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.

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.

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.

Syntheses and Photodynamic Activity of Pegylated Cationic Zn(II-Phthalocyanines in HEp2 Cells

Directory of Open Access Journals (Sweden)

Benson G. Ongarora, Xiaoke Hu, Susan D. Verberne-Sutton, Jayne C. Garno, M. Graça H. Vicente

2012-01-01

Full Text Available Di-cationic Zn(II-phthalocyanines (ZnPcs are promising photosensitizers for the photodynamic therapy (PDT of cancers and for photoinactivation of viruses and bacteria. Pegylation of photosensitizers in general enhances their water-solubility and tumor cell accumulation. A series of pegylated di-cationic ZnPcs were synthesized from conjugation of a low molecular weight PEG group to a pre-formed Pc macrocycle, or by mixed condensation involving a pegylated phthalonitrile. All pegylated ZnPcs were highly soluble in polar organic solvents but were insoluble in water; they have intense Q absorptions centered at 680 nm and fluorescence quantum yields of ca. 0.2 in DMF. The non-pegylated di-cationic ZnPc 6a formed large aggregates, which were visualized by atomic force microscopy. The cytotoxicity, cellular uptake and subcellular distribution of all cationic ZnPcs were investigated in human carcinoma HEp2 cells. The most phototoxic compounds were found to be the α-substituted Pcs. Among these, Pcs 4a and 16a were the most effective (IC50 ca. 10 μM at 1.5 J/cm2, in part due to the presence of a PEG group and the two positive charges in close proximity (separated by an ethylene group in these macrocycles. The β-substituted ZcPcs 6b and 4b accumulated the most within HEp2 cells but had low photocytoxicity (IC50 > 100 μM at 1.5 J/cm2, possibly as a result of their lower electron density of the ring and more extended conformations compared with the α-substituted Pcs. The results show that the charge distribution about the Pc macrocycle and the intracellular localization of the cationic ZnPcs mainly determine their photodynamic activity.

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.)

Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines.

Science.gov (United States)

Majeed, Shereen A; Ghazal, Basma; Nevonen, Dustin E; Goff, Philip C; Blank, David A; Nemykin, Victor N; Makhseed, Saad

2017-10-02

2,3,9,10,16,17,23·24-Octakis-(9H-carbazol-9-yl) phthalocyaninato zinc(II) (3) and 2,3,9,10,16,17,23·24-octakis-(3,6-di-tert-butyl-9H-carbazole) phthalocyaninato zinc(II) (4) complexes were prepared and characterized by NMR and UV-vis spectroscopies, magnetic circular dichroism (MCD), matrix-assisted laser desorption ionization mass spectrometry, and X-ray crystallography. UV-vis and MCD data are indicative of the interligand charge-transfer nature of the broad band observed in 450-500 nm range for 3 and 4. The redox properties of 3 and 4 were probed by electrochemical and spectro-electrochemical methods, which are suggestive of phthalocyanine-centered first oxidation and reduction processes. Photophysics of 3 and 4 were investigated by steady-state fluorescence and time-resolved transient absorption spectroscopy demonstrating the influence of the carbazole substituents on deactivation from the first excited state in 3 and 4. Protonation of the meso-nitrogen atoms in 3 results in much faster deactivation kinetics from the first excited state. Spectroscopic data were correlated with density functional theory (DFT) and time-dependent DFT calculations on 3 and 4.

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

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.

Seaweeds for the remediation of wastewaters contaminated with zinc(II) ions

International Nuclear Information System (INIS)

Senthilkumar, R.; Vijayaraghavan, K.; Thilakavathi, M.; Iyer, P.V.R.; Velan, M.

2006-01-01

Eleven different species of marine macroalgae were screened at different pH conditions on the basis of zinc(II) biosorption potential. Among the seaweeds, a green alga, Ulva reticulata, exhibited a highest uptake of 36.1 mg/g at pH 5.5 and 100 mg/l initial zinc(II) concentration. Further experiments were conducted to evaluate the zinc(II) biosorption potential of U. reticulata. Sorption isotherm data obtained at different pH (5-6) and temperature (25-35 deg. C) conditions were fitted well with Sips model followed by Freundlich, Redlich-Peterson and Langmuir models. A maximum zinc(II) biosorption capacity of 135.5 mg/g was observed at optimum conditions of 5.5 (pH) and 30 deg. C (temperature), according to the Langmuir model. It was observed from the kinetic data that the zinc(II) biosorption process using U. reticulata follows pseudo-second-order kinetics. Various thermodynamic parameters, such as ΔG o , ΔH o and ΔS o were calculated and they indicated that the present system was a spontaneous and an endothermic process. The influence of the co-ions (Na + , K + , Ca 2+ and Mg 2+ ) along with zinc(II) present in the wastewater was also studied. Desorption of zinc(II) ions from the zinc(II)-loaded biomass were examined using 0.1 M CaCl 2 at different pH conditions in three sorption-desorption cycles. A fixed-bed column (2 cm i.d. and 35 cm height) was employed to evaluate the continuous biosorption performance of U. reticulata. The column experiments at different bed heights and flow rates revealed that the maximum zinc(II) uptake was obtained at the highest bed height (25 cm) and the lowest flow rate (5 ml/min). Column data were fitted well with Thomas, Yoon-Nelson and modified dose-response models. The column regeneration studies were carried out for three sorption-desorption cycles. A loss of sorption performance was observed during regeneration cycles indicated by a shortened breakthrough time and a decreased zinc(II) uptake

Supramolecular assemblies of pyridyl porphyrin and diazadithia phthalocyanine

Directory of Open Access Journals (Sweden)

OZER BEKAROGLU

1999-08-01

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

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.

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.

Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups

International Nuclear Information System (INIS)

Taştemel, Ayşegül; Karaca, Birsen Yılmaz; Durmuş, Mahmut; Bulut, Mustafa

2015-01-01

Tetra-peripherally and non-peripherally 7-oxy-3-(m-methoxyphenyl)coumarin-substituted zinc(II) (4a and 5a), indium(III)acetate (4b and 5b) and magnesium(II) (4c and 5c) phthalocyanines were synthesized for the first time. These phthalocyanines were characterized by elemental analysis, FT-IR, 1 H NMR, UV–vis spectroscopy and mass spectra. The novel phthalocyanines showed excellent solubility in general organic solvents, such as dichloromethane, chloroform, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The photophysical and photochemical properties of these phthalocyanines were investigated in DMF. The effects of the central metal ions (Zn 2+ , Mg 2+ , In +3 ) and the position (peripheral or non-peripheral) of the substituents on the photophysical and photochemical parameters were reported for comparison. The singlet oxygen quantum yield values of novel phthalocyanines ranged from 0.29 to 0.82 in DMF. In this study, the fluorescence quenching behavior of the studied zinc(II) and magnesium(II) phthalocyanine complexes was also described by the addition of 1,4-benzoquinone. - Highlights: • 7-oxy-3-(m-methoxyphenyl)coumarin-substituted Zn, In(III)OAc and Mg phthalocyanines. • Investigation of their photophysical and photochemical properties in DMF. • The effects of metal types and position of the substituents on these properties.

Metal-Cation Recognition in Water by a Tetrapyrazinoporphyrazine-Based Tweezer Receptor

Czech Academy of Sciences Publication Activity Database

Lochman, L.; Švec, J.; Roh, J.; Kirakci, Kaplan; Lang, Kamil; Zimčík, P.; Nováková, V.

2016-01-01

Roč. 22, č. 7 (2016), s. 2417-2426 ISSN 0947-6539 Institutional support: RVO:61388980 Keywords : cation s * crown compounds * fluorescent probes * phthalocyanines * sensors Subject RIV: CA - Inorganic Chemistry Impact factor: 5.317, year: 2016

Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups

Energy Technology Data Exchange (ETDEWEB)

Taştemel, Ayşegül; Karaca, Birsen Yılmaz [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy-Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, P.O. Box 141, Gebze 41400, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy-Istanbul (Turkey)

2015-12-15

Tetra-peripherally and non-peripherally 7-oxy-3-(m-methoxyphenyl)coumarin-substituted zinc(II) (4a and 5a), indium(III)acetate (4b and 5b) and magnesium(II) (4c and 5c) phthalocyanines were synthesized for the first time. These phthalocyanines were characterized by elemental analysis, FT-IR, {sup 1}H NMR, UV–vis spectroscopy and mass spectra. The novel phthalocyanines showed excellent solubility in general organic solvents, such as dichloromethane, chloroform, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The photophysical and photochemical properties of these phthalocyanines were investigated in DMF. The effects of the central metal ions (Zn{sup 2+}, Mg{sup 2+}, In{sup +3}) and the position (peripheral or non-peripheral) of the substituents on the photophysical and photochemical parameters were reported for comparison. The singlet oxygen quantum yield values of novel phthalocyanines ranged from 0.29 to 0.82 in DMF. In this study, the fluorescence quenching behavior of the studied zinc(II) and magnesium(II) phthalocyanine complexes was also described by the addition of 1,4-benzoquinone. - Highlights: • 7-oxy-3-(m-methoxyphenyl)coumarin-substituted Zn, In(III)OAc and Mg phthalocyanines. • Investigation of their photophysical and photochemical properties in DMF. • The effects of metal types and position of the substituents on these properties.

Elementary sulfur in effluent from denitrifying sulfide removal process as adsorbent for zinc(II).

Science.gov (United States)

Chen, Chuan; Zhou, Xu; Wang, Aijie; Wu, Dong-hai; Liu, Li-hong; Ren, Nanqi; Lee, Duu-Jong

2012-10-01

The denitrifying sulfide removal (DSR) process can simultaneously convert sulfide, nitrate and organic compounds into elementary sulfur (S(0)), di-nitrogen gas and carbon dioxide, respectively. However, the S(0) formed in the DSR process are micro-sized colloids with negatively charged surface, making isolation of S(0) colloids from other biological cells and metabolites difficult. This study proposed the use of S(0) in DSR effluent as a novel adsorbent for zinc removal from wastewaters. Batch and continuous tests were conducted for efficient zinc removal with S(0)-containing DSR effluent. At pHremoval rates of zinc(II) were increased with increasing pH. The formed S(0) colloids carried negative charge onto which zinc(II) ions could be adsorbed via electrostatic interactions. The zinc(II) adsorbed S(0) colloids further enhanced coagulation-sedimentation efficiency of suspended solids in DSR effluents. The DSR effluent presents a promising coagulant for zinc(II) containing wastewaters. Copyright © 2012 Elsevier Ltd. All rights reserved.

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.

Zinc(II) halide complexes with 2-methoxyaniline ligand: Synthesis, characterization, thermal analyses, crystal structure determination and luminescent properties

Science.gov (United States)

Amani, Vahid

2018-03-01

Three new mononuclear zinc(II) complexes, [Zn(2-MeO-C6H4NH2)2X2] (X is Cl in 1, Br in 2 and I in 3), were prepared from the reactions of ZnX2 with 2-methoxyaniline (2-MeO-C6H4NH2) ligand in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurements by slow evaporation of methanol solution at room temperature. The three complexes were thoroughly characterized by thermogravimetric analysis, elemental analysis (CHNO), spectral methods (IR, UV-Vis, 13C{1H}NMR, 1H NMR and luminescence), and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the zinc(II) cation is four-coordinated in a distorted tetrahedral configuration by two N atoms from two 2-methoxyanyline ligands and two halide anions. Also, in these complexes intermolecular interactions, for example Nsbnd H⋯X hydrogen bonds (in 1-3), Csbnd H⋯X hydrogen bonds (in 3), Csbnd H⋯π interactions (in 1 and 2) and π⋯π interactions (in 3), are effective in the stabilization of the crystal structures. In addition, the luminescence spectra of all complexes in methanolic solution show that the intensity of their emission bands is stronger than that for free 2-methoxyaniline ligand.

Luminescence properties of copper(I), zinc(II) and cadmium(II) coordination compounds with picoline ligands

Energy Technology Data Exchange (ETDEWEB)

Małecki, Jan Grzegorz, E-mail: gmalecki@us.edu.pl; Maroń, Anna

2017-06-15

Mononuclear coordination compounds of copper(I) – [Cu(PPh{sub 3}){sub 2}(picoline)(NO{sub 3})], zinc(II) – [ZnCl{sub 2}(picoline){sub 2}] (picoline=3– and 4–methylpyridine) and polymeric cadmium(II) – [CdCl{sub 2}(β-picoline){sub 2}]{sub n} were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. Single crystal X-ray crystallography revealed distorted tetrahedral geometry around the central ions of the compounds. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. The emission of copper(I) compounds originated from metal-to-ligand charge transfer state combined with nitrato-to-picoline charge transfer state i.e. ({sup 1}(M+X)LCT). The presence of nitrato ligand in the coordination sphere of copper(I) compounds quenches the emission. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution). - Graphical abstract: Coordination compounds of copper(I), zinc(II) and polymeric cadmium(II) with picoline ligands were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. Emission of copper(I) compounds originated from {sup 1}(M+X)LCT state. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution).

1 SUPPLEMENTARY INFORMATION A novel zinc(II) complex ...

Indian Academy of Sciences (India)

BİLGİSAYAR

1. SUPPLEMENTARY INFORMATION. A novel zinc(II) complex containing square pyramidal, octahedral and tetrahedral geometries on the same polymeric chain constructed from pyrazine-2,3-dicarboxylic acid and 1-vinylimidazole. HAKAN YILMAZ* and OMER ANDAC. Department of Chemistry, Ondokuz Mayis University, ...

Ultrasonic synthesis of two new zinc(II) bipyridine coordination polymers: New precursors for preparation of zinc(II) oxide nano-particles.

Science.gov (United States)

Fard, Mohammad Jaafar Soltanian; Hayati, Payam; Firoozadeh, Azita; Janczak, Jan

2017-03-01

Nanoparticles of two zinc(II) coordination polymers (CPs), [Zn(μ-4,4'-bipy)Cl 2 ] n (1) and [Zn(μ-4,4'-bipy)Br 2 ] n (2) L=bpy=4,4'-bipyridine ligand, have been synthesized by use of a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR) spectroscopy and elemental analyses. The single crystal X-ray data of compounds 1 and 2 imply that the Zn +2 ions are four coordinated. Topological analysis shows that 1D coordination networks of 1 and 2 can be classified as underlying nets of topological types 2C1. Nanoparticles of zinc(II) oxide have been prepared by calcination of two different zinc (II) CPs at 450°C that were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and IR spectroscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Cationic Zn-Porphyrin Polymer Coated onto CNTs as a Cooperative Catalyst for the Synthesis of Cyclic Carbonates.

Science.gov (United States)

Jayakumar, Sanjeevi; Li, He; Chen, Jian; Yang, Qihua

2018-01-24

The development of solid catalysts containing multiple active sites that work cooperatively is very attractive for biomimetic catalysis. Herein, we report the synthesis of bifunctional catalysts by supporting cationic porphyrin-based polymers on carbon nanotubes (CNTs) using the direct reaction of 5,10,15,20-tetrakis(4-pyridyl)porphyrin zinc(II), di(1H-imidazol-1-yl)methane, and 1,4-bis(bromomethyl)benzene in the presence of CNTs. The bifunctional catalysts could efficiently catalyze the cycloaddition reaction of epoxides and CO 2 under solvent-free conditions with porphyrin zinc(II) as the Lewis acid site and a bromine anion as a nucleophilic agent working in a cooperative way. Furthermore, a relative amount of porphyrin zinc(II) and quaternary ammonium bromide could be facilely adjusted for facilitating cooperative behavior. The bifunctional catalyst with a TOF up to 2602 h -1 is much more active than the corresponding homogeneous counterpart and is one of the most active heterogeneous catalysts ever reported under cocatalyst-free conditions. The high activity is mainly attributed to the enhanced cooperation effect of the bifunctional catalyst. With a wide substrate scope, the bifunctional catalyst could be stably recycled. This work demonstrates a new approach for the generation of a cooperative activation effect for solid catalysts.

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

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.

Syntheses, structures and luminescence behaviour of some zinc(II ...

Indian Academy of Sciences (India)

2, the zinc(II) centre is bound by four N atoms of the tailored Schiff base L2 and two O atoms of the chelated acetate. .... determination parameters for 1 and 2 is given in table 1. 3. Results ..... Shields G P, Taylor R, Towler M and van de Streek J.

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.

Room temperature ferromagnetism in a phthalocyanine based carbon material

International Nuclear Information System (INIS)

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

2014-01-01

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

Room temperature ferromagnetism in a phthalocyanine based carbon material

Energy Technology Data Exchange (ETDEWEB)

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

2014-02-07

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

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Novel eugenol-substituted zinc(II) azaphthalocyanines (ZnAzaPcs)were synthesised and their lipase inhibition and DNA binding properties compared with phthalocyanines (Pcs) containing eugenol. This is the first study on lipase inhibition and DNA binding of Pcs and AzaPcs containing a pharmacophore group, such as ...

Comparisons of the spectroscopic and microbiological activities among coumarin-3-carboxylate, o-phenanthroline and zinc(II) complexes

Science.gov (United States)

Islas, María S.; Martínez Medina, Juan J.; Piro, Oscar E.; Echeverría, Gustavo A.; Ferrer, Evelina G.; Williams, Patricia A. M.

2018-06-01

Coumarins (2H-chromen-2-one) are oxygen-containing heterocyclic compounds that belong to the benzopyranones family. In this work we have synthesized different coordination complexes with coumarin-3-carboxylic acid (HCCA), o-phenanthroline (phen) and zinc(II). In the reported [Zn(CCA)2(H2O)2] complex, coumarin-3-carboxylate (CCA) is acting as a bidentate ligand while in the two prepared complexes, [Zn(phen)3]CCA(NO3) (obtained as a single crystal) and [Zn(CCA)2phen].4H2O, CCA is acting as a counterion of the complex cation [Zn(phen)3]+2 or coordinated to the metal center along with phen, respectively. These compounds were characterized on the basis of elemental analysis and thermogravimetry. NMR, FTIR and Raman spectroscopies of the compounds and the CCA potassium salt (KCCA) allow to determine several similarities and differences among them. Finally, their behavior against alkaline phosphatase enzyme and their antimicrobial activities were also measured.

Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

Science.gov (United States)

Yang, Yang

2010-12-23

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

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.

Synthesis, thermal, spectral, and biological properties of zinc(II) 4-aminobenzoate complexes

Czech Academy of Sciences Publication Activity Database

Homzová, K.; Györyová, K.; Hudecová, D.; Koman, M.; Melník, M.; Kovářová, Jana

2017-01-01

Roč. 129, č. 2 (2017), s. 1065-1082 ISSN 1388-6150 Institutional support: RVO:61389013 Keywords : zinc(II) 4-aminobenzoate * thermal * spectral Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 1.953, year: 2016

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.

Studies of zinc(II in pharmaceutical and biological samples by extractive spectrophotometry: using pyridoxal-4-phenyl-3-thiosemicarbazone as chelating reagent

Directory of Open Access Journals (Sweden)

Sarma L. Subramanyam

2006-01-01

Full Text Available Pyridoxal-4-phenyl-3-thiosemicarbazone (PPT is proposed as a new sensitive reagent for the sensitive extractive spectrophotometric determination of zinc(II. PPT reacts with zinc(II in the pH range 5.0-6.0 to form a yellow colored complex, which was well extracted into n-butanol. The absorbance value of Zn(II-PPT complex was measured at different intervals of time at 430 nm, to ascertain the stability of the complex. It was observed that the color development was instantaneous and stable for more than 48 h. The system obeyed Beer's law up to 6.0 µg mL-1 of zinc(II, with an excellent linearity in terms of correlation coefficient value of 0.999. The molar absorptivity and Sandell's sensitivity of the extracted species is 1.6 X 10(4 L mol-1 cm-1 and 4.085 X 10-3 µg cm-2 at 430 nm. The detection limit of the method is 0.04 µg mL-1. To assess precision of the method, determinations were carried out at different concentrations; the relative standard deviation does not exceed 3.1%. The composition of the zinc(II complex with PPT was studied by the method of Job's continuous variation, molar ratio method, Asmus' method and slope ratio method. It has been satisfactorily applied for the determination of zinc(II, when present alone or in presence of diverse ions, which are usually associated with zinc(II in pharmaceutical and biological samples. Various certified reference materials (NIST 1573, NBS 1572 and NIST SRM 8435 have been tested for the determination of zinc for evaluating the accuracy of the developed method. The results of the proposed method are in agreement with flame atomic absorption spectometry.

Synthesis and characterization of two new zinc(II) coordination polymers with bidentate flexible ligands: Formation of a 2D structure with (44.62)-sql topology

Science.gov (United States)

Lalegani, Arash; Khaledi Sardashti, Mohammad; Gajda, Roman; Woźniak, Krzysztof

2017-12-01

Zinc(II) coordination polymers [Zn(bip)2(NCS)2]n (1) and [Zn(μ-bbd)(N3)2]n (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd) and 1,3-bis(imidazolyl)propane (bip), mono-anionic NCS- or N3-ligand and zinc(II) chloride salts. The results of the X-ray analyses demonstrate that in the structure of 1, the zinc(II) ion is located on an inversion center and exhibits an ZnN6 octahedral arrangement while, in the structure of 2, the zinc(II) ion adopts an ZnN4 tetrahedral geometry. In the polymer 1, the NCS groups are terminally N-bonded to the metal center and the each bip with anti-gauche conformation acts as bridging connecting four zinc(II) ions to form a two-dimensional network with a sql [point symbol (44.62)] topology while, in the polymer 1, the N3 groups are terminally bonded to the metal center and each bbd with anti-anti-anti conformation acts as bridging ligand connecting two zinc(II) ions to form a one-dimensional zig-zag chain. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analyses of polymers were also presented.

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

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...

Non-covalently anchored multi-walled carbon nanotubes with hexa-decafluorinated zinc phthalocyanine as ppb level chemiresistive chlorine sensor

Science.gov (United States)

Sharma, Anshul Kumar; Mahajan, Aman; Bedi, R. K.; Kumar, Subodh; Debnath, A. K.; Aswal, D. K.

2018-01-01

A cost effective solution assembly method has been explored for preparing zinc(II)1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexa-decafluoro-29H,31H-phthalocyanine/multi-walled carbon nanotubes (F16ZnPc/MWCNTs-COOH) hybrid. Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE-SEM) investigations confirm the non-covalent anchoring of F16ZnPc onto MWCNTs-COOH through п-п stacking interactions. Further, a highly sensitive and selective chemiresistive Cl2 sensor has been fabricated using F16ZnPc/MWCNTs-COOH hybrid. The response of sensor is found to be 21.28% for 2 ppm of Cl2 with a response time of 14 s and theoretical detection limit of the sensor is found down to 0.06 ppb. The improved Cl2 sensing characteristics of hybrid are found to be originated from the synergetic interaction between F16ZnPc and MWCNTs-COOH. The underlying mechanism for improved gas sensing performance of F16ZnPc/MWCNTs-COOH sensor towards Cl2 has been explained using Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) studies.

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.

Indirect spectrophotometric determination of trace cyanide with cationic porphyrins.

Science.gov (United States)

Ishii, H; Kohata, K

1991-05-01

Three highly sensitive methods for the determination of cyanide have been developed, based on the fact that the complexation of silver ions with three cationic porphyrins, 5,10,15,20-tetrakis-(1-methyl-2-pyridinio)porphine [T(2-MPy)P], 5,10,15,20-tetrakis(1-methyl-3-pyridinio)porphine [T(3-MPy)P] and 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphine [T(4-MPy)P], in alkaline media is inhibited by cyanide and the decrease in absorbance of the silver(II) complex is proportional to the cyanide concentration. Sensitivities of the procedures developed are 0.133, 0.126 and 0.234 ng/cm(2), respectively for an absorbance of 0.001. Cadmium(II), copper(II), mercury(II), zinc(II), iodide and sulfide interfere with the cyanide determination. One of the proposed methods was applied to the determination of cyanide in waste-water samples, with satisfactory results.

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

Science.gov (United States)

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

2008-07-31

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

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.

[Sensitive Determination of Chondroitin Sulfate by Fluorescence Recovery of an Anionic Aluminum Phthalocyanine-Cationic Surfactant Ion-Association Complex Used as a Fluorescent Probe Emitting at Red Region].

Science.gov (United States)

Chen, Lin; Huang, Ping; Yang, Hui-qing; Deng, Ya-bin; Guo, Meng-lin; Li, Dong-hui

2015-08-01

Determination of chondroitin sulfate in the biomedical field has an important value. The conventional methods for the assay of chondroitin sulfate are still unsatisfactory in sensitivity, selectivity or simplicity. This work aimed at developing a novel method for sensitive and selective determination of chondroitin sulfate by fluorimetry. We found that some kinds of cationic surfactants have the ability to quench the fluorescence of tetrasulfonated aluminum phthalocyanine (AlS4Pc), a strongly fluorescent compound which emits at red region, with high efficiency. But, the fluorescence of the above-mentioned fluorescence quenching system recovered significantly when chondroitin sulfate (CS) exits. Tetradecyl dimethyl benzyl ammonium chloride(TDBAC) which was screened from all of the candidates of cationic surfactants was chosen as the quencher because it shows the most efficient quenching effect. It was found that the fluorescence of AlS4Pc was extremely quenched by TDBAC because of the formation of association complex between AlS4Pc and TDBAC. Fluorescence of the association complex recovered dramatically after the addition of chondroitin sulfate (CS) due to the ability of chondroitin sulfate to shift the association equilibrium of the association, leading to the release of AlS4Pc, thus resulting in an increase in the fluorescence of the reaction system. Based on this phenomenon, a novel method with simplicity, accuracy and sensitivity was developed for quantitative determination of CS. Factors including the reaction time, influencing factors and the effect of coexisting substances were investigated and discussed. Under optimum conditions the linear range of the calibration curve was 0.20~10.0 μg · mL(-1). The detection limit for CS was 0.070 μg · mL(-1). The method has been applied to the analysis of practical samples with satisfied results. This work expands the applications of AlS4Pc in biomedical area.

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

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.

Thermoanalytical investigation and biological properties of zinc(II) 4-chloro- and 5-chlorosalicylates with N-donor ligands

Czech Academy of Sciences Publication Activity Database

Bujdošová, Z.; Györyová, K.; Mudroňová, D.; Hudecová, D.; Kovářová, Jana

2012-01-01

Roč. 110, č. 1 (2012), s. 167-176 ISSN 1388-6150 Institutional support: RVO:61389013 Keywords : chlorosalicylate * zinc(II) * nicotinamide derivatives Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.982, year: 2012

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.

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.

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.

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.

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.

Synthesis, biological and physicochemical properties of Zinc(II) salicylate and 5-chlorosalicylate complexes with theophylline and urea

Czech Academy of Sciences Publication Activity Database

Bujdošová, Z.; Gyoryova, K.; Kovářová, Jana; Hudecová, D.; Halás, L.

2009-01-01

Roč. 98, č. 1 (2009), s. 151-159 ISSN 1388-6150 Institutional research plan: CEZ:AV0Z40500505 Keywords : zinc(II) salicylate * theophylline * urea Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.587, year: 2009

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.

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.

Use of emanation thermal analysis and evolved gas analysis in thermal study of zinc(II) benzoate complex compounds

Czech Academy of Sciences Publication Activity Database

Findoráková, L.; Györyová, K.; Večerníková, Eva; Balek, V.

2009-01-01

Roč. 98, č. 3 (2009), s. 765-769 ISSN 1388-6150 Institutional research plan: CEZ:AV0Z40320502 Keywords : zinc(II) benzoate * caffeine * urea * thermogravimetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.587, year: 2009

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

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.

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) ...

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

Directory of Open Access Journals (Sweden)

KATALIN MÉSZÁROS SZÉCSÉNYI

2009-11-01

Full Text Available The work is concerned with the crystal and molecular structures of zinc(II and mercury(II complexes with 4-acetyl-3-amino-5-methyl-pyrazole (aamp of the coordination formulae [Zn(NCS2(aamp2] and (Haamp2[Hg(SCN4]. The zinc(II complex was obtained by the reaction of a warm methanolic solution of aamp with a mixture of zinc(II nitrate and ammonium thiocyanate, whereas the mercury(II complex was prepared by the reaction of a warm ethanolic solution of aamp and a warm, slightly acidified aqueous solution of [Hg(SCN4]2-. Both complexes have a tetrahedral geometry, which in the case of zinc complex is formed by monodentate coordination of two aamp molecules and two isothiocyanate groups. The Zn(II and Hg(II atoms have significantly deformed coordination geometry. In both crystal structures the pyrazole derivative has a planar form, probably stabilized by an intramolecular N–H···O hydrogen bond. Apart from the X-ray structural analysis, the isolated complexes were characterized by elemental analysis, IR spectroscopy, conductometric measurements and thermal analysis.

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.

Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

Science.gov (United States)

Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

2012-11-05

In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

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.

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 

Sequential injection chromatography with post-column reaction/derivatization for the determination of transition metal cations in natural water samples.

Science.gov (United States)

Horstkotte, Burkhard; Jarošová, Patrícia; Chocholouš, Petr; Sklenářová, Hana; Solich, Petr

2015-05-01

In this work, the applicability of Sequential Injection Chromatography for the determination of transition metals in water is evaluated for the separation of copper(II), zinc(II), and iron(II) cations. Separations were performed using a Dionex IonPAC™ guard column (50mm×2mm i.d., 9 µm). Mobile phase composition and post-column reaction were optimized by modified SIMPLEX method with subsequent study of the concentration of each component. The mobile phase consisted of 2,6-pyridinedicarboxylic acid as analyte-selective compound, sodium sulfate, and formic acid/sodium formate buffer. Post-column addition of 4-(2-pyridylazo)resorcinol was carried out for spectrophotometric detection of the analytes׳ complexes at 530nm. Approaches to achieve higher robustness, baseline stability, and detection sensitivity by on-column stacking of the analytes and initial gradient implementation as well as air-cushion pressure damping for post-column reagent addition were studied. The method allowed the rapid separation of copper(II), zinc(II), and iron(II) within 6.5min including pump refilling and aspiration of sample and 1mmol HNO3 for analyte stacking on the separation column. High sensitivity was achieved applying an injection volume of up to 90µL. A signal repeatability of<2% RSD of peak height was found. Analyte recovery evaluated by spiking of different natural water samples was well suited for routine analysis with sub-micromolar limits of detection. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Mononuclear zinc(II) complexes of 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols: Synthesis, structural characterization, DNA binding and cheminuclease activities

Science.gov (United States)

Ravichandran, J.; Gurumoorthy, P.; Karthick, C.; Kalilur Rahiman, A.

2014-03-01

Four new zinc(II) complexes [Zn(HL1-4)Cl2] (1-4), where HL1-4 = 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols, have been isolated and fully characterized using various spectro-analytical techniques. The X-ray crystal structure of complex 4 shows the distorted trigonal-bipyramidal coordination geometry around zinc(II) ion. The crystal packing is stabilized by intermolecular NH⋯O hydrogen bonding interaction. The complexes display no d-d electronic band in the visible region due to d10 electronic configuration of zinc(II) ion. The electrochemical properties of the synthesized ligands and their complexes exhibit similar voltammogram at reduction potential due to electrochemically innocent Zn(II) ion, which evidenced that the electron transfer is due to the nature of the ligand. Binding interaction of complexes with calf thymus DNA was studied by UV-Vis absorption titration, viscometric titration and cyclic voltammetry. All complexes bind with CT DNA by intercalation, giving the binding affinity in the order of 2 > 1 ≫ 3 > 4. The prominent cheminuclease activity of complexes on plasmid DNA (pBR322 DNA) was observed in the absence and presence of H2O2. Oxidative pathway reveals that the underlying mechanism involves hydroxyl radical.

Zinc(II) complexes with intramolecular amide oxygen coordination as models of metalloamidases.

Science.gov (United States)

Rivas, Juan C Mareque; Salvagni, Emiliano; Prabaharan, Ravi; de Rosales, Rafael Torres Martin; Parsons, Simon

2004-01-07

Polydentate ligands (6-R1-2-pyridylmethyl)-R2(R1= NHCOtBu, R2= bis(2-pyridylmethyl)amine L1, bis(2-(methylthio)ethyl)amine L2 and N(CH2CH2)2S L3) form mononuclear zinc(II) complexes with intramolecular amide oxygen coordination and a range of coordination environments. Thus, the reaction of Zn(ClO4)2.6H2O with L1-3 in acetonitrile affords [(L)Zn](ClO4)2(L=L1, 1; L2, 2) and [(L3)Zn(H2O)(NCCH3)](ClO4)2 3. The simultaneous amide/water binding in resembles the motif that has been proposed to be involved in the double substrate/nucleophile Lewis acidic activation and positioning mechanism of amide bond hydrolysis in metallopeptidases. X-ray diffraction, 1H and 13C NMR and IR data suggests that the strength of amide oxygen coordination follows the trend 1>2 >3. L1-3 and undergo cleavage of the tert-butylamide upon addition of Me4NOH.5H2O (1 equiv.) in methanol at 50(1)degrees C. The rate of amide cleavage follows the order 1> 2> 3, L1-3. The extent by which the amide cleavage reaction is accelerated in 1-3 relative to the free ligands, L1-3, is correlated with the strength of amide oxygen binding and Lewis acidity of the zinc(II) centre in deduced from the X-ray, NMR and IR studies.

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.

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

Actinide cation-cation complexes

International Nuclear Information System (INIS)

Stoyer, N.J.; Seaborg, G.T.

1994-12-01

The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

The speciation of aqueous zinc(II) bromide solutions to 500 °C and 900 MPa determined using Raman spectroscopy

Science.gov (United States)

Mibe, Kenji; Chou, I-Ming; Anderson, Alan J.; Mayanovic, Robert A.; Bassett, William A.

2009-01-01

A Raman spectral study was carried out on 3 solutions of varying concentration and bromide/zinc ratios. Spectra were collected at 11 different temperature-pressure conditions ranging from ambient to 500????C-0.9??GPa. Raman band assignments for zinc(II) bromide species reported in previous studies were used to determine the relative concentrations of ZnBr42-, ZnBr3-, ZnBr2, and ZnBr+ species at various temperatures and pressures. Our results are in close agreement with X-ray absorption spectroscopic (XAS) data, and confirm that the tetrabromo zinc(II) complex, ZnBr42-, is the predominant species up to 500????C in solutions having high Zn concentrations (1??m) and high bromide/zinc molar ratios ([Br]/[Zn] = 8). In agreement with previous solubility and Raman spectroscopic experiments, our measurements indicate that species with a lower number of halide ligands and charge are favored with increasing temperature in dilute solutions, and solutions with low bromide/zinc ratios ([Br]/[Zn] Raman technique provides an independent experimental means of evaluating the quality of XAS analyses of data obtained from high temperature disordered systems. The combination of these two techniques provides complementary data on speciation and the structure of zinc(II) bromide complexes. The preponderance of the ZnBr42- species in highly saline brines at high temperature is consistent with the predominance of ZnCl42- in chloride-rich brines reported in previous XAS studies. Knowledge of Zn complexing in metal-rich highly saline brines is important for numerical models of ore deposition in high temperature systems such as skarns and porphyry-type deposits. ?? 2008 Elsevier B.V.

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 ...

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-10-15

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

Steric Effects on the Binding of Phosphate and Polyphosphate Anions by Zinc(II) and Copper(II) Dinuclear Complexes of m-Xylyl-bis-cyclen.

Science.gov (United States)

Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita

2018-05-11

The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.

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.

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.

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

International Nuclear Information System (INIS)

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

2007-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-06-28

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

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.

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

Development of a Novel Biosensor Using Cationic Antimicrobial Peptide and Nickel Phthalocyanine Ultrathin Films for Electrochemical Detection of Dopamine

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Maysa F. Zampa

2012-01-01

Full Text Available The antimicrobial peptide dermaseptin 01 (DS 01, from the skin secretion of Phyllomedusa hypochondrialis frogs, was immobilized in nanostructured layered films in conjunction with nickel tetrasulfonated phthalocyanines (NiTsPc, widely used in electronic devices, using layer-by-layer technique. The films were used as a biosensor to detect the presence of dopamine (DA, a neurotransmitter associated with diseases such as Alzheimer's and Parkinson's, with detection limits in the order of 10−6 mol L−1. The use of DS 01 in LbL film generated selectivity in the detection of DA despite the presence of ascorbic acid found in biological fluids. This work is the first to report that the antimicrobial peptide and NiTsPc LbL film exhibits electroanalytical activity to DA oxidation. The selectivity in the detection of DA is a fundamental aspect for the development of electrochemical sensors with potential applications in the biomedical and pharmaceutical industries.

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

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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.

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

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

Zinc(II) complexes with potent cyclin-dependent kinase inhibitors derived from 6-benzylaminopurine: synthesis, characterization, X-ray structures and biological activity

Czech Academy of Sciences Publication Activity Database

Trávníček, Zdeněk; Kryštof, Vladimír; Šipl, M.

2006-01-01

Roč. 100, č. 2 (2006), s. 214-225 ISSN 0162-0134 R&D Projects: GA ČR GA203/04/1168 Institutional research plan: CEZ:AV0Z50380511 Keywords : Zinc(II) complexes * 6-Benzylaminopurine derivatives * Bohemine * Olomoucine * X-ray structures Subject RIV: CA - Inorganic Chemistry Impact factor: 2.654, year: 2006

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)

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.

Exploitation of knowledge databases in the synthesis of zinc(II malonates with photo-sensitive and photo-insensitive N,N′-containing linkers

Directory of Open Access Journals (Sweden)

Ekaterina N. Zorina-Tikhonova

2018-05-01

Full Text Available Photoinitiated solid-state reactions are known to affect the physical properties of coordination polymers, such as fluorescence and sorption behaviour, and also afford extraordinary architectures (e.g. three-periodic structures with polyorganic ligands. However, the construction of novel photo-sensitive coordination polymers requires an understanding of the factors which govern the mutual disposition of reactive fragments. A series of zinc(II malonate complexes with 1,2-bis(pyridin-4-ylethylene and its photo-insensitive analogues has been synthesized for the purpose of systematic analysis of their underlying nets and mutual disposition of N-donor ligands. The application of a big data-set analysis for the prediction of a variety of possible complex compositions, coordination environments and networks for a four-component system has been demonstrated for the first time. Seven of the nine compounds possess one of the highly probable topologies for their underlying nets; in addition, two novel closely related four-coordinated networks were obtained. Complexes containing 1,2-bis(pyridin-4-ylethylene and 1,2-bis(pyridin-4-ylethane form isoreticular compounds more readily than those with 4,4′-bipyridine and 1,2-bis(pyridin-4-ylethylene. The effects of the precursor, either zinc(II nitrate or zinc(II acetate, on the composition and dimensionality of the resulting architecture are discussed. For three of the four novel complexes containing 1,2-bis(pyridin-4-ylethylene, the single-crystal-to-single-crystal [2 + 2] cycloaddition reactions were carried out. UV irradiation of these crystals afforded either the 0D→1D or the 3D→3D transformations, with and without network changes. One of the two 3D→3D transformations was accompanied by solvent (H2O cleavage.

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

International Nuclear Information System (INIS)

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

2009-01-01

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

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.

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

NARCIS (Netherlands)

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

2015-01-01

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

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

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.

Synthesis, structure and photoluminescence of (PLAGH)2[ZnCl4] and comparative analysis of photoluminescence properties with tris(2,2′-bipyridine)ruthenium(II)

International Nuclear Information System (INIS)

Radanović, Mirjana M.; Jelić, Miodrag G.; Romčević, Nebojša Ž.; Boukos, Nikos; Vojinović-Ješić, Ljiljana S.; Leovac, Vukadin M.; Hadžić, Branka B.; Bajac, Branimir M.; Nađ, Laslo F.; Chandrinou, Chrysoula; Baloš, Sebastian S.

2015-01-01

Highlights: • New zinc(II) complex with pyridoxalaminoguanidine was synthesized. • The enhancement of the photoluminescence due to the compound formation was achieved. • Very high photoluminescence of Zn(II) compound was noticed. • Comparative analysis of photoluminescence with tris(2,2′-bipyridine) ruthenium(II) was provided. - Abstract: The first compound of zinc(II) containing pyridoxalaminoguanidine has been synthesized and characterized by elemental analysis, infrared spectra, conductometric measurements and X-ray crystallography. Single crystals of the compound were obtained in the reaction of methanolic solution of zinc(II) chloride and pyridoxalaminoguanidine hydrochloride. In this compound the coordination of chelate ligand is absent and tetrachlorido complex of zinc(II) with pyridoxalaminuguanidinium cation as contraion is obtained. Photoluminescence spectra were measured. Lorentzian multipeak technique was used to determine peak wavelengths and their intensities. Photoluminescence spectroscopy upon 325, 488 and 514 nm laser excitation light was used to obtain results. This novel compound of zinc(II) was compared to the well-known organic light emitting diode material—ruthenium(II) complex with bypiridine i.e., tris(2,2′-bipyridine)ruthenium(II), under the same circumstances and the identical experimental setup. A scheme of energy levels and transitions is proposed to explain the obtained experimental results

Synthesis, structure and photoluminescence of (PLAGH){sub 2}[ZnCl{sub 4}] and comparative analysis of photoluminescence properties with tris(2,2′-bipyridine)ruthenium(II)

Energy Technology Data Exchange (ETDEWEB)

Radanović, Mirjana M. [University of Novi Sad, Faculty of Sciences, Novi Sad (Serbia); Jelić, Miodrag G., E-mail: jelicmgm@uns.ac.rs [University of Novi Sad, Faculty of Technical Sciences, Novi Sad (Serbia); Romčević, Nebojša Ž. [University of Belgrade, Institute of Physics, Belgrade (Serbia); Boukos, Nikos [National Centre for Scientific Research “Demokritos”, Institute of Materials Science, Athens (Greece); Vojinović-Ješić, Ljiljana S.; Leovac, Vukadin M. [University of Novi Sad, Faculty of Sciences, Novi Sad (Serbia); Hadžić, Branka B. [University of Belgrade, Institute of Physics, Belgrade (Serbia); Bajac, Branimir M. [University of Novi Sad, Faculty of Technology, Novi Sad (Serbia); Nađ, Laslo F. [University of Novi Sad, Faculty of Technical Sciences, Novi Sad (Serbia); Chandrinou, Chrysoula [National Centre for Scientific Research “Demokritos”, Institute of Materials Science, Athens (Greece); Baloš, Sebastian S. [University of Novi Sad, Faculty of Technical Sciences, Novi Sad (Serbia)

2015-10-15

Highlights: • New zinc(II) complex with pyridoxalaminoguanidine was synthesized. • The enhancement of the photoluminescence due to the compound formation was achieved. • Very high photoluminescence of Zn(II) compound was noticed. • Comparative analysis of photoluminescence with tris(2,2′-bipyridine) ruthenium(II) was provided. - Abstract: The first compound of zinc(II) containing pyridoxalaminoguanidine has been synthesized and characterized by elemental analysis, infrared spectra, conductometric measurements and X-ray crystallography. Single crystals of the compound were obtained in the reaction of methanolic solution of zinc(II) chloride and pyridoxalaminoguanidine hydrochloride. In this compound the coordination of chelate ligand is absent and tetrachlorido complex of zinc(II) with pyridoxalaminuguanidinium cation as contraion is obtained. Photoluminescence spectra were measured. Lorentzian multipeak technique was used to determine peak wavelengths and their intensities. Photoluminescence spectroscopy upon 325, 488 and 514 nm laser excitation light was used to obtain results. This novel compound of zinc(II) was compared to the well-known organic light emitting diode material—ruthenium(II) complex with bypiridine i.e., tris(2,2′-bipyridine)ruthenium(II), under the same circumstances and the identical experimental setup. A scheme of energy levels and transitions is proposed to explain the obtained experimental results.

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.

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.

Controlling the Orbital Sequence in Individual Cu-Phthalocyanine Molecules

NARCIS (Netherlands)

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

2013-01-01

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

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)

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.

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

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...

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

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.

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.

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

Directory of Open Access Journals (Sweden)

Fabio Lupo

2014-11-01

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

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.

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

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)

Luminescent zinc(ii) and copper(i) complexes for high-performance solution-processed monochromic and white organic light-emitting devices.

Science.gov (United States)

Cheng, Gang; So, Gary Kwok-Ming; To, Wai-Pong; Chen, Yong; Kwok, Chi-Chung; Ma, Chensheng; Guan, Xiangguo; Chang, Xiaoyong; Kwok, Wai-Ming; Che, Chi-Ming

2015-08-01

The synthesis and spectroscopic properties of luminescent tetranuclear zinc(ii) complexes of substituted 7-azaindoles and a series of luminescent copper(i) complexes containing 7,8-bis(diphenylphosphino)-7,8-dicarba- nido -undecaborate ligand are described. These complexes are stable towards air and moisture. Thin film samples of the luminescent copper(i) complexes in 2,6-dicarbazolo-1,5-pyridine and zinc(ii) complexes in poly(methyl methacrylate) showed emission quantum yields of up to 0.60 (for Cu-3 ) and 0.96 (for Zn-1 ), respectively. Their photophysical properties were examined by ultrafast time-resolved emission spectroscopy, temperature dependent emission lifetime measurements and density functional theory calculations. Monochromic blue and orange solution-processed OLEDs with these Zn(ii) and Cu(i) complexes as light-emitting dopants have been fabricated, respectively. Maximum external quantum efficiency (EQE) of 5.55% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.16, 0.19) were accomplished with the optimized Zn-1 -OLED while these values were, respectively 15.64% and (0.48, 0.51) for the optimized Cu-3 -OLED. Solution-processed white OLEDs having maximum EQE of 6.88%, CIE coordinates of (0.42, 0.44), and colour rendering index of 81 were fabricated by using these luminescent Zn(ii) and Cu(i) complexes as blue and orange light-emitting dopant materials, respectively.

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

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.

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.

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

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.

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.

Sonochemical synthesis and characterization of nano-sized zinc(II coordination complex as a precursor for the preparation of pure-phase zinc(II oxide nanoparticles

Directory of Open Access Journals (Sweden)

Maryam Ranjbar

2017-01-01

Full Text Available In current study, nanoparticles and single crystals of a Zn(II coordination complex, [Zn(dmphI2](1, {dmph=2,9-dimethyl-1,10-phenanthroline(neocuproine}, have been synthesized by the reaction of zinc(II acetate, KI and neocuproine as ligand in methanol using sonochemical and heat gradient methods, respectively. The nanostructure of 1 was characterized by scanning electron microscopy (SEM, X-ray powder diffraction (XRD, FT-IR spectroscopy and elemental analyses, and the structure of compound 1 was determined by single-crystal X-ray diffraction. The thermal stability of nano-sized 1 has been studied by thermogravimetric (TG and differential thermal analyses (DTA. Structural determination of compound 1 reveals the Zn(II ion is four-coordinated in a distorted tetrahedral configuration by two N atoms from a 2,9-dimethyl-1,10-Phenanthroline ligand and two terminal I atoms. The effect of supercritical condition on stability, size and morphology of nano-structured compound 1 has also been studied. The XRD pattern of the residue obtained from thermal decomposition of nano-sized compound 1 at 600 °C under air atmosphere provided pure phase of ZnO with the average particles size of about 31 nm.

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

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.

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.

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.

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.

Surfactant controlled low-temperature thermal decomposition route to zinc oxide nanorods from zinc(II) acetylacetonate monohydrate

Energy Technology Data Exchange (ETDEWEB)

Purkayastha, Debraj Dhar; Sarma, Bedabrat; Bhattacharjee, Chira R., E-mail: crbhattacharjee@rediffmail.com

2014-10-15

Zinc oxide (ZnO) nanorods were synthesized via a low-temperature thermal decomposition of zinc(II) acetylacetonate monohydrate, [Zn(C{sub 5}H{sub 7}O{sub 2}){sub 2}].H{sub 2}O. A relatively inexpensive surfactant, octadecylamine (C{sub 18}H{sub 37}NH{sub 2}) served both as a reaction solvent and a capping agent during the synthesis of ZnO nanorods. The synthesized nanorods were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, UV–visible, and photoluminescence (PL) studies. The XRD spectrum furnished evidence for the hexagonal wurtzite structure of ZnO. TEM images revealed the material to be rod shaped having diameter 30 nm and length 200 nm. The HRTEM image showed that the lattice fringes between the two adjacent planes are 0.244 nm apart, which corresponds to the interplanar separation of the (1 0 1) plane of hexagonal ZnO. The electron diffraction (ED) pattern confirmed the single crystalline nature of the nanorods. The PL spectrum showed two UV emissions at 356 nm (∼3.48 eV) and 382 nm (∼3.25 eV). ZnO nanorods also showed very weak blue bands at 445, 453 and 470 nm. - Highlights: Low temperature thermal decomposition of zinc(II) acetylacetonate monohydrate gave zinc oxide nanorods. Powder XRD showed hexagonal wurtzite structure of ZnO having average diameter about 24 nm. TEM images revealed the material to be of rod shape having diameter 30 nm and length 200 nm. ZnO showed band gap luminescence at 356 nm, excitonic emission at 382 nm and defect related blue bands. The synthesis is simple and can act as a paradigm for obtaining various metal oxide nanomaterials.

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.

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

Directory of Open Access Journals (Sweden)

S. O. PODUNAVAC-KUZMANOVIC

1999-05-01

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

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.

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.

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

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

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.

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)

Azaphthalocyanines: Red Fluorescent Probes for Cations

Czech Academy of Sciences Publication Activity Database

Nováková, V.; Lochman, L.; Zajícová, I.; Kopecký, K.; Miletin, M.; Lang, Kamil; Kirakci, Kaplan; Zimcik, P.

2013-01-01

Roč. 19, č. 16 (2013), s. 5025-5028 ISSN 0947-6539 R&D Projects: GA ČR GAP208/10/1678 Institutional support: RVO:61388980 Keywords : crown compounds * fluorescent probes * phthalocyanine s * potassium * sodium Subject RIV: CA - Inorganic Chemistry Impact factor: 5.696, year: 2013

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.

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.

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

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...

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

Structural and energetic study of cation-π-cation interactions in proteins.

Science.gov (United States)

Pinheiro, Silvana; Soteras, Ignacio; Gelpí, Josep Lluis; Dehez, François; Chipot, Christophe; Luque, F Javier; Curutchet, Carles

2017-04-12

Cation-π interactions of aromatic rings and positively charged groups are among the most important interactions in structural biology. The role and energetic characteristics of these interactions are well established. However, the occurrence of cation-π-cation interactions is an unexpected motif, which raises intriguing questions about its functional role in proteins. We present a statistical analysis of the occurrence, composition and geometrical preferences of cation-π-cation interactions identified in a set of non-redundant protein structures taken from the Protein Data Bank. Our results demonstrate that this structural motif is observed at a small, albeit non-negligible frequency in proteins, and suggest a preference to establish cation-π-cation motifs with Trp, followed by Tyr and Phe. Furthermore, we have found that cation-π-cation interactions tend to be highly conserved, which supports their structural or functional role. Finally, we have performed an energetic analysis of a representative subset of cation-π-cation complexes combining quantum-chemical and continuum solvation calculations. Our results point out that the protein environment can strongly screen the cation-cation repulsion, leading to an attractive interaction in 64% of the complexes analyzed. Together with the high degree of conservation observed, these results suggest a potential stabilizing role in the protein fold, as demonstrated recently for a miniature protein (Craven et al., J. Am. Chem. Soc. 2016, 138, 1543). From a computational point of view, the significant contribution of non-additive three-body terms challenges the suitability of standard additive force fields for describing cation-π-cation motifs in molecular simulations.

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

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.

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.

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

Photodynamic therapy with water-soluble phtalocyanines against bacterial biofilms in teeth root canals

Science.gov (United States)

Gergova, Raina; Georgieva, Tzvetelina; Angelov, Ivan; Mantareva, Vanya; Valkanov, Serjoga; Mitov, Ivan; Dimitrov, Slavcho

2012-06-01

The study presents the PDT with metal phthalocyanines on biofilms grown in root canals of ten representatives of the Gram-positive and the Gram-negative bacterial species and a fungus Candida albicans which cause aqute teeth infections in root canals.. The extracted human single-root teeth infected for 48 h with microorganisms in conditions to form biofilms of the above pathogens were PDT treated. The stage of biofilm formation and PDT effect of the samples of the teeth were determined by the scaning electron microscopy and with standard microbial tests. The PDT treating procedure included 10 min incubation with the respected phthalocyanine and irradiated with 660 nm Diode laser for 10 min. The most strongly antibacterial activity was achieved with zinc(II) phthalocyanine (ZnPc) against Enterococcus faecalis, Staphylococcus aureus and Moraxella catarrhalis. The other Gram-negative bacteria and Candida albicans were 10-100 times more resistant than the Gram-positive species. The Gram-negative Moraxella catarrhalis and Acinetobacter baumannii were more sensitive than the enterobacteria, but eradication of Pseudomonas aeruginosa in biofilm was insignificant. The influence of the stage of biofilm formation and the initial conditions (bacterial density, photosensitizer concentration and energy fluence of radiation) to the obtained level of inactivation of biofilms was investigated. The PDT with ZnPc photosensitizers show a powerful antimicrobial activity against the most frequent pathogens in endodontic infections and this method for inactivation of pathogens may be used with sucsses for treatment of the bacterial biofilms in the root canals.

Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

Science.gov (United States)

Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

2016-05-28

Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

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

Cation or Solvent-Induced Supermolecular Phthalocyanine Formation: Crown Ether Substituted Phthalocyanines.

Science.gov (United States)

1987-06-01

spectra were obtained with a Varian SF330 spectrofluorimeter with appropriate filters to eliminate scattered light. Fluorescence quantum yields were...initiator. Recrystallisation from ethanol gave colorless plates in 51Z yield . Anal.calcd. for C1 4 Hi 8 Br 2 O5 : C,39.5; H,4.3. Found: C, 39.6; H,4.3Z. 1 H...olive-green product was soxhlet extracted with diethyl ether for 3 days. Benzene recrystallisation provided 2.02g (31Z) of colorless small needles

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

Stability constants of salicylate of zinc(II), cobalt(II), uranyl(II) and thorium(IV) by paper electrophoresis

International Nuclear Information System (INIS)

Singh, R.K.P.; Yadava, J.R.; Yadava, P.C.; Yadava, K.L.

1983-01-01

Stability constants of zinc(II), cobalt(II), uranyl(II) and thorium(IV) have been determined by paper electrophoresis. Salicylic acid (0.005 mol dm - 3 ) was added to the background electrolyte: 0.1 mol dm - 3 HClO 4 . The proportions of C 6 H 4 OHCOO - and C 6 H 4 OCOO/sup =/ were varied by changing the pH of the electrolyte. These anions yielded the complexes, ZnC 6 H 4 OHCOO + , CoC 6 H 4 OHCOO + , Th(C 6 H 4 OHCOO) 4 and UO 2 (C 6 H 4 OCOO) 2 /sup =/ whose stability constants are found to be 10/sup 3.1/, 10/sup 3.2/, 10/sup 11.6/ and 10/sup 22.2/, respectively (μ = 0.1, temp. 40 0 C). (author)

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.

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

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

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

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

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.

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.

Photocatalytic Conversion of Carbon Dioxide Using Zn–Cu–Ga Layered Double Hydroxides Assembled with Cu Phthalocyanine: Cu in Contact with Gaseous Reactant is Needed for Methanol Generation

Directory of Open Access Journals (Sweden)

Kawamura Shogo

2015-09-01

Full Text Available Photocatalytic conversion of CO2 into fuels is an attractive option in terms of both reducing the increased concentration of atmospheric CO2 as well as generating renewable hydrocarbon fuels. It is necessary to investigate good catalysts for CO2 conversion and to clarify the mechanism irradiated by natural light. Layered Double Hydroxides (LDH have been attracting attention for CO2 photoreduction with the expectation of sorption capacity for CO2 in the layered space and tunable semiconductor properties as a result of the choice of metal cations. This study first clarifies the effects of Cu doping to LDH comprising Zn and Al or Ga. Cu could be incorporated in the cationic layers of LDH as divalent metal cations and/or interlayer anions as Cu(OH42−. The formation rates of methanol and CO were optimized for [Zn1.5Cu1.5Ga(OH8]+2Cu(OH42−·mH2O at a total rate of 560 nmol h−1 gcat−1 irradiated by UV–visible light. Cu phthalocyanine tetrasulfonate hydrate (CuPcTs4− and silver were effective as promoters of LDH for CO2 photoreduction. Especially, the total formation rate using CuPcTs-[Zn3Ga(OH8]+2CO32−·mH2O irradiated by visible light was 73% of that irradiated by UV–visible light. The promotion was based on HOMO–LUMO excitation of CuPcTs4− by visible light. The LUMO was distributed on N atoms of pyrrole rings bound to central Cu2+ ions. The photogenerated electrons diffused to the Cu site would photoreduce CO2 progressively in a similar way to inlayer and interlayer Cu sites in the LDH in this study.

Exploring backbone-cation alkyl spacers for multi-cation side chain anion exchange membranes

Science.gov (United States)

Zhu, Liang; Yu, Xuedi; Hickner, Michael A.

2018-01-01

In order to systematically study how the arrangement of cations on the side chain and length of alkyl spacers between cations impact the performance of multi-cation AEMs for alkaline fuel cells, a series of polyphenylene oxide (PPO)-based AEMs with different cationic side chains were synthesized. This work resulted in samples with two or three cations in a side chain pendant to the PPO backbone. More importantly, the length of the spacer between cations varied from 3 methylene (-CH2-) (C3) groups to 8 methylene (C8) groups. The highest conductivity, up to 99 mS/cm in liquid water at room temperature, was observed for the triple-cation side chain AEM with pentyl (C5) or hexyl (C6) spacers. The multi-cation AEMs were found to have decreased water uptake and ionic conductivity when the spacer chains between cations were lengthened from pentyl (C5) or hexyl (C6) to octyl (C8) linking groups. The triple-cation membranes with pentyl (C5) or hexyl (C6) groups between cations showed greatest stability after immersion in 1 M NaOH at 80 °C for 500 h.

Effect of temperature on the optical and structural properties of hexadecylamine capped ZnS nanoparticles using Zinc(II) N-ethyl-N-phenyldithiocarbamate as single source precursor

Energy Technology Data Exchange (ETDEWEB)

Onwudiwe, Damian C., E-mail: dconwudiwe@webmail.co.za [Chemical Resource Beneficiation, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Strydom, Christien [Chemical Resource Beneficiation, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Oluwafemi, Oluwatobi S., E-mail: oluwafemi.oluwatobi@gmail.com [Department of Chemistry and Chemical Technology, Walter Sisulu University, Mthatha Campus, Private Bag X1, Mthatha (South Africa); Songca, Sandile P. [Faculty of Science, Engineering and Technology, Walter Sisulu University, P.O. Box 19712, Tecoma, East London (South Africa)

2012-12-15

Graphical abstract: Display Omitted Highlights: ► HDA-capped ZnS nanoparticles were synthesized via thermolysis of a single source precursor. ► Zinc(II) N-ethyl-N-phenyldithiocarbamate was used as the single source precursor. ► The growth temperature was varied to study the optical properties of the nanocrystals. ► Change in growth temperature affects the structural properties of the ZnS nanoparticles. ► Hexagonal wurtzite phase was obtained at lower temperatures while cubic sphalerite phase was obtained at higher growth temperatures. -- Abstract: Reported in this work is the synthesis of HDA (hexadecylamine)-capped ZnS nanoparticles by a single source route using Zinc(II) N-ethyl-N-phenyldithiocarbamate as a precursor. By varying the growth temperature, the temporal evolution of the optical properties and morphology of the nanocrystals were investigated. The as-synthesized nanoparticles were characterized using UV–vis absorption and photoluminescence (PL) spectroscopy, transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). All the particles exhibited quantum confinement in their optical properties with band edge emission at the early stage of the reaction. The XRD showed transition from hexagonal wurtzite phase to cubic sphalerite phase as the growth temperature increases. The TEM image showed that the particles are small and spherical in shape while the HRTEM image confirmed the crystalline nature of the material.

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

Stability constants of glutarate complexes of copper(II), zinc(II), cobalt(II) and uranyl(II) by paper electrophoresis

International Nuclear Information System (INIS)

Singh, R.K.P.; Yadava, J.R.; Yadava, K.L.

1981-01-01

Stability constants of Copper(II), Zinc(II), Cobalt(II) and Uranyl(II) glutarates have been determined by paper electrophoresis. Glutaric acid (0.005 mol dmsup(-3)) was added to the background electrolyte : 0.1 mol dmsup(-3) HClO 4 . The proportions of (CH 2 ) 3 COOH COO - and (CH 2 ) 3 C 2 O 4 2- were varied by changing the pH of the electrolyte. These anions yielded the complexes Cu(CH 2 ) 3 C 2 O 4 , [Zn(CH 2 ) 3 COOH COO] + [Co(CH 2 ) 3 COOH COO] + and UO 2 (CH 2 ) 3 C 2 O 4 whose stability constants are found to be 10sup(3.9), 10sup(2.9), 10sup(2.7) and 10sup(13.5) respectively. (author)

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

Science.gov (United States)

Umari, P; Fabris, S

2012-05-07

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

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.

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

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.

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...

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

International Nuclear Information System (INIS)

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

2006-01-01

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

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.

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

NARCIS (Netherlands)

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

2002-01-01

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

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.

The cation-π interaction.

Science.gov (United States)

Dougherty, Dennis A

2013-04-16

The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author's perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction (Li(+) binds to benzene with 38 kcal/mol of binding energy; NH4(+) with 19 kcal/mol) distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2-5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) C(δ-)-H(δ+) bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li(+) > Na(+) > K(+) > Rb(+): as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane is

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

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

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

Synthetic cation-selective nanotube: permeant cations chaperoned by anions.

Science.gov (United States)

Hilder, Tamsyn A; Gordon, Dan; Chung, Shin-Ho

2011-01-28

The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

Synthesis, spectral properties and thermal behaviour of zinc(II) acetylsalicylate

Energy Technology Data Exchange (ETDEWEB)

Lambi, John N.; Nsehyuka, Alfred T.; Egbewatt, Nkongho; Cafferata, Lazaro F.R.; Arvia, Alejandro J

2003-03-05

The thermal behaviour of zinc(II) acetylsalicylate [Zn(acsa){sub 2}(H{sub 2}O){sub 2}] with respect to phase transitions, pyrolysis both in air and inert (N{sub 2}) atmosphere, and product identification has been investigated. The complex was synthesised by metathesis in hot ethanol solution using aspirin (acetylsalicylic acid) as precursor and characterised via electronic and IR spectral analyses. Optical observations showed that the white salt does not undergo a direct transition from the solid to the liquid phase but rather goes slowly through an intermediate mesophase around 80 deg. C before melting rapidly to the brick-brown isotropic liquid around 134-136 deg. C. No liquid crystalline phases are however formed. This result was complemented by that from thermogravimetric (TG) studies in the ca. 25-600 deg. C range, which showed three main weight-loss phases of 8.0, 50.0 and 14.0% (around 200, 250 and 400 deg. C) corresponding, respectively, to the elimination of CO{sub 2}, xanthone and acetic acid. The pyrolysis products, as identified using a combination of instrumental (GC-MS) and wet chemical techniques are: CO{sub 2}; non-stoichiometric zinc oxide, most likely in the form: Zn{sub 1+x}O (where 0.0000{<=}x{<=}0.0003); and a mixture of organic products resulting from further decomposition, charring and other attendant thermal effects at the relatively high temperatures (ca. 600 deg. C) involved. Six of the principal organic products were identified and included salsalate and benorylate which are pro-drugs of salicylic acid, a well-known pharmaceutical.

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.

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.

Computational Investigation of the Influence of Halogen Atoms on the Photophysical Properties of Tetraphenylporphyrin and Its Zinc(II) Complexes.

Science.gov (United States)

De Simone, Bruna C; Mazzone, Gloria; Russo, Nino; Sicilia, Emilia; Toscano, Marirosa

2018-03-15

How the tetraphenylporphyrin (TPP) and its zinc(II) complexes (ZnTPP) photophysical properties (absorption energies, singlet-triplet energy gap and spin-orbit coupling contributions) can change due to the presence of an increasing number of heavy atoms in their molecular structures has been investigated by means of density functional theory and its time-dependent formulation. Results show that the increase of the atomic mass of the substituted halogen strongly enhances the spin-orbit coupling values, allowing a more efficient singlet-triplet intersystem crossing. Different deactivation channels have been considered and rationalized on the basis of El-Sayed and Kasha rules. Most of the studied compounds possess the appropriate properties to generate cytotoxic singlet molecular oxygen ( 1 Δ g ) and, consequently, they can be proposed as photosensitizers in photodynamic therapy.

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

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

The influence of zinc(II) on thioredoxin/glutathione disulfide exchange: QM/MM studies to explore how zinc(II) accelerates exchange in higher dielectric environments.

Science.gov (United States)

Kurian, Roby; Bruce, Mitchell R M; Bruce, Alice E; Amar, François G

2015-08-01

QM/MM studies were performed to explore the energetics of exchange reactions of glutathione disulfide (GSSG) and the active site of thioredoxin [Cys32-Gly33-Pro34-Cys35] with and without zinc(II), in vacuum and solvated models. The activation energy for exchange, in the absence of zinc, is 29.7 kcal mol(-1) for the solvated model. This is 3.3 kcal mol(-1) higher than the activation energy for exchange in the gas phase, due to ground state stabilization of the active site Cys-32 thiolate in a polar environment. In the presence of zinc, the activation energy for exchange is 4.9 kcal mol(-1) lower than in the absence of zinc (solvated models). The decrease in activation energy is attributed to stabilization of the charge-separated transition state, which has a 4-centered, cyclic arrangement of Zn-S-S-S with an estimated dipole moment of 4.2 D. A difference of 4.9 kcal mol(-1) in activation energy would translate to an increase in rate by a factor of about 4000 for zinc-assisted thiol-disulfide exchange. The calculations are consistent with previously reported experimental results, which indicate that metal-thiolate, disulfide exchange rates increase as a function of solvent dielectric. This trend is opposite to that observed for the influence of the dielectric environment on the rate of thiol-disulfide exchange in the absence of metal. The results suggest a dynamic role for zinc in thiol-disulfide exchange reactions, involving accessible cysteine sites on proteins, which may contribute to redox regulation and mechanistic pathways during oxidative stress.

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

Further Aspects of Ochratoxin A-Cation Interactions: Complex Formation with Zinc Ions and a Novel Analytical Application of Ochratoxin A-Magnesium Interaction in the HPLC-FLD System

Directory of Open Access Journals (Sweden)

Miklós Poór

2014-04-01

Full Text Available Ochratoxin A (OTA is a mycotoxin produced by different Aspergillus and Penicillium species. Since its mechanism of action is not fully understood yet, it is important to gain further insight into different interactions of OTA at the molecular level. OTA is found worldwide in many foods and drinks. Moreover, it can also be detected in human and animal tissues and body fluids, as well. Therefore, the development of highly sensitive quantitative methods for the determination of OTA is of utmost importance. OTA most likely forms complexes with divalent cations, both in cells and body fluids. In the present study, the OTA-zinc interaction was investigated and compared to OTA-magnesium complex formation using fluorescence spectroscopy and molecular modeling. Our results show that zinc(II ion forms a two-fold higher stable complex with OTA than magnesium(II ion. In addition, based on the enhanced fluorescence emission of OTA in its magnesium-bound form, a novel RP-HPLC-fluorescence detector (FLD method was also established. Our results highlight that the application of magnesium chloride in alkaline eluents results in an approximately two-fold increase in sensitivity using the HPLC-FLD technique.

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

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

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

NARCIS (Netherlands)

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

2006-01-01

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

Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

Science.gov (United States)

Elicharova, Hana; Sychrova, Hana

2014-08-01

Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

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

EFFECT OF CONTINUOUS CRYSTALLIZER PERFORMANCE ON STRUVITE CRYSTALS PRODUCED IN REACTION CRYSTALLIZATION FROM SOLUTIONS CONTAINING PHOSPHATE(V AND ZINC(II IONS

Directory of Open Access Journals (Sweden)

N. Hutnik

Full Text Available Abstract Continuous reaction crystallization of struvite from aqueous solutions containing phosphate(V (1.0 mass % and zinc(II ions (from 0.1 to 2.0 mg kg-1 in a continuous DT MSMPR crystallizer was investigated. The influence of pH (9 - 11 and mean residence time (900 - 3600 s on the product characteristics and its chemical composition was tested. Struvite crystals of mean size 22-41 µm were produced. An increase in Zn2+ concentration decreased the mean crystal size and homogeneity. An elevation of the pH also decreased the struvite crystal size. Augmenting the mean residence time influenced product quality advantageously. Coexistence of struvite and Zn(OH2 in the product was confirmed analytically.

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

Preparation, infrared, raman and nmr spectra of N,N'-diethylthiourea complexes with zinc(II), cadmium(II) and mercury(II) halides

Energy Technology Data Exchange (ETDEWEB)

Marcotrigiano, G [Bari Univ. (Italy). Cattedra di Chimica, Facolta di Medicina-Veterinaria

1976-05-01

Several complexes of N,N'-diethylthiourea (Dietu) with zinc(II), cadmium(II) and mercury(II) halides were prepared and characterized by i.r. (4000-60 cm/sup -1/), raman (400-60 cm/sup -1/), in the solid state and n.m.r. and conductometric methods in solution. The complexes Zn(Dietu)/sub 2/X/sub 2/, Cd(Dietu)/sub 2/X/sub 2/ (X=Cl, Br, I) and Hg(Dietu)/sub 2/X/sub 2/ (X=Br, I) are tetrahedral species in which intramolecular -NH...X interactions have been observed. The 1:1 mercury(II) complexes, Hg(Dietu)X/sub 2/ (X=Cl, Br), appear to have a dimeric tetrahedral halide-bridged structure in the solid state. In all these complexes N,N'-diethylthiourea is sulphur-bonded to the metal.

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 

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.

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.

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

Synthesis, crystal structures and luminescent properties of zinc(II) metal–organic frameworks constructed from terpyridyl derivative ligand

International Nuclear Information System (INIS)

Yang, Xiao-Le; Shangguan, Yi-Qing; Hu, Huai-Ming; Xu, Bing; Wang, Bao-Cheng; Xie, Juan; Yuan, Fei; Yang, Meng-Lin; Dong, Fa-Xin; Xue, Gang-Lin

2014-01-01

Five zinc(II) metal–organic frameworks, [Zn 3 (344-pytpy) 2 Cl 6 ] n ·n(H 2 O) (1), [Zn(344-pytpy)(ox)] n (2), [Zn 2 (344-pytpy)(bdc) 2 ] n ·1.5n(H 2 O) (3), [Zn 2 (344-pytpy) 2 (sfdb) 2 ] n ·1.5n(H 2 O) (4) and [Zn 3 (344-pytpy) 2 (btc) 2 ] n ·2n(H 2 O) (5), (344-pytpy=4′-(3-pyridyl)-4,2′:6′,4″-terpyridine, H 2 ox=oxalic acid, H 2 bdc=1,4-benzenedi-carboxylic acid, H 2 sfdb=4,4′-sulfonyldibenzoic acid and H 3 btc=1,3,5-benzene-tricarboxylic acid) have been prepared by hydrothermal reactions. Compound 1 is a 1D chain structure, in which 344-pytpy ligand links three Zn II centers through three of terminal N-donors. Compound 2 is a 4-connected 3D framework with the dia topological net and the Schläfli symbol of 6 6 . Compound 3 displays a unusual 3-fold interpenetrating 3D coordination network which exhibits a new intriguing (3,3,4)-connected topological net with the Schläfli symbol of (4.8 2 )(4.8 5 )(8 3 ). Compound 4 features a two-fold interpenetrating 4-connected 2D framework with the sql topological net and the Schläfli symbol of (4 4 .6 2 ). Compound 5 is a new self-interpenetrating (3,3,4,4)-connected topological net with the Schläfli symbol of (6.8 2 ) 2 (6 2 .8 2 .10.12)(6 2 .8 3 .10) 2 (6 2 .8) 2 . The luminescence properties of 1–5 have been investigated by emission spectra and they possess great thermal stabilities which can be stable up to around 400 °C. - Graphical abstract: Five new Zn(II) metal–organic frameworks based on dicarboxylate and terpyridyl derivative ligands have been synthesized by hydrothermal reactions, giving networks from 1D to 3D structures. The thermal stability and luminescent property have been investigated. - Highlights: • Five zinc(II) metal–organic frameworks have been prepared under hydrothermal conditions. • Their crystal and topological structures have been investigated. • The luminescent properties have been investigated. • They possess great thermal stabilities which can be stable up to

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).

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.

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

Liquid-solid extraction of cationic metals by cationic amphiphiles

International Nuclear Information System (INIS)

Muller, W.

2010-01-01

In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

Liquid-solid extraction of metallic cations by cationic amphiphiles

International Nuclear Information System (INIS)

Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

2012-01-01

In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

Synthesis and crystal structure of a polymeric zinc(II complex derived from 4-nitro- phenylacetic acid and propane-1,3-diamine

Directory of Open Access Journals (Sweden)

G-H. Sheng

2014-05-01

Full Text Available A new polymeric zinc(II complex, [ZnL2(PDA]n, has been prepared by the reaction of zinc sulfate, 4-nitrophenylacetic acid, and propane-1,3-diamine (PDA in water. Structure of the complex has been characterized by single-crystal X-ray diffraction. The complex crystallizes as orthorhombic space group Pnma, with unit cell dimensions a = 15.732(1 Å, b = 23.912(1 Å, c = 5.5565(3 Å, V = 2090.2(2 Å3, Z = 4, R1 = 0.0427, wR2 = 0.0968, S = 1.048. The Zn atom is coordinated in a tetrahedral geometry. Single crystals of the complex are stabilized by hydrogen bonds and p···p interactions. DOI: http://dx.doi.org/10.4314/bcse.v28i2.17

NMR investigation of dynamic processes in complexes of nickel(II) and zinc(II) with iminodiacetate, n-methyliminodiacetate and n-ethyliminodiacetate

International Nuclear Information System (INIS)

Wagner, M.R.

1985-11-01

Analysis of oxygen-17 bulk water relaxation rates with an aqueous solution of 1:1 Ni(II):ida reveals that two rate-limiting processes are involved with solvent exchange. Analysis of carbon-13 longitudinal relaxation rates of the bis-ligand complexes with zinc(II) are used to determine molecular tumbling rates and methyl rotation rates. The carbon-13 transverse relaxation rates for the carbons in the bis-ligand complex with Ni(II) are adequately fitted to the Solomon-Bloembergen equation. Three carboxylate carbon peaks are seen with the 13 C spectrum of the 1:2 Ni(II):ida complex, which coalesce into a single peak above about 360 K. The mechanism and rate of ligand exchange are determined for the complexes Zn(II)L 2 -2 (L = mida, eida) in aqueous solution by total lineshape analysis of the proton spectrum at 500 MHz

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

Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

Energy Technology Data Exchange (ETDEWEB)

Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

2010-07-01

Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

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...

Structure relationship of cationic lipids on gene transfection mediated by cationic liposomes.

Science.gov (United States)

Paecharoenchai, Orapan; Niyomtham, Nattisa; Apirakaramwong, Auayporn; Ngawhirunpat, Tanasait; Rojanarata, Theerasak; Yingyongnarongkul, Boon-ek; Opanasopit, Praneet

2012-12-01

The aim of this study was to investigate the transfection efficiency of cationic liposomes formulated with phosphatidylcholine (PC) and novel synthesized diethanolamine-based cationic lipids at a molar ratio of 5:1 in comparison with Lipofectamine™ 2000. Factors affecting transfection efficiency and cell viability, including the chemical structure of the cationic lipids, such as different amine head group (diamine and polyamine; and non-spermine and spermine) and acyl chain lengths (C14, C16, and C18) and the weight ratio of liposomes to DNA were evaluated on a human cervical carcinoma cell line (HeLa cells) using the pDNA encoding green fluorescent protein (pEGFP-C2). Characterizations of these lipoplexes in terms of size and charge measurement and agarose gel electrophoresis were performed. The results from this study revealed that almost no transfection was observed in the liposome formulations composed of cationic lipids with a non-spermine head group. In addition, the transfection efficiency of these cationic liposomes was in the following order: spermine-C14 > spermine-C16 > spermine-C18. The highest transfection efficiency was observed in the formulation of spermine-C14 liposomes at a weight ratio of 25; furthermore, this formulation was safe for use in vitro. In conclusion, cationic liposomes containing spermine head groups demonstrated promising potential as gene carriers.

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.

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.

Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

Science.gov (United States)

Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J A; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

2013-01-01

It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+), Ca(2+) or Na(+), respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>2 h) than deprotonation of functional groups (cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

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

The Free Tricoordinated Silyl Cation Problem

Directory of Open Access Journals (Sweden)

Čičak, H.

2010-03-01

Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

Science.gov (United States)

Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

2017-06-06

With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for

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

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.

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

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

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.

Cation depletion by the sodium pump in red cells with pathologic cation leaks. Sickle cells and xerocytes.

Science.gov (United States)

Joiner, C H; Platt, O S; Lux, S E

1986-12-01

The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blocked by ouabain, removal of external potassium, or pretreatment with 4,4'-diisothiocyanostilbene-2,2'-disulfonate, which blocks the increase in cation permeability induced by deoxygenation. The loss of cation exhibited by oxygenated xerocytes similarly incubated was also blocked by ouabain. These data support the hypothesis that the elevated "passive" cation fluxes of xerocytes and deoxygenated sickle cells are not directly responsible for cation depletion of these cells; rather, these pathologic leaks interact with the sodium pump to produce a net loss of cellular cation.

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.

Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

Directory of Open Access Journals (Sweden)

Yamuna Kunhi Mouvenchery

Full Text Available It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM molecules via cation bridges (CaB. The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+, Ca(2+ or Na(+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h than deprotonation of functional groups (<2 h and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB and molecular mobility of water (NMR analysis suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is

A separation method to overcome the interference of aluminium on zinc determination by inductively coupled plasma atomic emission spectroscopy

OpenAIRE

Jesus, Djane S. de; Korn, Maria das Graças Andrade; Ferreira, Sergio Luis Costa; Carvalho, Marcelo Souza de

2000-01-01

Texto completo: acesso restrito. p.389–394 The use of polyurethane foam (PUF) to separate zinc from large amounts of aluminium and its determination by inductively coupled plasma atomic emission spectroscopy technique (ICP-AES) in aluminium matrices is described. The proposed method is based on the solid-phase extraction of the zinc(II) cation as a thiocyanate complex. Parameters such as effect of pH on zinc sorption, zinc desorption from the foam and analytical features of the procedure w...

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

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....

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.

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.

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

Cation disorder in Ga1212.

Science.gov (United States)

Greenwood, K B; Ko, D; Vander Griend, D A; Sarjeant, G M; Milgram, J W; Garrity, E S; DeLoach, D I; Poeppelmeier, K R; Salvador, P A; Mason, T O

2000-07-24

Substitution of calcium for strontium in LnSr2-xCaxCu2GaO7 (Ln = La, Pr, Nd, Gd, Ho, Er, Tm, and Yb) materials at ambient pressure and 975 degrees C results in complete substitution of calcium for strontium in the lanthanum and praseodymium systems and partial substitution in the other lanthanide systems. The calcium saturation level depends on the size of the Ln cation, and in all cases, a decrease in the lattice parameters with calcium concentration was observed until a common, lower bound, average A-cation size is reached. Site occupancies from X-ray and neutron diffraction experiments for LnSr2-xCaxCu2GaO7 (x = 0 and x = 2) confirm that the A-cations distribute between the two blocking-layer sites and the active-layer site based on size. A quantitative link between cation distribution and relative site-specific cation enthalpy for calcium, strontium, and lanthanum within the gallate structure is derived. The cation distribution in other similar materials can potentially be modeled.

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

Cationic niosomes an effective gene carrier composed of novel spermine-derivative cationic lipids: effect of central core structures.

Science.gov (United States)

Opanasopit, Praneet; Leksantikul, Lalita; Niyomtham, Nattisa; Rojanarata, Theerasak; Ngawhirunpat, Tanasait; Yingyongnarongkul, Boon-Ek

2017-05-01

Cationic niosomes formulated from Span 20, cholesterol (Chol) and novel spermine-based cationic lipids of multiple central core structures (di(oxyethyl)amino, di(oxyethyl)amino carboxy, 3-amino-1,2-dioxypropyl and 2-amino-1,3-dioxypropyl) were successfully prepared for improving transfection efficiency in vitro. The niosomes composed of spermine cationic lipid with central core structure of di(oxyethyl)amino revealed the highest gene transfection efficiency. To investigate the factors affecting gene transfection and cell viability including differences in the central core structures of cationic lipids, the composition of vesicles, molar ratio of cationic lipids in formulations and the weight ratio of niosomes to DNA. Cationic niosomes composed of nonionic surfactants (Span20), cholesterol and spermine-based cationic lipids of multiple central core structures were formulated. Gene transfection and cell viability were evaluated on a human cervical carcinoma cell line (HeLa cells) using pDNA encoding green fluorescent protein (pEGFP-C2). The morphology, size and charge were also characterized. High transfection efficiency was obtained from cationic niosomes composed of Span20:Chol:cationic lipid at the molar ratio of 2.5:2.5:0.5 mM. Cationic lipids with di(oxyethyl)amino as a central core structure exhibited highest transfection efficiency. In addition, there was also no serum effect on transfection efficiency. These novel cationic niosomes may constitute a good alternative carrier for gene transfection.

Novel hybrid materials based on the vanadium oxide nanobelts

Energy Technology Data Exchange (ETDEWEB)

Zabrodina, G.S., E-mail: kudgs@mail.ru [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Makarov, S.G.; Kremlev, K.V. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Yunin, P.A.; Gusev, S.A. [Institute for Physics of Microstructures Russian Academy of Sciences, Nizhny Novgorod 603087 (Russian Federation); Kaverin, B.S.; Kaverina, L.B. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Ketkov, S.Yu. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation)

2016-04-15

Graphical abstract: - Highlights: • Flat and curved vanadium oxide nanobelts have been synthesized. • Hybrid material was prepared via decoration of flexible nanobelts with zinc phthalocyanine. • Investigations of the thermal stability, morphologies and structures were carried out. - Abstract: Novel hybrid materials based on zinc phthalocyanine and nanostructured vanadium oxides have attracted extensive attention for the development of academic research and innovative industrial applications such as flexible electronics, optical sensors and heterogeneous catalysts. Vanadium oxides nanobelts were synthesized via a hydrothermal treatment V{sub 2}O{sub 5}·nH{sub 2}O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB – cetyltrimethylammonium bromide, TBAB – tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA){sub 0.33}V{sub 2}O{sub 5} flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA){sub 0.33}V{sub 2}O{sub 5}, (TBA){sub 0.16}V{sub 2}O{sub 5} nanobelts and zinc phthalocyanine exchange product were carried out. The hybrid materials based on the nanostructured vanadium oxide and zinc phthalocyanine were tested as photocatalysts for oxidation of citronellol and 2-mercaptoethanol by dioxygen.

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.

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.

Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

International Nuclear Information System (INIS)

Barnabas, M.V.; Trifunac, A.D.

1994-01-01

Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

Synthesis and characterization of 5,7-dimethyl-8-hydroxyquinoline and 2-(2-pyridyl)benzimidazole complexes of zinc(II) for optoelectronic application

Science.gov (United States)

Singh, Kapoor; Kumar, Amit; Srivastava, Ritu; Kadyan, Partap S.; Kamalasanan, Modeeparampil N.; Singh, Ishwar

2011-11-01

Bis(5,7-dimethyl-8-hydroxyquinolinato)zinc(II) (Me 2q) 2Zn and 5,7-dimethyl-8-hydroxyquinolinato(2-(2-pyridyl)benzimidazole) zinc(II) Me 2q(pbi)Zn have been synthesized and characterized by various techniques. These metal complexes have high thermal stability (>300 °C) and high glass transition temperatures (>150 °C). The vacuum deposited films of these materials show good film forming property and are suitable for opto-electronic applications. Multilayered organic electroluminescent (EL) devices have been fabricated having structure ITO/α-NPD/zinc complex/BCP/Alq 3/LiF/Al, which produce emission with chromaticity having Commission Internationale d'Eclairage (CIE) coordinates x = 0.506 and y = 0.484 for (Me 2q) 2Zn; x = 0.47 and y = 0.52 for (Me 2q)(pbi)Zn complex. The electroluminescence spectra show peak emission centered at 572 and 561 nm respectively for these materials.

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

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 .

Converting Hg-1212 to Tl-2212 via Tl-Hg cation exchange in combination with Tl cation intercalation

International Nuclear Information System (INIS)

Zhao Hua; Wu, Judy Z

2007-01-01

In a cation exchange process developed recently for epitaxy of HgBa 2 CaCu 2 O 6 (Hg-1212) thin films, TlBa 2 CaCu 2 O 7 (Tl-1212) or Tl 2 Ba 2 CaCu 2 O 9 (Tl-2212) precursor films were employed as the precursor matrices and Hg-1212 was obtained by replacing Tl cations on the precursor lattice with Hg cations. The reversibility of the cation exchange dictates directly the underlying mechanism. Following our recent success in demonstrating a complete reversibility within '1212' structure, we show the conversion from Hg-1212 to Tl-2212 can be achieved via two steps: conversion from Hg-1212 to Tl-1212 followed by Tl intercalation to form double Tl-O plans in each unit cell. The demonstrated reversibility of the cation exchange process has confirmed the process is a thermal perturbation of weakly bonded cations on the lattice and the direction of the process is determined by the population ratio between the replacing cations and that to be replaced

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.

New double-cation borohydrides

Energy Technology Data Exchange (ETDEWEB)

Lindemann, Inge; Domenech Ferrer, Roger; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, Institute for Metallic Materials, P.O. Box 270016, 01171 Dresden (Germany); Filinchuk, Yaroslav [Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble (France); Hagemann, Hans; Cerny, Radovan [Department of Physical Chemistry and Crystallography, University of Geneva, 1211 Geneva (Switzerland)

2011-07-01

Complex hydrides are under consideration for on-board hydrogen storage due to their high hydrogen density. However, up to now conventional borohydrides are either too stable or unstable for applications as in PEM fuel cells (60-120 C). Recently, double-cation borohydride systems have attracted great interest. The desorption temperature of the borohydrides decreases with increasing electronegativity of the cation. Consequently, it is possible to tailor a feasible on-board hydrogen storage material by the combination of appropriate cations. The stability was found to be intermediate between the single-cation borohydride systems. Two combinations were sucessfully synthesised by metathesis reaction via high energy ball milling. Al-Li-borohydride shows desorption at about 70 C combined with a very high hydrogen density (17.2 wt.%) and the Na-Al-borohydride (14.2 wt.%) decomposes around 90 C. Both desorption temperatures are in the target range for applications. The decomposition pathways were observed by in-situ-Raman spectroscopy, DSC (Differential Scanning Calorimetry), TG (Thermogravimetry) and thermal desorption measurements.

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.

High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography.

Science.gov (United States)

Rey, M A

2001-06-22

One of the advantages of ion chromatography [Anal Chem. 47 (1975) 1801] as compared to other analytical techniques is that several ions may be analyzed simultaneously. One of the most important contributions of cation-exchange chromatography is its sensitivity to ammonium ion, which is difficult to analyze by other techniques [J. Weiss, in: E.L. Johnson (Ed.), Handbook of Ion Chromatography, Dionex, Sunnyvale, CA, USA]. The determination of low concentrations of ammonium ion in the presence of high concentrations of sodium poses a challenge in cation-exchange chromatography [J. Weiss, Ion Chromatography, VCH, 2nd Edition, Weinheim, 1995], as both cations have similar selectivities for the common stationary phases containing either sulfonate or carboxylate functional groups. The task was to develop a new cation-exchange stationary phase (for diverse concentration ratios of adjacent peaks) to overcome limitations experienced in previous trails. Various cation-exchange capacities and column body formats were investigated to optimize this application and others. The advantages and disadvantages of two carboxylic acid columns of different cation-exchange capacities and different column formats will be discussed.

Cation-π interactions in structural biology

OpenAIRE

Gallivan, Justin P.; Dougherty, Dennis A.

1999-01-01

Cation-pi interactions in protein structures are identified and evaluated by using an energy-based criterion for selecting significant sidechain pairs. Cation-pi interactions are found to be common among structures in the Protein Data Bank, and it is clearly demonstrated that, when a cationic sidechain (Lys or Arg) is near an aromatic sidechain (Phe, Tyr, or Trp), the geometry is biased toward one that would experience a favorable cation-pi interaction. The sidechain of Arg is more likely tha...

Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

Science.gov (United States)

Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

2013-09-05

This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

Science.gov (United States)

Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

2016-06-01

We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.

[Noncovalent cation-π interactions--their role in nature].

Science.gov (United States)

Fink, Krzysztof; Boratyński, Janusz

2014-11-07

Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions--cation-π interactions--is gaining increasing attention. These interactions occur between a cation and a π system. The main contributors to cation-π interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-π interactions were studied in a gas phase, with metal cation-aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-π interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-π interactions occur in environments with lower accessibility to a polar solvent. Cation-π interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-π interactions are abundant and play an important role in many biological processes.

Stressor states and the cation crossroads.

Science.gov (United States)

Weber, Karl T; Bhattacharya, Syamal K; Newman, Kevin P; Soberman, Judith E; Ramanathan, Kodangudi B; McGee, Jesse E; Malik, Kafait U; Hickerson, William L

2010-12-01

Neurohormonal activation involving the hypothalamic-pituitary-adrenal axis and adrenergic nervous and renin-angiotensin-aldosterone systems is integral to stressor state-mediated homeostatic responses. The levels of effector hormones, depending upon the degree of stress, orchestrate the concordant appearance of hypokalemia, ionized hypocalcemia and hypomagnesemia, hypozincemia, and hyposelenemia. Seemingly contradictory to homeostatic responses wherein the constancy of extracellular fluid would be preserved, upregulation of cognate-binding proteins promotes coordinated translocation of cations to injured tissues, where they participate in wound healing. Associated catecholamine-mediated intracellular cation shifts regulate the equilibrium between pro-oxidants and antioxidant defenses, a critical determinant of cell survival. These acute and chronic stressor-induced iterations in extracellular and intracellular cations are collectively referred to as the cation crossroads. Intracellular cation shifts, particularly excessive accumulation of Ca2+, converge on mitochondria to induce oxidative stress and raise the opening potential of their inner membrane permeability transition pores (mPTPs). The ensuing loss of cationic homeostasis and adenosine triphosphate (ATP) production, together with osmotic swelling, leads to organellar degeneration and cellular necrosis. The overall impact of iterations in extracellular and intracellular cations and their influence on cardiac redox state, cardiomyocyte survival, and myocardial structure and function are addressed herein.

Cationic electrodepositable coating composition comprising lignin

Science.gov (United States)

Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

2013-07-30

A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

A theoretical study of complexes formed between cations and curved aromatic systems: electrostatics does not always control cation-π interaction.

Science.gov (United States)

Carrazana-García, Jorge A; Cabaleiro-Lago, Enrique M; Rodríguez-Otero, Jesús

2017-04-19

The present work studies the interaction of two extended curved π-systems (corannulene and sumanene) with various cations (sodium, potassium, ammonium, tetramethylammonium, guanidinium and imidazolium). Polyatomic cations are models of groups found in important biomolecules in which cation-π interaction plays a fundamental role. The results indicate an important size effect: with extended π systems and cations of the size of potassium and larger, dispersion is much more important than has been generally recognized for cation-π interactions. In most of the systems studied here, the stability of the cation-π complexes is the result of a balanced combination of electrostatic, induction and dispersion contributions. None of the systems studied here owes its stability to the electrostatic interaction more than 42%. Induction dominates stabilization in complexes with sodium, and in some of the potassium and ammonium complexes. In complexes with large cations and with flat cations dispersion is the major stabilizing contribution and can provide more than 50% of the stabilization energy. This implies that theoretical studies of the cation-π interaction involving large or even medium-size fragments require a level of calculation capable of properly modelling dispersion. The separation between the cation and the π system is another important factor to take into account, especially when the fragments of the cation-π complex are bound (for example, to a protein backbone) and cannot interact at the most favourable distance.

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

Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities.

Science.gov (United States)

Rijnaarts, Timon; Huerta, Elisa; van Baak, Willem; Nijmeijer, Kitty

2017-11-07

Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg 2+ and Ca 2+ ) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

Formation of radical cations of diaryloxadiazoles

International Nuclear Information System (INIS)

Helmstreit, W.

1988-01-01

The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

Removal of heavy metals from aqueous solution by Carrot residues

International Nuclear Information System (INIS)

Eslamzadeh, T.; Nasernejad, B.; Bonakdar Pour, B.; Zamani, A.; Esmaail-Beygi, M.

2004-01-01

The removal of Copper(II), Zinc(II), and Chromium (III) from wastewater by carrot residues was investigated to evaluate cation exchange capacity. The effects of solution P H and co-ions were studied in batch experiments. Adsorption equilibria were initially rapidly established, and then decreased markedly after 10 min. Column experiments were carried out in a glass column filled with carrot residues to evaluate the metal removal capacity. The influences of the feed concentration and feed rate were also studied in order to compare the dynamic capacity for metal binding in different feed concentrations

Cationic polymers and porous materials

KAUST Repository

Han, Yu

2017-04-27

According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

Cationic polymers and porous materials

KAUST Repository

Han, Yu; Tian, Qiwei; Dong, Xinglong; Liu, Zhaohui; Basset, Jean-Marie; Saih, Youssef; Sun, Miao; Xu, Wei; Shaikh, Sohel

2017-01-01

According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

aDepartment of Chemist.r__v_. University of Nairobi

African Journals Online (AJOL)

lead (Tl) phthalocyanine. where the ligand is reduced fast followed by a slow dernetalation process (13). Nor i.s it similar to the ciemetalation rnechanisrn of silver and thallium porphyriris, where the central cation is reduced and then expelled owing to the large increase in its size, which the ligand cannot accomodate (141.

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.

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.

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.

Cation-π interaction of the univalent sodium cation with [2.2.2]paracyclophane: Experimental and theoretical study

Science.gov (United States)

Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Vaňura, Petr

2018-02-01

By employing electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent sodium cation (Na+) forms with [2.2.2]paracyclophane (C24H24) the cationic complex [Na(C24H24)]+. Further, applying quantum chemical DFT calculations, the most probable structure of the [Na(C24H24)]+ complex was derived. In the resulting complex with a symmetry very close to C3, the "central" cation Na+, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Na(C24H24)]+ was found to be -267.3 kJ/mol, confirming the formation of this fascinating complex species as well.

Zinc(II) and mercury(II) complexes [Zn((2,6-Cl-ba).sub.2./sub.en)I.sub.2./sub.] and [Hg((2,6-Cl-ba).sub.2./sub.en)Br.sub.2./sub.] with the bidentate Schiff base ligand (2,6-Cl-ba).sub.2./sub.en: synthesis, characterization and crystal structures

Czech Academy of Sciences Publication Activity Database

Khalaji, A.D.; Grivani, G.; Seyyedi, M.; Fejfarová, Karla; Dušek, Michal

2013-01-01

Roč. 49, č. 1 (2013), 19-23 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : zinc(II) * mercury(II) * Schiff base * single-crystal Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.047, year: 2013

Cations form sequence selective motifs within DNA grooves via a combination of cation-pi and ion-dipole/hydrogen bond interactions.

Science.gov (United States)

Stewart, Mikaela; Dunlap, Tori; Dourlain, Elizabeth; Grant, Bryce; McFail-Isom, Lori

2013-01-01

The fine conformational subtleties of DNA structure modulate many fundamental cellular processes including gene activation/repression, cellular division, and DNA repair. Most of these cellular processes rely on the conformational heterogeneity of specific DNA sequences. Factors including those structural characteristics inherent in the particular base sequence as well as those induced through interaction with solvent components combine to produce fine DNA structural variation including helical flexibility and conformation. Cation-pi interactions between solvent cations or their first hydration shell waters and the faces of DNA bases form sequence selectively and contribute to DNA structural heterogeneity. In this paper, we detect and characterize the binding patterns found in cation-pi interactions between solvent cations and DNA bases in a set of high resolution x-ray crystal structures. Specifically, we found that monovalent cations (Tl⁺) and the polarized first hydration shell waters of divalent cations (Mg²⁺, Ca²⁺) form cation-pi interactions with DNA bases stabilizing unstacked conformations. When these cation-pi interactions are combined with electrostatic interactions a pattern of specific binding motifs is formed within the grooves.

Isomerization of propargyl cation to cyclopropenyl cation ...

Indian Academy of Sciences (India)

step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

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.

Adsorption and photocatalytic properties of transition metal Zinc(II) complex based on 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid

Science.gov (United States)

Qiao, Yu; Ren, Shan-Shan; Liu, Li-Hui; Guan, Wei-Sheng; Li, Zhi-Min; Che, Guang-Bo; Liu, Chun-Bo; Wang, Yan-Yan; Wang, Qing-Wei; Li, Xiu-Ying; Zhu, En-Wei

2018-06-01

A new coordination polymeric zinc(II) complex, namely, [Zn2(L)(H2O)3]n·nNO3(1), (H3L = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid) has been synthesized under solvothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction analysis and powder X-ray diffraction. Complex 1 exhibits a three-dimensional structure with a Schläfli symbol of 44•69•82 topologies, constructed from two crystallographically independent five and six coordinated mode with metal center and connected H3L ligands. The complex has good thermal stability and excellent photoluminescent property. Furthermore, by comparing the photoluminescent and photocatalytic mutation results induced by interconversion of metal ions, we confirm that the properties mutation induced by metal ions is much controllable and obvious. In addition, the complex exhibits significantly enhanced photocatalytic activity for methylene blue (MB) under UV light irradiation (λ < 400 nm), and the degradation rate could reach 75% in 80 min. Meanwhile trapping experiments indicated that the •O2- and h+ are the main activated species.

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

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.

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.

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.

Luminescent sulfides of monovalent and trivalent cations

International Nuclear Information System (INIS)

1975-01-01

The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

ADSORPTION METHOD FOR SEPARATING METAL CATIONS

Science.gov (United States)

Khym, J.X.

1959-03-10

The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

Radiochemical study of isomerization of free butyl cations

International Nuclear Information System (INIS)

Sinotova, E.N.; Nefedov, V.D.; Skorokhodov, S.S.; Arkhipov, Yu.M.

1987-01-01

Ion-molecular reactions of free butyl cations, generated by nuclear chemical method, with carbon monoxide containing small quantities of ethanol vapors are studied. Carbon monoxide was used to fix instable butyl cations in the form of corresponding acyl ions. Ester of α-methyl-butyric acid appears to be the only product of free butyl cation interaction with carbon monoxide in the presence of ethanol vapors. That means, that up to the moment of butyl cation reaction with carbon monoxide, the primary butyl cations are almost completely isomerized into secondary in agreement with results of previous investigations. This allows one to study free butyl cation isomerization process according to ion-molecular reaction product isomeric composition

Gas phase chemistry of N-benzylbenzamides with silver(I) cations: characterization of benzylsilver cation.

Science.gov (United States)

Sun, Hezhi; Jin, Zhe; Quan, Hong; Sun, Cuirong; Pan, Yuanjiang

2015-03-07

The benzylsilver cation which emerges from the collisional dissociation of silver(I)-N-benzylbenzamide complexes was characterized by deuterium-labeling experiments, theoretical calculations, breakdown curves and substituent effects. The nucleophilic attack of the carbonyl oxygen on an α-hydrogen results in the generation of the benzylsilver cation, which is competitive to the AgH loss with the α-hydrogen.

Synthesis and characterization of monomeric and dimeric manganese(II and zinc(II complexes of pyridine-2-carbaldoxime

Directory of Open Access Journals (Sweden)

Jørgen Glerup

2000-12-01

Full Text Available The syntheses and characterization of two complexes of manganese(II and one complex of zinc(II with the ligand pyridine-2-carbaldoxime, C6H6N2O, are described. The monomeric manganese(II complex cis-[Mn(C6H6N2O 2Cl2] (1 crystallizes in the orthorhombic space group Pbcn with 4 formula units in a cell of dimensions a = 12.479(3 Å, b = 10.348(2 Å, and c = 11. 974(2 Å. The structure has been refined to a final value of the conventional R-factor of 0.0330 based on 1513 observed independent reflections. The analogous zinc(II complex, cis-[Zn(C6H6N2O2Cl2] (2 also crystallizes in the orthorhombic space group Pbcn with 4 formula units in a cell of dimensions a = 12.215(2 Å, b = 10.383(2 Å, and c = 12. 016(2 Å. The structure has been refined to a final value of the conventional R-factor of 0.0377 based on 1117 observed independent reflections. The two complexes are isostructural, with the central metal atom lying on a crystallographic 2-fold axis. Both complexes are approximately octahedral, the coordination being provided by two trans pyridine nitrogen atoms and two cis amine nitrogen atoms from the oxime ligands, and by two cis chlorides. The dimeric manganese(II complex [(C6H6N2O(CH3OHClMnCl2MnCl(CH3OH(C6H6N2O] (3 crystallizes in the monoclinic space group P21/n with 2 formula units in a cell of dimensions a = 7.895(2 Å, b = 11.196(3 Å, and c = 12. 544(2 Å, and b = 98.39(2o. The structure has been refined to a final value of the conventional R-factor of 0.0312 based on 1568 observed independent reflections. There is a crystallographic inversion center in the middle of the dimer relating one manganese center to the other. The geometry at each manganese(II center is again roughly octahedral, coordination being provided by two nitrogen atoms from the oxime ligand, a terminal chloride ion trans to the amine nitrogen, the oxygen atom of the coordinated methanol molecule, and two bridging chlorides that link the two halves of the dimer. The Mn

Cationic uremic toxins affect human renal proximal tubule cell functioning through interaction with the organic cation transporter.

Science.gov (United States)

Schophuizen, Carolien M S; Wilmer, Martijn J; Jansen, Jitske; Gustavsson, Lena; Hilgendorf, Constanze; Hoenderop, Joost G J; van den Heuvel, Lambert P; Masereeuw, Rosalinde

2013-12-01

Several organic cations, such as guanidino compounds and polyamines, have been found to accumulate in plasma of patients with kidney failure due to inadequate renal clearance. Here, we studied the interaction of cationic uremic toxins with renal organic cation transport in a conditionally immortalized human proximal tubule epithelial cell line (ciPTEC). Transporter activity was measured and validated in cell suspensions by studying uptake of the fluorescent substrate 4-(4-(dimethylamino)styryl)-N-methylpyridinium-iodide (ASP(+)). Subsequently, the inhibitory potencies of the cationic uremic toxins, cadaverine, putrescine, spermine and spermidine (polyamines), acrolein (polyamine breakdown product), guanidine, and methylguanidine (guanidino compounds) were determined. Concentration-dependent inhibition of ASP(+) uptake by TPA, cimetidine, quinidine, and metformin confirmed functional endogenous organic cation transporter 2 (OCT2) expression in ciPTEC. All uremic toxins tested inhibited ASP(+) uptake, of which acrolein required the lowest concentration to provoke a half-maximal inhibition (IC50 = 44 ± 2 μM). A Dixon plot was constructed for acrolein using three independent inhibition curves with 10, 20, or 30 μM ASP(+), which demonstrated competitive or mixed type of interaction (K i = 93 ± 16 μM). Exposing the cells to a mixture of cationic uremic toxins resulted in a more potent and biphasic inhibitory response curve, indicating complex interactions between the toxins and ASP(+) uptake. In conclusion, ciPTEC proves a suitable model to study cationic xenobiotic interactions. Inhibition of cellular uptake transport was demonstrated for several uremic toxins, which might indicate a possible role in kidney disease progression during uremia.

Electronic spectra of astrophysically interesting cations

Energy Technology Data Exchange (ETDEWEB)

Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch; Johnson, Anatoly, E-mail: j.p.maier@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstr. 80, CH-4056 Basel (Switzerland)

2015-01-22

The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.

How the cation-cation π-π stacking occurs: A theoretical investigation into ionic clusters of imidazolium.

Science.gov (United States)

Gao, Wei; Tian, Yong; Xuan, Xiaopeng

2015-07-01

The cation-cation π-π stacking is uncommon but it is essential for the understanding of some supramolecular structures. We explore theoretically the nature of non-covalent interaction occurring in the stacked structure within modeled clusters of 1,3-dimethylimidazolium and halide. The evidences of the energy decomposition analysis (EDA) and reduced density gradient (RDG) approach are different from those of common π-π interaction. Isosurfaces with RDG also illustrate the strength of the titled π-π interaction and their region. Additionally, we find that the occurrence of this interaction is attributed to a few C-H···X interactions, as depicted using atom in molecule (AIM) method. This work presents a clear picture of the typical cation-cation π-π interaction and can serve to advance the understanding of this uncommon interaction. Copyright © 2015 Elsevier Inc. All rights reserved.

Cation depletion by the sodium pump in red cells with pathologic cation leaks. Sickle cells and xerocytes.

OpenAIRE

Joiner, C H; Platt, O S; Lux, S E

1986-01-01

The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blo...

Anchoring cationic amphiphiles for nucleotide delivery: significance of DNA release from cationic liposomes for transfection.

Science.gov (United States)

Hirashima, Naohide; Minatani, Kazuhiro; Hattori, Yoshifumi; Ohwada, Tomohiko; Nakanishi, Mamoru

2007-06-01

We have designed and synthesized lithocholic acid-based cationic amphiphile molecules as components of cationic liposomes for gene transfection (lipofection). To study the relationship between the molecular structures of those amphiphilic molecules, particularly the extended hydrophobic appendant (anchor) at the 3-hydroxyl group, and transfection efficiency, we synthesized several lithocholic and isolithocholic acid derivatives, and examined their transfection efficiency. We also compared the physico-chemical properties of cationic liposomes prepared from these derivatives. We found that isolithocholic acid derivatives exhibit higher transfection efficiency than the corresponding lithocholic acid derivatives. This result indicates that the orientation and extension of hydrophobic regions influence the gene transfection process. Isolithocholic acid derivatives showed a high ability to encapsulate DNA in a compact liposome-DNA complex and to protect it from enzymatic degradation. Isolithocholic acid derivatives also facilitated the release of DNA from the liposome-DNA complex, which is a crucial step for DNA entry into the nucleus. Our results show that the transfection efficiency is directly influenced by the ability of the liposome complex to release DNA, rather than by the DNA-encapsulating ability. Molecular modeling revealed that isolithocholic acid derivatives take relatively extended conformations, while the lithocholic acid derivatives take folded structures. Thus, the efficiency of release of DNA from cationic liposomes in the cytoplasm, which contributes to high transfection efficiency, appears to be dependent upon the molecular shape of the cationic amphiphiles.

Simultaneous anion and cation mobility in polypyrrole

DEFF Research Database (Denmark)

Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

2003-01-01

and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

Identifi cation of Sectarianism

Directory of Open Access Journals (Sweden)

Martinovich Vladimir

2016-03-01

Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

Cation radicals of xanthophylls.

Science.gov (United States)

Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

2007-10-01

Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

Comparative analysis of cation/proton antiporter superfamily in plants.

Science.gov (United States)

Ye, Chu-Yu; Yang, Xiaohan; Xia, Xinli; Yin, Weilun

2013-06-01

The cation/proton antiporter superfamily is associated with the transport of monovalent cations across membranes. This superfamily was annotated in the Arabidopsis genome and some members were functionally characterized. In the present study, a systematic analysis of the cation/proton antiporter genes in diverse plant species was reported. We identified 240 cation/proton antiporters in alga, moss, and angiosperm. A phylogenetic tree was constructed showing these 240 members are separated into three families, i.e., Na(+)/H(+) exchangers, K(+) efflux antiporters, and cation/H(+) exchangers. Our analysis revealed that tandem and/or segmental duplications contribute to the expansion of cation/H(+) exchangers in the examined angiosperm species. Sliding window analysis of the nonsynonymous/synonymous substitution ratios showed some differences in the evolutionary fate of cation/proton antiporter paralogs. Furthermore, we identified over-represented motifs among these 240 proteins and found most motifs are family specific, demonstrating diverse evolution of the cation/proton antiporters among three families. In addition, we investigated the co-expressed genes of the cation/proton antiporters in Arabidopsis thaliana. The results showed some biological processes are enriched in the co-expressed genes, suggesting the cation/proton antiporters may be involved in these biological processes. Taken together, this study furthers our knowledge on cation/proton antiporters in plants. Copyright © 2013 Elsevier B.V. All rights reserved.

Radioimmunoassay of human eosinophil cationic protein

International Nuclear Information System (INIS)

Venge, P.; Roxin, L.E.; Olsson, I.

1977-01-01

A radioimmunosorbent assay has been developed which allows the detection in serum of a cationic protein derived from eosinophil granulocytes. In 34 healthy individuals the mean level was 31 μg/l. with a range of 5 to 55 μg/l. The serum concentration of 'eosinophil' cationic protein was correlated (P<0.001) to the number of eosinophil granulocytes in peripheral blood. Quantitiation of 'eosinophil' cationic protein in serum might be useful in the study of eosinophil granulocyte turnover and function in vivo. (author)

Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations.

Science.gov (United States)

Kutzner, Susann; Schaffer, Mario; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard

2014-05-01

Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Asymmetric Aminalization via Cation-Binding Catalysis

DEFF Research Database (Denmark)

Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

2018-01-01

Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope of the...

Uranium isotope separation using styrene cation exchangers

International Nuclear Information System (INIS)

Kahovec, J.

1980-01-01

The separation of 235 U and 238 U isotopes is carried out either by simple isotope exchange in the system uranium-cation exchanger (sulphonated styrene divinylbenzene resin), or by combination of isotope exchange in a uranium-cation exchanger (Dowex 50, Amberlite IR-120) system and a chemical reaction. A review is presented of elution agents used, the degree of cation exchanger cross-linking, columns length, and 235 U enrichment. The results are described of the isotope effect study in a U(IV)-U(VI)-cation exchanger system conducted by Japanese and Romanian authors (isotope exchange kinetics, frontal analysis, reverse (indirect) frontal analysis). (H.S.)

Heavy metal cations permeate the TRPV6 epithelial cation channel.

Science.gov (United States)

Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A

2011-01-01

TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications. Copyright © 2010 Elsevier Ltd. All rights reserved.

Cationic mobility in polystyrene sulfone exchangers - Application to the elution of a cation on an exchange column

International Nuclear Information System (INIS)

Menin, Jean-Pierre

1969-01-01

The aim of this work is to improve elutions and separations carried out on inorganic exchangers by selective electromigration of the ionic species to be displaced. To do this, it has been found indispensable to make a fundamental study of the mobility of cations in exchangers. As the field for this research we have chosen those organic exchangers whose structure and behaviour with respect to ion-exchange are much better known that in the case of their inorganic equivalents. We have related the idea of the equivalent conductivity to that of the cation mobility in the exchanger, and this has entailed determining the specific conductivity of the exchanger and the cation concentration in the resin. The results obtained have allowed us to draw up a hypothesis concerning the cation migration mechanism in the exchanger. The third part of our work has been the application of the preceding results to an operation on an ion-exchange column, viz. the elution by an acid solution of a single fixed ion, magnesium or strontium. This work has enabled us to show that the electromigration of a cation during its elution can markedly accelerate or retard this elution. (author) [fr

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

Selective alkylation by photogenerated aryl and vinyl cation

NARCIS (Netherlands)

Slegt, Micha

2006-01-01

Seven para-substituted phenyl cations and the parent phenyl cation were prepared from iodonium salt precursors. Product studies revealed remarkable chemoselectivity and regioselectivity that could be related to the spin multiplicity of the cations. Also an universal method to fingerprint singlet and

(4 + 3) Cycloadditions of Nitrogen-Stabilized Oxyallyl Cations

Science.gov (United States)

Lohse, Andrew G.; Hsung, Richard P.

2011-01-01

The use of heteroatom-substituted oxyallyl cations in (4 + 3) cycloadditions has had a tremendous impact on the development of cycloaddition chemistry. Extensive efforts have been exerted toward investigating the effect of oxygen-, sulfur-, and halogen-substituents on the reactivity of oxyallyl cations. Most recently, the use of nitrogen-stabilized oxyallyl cations has gained prominence in the area of (4 + 3) cycloadditions. The following article will provide an overview of this concept utilizing nitrogen-stabilized oxyallyl cations. PMID:21384451

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.

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.

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.

Cationic polymers and their therapeutic potential

NARCIS (Netherlands)

Samal, S.K.; Dash, M.; van Vlierberghe, S.; Kaplan, D.; Chiellini, E.; van Blitterswijk, Clemens; Moroni, Lorenzo; Dubruel, P.

2012-01-01

The last decade has witnessed enormous research focused on cationic polymers. Cationic polymers are the subject of intense research as non-viral gene delivery systems, due to their flexible properties, facile synthesis, robustness and proven gene delivery efficiency. Here, we review the most recent

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)

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.

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...

Thermochemical stability of Soviet macroporous sulfonated cation-exchangers

Energy Technology Data Exchange (ETDEWEB)

Rukhlyada, N.N.; Plotnikova, V.P.; Roginskaya, B.S.; Znamenskii, Yu.P.; Zavodovskaya, A.S.; Dobrova, E.I.

1988-10-20

The purpose of this work was to study the influence of macroporosity on the thermochemical stability of sulfonated cation-exchangers. The investigations were carried out on commercial macroporous sulfonated cation-exchangers based on styrene-divinylbenzene copolymers. Study of the thermochemical stability of macroporous sulfonated cation-exchangers in dilute hydrogen peroxide solutions showed that the type of macroporosity has virtually no influence on their stability. The determining factor in thermal stability of macroporous cation-exchangers, as of the gel type, is the degree of cross-linking of the polymer matrix. The capacity loss of macroporous cation-exchangers during oxidative thermolysis is caused by destruction of the macromolecular skeleton and elution of fragments of polar chains containing sulfo groups into the solution.

Cationic antimicrobial peptides inactivate Shiga toxin-encoding bacteriophages

Science.gov (United States)

Del Cogliano, Manuel E.; Hollmann, Axel; Martinez, Melina; Semorile, Liliana; Ghiringhelli, Pablo D.; Maffía, Paulo C.; Bentancor, Leticia V.

2017-12-01

Shiga toxin (Stx) is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC) infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs) are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: 1) direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, 2) cationic properties are necessary but not sufficient for bacteriophage inactivation, and 3) inactivation by cationic peptides could be sequence (or structure) specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

Cationic Antimicrobial Peptides Inactivate Shiga Toxin-Encoding Bacteriophages

Directory of Open Access Journals (Sweden)

Manuel E. Del Cogliano

2017-12-01

Full Text Available Shiga toxin (Stx is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non-alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: (1 direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, (2 cationic properties are necessary but not sufficient for bacteriophage inactivation, and (3 inactivation by cationic peptides could be sequence (or structure specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

Energy Technology Data Exchange (ETDEWEB)

Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

2011-06-30

Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

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

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.

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.

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.

Accelerators for forming cationic technetium complexes useful as radiodiagnostic images

International Nuclear Information System (INIS)

Tweedle, M.F.

1985-01-01

This invention relates to compositions for making cationic radiodiagnostic agents and, in particular, to accelerator compounds for labelling such cationic radiodiagnostic agents, kits for preparing such 99m Tc-labelled cationic radiodiagnostic agents with technetium, and methods for labelling such cationic radiodiagnostic agents with technetium

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.

Development of a novel device to trap heavy metal cations: application of the specific interaction between heavy metal cation and mismatch DNA base pair.

Science.gov (United States)

Torigoe, Hidetaka; Miyakawa, Yukako; Fukushi, Miyako; Ono, Akira; Kozasa, Tetsuo

2009-01-01

We have already found that Hg(II) cation specifically binds to T:T mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving T:T mismatch base pair by about 4 degrees C. We have also found that Ag(I) cation specifically binds to C:C mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving C:C mismatch base pair by about 4 degrees C. Using the specific interaction, we developed a novel device to trap each of Hg(II) and Ag(I) cation. The device is composed of 5'-biotinylated T-rich or C-rich DNA oligonucleotides, BIO-T20: 5'-Bio-T(20)-3' or BIO-C20: 5'-Bio-C(20)-3' (Bio is a biotin), immobilized on streptavidin-coated polystylene beads. When the BIO-T20-immobilized beads were added to a solution containing Hg(II) cation, and the beads trapping Hg(II) cation were collected by centrifugation, almost all of Hg(II) cation were removed from the solution. Also, when the BIO-C20-immobilized beads were added to a solution containing Ag(I) cation, and the beads trapping Ag(I) cation were collected by centrifugation, almost all of Ag(I) cation were removed from the solution. We conclude that, using the novel device developed in this study, Hg(II) and Ag(I) cation can be effectively removed from the solution.

Tripodal receptors for cation and anion sensors

NARCIS (Netherlands)

Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

2006-01-01

This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

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.

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.)

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.

Cation interdiffusion in polycrystalline calcium and strontium titanate

International Nuclear Information System (INIS)

Butler, E.P.; Jain, H.; Smyth, D.M.

1991-01-01

This paper discusses a method that has been developed to study bulk lattice interdiffusion between calcium and strontium titanate by fabrication of a diffusion couple using cosintering. The measured interdiffusion coefficients, D(C), indicate that strontium impurity diffusion in calcium titanate occurs at a faster rate than calcium impurity diffusion in strontium titanate. These interdiffusion coefficients are composition independent when the concentration of the calcium cation exceeds that of the strontium cation; otherwise D(C) is strongly composition dependent. Investigations into the effect of cation nonstoichiometry give results that are consistent with a defect incorporation reaction in which excess TiO 2 , within the solid solubility limit, produces A-site cation vacancies as compensating defects. The interdiffusion coefficients increase with increasing concentrations of TiO 2 , so it is concluded that interdiffusion of these alkaline-earth cations in their titanates occurs via a vacancy mechanism

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.

Designer Ligands. Part 13. Synthesis and Catalytic Activity of ...

African Journals Online (AJOL)

Copper(I), copper(II), cobalt(II) and zinc(II) complexes of a macrocyclic, multidentate Schiff-base ligand have been prepared and, with the exception of the zinc(II) complex, have been shown to exhibit biomimetic catecholase activity. Keywords: Copper(II);Cobalt(II); Zinc(II); Biomimetic complexes; Catecholase activity

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.

A computational study of anion-modulated cation-π interactions.

Science.gov (United States)

Carrazana-García, Jorge A; Rodríguez-Otero, Jesús; Cabaleiro-Lago, Enrique M

2012-05-24

The interaction of anions with cation-π complexes formed by the guanidinium cation and benzene was thoroughly studied by means of computational methods. Potential energy surface scans were performed in order to evaluate the effect of the anion coming closer to the cation-π pair. Several structures of guanidinium-benzene complexes and anion approaching directions were examined. Supermolecule calculations were performed on ternary complexes formed by guanidinium, benzene, and one anion and the interaction energy was decomposed into its different two- and three-body contributions. The interaction energies were further dissected into their electrostatic, exchange, repulsion, polarization and dispersion contributions by means of local molecular orbital energy decomposition analysis. The results confirm that, besides the electrostatic cation-anion attraction, the effect of the anion over the cation-π interaction is mainly due to polarization and can be rationalized following the changes in the anion-π and the nonadditive (three-body) terms of the interaction. When the cation and the anion are on the same side of the π system, the three-body interaction is anticooperative, but when the anion and the cation are on opposite sides of the π system, the three-body interaction is cooperative. As far as we know, this is the first study where this kind of analysis is carried out with a structured cation as guanidinium with a significant biological interest.

Synthesis of Cationic Core-Shell Latex Particles

NARCIS (Netherlands)

Dziomkina, N.; Hempenius, Mark A.; Vancso, Gyula J.

2006-01-01

Surfactant-free seeded (core-shell) polymerization of cationic polymer colloids is presented. Polystyrene core particles with sizes between 200 nm and 500 nm were synthesized. The number average diameter of the colloidal core particles increased with increasing monomer concentration. Cationic shells

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.

IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

NARCIS (Netherlands)

Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

2013-01-01

The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both

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.

Test procedure for cation exchange chromatography

International Nuclear Information System (INIS)

Cooper, T.D.

1994-01-01

The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction

Increasing Base Cations in Streams: Another Legacy of Deicing Salts?

Science.gov (United States)

Helton, A. M.; Barclay, J. R.; Bellucci, C.; Rittenhouse, C.

2017-12-01

Elevated use of deicing salts directly increases sodium chloride inputs to watersheds. Sodium can accumulate in soils over time and has the potential to leach other cations (e.g., calcium, magnesium, and potassium) from the soil through cation exchange. We hypothesize that increased use of deicing salts results in a legacy of soils depleted in non-sodium base cations with loss of cations to receiving waters. The goal of this project is to quantify temporal trends in base cations and chloride in streams and rivers across the United States. We used Weighted Regressions on Time, Discharge, and Season (WRTDS) to analyze trends in base cations. Our preliminary analysis of 10 rivers in Connecticut with chemical periods of record ranging from 24 - 64 years (median = 55 years), shows that the flux of base cations is increasing in all sites (25 - 366 103 meq ha-1 yr-1 yr-1), driven largely by increases in sodium (23 - 222 103 meq ha-1 yr-1 yr-1), the dominant cation in 7 of the sites. Chloride is also increasing at all sites (26 - 261 103 meq ha-1 yr-1 yr-1), which, in combination with salt use trends, suggests a road salt source for the increased sodium. Non-sodium cations are also increasing in 9 of the sites (8 - 54 103 meq ha-1 yr-1 yr-1), though they are not directly added with most deicing salts. We will compare these trends to other long-term sites across the United States, and quantify relationships between cation trends and land cover, road density, and snowfall.

Selective crystallization of cations with crown ethers

International Nuclear Information System (INIS)

Heffels, Dennis Egidius

2014-01-01

The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

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

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.

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

Tunable states of interlayer cations in two-dimensional materials

International Nuclear Information System (INIS)

Sato, K.; Numata, K.; Dai, W.; Hunger, M.

2014-01-01

The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of 23 Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and 23 Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed

Tunable states of interlayer cations in two-dimensional materials

Energy Technology Data Exchange (ETDEWEB)

Sato, K.; Numata, K. [Department of Environmental Sciences, Tokyo Gakugei University, Koganei, Tokyo 184-8501 (Japan); Dai, W. [Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 (China); Hunger, M. [Institute of Chemical Technology, University of Stuttgart, 70550 Stuttgart (Germany)

2014-03-31

The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of {sup 23}Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and {sup 23}Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed.

Comparative investigation on cation-cation (Al-Sn) and cation-anion (Al-F) co-doping in RF sputtered ZnO thin films: Mechanistic insight

Energy Technology Data Exchange (ETDEWEB)

Mallick, Arindam; Basak, Durga, E-mail: sspdb@iacs.res.in

2017-07-15

Highlights: • Comparative study on Al, Al-Sn and Al-F doped ZnO films has been carried out. • High transparent Al-F co-doped film shows three times enhanced carrier density. • Al-F co-doped film shows larger carrier relaxation time. • Al-Sn co-doped films shows carrier transport dominated by impurity scattering. • Al-F co-doped ZnO film can be applied as transparent electrode. - Abstract: Herein, we report a comparative mechanistic study on cation-cation (Al-Sn) and cation-anion (Al-F) co-doped nanocrystalline ZnO thin films grown on glass substrate by RF sputtering technique. Through detailed analyses of crystal structure, surface morphology, microstructure, UV-VIS-NIR transmission-reflection and electrical transport property, the inherent characteristics of the co-doped films were revealed and compared. All the nanocrystalline films retain the hexagonal wurtzite structure of ZnO and show transparency above 90% in the visible and NIR region. As opposed to expectation, Al-Sn (ATZO) co-doped film show no enhanced carrier concentration consistent with the probable formation of SnO{sub 2} clusters supported by the X-ray photoelectron spectroscopy study. Most interestingly, it has been found that Al-F (AFZO) co-doped film shows three times enhanced carrier concentration as compared to Al doped and Al-Sn co-doped films attaining a value of ∼9 × 10{sup 20} cm{sup −3} due to the respective cation and anion substitution. The carrier relaxation time increases in AFZO while it decreases significantly for ATZO film consistent with the concurrence of the impurity scattering in the latter.

Comparison of "type I" and "type II" organic cation transport by organic cation transporters and organic anion-transporting polypeptides

NARCIS (Netherlands)

Van Montfoort, JE; Muller, M; Groothuis, GMM; Meijer, DKF; Koepsell, H; Meier, PJ

Previous inhibition studies with taurocholate and cardiac glycosides suggested the presence of separate uptake systems for small "type I" (system1) and for bulky "type II" (system2) organic cations in rat hepatocytes. To identify the transport systems involved in type I and type II organic cation

Cation-enhanced capillary electrophoresis separation of atropoisomer anions.

Science.gov (United States)

Na, Yun-Cheol; Berthod, Alain; Armstrong, Daniel W

2015-12-01

CE was used to study the separation of the atropoisomers of four phosphoric acids and two sulfonic acids and the enantiomers of two phosphoric acids. All solutes are in their anionic forms in aqueous electrolytes. The chiral additives were two hydroxypropyl cyclodextrins (CDs) and cyclofructan 6 (CF6). The CDs were able to separate four solutes and the CF6 additive could separate only one: 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (BHP). Since CF6 is able to bind with cations, nitrate of alkaline metals, Ba(2+) , and Pb(2+) were added, greatly improving the BHP separation at the expense of longer migration times. There seems to be a link between CF6-cation-binding constants and BHP resolution factors. Cation additions were also performed with CD selectors that are less prone to form complexes with cations. Significant improvements of enantiomer or atropoisomer separations were observed also associated with longer migration times. It is speculated that the anionic solutes associate with the added cations forming larger entities better differentiated by CDs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

AlPcS4-PDT for gastric cancer therapy using gold nanorod, cationic liposome, and Pluronic® F127 nanomicellar drug carriers.

Science.gov (United States)

Xin, Jing; Wang, Sijia; Wang, Bing; Wang, Jiazhuang; Wang, Jing; Zhang, Luwei; Xin, Bo; Shen, Lijian; Zhang, Zhenxi; Yao, Cuiping

2018-01-01

As a promising photodynamic therapy (PDT) agent, Al(III) phthalocyanine chloride tetrasulfonic acid (AlPcS 4 ) provides deep penetration into tissue, high quantum yields, good photostability, and low photobleaching. However, its low delivery efficiency and high binding affinity to serum albumin cause its low penetration into cancer cells, further limiting its PDT effect on gastric cancer. In order to improve AlPcS 4 /PDT effect, the AlPcS 4 delivery sys tems with different drug carriers were synthesized and investigated. Gold nanorods, cationic liposomes, and Pluronic ® F127 nanomicellars were used to formulate the AlPcS 4 delivery systems. The anticancer effect was evaluated by CCK-8 assay and colony formation assay. The delivery efficiency of AlPcS 4 and the binding affinity to serum proteins were determined by fluorescence intensity assay. The apoptosis and necrosis ability, reactive oxygen species and singlet oxygen generation, mitochondrial transmembrane potential and ([Ca 2+ ] i ) concentration were further measured to evaluate the mechanism of cell death. The series of synthesized AlPcS 4 delivery systems with different drug carriers improve the limited PDT effect in varying degrees. In contrast, AlPcS 4 complex with gold nanorods has significant anticancer effects because gold nanorods are not only suitable for AlPcS 4 delivery, but also exhibit enhanced singlet oxygen generation effect and photothermal effect to induce cell death directly. Moreover, AlPcS 4 complex with cationic liposomes shows the potent inhibition effect because of its optimal AlPcS 4 delivery efficiency and ability to block serum albumin. In addition, AlPcS 4 complex with Pluronic F127 exhibits inferior PDT effect but presents lower cytotoxicity, slower dissociation rate, and longer retention time of incorporated drugs; thus, F127-AlPcS 4 is used for prolonged gastric cancer therapy. The described AlPcS 4 drug delivery systems provide promising agents for gastric cancer therapy.

Cation distributions on rapidly solidified cobalt ferrite

Science.gov (United States)

De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.

1990-01-01

The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

Effect of cation exchange of major cation chemistry in the large scale redox experiment at Aespoe. Revision 1

International Nuclear Information System (INIS)

Viani, B.E.; Bruton, C.J.

1996-06-01

Geochemical modeling was used to test the hypothesis that cation exchange with fracture-lining clays during fluid mixing in the Aespoe Hard Rock Laboratory can significantly affect major element chemistry. Conservative mixing models do not adequately account for changes in Na, Ca and Mg concentrations during mixing. Mixing between relatively dilute shallow waters and more concentrated waters at depth along fracture zones was modeled using the EQ3/6 geochemical modeling package. A cation exchange model was added to the code to describe simultaneously aqueous speciation, mineral precipitation/dissolution, and equilibration between a fluid and a cation exchanger. Fluid chemistries predicted to result from mixing were compared with those monitored from boreholes intersecting the fracture zone. Modeling results suggest that less than 0.1 equivalent of a smectite exchanger per liter of groundwater is necessary to account for discrepancies between predictions from a conservative mixing model and measured Na and Ca concentrations. This quantity of exchanger equates to an effective fracture coating thickness of 20 microm or less given a fracture aperture width of 1,000 microm or less. Trends in cation ratios in the fluid cannot be used to predict trends in cation ratios on the exchanger because of the influence of ionic strength on heterovalent exchange equilibrium. It is expected that Na for Ca exchange will dominate when shallow waters such as HBHO2 are mixed with deeper waters. In contrast, Na for Mg exchange will dominate mixing between deeper waters

Quantum-chemical, NMR, FT IR, and ESI MS studies of complexes of colchicine with Zn(II).

Science.gov (United States)

Jankowski, Wojciech; Kurek, Joanna; Barczyński, Piotr; Hoffmann, Marcin

2017-04-01

Colchicine is a tropolone alkaloid from Colchicinum autumnale. It shows antifibrotic, antimitotic, and anti-inflammatory activities, and is used to treat gout and Mediterranean fever. In this work, complexes of colchicine with zinc(II) nitrate were synthesized and investigated using DFT, 1 H and 13 C NMR, FT IR, and ESI MS. The counterpoise-corrected and uncorrected interaction energies of these complexes were calculated. We also calculated their 1 H, 13 C NMR, and IR spectra and compared them with the corresponding experimentally obtained data. According to the ESI MS mass spectra, colchicine forms stable complexes with zinc(II) nitrate that have various stoichiometries: 2:1, 1:1:1, and 2:1:1 with respect to colchichine, Zn(II), and nitrate ion. All of the complexes were investigated using the quantum theory of atoms in molecules (QTAIM). The calculated and the measured spectra showed differences before and after the complexation process. Calculated electron densities and bond critical points indicated the presence of bonds between the ligands and the central cation in the investigated complexes that satisfied the quantum theory of atoms in molecules. Graphical Abstract DFT, NMR, FT IR, ESI MS, QTAIM and puckering studies of complexes of colchicine with Zn(II).

Organic cation rhodamines for screening organic cation transporters in early stages of drug development.

Science.gov (United States)

Ugwu, Malachy C; Oli, Angus; Esimone, Charles O; Agu, Remigius U

The aim of this study was to investigate the suitability of rhodamine-123, rhodamine-6G and rhodamine B as non-radioactive probes for characterizing organic cation transporters in respiratory cells. Fluorescent characteristics of the compounds were validated under standard in vitro drug transport conditions (buffers, pH, and light). Uptake/transport kinetics and intracellular accumulation of the compounds were investigated. Uptake/transport mechanisms were investigated by comparing the effect of pH, temperature, concentration, polarity, OCTs/OCTNs inhibitors/substrates, and metabolic inhibitors on the cationic dyes uptake in Calu-3 cells. Fluorescence stability and intensity of the compounds were altered by buffer composition, light, and pH. Uptake of the dyes was concentration-, temperature- and pH-dependent. OCTs/OCTNs inhibitors significantly reduced intracellular accumulation of the compounds. Whereas rhodamine-B uptake was sodium-dependent, pH had no effect on rhodamine-123 and rhodamine-6G uptake. Transport of the dyes across the cells was polarized: (AP→BL>BL→AP transport) and saturable: {V max =14.08±2.074, K m =1821±380.4 (rhodamine-B); V max =6.555±0.4106, K m =1353±130.4 (rhodamine-123) and V max =0.3056±0.01402, K m =702.9±60.97 (rhodamine-6G)}. The dyes were co-localized with MitoTracker®, the mitochondrial marker. Cationic rhodamines, especially rhodamine-B and rhodamine- 6G can be used as organic cation transporter substrates in respiratory cells. During such studies, buffer selection, pH and light exposure should be taken into consideration. Copyright © 2016 Elsevier Inc. All rights reserved.

Asymmetric cation-binding catalysis

DEFF Research Database (Denmark)

Oliveira, Maria Teresa; Lee, Jiwoong

2017-01-01

The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel.

Science.gov (United States)

Gurnev, Philip A; Bezrukov, Sergey M

2012-11-13

We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the "charge inversion" phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification, which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations, which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine.

Tripodal Receptors for Cation and Anion Sensors

Directory of Open Access Journals (Sweden)

David N. Reinhoudt

2006-08-01

Full Text Available This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing are emphasised, along with their potential applications in optical sensors or optodes.

Chemical reactivity of cation-exchanged zeolites

OpenAIRE

Pidko, E.A.

2008-01-01

Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

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.

Effect of cations on the hydrated proton.

Science.gov (United States)

Ottosson, Niklas; Hunger, Johannes; Bakker, Huib J

2014-09-17

We report on a strong nonadditive effect of protons and other cations on the structural dynamics of liquid water, which is revealed using dielectric relaxation spectroscopy in the frequency range of 1-50 GHz. For pure acid solutions, protons are known to have a strong structuring effect on water, leading to a pronounced decrease of the dielectric response. We observe that this structuring is reduced when protons are cosolvated with salts. This reduction is exclusively observed for combinations of protons with other ions; for all studied solutions of cosolvated salts, the effect on the structural dynamics of water is observed to be purely additive, even up to high concentrations. We derive an empirical model that quantitatively describes the nonadditive effect of cosolvated protons and cations. We argue that the effect can be explained from the special character of the proton in water and that Coulomb fields exerted by other cations, in particular doubly charged cations like Mg(2+)aq and Ca(2+)aq, induce a localization of the H(+)aq hydration structures.

Cation exchange properties of zeolites in hyper alkaline aqueous media.

Science.gov (United States)

Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric

2015-02-03

Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

Absorptive-mediated endocytosis of cationized albumin and a beta-endorphin-cationized albumin chimeric peptide by isolated brain capillaries. Model system of blood-brain barrier transport

International Nuclear Information System (INIS)

Kumagai, A.K.; Eisenberg, J.B.; Pardridge, W.M.

1987-01-01

Cationized albumin (pI greater than 8), unlike native albumin (pI approximately 4), enters cerebrospinal fluid (CSF) rapidly from blood. This suggests that a specific uptake mechanism for cationized albumin may exist at the brain capillary wall, i.e. the blood-brain barrier. Isolated bovine brain capillaries rapidly bound cationized [ 3 H]albumin and approximately 70% of the bound radioactivity was resistant to mild acid wash, which is assumed to represent internalized peptide. Binding was saturable and a Scatchard plot gave a maximal binding capacity (Ro) = 5.5 +/- 0.7 micrograms/mgp (79 +/- 10 pmol/mgp), and a half-saturation constant (KD) = 55 +/- 8 micrograms/ml (0.8 +/- 0.1 microM). The binding of cationized [ 3 H]albumin (pI = 8.5-9) was inhibited by protamine, protamine sulfate, and polylysine (molecular weight = 70,000) with a Ki of approximately 3 micrograms/ml for all three proteins. The use of cationized albumin in directed delivery of peptides through the blood-brain barrier was examined by coupling [ 3 H]beta-endorphin to unlabeled cationized albumin (pI = 8.5-9) using the bifunctional reagent, N-succinimidyl 3-(2-pyridyldithio)proprionate. The [ 3 H]beta-endorphin-cationized albumin chimeric peptide was rapidly bound and endocytosed by isolated bovine brain capillaries, and this was inhibited by unlabeled cationized albumin but not by unconjugated beta-endorphin or native bovine albumin. Cationized albumin provides a new tool for studying absorptive-mediated endocytosis at the brain capillary and may also provide a vehicle for directed drug delivery through the blood-brain barrier

Absorptive-mediated endocytosis of cationized albumin and a beta-endorphin-cationized albumin chimeric peptide by isolated brain capillaries. Model system of blood-brain barrier transport

Energy Technology Data Exchange (ETDEWEB)

Kumagai, A.K.; Eisenberg, J.B.; Pardridge, W.M.

1987-11-05

Cationized albumin (pI greater than 8), unlike native albumin (pI approximately 4), enters cerebrospinal fluid (CSF) rapidly from blood. This suggests that a specific uptake mechanism for cationized albumin may exist at the brain capillary wall, i.e. the blood-brain barrier. Isolated bovine brain capillaries rapidly bound cationized (/sup 3/H)albumin and approximately 70% of the bound radioactivity was resistant to mild acid wash, which is assumed to represent internalized peptide. Binding was saturable and a Scatchard plot gave a maximal binding capacity (Ro) = 5.5 +/- 0.7 micrograms/mgp (79 +/- 10 pmol/mgp), and a half-saturation constant (KD) = 55 +/- 8 micrograms/ml (0.8 +/- 0.1 microM). The binding of cationized (/sup 3/H)albumin (pI = 8.5-9) was inhibited by protamine, protamine sulfate, and polylysine (molecular weight = 70,000) with a Ki of approximately 3 micrograms/ml for all three proteins. The use of cationized albumin in directed delivery of peptides through the blood-brain barrier was examined by coupling (/sup 3/H)beta-endorphin to unlabeled cationized albumin (pI = 8.5-9) using the bifunctional reagent, N-succinimidyl 3-(2-pyridyldithio)proprionate. The (/sup 3/H)beta-endorphin-cationized albumin chimeric peptide was rapidly bound and endocytosed by isolated bovine brain capillaries, and this was inhibited by unlabeled cationized albumin but not by unconjugated beta-endorphin or native bovine albumin. Cationized albumin provides a new tool for studying absorptive-mediated endocytosis at the brain capillary and may also provide a vehicle for directed drug delivery through the blood-brain barrier.

Does the cation really matter? The effect of modifying an ionic liquid cation on an SN2 process.

Science.gov (United States)

Tanner, Eden E L; Yau, Hon Man; Hawker, Rebecca R; Croft, Anna K; Harper, Jason B

2013-09-28

The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.

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)

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

Spectroscopic and computer modelling studies of mixed-cation superionic fluorites

CSIR Research Space (South Africa)

Netshisaulu, TT

2005-10-19

Full Text Available into the local environments of the Cd and Pb cations (as a function of composition and temperature) in CdF2 (xPbF(2)) mixed-cation superionic fluorites. A high degree of disorder is shown around both cations. However, the extent of disorder is even larger around...

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.

pi-Dimers of end-capped oligopyrrole cation radicals

NARCIS (Netherlands)

Haare, van J.A.E.H.; Groenendaal, L.; Havinga, E.E.; Janssen, R.A.J.; Meijer, E.W.

1996-01-01

In two consecutive one-electron oxidations, oligopyrroles substituted with phenyl capping groups (PhPynPh, n = 2–4) can be oxidized reversibly to give stable cation radicals and dications. Spectroelectrochemical studies give direct evidence that diamagnetic p-dimers of cation radicals are formed in

Cation-pi interaction of the univalent silver cation with racemic [6]helicene in the gas phase and in the solid state

Czech Academy of Sciences Publication Activity Database

Klepetářová, Blanka; Makrlík, E.; Sýkora, D.; Böhm, S.; Vaňura, P.

2016-01-01

Roč. 117, Oct 15 (2016), s. 1-6 ISSN 0277-5387 Institutional support: RVO:61388963 Keywords : univalent silver cation * [6]helicene * cation -pi interaction * DFT calculations * X-ray crystallography Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.926, year: 2016

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

Al cation induces aggregation of serum proteins.

Science.gov (United States)

Chanphai, P; Kreplak, L; Tajmir-Riahi, H A

2017-07-15

Al cation is known to induce protein fibrillation and causes several neurodegenerative disorders. We report the spectroscopic, thermodynamic analysis and AFM imaging for the Al cation binding process with human serum albumin (HSA), bovine serum albumin (BSA) and milk beta-lactoglobulin (b-LG) in aqueous solution at physiological pH. Hydrophobicity played a major role in Al-protein interactions with more hydrophobic b-LG forming stronger Al-protein complexes. Thermodynamic parameters ΔS, ΔH and ΔG showed Al-protein bindings occur via hydrophobic and H-bonding contacts for b-LG, while van der Waals and H-bonding interactions prevail in HSA and BSA adducts. AFM clearly indicated that aluminum cations are able to force BSA and b-LG into larger or more robust aggregates than HSA, with HSA 4±0.2 (SE, n=801) proteins per aggregate, for BSA 17±2 (SE, n=148), and for b-LG 12±3 (SE, n=151). Thioflavin T test showed no major protein fibrillation in the presence of Al cation. Al complexation induced major alterations of protein conformations with the order of perturbations b-LG>BSA>HSA. Copyright © 2017 Elsevier B.V. All rights reserved.

Cation Exchange Water Softeners

Science.gov (United States)

WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

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.

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.