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.

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

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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.

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.

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

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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.

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.

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.

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.

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

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.

A first-principles study of gas molecule adsorption on borophene

Directory of Open Access Journals (Sweden)

Tingting Liu

2017-12-01

Full Text Available Borophene, a new two-dimensional material, was recently synthesized. The unique anisotropic structure and excellent properties of borophene have attracted considerable research interest. This paper presents a first-principles study of the adsorption of gas molecules (CO, CO2, NH3, NO, NO2 and CH4 on borophene. The adsorption configurations, adsorption energies and electronic properties of the gas molecules absorpted on borophene are determined, and the mechanisms of the interactions between the gas molecules and borophene are evaluated. We find that CO, CO2, NH3, NO and NO2 are chemisorbed on borophene, while CH4 is physisorbed on borophene. Furthermore, our calculation also indicate that CO and CO2 are chemisorbed on borophene with moderate adsorption energy and NO, NO2 and NH3 are chemisorbed on borophene via strong covalent bonds. Moreover, CO is found as an electron donor, while CO2 an electron acceptor. The chemisorption of CO and CO2 on borophene increases the electrical conductivity, so It seems that borophene has the potential to be used in high-sensitivity CO and CO2 gas sensors.

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

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

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.

Oxygen- and nitrogen-chemisorbed carbon nanostructures for Z-scheme photocatalysis applications

International Nuclear Information System (INIS)

Qian Zhao; Pathak, Biswarup; Nisar, Jawad; Ahuja, Rajeev

2012-01-01

Here focusing on the very new experimental finding on carbon nanomaterials for solid-state electron mediator applications in Z-scheme photocatalysis, we have investigated different graphene-based nanostructures chemisorbed by various types and amounts of species such as oxygen (O), nitrogen (N) and hydroxyl (OH) and their electronic structures using density functional theory. The work functions of different nanostructures have also been investigated by us to evaluate their potential applications in Z-scheme photocatalysis for water splitting. The N-, O–N-, and N–N-chemisorbed graphene-based nanostructures (32 carbon atoms supercell, corresponding to lattice parameter of about 1 nm) are found promising to be utilized as electron mediators between reduction level and oxidation level of water splitting. The O- or OH-chemisorbed nanostructures have potential to be used as electron conductors between H 2 -evolving photocatalysts and the reduction level (H + /H 2 ). This systematic study is proposed to understand the properties of graphene-based carbon nanostructures in Z-scheme photocatalysis and guide experimentalists to develop better carbon-based nanomaterials for more efficient Z-scheme photocatalysis applications in the future.

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

Science.gov (United States)

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

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...

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.

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.

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

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.

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.

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

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.

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.

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.

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

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

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.

Surface reactivity and layer analysis of chemisorbed reaction films in ...

Indian Academy of Sciences (India)

Administrator

Surface reactivity and layer analysis of chemisorbed reaction films in ... in the nitrogen environment. Keywords. Surface reactivity ... sium (Na–K) compounds in the coating or core of the ..... Barkshire I R, Pruton M and Smith G C 1995 Appl. Sur.

Chemisorbed and physisorbed structures for 1,10-phenanthroline and dipyrido[3,2-a : 2 ',3 '-c]phenazine on au(111)

DEFF Research Database (Denmark)

Cafe, P.F.; Larsen, Allan G.; Yang, W.R.

2007-01-01

physisorbed structures are not pitted and fluctuate dynamically, involving aligned (4 x 4) surface domains with shortrange (ca. 20 molecules) order for PHEN but unaligned chains with medium-range (ca. 100 molecules) order for DPPZ. In contrast, the chemisorbed PHEN monolayers remain stable for days...... structures are optimized using plane-wave density-functional theory (DFT) calculations for the surface structure. Realistic binding energies are then obtained adding dispersive corrections determined using complete-active-space self-consistent field calculations using second-order perturbation theory (CASPT2......) applied to cluster-interaction models. A fine balance between the large adsorbate -adsorbate dispersive forces, adsorbate-surface dispersive forces, gold ligation energy, and surface mining energy is shown to dictate the observed phenomena, leading to high surface mobility and substrate/surface lattice...

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.

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.

Low-energy electron-induced dissociation in condensed-phase L-cysteine II: a comparative study on anion desorption from chemisorbed and physisorbed films

International Nuclear Information System (INIS)

Alizadeh, E.; Rowntree, P.A.; Massey, S.; Sanche, L.

2016-01-01

In recent years it has become apparent that dissociative attachment of low energy electrons (DEA) is important for the description of radiation damage to biologically relevant molecules and living cells. Due to its multifunctional structure, cysteine is becoming an ideal model molecule for investigating the complex interactions of proteins with metallic surfaces such as gold nanoparticles. We report herein the results of low-energy electron induced degradation of L-cysteine films, chemisorbed on a gold substrate via the thiol group or physisorbed into a clean gold surface. The data were recorded under ultra-high vacuum conditions at room temperature. Anion yields desorbed from these films by the impact of 0.5 to 19 eV electrons provide clear evidence of the efficient decomposition of this amino acid via dissociative electron attachment (i.e., from dissociation of intermediate transient anions located between 5 and 14 eV). The peaks in the desorbed-anion yield functions, associated with DEA, are superimposed on a continuously rising signal attributed to dipolar dissociation. Similar to the results previously observed from physisorbed films, light anionic species, with masses lower than 35 amu, have been detected. In addition, we measured for first time fragments at 14 amu (CH_2"-) and 15 amu (CH_3"-) desorbing from physisorbed films, as well as heavier fragments of mass 45 and 46 amu desorbing from chemisorbed films

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.

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.

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.

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.

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.

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.

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.

Photoelectron Diffraction Imaging for C2H2 and C2H4 Chemisorbed on Si(100) Reveals a New Bonding Configuration

International Nuclear Information System (INIS)

Xu, S. H.; Keeffe, M.; Yang, Y.; Chen, C.; Yu, M.; Lapeyre, G. J.; Rotenberg, E.; Denlinger, J.; Yates, J. T. Jr.

2000-01-01

A new adsorption site for adsorbed acetylene on Si(100) is observed by photoelectron imaging based on the holographic principle. The diffraction effects in the carbon 1s angle-resolved photoemission are inverted (including the small-cone method) to obtain an image of the atom's neighboring carbon. The chemisorbed acetylene molecule is bonded to four silicon surface atoms. In contrast to the C 2 H 2 case, the image for adsorbed C 2 H 4 shows it bonded to two Si surface atoms. (c) 2000 The American Physical Society

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

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.

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.

Density functional study the interaction of oxygen molecule with defect sites of graphene

Energy Technology Data Exchange (ETDEWEB)

Qi Xuejun [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Guo Xin, E-mail: guoxin@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Zheng Chuguang [State Key Laboratory of Coal Combustion, Wuhan 430074 (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer The defect sites existed on the graphite surface create active sites and enhance the reactivity of carbonaceous material. Black-Right-Pointing-Pointer Oxygen molecule more favor chemisorbed on the graphene surface contains defect sites than the perfect surface. Black-Right-Pointing-Pointer The single active oxygen atom adsorbed on the defect surfaces, it completely insert into the surface. - Abstract: The present article reports a theoretical study of oxygen interacted with graphene surface containing defect sites on the atomic level by employing the density functional theory combined with the graphene cluster model. It was founded that oxygen molecule prefers to be chemisorbed on the graphene surface containing defect sites compared to the perfect surface. The adsorption energy of O{sub 2} on the double defect site is about 2.5 times as large as that on the perfect graphene surface. Moreover, the oxygen molecule interacts with S-W defect site gives rise to stable epoxy structure, which pulling the carbon atom outward from the original site in the direction perpendicular to the surface. If the oxygen molecule is adsorbed on the single vacancy site, two C-O bonds are formed on the graphene surface. However, when the oxygen molecule is chemisorbed on the double vacancy site, the oxygen atoms substitute the missing carbon atom's position in the carbon plane and form a hexagonal structure on the graphene network. The results indicate that single active oxygen atom approaches the defect site, it's completely adsorbed in the plane and high energy is released. In all cases, the interaction of an oxygen atom with defect surface involves an exothermic process. The defect site creates active sites on the surface of graphene and produces catalytic effects during the process of oxidation of carbonaceous materials.

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.

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.

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

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

In situ polyphenyl derivatisation and the effect of thermal decomposition of adsorbed and chemisorbed polyphenyls on the structure of multi-wall carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Gergely, Andras, E-mail: doohan11@chemres.hu [Department of Surface Modification and Nanostructures, Institute of Nanochemistry and Catalysis, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary); Ujszaszy, Kalman [Mass Spectrometry Department, Institute of Structural Chemistry, Pusztaszeri ut 59-67, Chemical Research Center of the Hungarian Academy of Sciences, Budapest 1025 (Hungary); Peltz, Csaba [EGIS Pharmaceuticals PLC, Kereszturi ut 30-38, Budapest 1106 (Hungary); Kiraly, Peter; Tarkanyi, Gabor [NMR Spectroscopy Department, Institute of Structural Chemistry, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary); Mihaly, Judith [Department of Biological Nanochemistry, Institute of Nanochemistry and Catalysis, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary); Kalman, Erika [Department of Surface Modification and Nanostructures, Institute of Nanochemistry and Catalysis, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary)

2011-05-01

This study presents the exploitation of an alternative reaction route of deamination of arylamines to perform in situ derivatisation of multi-walled carbon nanotubes (MWCNTs) with polyphenyl (PPh) species of various masses. As a result of consecutive derivatisation, high conversion of PPh grafting of the MWCNTs was realised with the collateral outgrowth of physical modification with adsorbed additional PPhs. Applied derivatisation process exceeds the monolayer coverage related superficial saturation limitations in the overall grafting yield of the nanotubes. Thus, a linear relationship was recognized between the overall quantities of chemisorbed PPhs composed of D{sub 5}-phenylene oligomers and the applied excess of diazonium activated reagents, corresponding to {sup 2}H MAS NMR spectroscopy results. According to mass spectrometry (MS) investigations, uniform thermal decomposition of the chemisorbed PPhs modified MWCNTs was found besides the more intense and altered decomposition characteristic-featured adsorbate-chemisorbate PPhs contained MWCNTs during sequential pyrolysis under inert atmosphere. This is attributed to the pyrolysis provoked isomerisation, decomposition and the formation of adsorbed and chemisorbed PPh moieties. As a result, a mediated and an even more pronounced degradation in the order of graphitic lattice of the MWCNTs were evidenced in the adsorbate-chemisorbate and the chemisorbate PPhs contained samples by FT-Raman spectroscopy and transmission electron microscopy (TEM), respectively. {sup 2}H MAS NMR supplied results of relevant amount of deuterium in the chemisorbate PPh contained sample without traces of aromatic related MS detected volatile products, these allow us to conclude about a thermally stable derivatisation that is interpreted as an endohedral modification of the nanotubes.

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

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...

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.

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.

Methane reacts with heteropolyacids chemisorbed on silica to produce acetic acid under soft conditions

KAUST Repository

Sun, Miao; Abou-Hamad, Edy; Rossini, Aaron J.; Zhang, Jizhe; Lesage, Anne; Zhu, Haibo; Pelletier, Jeremie; Emsley, Lyndon; Caps, Valerie; Basset, Jean-Marie

2013-01-01

Selective functionalization of methane at moderate temperature is of crucial economic, environmental, and scientific importance. Here, we report that methane reacts with heteropolyacids (HPAs) chemisorbed on silica to produce acetic acid under soft

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.

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

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.

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

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

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.

Low-energy electron-induced dissociation in condensed-phase L-cysteine II: a comparative study on anion desorption from chemisorbed and physisorbed films

Science.gov (United States)

Alizadeh, Elahe; Massey, Sylvain; Sanche, Léon; Rowntree, Paul A.

2016-04-01

Due to its multifunctional structure, cysteine is becoming an ideal model molecule for investigating the complex interactions of proteins with metallic surfaces such as gold nanoparticles. We report herein the results of low-energy electron induced degradation of L-cysteine films, chemisorbed on a gold substrate via the thiol group or physisorbed into a clean gold surface. The data were recorded under ultra-high vacuum conditions at room temperature. Anion yields desorbed from these films by the impact of 0.5 to 19 eV electrons provide clear evidence of the efficient decomposition of this amino acid via dissociative electron attachment (i.e., from dissociation of intermediate transient anions located between 5 and 14 eV). The peaks in the desorbed-anion yield functions, associated with DEA, are superimposed on a continuously rising signal attributed to dipolar dissociation. Similar to the results previously observed from physisorbed films, light anionic species, with masses lower than 35 amu, have been detected. In addition, we measured for first time fragments at 14 amu (CH2-) and 15 amu (CH3-) desorbing from physisorbed films, as well as heavier fragments of mass 45 and 46 amu desorbing from chemisorbed films. Contribution to the Topical Issue "Low-Energy Interactions related to Atmospheric and Extreme Conditions", edited by S. Ptasinska, M. Smialek-Telega, A. Milosavljevic, B. Sivaraman.

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.)

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

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

Effect of chemisorbed surface species on the photocatalytic activity of TiO2 nanoparticulate films

International Nuclear Information System (INIS)

Cao Yaan; Yang Wensheng; Chen Yongmei; Du Hui; Yue, Polock

2004-01-01

TiO 2 sols prepared in acidic and basic medium were deposited into films by a spin coating method. Photodegradation experiments showed that photocatalytic activity of the films prepared from acidic sol was much higher than that from basic sol. It is identified that there are more chemisorbed species of CO 2 on the surface of the TiO 2 films from the basic sol than on the surface of the TiO 2 films from the acidic sol. The chemisorbed species of CO 2 reduce the concentration of active species such as hydroxyl group and bridging oxygen on surface of the TiO 2 film and contribute to the formation of surface electron traps in the band gap which are detrimental to charge separation, thus lowering the photocatalytic activity

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

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.

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.

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.

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.

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.

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

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

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

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

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.

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.

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.)

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.

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

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.

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.

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.

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

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.

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.

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.

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

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.

Infrared spectroscopy of physisorbed and chemisorbed N-2 in the Pt(111)(3x3)N-2 structure

DEFF Research Database (Denmark)

Gustafsson, K.; Karlberg, Gustav; Andersson, Sven

2007-01-01

Using infrared spectroscopy and low electron energy diffraction, we have investigated the adsorption of N-2, at 30 K, on the Pt(111) and the Pt(111)(1x1)H surfaces. At monolayer coverage, N-2 orders in commensurate (3x3) structures on both surfaces, and we propose that the unit cells contain four...... molecules in each case. The infrared spectra reveal that N-2 exclusively physisorbs on the Pt(111)(1x1)H surface, while both physisorbed and chemisorbed N-2 is detected on the Pt(111) surface. Physisorbed N-2 is the majority species in the latter case, and the two adsorption states show an almost identical...... uptake behavior, which indicates that they are intrinsic constituents of the growing (3x3) N-2 islands. An analysis of the infrared absorbance data, based on a simple scaling concept suggested by density functional theory calculations, supports a model in which the (3x3) unit cell contains one...

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.

Methane reacts with heteropolyacids chemisorbed on silica to produce acetic acid under soft conditions

KAUST Repository

Sun, Miao

2013-01-16

Selective functionalization of methane at moderate temperature is of crucial economic, environmental, and scientific importance. Here, we report that methane reacts with heteropolyacids (HPAs) chemisorbed on silica to produce acetic acid under soft conditions. Specially, when chemisorbed on silica, H 4SiW12O40, H3PW12O 40, H4SiMo12O40, and H 3PMo12O40 activate the primary C-H bond of methane at room temperature and atmospheric pressure. With these systems, acetic acid is produced directly from methane, in a single step, in the absence of Pd and without adding CO. Extensive surface characterization by solid-state NMR spectroscopy, IR spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy suggests that C-H activation of methane is triggered by the protons in the HPA-silica interface with concerted reduction of the Keggin cage, leading to water formation and hydration of the interface. This is the simplest and mildest way reported to date to functionalize methane. © 2012 American Chemical Society.

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.

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.)

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....

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.

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...

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

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

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

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...

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)

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.

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)

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

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) ...

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.

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.

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.

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

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

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.

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.

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.

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.

Temperature-dependent evolution of chemisorbed digermane in Ge thin film growth

International Nuclear Information System (INIS)

Eres, D.; Sharp, J.W.

1992-01-01

The formation and evolution of chemisorbed digermane layers in context with germanium thin film growth was investigated by time- resolved surface reflectometry. Modulation of the source gas supply made possible the separation and independent study of the temperature dependence of the adsorption and desorption processes. The regeneration of active sites by molecular hydrogen desorption was identified as the rate-limiting step at low substrate temperatures. A dynamic method of thin film growth was demonstrated by repetitively replenishing the active film growth sites regenerated between two successive source gas pulses. The film growth rate was shown to be related to the substrate temperature and the delay time between successive source gas pulses

Investigation into interaction of CO/sub 2/ molecules with zeolites by infrared spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Ignat' eva, L A; Levshin, L V; Chukin, G D; Efimenko, L V; Kozlova, T I [Moskovskij Gosudarstvennyj Univ. (USSR). Kafedra Optiki

1975-07-01

Interaction of CO/sub 2/ molecules with zeolites, particularly with SrNaJ was studied by infrared-spectroscopy. To obtain infrared-spectra the zeolites were pressed into tablets and were calcinated at 500 deg. In the spectra the bands of chemisorbed CO/sub 2/ absorption were found in the range 1300 - 1600 cm/sup -1/. The CO/sub 2/ molecule was found to be strongly deformed due to chemisorption. In terms of electronic structure of the zeolite crystalline skeleton several types of CO/sub 2/ molecules interaction with different active zeolites were found. The position of the high-frequency band of CO/sub 2/ absorption in zeolites spectra was found to be a linear function of electrostatic field of the cations.

Electrocatalytic hydrogenation of organic molecules on conductive new catalytic material

Energy Technology Data Exchange (ETDEWEB)

Tountian, D. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide; Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Brisach-Wittmeyer, A.; Menard, H. [Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Nkeng, P.; Poillerat, G. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide

2008-07-01

Electrocatalytic hydrogenation (ECH) of organic molecules is a process where chemisorbed hydrogen is produced by electroreduction of water which reacts with the species in bulk. Greater emphasis is being placed on improving the nature of the building material of the electrodes in order to increase ECH efficiency. The effectiveness of the ECH is known to be linked to the nature of electrode materials used and their adsorption properties. This work presented the effect of conductive support material on ECH. The conductive catalysts were obtained from tin dioxide which is chemically stable. Palladium was the catalytic metal used in this study. The production of chemisorbed hydrogen was shown to depend on the quantity of metallic nanoaggregates in electrical contact with the reticulated vitreous carbon use as electrode. The conductive support, F-doped tin dioxide, was obtained by the sol-gel method. The electrocatalysts were characterized by different methods as resistivity measurements, linear sweep voltammetry, XRD, SEM, TGA/DSC, and FTIR analysis. The effects of temperature and time of calcination were also investigated. The study showed that the F-doped SnO2 electrocatalyst appeared to increase the rate of phenol electrohydrogenation. It was concluded that the improved electrocatalytic activity of Pd/F-doped SnO2 can be attributed to the simultaneous polarization of all the metallic Pd nanoaggregates present on the surface as well as in the pores of the matrix by contact with RVC. This results in a better production of chemisorbed atomic hydrogen with a large number of adlienation points. 9 refs., 3 figs.

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.

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.

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 

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.

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

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.

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

Hydrogen Temperature-Programmed Desorption in Platinum Catalysts: Decomposition and Isotopic Exchange by Spillover Hydrogen of Chemisorbed Ammonia.

NARCIS (Netherlands)

Koningsberger, D.C.; Miller, J.T.; Meyers, B.L.; Barr, M.K.; Modica, F.S.

1996-01-01

H{2}-TPD of Pt/alumina catalysts display multiple hydrogendesorptions. In addition to chemisorbed hydrogen (Peak I) atapproximately 175}o{C, there is a small hydrogen desorption (PeakII) at about 250}o{C and a large, irreversible hydrogen desorption(Peak III) at 450}o{C. The quantity of hydrogen

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.

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.

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

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.

The nature of chemisorbates formed from ammonia on gold and palladium electrodes as discerned from surface-enhanced Raman spectroscopy

NARCIS (Netherlands)

Vooys, de A.C.A.; Mrozek, M.F.; Koper, M.T.M.; Santen, van R.A.; Veen, van J.A.R.; Weaver, M.J.

2001-01-01

The chemisorbates formed from ammonia-containing alkaline electrolyte on gold and palladium electrodes have been identified using surface-enhanced Raman spectroscopy (SERS). On gold, a potential-dependent band at ca. 365-385 cm(-1) is observed, consistent with the metal-nitrogen stretch for

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.

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.

Entropy and mobility of argon physically adsorbed on pure nickel oxide or containing chemisorbed phases

International Nuclear Information System (INIS)

Ranc, Rene

1960-01-01

This research thesis addresses the adsorption thermodynamic mechanism. It reports the calculation of the variations of differential entropy in order to determine the adsorption model for argon on nickel oxide at low temperatures. It is based on the use of De Boer and Kruyer method. The result does not reveal any important difference between a naked surface and a surface containing chemisorbed elements. The author discusses the various application of this entropy calculation [fr

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

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.

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 ...

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.

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.

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

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

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

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.

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.

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.

Ro-vibrational laser spectroscopy of ESD neutrals from chemisorbed species

International Nuclear Information System (INIS)

Burns, A.R.; Stechel, E.B.; Jennison, D.R.

1987-01-01

Ever since the introduction of intense tunable laser radiation, the fields of molecular spectroscopy and dynamics have expanded tremendously. Indeed, with each technical improvement in laser resolution and output power, new applications have emerged with correspondingly increased levels of sophistication and information. In the field of electron-stimulated desorption (ESD), not only has the utilization of lasers resulted in the detection of neutral species, which were previously difficult to observe without specially-designed analyzers, but also the quantum-specific nature of the resonant laser interaction with the neutrals has yielded valuable information concerning internal energies. In this article, we will discuss some of the experimental methods in the application of laser resonance-ionization spectroscopy (RIS) to the study of the ESD of neutrals, in particular, chemisorbed NO and CO desorption from Pt(111). We will also show how the detailed information obtained in these experiments has identified a new desorption mechanism

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

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

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.

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

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.

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.

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

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

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

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.

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.

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

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.

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.

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.

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)

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.

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.

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.

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.

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.

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.

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.

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

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.

Manipulation of polyatomic molecules with the scanning tunnelling microscope at room temperature: chlorobenzene adsorption and desorption from Si(111)-(7 x 7)

International Nuclear Information System (INIS)

Sloan, P A; Palmer, R E

2006-01-01

We report the imaging of chlorobenzene molecules chemisorbed on the Si(111)-(7 x 7) surface at room temperature with the scanning tunnelling microscope, and the desorption of the molecules by the tunnelling current. Detailed voltage-dependent imaging (at positive bias) allows the elucidation of the number and orientation of all the adsorbate configurations in the 7 x 7 unit cell. At negative bias the adsorbate was observed to affect the imaging properties of neighbouring half unit cells. The threshold voltage required for desorption of the chlorobenzene molecules was invariant to small changes in the tip-state, the adsorption site (corner adatom, middle adatom, faulted or unfaulted half of the unit cell) and the kind of doping of the substrate (n or p type)

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.

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.

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.

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)

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.

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

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.

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.

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...

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

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

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

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.

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.

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-11-09

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

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.

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.

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.

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

Infrared spectroscopy of model electrochemical interfaces in ultrahigh vacuum: some implications for ionic and chemisorbate solvation at electrode surfaces

Science.gov (United States)

Villegas, Ignacio; Kizhakevariam, Naushad; Weaver, Michael J.

1995-07-01

The utility of infrared reflection-absorption spectroscopy (IRAS) for examining structure and bonding for model electrochemical interfaces in ultrahigh vacuum (UHV) is illustrated, focusing specifically on the solvation of cations and chemisorbed carbon monoxide on Pt(111). These systems were chosen partly in view of the availability of IRAS data (albeit limited to chemisorbate vibrations) for the corresponding in-situ metal-solution interfaces, enabling direct spectral comparisons to be made with the "UHV electrochemical model" systems. Kelvin probe measurements of the metal-UHV surface potential changes (ΔΦ) attending alterations in the interfacial composition are also described: these provide the required link to the in-situ electrode potentials as well as yielding additional insight into surface solvation. Variations in the negative electronic charge density and, correspondingly, in the cation surface concentration (thereby mimicking charge-induced alterations in the electrode potential below the potential of zero charge) are achieved by potassium atom dosage onto Pt(111). Of the solvents selected for discussion here — deuterated water, methanol, and acetonitrile — the first two exhibit readily detectable vibrational bands which provide information on the ionic solvation structure. Progressively dosing these solvents onto Pt(111) in the presence of low potassium coverages yields marked alterations in the solvent vibrational bands which can be understood in terms of sequential cation solvation. Comparison between these spectra for methanol with analogous data for sequential methanol solvation of gas-phase alkali cations enables the influence of the interfacial environment to be assessed. The effects of solvating chemisorbed CO are illustrated for acetonitrile; the markedly larger shifts in CO frequencies and binding sites for dilute CO adlayers can be accounted for in terms of short-range coadsorbate interactions in addition to longer-range Stark effects

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

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

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)

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.

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)

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-02-15

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

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

Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates.

Science.gov (United States)

Wang, Zhijiang; Wu, Lina; Sun, Kun; Chen, Ting; Jiang, Zhaohua; Cheng, Tao; Goddard, William A

2018-05-23

We have explored functionalizing metal catalysts with surface ligands as an approach to facilitate electrochemical carbon dioxide reduction reaction (CO 2 RR). To provide a molecular level understanding of the mechanism by which this enhancement occurs, we combine in situ spectroscopy analysis with an interpretation based on quantum mechanics (QM) calculations. We find that a surface ligand can play a critical role in stabilizing the chemisorbed CO 2 , which facilitates CO 2 activation and leads to a 0.3 V decrease in the overpotential for carbon monoxide (CO) formation. Moreover, the presence of the surface ligand leads to nearly exclusive CO production. At -0.6 V (versus reversible hydrogen electrode, RHE), CO is the only significant product with a faradic efficiency of 93% and a current density of 1.9 mA cm -2 . This improvement corresponds to 53-fold enhancement in turnover frequency compared with the Ag nanoparticles (NPs) without surface ligands.

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.

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

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.

Quantitative positron annihilation studies in citrates, halides and oxyhalides chemisorbed on γ-alumina catalyst

International Nuclear Information System (INIS)

Luo, X.H.; Jean, Y.C.; Cheng, K.L.

1987-01-01

A quantitative study of the γ-alumina catalyst chemisorbed by nitrates, halides, and oxyhalides has been conducted with the positron annihilation spectroscopy (PAS). Catalysts containing Fe, Co, or Ni have been extensively used in chemical industry and petroleum refining. The positron or Ps annihilation can provide a profile information about the bulk, near surface, and void. It is an in-situ surface technique. The PAS technique has shown its capability to determine the nitrate or chloride in γ-alumina as low as 0.02% in solids. It is interesting to note that the PAS may offer the oxidation state information in solids. This is not surprising because the positron annihilation is sensitive to the electron density variation in environments. Positron annihilation models for halides and oxyhalides are proposed

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.

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.

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.

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).

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

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).

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

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.

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

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.

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.

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...

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.

Core Level Spectra of Organic Molecules Adsorbed on Graphene

Directory of Open Access Journals (Sweden)

Abhilash Ravikumar

2018-03-01

Full Text Available We perform first principle calculations based on density functional theory to investigate the effect of the adsorption of core-excited organic molecules on graphene. We simulate Near Edge X-ray absorption Fine Structure (NEXAFS and X-ray Photoemission Spectroscopy (XPS at the N and C edges for two moieties: pyridine and the pyridine radical on graphene, which exemplify two different adsorption characters. The modifications of molecular and graphene energy levels due to their interplay with the core-level excitation are discussed. We find that upon physisorption of pyridine, the binding energies of graphene close to the adsorption site reduce mildly, and the NEXAFS spectra of the molecule and graphene resemble those of gas phase pyridine and pristine graphene, respectively. However, the chemisorption of the pyridine radical is found to significantly alter these core excited spectra. The C 1s binding energy of the C atom of graphene participating in chemisorption increases by ∼1 eV, and the C atoms of graphene alternate to the adsorption site show a reduction in the binding energy. Analogously, these C atoms also show strong modifications in the NEXAFS spectra. The NEXAFS spectrum of the chemisorbed molecule is also modified as a result of hybridization with and screening by graphene. We eventually explore the electronic properties and magnetism of the system as a core-level excitation is adiabatically switched on.

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).

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.

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.

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.

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.

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

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.

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.

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

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.

HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

International Nuclear Information System (INIS)

Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

2004-01-01

We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

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

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

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.

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.

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.

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.

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)

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.

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.

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

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.

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

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...

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

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

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.

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

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

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

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

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)

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.

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

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

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.

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

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

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)

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

Limitations of superfluid helium droplets as host system revealed by electronic spectroscopy of embedded molecules

Energy Technology Data Exchange (ETDEWEB)

Premke, Tobias

2016-02-19

Superfluid helium nanodroplets serve a unique cryogenic host system ideal to prepare cold molecules and clusters. Structures as well as dynamic processes can be examined by means of high resolution spectroscopy. Dopant spectra are accompanied by helium-induced spectroscopic features which reveal information on the dopant to helium interaction. For this reason the experimental research focuses on the investigation of such helium-induced effects in order to provide new information on the microsolvation inside the droplets. Since the quantitative understanding of helium-induced spectral features is essential to interpret molecular spectra recorded in helium droplets, this study contributes further experimental details on microsolvation in superfluid helium droplets. For this purpose two contrary systems were examined by means of high resolution electronic spectroscopy. The first one, phthalocyanine (Pc), is a planar organic molecule offering a huge and planar surface to the helium atoms and thus, the non-superfluid helium solvation layer can form different structures. The second system is iodine and in contrast to Pc it is of simple molecular shape. That means that in this case different complex structures of the non-superfluid helium solvation layer and the dopant can be expected to be avoided. Thus, both molecules should show clear differences in their microsolvation behavior. In this work a detailed examination of different spectroscopic properties of phthalocyanine is given by means of fluorescence excitation and dispersed emission spectroscopy. It raises legitimate doubts about the assignment of experimentally observed signals to features predicted by the model of the microsolvation. Even though there are no experimental observations which disprove the empirical model for the solvation in helium droplets, an unambiguous assignment of the helium-induced spectroscopic structures is often not possible. In the second part of this work, the investigation of the

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.

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

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

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.

Sandwich-type mixed tetrapyrrole rare-earth triple-decker compounds. Effect of the coordination geometry on the single-molecule-magnet nature.

Science.gov (United States)

Kan, Jinglan; Wang, Hailong; Sun, Wei; Cao, Wei; Tao, Jun; Jiang, Jianzhuang

2013-08-05

Employment of the raise-by-one step method starting from M(TClPP)(acac) (acac = monoanion of acetylacetone) and [Pc(OPh)8]M'[Pc(OPh)8] led to the isolation and free modulation of the two rare-earth ions in the series of four mixed tetrapyrrole dysprosium sandwich complexes {(TClPP)M[Pc(OPh)8]M'[Pc(OPh)8]} [1-4; TClPP = dianion of meso-tetrakis(4-chlorophenyl)porphyrin; Pc(OPh)8 = dianion of 2,3,9,10,16,17,23,24-octa(phenoxyl)phthalocyanine; M-M' = Dy-Dy, Y-Dy, Dy-Y, and Y-Y]. Single-crystal X-ray diffraction analysis reveals different octacoordination geometries for the two metal ions in terms of the twist angle (defined as the rotation angle of one coordination square away from the eclipsed conformation with the other) between the two neighboring tetrapyrrole rings for the three dysprosium-containing isostructural triple-decker compounds, with the metal ion locating between an inner phthalocyanine ligand and an outer porphyrin ligand with a twist angle of 9.64-9.90° and the one between two phthalocyanine ligands of 25.12-25.30°. Systematic and comparative studies over the magnetic properties reveal magnetic-field-induced single-molecule magnet (SMM), SMM, and non-SMM nature for 1-3, respectively, indicating the dominant effect of the coordination geometry of the spin carrier, instead of the f-f interaction, on the magnetic properties. The present result will be helpful for the future design and synthesis of tetrapyrrole lanthanide SMMs with sandwich molecular structures.

An important rule for realizing metal → half-metal → semiconductor transition in single-molecule junctions

Science.gov (United States)

Zeng, Jing; Chen, Ke-Qiu; Long, Mengqiu

2017-06-01

Recently, Zhong et al (2015 Nano Lett. 15 8091) found that two additional hydrogen atoms can be adsorbed to the opposite aza-bridging nitrogen atoms of the manganese phthalocyanine (MnPc) macrocycle when exposed to H2. Thus the symmetry of the MnPc molecule is changed from 4-fold to 2-fold. Motivated by this recent experiment, we theoretically investigate a MnPc-based single-molecule junction in this work and propose a simple and reliable way to realize the transition of its electronic properties. On the basis of spin-polarized density-functional theory calculations combined with the Keldysh nonequilibrium Green’s technique, we find that the gradual hydrogenation in MnPc molecules gives rise to the changes of the hardness of the electron density and spin-selective orbital decoupling, which eventually leads to the realization of the first ever metal  →  half-metal  →  semiconductor transition behavior in single-molecule junctions. Analysis of molecular projected self-consistent Hamiltonian, Mulliken population, and local density of states also reveals an important rule for realizing this transition behavior. Our research confirms that the hydrogenation of MnPc molecules can realize various molecular functionalities in unitary material background.

An important rule for realizing metal → half-metal → semiconductor transition in single-molecule junctions

International Nuclear Information System (INIS)

Zeng, Jing; Chen, Ke-Qiu; Long, Mengqiu

2017-01-01

Recently, Zhong et al (2015 Nano Lett . 15 8091) found that two additional hydrogen atoms can be adsorbed to the opposite aza-bridging nitrogen atoms of the manganese phthalocyanine (MnPc) macrocycle when exposed to H 2 . Thus the symmetry of the MnPc molecule is changed from 4-fold to 2-fold. Motivated by this recent experiment, we theoretically investigate a MnPc-based single-molecule junction in this work and propose a simple and reliable way to realize the transition of its electronic properties. On the basis of spin-polarized density-functional theory calculations combined with the Keldysh nonequilibrium Green’s technique, we find that the gradual hydrogenation in MnPc molecules gives rise to the changes of the hardness of the electron density and spin-selective orbital decoupling, which eventually leads to the realization of the first ever metal  →  half-metal  →  semiconductor transition behavior in single-molecule junctions. Analysis of molecular projected self-consistent Hamiltonian, Mulliken population, and local density of states also reveals an important rule for realizing this transition behavior. Our research confirms that the hydrogenation of MnPc molecules can realize various molecular functionalities in unitary material background. (paper)

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)

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.

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.

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.

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

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.

Radiation synthesis and characterization of zinc phthalocyanine composite based on 2-hydroxyethyl methacrylate/methyl methacrylate copolymer

International Nuclear Information System (INIS)

Abdel Ghaffar, A.M.; Youssef, Tamer E.; Mohamed, Hanan H.

2016-01-01

The synthesis and characterization of new 2-hydroxyethyl methacrylate-co-methyl methacrylate/zinc phthalocyanine composite Poly(HEMA/MMA/ZnPc) is described for the first time in this study. The aim of this research is to present possibility of radiation synthesis of the newly zinc phthalocyanine composites as potential candidates for wide range of applications. Gel (%) and swelling for Poly(hydroxyethyl methacrylate) Poly(HEMA) and the based Poly(hydroxyethyl methacrylate/methyl methacrylate) copolymer Poly(HEMA/MMA) with different composition 100/0, 95/5, 90/10 and 80/20 wt % were evaluated. It was found that Poly(HEMA/MMA) copolymer with composition 95/5 wt % characterized by its high swelling property at pH 7.4. The prepared composites I and II Poly(HEMA/MMA/ZnPc) with composition (95/5/1 wt%) and (95/5/1.5 wt%) respectively have been characterized by FTIR and TGA. The effect of gamma irradiation on the chemical properties of composite I was described. It is observed that the Zinc phthalocyanine with low concentration 1 wt % enhance chemical, thermal properties and stabilization against gamma radiation of the prepared composite I. - Highlights: • The preparation of Poly(HEMA/MMA/ZnPc) by radiation forming modified composites. • The low concentration of ZcPc (1 or 1.5 wt %) lead to form outstanding properties. • These composites are a potential candidate for wide range of applications.

Radiation synthesis and characterization of zinc phthalocyanine composite based on 2-hydroxyethyl methacrylate/methyl methacrylate copolymer

Energy Technology Data Exchange (ETDEWEB)

Abdel Ghaffar, A.M., E-mail: am_abdelghaffar@yahoo.com [Radiation Research of Polymer Chemistry Department, Industrial Irradiation Division, National Center for Radiation Research and Technology, Atomic Energy Authority P.O. Box 29, Nasr City, Cairo (Egypt); Youssef, Tamer E. [Applied Organic Chemistry Department, Chemical Industries Research Division, National Research Center, Dokki, Cairo, 12622 (Egypt); Chemical and Materials Engineering Department, Faculty of Engineering, King Abdulaziz University, P.O. Box 80204, Jeddah, 21589 (Saudi Arabia); Mohamed, Hanan H. [Chemistry Department, Faculty of Science, Helwan University, Ain Helwan, Cairo (Egypt)

2016-08-01

The synthesis and characterization of new 2-hydroxyethyl methacrylate-co-methyl methacrylate/zinc phthalocyanine composite Poly(HEMA/MMA/ZnPc) is described for the first time in this study. The aim of this research is to present possibility of radiation synthesis of the newly zinc phthalocyanine composites as potential candidates for wide range of applications. Gel (%) and swelling for Poly(hydroxyethyl methacrylate) Poly(HEMA) and the based Poly(hydroxyethyl methacrylate/methyl methacrylate) copolymer Poly(HEMA/MMA) with different composition 100/0, 95/5, 90/10 and 80/20 wt % were evaluated. It was found that Poly(HEMA/MMA) copolymer with composition 95/5 wt % characterized by its high swelling property at pH 7.4. The prepared composites I and II Poly(HEMA/MMA/ZnPc) with composition (95/5/1 wt%) and (95/5/1.5 wt%) respectively have been characterized by FTIR and TGA. The effect of gamma irradiation on the chemical properties of composite I was described. It is observed that the Zinc phthalocyanine with low concentration 1 wt % enhance chemical, thermal properties and stabilization against gamma radiation of the prepared composite I. - Highlights: • The preparation of Poly(HEMA/MMA/ZnPc) by radiation forming modified composites. • The low concentration of ZcPc (1 or 1.5 wt %) lead to form outstanding properties. • These composites are a potential candidate for wide range of applications.

Bis(tri-n-hexylsilyl oxide) silicon phthalocyanine: a unique additive in ternary bulk heterojunction organic photovoltaic devices.

Science.gov (United States)

Lessard, Benoît H; Dang, Jeremy D; Grant, Trevor M; Gao, Dong; Seferos, Dwight S; Bender, Timothy P

2014-09-10

Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS)2-SiPc) as an additive in a P3HT:PC61BM cascade ternary bulk heterojunction organic photovoltaic (BHJ OPV) device results in an increase in the short circuit current (J(SC)) and efficiency (η(eff)) of up to 25% and 20%, respectively. The previous studies have attributed the increase in performance to the presence of (3HS)2-SiPc at the BHJ interface. In this study, we explored the molecular characteristics of (3HS)2-SiPc which makes it so effective in increasing the OPV device J(SC) and η(eff. Initially, we synthesized phthalocyanine-based additives using different core elements such as germanium and boron instead of silicon, each having similar frontier orbital energies compared to (3HS)2-SiPc and tested their effect on BHJ OPV device performance. We observed that addition of bis(tri-n-hexylsilyl oxide) germanium phthalocyanine ((3HS)2-GePc) or tri-n-hexylsilyl oxide boron subphthalocyanine (3HS-BsubPc) resulted in a nonstatistically significant increase in JSC and η(eff). Secondly, we kept the silicon phthalocyanine core and substituted the tri-n-hexylsilyl solubilizing groups with pentadecyl phenoxy groups and tested the resulting dye in a BHJ OPV. While an increase in JSC and η(eff) was observed at low (PDP)2-SiPc loadings, the increase was not as significant as (3HS)2-SiPc; therefore, (3HS)2-SiPc is a unique additive. During our study, we observed that (3HS)2-SiPc had an extraordinary tendency to crystallize compared to the other compounds in this study and our general experience. On the basis of this observation, we have offered a hypothesis that when (3HS)2-SiPc migrates to the P3HT:PC61BM interface the reason for its unique performance is not solely due to its frontier orbital energies but also might be due to a high driving force for crystallization.

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

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

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-08-31

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

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...

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.

Coupling between diffusion and orientation of pentacene molecules on an organic surface.

Science.gov (United States)

Rotter, Paul; Lechner, Barbara A J; Morherr, Antonia; Chisnall, David M; Ward, David J; Jardine, Andrew P; Ellis, John; Allison, William; Eckhardt, Bruno; Witte, Gregor

2016-04-01

The realization of efficient organic electronic devices requires the controlled preparation of molecular thin films and heterostructures. As top-down structuring methods such as lithography cannot be applied to van der Waals bound materials, surface diffusion becomes a structure-determining factor that requires microscopic understanding. Scanning probe techniques provide atomic resolution, but are limited to observations of slow movements, and therefore constrained to low temperatures. In contrast, the helium-3 spin-echo (HeSE) technique achieves spatial and time resolution on the nm and ps scale, respectively, thus enabling measurements at elevated temperatures. Here we use HeSE to unveil the intricate motion of pentacene admolecules diffusing on a chemisorbed monolayer of pentacene on Cu(110) that serves as a stable, well-ordered organic model surface. We find that pentacene moves along rails parallel and perpendicular to the surface molecules. The experimental data are explained by admolecule rotation that enables a switching between diffusion directions, which extends our molecular level understanding of diffusion in complex organic systems.

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...

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.

Structural and vibrational studies of clean and chemisorbed metal surfaces

International Nuclear Information System (INIS)

Jiang, Qing-Tang.

1992-01-01

Using Medium Energy Ion Scattering, we have studied the structural and vibrational properties of a number of clean and chemisorbed metal surfaces. The work presented in this thesis is mainly of a fundamental nature. However, it is believed that an atomistic understanding of the forces that affect surface structural and vibrational properties can have a beneficial impact on a large number of areas of applied nature. We find that the surface structure of Cu(001) follows the common trend for metal surfaces, where a small oscillatory relaxation exists beginning with a slight contraction in the top layer. In addition, the surface vibrational amplitude is enhanced (as s usually the case) by ∼80%. A detailed analysis of our data shows an unexpected anisotropy of the vibrational amplitude, such that the out-of-plane vibrational amplitude is 30% smaller than the in-plane vibrational amplitude. The unexpected results may imply a large tensile stress on Cu(001). Upon adsorption of 1/4 of a monolayer of S, a p(2 x 2)-S/Cu(001) surface is created. This submonolayer amount of S atoms makes the surface bulk-like, in which the anisotropy of the surface vibrations is removed and the first interlayer contraction is lifted. By comparing our model to earlier contradictory results on this controversial system. We find excellent agreement with a recent LEED study. The presence of 0.1 monolayer of Ca atoms on the Au(113) surface induces a drastic atomic rearrangements, in which half of the top layer Au atoms are missing and a (1 x 2) symmetry results. In addition, the first interlayer spacing of Au(113) is significantly reduced. Our results are discussed in terms of the energy balance between competing surface electronic charge densities

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....

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.

Manipulating the dipole layer of polar organic molecules on metal surfaces via different charge-transfer channels

Science.gov (United States)

Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Wang, Chin-Yung; Pi, Tun-Wen; Ishii, Hisao; Tang, S.-J.

The key properties of organic films such as energy level alignment (ELA), work functions, and injection barriers are closely linked to this dipole layer. Using angle resolved photoemission spectroscopy (ARPES), we systemically investigate the coverage-dependent work functions and spectra line shapes of occupied molecular orbital states of a polar molecule, chloroaluminium phthalocyanine (ClAlPc), grown on Ag(111) to show that the orientations of the first ClAlPc layer can be manipulated via the molecule deposition rate and post annealing, causing ELA at organic-metal interface to differ for about 0.3 eV between Cl-up and Cl-down configuration. Moreover, by comparing the experimental results with the calculations based on both gas-phase model and realistic model of ClAlPc on Ag(111) , we evidence that the different orientations of ClAlPc dipole layers lead to different charge-transfer channels between ClAlPc and Ag, a key factor that controls the ELA at organic-metal interface.

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...

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

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

Spins of adsorbed molecules investigated by the detection of Kondo resonance

Science.gov (United States)

Komeda, Tadahiro

2014-12-01

Surface magnetism has been one of the platforms to explore the magnetism in low dimensions. It is also a key component for the development of quantum information processes, which utilizes the spin degree of freedom. The Kondo resonance is a phenomenon that is caused by an interaction between an isolated spin and conduction electrons. First observed in the 1930s as an anomalous increase in the low-temperature resistance of metals embedded with magnetic atoms, the Kondo physics mainly studied the effects of bulk magnetic impurities in the resistivity. In the last 15 years it has undergone a revival by a scanning tunneling microscope (STM) which enables the measurement of the Kondo resonance at surfaces using an atomic scale point contact. The detection of the Kondo resonance can be a powerful tool to explore surface magnetism. In this article, I review recent studies of the surface spin of adsorbed molecules by the detection of the Kondo resonance. Researches on metal phthalocyanine (MPc) and porphyrin molecules will be examined. In addition, the Kondo resonance for double-decker lanthanoide Pc molecules will be discussed. Some of the double-decker Pc molecules show single-molecule magnet (SMM) behavior, which attracts attention as a material for electronic devices. For both classes, the ligand plays a crucial role in determining the parameters of the Kondo resonance, such as the Kondo temperature and the change of the shape from peak to Fano-dip. In addition, the spin in delocalized molecular orbital forms the Kondo resonance, which shows significant differences from the Kondo resonance formed by the metal spins. Since molecular orbital can be tuned in a flexible manner by the design of the molecule, the Kondo resonance formed by delocalized molecular orbital might expand the knowledge of this field.

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.

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.

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

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.

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.

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

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.

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

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

Chemistry at molecular junctions: Rotation and dissociation of O2 on the Ag(110) surface induced by a scanning tunneling microscope.

Science.gov (United States)

Roy, Sharani; Mujica, Vladimiro; Ratner, Mark A

2013-08-21

The scanning tunneling microscope (STM) is a fascinating tool used to perform chemical processes at the single-molecule level, including bond formation, bond breaking, and even chemical reactions. Hahn and Ho [J. Chem. Phys. 123, 214702 (2005)] performed controlled rotations and dissociations of single O2 molecules chemisorbed on the Ag(110) surface at precise bias voltages using STM. These threshold voltages were dependent on the direction of the bias voltage and the initial orientation of the chemisorbed molecule. They also observed an interesting voltage-direction-dependent and orientation-dependent pathway selectivity suggestive of mode-selective chemistry at molecular junctions, such that in one case the molecule underwent direct dissociation, whereas in the other case it underwent rotation-mediated dissociation. We present a detailed, first-principles-based theoretical study to investigate the mechanism of the tunneling-induced O2 dynamics, including the origin of the observed threshold voltages, the pathway dependence, and the rate of O2 dissociation. Results show a direct correspondence between the observed threshold voltage for a process and the activation energy for that process. The pathway selectivity arises from a competition between the voltage-modified barrier heights for rotation and dissociation, and the coupling strength of the tunneling electrons to the rotational and vibrational modes of the adsorbed molecule. Finally, we explore the "dipole" and "resonance" mechanisms of inelastic electron tunneling to elucidate the energy transfer between the tunneling electrons and chemisorbed O2.

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

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

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

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 

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.

Enhanced fluorescence of tetrasulfonated zinc phthalocyanine by graphene quantum dots and its application in molecular sensing/imaging.

Science.gov (United States)

Wang, Jian; Zhang, Yanjun; Ye, Jiqing; Jiang, Zhou

2017-06-01

When excited at 435 nm, tetra-sulfonate zinc phthalocyanine (ZnPcS 4 ) emitted dual fluorescence at 495 and 702 nm. The abnormal fluorescence at 495 nm was experimentally studied and analyzed in detail for the first time. The abnormal fluorescence at 495 nm was deduced to originate from triplet-triplet (T-T) energy transfer of excited phthalocyanine ( 3 *ZnPcS 4 ). Furthermore, graphene quantum dots (GQDs) enhanced the 495 nm fluorescence quantum yield (Q) of ZnPcS 4 . The fluorescence properties of ZnPcS 4 -GQDs conjugate were retained in a cellular environment. Based on the fluorescence of ZnPcS 4 -GQDs conjugate, we designed and prepared an Apt29/thrombin/Apt15 sandwich thrombin sensor with high specificity and affinity. This cost-saving, simple operational sensing strategy can be extended to use in sensing/imaging of other biomolecules. Copyright © 2016 John Wiley & Sons, Ltd.

Electron and Cooper-pair transport across a single magnetic molecule explored with a scanning tunneling microscope

Science.gov (United States)

Brand, J.; Gozdzik, S.; Néel, N.; Lado, J. L.; Fernández-Rossier, J.; Kröger, J.

2018-05-01

A scanning tunneling microscope is used to explore the evolution of electron and Cooper-pair transport across single Mn-phthalocyanine molecules adsorbed on Pb(111) from tunneling to contact ranges. Normal-metal as well as superconducting tips give rise to a gradual transition of the Bardeen-Cooper-Schrieffer energy gap in the tunneling range into a zero-energy resonance close to and at contact. Supporting transport calculations show that in the normal-metal-superconductor junctions this resonance reflects the merging of in-gap Yu-Shiba-Rusinov states as well as the onset of Andreev reflection. For the superconductor-superconductor contacts, the zero-energy resonance is rationalized in terms of a finite Josephson current that is carried by phase-dependent Andreev and Yu-Shiba-Rusinov levels.

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

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

Science.gov (United States)

Plint, Trevor; Lessard, Benoît H.; Bender, Timothy P.

2016-04-01

In this study, we have assessed the potential application of group 13 and 14 metal and metalloid phthalocyanines ((X)n-MPcs) and their axially substituted derivatives as hole-transporting layers in organic light emitting diodes (OLEDs). OLEDs studied herein have the generic structure of glass/ITO/(N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB) or (X)n-MPc)(50 nm)/Alq3 (60 nm)/LiF (1 nm)/Al (80 nm), where X is an axial substituent group. OLEDs using chloro aluminum phthalocyanine (Cl-AlPc) showed good peak luminance values of 2620 ± 113 cd/m2 at 11 V. To our knowledge, Cl-AlPc has not previously been shown to work as a hole transport material (HTL) in OLEDs. Conversely, the di-chlorides of silicon, germanium, and tin phthalocyanine (Cl2-SiPc, Cl2-GePc, and Cl2-SnPc, respectively) showed poor performance compared to Cl-AlPc, having peak luminances of only 38 ± 4 cd/m2 (12 V), 23 ± 1 cd/m2 (8.5 V), and 59 ± 5 cd/m2 (13.5 V), respectively. However, by performing a simple axial substitution of the chloride groups of Cl2-SiPc with pentafluorophenoxy groups, the resulting bis(pentafluorophenoxy) silicon phthalocyanine (F10-SiPc) containing OLED had a peak luminance of 5141 ± 941 cd/m2 (10 V), a two order of magnitude increase over its chlorinated precursor. This material showed OLED characteristics approaching those of a baseline OLED based on the well-studied triarylamine NPB. Attempts to attach the pentafluorophenoxy axial group to both SnPc and GePc were hindered by synthetic difficulties and low thermal stability, respectively. In light of the performance improvements observed by simple axial substitution of SiPc in OLEDs, the use of axially substituted MPcs in organic electronic devices remains of continuing interest to us and potentially the field in general.

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

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

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.)

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).

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 .

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

Fluorination of Metal Phthalocyanines: Single-Crystal Growth, Efficient N-Channel Organic Field-Effect Transistors, and Structure-Property Relationships

Science.gov (United States)

Jiang, Hui; Ye, Jun; Hu, Peng; Wei, Fengxia; Du, Kezhao; Wang, Ning; Ba, Te; Feng, Shuanglong; Kloc, Christian

2014-01-01

The fluorination of p-type metal phthalocyanines produces n-type semiconductors, allowing the design of organic electronic circuits that contain inexpensive heterojunctions made from chemically and thermally stable p- and n-type organic semiconductors. For the evaluation of close to intrinsic transport properties, high-quality centimeter-sized single crystals of F16CuPc, F16CoPc and F16ZnPc have been grown. New crystal structures of F16CuPc, F16CoPc and F16ZnPc have been determined. Organic single-crystal field-effect transistors have been fabricated to study the effects of the central metal atom on their charge transport properties. The F16ZnPc has the highest electron mobility (~1.1 cm2 V−1 s−1). Theoretical calculations indicate that the crystal structure and electronic structure of the central metal atom determine the transport properties of fluorinated metal phthalocyanines. PMID:25524460

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

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...

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

KAUST Repository

Kim, Inho

2010-11-15

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 different device structures such as ZnPc/ZnPc:C60/C60, PdPc/PdPc:C60/C60, and PdPc/ZnPc:C60/C60 with varying thickness of mixed interlayers were fabricated by thermal evaporation. The mixed i-layers were deposited by co-evaporation of MPc (M=Zn,Pd) and C60 by 1:1 ratio. PCE of 3.7% was obtained for optimized cells consisting of PdPc/ZnPc:C60/C60, while cells with device structure of ZnPc/ZnPc:C60/C60 showed PCE of 3.2%.

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

International Nuclear Information System (INIS)

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

2011-01-01

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

DFT study of adsorption behavior of NO, CO, NO2, and NH3 molecules on graphene-like BC3: A search for highly sensitive molecular sensor

Science.gov (United States)

Mehdi Aghaei, Sadegh; Monshi, M. M.; Torres, I.; Zeidi, S. M. J.; Calizo, I.

2018-01-01

The adsorption behaviors of toxic gas molecules (NO, CO, NO2, and NH3) on the graphene-like boron carbide (BC3) are investigated using first-principle density functional theory. The graphene-like BC3 monolayer is a semiconductor with a band gap of 0.733 eV. It is discovered that all the above gas molecules are chemisorbed on the BC3 sheet while they retain their molecular forms. It is also revealed that the NO2 gas molecule could be dissociated into NO and O species through the adsorption process. The amounts of charge transfer upon adsorption of CO and NH3 gas molecules on the BC3 are found to be small. The band gap changes in BC3 as a result of interactions with CO and NH3 are only 4.63% and 16.7%, indicating that the BC3-based sensor has a low and moderate sensitivity to CO and NH3, respectively. Contrariwise, upon adsorption of NO or NO2 on the BC3, significant charges are transferred from the molecules to the BC3 sheet, causing a semiconductor-metal and semiconductor-p type semiconductor transition. Our study suggests that the BC3-based sensor has a high potential for NO and NO2 detection due to the significant conductance changes, moderate adsorption energy, and short recovery time. More excitingly, the BC3 is a likely catalyst for dissociation of the NO2 gas molecule.

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

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.

Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

Science.gov (United States)

He, Xin; Kim, Seong H

2018-02-20

Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

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

International Nuclear Information System (INIS)

Nyoni, Stephen; Nyokong, Tebello

2014-01-01

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

Plasmon-enhanced photocurrent generation from self-assembled monolayers of phthalocyanine by using gold nanoparticle films.

Science.gov (United States)

Sugawa, Kosuke; Akiyama, Tsuyoshi; Kawazumi, Hirofumi; Yamada, Sunao

2009-04-09

The effect of localized electric fields on the photocurrent responses of phthalocyanine that was self-assembled on a gold nanoparticle film was investigated by comparing the conventional and the total internal reflection (TIR) experimental systems. In the case of photocurrent measurements, self-assembled monolayers (SAMs) of a thiol derivative of palladium phthalocyanine (PdPc) were prepared on the surface of gold-nanoparticle film that was fixed on the surface of indium-tin-oxide (ITO) substrate via a polyion (PdPc/AuP/polyion/ITO) or on the ITO surface (PdPc/ITO). Photocurrent action spectra from the two samples were compared by using the conventional spectrometer, and were found that PdPc/AuP/polyion/ITO gave considerably larger photocurrent signals than PdPc/ITO under the identical concentration of PdPc. In the case of the TIR experiments for the PdPc/AuP/polyion/ITO and the PdPc/AuP/Glass systems, incident-angle profiles of photocurrent and emission signals were correlated with each other, and they were different from that of the PdPc/ITO system. Accordingly, it was demonstrated that the photocurrent signals were certainly enhanced by the localized electric fields of the gold-nanoparticle film.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-04-14

In this study, we have assessed the potential application of group 13 and 14 metal and metalloid phthalocyanines ((X){sub n}-MPcs) and their axially substituted derivatives as hole-transporting layers in organic light emitting diodes (OLEDs). OLEDs studied herein have the generic structure of glass/ITO/(N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) or (X){sub n}-MPc)(50 nm)/Alq{sub 3} (60 nm)/LiF (1 nm)/Al (80 nm), where X is an axial substituent group. OLEDs using chloro aluminum phthalocyanine (Cl-AlPc) showed good peak luminance values of 2620 ± 113 cd/m{sup 2} at 11 V. To our knowledge, Cl-AlPc has not previously been shown to work as a hole transport material (HTL) in OLEDs. Conversely, the di-chlorides of silicon, germanium, and tin phthalocyanine (Cl{sub 2}-SiPc, Cl{sub 2}-GePc, and Cl{sub 2}-SnPc, respectively) showed poor performance compared to Cl-AlPc, having peak luminances of only 38 ± 4 cd/m{sup 2} (12 V), 23 ± 1 cd/m{sup 2} (8.5 V), and 59 ± 5 cd/m{sup 2} (13.5 V), respectively. However, by performing a simple axial substitution of the chloride groups of Cl{sub 2}-SiPc with pentafluorophenoxy groups, the resulting bis(pentafluorophenoxy) silicon phthalocyanine (F{sub 10}-SiPc) containing OLED had a peak luminance of 5141 ± 941 cd/m{sup 2} (10 V), a two order of magnitude increase over its chlorinated precursor. This material showed OLED characteristics approaching those of a baseline OLED based on the well-studied triarylamine NPB. Attempts to attach the pentafluorophenoxy axial group to both SnPc and GePc were hindered by synthetic difficulties and low thermal stability, respectively. In light of the performance improvements observed by simple axial substitution of SiPc in OLEDs, the use of axially substituted MPcs in organic electronic devices remains of continuing interest to us and potentially the field in general.

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.

Facile fabrication of dual emissive nanospheres via the self-assembling of CdSe@CdS and zinc phthalocyanine and their application for silver ion detection

Science.gov (United States)

Liu, Shuning; Liu, Chenchen; Luan, Xinying; Yao, Rui; Feng, Yakai

2017-09-01

The far-red/near infrared photoluminescence of zinc phthalocyanines would be strongly quenched once they are aggregated, which will obviously hinder their wide applications in environmental, energy related and biomedical fields. Herein, the ultra-small sized semiconductor quantum dots with core-shell structures (CdSe@CdS) have been firstly synthesized and then assembled with a dendritic zinc phthalocyanine (ZnPc) in the H2O/DMF mixed solvent to obtain monodispersed nanospheres. Finally, it was found that the resultant ethanolic colloids can be employed as a sensitive and specific fluorescent nanoprobe for silver ions discrimination with a limit of detection (LOD) approaching to 10-8 mol/L.

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).

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.

A theoretical study of the relaxation of a phenyl group chemisorbed to an RDX freestanding thin film

Energy Technology Data Exchange (ETDEWEB)

Pereverzev, Andrey, E-mail: pereverzeva@missouri.edu; Sewell, Thomas D., E-mail: sewellt@missouri.edu [Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211-7600 (United States)

2016-08-07

Energy relaxation from an excited phenyl group chemisorbed to the surface of a crystalline thin film of α-1,3,5-trinitro-1,3,5-triazacyclohexane (α-RDX) at 298 K and 1 atm is simulated using molecular dynamics. Two schemes are used to excite the phenyl group. In the first scheme, the excitation energy is added instantaneously as kinetic energy by rescaling momenta of the 11 atoms in the phenyl group. In the second scheme, the phenyl group is equilibrated at a higher temperature in the presence of static RDX geometries representative of the 298 K thin film. An analytical model based on ballistic phonon transport that requires only the harmonic part of the total Hamiltonian and includes no adjustable parameters is shown to predict, essentially quantitatively, the short-time dynamics of the kinetic energy relaxation (∼200 fs). The dynamics of the phenyl group for times longer than about 6 ps follows exponential decay and agrees qualitatively with the dynamics described by a master equation. Long-time heat propagation within the bulk of the crystal film is consistent with the heat equation.

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.

Phthalocyanines with eight oligo(ethylene oxide) alkoxy units: thermotropic phase behavior, aggregate formation and ion complexation with redox-active ions

NARCIS (Netherlands)

Piet, D.P.; Verheij, H.J.; Zuilhof, H.

2003-01-01

The thermotropic phase behavior of phthalocyanines (Pc's) with eight oligo(ethylene oxide) alkoxy side chains has been investigated. An increase in the number of ethylene oxide units results in a decrease in the solid-to-mesophase and isotropization temperatures. The investigated compounds display a

Theoretical investigation on the alkali-metal doped BN fullerene as a material for hydrogen storage

International Nuclear Information System (INIS)

Venkataramanan, Natarajan Sathiyamoorthy; Belosludov, Rodion Vladimirovich; Note, Ryunosuke; Sahara, Ryoji; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

2010-01-01

Graphical abstract: First-principles calculations have been used to investigate hydrogen adsorption on alkali atom doped B 36 N 36 clusters. Adsorption of alkali atoms involves a charge transfer process, creating positively-charged alkali atoms and this polarizes the H 2 molecules and increases their binding energy. The maximum hydrogen storage capacity of Li doped BN fullerene is 8.9 wt.% in which 60 hydrogen atoms were chemisorbed and 12 H 2 were adsorbed in molecular form. - Abstract: First-principles calculations have been used to investigate hydrogen adsorption on alkali atom doped B 36 N 36 clusters. The alkali atom adsorption takes place near the six tetragonal bridge sites available on the cage, thereby avoiding the notorious clustering problem. Adsorption of alkali atoms involves a charge transfer process, creating positively charged alkali atoms and this polarizes the H 2 molecules thereby, increasing their binding energy. Li atom has been found to adsorb up to three hydrogen molecules with an average binding energy of 0.189 eV. The fully doped Li 6 B 36 N 36 cluster has been found to hold up to 18 hydrogen molecules with the average binding energy of 0.146 eV. This corresponds to a gravimetric density of hydrogen storage of 3.7 wt.%. Chemisorption on the Li 6 B 36 N 36 has been found to be an exothermic reaction, in which 60 hydrogen atoms chemisorbed with an average chemisorption energy of -2.13 eV. Thus, the maximum hydrogen storage capacity of Li doped BN fullerene is 8.9 wt.% in which 60 hydrogen atoms were chemisorbed and 12 hydrogen molecules were adsorbed in molecular form.

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.

Discrete variational methods and their application to electronic structures

International Nuclear Information System (INIS)

Ellis, D.E.

1987-01-01

Some general concepts concerning Discrete Variational methods are developed and applied to problems of determination of eletronic spectra, charge densities and bonding of free molecules, surface-chemisorbed species and bulk solids. (M.W.O.) [pt

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.

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

Real-Time Observation of Surface Bond Breaking with an X-ray Laser

DEFF Research Database (Denmark)

Dell'Angela, M.; Anniyev, T.; Beye, M.

2013-01-01

molecules interact weakly with the surface but translate along it and exchange energy without forming localized surface bonds. Dell'Angela et al. (p. 1302) found evidence for such a state in changes in x-ray absorption and emission spectra of CO molecules adsorbed on a ruthenium surface after optical...... and that are bonded less strongly than the chemisorbed state....

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.

The effect of topological defects and oxygen adsorption on the electronic transport properties of single-walled carbon-nanotubes

International Nuclear Information System (INIS)

Grujicic, M.; Cao, G.; Singh, R.

2003-01-01

Ab initio density functional theory (DFT) calculations of the interactions between isolated infinitely-long semiconducting zig-zag (10, 0) or isolated infinitely-long metallic arm-chair (5, 5) single-walled carbon-nanotubes (SWCNTs) and single oxygen-molecules are carried out in order to determine the character of molecular-oxygen adsorption and its effect on electronic transport properties of these SWCNTs. A Green's function method combined with a nearest-neighbor tight-binding Hamiltonian in a non-orthogonal basis is used to compute the electrical conductance of SWCNTs and its dependence on the presence of topological defects in SWCNTs and of molecular-oxygen adsorbates. The computational results obtained show that in both semiconducting and metallic SWCNTs, oxygen-molecules are physisorbed to the defect-free nanotube walls, but when such walls contain topological defects, oxygen-molecules become strongly chemisorbed. In semiconducting (10, 0) SWCNTs, physisorbed O 2 -molecules are found to significantly increase electrical conductance while the effect of 7-5-5-7 defects is practically annulled by chemisorbed O 2 -molecules. In metallic (5, 5) SWCNTs, both O 2 adsorbates and 7-5-5-7 defects are found to have a relatively small effect on electrical conductance of these nanotubes

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-11-01

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

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 .

Al(III), Pd(II), and Zn(II) phthalocyanines for inactivation of dental pathogen Aggregatibacter actinomycetemcomitans as planktonic and biofilm-cultures

Science.gov (United States)

Kussovski, V.; Mantareva, V.; Angelov, I.; Avramov, L.; Popova, E.; Dimitrov, S.

2012-06-01

The Gram-negative, oral bacterium Aggregatibacter actinomycetemcomitans has been implicated as the causative agent of several forms of periodontal disease in humans. The new periodontal disease treatments are emergence in order to prevent infection progression. Antimicrobial photodynamic therapy (a-PDT) can be a useful tool for this purpose. It involves the use of light of specific wavelength to activate a nontoxic photosensitizing agent in the presence of oxygen for eradication of target cells, and appears effective in photoinactivation of microorganisms. The phthalocyanine metal complexes of Pd(II)- (PdPcC) and Al(III)- (AlPc1) were evaluated as photodynamic sensitizers towards a dental pathogen A. actinomycetemcomitans in comparison to the known methylpyridyloxy-substituted Zn(II) phthalocyanine (ZnPcMe). The planktonic and biofilm-cultivated species of A. actinomycetemcomitans were treated. The photophysical results showed intensive and far-red absorbance with high tendency of aggregation for Pd(II)-phthalocyanine. The dark toxicities of both photosensitizers were negligible at concentrations used (bacteria was full photoinactivation after a-PDT with ZnPcMe. In case of the newly studied complexes, the effect was lower for PdPcC (4 log) as well as for AlPc1 (1.5-2 log). As it is known the bacterial biofilms were more resistant to a-PDT, which was confirmed for A. actinomycetemcomitans biofilms with 3 log reductions of viable cells after treatment with ZnPcMe and approximately 1 log reduction of biofilms after PdPcC and AlPc1. The initial results suggest that a-PDT can be useful for effective inactivation of dental pathogen A. actinomycetemcomitans.

Comparison of two photosensitizers Al(III) phthalocyanine chloride tetrasulfonic acid and meso-tetrakis(4-sulfonatophenyl)porphyrin in the photooxidation of n-butylparaben

Czech Academy of Sciences Publication Activity Database

Gmurek, M.; Kubát, Pavel; Mosinger, Jiří; Miller, J. S.

2011-01-01

Roč. 223, č. 1 (2011), s. 50-56 ISSN 1010-6030 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40320502 Keywords : photosensitization * porphyrin * phthalocyanine Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.421, year: 2011

Layer-by-layer composite film of nickel phthalocyanine and montmorillonite clay for synergistic effect on electrochemical detection of dopamine

Science.gov (United States)

de Lucena, Nathalia C.; Miyazaki, Celina M.; Shimizu, Flávio M.; Constantino, Carlos J. L.; Ferreira, Marystela

2018-04-01

Dopamine (DA) abnormal levels are related to diseases which makes important the development of fast, reliable, low-cost and sensitive devices for diagnosis and pharmaceutical controls. Nanostructured film composite of sodium montmorillonite clay (Na+MMT) and nickel phthalocyanine (NiTsPc) was self-assembled by layer-by-layer (LbL) technique and applied as electrochemical sensor for DA in the presence of common natural interferents as ascorbic acid (AA) and uric acid (UA). Three different LbL architecture films were investigated: LbL films of clay (PEI/Na+MMT) and phthalocyanine (PEI/NiTsPc) in a bilayer structure with a conventional polyelectrolyte (PEI) and a composite film formed by both materials to verify the synergistic effect in the LbL film in a quadri-layer assembly (PEI/Na+MMT/PEI/NiTsPc). Structural characterization indicated molecular level interactions between the layers forming the LbL films. The ITO/(PEI/Na+MMT/PEI/NiTsPc)10 electrode exhibited a LOD of 1.0 μmol L-1 and linear range 5-150 μmol L-1.

Novel water soluble morpholine substituted Zn(II) phthalocyanine: Synthesis, characterization, DNA/BSA binding, DNA photocleavage and topoisomerase I inhibition.

Science.gov (United States)

Barut, Burak; Demirbaş, Ümit; Özel, Arzu; Kantekin, Halit

2017-12-01

In this study, novel peripherally tetra 3-morpholinophenol substituted zinc(II) phthalocyanine (4) and its water soluble form quaternized zinc(II) phthalocyanine (ZnQ) were synthesized for the first time. These novel compounds were characterized by a combination of different spectroscopic techniques such as FT-IR, 1 H NMR, 13 C NMR, UV-vis and mass. The DNA binding of ZnQ was investigated using UV-vis absorption titration, competitive ethidium bromide, thermal denaturation and viscosity experiments that the ZnQ bound to CT-DNA via intercalation mode. ZnQ indicated photocleavage activity on supercoiled pBR322 plasmid DNA via formation of singlet oxygen under irradiation at 700nm. Besides, the topoisomerase I inhibitory effect experiments showed that ZnQ inhibited topoisomerase I enzyme in a concentration-dependent manner. The bovine serum albumin (BSA) binding experiments indicated that ZnQ bound to proteins through a static quenching mechanism. All of these results claim that ZnQ has potential agent for photodynamic therapy owing to its nucleic acid interactions and photobiological or photochemical properties. Copyright © 2017 Elsevier B.V. All rights reserved.

Raman spectroscopic studies of the interaction of oxalic acid and sodium oxalate used as corrosion inhibitors with copper

Science.gov (United States)

Jeziorowski, H.; Moser, B.

1985-09-01

The Raman spectra of the liquid-solid interface recorded in situ show the formation of a salt complex of the inhibitor molecules and the copper ions. This suggests that this chemisorbed surface species produces the protective layer.

Electrochemical Investigations of the Interface at Li/Li+ Ion Conducting Channel

Science.gov (United States)

2006-10-04

range of applications.1 Presently, these molecules are of particular interest in non-linear optics, as liquid crystals, as Langmuir - Blodgett films, for...cathode material in non-aqueous liquid electrolyte medium Since Li2Pc is a mixed ionic and electronic conductor, and some metal phthalocyanines are...14. ABSTRACT Dilithium phthalocyanine (Li2Pc) possesses mixed electronic- ionic conductivity due to overlap of - orbitals (electronic

Assessing the potential roles of silicon and germanium phthalocyanines in planar heterojunction organic photovoltaic devices and how pentafluoro phenoxylation can enhance π-π interactions and device performance.

Science.gov (United States)

Lessard, Benoît H; White, Robin T; Al-Amar, Mohammad; Plint, Trevor; Castrucci, Jeffrey S; Josey, David S; Lu, Zheng-Hong; Bender, Timothy P

2015-03-11

In this study, we have assessed the potential application of dichloro silicon phthalocyanine (Cl2-SiPc) and dichloro germanium phthalocyanine (Cl2-GePc) in modern planar heterojunction organic photovoltaic (PHJ OPV) devices. We have determined that Cl2-SiPc can act as an electron donating material when paired with C60 and that Cl2-SiPc or Cl2-GePc can also act as an electron acceptor material when paired with pentacene. These two materials enabled the harvesting of triplet energy resulting from the singlet fission process in pentacene. However, contributions to the generation of photocurrent were observed for Cl2-SiPc with no evidence of photocurrent contribution from Cl2-GePc. The result of our initial assessment established the potential for the application of SiPc and GePc in PHJ OPV devices. Thereafter, bis(pentafluoro phenoxy) silicon phthalocyanine (F10-SiPc) and bis(pentafluoro phenoxy) germanium phthalocyanine (F10-GePc) were synthesized and characterized. During thermal processing, it was discovered that F10-SiPc and F10-GePc underwent a reaction forming small amounts of difluoro SiPc (F2-SiPc) and difluoro GePc (F2-GePc). This undesirable reaction could be circumvented for F10-SiPc but not for F10-GePc. Using single crystal X-ray diffraction, it was determined that F10-SiPc has significantly enhanced π-π interactions compared with that of Cl2-SiPc, which had little to none. Unoptimized PHJ OPV devices based on F10-SiPc were fabricated and directly compared to those constructed from Cl2-SiPc, and in all cases, PHJ OPV devices based on F10-SiPc had significantly improved device characteristics compared to Cl2-SiPc.

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

Deposition of low sheet resistance indium tin oxide directly onto functional small molecules

KAUST Repository

Franklin, Joseph B.; Fleet, Luke R.; Burgess, Claire H.; McLachlan, Martyn A.

2014-01-01

© 2014 Elsevier B.V. All rights reserved. We outline a methodology for depositing tin-doped indium oxide (ITO) directly onto semiconducting organic small molecule films for use as a transparent conducting oxide top-electrode. ITO films were grown using pulsed laser deposition onto copper(II)phthalocyanine (CuPc):buckminsterfullerene (C60) coated substrates. The ITO was deposited at a substrate temperature of 150 °C over a wide range of background oxygen pressures (Pd) (0.67-10 Pa). Deposition at 0.67 ≤ Pd ≤ 4.7 Pa led to delamination of the organic films owing to damage induced by the high energy ablated particles, at intermediate 4.7 ≤ Pd < 6.7 Pa pressures macroscopic cracking is observed in the ITO. Increasing Pd further, ≥ 6.7 Pa, supports the deposition of continuous, polycrystalline and highly transparent ITO films without damage to the CuPc:C60. The free carrier concentration of ITO is strongly influenced by Pd; hence growth at > 6.7 Pa induces a significant decrease in conductivity; with a minimum sheet resistance (Rs) of 145 /□ achieved for 300 nm thick ITO films. To reduce the Rs a multi-pressure deposition was implemented, resulting in the formation of polycrystalline, highly transparent ITO with an Rs of - 20/□ whilst maintaining the inherent functionality and integrity of the small molecule substrate.

Deposition of low sheet resistance indium tin oxide directly onto functional small molecules

KAUST Repository

Franklin, Joseph B.

2014-11-01

© 2014 Elsevier B.V. All rights reserved. We outline a methodology for depositing tin-doped indium oxide (ITO) directly onto semiconducting organic small molecule films for use as a transparent conducting oxide top-electrode. ITO films were grown using pulsed laser deposition onto copper(II)phthalocyanine (CuPc):buckminsterfullerene (C60) coated substrates. The ITO was deposited at a substrate temperature of 150 °C over a wide range of background oxygen pressures (Pd) (0.67-10 Pa). Deposition at 0.67 ≤ Pd ≤ 4.7 Pa led to delamination of the organic films owing to damage induced by the high energy ablated particles, at intermediate 4.7 ≤ Pd < 6.7 Pa pressures macroscopic cracking is observed in the ITO. Increasing Pd further, ≥ 6.7 Pa, supports the deposition of continuous, polycrystalline and highly transparent ITO films without damage to the CuPc:C60. The free carrier concentration of ITO is strongly influenced by Pd; hence growth at > 6.7 Pa induces a significant decrease in conductivity; with a minimum sheet resistance (Rs) of 145 /□ achieved for 300 nm thick ITO films. To reduce the Rs a multi-pressure deposition was implemented, resulting in the formation of polycrystalline, highly transparent ITO with an Rs of - 20/□ whilst maintaining the inherent functionality and integrity of the small molecule substrate.

Two dimensional self-assembly zinc porphyrin and zinc phthalocyanine heterojunctions with record high power conversion efficiencies

Science.gov (United States)

Yu, Junting; Jiang, Zhou; Hao, Yifan; Zhu, Qianhong; Zhao, Mingliang; Jiang, Xue; Zhao, Jijun

2018-06-01

Compared to inorganic solar cells, the power conversion efficiencies (PCEs) of organic solar cells are much lower, but they are compensated by many merits such as lower cost, less weight, and tunable structures, making them prospective for further applications. Porphyrin and phthalocyanine are the two most significant materials for organic solar cells due to their strong light-absorbing properties and semiconductor characteristics. However, there is little research on the 2D heterojunction solar cells based on these two materials, meanwhile the PCEs of them are still low. Here we have self-assembled several 2D zinc porphyrins (ZnPors) and performed first-principles simulation to demonstrate their good stability, suitable light harvesting, and high charge carrier mobility. By perfectly matching lattice constants and molecular energy levels between those 2D ZnPors and our previous proposed zinc phthalocyanines (ZnPcs), 11 type-II organic heterojunctions are constructed to further improve their charge separation capability. Those advantages endow 2D ZnPors and ZnPcs appreciable PCEs for solar cells. Among them, the theoretical PCE of 2D ZnPors/ZnPcs heterojunctions achieves as high as 19.84%, which exceeds all reported organic solar cells, and even approaches the PCEs of inorganic solar cells. These results indicate that our 2D ZnPors and 2D ZnPcs are good candidate materials for future organic solar cells.

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.

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.

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.

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

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.

Studies on phase transformation and molecular orientation in nanostructured zinc phthalocyanine thin films annealed at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Chowdhury, Avijit; Biswas, Bipul; Majumder, Manisree; Sanyal, Manik Kumar; Mallik, Biswanath, E-mail: spbm@iacs.res.in

2012-08-31

Studies on the electronic and optical properties of thin films of organometallic compounds such as phthalocyanine are very important for the development of devices based on these compounds. The nucleation and grain growth mechanism play an important role for the final electronic as well as optoelectronic properties of the organic and organometallic thin films. The present article deals with the change in the film morphology, grain orientation of nanocrystallites and optical properties of zinc phthalocyanines (ZnPc) thin films as a function of the post deposition annealing temperature. The effect of annealing temperature on the optical and structural property of vacuum evaporated ZnPc thin films deposited at room temperature (30 Degree-Sign C) on quartz glass and Si(100) substrates has been investigated. The thin films have been characterized by the UV-vis optical absorption spectra, X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. From the studies of UV-vis absorption spectra and XRD data, a metastable {alpha} to {beta}-phase transformation has been observed when the thin films were annealed at a temperature greater than about 250 Degree-Sign C. The FESEM images have shown the particlelike structure at room temperature and the structure became rodlike when the films were annealed at high temperatures. TEM image of ZnPc film dissolved in ethanol has shown spectacular rod-shaped crystallites. High resolution transmission electron microscopy image of a single nanorod has shown beautiful 'honey-comb' like structure. Particle size and root mean square roughness were calculated from AFM images. The changes in band gap energy with increase in annealing temperature have been evaluated. - Highlights: Black-Right-Pointing-Pointer Morphology and orientation of grains in zinc phthalocyanine (ZnPc) thin films. Black

Probing the Influence of the Conjugated Structure and Halogen Atoms of Poly-Iron-Phthalocyanine on the Oxygen Reduction Reaction by X-ray Absorption Spectroscopy and Density Functional Theory

International Nuclear Information System (INIS)

Peng, Yingxiang; Cui, Lufang; Yang, Shifeng; Fu, Jingjing; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia; Xia, Dingguo

2015-01-01

Metal-phthalocyanine (MPc) macrocyclic catalysts have been perceived as promising alternatives to Pt and Pt-based catalysts for the oxygen reduction reaction (ORR). However, the effect of different MPc molecular structures on the ORR has rarely been reported in depth. Herein, iron-phthalocyanine polymers (poly-FePcs) and multi-walled carbon nanotubes (MWCNTs) composites with different structures were synthesized using microwave method. The relationship between their molecular structure and electrocatalytic activity was fully revealed by density functional theory (DFT) and X-ray fine absorption spectroscopy (XAFS). DFT calculations revealed that the introduction of halogen atoms can increase the ion potential (IP) and the dioxo-binding energy () of the poly-FePcs. Meanwhile, their conjugated structure not only facilitates electronic transmission, but also significantly increases . XAFS analysis indicated that the poly-FePc/MWCNTs composites had a square planar structure and a smaller of phthalocyanine ring (Fe-N 4 structure) skeleton structure radius when a larger conjugated structure or introduced halogen atoms was present. The experimental results suggest that the these changes in properties arising from the different structures of the MPc macrocyclic compounds led to a huge effect on their ORR electrochemical activities, and provide a guide to obtaining promising electrochemical catalysts

Improving reversible capacities of high-surface lithium insertion materials – the case of amorphous TiO2

NARCIS (Netherlands)

Ganapathy, S.; Basak, S.; Lefering, A.; Rogers, E.; Zandbergen, H.W.; Wagemaker, M.

2014-01-01

Chemisorbed water and solvent molecules and their reactivity with components from the electrolyte in high-surface nano-structured electrodes remains a contributing factor toward capacity diminishment on cycling in lithium ion batteries due to the limit in maximum annealing temperature. Here, we

Immobilization of ruthenium phthalocyanine on silica-coated multi-wall partially oriented carbon nanotubes: Electrochemical detection of fenitrothion pesticide

Energy Technology Data Exchange (ETDEWEB)

Canevari, Thiago C., E-mail: tccanevari@gmail.com [Engineering School, Mackenzie Presbyterian University, 01302-907 São Paulo, SP (Brazil); Prado, Thiago M.; Cincotto, Fernando H.; Machado, Sergio A.S. [Institute of Chemistry, State University of São Paulo, P.O. Box 780, 13560-970 São Carlos, SP (Brazil)

2016-04-15

Highlights: • Hybrid material, SiO{sub 2}/MWCNTs containing ruthenium phthalocyanine (RuPc) synthesized in situ. • Silica containing multi-walled carbon nanotube partially oriented. • Determination of pesticide fenitrothion in orange juice. - Abstract: This paper reports on the determination of the pesticide fenitrothion using a glassy carbon electrode modified with silica-coated, multi-walled, partially oriented carbon nanotubes, SiO{sub 2}/MWCNTs, containing ruthenium phthalocyanine (RuPc) synthesized in situ. The hybrid SiO{sub 2}/MWCNTs/RuPc material was characterized by UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and differential pulse voltammetry. The modified electrode showed well-defined peaks in the presence of fenitrothion in acetate buffer, pH 4.5, with a sensitivity of 0.0822 μA μM{sup −1} mm{sup −2} and a detection limit of 0.45 ppm. Notably, the modified SiO{sub 2}/MWCNTs/RuPc electrodes with did not suffer from significant influences in the presence of other organophosphorus pesticides during the determination of the fenitrothion pesticide. Moreover, this modified electrode showed excellent performance in the determination of fenitrothion in orange juice.

Effects of adatom and gas molecule adsorption on the physical properties of tellurene: a first principles investigation.

Science.gov (United States)

Wang, Xiao Hua; Wang, Da Wei; Yang, Ai Jun; Koratkar, Nikhil; Chu, Ji Feng; Lv, Pin Lei; Rong, Ming Zhe

2018-02-07

Tellurene is a new member of the two-dimensional (2D) materials' family, whose existence has been recently confirmed by first principles calculation and experimental work. Tellurene is also the first 2D mono-elemental material of group-VI predicted by scientists, and investigations of its basic properties are still in their infancy. In this study, we use first principles calculation based on density functional theory to investigate the adsorption of nineteen typical adatoms (Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Ag, Au, Pd, Pt, B, N, O, Si, Cl, and Al), and five typical gas molecules (H 2 , O 2 , H 2 O, NO 2 , and NH 3 ) on α-phase as well as β-phase tellurene sheets. Our calculations shows that most adatoms are chemisorbed on tellurene sheets with large adsorption energies. Moreover, some of the adatoms are observed to give rise to distinct structural deformations and even local reconstructions. We report that a variety of electronic states are induced by the adatoms, which implies that different electronic structures can be engineered by the adsorption of adatoms. In fact, n-type doping, p-type doping, half-metal, and spin-gapless semiconductor features can be acquired by doping adatoms on tellurene sheets. Our calculations also show that the five gas molecules are all physisorbed on tellurene sheets, and no splitting behaviors are observed. Therefore, the adsorption of the five gas molecules has a weak effect on the electronic properties of tellurene. To conclude, our results indicate that adatom engineering may be used to greatly expand the potential applications of 2D tellurene.

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)

Power losses in bilayer inverted small molecule organic solar cells

KAUST Repository

Trinh, Cong; Bakke, Jonathan R.; Brennan, Thomas P.; Bent, Stacey F.; Navarro, Francisco; Bartynski, Andrew; Thompson, Mark E.

2012-01-01

Inverted bilayer organic solar cells using copper phthalocyanine (CuPc) as a donor and C60 as an acceptor with the structure: glass/indium tin oxide (ITO)/ZnO/C60/CuPc/MoO3/Al, in which the zinc oxide (ZnO) was deposited by atomic layer deposition

Heterojunction nanowires having high activity and stability for the reduction of oxygen: Formation by self-assembly of iron phthalocyanine with single walled carbon nanotubes (FePc/SWNTs)

KAUST Repository

Zhu, Jia; Jia, Nana; Yang, Lijun; Su, Dong; Park, Jinseong; Choi, YongMan; Gong, Kuanping

2014-01-01

A self-assembly approach to preparing iron phthalocyanine/single-walled carbon nanotube (FePc/SWNT) heterojunction nanowires as a new oxygen reduction reaction (ORR) electrocatalyst has been developed by virtue of water-adjusted dispersing in 1

Frenkel-Charge-Transfer exciton intermixing theory for molecular crystals with two isolated Frenkel exciton states.

Science.gov (United States)

Bondarev, Igor; Popescu, Adrian

We develop an analytical theory for the intra-intermolecular exciton intermixing in periodic 1D chains of planar organic molecules with two isolated low-lying Frenkel exciton states, typical of copper phthalocyanine (CuPc) and other transition metal phthalocyanine molecules. We formulate the Hamiltonian and use the exact Bogoliubov diagonalization procedure to derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer (CT) exciton state. By comparing our theoretical spectrum with available experimental CuPc absorption data, we obtain the parameters of the Frenkel-CT exciton intermixing in CuPc thin films. The two Frenkel exciton states here are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the CT exciton, showing the coupling constant 0.17 eV in agreement with earlier electron transport experiments. Our results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines. DOE-DE-SC0007117 (I.B.), UNC-GA ROI Grant (A.P.).

Temperature-dependent chemisorption of C60 on Mo(110) : precursors to cage destruction

NARCIS (Netherlands)

Hunt, Michael R.C.; Rajogopal, Aparna; Caudano, Roland; Rudolf, Petra

2000-01-01

The catalytically promoted decomposition of C60 has recently been observed on a variety of surfaces upon which the molecule can chemisorb strongly. It is now becoming clear that destruction occurs via conversion of a relatively weakly bound state arising from room-temperature adsorption into a

Phthalocyanine-conjugated upconversion NaYF4:Yb3+/Er3+@SiO2 nanospheres for NIR-triggered photodynamic therapy in a tumor mouse model

Czech Academy of Sciences Publication Activity Database

Kostiv, Uliana; Patsula, Vitalii; Noculak, A.; Podhorodecki, A.; Větvička, D.; Poučková, P.; Sedláková, Zdeňka; Horák, Daniel

2017-01-01

Roč. 12, Issue 24 (2017), s. 2066-2073 ISSN 1860-7179 R&D Projects: GA ČR(CZ) GA15-01897S Institutional support: RVO:61389013 Keywords : upconversion nanospheres * phthalocyanine * photodynamic therapy Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 3.225, year: 2016

Synthesis of zinc phthalocyanine with large steric hindrance and its photovoltaic performance for dye-sensitized solar cells.

Science.gov (United States)

Lin, Li; Peng, Bosi; Shi, Wenye; Guo, Yingying; Li, Renjie

2015-03-28

A zinc phthalocyanine (ZnPc) derivative (Zn-tri-PcNc-8) containing tri-benzonaphtho-condensed porphyrazine with one carboxylic and six diphenylphenoxy peripheral substitutions was designed and synthesized as a sensitizer for dye-sensitized solar cells (DSSCs). For the purpose of extending the absorption spectra while minimizing the formation of ZnPc molecular aggregates, bulky 2,6-diphenylphenoxy groups were used as electron donor moieties, and the carboxylic group as an anchoring group to graft the sensitizer onto the semiconductor. It was found that a TiO2-based solar cell sensitized by Zn-tri-PcNc-8 shows a maximum incident photon-to-current conversion efficiency in the red/near-IR light range (650-750 nm), and a solar cell sensitized at near room temperature (30 °C) for 48 h exhibits the best efficiency (3.01%). The efficiency was much higher than that (1.96%) for a solar cell sensitized by its analogue (Zn-tri-PcNc-2) having one carboxyl and three tert-butyl groups without chenodeoxycholic acid (CDCA), indicating that the introduction of six bulky diphenylphenoxy substitutions with large steric hindrance in the ZnPc macrocycle can effectively suppress the molecular aggregates, thus resulting in an improved conversion efficiency. The present results shed light on an effective solution to adjust the ZnPc property via chemical modification such as changing the "push-pull" effect and adding large steric hindrance substituents to further improve the efficiency of the phthalocyanine-sensitized solar cell.

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).

Oxygen reduction reaction properties of nitrogen-incorporated nanographenes synthesized using in-liquid plasma from mixture of ethanol and iron phthalocyanine

Science.gov (United States)

Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

2018-04-01

Nanographenes were synthesized using in-liquid plasma from a mixture of iron phthalocyanine and ethanol. In a previous study, micrometer-scale flakes with nitrogen incorporation were obtained. A nonprecious metal catalytic activity was observed with 3.13 electrons in an oxygen reduction reaction under an acidic solute condition. Large-surface-area, high-graphene-crystallinity, and iron-carbon-bonding sites were found owing to a high catalytic activity in Fe-N/nanographene.

Tunneling rates in electron transport through double-barrier molecular junctions in a scanning tunneling microscope

OpenAIRE

Nazin, G. V.; Wu, S. W.; Ho, W.

2005-01-01

The scanning tunneling microscope enables atomic-scale measurements of electron transport through individual molecules. Copper phthalocyanine and magnesium porphine molecules adsorbed on a thin oxide film grown on the NiAl(110) surface were probed. The single-molecule junctions contained two tunneling barriers, vacuum gap, and oxide film. Differential conductance spectroscopy shows that electron transport occurs via vibronic states of the molecules. The intensity of spectral peaks correspondi...

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.

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.

A high resolution helium atom scattering and far infrared study of the dynamics and the lateral potential energy surface of CO molecules chemisorbed on Cu(001)

International Nuclear Information System (INIS)

Graham, A.P.; Hofmann, F.; Toennies, J.P.; Williams, G.P.; Hirschmugl, C.J.; Ellis, J.

1998-01-01

Inelastic helium scattering (HAS) and infrared reflection adsorption spectroscopy (IRAS) have been used to measure the isotope shifts of the frequencies of both the parallel and perpendicular frustrated translation modes, as well as the frustrated rotation mode of CO molecules at on top sites on Cu(001). The measured isotope shifts for four different isotopomers indicates a significant rotational contribution to the parallel frustrated translation (T-mode), where the vibrational amplitude of the oxygen atom is significantly larger than for the carbon atom. Conversely, for the frustrated rotation the vibrational amplitude of the carbon atom was observed to be larger than for the oxygen atom. At surface temperatures above T s =100 K a careful analysis of the peak shape of the HAS quasielastic peak shows a small broadening, which is attributed to a rapid diffusion of the CO molecules. The measured dynamic diffusion barrier of 31±10 meV is compatible with the shape of the potential at the on-top site and makes it possible to extend the potential energy surface to the region between the on-top sites. copyright 1998 American Institute of Physics

Synthesis and Anchoring of Antineoplastic Ferrocene and Phthalocyanine Derivatives on Water-Soluble Polymeric Drug Carriers Derived from Lysine and Aspartic Acid

OpenAIRE

Maree, M. David; Neuse, Eberhard W.; Erasmus, Elizabeth; Swarts, Jannie C.

2007-01-01

The general synthetic strategy towards water-soluble biodegradable drug carriers and the properties that they must have are discussed. The syntheses of water-soluble biodegradable copolymers of lysine and aspartic acid as potential drug-delivering devices, having amine-functionalised side chains are then described. Covalent anchoring of carboxylic acid derivatives of the antineoplastic ferrocene and photodynamically active phthalocyanine moieties to the amine-containing drug carrier copolymer...

Ambipolar organic heterojunction transistors with various p-type semiconductors

International Nuclear Information System (INIS)

Shi Jianwu; Wang Haibo; Song De; Tian Hongkun; Geng Yanhou; Yan Donghang

2008-01-01

Ambipolar transport has been realized in organic heterojunction transistors with metal phthalocyanines, phenanthrene-based conjugated oligomers as the first semiconductors and copper-hexadecafluoro-phthalocyanine as the second semiconductor. The electron and hole mobilities of ambipolar devices with rod-like molecules were comparable to the corresponding single component devices, while the carrier mobility of ambipolar devices with disk-like molecules was much lower than the corresponding single component devices. The much difference of their device performance was attributed to the roughness of the first semiconductor films, which was original from their distinct growth habits. The flat and continuous films for the first semiconductors layer can lead to a smooth heterojunction interface, and obtained a high device performance for ambipolar organic heterojunction transistors

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

Directory of Open Access Journals (Sweden)

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

2011-01-01

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

Structural and electrical studies on tetrameric cobalt phthalocyanine and polyaniline composites

International Nuclear Information System (INIS)

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

2006-01-01

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

Phototoxic effects of silicon bis (dimetilaminoetanoxi)-phthalocyanine (SiPc) on the viability of Leishmania major and Leishmania braziliensis promastigotes

Science.gov (United States)

Guerra Pinto, Juliana; Ferreira-Strixino, Juliana; Mittmann, Josane

2016-06-01

American cutaneous leishmaniasis (ACL) is an infectious disease caused by protozoans of the genus Leishmania. The treatment may consist of pentavalent antimonials or pentamidine and amphotericin. However, these treatments are extremely aggressive. Photodynamic antimicrobial chemotherapy (PACT) involves the same mechanism of photodynamic therapy which associates a photosensitizer with oxygen and a light source generating a photochemical reaction leading to cell death. The aim of this study was to verify the potential use of silicon bis (dimetilaminoetanoxi)-phthalocyanine (SiPc) compound in photodynamic treatment through evaluation of its phototoxic effect in promastigotes of the genus Leishmania braziliensis and Leishmania major. Treatment with SiPc was able to drastically affect the viability of the parasites as well as affect their growth and morphology, after PACT treatment. The data shown in this study allows us to conclude that SiPc is a promising photosensitizer (PS) since it does not affect parasite growth and viability in the dark. After PACT with this phthalocyanine, over 99% of parasites were killed with the higher concentration and a light dose used. These results suggest that SiPc can be used in future to treat CL, however, further studies are necessary to determine whether the PS are toxic to mononuclear phagocytic cells and epithelial cells which will also be affected by therapy when applied topically.

Physical aspects of relaxation and shake-up effects in XPS and core →2π* absorption spectra of CO chemisorbed on Ni (111)

International Nuclear Information System (INIS)

Gumhalter, B.

1985-07-01

The physical origin of the peculiar relaxation shifts and spectral shapes appearing in x-ray induced core-to-valence excitation and core level photoemission spectra of CO chemisorbed on Ni(111) are discussed and interpreted within a unique framework. Within the model presented the electronic transitions in core-to-valence excitation spectroscopy and XPS are shown to give rise to drastic electronic rearrangements within the adsorption system and to the charge shake-up in the CO 2π* derived resonance partly filled via the backdonation mechanism. Such singular relaxation processes, common to both spectroscopies, are closely related and can be treated on the same footing. This makes possible to establish unique relaxation shifts and spectral characteristics for two seemingly different experimental situations. The use of this formalism in analysing the experimental data enables one to estimate and distinguish between the extra-adsorbate (image or nonbonding) and intra-adsorbate (chemically induced) screening of the core holes created either by x-ray induced core-to-valence electronic transitions or core level photoionization in CO/Ni(111). (author)

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.

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.

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...

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.

Conjugation of isoniazid to a zinc phthalocyanine via hydrazone linkage for pH-dependent liposomal controlled release

Science.gov (United States)

Nkanga, Christian Isalomboto; Krause, Rui Werner Maçedo

2018-05-01

Tuberculosis (TB) remains the leading cause of mortality from infectious diseases. Extended TB treatment and frequent adverse effects, due to poor bioavailability of anti-tubercular drugs (ATBDs), represent the main rationales behind liposomal encapsulation for controlled delivery. Liposomes have been reported as potential vehicles for targeted delivery of ATBDs due to their rapid uptake by macrophages, which are known as the main host cells for TB causative agent (Mycobacterium tuberculosis). Additionally, the need for controlled release of ATBDs arises because leakage is part of the key liposome challenges for hydrophilic compounds like isoniazid (INH). In this study, INH was conjugated to a highly hydrophobic photosensitizer, zinc (II) phthalocyanine (PC), through hydrazone bonding. The obtained conjugate (PC-INH) was encapsulated in liposomes by film hydration method. PC-INH loaded liposomes (PILs) were characterized using dynamic light scattering, transmission electron microscopy, energy-dispersive X-ray spectrometry and UV-Vis absorption spectrometry, which was used also for estimation of encapsulation efficiency (%EE). INH release was evaluated in different pH media using dialysis. Particle size, zeta potential and %EE of PILs were about 506 nm, - 55 mV and 72%, respectively. Over 12 h, PILs exhibited 22, 41, 97 and 100% of INH, respectively, released in pH 7.4, 6.4, 5.4 and 4.4 media. This pH-dependent behavior is attractive for site-specific delivery. These findings suggest the conjugation of chemotherapeutics to phthalocyanines using pH-labile linkages as a potential strategy for liposomal controlled release.

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.

Large-scale synthesis of high-purity well-aligned carbon nanotubes using pyrolysis of iron(II) phthalocyanine and acetylene

Science.gov (United States)

Liu, B. C.; Lee, T. J.; Lee, S. H.; Park, C. Y.; Lee, C. J.

2003-08-01

Well-aligned carbon nanotubes (CNTs) with high purity have been produced by pyrolysis of iron(II) phthalocyanine and acetylene at 800 °C. The synthesized CNTs have a length of 75 μm and diameters ranging from 20 to 60 nm. The CNTs have a bamboo-like structure and exhibit good crystallinity of graphite sheets. The growth rate of the CNTs was rapidly increased with adding C 2H 2. Our results demonstrate that the proposed growth method is suitable to large-scale synthesis of high-purity well-aligned CNTs on various substrates.

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.

Transformation of metallic boron into substitutional dopants in graphene on 6H-SIC(0001)

Czech Academy of Sciences Publication Activity Database

Sforzini, J.; Telychko, Mykola; Krejčí, Ondřej; Vondráček, Martin; Švec, Martin; Bocquet, F.C.; Tautz, F.S.

2016-01-01

Roč. 93, č. 4 (2016), 1-4, č. článku 041302. ISSN 1098-0121 R&D Projects: GA ČR GA15-07172S Institutional support: RVO:68378271 Keywords : heavily nitrogenated graphene * chemisorbed molecules * recent progress * performance Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.736, year: 2014

Prototype Tests for the Recovery and Conversion of UF6 Chemisorbed in NaF Traps for the Molten Salt Reactor Remediation Project

International Nuclear Information System (INIS)

Del Cul, G.D.; Icenhour, A.S.; Simmons, D.W.

2000-01-01

The remediation of the Molten Salt Reactor Experiment (MSRE) site includes the removal of about 37 kg of uranium. Of that inventory, about 23 kg have already been removed from the piping system and chemisorbed in 25 NaF traps. This material is being stored in Building 3019. The planned recovery of -11 kg of uranium from the fuel salt will generate another 15 to 19 NaF traps. The remaining 2 to 3 kg of uranium are present in activated charcoal beds, which are also scheduled to be removed from the reactor site. Since all of these materials (NaF traps and the uranium-laden charcoal) are not suitable for long-term storage, they will be converted to a chemical form (uranium oxide), which is suitable for long-term storage. This document describes the process that will be used to recover and convert the uranium in the NaF traps into a stable oxide for long-term storage. Included are a description of the process, equipment, test results, and lessons learned. The process was developed for remote operation in a hot cell. Lessons learned from the prototype testing were incorporated into the process design

Prototype Tests for the Recovery and Conversion of UF6 Chemisorbed in NaF Traps for the Molten Salt Reactor Remediation Project

Energy Technology Data Exchange (ETDEWEB)

Del Cul, G.D.; Icenhour, A.S.; Simmons, D.W.

2000-04-01

The remediation of the Molten Salt Reactor Experiment (MSRE) site includes the removal of about 37 kg of uranium. Of that inventory, about 23 kg have already been removed from the piping system and chemisorbed in 25 NaF traps. This material is being stored in Building 3019. The planned recovery of -11 kg of uranium from the fuel salt will generate another 15 to 19 NaF traps. The remaining 2 to 3 kg of uranium are present in activated charcoal beds, which are also scheduled to be removed from the reactor site. Since all of these materials (NaF traps and the uranium-laden charcoal) are not suitable for long-term storage, they will be converted to a chemical form [uranium oxide], which is suitable for long-term storage. This document describes the process that will be used to recover and convert the uranium in the NaF traps into a stable oxide for long-term storage. Included are a description of the process, equipment, test results, and lessons learned. The process was developed for remote operation in a hot cell. Lessons learned from the prototype testing were incorporated into the process design.

Iron(III) phthalocyanine supported on a spongin scaffold as an advanced photocatalyst in a highly efficient removal process of halophenols and bisphenol A.

Science.gov (United States)

Norman, Małgorzata; Żółtowska-Aksamitowska, Sonia; Zgoła-Grześkowiak, Agnieszka; Ehrlich, Hermann; Jesionowski, Teofil

2018-04-05

This study investigated for the first time the degradation of phenol, chlorophenol, fluorophenol and bisphenol A (BPA) by the novel iron phthalocyanine/spongin hybrid material under various process conditions: hydrogen peroxide and UV irradiation. The heterogeneous catalyst, iron phthalocyanine/spongin (SFe), was produced by an adsorption process. The product obtained was investigated by a variety of spectroscopic techniques - X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) and carbon-13 nuclear magnetic resonance ( 13 C NMR) - as well as elemental and thermal analysis. The study confirmed the stable immobilization of the dye on the biopolymer. The results demonstrate that the degradation of phenols and BPA followed pseudo-second-order kinetics under different experimental conditions. The synergy of SFe, H 2 O 2 and UV was found to produce a significant increase in the removal efficiency and resulted in complete removal of contaminants in a short time of 1 h. The reaction products were identified by high-performance liquid chromatography/mass spectrometry (HPLC-MS) and possible degradation pathways were proposed, featuring a series of steps including cleavage of CC bonds and oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Monolayer Cu2Si as a potential gas sensor for NOx and COx (x = 1, 2): A first-principles study

Science.gov (United States)

Zhu, Hao-Hao; Ye, Xiao-Juan; Liu, Chun-Sheng; Yan, Xiao-Hong

2018-02-01

Although the metal-decoration can enhance the sensing properties of two-dimensional (2D) materials, the cyclic utilization of materials is hindered by the clustering tendency of metal atoms. Furthermore, there exists a risk of explosion of combustible gases with the electrical measure. Based on first-principles calculations, we investigate the adsorption of various gas molecules (O2, NO, NO2, NH3, N2, CO, CH4 and CO2) on the 2D Cu-Si extended system (Cu2Si). The NOx molecules are chemisorbed on the Cu2Si monolayer, while other gas molecules (except CH4 and N2) are held by an interaction intermediating between the physisorbed and chemisorbed states. The strong hybridizations between N 2p and Si 3p (Cu 4p) orbitals lead to the large adsorption energies. Interestingly, the adsorption of NOx (1 μB) and CO2 (2 μB) can induce magnetic moments on the intrinsically nonmagnetic Cu2Si monolayer. The magnetic moment of NO-Cu2Si mainly arises from the molecule, while the magnetic moments for the NO2 and CO2 adsorption almost origin from the monolayer. In addition, an antiferromagnetic coupling is found in CO-Cu2Si. The changes in magnetization upon the gas adsorption may be detected sensitively and safely, suggesting the Cu2Si monolayer is potential for gas sensing.

Effect of oxide insertion layer on resistance switching properties of copper phthalocyanine

Science.gov (United States)

Joshi, Nikhil G.; Pandya, Nirav C.; Joshi, U. S.

2013-02-01

Organic memory device showing resistance switching properties is a next-generation of the electrical memory unit. We have investigated the bistable resistance switching in current-voltage (I-V) characteristics of organic diode based on copper phthalocyanine (CuPc) film sandwiched between aluminum (Al) electrodes. Pronounced hysteresis in the I-V curves revealed a resistance switching with on-off ratio of the order of 85%. In order to control the charge injection in the CuPc, nanoscale indium oxide buffer layer was inserted to form Al/CuPc/In2O3/Al device. Analysis of I-V measurements revealed space charge limited switching conduction at the Al/CuPc interface. The traps in the organic layer and charge blocking by oxide insertion layer have been used to explain the absence of resistance switching in the oxide buffer layered memory device cell. Present study offer potential applications for CuPc organic semiconductor in low power non volatile resistive switching memory and logic circuits.

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)

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.

Diffusion of 1,4-butanedithiol radicals on Au(111) and Au(100): A DFT-based comparison

Energy Technology Data Exchange (ETDEWEB)

Franke, Andreas; Pehlke, Eckhard [Institut fuer Theoretische Physik und Astrophysik, Universitaet Kiel, 24098 Kiel (Germany)

2010-07-01

Organic molecules chemisorbed on surfaces hold the perspective of surface functionalization. The 1,4-butanedithiol radical chemisorbed at the Au(111) or Au(100) surface serves as a model system for the S-Au molecule-substrate bond. Density functional total-energy calculations have been carried out for the chemisorption of the radical on the unreconstructed Au surfaces, which are both known to be stabilized under electrochemical conditions. Local minima with close-by energies indicate multi-valley potential-energy surfaces, which originate from the interplay between the two S-Au adsorbate-substrate bonds and the internal degrees of freedom of the butanedithiol radical. Diffusion paths of the radical on both Au surfaces have been calculated within DFT using VASP. The diffusion barriers for translation and rotation of the radical differ. They can be fine-tuned by varying the applied potential in the electrochemical cell. This is considered theoretically by inspecting the variation of the dipole moment along the reaction paths. Consequences for the dynamics of succeeding diffusion hops are discussed.

Photodynamic antimicrobial chemotherapy using zinc phthalocyanine derivative for bacterial skin infection

Science.gov (United States)

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

2014-09-01

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

Mechanism of photodynamic inactivation of hepatocarcinoma cells with sulfonated aluminum phthalocyanine

Science.gov (United States)

Yu, Hong-Yu; Dong, Rong-Chun; Chen, Ji-Yao; Cai, Huai-Xin

1993-03-01

The mechanism of photodynamic therapy (PDT) with sulfonated aluminum phthalocyanine (AlSPC) studied with the human hepatocellular carcinoma cell line in culture is reported herein. Photofrin II (PII) was chosen as the control photosensitizer of AlSPC. Deuterium oxide (D2O), an enhancer of singlet oxygen (1O2); 1,3-diphenylisobenzofuran (DPBF), a quencher of 1O2: glycerol, a quencher of OH radical (OH(DOT)); superoxide dismutase (SOD), a quencher of O2- radical (O2-(DOT)); diethyldithiocarbamate (DDC), an inhibitor of SOD and glutathione peroxidase; were introduced into both the processes of photodynamic inactivation of human liver cancer cells in culture with AlSPC (AlSPC-PDT) and with PII (PII-PDT). The results suggest that: 1O2 is dominantly involved in both PII-PDT and AlSPC-PDT; O2-(DOT) is involved in AlSPC-PDT in a lower degree than 1O2, while almost not involved in PII-PDT; OH(DOT) is involved in PII-PDT in a lower degree than 1O2, while almost not involved in AlSPC-PDT.

Inversed linear dichroism in F K-edge NEXAFS spectra of fluorinated planar aromatic molecules

DEFF Research Database (Denmark)

de Oteyza, D. G.; Sakko, A.; El-Sayed, A.

2012-01-01

The symmetry and energy distribution of unoccupied molecular orbitals is addressed in this work by means of NEXAFS and density functional theory calculations for planar, fluorinated organic semiconductors (perfluorinated copper phthalocyanines and perfluoropentacene). We demonstrate how molecular...

The carbon matrices made of pyrolyzed phthalocyanines as a base for encapsulation of the long-lived nuclides of iodine, technetium and minor actinides

International Nuclear Information System (INIS)

Tikhonov, V.I.; Moskalev, P.N.; Kapustin, V.K.

2007-01-01

The creation and careful investigation of suitable materials and forms for transmutation of the long-lived radioactive waste (RW) is mainly in the starting stage. A new carbon material formed as a result of pyrolysis of bis-phthalocyanine, Pc2Me, gives a chance to solve this goal successfully. The pyrolysis takes place under an argon (Ar) atmosphere at temperature of 700 - 800 deg. C. The release of atoms encapsulated inside this carbon matrix occurs only at temperatures above 1200 deg. C, and a correlation between the efficiency of the atoms' release and their atomic radius has been revealed. It is caused with creation of closed micro-cavities in the carbon skeleton during pyrolysis of MeC 2. Due to inert features and high thermostability of carbon, an inculcation of the long-lived radionuclides in these micro-cavities by means of their phthalocyanines pyrolysis gives unique opportunities for both their transmutation and storage. The first results on encapsulation within matrixes of radionuclides of europium (Eu), technetium (Te), iodine (I) and 'minor actinides' are presented. The efficiency of encapsulation is close to 100% for all studied elements excluding iodine, for the last one, it is near 85-90%. The results on thermochemical stability, leaching and other tests of these matrixes are presented. (authors)

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

Science.gov (United States)

Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

2017-06-27

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

The surface oxide as a source of oxygen on Rh(1 1 1)

Energy Technology Data Exchange (ETDEWEB)

Lundgren, E. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden)]. E-mail: edvin.lundgren@sljus.lu.se; Gustafson, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Resta, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Weissenrieder, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Mikkelsen, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Andersen, J.N. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Koehler, L. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Kresse, G. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Klikovits, J. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Biederman, A. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Schmid, M. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Varga, P. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria)

2005-06-15

The reduction of a thin surface oxide on the Rh(1 1 1) surface by CO is studied in situ by photoemission spectroscopy, scanning tunneling microscopy, and density functional theory. CO molecules are found not to adsorb on the surface oxide at a sample temperature of 100 K, in contrast to on the clean and chemisorbed oxygen covered surface. Despite this behavior, the surface oxide may still be reduced by CO, albeit in a significantly different fashion as compared to the reduction of a phase containing only chemisorbed on surface oxygen. The experimental observations combined with theoretical considerations concerning the stability of the surface oxide, result in a model of the reduction process at these pressures suggesting that the surface oxide behaves as a source of oxygen for the CO-oxidation reaction.

Orbital tomography: Molecular band maps, momentum maps and the imaging of real space orbitals of adsorbed molecules

Energy Technology Data Exchange (ETDEWEB)

Offenbacher, Hannes; Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg, E-mail: georg.koller@uni-graz.at; Puschnig, Peter; Ramsey, Michael G., E-mail: michael.ramsey@uni-graz.at

2015-10-01

Highlights: • Orbital tomography within the plane wave final state approximation. • One electron orbital predictions versus angle resolved photoemission experiment. • Geometric and electronic structure of organic thin films elucidated by ARUPS. • Influence of molecular conformation and orientation on ARUPS. • Retrieval of sexiphenyl and pentacene orbitals in real space. - Abstract: The frontier orbitals of molecules are the prime determinants of their chemical, optical and electronic properties. Arguably, the most direct method of addressing the (filled) frontier orbitals is ultra-violet photoemission spectroscopy (UPS). Although UPS is a mature technique from the early 1970s on, the angular distribution of the photoemitted electrons was thought to be too complex to be analysed quantitatively. Recently angle resolved UPS (ARUPS) work on conjugated molecules both, in ordered thick films and chemisorbed monolayers, has shown that the angular (momentum) distribution of the photocurrent from orbital emissions can be simply understood. The approach, based on the assumption of a plane wave final state is becoming known as orbital tomography. Here we will demonstrate, with selected examples of pentacene (5A) and sexiphenyl (6P), the potential of orbital tomography. First it will be shown how the full angular distribution of the photocurrent (momentum map) from a specific orbital is related to the real space orbital by a Fourier transform. Examples of the reconstruction of 5A orbitals will be given and the procedure for recovering the lost phase information will be outlined. We then move to examples of sexiphenyl where we interrogate the original band maps of thick sexiphenyl in the light of our understanding of orbital tomography that has developed since then. With comparison to theoretical simulations of the molecular band maps, the molecular conformation and orientation will be concluded. New results for the sexiphenyl monolayer on Al(1 1 0) will then be

The properties of samarium-doped zinc oxide/phthalocyanine structure for optoelectronics prepared by pulsed laser deposition and organic molecular evaporation

Czech Academy of Sciences Publication Activity Database

Novotný, Michal; Marešová, Eva; Fitl, Přemysl; Vlček, Jan; Bergmann, M.; Vondráček, Martin; Yatskiv, Roman; Bulíř, Jiří; Hubík, Pavel; Hruška, Petr; Drahokoupil, Jan; Abdellaoui, N.; Vrňata, M.; Lančok, Ján

2016-01-01

Roč. 122, č. 3 (2016), 1-8, č. článku 225. ISSN 0947-8396 R&D Projects: GA MŠk(CZ) LG15050; GA ČR(CZ) GAP108/11/0958; GA MŠk(CZ) LM2011029; GA ČR(CZ) GA14-10279S; GA MŠk(CZ) 7AMB14FR010 Institutional support: RVO:68378271 ; RVO:67985882 Keywords : samarium-doped zinc oxide zinc/phthalocyanine deposition * evaporation * pulsed laser deposition * thin films Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.455, year: 2016

Influence of Fe{sub 3}O{sub 4}/Fe-phthalocyanine decorated graphene oxide on the microwave absorbing performance

Energy Technology Data Exchange (ETDEWEB)

Li, Jingwei; Wei, Junji; Pu, Zejun; Xu, Mingzhen; Jia, Kun, E-mail: jiakun@uestc.edu.cn; Liu, Xiaobo, E-mail: liuxb@uestc.edu.cn

2016-02-01

Novel graphene oxide@Fe{sub 3}O{sub 4}/iron phthalocyanine (GO@Fe{sub 3}O{sub 4}/FePc) hybrid materials were prepared through a facile one-step solvothermal method with graphene oxide (GO) sheets as template in ethylene glycol. The morphology and structure of the hybrid materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectrophotometer (FTIR) and X-ray diffraction (XRD), respectively. The results indicated that the monodispersed Fe{sub 3}O{sub 4}/FePc hybrid microspheres were uniformly self-assembled along the surface of GO sheets through electrostatic attraction and the morphology can be tuned by controlling the amount of 4,4′-bis(3,4-dicyanophenoxy)biphenyl (BPH). As the BPH content increases, magnetization measurement of the GO@Fe{sub 3}O{sub 4}/FePc hybrid materials showed that the coercivity increased, while saturation magnetizations decreased. Electromagnetic properties of the hybrid materials were measured in the range of 0.5–18.0 GHz. The microwave absorbing performance enhanced with the increase of BPH content and a maximum reflection loss of −27.92 dB was obtained at 10.8 GHz when the matching thickness was 2.5 mm. Therefore, the novel electromagnetic hybrid materials can be considered as potential materials in the microwave absorbing field. - Highlights: • Graphene oxide was employed to support Fe{sub 3}O{sub 4}/iron phthalocyanine hybrid particles. • The morphology and magnetic properties of obtained particles can be readily tuned. • A maximum microwave reflection loss of −27.92 dB was obtained at 10.8 GHz.

Raman excitation profiles of hybrid systems constituted by single-layer graphene and free base phthalocyanine: Manifestations of two mechanisms of graphene-enhanced Raman scattering

Czech Academy of Sciences Publication Activity Database

Uhlířová, T.; Mojzeš, P.; Melníková Komínková, Zuzana; Kalbáč, Martin; Sutrová, Veronika; Šloufová, I.; Vlčková, B.

2017-01-01

Roč. 48, č. 10 (2017), s. 1270-1281 ISSN 0377-0486 R&D Projects: GA ČR(CZ) GA15-01953S Institutional support: RVO:61388955 ; RVO:61389013 Keywords : graphene-enhanced Raman scattering * single-layer graphene * free base phthalocyanine * Raman excitation profiles * photoinduced charge transfer Subject RIV: CF - Physical ; Theoretical Chemistry; CD - Macromolecular Chemistry (UMCH-V) OBOR OECD: Physical chemistry; Polymer science (UMCH-V) Impact factor: 2.969, year: 2016

Analysis of functional organic molecules at noble metal surfaces by means of vibrational spectroscopies

Energy Technology Data Exchange (ETDEWEB)

Leyssner, Felix

2011-10-24

The goal of this work is to optimize the efficiency of photoinduced molecular switching processes on surfaces via controlled variations of the adsorption and electronic properties of the switch. We investigated the influence of external stimuli, i.e. photons and thermal activation, on surface bound molecular switches undergoing trans/cis-isomerizations and ring-opening/closing-reactions, respectively. High resolution electron energy loss spectroscopy (HREELS) and sum-frequency generation (SFG) spectroscopy have been used as the main tools to investigate the adsorption behavior and the molecular switching properties. Two basic concepts of coupling the molecular switch to the surface have been studied: (i) physisorbed or weakly chemisorbed systems deposited on noble metal surfaces under UHV conditions and (ii) molecular switches bound covalently via anchor groups. In the HREELS study following concept (i), we investigated the adsorption geometry and isomerization behavior of various molecular switches on metal substrates which are able to undergo a photoinduced trans/cis-isomerization in solution. We investigated three isoelectronic molecules on Au where we systematically changed the photochemically active group from the diazo-group in an azobenzene-derivative (on Cu(111)) to the imine-group, and the vinylene-group, respectively. Finding the photoisomerization quenched for all systems we observed considerable differences in their thermal isomerization behavior. Comparable we find the photoinduced ring-opening/closing-reaction of spiropyran quenched on Au(111) but a thermally induced ring-opening reaction resulting in the open form being strongly stabilized by the metal. SFG spectroscopy is employed to investigate the reversible, photoinduced trans/cis-isomerization of an azobenzene-functionalized self-assembled monolayer (SAM) on gold using a tripodal linker system. In consequence of the decoupling provided by the tripodal linker, the switching behavior of the

Influence of axial and peripheral ligands on the electronic structure of titanium phthalocyanines

DEFF Research Database (Denmark)

Pickup, David F.; García Lastra, Juan Maria; Rogero, Celia

2013-01-01

core-level binding energy was observed in the bidentate complex and compared to a calculated core-level stabilization. DFT predicts a change of the LUMO from the inner phthalocyanine ring to the Ti dxy orbital and a reversal of the high-lying dx2-y2 and d z2 orbitals. The N 1s edge was calculated using......-ray absorption spectroscopy and photoelectron spectroscopy were combined with density functional theory (DFT) and crystal-field multiplet calculations to characterize the Ti 3d and N 2p valence electrons that form the frontier orbitals. When a monodentate oxo axial ligand was replaced by a bidentate catechol...... ligand, the multiplet structure of the Ti 2p-to-3d transitions was found to change systematically. The most noticeable change was an additional transition into the low-lying 3dxy level, which is attributed to a reduction in local symmetry from 4-fold to 2-fold at the Ti center. An increase of the Ti 2p...

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-10-15

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

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

Directory of Open Access Journals (Sweden)

Yu-Long Wang

2015-10-01

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

Synthesis, structure, and optical properties of manganese phthalocyanine thin films and nanostructures

Directory of Open Access Journals (Sweden)

Lu Meng

2017-06-01

Full Text Available Manganese phthalocyanine (MnPc nanostructures with different morphologies were prepared on porous anodic alumina oxide (AAO at different substrate temperature (Ts=50 ℃, 80 ℃, 120 ℃, 180 ℃, 240 ℃ in an organic molecular beam deposition (OMBD system. The nanostructures morphologies were studied using scanning electron microscopy (SEM and the results showed that the nanostructures morphologies could be modulated by the control of Ts, as a result, the continuous film was obtained at 50 ℃, whereas the nanorods (NRs, nanoribbons (NBs, nanowires (NWs, nanosheets (NSs and nanoparticles (NPs were facilely generated as Ts increased. At the same time, the density and the uniformity of the nanostructures decreased. The results of X-ray diffraction (XRD indicated that only the β-phase polymorph formed throughout the growth process irrelevant to the Ts. Additionally, the ultraviolet visible (UV–Vis absorption spectra demonstrated that the main absorption bands of MnPc nanostructures showed a remarkable band broadening as the Ts was increased.

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.

Synergistic interaction between gold nanoparticles and nickel phthalocyanine in layer-by-layer (LbL) films: evidence of constitutional dynamic chemistry (CDC).

Science.gov (United States)

Alencar, Wagner S; Crespilho, Frank N; Martins, Marccus V A; Zucolotto, Valtencir; Oliveira, Osvaldo N; Silva, Welter C

2009-07-07

The concept of constitutional dynamic chemistry (CDC) based on the control of non-covalent interactions in supramolecular structures is promising for having a large impact on nanoscience and nanotechnology if adequate nanoscale manipulation methods are used. In this study, we demonstrate that the layer-by-layer (LbL) technique may be used to produce electroactive electrodes with ITO coated by tetrasulfonated nickel phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) incorporating gold nanoparticles (AuNP), in which synergy has been achieved in the interaction between the nanoparticles and NiTsPc. The catalytic activity toward hydrogen peroxide (H(2)O(2)) in multilayer films was investigated using cyclic voltammetry, where oxidation of H(2)O(2) led to increased currents in the PAH-AuNP/NiTsPc films for the electrochemical processes associated with the phthalocyanine ring and nickel at 0.52 and 0.81 V vs. SCE, respectively, while for PAH/NiTsPc films (without AuNP) only the first redox process was affected. In control experiments we found out that the catalytic activity was not solely due to the presence of AuNP, but rather to the nanoparticles inducing NiTsPc supramolecular structures that favored access to their redox sites, thus yielding strong charge transfer. The combined effects of NiTsPc and AuNP, which could only be observed in nanostructured LbL films, point to another avenue to pursue within the CDC paradigm.

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

Molecular distortion and charge transfer effects in ZnPc/Cu(111)

KAUST Repository

Amin, B.; Nazir, S.; Schwingenschlö gl, Udo

2013-01-01

The adsorption geometry and electronic properties of a zinc-phthalocyanine molecule on a Cu(111) substrate are studied by density functional theory. In agreement with experiment, we find remarkable distortions of the molecule, mainly as the central Zn atom tends towards the substrate to minimize the Zn-Cu distance. As a consequence, the Zn-N chemical bonding and energy levels of the molecule are significantly modified. However, charge transfer induces metallic states on the molecule and therefore is more important for the ZnPc/Cu(111) system than the structural distortions.

Molecular distortion and charge transfer effects in ZnPc/Cu(111)

KAUST Repository

Amin, B.

2013-04-23

The adsorption geometry and electronic properties of a zinc-phthalocyanine molecule on a Cu(111) substrate are studied by density functional theory. In agreement with experiment, we find remarkable distortions of the molecule, mainly as the central Zn atom tends towards the substrate to minimize the Zn-Cu distance. As a consequence, the Zn-N chemical bonding and energy levels of the molecule are significantly modified. However, charge transfer induces metallic states on the molecule and therefore is more important for the ZnPc/Cu(111) system than the structural distortions.

Theoretical Studies of the Structure and the Dynamics on Clean and Chemisorbed Metal Surfaces

Science.gov (United States)

Yang, Liqiu

Molecular dynamics (MD) and lattice dynamics (LD) techniques are employed to investigate several phenomena related to the structure and vibrations at metal surfaces. The MD simulations are performed with the many-body interaction potentials obtained using the Embedded-Atom Method (EAM). As specific examples, we present the results for Ag(100) at 300 K and Cu(100) at 150 K, 300 K, and 600 K. The calculated frequencies and polarizations of all surface modes and resonances at the high-symmetry points in the two-dimensional Brillouin zone are in good agreement with available data, as well as, existing lattice dynamics results with force constants obtained from first-principles calculations. Our calculated surface relaxation is also in reasonable agreement with the data. We also test a much simpler lattice dynamics model with nearest neighbor central force interactions, and conclude that it can reproduce the main features of the phonon modes, but only when adjustable surface parameters are used. Additionally, the temperature dependent studies of the phonon line-widths and the mean-square displacement (MSD) of surface atoms are indicative of enhanced surface anharmonicity. On several chemisorbed metal surfaces, for which force constants are not available from first-principles calculations or the EAM, we perform lattice dynamics studies of phonon dispersion curves using simple force-constant models. These studies provide reliable mean-square displacement of surface atoms and can distinguish between possible reconstruction patterns, the results being insensitive to the exact values of the surface parameters. On c(2 times 2)S-Ni(100), it is found that the parallel component of the mean-square displacement for sulfur is around 50% larger than the vertical component, but for the mean-square displacement of oxygen atoms in the system c(2 times 2)O-Ni(100), the opposite is the case. As regards surface reconstruction, for both p(2 times 1)O-Ag(110) and p(2 times 1)O-Ni(110

Some unusual properties of activated and reduced AgNaA zeolites

Energy Technology Data Exchange (ETDEWEB)

Jacobs, P.A. (Katholieke Univ. Leuven); Uytterhoeven, J.B.; Beyer, H.K.

1979-01-01

In a study of chemisorption on dehydrated silver-exchanged A zeolite by volumetric sorption and temperature-programed desorption techniques, an autoreductive process which created intense color centers, occurred on degassing the zeolite because of the formation of silver covalent bonds. The chemisorption of hydrogen was proportional to the amount of autoreduction, indicating that the process occurred on the color centers. Both oxygen and hydrogen chemisorbed dissociatively, as shown by tracing with labeled oxygen and by the ability of one water molecule to replace two hydrogen atoms. Carbon monoxide, however, was chemisorbed on the available silver ions in the zeolite supercages, whether or not they were a part of the cluster formation. Linear silver ion/silver/silver ion clusters are apparently formed in the zeolite cubo-octahedra upon activation; the ends form chemisorption sites for hydrogen and oxygen.

Quantum dynamics of the Eley-Rideal hydrogen formation reaction on graphite at typical interstellar cloud conditions.

Science.gov (United States)

Casolo, Simone; Martinazzo, Rocco; Bonfanti, Matteo; Tantardini, Gian Franco

2009-12-31

Eley-Rideal formation of hydrogen molecules on graphite, as well as competing collision induced processes, are investigated quantum dynamically at typical interstellar cloud conditions, focusing in particular on gas-phase temperatures below 100 K, where much of the chemistry of the so-called diffuse clouds takes place on the surface of bare carbonaceous dust grains. Collisions of gas-phase hydrogen atoms with both chemisorbed and physisorbed species are considered using available potential energy surfaces (Sha et al., J. Chem. Phys.2002 116, 7158), and state-to-state, energy-resolved cross sections are computed for a number of initial vibrational states of the hydrogen atoms bound to the surface. Results show that (i) product molecules are internally hot in both cases, with vibrational distributions sharply peaked around few (one or two) vibrational levels, and (ii) cross sections for chemisorbed species are 2-3x smaller than those for physisorbed ones. In particular, we find that H(2) formation cross sections out of chemically bound species decrease steadily when the temperature drops below approximately 1000 K, and this is likely due to a quantum reflection phenomenon. This suggests that such Eley-Rideal reaction is all but efficient in the relevant gas-phase temperature range, even when gas-phase H atoms happen to chemisorb barrierless to the surface as observed, e.g., for forming so-called para dimers. Comparison with results from classical trajectory calculations highlights the need of a quantum description of the dynamics in the astrophysically relevant energy range, whereas preliminary results of an extensive first-principles investigation of the reaction energetics reveal the importance of the adopted substrate model.

Photoinduced electron transfer through peptide-based self-assembled monolayers chemisorbed on gold electrodes: directing the flow-in and flow-out of electrons through peptide helices.

Science.gov (United States)

Venanzi, Mariano; Gatto, Emanuela; Caruso, Mario; Porchetta, Alessandro; Formaggio, Fernando; Toniolo, Claudio

2014-08-21

Photoinduced electron transfer (PET) experiments have been carried out on peptide self-assembled monolayers (SAM) chemisorbed on a gold substrate. The oligopeptide building block was exclusively formed by C(α)-tetrasubstituted α-aminoisobutyric residues to attain a helical conformation despite the shortness of the peptide chain. Furthermore, it was functionalized at the C-terminus by a pyrene choromophore to enhance the UV photon capture cross-section of the compound and by a lipoic group at the N-terminus for linking to gold substrates. Electron transfer across the peptide SAM has been studied by photocurrent generation experiments in an electrochemical cell employing a gold substrate modified by chemisorption of a peptide SAM as a working electrode and by steady-state and time-resolved fluorescence experiments in solution and on a gold-coated glass. The results show that the electronic flow through the peptide bridge is strongly asymmetric; i.e., PET from the C-terminus to gold is highly favored with respect to PET in the opposite direction. This effect arises from the polarity of the Au-S linkage (Au(δ+)-S(δ-), junction effect) and from the electrostatic field generated by the peptide helix.

Bulk functionalization of graphene using diazonium compounds and amide reaction

Science.gov (United States)

Peng, Chang; Xiong, Yuzi; Liu, Zhibo; Zhang, Fan; Ou, Encai; Qian, Jiangtao; Xiong, Yuanqin; Xu, Weijian

2013-09-01

An efficient and convenient method is applied to introduce varieties of simple functionalities onto the graphene surface for the bulk preparation, which begins with pristine graphite that does not require initial oxidative damage of the graphene basal planes. Diazonium compounds functionalized reaction is demonstrated and it successfully prevented the aggregation of graphene for which providing solubility in high polar organic media or even in volatile solvents such as ethanol and acetone. This approach is complemented by the phenyl carboxylic diazonium salt functionalized graphene (PCFG) attachment of a symmetrically substituted zinc phthalocyanine (PCFG-Pc) using the amide reaction, which is used for the covalent introduction of a complex phthalocyanine molecule.

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

Science.gov (United States)

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

2017-07-28

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

l-Tyrosine Contained in Dietary Supplement by Chemiluminescence Reaction of an Iron-Phthalocyanine Complex

Directory of Open Access Journals (Sweden)

Takao Ohtomo

2012-01-01

Full Text Available The chemiluminescence (CL signal immediately appeared when a hydrogen peroxide solution was injected into an iron-phthalocyanine tetrasulfonic acid (Fe-PTS aqueous solution. Moreover, the CL intensity of Fe-PTS decreased by adding L-tyrosine. Based on these results, the determination of trace amounts of L-tyrosine was developed using the quenching-chemiluminescence. The calibration curve of L-tyrosine was obtained in the concentration range of 2.0×10−7 M to 2.0×10−5 M. Moreover, the relative standard deviation (RSD was 1.63 % (=5 for 2.0×10−6 M L-tyrosine, and its detection limits (3σ were 1.81×10−7 M. The spike and recovery experiments for L-tyrosine were performed using a soft drink. Furthermore, the determination of L-tyrosine was applied to supplements containing various kinds of amino acids. Each satisfactory relative recovery was obtained at 98 to 102%.

Theoretical study of the binding nature of glassy carbon with nickel(II) phthalocyanine complexes

International Nuclear Information System (INIS)

Cortez, Luis; Berrios, Cristhian; Yanez, Mauricio; Cardenas-Jiron, Gloria I.

2009-01-01

A theoretical study at the semiempirical RHF/PM3(tm) level (tm: transition metal) of the binding nature between a glassy carbon (GC) cluster and a nickel(II) complex (nickel(II) phthalocyanine NiPc, nickel(II) tetrasulphophthalocyanine NiTSPc) was performed. Three types of interactions for GC...NiPc (NiTSPc) were studied: (a) through an oxo (O) bridge, (b) through an hydroxo (OH) bridge, and (c) non-bridge. One layer (NiPc, NiTSPc) and two layers (NiPc...NiPc) of complex were considered. The binding energy calculated showed that in both cases NiPc and NiTSPc, the oxo structures are more stable than the hydroxo ones, and than the non-bridge systems. Charge analysis (NAO) predicted that GC gained more electrons in an oxo structure than in the analogues hydroxo. The theoretical results showed an agreement with the experimental data available, an oxo binding between GC and a nickel complex (NiPc, NiTSPc) in aqueous alkaline solutions is formed.

Theoretical study of the binding nature of glassy carbon with nickel(II) phthalocyanine complexes

Energy Technology Data Exchange (ETDEWEB)

Cortez, Luis [Laboratorio de Quimica Teorica, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile); Berrios, Cristhian [Laboratorio de Electrocatalisis, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile); Yanez, Mauricio [Laboratorio de Recursos Renovables, Centro de Biotecnologia, Universidad de Concepcion, Casilla-160 C, Concepcion (Chile); Cardenas-Jiron, Gloria I., E-mail: gloria.cardenas@usach.cl [Laboratorio de Quimica Teorica, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile)

2009-11-26

A theoretical study at the semiempirical RHF/PM3(tm) level (tm: transition metal) of the binding nature between a glassy carbon (GC) cluster and a nickel(II) complex (nickel(II) phthalocyanine NiPc, nickel(II) tetrasulphophthalocyanine NiTSPc) was performed. Three types of interactions for GC...NiPc (NiTSPc) were studied: (a) through an oxo (O) bridge, (b) through an hydroxo (OH) bridge, and (c) non-bridge. One layer (NiPc, NiTSPc) and two layers (NiPc...NiPc) of complex were considered. The binding energy calculated showed that in both cases NiPc and NiTSPc, the oxo structures are more stable than the hydroxo ones, and than the non-bridge systems. Charge analysis (NAO) predicted that GC gained more electrons in an oxo structure than in the analogues hydroxo. The theoretical results showed an agreement with the experimental data available, an oxo binding between GC and a nickel complex (NiPc, NiTSPc) in aqueous alkaline solutions is formed.

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 ...

Improved Reliability of Small Molecule Organic Solar Cells by Double Anode Buffer Layers

Directory of Open Access Journals (Sweden)

Pao-Hsun Huang

2014-01-01

Full Text Available An optimized hybrid planar heterojunction (PHJ of small molecule organic solar cells (SM-OSCs based on copper phthalocyanine (CuPc as donor and fullerene (C60 as acceptor was fabricated, which obviously enhanced the performance of device by sequentially using both MoO3 and pentacene as double anode buffer layers (ABL, also known as hole extraction layer (HEL. A series of the vacuum-deposited ABL, acting as an electron and exciton blocking layer, were examined for their characteristics in SM-OSCs. The performance and reliability were compared between conventional ITO/ABL/CuPc/C60/BCP/Ag cells and the new ITO/double ABL/CuPc/C60/BCP/Ag cells. The effect on the electrical properties of these materials was also investigated to obtain the optimal thickness of ABL. The comparison shows that the modified cell has an enhanced reliability compared to traditional cells. The improvement of lifetime was attributed to the idea of double layers to prevent humidity and oxygen from diffusing into the active layer. We demonstrated that the interfacial extraction layers are necessary to avoid degradation of device. That is to say, in normal temperature and pressure, a new avenue for the device within double buffer layers has exhibited the highest values of open circuit voltage (Voc, fill factor (FF, and lifetime in this work compared to monolayer of ABL.

Reaction of hydrogen with Ag(111): binding states, minimum energy paths, and kinetics.

Science.gov (United States)

Montoya, Alejandro; Schlunke, Anna; Haynes, Brian S

2006-08-31

The interaction of atomic and molecular hydrogen with the Ag(111) surface is studied using periodic density functional total-energy calculations. This paper focuses on the site preference for adsorption, ordered structures, and energy barriers for H diffusion and H recombination. Chemisorbed H atoms are unstable with respect to the H(2) molecule in all adsorption sites below monolayer coverage. The three-hollow sites are energetically the most favorable for H chemisorption. The binding energy of H to the surface decreases slightly up to one monolayer, suggesting a small repulsive H-H interaction on nonadjacent sites. Subsurface and vacancy sites are energetically less favorable for H adsorption than on-top sites. Recombination of chemisorbed H atoms leads to the formation of gas-phase H(2) with no molecular chemisorbed state. Recombination is an exothermic process and occurs on the bridge site with a pronounced energy barrier. This energy barrier is significantly higher than that inferred from experimental temperature-programmed desorption (TPD) studies. However, there is significant permeability of H atoms through the recombination energy barrier at low temperatures, thus increasing the rate constant for H(2) desorption due to quantum tunneling effects, and improving the agreement between experiment and theory.

Highly active Pt nanoparticles on nickel phthalocyanine functionalized graphene nanosheets for methanol electrooxidation

International Nuclear Information System (INIS)

Zhong, Jing-Ping; Fan, You-Jun; Wang, Hui; Wang, Rui-Xiang; Fan, Li-Li; Shen, Xing-Can; Shi, Zu-Jin

2013-01-01

Highlights: • A new Pt-based catalyst using TSNiPc functionalized graphene as support is reported. • Pt nanoparticles are uniformly dispersed on the functionalized graphene surface. • The Pt/TSNiPc–graphene shows excellent catalytic performance for methanol oxidation. -- Abstract: A novel electrocatalyst using nickel (II) phthalocyanine-tetrasulfonic acid tetrasodium salt (TSNiPc) functionalized graphene (TSNiPc–graphene) composite as catalyst support for Pt nanoparticles is reported. The surface morphology, composition and structure of the prepared nanocomposites as well as their electrocatalytic properties toward methanol oxidation are characterized by UV–vis absorption spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical tests. Pt nanoparticles are found uniformly dispersed on the surface of TSNiPc–graphene composite, with the small particle size of about 3.1 nm. Studies of cyclic voltammetry and chronoamperometry demonstrate that the Pt/TSNiPc–graphene exhibits much higher electrocatalytic activity and stability than the Pt/graphene catalyst for methanol oxidation

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

Directory of Open Access Journals (Sweden)

H. Derouiche

2013-01-01

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

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

Directory of Open Access Journals (Sweden)

Benny Joseph

2008-01-01

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

Microscopic and Macroscopic Structures of Carbon Nanotubes Produced by Pyrolysis of Iron Phthalocyanine

International Nuclear Information System (INIS)

Huang Shaoming; Dai Liming

2002-01-01

By pyrolysis of iron phthalocyanine (FePc), either in a patterned or non-patterned fashion, under an Ar/H 2 atmosphere, we have demonstrated the large-scale production of aligned carbon nanotubes perpendicular to the substrate surface useful for building devices with three-dimensional structures. Depending on the particular pyrolytic conditions used, carbon nanotubes with a wide range of microscopic structures having curved, helical, coiled, branched, and tube-within-tube shapes have also been prepared by the pyrolysis of FePc. This, coupled with several microfabrication methods (photolithography, soft-lithography, self-assembling, micro-contact transfer, etc.), has enabled us to produce carbon nanotube arrays of various macroscopic architectures including polyhedral, flower-like, dendritic, circular, multilayered, and micropatterned geometries. In this article, we summarize our work on the preparation of FePc-generated carbon nanotubes with the large variety of microscopic and macroscopic structures and give a brief overview on the perspectives of making carbon nanotubes with tailor-made microscopic/macroscopic structures, and hence well-defined physicochemical properties, for specific applications

Organic thin film transistors using a liquid crystalline palladium phthalocyanine as active layer

Science.gov (United States)

Jiménez Tejada, Juan A.; Lopez-Varo, Pilar; Chaure, Nandu B.; Chambrier, Isabelle; Cammidge, Andrew N.; Cook, Michael J.; Jafari-Fini, Ali; Ray, Asim K.

2018-03-01

70 nm thick solution-processed films of a palladium phthalocyanine (PdPc6) derivative bearing eight hexyl (-C6H13) chains at non-peripheral positions have been employed as active layers in the fabrication of bottom-gate bottom-contact organic thin film transistors (OTFTs) deposited on highly doped p-type Si (110) substrates with SiO2 gate dielectric. The dependence of the transistor electrical performance upon the mesophase behavior of the PdPc6 films has been investigated by measuring the output and transfer characteristics of the OTFT having its active layer ex situ vacuum annealed at temperatures between 500 °C and 200 °C. A clear correlation between the annealing temperature and the threshold voltage and carrier mobility of the transistors, and the transition temperatures extracted from the differential scanning calorimetric curves for bulk materials has been established. This direct relation has been obtained by means of a compact electrical model in which the contact effects are taken into account. The precise determination of the contact-voltage drain-current curves allows for obtaining such a relation.

Systematic study on intermolecular valence-band dispersion in molecular crystalline films

International Nuclear Information System (INIS)

Yamane, Hiroyuki; Kosugi, Nobuhiro

2015-01-01

Highlights: • Intermolecular valence-band dispersion of crystalline films of phthalocyanines. • Intermolecular transfer integral versus lattice constant. • Site-specific intermolecular interaction and resultant valence-band dispersion. • Band narrowing effect induced by elevated temperature. - Abstract: Functionalities of organic semiconductors are governed not only by individual properties of constituent molecules but also by solid-state electronic states near the Fermi level such as frontier molecular orbitals, depending on weak intermolecular interactions in various conformations. The individual molecular property has been widely investigated in detail; on the other hand, the weak intermolecular interaction is difficult to investigate precisely due to the presence of the structural and thermal energy broadenings in organic solids. Here we show quite small but essential intermolecular valence band dispersions and their temperature dependence of sub-0.1-eV scale in crystalline films of metal phthalocyanines (H_2Pc, ZnPc, CoPc, MnPc, and F_1_6ZnPc) by using angle-resolved photoemission spectroscopy (ARPES) with synchrotron radiation. The observed bands show intermolecular and site dependent dispersion widths, phases, and periodicities, for different chemical substitution of terminal groups and central metals in the phthalocyanine molecule. The precise and systematic band-dispersion measurement would be a credible approach toward the comprehensive understanding of intermolecular interactions and resultant charge transport properties as well as their tuning by substituents in organic molecular systems.

Prototype Tests for the Recovery and Conversion of UF₆Chemisorbed in NaF Traps for the Molten Salt Reactor Remediation Project

Energy Technology Data Exchange (ETDEWEB)

Del Cul, G.D.

2000-06-07

The remediation of the Molten Salt Reactor Experiment (MSRE) site includes the removal of about 37 kg of uranium. Of that inventory, about 23 kg have already been removed from the piping system and chemisorbed in 25 NaF traps. This material is being stored in Building 3019. The planned recovery of {approx}11 kg of uranium from the fuel salt will generate another 15 to 19 NaF traps. The remaining 2 to 3 kg of uranium are present in activated charcoal beds, which are also scheduled to be removed from the reactor site. Since all of these materials (NaF traps and the uranium-laden charcoal) are not suitable for long-term storage, they will be converted to a chemical form [uranium oxide (U{sub 3}O{sub 8})], which is suitable for long-term storage. This document describes the process that will be used to recover and convert the uranium in the NaF traps into a stable oxide for long-term storage. Included are a description of the process, equipment, test results, and lessons learned. The process was developed for remote operation in a hot cell. Lessons learned from the prototype testing were incorporated into the process design.

Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

Science.gov (United States)

Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan; Gao, Ruimin; Zhao, Jianshe; Wang, Junlong

2015-05-01

M2(PcAN)2 (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M2(PcAN)2-W-HZSM-5) or the M2(PcTN)2 doping W-HZSM-5 (M2(PcTN)2/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu2(PcAN)2-W-HZSM-5 and Cu2(PcTN)2/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV-Vis and calcination temperature was obtained by TG-DSC for Cu2(PcTN)2/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N2 adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. The reaction process of ultra-deep desulfurization.

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:

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

1989-10-20

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

Spectroscopic analysis of the interaction between tetra-(p-sulfoazophenyl-4-aminosulfonyl-substituted aluminum (III phthalocyanines and serum albumins

Directory of Open Access Journals (Sweden)

Liqin Zheng

2017-03-01

Full Text Available The binding interaction between tetra-(p-sulfoazophenyl-4-aminosulfonyl-substituted aluminum (III phthalocyanine (AlPc, and two-serum albumins (bovine serum albumin (BSA and human serum albumin (HSA has been investigated. AlPc could quench the intrinsic fluorescence of BSA and HSA through a static quenching process. The primary and secondary binding sites of AlPc on BSA were domain I and III of BSA. The primary binding site of AlPc on HSA was domain I, and the secondary binding sites of AlPc on HSA were found at domains I and II. Our results suggest that AlPc readily interact with BSA and HSA implying that the amphiphilic substituents AlPc may contribute to their transportation in the blood.

Impact of Molecular Orientation and Spontaneous Interfacial Mixing on the Performance of Organic Solar Cells

KAUST Repository

Ngongang Ndjawa, Guy Olivier; Graham, Kenneth; Li, Ruipeng; Conron, Sarah M; Erwin, Patrick; Chou, Kang Wei; Burkhard, George; Zhao, Kui; Hoke, Eric T.; Thompson, Mark E; McGehee, Michael D.; Amassian, Aram

2015-01-01

A critically important question that must be answered to understand how organic solar cells operate and should be improved is how the orientation of the donor and acceptor molecules at the interface influences exciton diffusion, exciton dissociation by electron transfer and recombination. It is exceedingly difficult to probe the orientation in bulk heterojunctions because there are many interfaces and they are arranged with varying angles with respect to the substrate. One of the best ways to study the interface is to make bilayer solar cells with just one donor-acceptor interface. Zinc phthalocyanine is particularly interesting to study because its orientation can be adjusted by using a 2-nm-thick copper iodide seed layer before it is deposited. Previous studies have claimed that solar cells in which fullerene acceptor molecules touch the face of zinc phthalocyanine have more current than ones in which the fullerenes touch the edge of zinc phthalocyanine because of suppressed recombination. We have more thoroughly characterized the system using in situ x-ray photoelectron spectroscopy and found that the interfaces are not as sharp as previous studies claimed when formed at room temperature or above. Fullerenes have a much stronger tendency to mix into the face-on films than into the edge-on films. Moreover we show that almost all of the increase in the current with face-on films can be attributed to improved exciton diffusion and to the formation of a spontaneously mixed interface, not suppressed recombination. This work highlights the importance of spontaneous interfacial molecular mixing in organic solar cells, the extent of which depends on molecular orientation of frontier molecules in donor domains.

Impact of Molecular Orientation and Spontaneous Interfacial Mixing on the Performance of Organic Solar Cells

KAUST Repository

Ngongang Ndjawa, Guy Olivier

2015-07-28

A critically important question that must be answered to understand how organic solar cells operate and should be improved is how the orientation of the donor and acceptor molecules at the interface influences exciton diffusion, exciton dissociation by electron transfer and recombination. It is exceedingly difficult to probe the orientation in bulk heterojunctions because there are many interfaces and they are arranged with varying angles with respect to the substrate. One of the best ways to study the interface is to make bilayer solar cells with just one donor-acceptor interface. Zinc phthalocyanine is particularly interesting to study because its orientation can be adjusted by using a 2-nm-thick copper iodide seed layer before it is deposited. Previous studies have claimed that solar cells in which fullerene acceptor molecules touch the face of zinc phthalocyanine have more current than ones in which the fullerenes touch the edge of zinc phthalocyanine because of suppressed recombination. We have more thoroughly characterized the system using in situ x-ray photoelectron spectroscopy and found that the interfaces are not as sharp as previous studies claimed when formed at room temperature or above. Fullerenes have a much stronger tendency to mix into the face-on films than into the edge-on films. Moreover we show that almost all of the increase in the current with face-on films can be attributed to improved exciton diffusion and to the formation of a spontaneously mixed interface, not suppressed recombination. This work highlights the importance of spontaneous interfacial molecular mixing in organic solar cells, the extent of which depends on molecular orientation of frontier molecules in donor domains.

Exchange interaction of strongly anisotropic tripodal erbium single-ion magnets with metallic surfaces

DEFF Research Database (Denmark)

Dreiser, Jan; Wäckerlin, Christian; Ali, Md. Ehesan

2014-01-01

We present a comprehensive study of Er(trensal) single-ion magnets deposited in ultrahigh vacuum onto metallic surfaces. X-ray photoelectron spectroscopy reveals that the molecular structure is preserved after sublimation, and that the molecules are physisorbed on Au(111) while they are chemisorbed...... on a Ni thin film on Cu(100) single-crystalline surfaces. X-ray magnetic circular dichroism (XMCD) measurements performed on Au(111) samples covered with molecular monolayers held at temperatures down to 4 K suggest that the easy axes of the strongly anisotropic molecules are randomly oriented...... pathways toward optical addressing of surface-deposited single-ion magnets....

Monolayer self-assembly at liquid-solid interfaces: chirality and electronic properties of molecules at surfaces

International Nuclear Information System (INIS)

Amabilino, David B; Gomar-Nadal, Elba; Veciana, Jaume; Rovira, Concepcio; Iavicoli, Patrizia; PuigmartI-Luis, Josep; Feyter, Steven De; Abdel-Mottaleb, Mohamed M; Mamdouh, Wael; Psychogyiopoulou, Krystallia; Xu Hong; Lazzaroni, Roberto; Linares, Mathieu; Minoia, Andrea

2008-01-01

The spontaneous formation of supramolecular assemblies at the boundary between solids and liquids is a process which encompasses a variety of systems with diverse characteristics: chemisorbed systems in which very strong and weakly reversible bonds govern the assembly and physisorbed aggregates which are dynamic thanks to the weaker interactions between adsorbate and surface. Here we review the interest and advances in the study of chiral systems at the liquid-solid interface, and also the application of this configuration for the study of systems of interest in molecular electronics, self-assembled from the bottom up

Influence of iodine on the electrical and photoelectrical properties of zinc phthalocyanine thin film devices

Energy Technology Data Exchange (ETDEWEB)

Sharma, G.D. [Jodhpur Univ. (India). Dept. of Physics; Sangodkar, S.G. [Jodhpur Univ. (India). Dept. of Physics; Roy, M.S. [Camouflage Division, Defence Laboratory, Jodhpur (Raj.) (India)

1996-11-01

The electrical and photovoltaic properties of the zinc phthalocyanine (ZnPc) and I{sub 2} doped ZnPc thin films, sandwiched between indium tin oxide (ITO) and Al electrodes, were investigated. Doping with iodine brings adequate changes in the characteristics of the device. The devices constitute a metal-insulator-semiconductor (MIS) structure, in which depletion layer is formed in ZnPc, near Al-Al{sub 2}O{sub 3}/ZnPc. The depletion layer width and potential barrier height decrease with I{sub 2} doping. The charge transport phenomenon at higher voltage range appears to be space charge limited conduction (SCLC), in the presence of the discrete trapping level. The position of Fermi level shifts toward the valence band edge, which indicates that I{sub 2} doping increases the P-type conductivity. Various electrical and photovoltaic parameters were determined from the J-V and C-V analysis. The influence of the I{sub 2} doping has been discussed in detail. (orig.)

Synthesis, characterization and investigation of the spectroscopic properties of novel peripherally 2,3,5-trimethylphenoxy substituted Cu and Co phthalocyanines, the computational and experimental studies of the 4-(2,3,5-trimethylphenoxyphthalonitrile

Directory of Open Access Journals (Sweden)

Nesuhi Akdemir

2016-11-01

Full Text Available 4-(2,3,5-trimethylphenoxyphthalonitrile (3 was firstly prepared via aromatic nucleophilic substitution reaction and characterized by FT-IR, mass spectrometry, 1H and 13C NMR techniques. The molecular structure of the compound (3 was optimized using Density Functional Theory (DFT/B3LYP method with 6-311G(d,p basis set in the ground state. The molecular geometric parameters which were obtained by X-ray single crystal diffraction method and the spectral results were compared with computed bond lengths and angles, vibrational frequencies and 1H, 13C NMR chemical shifts values of the compound (3. Also, Cu(II and Co(II phthalocyanines were synthesized by the treatment of dinitrile derivative with anhydrous CuCl2 or CoCl2 under N2 atmosphere in dry n-pentanol at 140oC. The new compounds have been determined by elemental analysis, FT-IR and electronic absorption. The UV-Vis spectra of the Cu(II and Co(II phthalocyanines were recorded with different concentration in THF and also with different solvents as DMF, DMSO, DCM, CHCl3, toluene.

Layer-by-layer self-assembling copper tetrasulfonated phthalocyanine on carbon nanotube modified glassy carbon electrode for electro-oxidation of 2-mercaptoethanol

International Nuclear Information System (INIS)

Shaik, Mahabul; Rao, V.K.; Gupta, Manish; Pandey, P.

2012-01-01

This paper describes the electrocatalytic activity of layer-by-layer self-assembled copper tetrasulfonated phthalocyanine (CuPcTS) on carbon nanotube (CNT)-modified glassy carbon (GC) electrode. CuPcTS is immobilized on the negatively charged CNT surface by alternatively assembling a cationic poly(diallyldimethylammonium chloride) (PDDA) layer and a CuPcTS layer. UV–vis absorption spectra and electrochemical measurements suggested the successive linear depositions of the bilayers of CuPcTs and PDDA on CNT. The surface morphology was observed using scanning electron microscopy. The viability of this CuPcTS/PDDA/CNT modified GC electrode as a redox mediator for the anodic oxidation and sensitive amperometric determination of 2-mercaptoethanol (2-ME) in alkaline conditions is described. The effect of number of bilayers of CuPcTS/PDDA and pH on electrochemical oxidation of 2-ME was studied. The proposed electrochemical sensor displayed excellent characteristics towards the determination of 2-ME in 0.1 M NaOH; such as low overpotentials (− 0.15 V vs Ag/AgCl), linear concentration range of 3 × 10 −5 M to 6 × 10 −3 M, and with a detection limit of 2.5 × 10 −5 M using simple amperometry. - Highlights: ► Carbon nanotubes (CNT) were drop-dried on glassy carbon electrode (GCE). ► Copper tetrasulfonated phthalocyanine (CuPcTS) was deposited on CNT/GCE. ► Layer-by-layer self-assembling method is used for depositing CuPcTS. ► Electrocatalytic oxidation of 2-mercaptoethanol (ME) was studied at this electrode ► The detection limit of ME at modified electrode was 25 μM by amperometry.

First-principles study of H2 adsorption and dissociation on Zr(0 0 0 1)

International Nuclear Information System (INIS)

Zhang Peng; Wang Shuangxi; Zhao Jian; He Chaohui; Zhang Ping

2011-01-01

Highlights: → The stability of the equilibrium adsorption states is determined after the geometry optimization. → The origin of the stable chemisorbed state is analyzed by the electronic structure and charge redistribution calculation. → The dissociation energetics of H2 are investigated in details by the PES and CINEB calculation. - Abstract: The adsorption and dissociation of H 2 molecules on the Zr(0 0 0 1) surface are systematically investigated by using density functional theory within the generalized gradient approximation and a supercell approach. After geometry optimization, the most stable equilibrium adsorption state is found to be along the top-y entrance. By calculating the adiabatic potential energy surface, the chemisorbed molecular adsorption states are also identified to be along the parallel channel at the top site. The electronic properties of the stable chemisorbed molecular state are analyzed, which show that the interaction between the molecule and substrate is of covalent characteristic with a sizeable charge redistribution. On the other hand, the hcp site is turned out to be the most stable equilibrium adsorption site for hydrogen atom on Zr(0 0 0 1) surface after the dissociation of H 2 . The dissociation energetics of H 2 are studied by calculating the potential energy surface and the minimum energy path of the transition state is determined by using the climb image nudged elastic band method, wherein the fcc-y channel is found to be most stable and favorable for dissociative adsorption of H 2 among the five possible dissociative paths. Remarkably, we find that the adiabatic dissociation process of H 2 is an activated type but with a small energy barrier, which is well consistent with the macroscopic phenomenon that the zirconium metal is easily hydrogenated.

Molecular bridges

NARCIS (Netherlands)

Berkelaar, R.P.; Söde, H.; Mocking, T.F.; Kumar, Avijit; Poelsema, Bene; Zandvliet, Henricus J.W.

2011-01-01

The adsorption of Cu-phthalocyanine (CuPc) molecules on Au-modified Ge(001) surfaces has been studied with low-temperature scanning tunneling microscopy. The Au-modified Ge(001) surface consists of well-ordered arrays of perfectly straight nanowires, which are separated by 1.6 nm wide and about 0.6

Magnetic field modification of ultracold molecule-molecule collisions

International Nuclear Information System (INIS)

Tscherbul, T V; Suleimanov, Yu V; Aquilanti, V; Krems, R V

2009-01-01

We present an accurate quantum mechanical study of molecule-molecule collisions in the presence of a magnetic field. The work focuses on the analysis of elastic scattering and spin relaxation in collisions of O 2 ( 3 Σ g - ) molecules at cold (∼0.1 K) and ultracold (∼10 -6 K) temperatures. Our calculations show that magnetic spin relaxation in molecule-molecule collisions is extremely efficient except at magnetic fields below 1 mT. The rate constant for spin relaxation at T=0.1 K and a magnetic field of 0.1 T is found to be as large as 6.1x10 -11 cm -3 s -1 . The magnetic field dependence of elastic and inelastic scattering cross sections at ultracold temperatures is dominated by a manifold of Feshbach resonances with the density of ∼100 resonances per Tesla for collisions of molecules in the absolute ground state. This suggests that the scattering length of ultracold molecules in the absolute ground state can be effectively tuned in a very wide range of magnetic fields. Our calculations demonstrate that the number and properties of the magnetic Feshbach resonances are dramatically different for molecules in the absolute ground and excited spin states. The density of Feshbach resonances for molecule-molecule scattering in the low-field-seeking Zeeman state is reduced by a factor of 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}.

Efficient small-molecule organic solar cells incorporating a doped buffer layer

Energy Technology Data Exchange (ETDEWEB)

Chou, Dei-Wei [Department of aviation and Communication Electronics, Air Force Institute of Technology, Kaohsiung 820, Taiwan (China); Chen, Kan-Lin [Department of Electronic Engineering, Fortune Institute of Technology, Kaohsiung 831, Taiwan (China); Huang, Chien-Jung, E-mail: chien@nuk.edu.tw [Department of Applied Physics, National University of Kaohsiung, Nanzih, Kaohsiung 811, Taiwan (China); Tsao, Yao-Jen [Department of Applied Physics, National University of Kaohsiung, Nanzih, Kaohsiung 811, Taiwan (China); Chen, Wen-Ray; Meen, Teen-Hang [Department of Electronic Engineering, National Formosa University, Hu-Wei, Yunlin 632, Taiwan (China)

2013-06-01

Small-molecule organic solar cells (OSCs) with an optimized structure of indium tin oxide/poly (3,4-ethylenedioxythioxythiophene):poly(styrenesulfonate)/copper phthalocyanine (CuPc) (10 nm)/CuPc: fullerene (C{sub 60}) mixed (20 nm)/C{sub 60} (20 nm)/4,7-diphenyl-1,10-phenanthroline (BPhen) (5 nm)/Ag were fabricated. In this study, the cesium carbonate-doped BPhen (Cs{sub 2}CO{sub 3}:BPhen) was adopted as the buffer layer to enhance the efficiency of the OSCs. The photovoltaic parameters of the OSCs, such as the short-circuit current density and fill factor, depend on the doping concentration of Cs{sub 2}CO{sub 3} in the BPhen layer. The cell with a Cs{sub 2}CO{sub 3}:BPhen (1:4) cathode buffer layer exhibits a power conversion efficiency (PCE) of 3.51%, compared to 3.37% for the device with the pristine BPhen layer. The enhancement of PCE was attributed to the energy-level alignment between the C{sub 60} layer and the Cs{sub 2}CO{sub 3}:BPhen layer. In addition, the characterization measured using atomic force microscopy shows that the Cs{sub 2}CO{sub 3}:BPhen layers have smoother surfaces. - Highlight: • Cs2CO3-doped 4,7-diphenyl-1,10-phenanthroline (BPhen) cathode buffer layer. • Cs2CO3:BPhen layer with different ratios affects organic solar cells performance. • Cell with 1:4 (Cs2CO3:BPhen) ratio shows 3.51% power conversion efficiency.

The steady-state and time-resolved photophysical properties of a dimeric indium phthalocyanine complex

International Nuclear Information System (INIS)

Chen Yu; Araki, Yasuyuki; Dini, Danilo; Liu Ying; Ito, Osamu; Fujitsuka, Mamoru

2006-01-01

The steady-state and time-resolved photophysical properties and some molecular orbital calculation results of a dimeric indium phthalocyanine complex with an indium-indium bond, i.e., [tBu 4 PcIn] 2 .2tmed, have been described. The results regarding triplet excited state lifetimes can be ascribed to strong intramolecular interactions existing only in the excited state of this dimer because no significant difference in the absorption spectra of the tBu 4 PcInCl monomer and the [tBu 4 PcIn] 2 .2tmed dimer is observed, suggesting that no ground-state interaction can be assessed. The deactivation processes of the excited singlet state of [tBu 4 PcIn] 2 .2tmed are apparently faster than that of μ-oxo-bridged PcIn dimer [tBu 4 PcIn] 2 O. Molecular orbital calculation on the PcIn dimer shows no node between two indium atoms was found in the HOMO - 2 of the PcIn-InPc dimer, suggesting that bonding electrons distribute between two indium atoms

The Influence of Substituent Orientation on the Photovoltaic Performance of Phthalocyanine-Sensitized Solar Cells.

Science.gov (United States)

Tejerina, Lara; Martínez-Díaz, M Victoria; Nazeeruddin, Mohammad Khaja; Torres, Tomas

2016-03-18

Phthalocyanines (Pcs) are used as sensitizers in dye-sensitized solar cells (DSSCs) because of their stability and intense absorption in the red and near-IR regions. Impressive progress has been made in photovoltaic efficiencies by introduction of bulky peripheral substituents to help suppress macrocycle aggregation. To reach benchmark efficiencies reported for other related dyes, new designs need to be explored. Single carboxy-ZnPc regioisomers substituted at the non-peripheral positions by rigid aryl groups have now been studied, which has shed light on the influence of steric hindrance and/or orientation of the substituent around the anchoring group on the photovoltaic response. The regioisomer bearing the aryl group far away from the anchoring group produces a more effective sensitization of the TiO2 films and higher short-circuit photocurrent density (Jsc). Taking advantage of the good photovoltaic performance in the near-IR region of this ZnPc, it was combined with another appropriate dye for panchromatic sensitization of the mesoporous photoelectrode and an increase of the overall device efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron damage in organic crystals

International Nuclear Information System (INIS)

Howitt, D.G.; Thomas, G.

1977-01-01

The effects of radiation damage in three crystalline organic materials (l-valine, cytosine, copper phthalocyanine) have been investigated by electron microscopy. The degradation of these materials has been found to be consistent with a gradual collapse of their crystal structures brought about by ionization damage to the comprising molecules. It is inferred that the crystallinity of these materials is destroyed by ionizing radiation because the damaged molecules cannot be incorporated into the framework of their original structures. (author)

Control of in-plane orientation of phthalocyanine molecular columns using vicinal Si(001)-(2x1)-H

International Nuclear Information System (INIS)

Nakamura, Masakazu; Matsunobe, Takeshi; Tokumoto, Hiroshi

2001-01-01

In-plane crystal orientation of copper phthalocyanine (CuPc) films formed by organic molecular-beam epitaxy have been successfully controlled by using vicinal Si(001)-(2x1)-H as a substrate, containing atomic steps of an approximately 4 nm period. A continuous film was grown at 60 degree C and the film thickness ranged between 5 and 8 molecular layers. By observing a frictional force image of the film, 90% of the molecular columns were found to align across the substrate step rows. The preferential orientation is considered to be induced by artificial surface lattices, which result from the striped effective contact area between the rigid CuPc crystals and the stair-like surfaces. The anisotropic optical properties of the film have been also confirmed by polarized reflection measurements. [copyright] 2001 American Institute of Physics

Theoretical study of ozone adsorption on the surface of Fe, Co and Ni doped boron nitride nanosheets

Science.gov (United States)

Farmanzadeh, Davood; Askari Ardehjani, Nastaran

2018-06-01

In this work, the adsorption of ozone molecule on Fe, Co and Ni doped boron nitride nanosheets (BNNSs) were investigated using density functional theory. The most stable adsorption configurations, charge transfer and adsorption energy of ozone molecule on pure and doped BNNSs are calculated. It is shown that ozone molecule has no remarkable interaction with pure boron nitride nanosheet, it tends to be chemisorbed on Fe, Co and Ni doped BNNSs with adsorption energy in the range of -249.4 to -686.1 kJ/mol. In all configurations, the adsorption of ozone molecule generates a semiconductor by reducing Eg in the pure and Fe, Co and Ni doped boron nitride nanosheet. It shows that the conductance of BNNSs change over the adsorption of ozone molecule. The obtained results in this study can be used in developing BN-based sheets for ozone molecule removal.

Detecting high-density ultracold molecules using atom–molecule collision

International Nuclear Information System (INIS)

Chen, Jun-Ren; Kao, Cheng-Yang; Chen, Hung-Bin; Liu, Yi-Wei

2013-01-01

Utilizing single-photon photoassociation, we have achieved ultracold rubidium molecules with a high number density that provides a new efficient approach toward molecular quantum degeneracy. A new detection mechanism for ultracold molecules utilizing inelastic atom–molecule collision is demonstrated. The resonant coupling effect on the formation of the X 1 Σ + g ground state 85 Rb 2 allows for a sufficient number of more deeply bound ultracold molecules, which induced an additional trap loss and heating of the co-existing atoms owing to the inelastic atom–molecule collision. Therefore, after the photoassociation process, the ultracold molecules can be investigated using the absorption image of the ultracold rubidium atoms mixed with the molecules in a crossed optical dipole trap. The existence of the ultracold molecules was then verified, and the amount of accumulated molecules was measured. This method detects the final produced ultracold molecules, and hence is distinct from the conventional trap loss experiment, which is used to study the association resonance. It is composed of measurements of the time evolution of an atomic cloud and a decay model, by which the number density of the ultracold 85 Rb 2 molecules in the optical trap was estimated to be >5.2 × 10 11 cm −3 . (paper)

Oxidation of 2,4,6,-tri-chlorophenol catalyzed by iron phthalocyanines covalently bound to silica. Oxydation du 2,4,6-trichlorophenol catalyse par des phtalocyanines de fer greffees sur silice par liaisons covalentes

Energy Technology Data Exchange (ETDEWEB)

Sanchez, M.; Hadasch, A.; Meunier, B. (Centre National de la Recherche Scientifique (CNRS), 31 - Toulouse (France). Laboratoire de Chimie de Coordination); Rabion, A. (Elf-Atochem, 64 - Artix (France). Centre de Recherche)

1999-04-01

The degradation of recalcitrant pollutants remains a high priority in order to preserve our environment. For example, chlorinated aromatic compounds are extremely persistent in the environment because of their slow biodegradation by microorganisms. One of the most notable toxic offenders is 2,4,6-tri-chlorophenol (TCP) which is produced by paper mills and also used as a biocide. Thus TCP is an obvious benchmark for research on the decontamination of waste waters. In this work, the covalent attachment of an iron phthalocyanine with chloro-sulfonyl substituents (FePcSO[sub 2]Cl) onto a functionalized 3-amino-propyl-silica has been achieved. This supported catalyst FePcSO[sub 2]Cl-silica is able to degrade a recalcitrant pollutant like TCP with hydrogen peroxide as oxidant. In order to improve the catalytic efficiency of the grafted iron phthalocyanine complex, modifications of the macrocycle substituents, passivation of the silica surface, variation of the loading of the carrier and addition of an organic co solvent to the reaction mixture were carried out. (authors) 21 refs.

Fundamental properties of molecules on surfaces. Molecular switching and interaction of magnetic molecules with superconductors

Energy Technology Data Exchange (ETDEWEB)

Hatter, Nino

2016-12-14

In this thesis, we investigate individual molecular switches and metal-organic complexes on surfaces with scanning tunneling microscopy (STM) and spectroscopy (STS) at low temperatures. One focus addresses the switching ability and mechanism of diarylethene on Ag(111). The other focus lies on resolving and tuning magnetic interactions of individual molecules with superconductors. 4,4'-(4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis (5-methylthiophene-4,2-diyl)dip yridine (PDTE) is a prototypical photochromic switch. We can induce a structural change of individual PDTE molecules on Ag(111) with the STM tip. This change is accompanied by a reduction of the energy gap between the occupied and unoccupied molecular orbitals. Density functional theory (DFT) calculations reveal that the induced switching corresponds to a ring-closing reaction from an open isomer in a flat adsorption configuration to a ring-closed isomer with its methyl groups in a cis configuration. The final product is thermodynamically stabilized by strong dispersion interactions with the surface. A linear dependence of the switching threshold with the tip-sample distance with a minimal threshold of 1.4 V is found, which we assign to a combination of an electric-field induced process and a tunneling-electron contribution. DFT calculations suggest a large activation barrier for a ring-closing reaction from the open flat configuration into the closed cis configuration. The interaction of magnetic molecules with superconductors is studied on manganese phthalocyanine (MnPc) adsorbed on Pb(111). We find triplets of Shiba states inside the superconducting gap. Different adsorption sites of MnPc provide a large variety of exchange coupling strengths, which lead to a collective energy shift of the Shiba triplets. We can assign the splitting of the Shiba states to be an effect of magnetic anisotropy in the system. A quantum phase transition from a ''Kondo screened'' to a &apos

Laser induced florescence: application to spectroscopy and new microscopy imaging methods

International Nuclear Information System (INIS)

Galaup, L. P.

2012-01-01

Laser induced fluorescence is one of the light using techniques which allows the highest sensitivity for atoms and molecules detection, up to the single atom or single molecule level. This field is much too large for an extensive review; therefor we have chosen to focus on two main points: 1- the observation of laser stimulated fluorescence in phthalocyanine and porphyrin like molecules in rare gas and nitrogen matrices at low temperatures. 2- the presentation of laser induced fluorescence techniques suitable for achieving ultra-high spatial resolution imaging, below the diffraction limit of conventional microscopy, thanks to highly fluorescent molecules to be used as biological markers. (Author)

Tunneling rates in electron transport through double-barrier molecular junctions in a scanning tunneling microscope.

Science.gov (United States)

Nazin, G V; Wu, S W; Ho, W

2005-06-21

The scanning tunneling microscope enables atomic-scale measurements of electron transport through individual molecules. Copper phthalocyanine and magnesium porphine molecules adsorbed on a thin oxide film grown on the NiAl(110) surface were probed. The single-molecule junctions contained two tunneling barriers, vacuum gap, and oxide film. Differential conductance spectroscopy shows that electron transport occurs via vibronic states of the molecules. The intensity of spectral peaks corresponding to the individual vibronic states depends on the relative electron tunneling rates through the two barriers of the junction, as found by varying the vacuum gap tunneling rate by changing the height of the scanning tunneling microscope tip above the molecule. A simple, sequential tunneling model explains the observed trends.

Direct formation of a polyamide on Ag(111): Joint XPS and STM studies

Energy Technology Data Exchange (ETDEWEB)

Schmid, Martin; Steinrueck, Hans-Peter; Gottfried, J. Michael [Lehrstuhl fuer Physikalische Chemie II, Universitaet Erlangen-Nuernberg (Germany); Schmitz, Christoph H.; Ikonomov, Julian; Sokolowski, Moritz [Institut fuer Physikalische und Theoretische Chemie, Universitaet Bonn (Germany)

2011-07-01

The polymer poly(p-phenylene terephthalamide) (PPTA) was synthesized on Ag(111) by co-adsorption of the reactive monomer compounds terephthaloyl chloride (TPC) and p-phenylenediamine (PPD) at 300 K. The resulting adsorbate phases were characterised by photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). A detailed study of the chemical composition and morphology revealed a complex reaction mechanism, by which the formation of amide bonds leads to folded PPTA polymer chains. According to XPS, the chloride of the TPC precursor is not released as HCl as in the bulk reaction, but remains on the surface as chemisorbed Cl or AgCl. Further temperature-programmed XPS studies of pure TPC on Ag(111) reveal that the molecule decomposes already above 130 K, forming chemisorbed Cl (or AgCl) and a phenylene-dicarbonyl species, which is presumably stabilized by the substrate. The adsorbed chlorine partially desorbs above 800 K as molecular AgCl.

Secondary electron emission influenced by oxidation on the aluminum surface: the roles of the chemisorbed oxygen and the oxide layer

Science.gov (United States)

Li, Jiangtao; Hoekstra, Bart; Wang, Zhen-Bin; Qiu, Jie; Pu, Yi-Kang

2018-04-01

A relationship between the apparent secondary electron yield ({γ }{{se}}) and the oxygen coverage/oxide layer thickness on an aluminum cathode is obtained in an experiment under a controlled environment. The apparent secondary electron yield ({γ }{{se}}) is deduced from the breakdown voltage between two parallel plate electrodes in a 360 mTorr argon environment using a simple Townsend breakdown model with the assumption that the variation of the apparent secondary electron yield is dominated by the variation of the argon ion induced processes. The oxygen coverage/oxide layer thickness on the aluminum cathode is measured by a semi in situ x-ray photoemission spectroscopy equipment which is directly attached to the discharge chamber. It is found that three phases exist: (1) in the monomonolayer regime, as the oxygen coverage increases from 0 to 0.3, {γ }{{se}} decreases by nearly 40 % , (2) as the oxygen coverage increases from 0.3 to 1, {γ }{{se}} keeps nearly constant, (3) as the oxide layer thickness increases from about 0.3 nm to about 1.1 nm, {γ }{{se}} increases by 150 % . We propose that, in the submonolayer regime, the chemisorbed oxygen on the aluminum surface causes the decrease of {γ }{{se}} by creating a local potential barrier, which reduces the Auger neutralization rate and the energy gained by the Auger electrons. In the multilayer regime, as the oxide layer grows in thickness, there are three proposed mechanisms which cause the increase of {γ }{{se}}: (1) the work function decreases; (2) resonance neutralization and Auger de-excitation may exist. This is served as another channel for secondary electron production; (3) the kinetic energy of Auger electrons is increased on average, leading to a higher probability for electrons to overcome the surface potential barrier.

Growing interstellar molecules with ion-molecule reactions

International Nuclear Information System (INIS)

Bohme, D.K.

1989-01-01

Laboratory measurements of gas-phase ion-molecule reactions continue to provide important insights into the chemistry of molecular growth in interstellar environments. It is also true that the measurements are becoming more demanding as larger molecules capture our interest. While some of these measurements are motivated by current developments in chemical models of interstellar environments or by new molecular observations by astronomers, others explore novel chemistry which can lead to predictions of new interstellar molecules. Here the author views the results of some recent measurements, taken in the Ion Chemistry Laboratory at York University with the SIFT technique, which address some of the current needs of modellers and observers and which also provide some new fundamental insight into molecular growth, particularly when it occurs in the presence of large molecules such as PAH molecules which are now thought to have a major influence on the chemistry of interstellar environments in which they are present

Physical and Instrumental Considerations in the Use of Lithium Phthalocyanine for Measurements of the Concentration of the Oxygen

Science.gov (United States)

Smirnov, A. I.; Norby, S. W.; Walczak, T.; Liu, K. J.; Swartz, H. M.

The use of crystals of lithium phthalocyanine (LiPc) to measure the concentration of oxygen in vivo and in vitro by electron paramagnetic resonance leads to experimental constraints due to the very narrow EPR lines that may occur (as narrow as 11-13 mG in the absence of O 2), distortions induced by the automatic frequency control system, anisotropy in the spectra (orientation-dependent linewidth is 11-17 mG in the absence of O 2), microwave power saturation, and the effect of physiological motion. These constraints can be overcome if recognized. This article highlights the experimental and theoretical basis of these properties of the EPR signal of LiPc and suggests some technical solutions. It is most important to recognize that paramagnetic species such as LiPc present problems that are not commonly encountered in EPR spectroscopy.

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

Directory of Open Access Journals (Sweden)

Saptadip Saha

2016-01-01

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

Electronic Tongue Based on Nanostructured Hybrid Films of Gold Nanoparticles and Phthalocyanines for Milk Analysis

Directory of Open Access Journals (Sweden)

Luiza A. Mercante

2015-01-01

Full Text Available The use of gold nanoparticles combined with other organic and inorganic materials for designing nanostructured films has demonstrated their versatility for various applications, including optoelectronic devices and chemical sensors. In this study, we reported the synthesis and characterization of gold nanoparticles stabilized with poly(allylamine hydrochloride (Au@PAH NPs, as well as the capability of this material to form multilayer Layer-by-Layer (LbL nanostructured films with metal tetrasulfonated phthalocyanines (MTsPc. Film growth was monitored by UV-Vis absorption spectroscopy, atomic force microscopy (AFM, and Fourier transform infrared spectroscopy (FTIR. Once LbL films have been applied as active layers in chemical sensors, Au@PAH/MTsPc and PAH/MTsPc LbL films were used in an electronic tongue system for milk analysis regarding fat content. The capacitance data were treated using Principal Component Analysis (PCA, revealing the role played by the gold nanoparticles on the LbL films electrical properties, enabling this kind of system to be used for analyzing complex matrices such as milk without any prior pretreatment.