dual-doped chitin-derived carbon/graphene composites as effective metal-free electrocatalysts for dye sensitized solar cells

    Science.gov (United States)

    Di, Yi; Xiao, Zhanhai; Yan, Xiaoshuang; Ru, Geying; Chen, Bing; Feng, Jiwen

    2018-05-01

    The photovoltaic performance of dye-sensitized solar cell (DSSC) is strongly influenced by the electrocatalytic ability of its counter electrode (CE) materials. To obtain the affordable and high-performance electrocatalysts, the N/S dual-doped chitin-derived carbon materials SCCh were manufactured via in-situ S-doped method in the annealing process, where richer active sites are created compared to the pristine chitin-derived carbon matrix CCh, thus enhancing the intrinsic catalytic activity of carbon materials. When SCCh is incorporated with graphene, the yielded composites hold a further boosted catalytic activity due to facilitating the electronic fast transfer. The DSSC assembled with the optimizing rGO-SCCh-3 composite CE shows a favourable power conversion efficiency of 6.36%, which is comparable with that of the Pt-sputtering electrode (6.30%), indicate of the outstanding I3- reduction ability of the composite material. The electrochemical characterizations demonstrate that the low charge transfer resistance and excellent electrocatalytic activity all contribute to the superior photovoltaic performance. More importantly, the composite CE exhibits good electrochemical stability in the practical operation. In consideration of the low cost and the simple preparation procedure, the present metal-free carbonaceous composites could be used as a promising counter electrode material in future large scale production of DSSCs.

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

    KAUST Repository

    Haldar, Soumyajyoti

    2017-09-13

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

  18. Photodynamic therapy: anti-tumour potentialities of bis (tri π-hexyl-siloxy) silicon phthalocyanine against malignant achromic M6 melanocytes. EPR study of the photo-toxic mechanism

    International Nuclear Information System (INIS)

    Decreau, R.; Viola, A.; Julliard, M.; Hadjur, Ch.; Richard, M.J.; Favier, A.; Jeunet, A.

    1997-01-01

    Photodynamic therapy of cancerous cells is a technique relying upon the irradiation of tumorous cells after selective incorporation of a photo-sensitizer. The bis (tri n-hexyl-siloxy) silicon phthalocyanine is a second generation photo-sensitizer. Anti-cancerous potentialities of this molecule have been evaluated against the melanotic M6 cell line. Results have evidenced a high phototoxicity at low concentration and no dark toxicity under the same conditions. EPR studies on the photochemical pathways involved in phototoxicity processes have been realised in solvent and model membranes (liposomes). Results provide evidences for the production of singlet oxygen ( 1 O 2 ) as well as superoxide (O 2 0- ) and hydroxyl radical ( 0 OH). (authors)

  19. Environmentally friendly inhibition of pathogenic bacteria and algae propagation due phthalocyanine agents

    International Nuclear Information System (INIS)

    Rihova Ambrozova, J.; Bezdekova, E.; Louckova, E.; Nekovarova, J.

    2007-01-01

    From 2004, in the laboratory of The Institute of Chemical Technology in Prague is being solved the project FT-TA/034 'Environmentally friendly inhibition of pathogenic bacteria and algae propagation in the circulatory cooling systems of nuclear power stations and in other similar technological facilities' to determine effects of phthalocyanine agents. The project bearer is VUOS, Inc. in Rybitvi (Research Institute for Organic Synthesis Inc.), where are the new phthalocyanines synthesized. The aimed goal of the research is environmentally friendly liquidation of bacteria and algae by means of photodynamic generated singlet oxygen through impact of solar radiation in the circulation cooling waters of various technical and technological systems. The principle of the problem outlined is the applying of phthalocyanine agents on samples of pure bacterial, anabaenas and algae cultures to estimate the inhibition effect on the organism exposed. In the course of solution, it is assumed that in such way conducted inhibition of bacteria, anabaenas and algae as well of their proliferation would replace routinely used bactericidal and algicidal preparations, which demand permanent dosing into circulating waters or perhaps from time to time an application of shocking doses. The particular algicidal and bactericidal agents represents in this case in situ emerging singlet oxygen, that is harmless to water biocenoses and whose presence in the water is no reason to ban the outflow of waters treated in such a way into water streams. The goal should be also a direct estimation of the effect those agents on cooling waters samples e. g. from the nuclear power plant systems. The purpose of the tests performance is also elimination of filamentous green algae, emerging in the systems cooling towers. The applied preparations are not toxic and do not burden the living environment, they contain no substances interacting with surface materials of structures in the circulatory cooling circuit

  20. Photovoltaic behaviour of titanyl phthalocyanine thin films and titania bilayer films

    Czech Academy of Sciences Publication Activity Database

    Drabik, M.; Zachary, A. M.; Choi, Y.; Hanuš, J.; Toušek, J.; Toušková, J.; Cimrová, Věra; Slavinská, D.; Biederman, H.; Hanley, L.

    2008-01-01

    Roč. 268, č. 1 (2008), s. 57-60 ISSN 1022-1360. [Microsymposium on Advanced Polymer Materials for Photonics and Electronics /47./. Prague, 15.07.2007-19.07.2007] R&D Projects: GA MŠk(CZ) 1M06031 Grant - others:National Science Foundation(US) CHE0241425; GA MŠk(CZ) 1P05ME754 Institutional research plan: CEZ:AV0Z40500505 Keywords : conjugated polymers * photovoltaics * phthalocyanine * thin films * titania Subject RIV: BM - Solid Matter Physics ; Magnetism

  1. 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.

  2. Asymmetric Response toward Molecular Fluorination in Binary Copper–Phthalocyanine/Pentacene Assemblies

    DEFF Research Database (Denmark)

    de Oteyza, D. G.; García Lastra, Juan Maria; Goiri, E.

    2014-01-01

    We report a didactic and simple example of the subtleness in the balance of intermolecular and molecule–substrate interactions and its effect on molecular self-assembly. The study is performed on two closely related molecular blends of copper phthalocyanines and pentacene, in each of which one of...... intermolecular interactions and a larger corrugation in the molecule–substrate interaction potential, results in a disordered layer. However, the difference between the two blend’s structures vanishes when substrates with less corrugated interaction potentials are used....

  3. Microscopic study of carrier transport in the organic semiconductor zinc-phthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Duarte, Joao Piroto [ESTeSC, Polytechnic Institute of Coimbra, 3040-854 Coimbra (Portugal); CEMDRX, Physics Department, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal); Alberto, Helena Vieira; Vilao, Rui Cesar; Gil, Joao M.; Weidinger, Alois; Campos, Nuno Ayres de [CEMDRX, Physics Department, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal)

    2010-04-15

    Nominally undoped zinc-phthalocyanine (ZnPc) was investigated using Muon Spin Rotation ({mu}SR) to probe microscopic carrier transport properties. The study focused on the relaxation of the positive muon's polarisation produced by spin-flip scattering with charge carriers. An energy of 71(8) meV was found for the temperature activation of carrier jumps, a value that does not match the activation energies known in ZnPc from electrical measurements, and that was attributed to a fast transport component in this material. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. 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.

  5. 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.

  6. Preparation of thin phthalocyanine layers and their structural and absorption properties

    Czech Academy of Sciences Publication Activity Database

    Kment, Štěpán; Klusoň, Petr; Drobek, M.; Kužel, R.; Gregora, Ivan; Kohout, Michal; Hubička, Zdeněk

    2009-01-01

    Roč. 517, č. 17 (2009), s. 5274-5279 ISSN 0040-6090 R&D Projects: GA AV ČR KAN301370701; GA MŠk(CZ) 1M06002; GA AV ČR KAN400720701; GA ČR(CZ) GD203/08/H032 Institutional research plan: CEZ:AV0Z10100522; CEZ:AV0Z40720504 Keywords : vacuum sublimation * phthalocyanine s * sensors * thin fims Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.727, year: 2009

  7. 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.

  8. Charge carrier mobility in sulphonated and non-sulphonated Ni phthalocyanines: experiment and quantum chemical calculations

    Czech Academy of Sciences Publication Activity Database

    Šebera, Jakub; Nešpůrek, Stanislav; Kratochvílová, Irena; Záliš, Stanislav; Chaidogiannos, G.; Glezos, N.

    2009-01-01

    Roč. 72, č. 3 (2009), s. 385-395 ISSN 1434-6028 R&D Projects: GA MŠk OC 139; GA MŠk OC 137; GA AV ČR KAN401770651; GA AV ČR KAN200100801; GA ČR GA203/08/1594; GA MŠk OC 138 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40500505; CEZ:AV0Z10100520 Keywords : Ni Phthalocyanines * chemical calculations * polymers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.466, year: 2009

  9. 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.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  11. Metal-free bioconjugation reactions.

    Science.gov (United States)

    van Berkel, Sander S; van Delft, Floris L

    2013-01-01

    The recent strategy to apply chemical reactions to address fundamental biological questions has led to the emergence of entirely new conjugation reactions that are fast and irreversible, yet so mild and selective that they can be performed even in living cells or organisms. These so-called bioorthogonal reactions open novel avenues, not only in chemical biology research, but also in many other life sciences applications, including the modulation of biopharmaceuticals by site-specific modification approaches.

  12. 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

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

    KAUST Repository

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

    2016-01-01

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

  14. Raman spectra of zinc phthalocyanine monolayers absorbed on glassy carbon and gold electrodes by application of a confocal Raman microspectrometer

    NARCIS (Netherlands)

    Palys-Staron, B.J.; Palys, B.J.; Puppels, G.J.; Puppels, G.J.; van den Ham, D.M.W.; van den Ham, D.M.W.; Feil, D.; Feil, D.

    1992-01-01

    Raman spectra of zinc phthalocyanine monolayers, adsorbed on gold and on glassy carbon surfaces (electrodes), are presented. These spectra have been recorded with the electrodes inside and outside an electrochemical cell filled with an aqueous electrolyte. A confocal Raman microspectrometer was

  15. 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.

  16. Influence of intramolecular f-f interactions on nuclear spin driven quantum tunneling of magnetizations in quadruple-decker phthalocyanine complexes containing two terbium or dysprosium magnetic centers.

    Science.gov (United States)

    Fukuda, Takamitsu; Matsumura, Kazuya; Ishikawa, Naoto

    2013-10-10

    Nuclear spin driven quantum tunneling of magnetization (QTM) phenomena, which arise from admixture of more than two orthogonal electronic spin wave functions through the couplings with those of the nuclear spins, are one of the important magnetic relaxation processes in lanthanide single molecule magnets (SMMs) in the low temperature range. Although recent experimental studies have indicated that the presence of the intramolecular f-f interactions affects their magnetic relaxation processes, little attention has been given to their mechanisms and, to the best of our knowledge, no rational theoretical models have been proposed for the interpretations of how the nuclear spin driven QTMs are influenced by the f-f interactions. Since quadruple-decker phthalocyanine complexes with two terbium or dysprosium ions as the magnetic centers show moderate f-f interactions, these are appropriate to investigate the influence of the f-f interactions on the dynamic magnetic relaxation processes. In the present paper, a theoretical model including ligand field (LF) potentials, hyperfine, nuclear quadrupole, magnetic dipolar, and the Zeeman interactions has been constructed to understand the roles of the nuclear spins for the QTM processes, and the resultant Zeeman plots are obtained. The ac susceptibility measurements of the magnetically diluted quadruple-decker monoterbium and diterbium phthalocyanine complexes, [Tb-Y] and [Tb-Tb], have indicated that the presence of the f-f interactions suppresses the QTMs in the absence of the external magnetic field (H(dc)) being consistent with previous reports. On the contrary, the faster magnetic relaxation processes are observed for [Tb-Tb] than [Tb-Y] at H(dc) = 1000 Oe, clearly demonstrating that the QTMs are rather enhanced in the presence of the external magnetic field. Based on the calculated Zeeman diagrams, these observations can be attributed to the enhanced nuclear spin driven QTMs for [Tb-Tb]. At the H(dc) higher than 2000 Oe, the

  17. Hierarchical hybrid of Ni{sub 3}N/N-doped reduced graphene oxide nanocomposite as a noble metal free catalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Li, Yingjun; Li, Yetong [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Huang, Keke [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Zhang, Jun, E-mail: cejzhang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2017-04-01

    Highlights: • Hybrid of Ni{sub 3}N/N-RGO catalysts are synthesized by using a two-step method. • The catalysts manifest superior catalytic activity towards the ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: Novel nickel nitride (Ni{sub 3}N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni{sub 3}N/N-RGO nanocomposites are obtained. The Ni{sub 3}N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni{sub 3}N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni{sub 3}N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni{sub 3}N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni{sub 3}N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.

  18. Metal-free virucidal effects induced by g-C3N4 under visible light irradiation: Statistical analysis and parameter optimization.

    Science.gov (United States)

    Zhang, Chi; Li, Yi; Zhang, Wenlong; Wang, Peifang; Wang, Chao

    2018-03-01

    Waterborne viruses with a low infectious dose and a high pathogenic potential pose a serious risk for humans all over the world, calling for a cost-effective and environmentally-friendly inactivation method. Optimizing operational parameters during the disinfection process is a facile and efficient way to achieve the satisfactory viral inactivation efficiency. Here, the antiviral effects of a metal-free visible-light-driven graphitic carbon nitride (g-C 3 N 4 ) photocatalyst were optimized by varying operating parameters with response surface methodology (RSM). Twenty sets of viral inactivation experiments were performed by changing three operating parameters, namely light intensity, photocatalyst loading and reaction temperature, at five levels. According to the experimental data, a semi-empirical model was developed with a high accuracy (determination coefficient R 2  = 0.9908) and then applied to predict the final inactivation efficiency of MS2 (a model virus) after 180 min exposure to the photocatalyst and visible light illumination. The corresponding optimal values were found to be 199.80 mW/cm 2 , 135.40 mg/L and 24.05 °C for light intensity, photocatalyst loading and reaction temperature, respectively. Under the optimized conditions, 8 log PFU/mL of viruses could be completely inactivated by g-C 3 N 4 without regrowth within 240 min visible light irradiation. Our study provides not only an extended application of RSM in photocatalytic viral inactivation but also a green and effective method for water disinfection. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  20. Absorption Spectroscopy, Molecular Dynamics Calculations, and Multivariate Curve Resolution on the Phthalocyanine Aggregation

    International Nuclear Information System (INIS)

    Ajloo, Davood; Ghadamgahi, Maryam; Shaheri, Freshte; Zarei, Kobra

    2014-01-01

    Co(II)-tetrasulfonated phthalocyanine (CoTSP) is known to be aggregated to dimer at high concentration levels in water. A study on the aggregation of CoTSP using multivariate curve resolution analysis of the visible absorbance spectra over a concentration range of 30, 40 and 50 μM in the presence of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile (AN) and ethanol (EtOH) in the concentration range of 0 to 3.57 M is conducted. A hard modeling-based multivariate curve resolution method was applied to determine the dissociation constants of the CoTSP aggregates at various temperatures ranging from 25, 45 and 65 .deg. C and in the presence of various co-solvents. Dissociation constant for aggregation was increased and then decrease by temperature and concentration of phthalocyanine, respectively. Utilizing the vant Hoff relation, the enthalpy and entropy of the dissociation equilibriums were calculated. For the dissociation of both aggregates, the enthalpy and entropy changes were positive and negative, respectively. Molecular dynamics simulation of cosolvent effect on CoTSP aggregation was done to confirm spectroscopy results. Results of radial distribution function (RDF), root mean square deviation (RMSD) and distance curves confirmed more effect of polar solvent to decrease monomer formation

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-04-15

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

  2. The use of chloroaluminium phthalocyanine tetrasulfonate (AlPcTS) for time-delayed fluorescence imaging

    International Nuclear Information System (INIS)

    Gundy, Sarah; Putten, Wil van der; Shearer, Andy; Buckton, Daniel; Ryder, Alan G; Ball, Michael

    2004-01-01

    Phthalocyanine derivatives are currently under investigation for use in photodynamic therapy, which is a promising cancer treatment. These materials, which display preferential uptake in cancerous cells, also exhibit high fluorescence yields and can be used for tumour detection. Problems with steady-state fluorescence techniques such as excitation scatter and background autofluorescence can be eliminated by using time-resolved imaging techniques without the need for filters. A tissue phantom was assembled to test a constructed time-gated imaging system by drilling 36 wells of varying diameter and depth (10 mm to 1 mm) into a block of polymethyl methacrylate (PMMA). The system was used to record images of chloroaluminium phthalocyanine tetrasulfonate (AlPcTS) at differing concentrations in neat aqueous solvent and cell suspensions within the wells. A mixture of Intralipid (to mimic tissue scatter) and Evan's blue (to mimic tissue absorption) of depths ranging from 1 mm to 10 mm was placed on top of the PMMA block. The ensuing images were analysed using signal-to-noise ratios and contrast-detail curves. The results indicate that the time-gated imaging system can prevent background excitation scatter from distorting the fluorescence signal from a longer-lived photosensitizer without the need for filters

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-15

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

  4. Absorption Spectroscopy, Molecular Dynamics Calculations, and Multivariate Curve Resolution on the Phthalocyanine Aggregation

    Energy Technology Data Exchange (ETDEWEB)

    Ajloo, Davood; Ghadamgahi, Maryam; Shaheri, Freshte; Zarei, Kobra [Damghan Univ., Damghan (Iran, Islamic Republic of)

    2014-05-15

    Co(II)-tetrasulfonated phthalocyanine (CoTSP) is known to be aggregated to dimer at high concentration levels in water. A study on the aggregation of CoTSP using multivariate curve resolution analysis of the visible absorbance spectra over a concentration range of 30, 40 and 50 μM in the presence of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile (AN) and ethanol (EtOH) in the concentration range of 0 to 3.57 M is conducted. A hard modeling-based multivariate curve resolution method was applied to determine the dissociation constants of the CoTSP aggregates at various temperatures ranging from 25, 45 and 65 .deg. C and in the presence of various co-solvents. Dissociation constant for aggregation was increased and then decrease by temperature and concentration of phthalocyanine, respectively. Utilizing the vant Hoff relation, the enthalpy and entropy of the dissociation equilibriums were calculated. For the dissociation of both aggregates, the enthalpy and entropy changes were positive and negative, respectively. Molecular dynamics simulation of cosolvent effect on CoTSP aggregation was done to confirm spectroscopy results. Results of radial distribution function (RDF), root mean square deviation (RMSD) and distance curves confirmed more effect of polar solvent to decrease monomer formation.

  5. Effect of diblock copolymer properties on the photophysical properties of dendrimer silicon phthalocyanine nanoconjugates

    Science.gov (United States)

    Chen, Kuizhi; Pan, Sujuan; Zhuang, Xuemei; Lv, Hafei; Que, Shoulin; Xie, Shusen; Yang, Hongqin; Peng, Yiru

    2016-07-01

    1-2 generation poly(benzyl aryl ether) dendrimer silicon phthalocyanines with axially disubstituted cyano terminal functionalities (G n -DSiPc(CN)4 n , (G n = n-generation dendrimer, n = 1-2)) were synthesized. Their structures were characterized by elemental analysis, IR, 1H NMR, and ESI-MS. Polymeric nanoparticles (G n -DSiPc(CN)4 n /m) were formed through encapsulating G n -DSiPc(CN)4 n into three monomethoxyl poly(ethylene glycol)-poly(ɛ-caprolactone) diblock copolymers (MPEG-PCL) with different hydrophilic/hydrophobic proportion, respectively. The effect of dendritic generation and the hydrophilic/hydrophobic proportion of diblock copolymers on the UV/Vis and fluorescence spectra of G n -DSiPc(CN)4 n and G n -DSiPc(CN)4 n /m were studied. The photophysical properties of polymeric nanoparticles exhibited dendritic generation and hydrophilic/hydrophobic proportion dependence. The fluorescence intensities and lifetimes of G n -DSiPc(CN)4 n /m were lower than the corresponding free dendrimer phthalocyanines. G n -DSiPc(CN)4 n encapsulated into MPEG-PCL with hydrophilic/hydrophobic molecular weight ratio 2000:4000 exhibited excellent photophysical property. The mean diameter of MPEG2000-PCL2000 micelles was about 70 nm, which decreased when loaded with G n -DSiPc(CN)4 n .

  6. Physical and photophysical properties of mixed double- and triple-decker sandwiches of porphyrins and phthalocyanines

    International Nuclear Information System (INIS)

    Salabert, Isabelle

    1995-01-01

    The study of electron transfer and charge recombination processes in various oligomers of porphyrins and phthalocyanines is reported. Our objective is to determine the nature of processes which compete with electron transfer in such Systems. The first part of this thesis is devoted to the study of mixed double- and triple-decker sandwich compounds of porphyrins and phthalocyanines of cerium and praseodymium. The charge transfer reaction and geminated recombination from excited complexes in solution and in sublimated film are investigated by time-resolved absorption spectroscopy with femtosecond time scale resolution. These results show the influence of the magnetic nature of the metal ion and of the relative position of the chromophores in the complex on the photophysical processes. The physical and photophysical properties of complexes formed by pairing in solution porphyrins and porphyrazines bearing oppositely charged substituent are reported in the second part. The formation of mixed aggregates of high order (2 to 5) is observed and their nature are spectrally characterized. The photoproducts issued from these complexes are extremely stable. (author) [fr

  7. 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.

  8. Sodium doping in copper-phthalocyanine/C{sub 60} heterojunction for organic photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hui-Ju; Wu, Hsuan-Ta; Hung, Kuang-Teng; Fu, Sheng-Wen [Department of Electrical Engineering, National Cheng Kung University, Tainan, 70101, Taiwan (China); Shih, Chuan-Feng, E-mail: cfshih@mail.ncku.edu.tw [Department of Electrical Engineering, National Cheng Kung University, Tainan, 70101, Taiwan (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan, 70101, Taiwan (China)

    2013-10-01

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

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  10. Synchrotron-based measurements of the electronic structure of the organic semiconductor copper phthalocyanine

    International Nuclear Information System (INIS)

    Downes, J.E.

    2004-01-01

    Full text: Copper phthalocyanine (CuPc) is a prototypical molecular organic semiconductor that is currently used in the construction of many organic electronic devices such as organic light emitting diodes (OLEDs). Although the material is currently being used, and despite many experimental and theoretical studies, it's detailed electronic structure is still not completely understood. This is likely due to two key factors. Firstly, the interaction of the Cu 3d and phthalocyanine ligand 2p electrons leads to the formation of a complex arrangement of localized and delocalized states near the Fermi level. Secondly, thin films of the material are subject to damage by the photon beam used to make measurements of their electronic structure. Using the synchrotron-based techniques of soft x-ray emission spectroscopy (XES) and x-ray photoemission spectroscopy (XPS), we have measured the detailed electronic structure of in-situ grown thin film samples of CuPc. Beam damage was minimized by continuous translation of the sample during data acquisition. The results obtained differ significantly from previous XES and ultraviolet photoemission measurements, but are in excellent agreement with recent density functional calculations. The reasons for these discrepancies will be explained, and their implications for future measurements on similar materials will be explored

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-09-30

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

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

    Science.gov (United States)

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

    2016-09-01

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

  13. Synergistic enhancement of supercapacitance upon integration of nickel (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine with SWCNT-phenylamine

    CSIR Research Space (South Africa)

    Agboola, BO

    2010-06-01

    Full Text Available Supercapacitive behaviour of a novel functional material, nickel (II) octa [(3,5-biscarboxylate)-phenoxy] phthalocyanine (NiOBCPPc) upon covalent integration with phenylamine functionalized single-walled carbon nanotubes (SWCNT...

  14. Nanostructured nickel (II) phthalocyanine-MWCNTs as viable nanocomposite platform for electrocatalytic detection of asulam pesticide at neutral pH conditions

    CSIR Research Space (South Africa)

    Siswana, MP

    2010-08-01

    Full Text Available This work reports for the first time that nanostructured nickel (II) phthalocyanine/multiwalled carbon nanotubes composite supported on a basal plane pyrolytic electrode (NiPcNP/MWCNT-BPPGE) could potentially serve as a viable platform...

  15. Influence of deposition substrate temperature on the morphology and molecular orientation of chloroaluminum phthalocyanine films as well the performance of organic photovoltaic cells

    International Nuclear Information System (INIS)

    Zheng, Yan-Qiong; Zhang, Jing; Yang, Fang; Wei, Bin; Zhang, Jianhua; Wang, Zixing; Komino, Takeshi; Adachi, Chihaya; Pu, Wenhong; Yang, Changzhu

    2015-01-01

    The dependence of the morphology of neat chloroaluminum phthalocyanine (ClAlPc) films on substrate temperature (T_s_u_b) during deposition is investigated by variable angle spectroscopic ellipsometry (VASE), x-ray diffraction (XRD), and atomic force microscopy (AFM) to obtain detailed information about the molecular orientation, phase separation, and crystallinity. AFM images indicate that both grain size and root mean square (RMS) roughness noticeably increase with T_s_u_b both in neat and blend films. Increasing T_s_u_b from room temperature to 420 K increases the horizontal orientation of the ClAlPc molecules with an increase of the mean molecular tilt angle from 60.13° (300 K) to 65.86° (420 K). The UV–vis absorption band of the corresponding films increases and the peak wavelength slightly red shifts with the T_s_u_b increase. XRD patterns show a clear diffraction peak at T_s_u_b over 390 K, implying the π-stacking of interconnected ClAlPc molecules at high T_s_u_b. Planar and bulk heterojunction (BHJ) photovoltaic cells containing pristine ClAlPc films and ClAlPc:C_6_0 blend films fabricated at T_s_u_b of 390 K show increases in the power conversion efficiency (η_P_C_E) of 28% (η_P_C_E = 3.12%) and 36% (η_P_C_E = 3.58%), respectively, relative to devices as-deposited at room temperature. The maximum short circuit current in BHJs is obtained at 390 K in the T_s_u_b range from 300 K to 450 K. (paper)

  16. Facile Synthesis of Boron-doped Graphene Nanosheets with Hierarchical Microstructure at Atmosphere Pressure for Metal-free Electrochemical Detection of Hydrogen Peroxide

    International Nuclear Information System (INIS)

    Yeh, Min-Hsin; Li, Yan-Sheng; Chen, Guan-Lin; Lin, Lu-Yin; Li, Ta-Jen; Chuang, Hui-Min; Hsieh, Cheng-Yu; Lo, Shen-Chuan; Chiang, Wei-Hung; Ho, Kuo-Chuan

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: • B-doped graphene nanosheets (BGNs) were used as a catalyst for sensing H 2 O 2 . • BGNs were synthesized by an atmospheric-pressure carbothermal reaction. • BGNs with hierarchical microstructure provide more electron transport pathways. • B atoms act as the active sites by transferring charges to neighboring C atoms. • Electrocatalytic ability of BGNs was characterized by a rotating disk electrode. -- Abstract: Hydrogen peroxide (H 2 O 2 ) is an essential mediator for most of the oxidative biological reactions in enzyme-based biosensor systems, such as glucose oxidase, cholesterol oxidase, and alcohol oxidase. Synthesis of new catalysts to detect the concentration of H 2 O 2 more precisely is indispensable for enzyme-based electrochemical biosensors. In this study, boron-doped graphene nanosheets (BGNs) with 2.2 atomic percentage (at%) boron doping level and a hierarchical microstructure were synthesized by an atmospheric-pressure carbothermal reaction as a noble-metal free catalyst for sensing H 2 O 2 . The isolated boron atoms on the BGNs surface act as the electrocatalytic sites by transferring charges to neighbor carbon atoms, and the hierarchical microstructure provides multidimensional electron transport pathways for charge transfer and therefore enhances the electrocatalytic ability. BGNs possess a higher reduction current in the cyclic voltammetry (CV) measurement than that of pristine graphene nanosheets (GNs) over the detection range of 0.0 to 10.0 mM at −0.4 V (vs. Ag/AgCl). The BGNs modified electrochemical sensor shows a linear range from 1.0 to 20.0 mM of H 2 O 2 with a sensitivity of 266.7 ± 3.8 μA mM −1 cm −2 and limit of detection (LOD) of 3.8 μM at a signal-to-noise (S/N) ratio of 3. The beneficial hierarchical microstructure and the synergetic effects arising from doping boron in GNs accomplish the better performance of the BGNs modified electrochemical sensor

  17. Down-conversion phosphors as noble-metal-free co-catalyst in ZnO for efficient visible light photocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Chu, Haipeng [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Liu, Xinjuan, E-mail: lxj669635@126.com [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Liu, Jiaqing [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China); Lei, Wenyan [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Li, Jinliang [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China); Wu, Tianyang [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Li, Ping [Shanghai Nanotechnology Promotion Center, Shanghai 200237 (China); Li, Huili; Pan, Likun [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China)

    2017-01-01

    Graphical abstract: ZnO-Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} hybrid photocatalysts were synthesized via a fast microwave-assisted approach for visible light photocatalytic degradation of organic pollutions with a high degradation rate of 91%. - Highlights: • ZnO-Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} were synthesized via a facile microwave-assisted method. • Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} acts as co-catalyst to facilitates the self-sensitized degradation of MB. • ZnO-Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} exhibited enhanced visible light photocatalytic activity. • A high MB degradation rate of 91% was achieved under visible light irradiation. - Abstract: Exploring novel visible light responsive photocatalysts is one of greatly significant issues from the viewpoint of using solar energy. Here we report the yellow-orange emitting α-Si{sub 3}N{sub 4}-doped Lu{sub 3}Al{sub 5}O{sub 12}:Ce{sup 3+} (Lu{sub 3}Al{sub 5-x}Si{sub x}O{sub 12-x}N{sub x}:Ce{sup 3+}) phosphors as a noble-metal-free co-catalyst for enhanced visible light photocatalytic activity of ZnO. The results show that ZnO-Lu{sub 3}Al{sub 5-x}Si{sub x}O{sub 12-x}N{sub x}:Ce{sup 3+} hybrid photocatalysts using a fast microwave-assisted approach exhibits a 91% methylene blue (MB) degradation under visible light irradiation at 240 min, which evidence the synergistic effect of ZnO and Lu{sub 3}Al{sub 5-x}Si{sub x}O{sub 12-x}N{sub x}:Ce{sup 3+} that suppress the rate of charge recombination and increase the self-sensitized degradation of MB. ZnO-down conversion phosphors can be envisaged as potential candidate in environmental engineering and solar energy applications.

  18. 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

  19. Characterization of Langmuir and Langmuir–Blodgett films of an octasubstituted zinc phthalocyanine

    International Nuclear Information System (INIS)

    Torrent-Burgués, J.; Cea, P.; Giner, I.; Guaus, E.

    2014-01-01

    In this work we report the fabrication of Langmuir and Langmuir–Blodgett (LB) films of a substituted ZnPc (octakis(oxyoctyl)phthalocyanine of zinc), and their characterization by means of several techniques. These characterization techniques include surface pressure (π-A) and surface potential (ΔV-A) isotherms as well as UV–vis Reflection spectroscopy and Brewster Angle Microscopy (BAM) for the films at the air–water interface together with UV–vis absorption and IR spectroscopies and Atomic Force Microscopy (AFM) for the LB films. The π-A and ΔV-A isotherms and BAM images indicate a phase transition at a surface pressure of ca. 9 mN/m and a multilayer formation at surface pressures around 19–20 mN/m; at a surface pressure around 27 mN/m a disordered collapse of the film occurs. In addition, AFM images of LB films at π = 10 mN/m and π = 20 mN/m show a monomolecular and a multilayered film, respectively. The comparison of the UV–vis spectrum of ZnPc in solution, the reflection spectra of the Langmuir films and UV–vis spectra of LB films reveals a significant reduction in the Q band intensity for the films, indicative of an organization of ZnPc in the Langmuir and LB films versus the random distribution in solution. The UV–vis Reflection spectra are also consistent with multilayer formation at surface pressures around 19–20 mN/m. The relative intensities of the IR spectrum bands change from the KBr pellet to the LB film which is also attributable to orientation effects in the film. Cyclic voltammetric experiments of LB films incorporating the ZnPc derivative show peaks that can be correlated with redox processes occurring in the phthalocyanine ring. A small but significant influence of the surface pressure and the number of deposited layers in the electrochemical behaviour is observed. The electrochemical response of cast films exhibits some differences with respect to that of LB films which have been attributed to their different molecular

  20. 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

  1. Enantioselective small molecule synthesis by carbon dioxide fixation using a dual Brønsted acid/base organocatalyst.

    Science.gov (United States)

    Vara, Brandon A; Struble, Thomas J; Wang, Weiwei; Dobish, Mark C; Johnston, Jeffrey N

    2015-06-17

    Carbon dioxide exhibits many of the qualities of an ideal reagent: it is nontoxic, plentiful, and inexpensive. Unlike other gaseous reagents, however, it has found limited use in enantioselective synthesis. Moreover, unprecedented is a tool that merges one of the simplest biological approaches to catalysis-Brønsted acid/base activation-with this abundant reagent. We describe a metal-free small molecule catalyst that achieves the three component reaction between a homoallylic alcohol, carbon dioxide, and an electrophilic source of iodine. Cyclic carbonates are formed enantioselectively.

  2. 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.

  3. 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.

  4. Interface properties of Fe/MgO/Cu-phthalocyanine metal-insulator-organic semiconductor structures

    International Nuclear Information System (INIS)

    Lee, Nyunjong; Bae, Yujeong; Kim, Taehee; Ito, Eisuke; Hara, Masahiko

    2014-01-01

    Hybrid interface structures consisting of organic copper-phthalocyanine (CuPc) and ferromagnetic metal Fe(001) with and without a MgO(001) cover were investigated by using surface sensitive techniques of X-ray photoemission spectroscopy and ultraviolet photoemission spectroscopy. A systematic study of the energy level alignment at the interfaces was carried out. For the hybrid interfaces considered here, our results indicate that the insertion of an artificially-grown ultra-thin oxide layer MgO(001) can prevent Femi level pinning and induce a rather large interface dipole, thereby resulting in remarkable CuPc Fermi level shifts when the thickness of the CuPc film is less than 3 nm. This study provides a better understanding of spin filtering in MgO-based organic spin devices and a new way to alter the interface electronic structure of metal/organic semiconductor hybrid systems.

  5. On the mechanism of pulsed laser ablation of phthalocyanine nanoparticles in an aqueous medium

    Science.gov (United States)

    Kogan, Boris; Malimonenko, Nicholas; Butenin, Alexander; Novoseletsky, Nicholas; Chizhikov, Sergei

    2018-06-01

    Laser ablation of phthalocyanine nanoparticles has potential for cancer treatment. The ablation is accompanied by the formation of microbubbles and the sublimation of nanoparticles. This was investigated in a liquid medium simulating tissue using optical-acoustic and spectral-luminescent methods. The thresholds for the appearance of microbubbles have been determined as a function of nanoparticle size. For the minimal size particles (80 nm) this threshold is equal to about 20–25 mJ cm‑2 and for the maximal size particles (230 nm) this threshold is equal to about 7 mJ cm‑2. It was estimated that the particle temperature at which bubbles arise is near 145 °С.

  6. Nonvolatile organic write-once-read-many-times memory devices based on hexadecafluoro-copper-phthalocyanine

    Science.gov (United States)

    Wang, Lidan; Su, Zisheng; Wang, Cheng

    2012-05-01

    Nonvolatile organic write-once-read-many-times memory device was demonstrated based on hexadecafluoro-copper-phthalocyanine (F16CuPc) single layer sandwiched between indium tin oxide (ITO) anode and Al cathode. The as fabricated device remains in ON state and it can be tuned to OFF state by applying a reverse bias. The ON/OFF current ratio of the device can reach up to 2.3 × 103. Simultaneously, the device shows long-term storage stability and long retention time in air. The ON/OFF transition is attributed to the formation and destruction of the interfacial dipole layer in the ITO/F16CuPc interface, and such a mechanism is different from previously reported ones.

  7. Studies on the Electrical and Optical Properties of Magnesium Phthalocyanine Thin Films

    Directory of Open Access Journals (Sweden)

    T. G. Gopinathan

    2004-01-01

    Full Text Available Thin films of Magnesium Phthalocyanine (MgPc are prepared by thermal evaporation technique at a base pressure of 10-5 m.bar on thoroughly cleaned glass substrates kept at different constant temperatures. Films of thickness 2400 A.U. coated at room temperature are subjected to post deposition annealing in air by keeping them in a furnace at different constant temperatures, for one hour. The electrical conductivity studies are conducted in the temperature range 300 K to 525 K. The electrical conductivity is plotted as a function of absolute temperature. The conduction mechanism is observed to be hopping. The thermal activation energy is calculated in different cases and is observed to vary with substrate temperature and annealing temperature. A phase change is observed due to post-deposition annealing at around 523 K. The optical absorption studies are done in the UV-Visible region. The optical band gap energies of the samples are calculated.

  8. Titanyl phthalocyanine ambipolar thin film transistors making use of carbon nanotube electrodes

    Science.gov (United States)

    Coppedè, Nicola; Valitova, Irina; Mahvash, Farzaneh; Tarabella, Giuseppe; Ranzieri, Paolo; Iannotta, Salvatore; Santato, Clara; Martel, Richard; Cicoira, Fabio

    2014-12-01

    The capability of efficiently injecting charge carriers into organic films and finely tuning their morphology and structure is crucial to improve the performance of organic thin film transistors (OTFTs). In this work, we investigate OTFTs employing carbon nanotubes (CNTs) as the source-drain electrodes and, as the organic semiconductor, thin films of titanyl phthalocyanine (TiOPc) grown by supersonic molecular beam deposition (SuMBD). While CNT electrodes have shown an unprecedented ability to improve charge injection in OTFTs, SuMBD is an effective technique to tune film morphology and structure. Varying the substrate temperature during deposition, we were able to grow both amorphous (low substrate temperature) and polycrystalline (high substrate temperature) films of TiOPc. Regardless of the film morphology and structure, CNT electrodes led to superior charge injection and transport performance with respect to benchmark Au electrodes. Vacuum annealing of polycrystalline TiOPc films with CNT electrodes yielded ambipolar OTFTs.

  9. Titanyl phthalocyanine ambipolar thin film transistors making use of carbon nanotube electrodes

    International Nuclear Information System (INIS)

    Coppedè, Nicola; Tarabella, Giuseppe; Ranzieri, Paolo; Iannotta, Salvatore; Valitova, Irina; Cicoira, Fabio; Mahvash, Farzaneh; Santato, Clara; Martel, Richard

    2014-01-01

    The capability of efficiently injecting charge carriers into organic films and finely tuning their morphology and structure is crucial to improve the performance of organic thin film transistors (OTFTs). In this work, we investigate OTFTs employing carbon nanotubes (CNTs) as the source-drain electrodes and, as the organic semiconductor, thin films of titanyl phthalocyanine (TiOPc) grown by supersonic molecular beam deposition (SuMBD). While CNT electrodes have shown an unprecedented ability to improve charge injection in OTFTs, SuMBD is an effective technique to tune film morphology and structure. Varying the substrate temperature during deposition, we were able to grow both amorphous (low substrate temperature) and polycrystalline (high substrate temperature) films of TiOPc. Regardless of the film morphology and structure, CNT electrodes led to superior charge injection and transport performance with respect to benchmark Au electrodes. Vacuum annealing of polycrystalline TiOPc films with CNT electrodes yielded ambipolar OTFTs. (paper)

  10. 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}.

  11. High-efficiency THz modulator based on phthalocyanine-compound organic films

    International Nuclear Information System (INIS)

    He, Ting; Zhang, Bo; Shen, Jingling; Zang, Mengdi; Chen, Tianji; Hu, Yufeng; Hou, Yanbing

    2015-01-01

    We report a high efficiency, broadband terahertz (THz) modulator following a study of phthalocyanine-compound organic films irradiated with an external excitation laser. Both transmission and reflection modulations of each organic/silicon bilayers were measured using THz time-domain and continuous-wave systems. For very low intensities, the experimental results show that AlClPc/Si can achieve a high modulation factor for transmission and reflection, indicating that AlClPc/Si has a superior modulation efficiency compared with the other films (CuPc and SnCl 2 Pc). In contrast, the strong attenuation of the transmitted and reflected THz waves revealed that a nonlinear absorption process takes place at the organic/silicon interface

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1980-01-01

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

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

    DEFF Research Database (Denmark)

    Shen, Kongchao; Narsu, Bai; Ji, Gengwu

    2017-01-01

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

  14. Quinoline-substituted Zinc(II) phthalocyanine for the dual detection of ferric and zinc ions

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Ankush [Lyallpur Khalsa College of Engineering, Jalandhar (India); Kim, A Rong [Dong-A University, Busan (Korea, Republic of); Kim, Kyung Sub; Na, Kun [The Catholic University, Seoul (Korea, Republic of); Choi, Myung Seok [Konkuk University, Seoul (Korea, Republic of); Park, Jong S. [Pusan National University, Busan (Korea, Republic of)

    2015-09-15

    Here we present the synthesis and properties of quinoline-substituted zinc(II) phthalocyanine, Zn[Pc(O-QN){sub 4} ]. Zn[Pc(O-QN){sub 4} ] can function as a highly selective chemosensor against Fe{sup 3+} and Zn{sup 2+} ions, exhibiting efficient fluorescence quenching and enhancement, respectively. Various characterization techniques were employed to investigate the intermolecular interactions of Zn[Pc(O-QN){sub 4} ] with metal ions. A double-electron exchange and a forbidden photoinduced electron transfer behavior in Zn[Pc(O-QN){sub 4} ] were attributed to such opposite responses. Furthermore, by taking advantage of selectivity, we successfully employed Zn[Pc(O-QN)-4 ] to stain and record confocal fluorescence microscopy images of Chang liver cells in the presence of metal ions.

  15. Micro-Encapsulated Porphyrins and Phthalocyanines - New Formulations in Photodynamic Therapy

    Science.gov (United States)

    Ion, R. M.

    2017-06-01

    Photodynamic therapy (PDT), as an innovative method for cancer tretament is based on a concerted action of some drugs, called sensitizers, which generate reactive oxygen species via a photochemical mechanism, leading to cellular necrosis or apoptosis. The present work aims at loading some sensitizers, as porphyrins (P) and phthalocyanines (Pc) into alginate particles. Particles were prepared by dropping alginate into an aqueous solution containing P or Pc and CaCl2, which allows the formation of particles through ionic crosslinking. It was obtained P or Pc loaded alginate beads with an average diameter of about 100 μm. For these systems, this paper analyses the spectroscopic properties, encapsulation into microcapsules, controlled releasing action and their photosensitizer capacity (singlet oxygen generation).

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

    Science.gov (United States)

    Sharma, Anshul Kumar; Kumar, Pankaj; Saini, Rajan; Bedi, R. K.; Mahajan, Aman

    2016-05-01

    A kind of hybrid material is prepared by functionalizing multi-wall carbon nanotubes (MWCNTs-COOH) with substituted copper phthalocyanine and the formation of CuPcOC8/MWCNTs-COOH hybrid is confirmed by scanning electron microscopy and transmission electron microscopy. The results indicated that on the surface of nanotubes substituted CuPcOC8 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 NO2, NO, Cl2 and NH3 at operating temperature of 150˚C. It has been demonstrated that for Cl2 minimum detection limit of CuPcOC8/MWCNTs-COOH hybrid is 100 ppb. The response of hybrid sensor is found to be increased with increase in the concentration of Cl2.

  17. 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.

  18. Phthalocyanine-loaded graphene nanoplatform for imaging-guided combinatorial phototherapy

    Directory of Open Access Journals (Sweden)

    Taratula O

    2015-03-01

    Full Text Available Olena Taratula,1 Mehulkumar Patel,2 Canan Schumann,1 Michael A Naleway,1 Addison J Pang,1 Huixin He,2 Oleh Taratula1 1Department of Pharmaceutical Sciences, College of Pharmacy, Oregon State University, Portland, OR, USA; 2Department of Chemistry, Rutgers University-Newark, Newark, NJ, USA Abstract: We report a novel cancer-targeted nanomedicine platform for imaging and prospect for future treatment of unresected ovarian cancer tumors by intraoperative multimodal phototherapy. To develop the required theranostic system, novel low-oxygen graphene nanosheets were chemically modified with polypropylenimine dendrimers loaded with phthalocyanine (Pc as a photosensitizer. Such a molecular design prevents fluorescence quenching of the Pc by graphene nanosheets, providing the possibility of fluorescence imaging. Furthermore, the developed nanoplatform was conjugated with poly(ethylene glycol, to improve biocompatibility, and with luteinizing hormone-releasing hormone (LHRH peptide, for tumor-targeted delivery. Notably, a low-power near-infrared (NIR irradiation of single wavelength was used for both heat generation by the graphene nanosheets (photothermal therapy [PTT] and for reactive oxygen species (ROS-production by Pc (photodynamic therapy [PDT]. The combinatorial phototherapy resulted in an enhanced destruction of ovarian cancer cells, with a killing efficacy of 90%–95% at low Pc and low-oxygen graphene dosages, presumably conferring cytotoxicity to the synergistic effects of generated ROS and mild hyperthermia. An animal study confirmed that Pc loaded into the nanoplatform can be employed as a NIR fluorescence agent for imaging-guided drug delivery. Hence, the newly developed Pc-graphene nanoplatform has the significant potential as an effective NIR theranostic probe for imaging and combinatorial phototherapy. Keywords: graphene nanosheets, phthalocyanine, photothermal therapy, photodynamic therapy, theranostic 

  19. Development and evaluation of zinc phthalocyanine nanoemulsions for use in photodynamic therapy for Leishmania spp.

    Science.gov (United States)

    Betzler de Oliveira de Siqueira, Luciana; da Silva Cardoso, Verônica; Almeida Rodrigues, Igor; Lúcia Vazquez-Villa, Ana; Pereira dos Santos, Elisabete; da Costa Leal Ribeiro Guimarães, Bruno; dos Santos Cerqueira Coutinho, Cristal; Vermelho, Alane Beatriz; Ricci Junior, Eduardo

    2017-02-01

    Photodynamic therapy (PDT) combines light with photosensitizers (PS) for production of reactive oxygen species (ROS) that can kill infectious microorganisms such as bacteria, fungi and protozoa. The application of nanotechnology has enabled the advancement of PDT because many PS are insoluble in water, necessitating a nanocarrier as a physiologically acceptable carrier. Nanoemulsions are efficient nanocarriers for solubilizing liposoluble drugs, like the PS, in water. Cutaneous (CL) and mucocutaneous leishmaniasis (ML) are caused by different species of the genus Leishmania, transmitted to humans by sandfly bites. Parasites are hosted in skin macrophages producing ulcerative lesions. Thus, a topical treatment, effective and inexpensive, for CL and ML is preferable to systemic interventions. There are topical treatments like paromomycin and amphotericin B, but they have many local side effects or a very high cost, limiting their use. This work aimed to develop a zinc phthalocyanine (photosensitizer) oil-in-water nanoemulsion, essential clove oil and polymeric surfactant (Pluronic® F127) for the formulation of a topical delivery system for use in PDT against Leishmania amazonensis and Leishmania infantum. The nanoemulsion was produced by a high-energy method and characterized by size, polydispersity, morphology, pH, content and stability studies. The toxicity in the dark and the photobiological activity of the formulations were evaluated in vitro for Leishmania and macrophages. The formulation presented was pH compatible with topical use, approximately 30 nm in size, with a polydispersity index ≤0.1 and remained stable at room and refrigerator temperature during the stability study (60 days). The zinc phthalocyanine nanoemulsion is effective in PDT against Leishmania spp.; use against skin infections can be a future application of this topical formulation, avoiding the use of oral or injectable medications, decreasing systemic adverse effects.

  20. Facile synthesis of pegylated zinc(II) phthalocyanines via transesterification and their in vitro photodynamic activities.

    Science.gov (United States)

    Bai, Ming; Lo, Pui-Chi; Ye, Jing; Wu, Chi; Fong, Wing-Ping; Ng, Dennis K P

    2011-10-21

    Treatment of 4,5-bis[4-(methoxycarbonyl)phenoxy]phthalonitrile and 4,5-bis[3,5-bis(methoxycarbonyl)phenoxy]phthalonitrile with an excess of 1,3-diiminoisoindoline in the presence of Zn(OAc)(2)·2H(2)O and 1,8-diazabicyclo[5.4.0]undec-7-ene in triethylene glycol monomethyl ether or polyethylene glycol monomethyl ether (with an average molecular weight of 550) led to "3 + 1" mixed cyclisation and transesterification in one pot, affording the corresponding di-β-substituted zinc(II) phthalocyanines in 7-23% yield. As shown by absorption spectroscopy, these compounds were essentially non-aggregated in N,N-dimethylformamide and could generate singlet oxygen effectively. The singlet oxygen quantum yields (Φ(Δ) = 0.53-0.57) were comparable with that of the unsubstituted zinc(II) phthalocyanine (Φ(Δ) = 0.56). These compounds in Cremophor EL emulsions also exhibited photocytotoxicity against HT29 human colorectal adenocarcinoma and HepG2 human hepatocarcinoma cells with IC(50) values in the range of 0.25-3.72 μM. The analogue with four triethylene glycol chains was the most potent photosensitiser and localised preferentially in the mitochondria of HT29 cells. The bis(polyethylene glycol)-counterpart could form surfactant-free nanoparticles both in water and in the culture medium. The hydrodynamic radii, as determined by dynamic laser light scattering, ranged from 6.3 to 79.8 nm depending on the preparation methods and conditions. The photocytotoxicity of these nanoparticles (IC(50) = 0.43-0.56 μM) was comparable with that of the Cremophor EL-formulated system (IC(50) = 0.34 μM).

  1. Flexible heterostructures based on metal phthalocyanines thin films obtained by MAPLE

    Energy Technology Data Exchange (ETDEWEB)

    Socol, M., E-mail: cela@infim.ro [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); Preda, N.; Rasoga, O. [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); Breazu, C. [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); University of Bucharest, Faculty of Physics, 405 Atomistilor Street, PO Box MG-11, 077125 Bucharest-Magurele (Romania); Stavarache, I. [National Institute of Material Physics, 105 bis Atomistilor Street, PO Box MG-7, 077125 Bucharest-Magurele (Romania); Stanculescu, F. [University of Bucharest, Faculty of Physics, 405 Atomistilor Street, PO Box MG-11, 077125 Bucharest-Magurele (Romania); Socol, G.; Gherendi, F.; Grumezescu, V.; Popescu-Pelin, G. [National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Street, PO Box MG-36, 077125 Bucharest-Magurele (Romania); Girtan, M. [Laboratoire de Photonique d’Angers, Université d’Angers, 2, Bd. Lavoisier, 49045 Angers (France); Stefan, N. [National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Street, PO Box MG-36, 077125 Bucharest-Magurele (Romania)

    2016-06-30

    Highlights: • Organic heterostructures prepared by MAPLE having a large absorbtion domain. • Photogeneration process is evidenced in the structure with ZnPc:TPyP mixed layer. • An increase in current value is observed in the structure with MgPc:TPyP mixed layer. - Abstract: Heterostructures based on zinc phthalocyanine (ZnPc), magnesium phthalocyanine (MgPc) and 5,10,15,20-tetra(4-pyrydil)21H,23H-porphine (TPyP) were deposited on ITO flexible substrates by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. Organic heterostructures containing (TPyP/ZnPc(MgPc)) stacked or (ZnPc(MgPc):TPyP) mixed layers were characterized by X-ray diffraction-XRD, photoluminescence-PL, UV–vis and FTIR spectroscopy. No chemical decomposition of the initial materials was observed. The investigated structures present a large spectral absorption in the visible range making them suitable for organic photovoltaics applications (OPV). Scanning electron microscopy-SEM and atomic force microscopy-AFM revealed morphologies typical for the films prepared by MAPLE. The current–voltage characteristics of the investigated structures, measured in dark and under light, present an improvement in the current value (∼3 order of magnitude larger) for the structure based on the mixed layer (Al/MgPc:TPyP/ITO) in comparison with the stacked layer (Al/MgPc//TPyP/ITO). A photogeneration process was evidenced in the case of structures Al/ZnPc:TPyP/ITO with mixed layers.

  2. Effect of diblock copolymer properties on the photophysical properties of dendrimer silicon phthalocyanine nanoconjugates

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Kuizhi [Fujian Normal University, College of Materials Science & Engineering, Fujian Provincial Key Laboratory of Polymer Materials (China); Pan, Sujuan [Fujian Normal University, College of Chemistry & Engineering (China); Zhuang, Xuemei [Fuzhou No.2 Hospital (China); Lv, Hafei; Que, Shoulin [Fujian Normal University, College of Chemistry & Engineering (China); Xie, Shusen; Yang, Hongqin, E-mail: hqyang@fjnu.edu.cn [Fujian Normal University, Key Laboratory of Optoelectronic Science and Technology for Medicine of Ministry of Education (China); Peng, Yiru, E-mail: yirupeng@fjnu.edu.cn [Fujian Normal University, College of Chemistry & Engineering (China)

    2016-07-15

    1–2 generation poly(benzyl aryl ether) dendrimer silicon phthalocyanines with axially disubstituted cyano terminal functionalities (G{sub n}-DSiPc(CN){sub 4n}, (G{sub n} = n-generation dendrimer, n = 1–2)) were synthesized. Their structures were characterized by elemental analysis, IR, {sup 1}H NMR, and ESI-MS. Polymeric nanoparticles (G{sub n}-DSiPc(CN){sub 4n}/m) were formed through encapsulating G{sub n}-DSiPc(CN){sub 4n} into three monomethoxyl poly(ethylene glycol)-poly(ε-caprolactone) diblock copolymers (MPEG–PCL) with different hydrophilic/hydrophobic proportion, respectively. The effect of dendritic generation and the hydrophilic/hydrophobic proportion of diblock copolymers on the UV/Vis and fluorescence spectra of G{sub n}-DSiPc(CN){sub 4n} and G{sub n}-DSiPc(CN){sub 4n}/m were studied. The photophysical properties of polymeric nanoparticles exhibited dendritic generation and hydrophilic/hydrophobic proportion dependence. The fluorescence intensities and lifetimes of G{sub n}-DSiPc(CN){sub 4n}/m were lower than the corresponding free dendrimer phthalocyanines. G{sub n}-DSiPc(CN){sub 4n} encapsulated into MPEG–PCL with hydrophilic/hydrophobic molecular weight ratio 2000:4000 exhibited excellent photophysical property. The mean diameter of MPEG{sub 2000}–PCL{sub 2000} micelles was about 70 nm, which decreased when loaded with G{sub n}-DSiPc(CN){sub 4n}.Graphical abstract .

  3. Flexible heterostructures based on metal phthalocyanines thin films obtained by MAPLE

    International Nuclear Information System (INIS)

    Socol, M.; Preda, N.; Rasoga, O.; Breazu, C.; Stavarache, I.; Stanculescu, F.; Socol, G.; Gherendi, F.; Grumezescu, V.; Popescu-Pelin, G.; Girtan, M.; Stefan, N.

    2016-01-01

    Highlights: • Organic heterostructures prepared by MAPLE having a large absorbtion domain. • Photogeneration process is evidenced in the structure with ZnPc:TPyP mixed layer. • An increase in current value is observed in the structure with MgPc:TPyP mixed layer. - Abstract: Heterostructures based on zinc phthalocyanine (ZnPc), magnesium phthalocyanine (MgPc) and 5,10,15,20-tetra(4-pyrydil)21H,23H-porphine (TPyP) were deposited on ITO flexible substrates by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. Organic heterostructures containing (TPyP/ZnPc(MgPc)) stacked or (ZnPc(MgPc):TPyP) mixed layers were characterized by X-ray diffraction-XRD, photoluminescence-PL, UV–vis and FTIR spectroscopy. No chemical decomposition of the initial materials was observed. The investigated structures present a large spectral absorption in the visible range making them suitable for organic photovoltaics applications (OPV). Scanning electron microscopy-SEM and atomic force microscopy-AFM revealed morphologies typical for the films prepared by MAPLE. The current–voltage characteristics of the investigated structures, measured in dark and under light, present an improvement in the current value (∼3 order of magnitude larger) for the structure based on the mixed layer (Al/MgPc:TPyP/ITO) in comparison with the stacked layer (Al/MgPc//TPyP/ITO). A photogeneration process was evidenced in the case of structures Al/ZnPc:TPyP/ITO with mixed layers.

  4. Formation of Ultracold Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Cote, Robin [Univ. of Connecticut, Storrs, CT (United States)

    2016-01-28

    Advances in our ability to slow down and cool atoms and molecules to ultracold temperatures have paved the way to a revolution in basic research on molecules. Ultracold molecules are sensitive of very weak interactions, even when separated by large distances, which allow studies of the effect of those interactions on the behavior of molecules. In this program, we have explored ways to form ultracold molecules starting from pairs of atoms that have already reached the ultracold regime. We devised methods that enhance the efficiency of ultracold molecule production, for example by tuning external magnetic fields and using appropriate laser excitations. We also investigates the properties of those ultracold molecules, especially their de-excitation into stable molecules. We studied the possibility of creating new classes of ultra-long range molecules, named macrodimers, thousand times more extended than regular molecules. Again, such objects are possible because ultra low temperatures prevent their breakup by collision. Finally, we carried out calculations on how chemical reactions are affected and modified at ultracold temperatures. Normally, reactions become less effective as the temperature decreases, but at ultracold temperatures, they can become very effective. We studied this counter-intuitive behavior for benchmark chemical reactions involving molecular hydrogen.

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

    Science.gov (United States)

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

    2015-01-01

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

  6. Combination of hyperthermia and photodynamic therapy on mesenchymal stem cell line treated with chloroaluminum phthalocyanine magnetic-nanoemulsion

    International Nuclear Information System (INIS)

    Paula, Leonardo B. de; Primo, Fernando L.; Pinto, Marcelo R.; Morais, Paulo C.

    2015-01-01

    The present study reports on the preparation and the cell viability assay of two nanoemulsions loaded with magnetic nanoparticle and chloroaluminum phthalocyanine. The preparations contain equal amount of chloroaluminum phthalocyanine (0.05 mg/mL) but different contents of magnetic nanoparticle (0.15×10 13 or 1.50×10 13 particle/mL). The human bone marrow mesenchymal stem cell line was used as the model to assess the cell viability and this type of cell can be used as a model to mimic cancer stem cells. The cell viability assays were performed in isolated as well as under combined magnetic hyperthermia and photodynamic therapy treatments. We found from the cell viability assay that under the hyperthermia treatment (1 MHz and 40 Oe magnetic field amplitude) the cell viability reduction was about 10%, regardless the magnetic nanoparticle content within the magnetic nanoparticle/chloroaluminum phthalocyanine formulation. However, cell viability reduction of about 50% and 60% were found while applying the photodynamic therapy treatment using the magnetic nanoparticle/chloroaluminum phthalocyanine formulation containing 0.15×10 13 or 1.50×10 13 magnetic particle/mL, respectively. Finally, an average reduction in cell viability of about 66% was found while combining the hyperthermia and photodynamic therapy treatments. - Highlights: • Current protocols in nanotechnology allow for biocompatible magnetic nanoparticles being associated with photosensitizer photoactive drugs, which could lead to perfectly controlled drug release. • The combination of the HPT and PDT therapies can be useful to develop further protocols for both advanced in vitro and in vivo assays. • Magnetic nanodevices associated with therapies have led to the decreased of proliferation of cell population that provides a favorable environment for tumor progression

  7. Combination of hyperthermia and photodynamic therapy on mesenchymal stem cell line treated with chloroaluminum phthalocyanine magnetic-nanoemulsion

    Energy Technology Data Exchange (ETDEWEB)

    Paula, Leonardo B. de [Departamento de Química, Centro de Nanotecnologia e Engenharia Tecidual, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14040-901 (Brazil); Departamento de Genética, Faculdade de Medicina de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14049-900 (Brazil); Primo, Fernando L. [Departamento de Química, Centro de Nanotecnologia e Engenharia Tecidual, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14040-901 (Brazil); Nanophoton Company, SUPERA Innovation and Technology Park, Av. Doutora Nadir de Aguiar, 1805, Universidade de São Paulo, Ribeirão Preto, P 14056-680 (Brazil); Pinto, Marcelo R. [Departamento de Química, Laboratório de Enzimologia, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP 14040-901 (Brazil); Morais, Paulo C. [Instituto de Física, Universidade de Brasília, Brasília, DF 70910-900 (Brazil); School of Automation, Huazhong University of Science and Technology, Wuhan 430074 (China); and others

    2015-04-15

    The present study reports on the preparation and the cell viability assay of two nanoemulsions loaded with magnetic nanoparticle and chloroaluminum phthalocyanine. The preparations contain equal amount of chloroaluminum phthalocyanine (0.05 mg/mL) but different contents of magnetic nanoparticle (0.15×10{sup 13} or 1.50×10{sup 13} particle/mL). The human bone marrow mesenchymal stem cell line was used as the model to assess the cell viability and this type of cell can be used as a model to mimic cancer stem cells. The cell viability assays were performed in isolated as well as under combined magnetic hyperthermia and photodynamic therapy treatments. We found from the cell viability assay that under the hyperthermia treatment (1 MHz and 40 Oe magnetic field amplitude) the cell viability reduction was about 10%, regardless the magnetic nanoparticle content within the magnetic nanoparticle/chloroaluminum phthalocyanine formulation. However, cell viability reduction of about 50% and 60% were found while applying the photodynamic therapy treatment using the magnetic nanoparticle/chloroaluminum phthalocyanine formulation containing 0.15×10{sup 13} or 1.50×10{sup 13} magnetic particle/mL, respectively. Finally, an average reduction in cell viability of about 66% was found while combining the hyperthermia and photodynamic therapy treatments. - Highlights: • Current protocols in nanotechnology allow for biocompatible magnetic nanoparticles being associated with photosensitizer photoactive drugs, which could lead to perfectly controlled drug release. • The combination of the HPT and PDT therapies can be useful to develop further protocols for both advanced in vitro and in vivo assays. • Magnetic nanodevices associated with therapies have led to the decreased of proliferation of cell population that provides a favorable environment for tumor progression.

  8. Evaluation of Topical Photodynamic Therapy of Mammary Carcinoma with an Experimental Gel Containing Liposomal Hydroxyl-aluminium Phthalocyanine

    Czech Academy of Sciences Publication Activity Database

    Sutoris, K.; Větvička, D.; Horák, L.; Beneš, J.; Nekvasil, Miloš; Ježek, Petr; Zadinová, M.; Poučková, P.

    2012-01-01

    Roč. 32, č. 9 (2012), s. 3769-3774 ISSN 0250-7005 R&D Projects: GA MPO(CZ) 2A-1TP1/026; GA MŠk(CZ) OE09026; GA TA ČR(CZ) TA01010781 Institutional research plan: CEZ:AV0Z50110509 Institutional support: RVO:67985823 Keywords : photodynamic therapy * phthalocyanine * liposomal sensitizer Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 1.713, year: 2012

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

    Science.gov (United States)

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

    2017-07-25

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

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

    KAUST Repository

    Ziani, Ahmed

    2016-11-04

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-02-01

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

  12. Study of charge transfer processes in porphyrins- and phthalocyanins-based materials: from the liquid phase to the solid state

    International Nuclear Information System (INIS)

    Fournier, Thierry

    1994-01-01

    In order to efficiently conceive and build supramolecular materials for molecular electronics and optoelectronics, one need to have access to a large data base on the interactions between the elementary pieces of the material. Such a data base can be established only through the study of model Systems and model media. Oligomers of porphyrins and phthalocyanines constitute models of choice: due to the chemical versatility of the compounds, their physical and photophysical properties can be adjusted to produce a targeted function. The first part of this thesis is concerned with double- and triple-Decker mixed porphyrin and Phthalocyanines sandwich compounds of cerium. Then we study the photophysical properties of complexes formed by pairing in solution porphyrins and phthalocyanines bearing oppositely charged substituents. The charge transfer reactions and geminated recombinations are investigated by time-resolved absorption spectroscopy (from the femto- to millisecond time scales) for excited complexes either in solution, or confined in sol-gel matrices or in Langmuir-Blodgett films. The results obtained in the various media are compared and analysed by the Marcus theory. They allow to show that, for strongly coupled complexes, the solvent does not play any key role in the forward and backward electron transfer. We conclude this work by introducing a few targeted projects based on of the photophysical properties of these complexes, namely photodynamic therapy of cancers, nonlinear optics and the generation of photovoltage. (author) [fr

  13. Effect of pentacene/Ag anode buffer and UV-ozone treatment on durability of small-molecule organic solar cells

    International Nuclear Information System (INIS)

    Inagaki, S; Sueoka, S; Harafuji, K

    2017-01-01

    Three surface modifications of indium tin oxide (ITO) are experimentally investigated to improve the performance of small-molecule organic solar cells (OSCs) with an ITO/anode buffer layer (ABL)/copper phthalocyanine (CuPc)/fullerene/bathocuproine/Ag structure. An ultrathin Ag ABL and ultraviolet (UV)-ozone treatment of ITO independently improve the durability of OSCs against illumination stress. The thin pentacene ABL provides good ohmic contact between the ITO and the CuPc layer, thereby producing a large short-circuit current. The combined use of the abovementioned three modifications collectively achieves both better initial performance and durability against illumination stress. (paper)

  14. Effect of pentacene/Ag anode buffer and UV-ozone treatment on durability of small-molecule organic solar cells

    Science.gov (United States)

    Inagaki, S.; Sueoka, S.; Harafuji, K.

    2017-06-01

    Three surface modifications of indium tin oxide (ITO) are experimentally investigated to improve the performance of small-molecule organic solar cells (OSCs) with an ITO/anode buffer layer (ABL)/copper phthalocyanine (CuPc)/fullerene/bathocuproine/Ag structure. An ultrathin Ag ABL and ultraviolet (UV)-ozone treatment of ITO independently improve the durability of OSCs against illumination stress. The thin pentacene ABL provides good ohmic contact between the ITO and the CuPc layer, thereby producing a large short-circuit current. The combined use of the abovementioned three modifications collectively achieves both better initial performance and durability against illumination stress.

  15. The status of molecules

    International Nuclear Information System (INIS)

    Barnes, T.; Oak Ridge National Lab., TN; Tennessee Univ., Knoxville, TN

    1994-06-01

    This report summarizes the experimental and theoretical status of hadronic molecules, which are weakly-bound states of two or more hadrons. We begin with a brief history of the subject and discuss a few good candidates, and then abstract some signatures for molecules which may be of interest in the classification of possible molecule states. Next we argue that a more general understanding of 2 → 2 hadron-hadron scattering amplitudes will be crucial for molecule searches, and discuss some of our recent work in this area. We conclude with a discussion of a few more recent molecule candidates (notably the f o (1710)) which are not well established as molecules but satisfy some of the expected signatures. (Author)

  16. Transition-metal-free synthesis of imidazo[2,1-b]thiazoles and thiazolo[3,2-a]benzimidazoles via an S-propargylation/5-exo-dig cyclization/isomerization sequence using propargyl tosylates as substrates.

    Science.gov (United States)

    Omar, Mohamed A; Frey, Wolfgang; Conrad, Jürgen; Beifuss, Uwe

    2014-11-07

    A transition-metal-free route for the synthesis of several N-fused heterocycles, including thiazolo[3,2-a]benzimidazoles and imidazo[2,1-b]thiazoles, is reported. The reaction between propargyl tosylates and 2-mercaptobenzimidazoles under basic conditions results in 3-substituted thiazolo[3,2-a]benzimidazoles, in yields up to 92% in a single synthesis step. With 2-mercaptoimidazoles as the substrate, the corresponding imidazo[2,1-b]thiazoles were exclusively obtained. The transformation is considered to proceed as an intermolecular S-propargylation that is followed by 5-exo-dig ring closure and double-bond isomerization.

  17. Cold Rydberg molecules

    Science.gov (United States)

    Raithel, Georg; Zhao, Jianming

    2017-04-01

    Cold atomic systems have opened new frontiers at the interface of atomic and molecular physics. These include research on novel types of Rydberg molecules. Three types of molecules will be reviewed. Long-range, homonuclear Rydberg molecules, first predicted in [1] and observed in [2], are formed via low-energy electron scattering of the Rydberg electron from a ground-state atom within the Rydberg atom's volume. The binding mostly arises from S- and P-wave triplet scattering. We use a Fermi model that includes S-wave and P-wave singlet and triplet scattering, the fine structure coupling of the Rydberg atom and the hyperfine structure coupling of the 5S1/2 atom (in rubidium [3]). The hyperfine structure gives rise to mixed singlet-triplet potentials for both low-L and high-L Rydberg molecules [3]. A classification into Hund's cases [3, 4, 5] will be discussed. The talk further includes results on adiabatic potentials and adiabatic states of Rydberg-Rydberg molecules in Rb and Cs. These molecules, which have even larger bonding length than Rydberg-ground molecules, are formed via electrostatic multipole interactions. The leading interaction term of neutral Rydberg-Rydberg molecules is between two dipoles, while for ionic Rydberg molecules it is between a dipole and a monopole. NSF (PHY-1506093), NNSF of China (61475123).

  18. Inter-molecule interaction for magnetic property of vanadyl tetrakis(thiadiazole) porphyrazine film on Au(1 1 1)

    Science.gov (United States)

    Hou, Jie; Wang, Yu; Eguchi, Keitaro; Nanjo, Chihiro; Takaoka, Tsuyoshi; Sainoo, Yasuyuki; Awaga, Kunio; Komeda, Tadahiro

    2018-05-01

    We report scanning tunneling microscope (STM) observation of vanadyl tetrakis(thiadiazole) porphyrazine (VOTTDPz) molecules, which is a family molecule of phthalocyanine (Pc) but without Csbnd H termination in the perimeter, deposited on Au(1 1 1) surface. Well-ordered film corresponding to 4 × 4 superstructure with respect to Au(1 1 1) surface is formed, in which the centers of the molecules are separated by 1.12 nm, which is much smaller than that observed for a VOPc molecule on Au(1 1 1), due to the absence of Csbnd H termination. At the same time, the azimuthal angles of neighboring molecules rotate with each other by 30°. A contrast variation of bright and dark molecules is observed, which are interpreted as O-up and O-down molecules, respectively, based on the density functional theory simulation. Spin-polarized local density of states calculation shows spin-polarized V 3d state, which is delocalized over the ring. Spin detection is executed by measuring Kondo resonance in the tunneling spectroscopy near the Fermi level, which is caused by the interaction of an isolated spin and conduction electron of the substrate. We detected asymmetric and weak Kondo peak for out-of-plane outer magnetic field of 0 T, which becomes strong and symmetric peak at 5 T, which is understood by the shift of the spin center of the Kondo resonance from V 3d to delocalized π state in ring with the magnetic field.

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

    Directory of Open Access Journals (Sweden)

    Han Huang

    2016-09-01

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

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Tianjun Liu

    2012-05-01

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

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

    Directory of Open Access Journals (Sweden)

    A. Luna-Flores

    2017-01-01

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

  3. Molecule of the Month

    Indian Academy of Sciences (India)

    Atoms in a molecule generally prefer, particularly among the neighbouring ones, certain optimmn geometrical relationships. These are manifested in specific ranges of bond lengths, bond angles, torsion angles etc. As it always happens, chemists are interested in making molecules where these 'standard relationships' are ...

  4. Molecule of the Month

    Indian Academy of Sciences (India)

    Cyclo bu tadiene (1) has been one of the most popular molecules for experimentalists and theoreticians. This molecule is unstable as . it is antiaromatic ( 4,n electrons in a cyclic array). Even though some highly substituted cyclobutadienes, for example, compound 2 and the Fe(CO)3 complex of cyclobutadiene (3) are ...

  5. Single-Molecule Spectroscopy

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 20; Issue 2. Single-Molecule Spectroscopy: Every Molecule is Different! Kankan Bhattacharyya. General Article Volume 20 Issue 2 February 2015 pp 151-164. Fulltext. Click here to view fulltext PDF. Permanent link:

  6. Single molecule conductance

    NARCIS (Netherlands)

    Willems, R.

    2008-01-01

    This thesis represents an excursion into the world of molecular electronics, i.e. the field of research trying to use individual (organic) molecules as electronic components; in this work various experimental methods have been explored to connect individual molecules to metallic contacts and

  7. Molecules in stars

    International Nuclear Information System (INIS)

    Tsuji, T.

    1986-01-01

    Recently, research related to molecules in stars has rapidly expanded because of progress in related fields. For this reason, it is almost impossible to cover all the topics related to molecules in stars. Thus, here the authors focus their attention on molecules in the atmospheres of cool stars and do not cover in any detail topics related to circumstellar molecules originating from expanding envelopes located far from the stellar surface. However, the authors do discuss molecules in quasi-static circumstellar envelopes (a recently discovered new component of circumstellar envelopes) located near the stellar surface, since molecular lines originating from such envelopes show little velocity shift relative to photospheric lines, and hence they directly affect the interpretation and analysis of stellar spectra

  8. Metal-Free Catalytic Enantioselective C–B Bond Formation: (Pinacolato)boron Conjugate Additions to α,β-Unsaturated Ketones, Esters, Weinreb Amides and Aldehydes Promoted by Chiral N-Heterocyclic Carbenes

    Science.gov (United States)

    Wu, Hao; Radomkit, Suttipol; O’Brien, Jeannette M.; Hoveyda, Amir H.

    2012-01-01

    The first broadly applicable metal-free enantioselective method for boron conjugate addition (BCA) to α,β-unsaturated carbonyls is presented. The C–B bond forming reactions are promoted in the presence of 2.5–7.5 mol % of a readily accessible C1-symmetric chiral imidazolinium salt, which is converted, in situ, to the catalytically active diastereo- and enantiomerically pure N-heterocyclic carbene (NHC) by the common organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu). In addition to the commercially available bis(pinacolato)diboron [B2(pin)2], and in contrast to reactions with the less sterically demanding achiral NHCs, the presence of MeOH is required for high efficiency. Acyclic and cyclic α,β-unsaturated ketones, as well as acyclic esters, Weinreb amides and aldehydes can serve as suitable substrates; the desired β-boryl carbonyls are isolated in up to 94% yield and >98:2 enantiomer ratio (er). Transformations are often carried out at ambient temperature. In certain cases, such as when the relatively less reactive unsaturated amides are used, elevated temperatures are required (50–66 °C); nonetheless, reactions remain highly enantioselective. The utility of the NHC-catalyzed method is demonstrated through comparison with the alternative Cu-catalyzed protocols; in cases involving a polyfunctional substrate, unique profiles in chemoselectivity are exhibited by the metal-free approach (e.g., conjugate addition vs reaction with an alkyne, allene or aldehyde). PMID:22559866

  9. Transition-Metal-Free Diarylannulated Sulfide and Selenide Construction via Radical/Anion-Mediated Sulfur-Iodine and Selenium-Iodine Exchange.

    Science.gov (United States)

    Wang, Ming; Fan, Qiaoling; Jiang, Xuefeng

    2016-11-04

    A facile, straightforward protocol was established for diarylannulated sulfide and selenide construction through S-I and Se-I exchange without transition metal assistance. Elemental sulfur and selenium served as the chalcogen source. Diarylannulated sulfides were systematically achieved from a five- to eight-membered ring. A trisulfur radical anion was demonstrated as the initiator for this radical process via electron paramagnetic resonance (EPR) study. OFET molecules [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and [1]benzothieno[3,2-b][1]benzoselenophene (BTBS) were efficiently established.

  10. Dynamics of Activated Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mullin, Amy S. [Univ. of Maryland, College Park, MD (United States)

    2016-11-16

    Experimental studies have been performed to investigate the collisional energy transfer processes of gas-phase molecules that contain large amounts of internal energy. Such molecules are prototypes for molecules under high temperature conditions relevant in combustion and information about their energy transfer mechanisms is needed for a detailed understanding and modeling of the chemistry. We use high resolution transient IR absorption spectroscopy to measure the full, nascent product distributions for collisions of small bath molecules that relax highly vibrationally excited pyrazine molecules with E=38000 cm-1 of vibrational energy. To perform these studies, we developed new instrumentation based on modern IR light sources to expand our experimental capabilities to investigate new molecules as collision partners. This final report describes our research in four areas: the characterization of a new transient absorption spectrometer and the results of state-resolved collision studies of pyrazine(E) with HCl, methane and ammonia. Through this research we have gained fundamental new insights into the microscopic details of relatively large complex molecules at high energy as they undergo quenching collisions and redistribute their energy.

  11. Dissociation in small molecules

    International Nuclear Information System (INIS)

    Dehmer, P.M.

    1982-01-01

    The study of molecular dissociation processes is one of the most interesting areas of modern spectroscopy owing to the challenges presented bt even the simplest of diatomic molecules. This paper reviews the commonly used descriptions of molecular dissociation processes for diatomic molecules, the selection rules for predissociation, and a few of the principles to be remembered when one is forced to speculate about dissociation mechanisms in a new molecule. Some of these points will be illustrated by the example of dissociative ionization in O 2

  12. Single molecules and nanotechnology

    CERN Document Server

    Vogel, Horst

    2007-01-01

    This book focuses on recent advances in the rapidly evolving field of single molecule research. These advances are of importance for the investigation of biopolymers and cellular biochemical reactions, and are essential to the development of quantitative biology. Written by leading experts in the field, the articles cover a broad range of topics, including: quantum photonics of organic dyes and inorganic nanoparticles their use in detecting properties of single molecules the monitoring of single molecule (enzymatic) reactions single protein (un)folding in nanometer-sized confined volumes the dynamics of molecular interactions in biological cells The book is written for advanced students and scientists who wish to survey the concepts, techniques and results of single molecule research and assess them for their own scientific activities.

  13. Electron-molecule collisions

    CERN Document Server

    Takayanagi, Kazuo

    1984-01-01

    Scattering phenomena play an important role in modern physics. Many significant discoveries have been made through collision experiments. Amongst diverse kinds of collision systems, this book sheds light on the collision of an electron with a molecule. The electron-molecule collision provides a basic scattering problem. It is scattering by a nonspherical, multicentered composite particle with its centers having degrees of freedom of motion. The molecule can even disintegrate, Le., dissociate or ionize into fragments, some or all of which may also be molecules. Although it is a difficult problem, the recent theoretical, experimental, and computational progress has been so significant as to warrant publication of a book that specializes in this field. The progress owes partly to technical develop­ ments in measurements and computations. No less important has been the great and continuing stimulus from such fields of application as astrophysics, the physics of the earth's upper atmosphere, laser physics, radiat...

  14. Molecules to Materials

    Indian Academy of Sciences (India)

    evolved as a new line of thinking wherein a single molecule or perhaps a collection .... In photonic communication processes, laser light has to be modulated and .... The author wishes to thank G Rajaram for a critical reading of the manuscript.

  15. Single-Molecule Spectroscopy

    Indian Academy of Sciences (India)

    IAS Admin

    overall absorption spectrum of a molecule is a superposition of many such sharp lines .... dilute solution of the enzyme and the substrate over few drops of silicone oil placed ..... Near-field Scanning Optical Microscopy (NSOM): Development.

  16. Quantum dot molecules

    CERN Document Server

    Wu, Jiang

    2014-01-01

    This book reviews recent advances in the exciting and rapidly growing field of quantum dot molecules (QDMs). It offers state-of-the-art coverage of novel techniques and connects fundamental physical properties with device design.

  17. Molecule of the Month

    Indian Academy of Sciences (India)

    Molecule of the Month - Adamantane - A Plastic Piece of Diamond. J Chandrasekhar. Volume 16 Issue 12 ... Keywords. Adamantane; diamondoid systems; plastic crystals. ... Resonance – Journal of Science Education | News. © 2017 Indian ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-02-15

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

  19. ELECTROCATALYTIC ACTIVITY FOR O2 REDUCTION OF UNSUBSTITUTED AND PERCHLORINATED IRON PHTHALOCYANINES ADSORBED ON AMINO-TERMINATED MULTIWALLED CARBON NANOTUBES DEPOSITED ON GLASSY CARBON ELECTRODES

    OpenAIRE

    CAÑETE, PAULINA; SILVA, J. FRANCISCO; ZAGAL, JOSÉ H

    2014-01-01

    Amino-functionalized multiwalled carbon nanotubes (MWCNT-NH2) were modified with Fe phthalocyanine (FePc) and perchlorinated Fe phthalocyanine (16(Cl)FePc) and deposited on glassy carbon electrodes (GCE). The electrocatalytic activity of these hybrid electrodes was examined for the reduction of molecular oxygen in alkaline media (0.2 M NaOH) using stationary and rotating disk electrodes. Electrodes containing 16(Cl)FePc are more active than those containing FePc. Electrodes containing CNTs ar...

  20. Changes in the Spectral Features of Zinc Phthalocyanine Induced by Nitrogen Dioxide Gas in Solution and in Solid Polymer Nanofiber Media.

    Science.gov (United States)

    Zugle, Ruphino; Tetteh, Samuel

    2017-03-01

    The changes in the spectral features of zinc phthalocyanine in the visible domain as a result of its interaction with nitrogen dioxide gas were assessed in this work. This was done both in solution and when the phthalocyanine was incorporated into a solid polystyrene polymer nanofiber matrix. The spectral changes were found to be spontaneous and marked in both cases suggesting a rapid response criterion for the detection of the gas. In particular, the functionalised nano-fabric material could serve as a practical fire alarm system as it rapidly detects the nitrogen dioxide gas generated during burning.