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Sample records for manganese porphyrins anchored

  1. Functionalized Nanostructures: Redox-Active Porphyrin Anchors for Supramolecular DNA Assemblies

    KAUST Repository

    Börjesson, Karl; Wiberg, Joanna; El-Sagheer, Afaf H.; Ljungdahl, Thomas; Må rtensson, Jerker; Brown, Tom; Nordén, Bengt; Albinsson, Bo

    2010-01-01

    , such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore

  2. Functionalized Nanostructures: Redox-Active Porphyrin Anchors for Supramolecular DNA Assemblies

    KAUST Repository

    Börjesson, Karl

    2010-09-28

    We have synthesized and studied a supramolecular system comprising a 39-mer DNA with porphyrin-modified thymidine nucleosides anchored to the surface of large unilamellar vesicles (liposomes). Liposome porphyrin binding characteristics, such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore, the binding characteristics and hybridization capabilities were studied as a function of anchor size and number of anchoring points, properties that are of importance for our future plans to use the addressability of these redox-active nodes in larger DNA-based nanoconstructs. Electron transfer from photoexcited porphyrin to a lipophilic benzoquinone residing in the lipid membrane was characterized by steady-state and time-resolved fluorescence and verified by femtosecond transient absorption. © 2010 American Chemical Society.

  3. Lipophilic manganese porphyrin crosses blood-brain barrier

    International Nuclear Information System (INIS)

    Nelson, J.A.; Cegnar, J.; Spence, A.M.; Richards, T.L.; Golden, R.N.; Muzi, M.

    1987-01-01

    Most reports on manganese porphyrins as MR imaging contrast agents have focused on a water-soluble compound, Mn-TPPS4. Phototherapy researchers have noted that lipophilic components of hematoporphyrin derivative sensitize normal brain tissue to light-stimulated photodestruction. This observation suggests that a lipophilic paramagnetic agent might be useful for brain contrast enhancement. The current experiments were designed to test the MR imaging effects of a lipid-soluble compound, Mn-mesoporphyrin. An intravenous injection of 0.05 μmoles/kg was administered to rats with a well-characterized astrocytic glioma implanted into the right cerebral hemisphere. MR imaging experiments performed at 2 T on a General Electric CSI-II system revealed T1 relaxation shortening in both normal brain and tumor. Delayed images at 24 hours revealed persistent selective contrast agent enhancement at the gross tumor site

  4. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Directory of Open Access Journals (Sweden)

    Cláudia M. B. Neves

    2012-01-01

    Full Text Available This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H2O2, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy.

  5. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Neves, Claudia M.B.; Simoes, Mario M.Q.; Domingues, Fernando M.J.; Neves, M. Graca P.M.S.; Cavaleiro, Jose A.S., E-mail: msimoes@ua.pt [Dept. de Quimica, QOPNA, Universidade de Aveiro (Portugal)

    2012-07-01

    This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H{sub 2}O{sub 2}, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy. (author)

  6. Biomimetic oxidation of piperine and piplartine catalyzed by iron(III) and manganese(III) porphyrins.

    Science.gov (United States)

    Schaab, Estela Hanauer; Crotti, Antonio Eduardo Miller; Iamamoto, Yassuko; Kato, Massuo Jorge; Lotufo, Letícia Veras Costa; Lopes, Norberto Peporine

    2010-01-01

    Synthetic metalloporphyrins, in the presence of monooxygen donors, are known to mimetize various reactions of cytochrome P450 enzymes systems in the oxidation of drugs and natural products. The oxidation of piperine and piplartine by iodosylbenzene using iron(III) and manganese(III) porphyrins yielded mono- and dihydroxylated products, respectively. Piplartine showed to be a more reactive substrate towards the catalysts tested. The structures of the oxidation products were proposed based on electrospray ionization tandem mass spectrometry.

  7. Dissection of the mechanism of manganese porphyrin-catalyzed chlorine dioxide generation.

    Science.gov (United States)

    Umile, Thomas P; Wang, Dong; Groves, John T

    2011-10-17

    Chlorine dioxide, an industrially important biocide and bleach, is produced rapidly and efficiently from chlorite ion in the presence of water-soluble, manganese porphyrins and porphyrazines at neutral pH under mild conditions. The electron-deficient manganese(III) tetra-(N,N-dimethyl)imidazolium porphyrin (MnTDMImP), tetra-(N,N-dimethyl)benzimidazolium (MnTDMBImP) porphyrin, and manganese(III) tetra-N-methyl-2,3-pyridinoporphyrazine (MnTM23PyPz) were found to be the most efficient catalysts for this process. The more typical manganese tetra-4-N-methylpyridiumporphyrin (Mn-4-TMPyP) was much less effective. Rates for the best catalysts were in the range of 0.24-32 TO/s with MnTM23PyPz being the fastest. The kinetics of reactions of the various ClO(x) species (e.g., chlorite ion, hypochlorous acid, and chlorine dioxide) with authentic oxomanganese(IV) and dioxomanganese(V)MnTDMImP intermediates were studied by stopped-flow spectroscopy. Rate-limiting oxidation of the manganese(III) catalyst by chlorite ion via oxygen atom transfer is proposed to afford a trans-dioxomanganese(V) intermediate. Both trans-dioxomanganese(V)TDMImP and oxoaqua-manganese(IV)TDMImP oxidize chlorite ion by 1-electron, generating the product chlorine dioxide with bimolecular rate constants of 6.30 × 10(3) M(-1) s(-1) and 3.13 × 10(3) M(-1) s(-1), respectively, at pH 6.8. Chlorine dioxide was able to oxidize manganese(III)TDMImP to oxomanganese(IV) at a similar rate, establishing a redox steady-state equilibrium under turnover conditions. Hypochlorous acid (HOCl) produced during turnover was found to rapidly and reversibly react with manganese(III)TDMImP to give dioxoMn(V)TDMImP and chloride ion. The measured equilibrium constant for this reaction (K(eq) = 2.2 at pH 5.1) afforded a value for the oxoMn(V)/Mn(III) redox couple under catalytic conditions (E' = 1.35 V vs NHE). In subsequent processes, chlorine dioxide reacts with both oxomanganese(V) and oxomanganese(IV)TDMImP to afford chlorate

  8. Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

    Science.gov (United States)

    Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

    2018-01-26

    The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Porphyrins

    Science.gov (United States)

    Gotelli, George R.; Wall, Jeffrey H.; Kabra, Pokar M.; Marton, Laurence J.

    Historically the term porphyria has been used since it was coined in 1871 to describe a purple colored material extracted from pathological feces (1). The first case of porphyria was reported in 1874, (2, 3), but until the 1930 Nobel Prize winning work of Hans Fischer on the synthesis of protoporphyrin, there was little more than academic interest in porphyrin analysis. During the forty years between 1930 and 1970, the biosynthetic pathways leading to the formation of heme, and the details of porphyrin metabolism, were elucidated. During this time quantitative methods for porphyrins in biological fluids used complex and laborious solvent extraction techniques, requiring large sample volumes and hours to complete. We now know that these methods only partially separated the complex mixture of porphyrins found in biological fluids. These solvent extraction procedures fractionated the porphyrins into two broad groups, uroporphyrins (octacarboxylic) and coproporphyrins (tetracarboxylic). However, intermediate carboxylated porphyrin containing 2, 3, 5, 6, and 7 carboxyl groups are now known to exist in normal and pathlogical excreta, which were not differentiated, but which were included in the two broad uroporphyrin and copropophyrin groups.

  10. Manganese(III Porphyrin-based Potentiometric Sensors for Diclofenac Assay in Pharmaceutical Preparations

    Directory of Open Access Journals (Sweden)

    Eugenia Fagadar-Cosma

    2010-09-01

    Full Text Available Two manganese(III porphyrins: manganese(III tetraphenylporphyrin chloride and manganese(III-tetrakis(3-hydroxyphenylporphyrin chloride were tested as ionophores for the construction of new diclofenac−selective electrodes. The electroactive material was incorporated either in PVC or a sol−gel matrix. The effect of different plasticizers and additives (anionic and cationic on the potentiometric response was studied. The best results were obtained for the PVC membrane plasticized with dioctylphtalate and having sodium tetraphenylborate as a lipophilic anionic additive incorporated. The sensor response was linear in the concentration range 3 × 10−6 – 1 × 10−2 M with a slope of −59.7 mV/dec diclofenac, a detection limit of 1.5 × 10−6 M and very good selectivity coefficients. It was used for the determination of diclofenac in pharmaceutical preparations, by direct potentiometry. The results were compared with those obtained by the HPLC reference method and a good agreement was found between the two methods.

  11. Electrocatalytic behaviour and application of manganese porphyrin/gold nanoparticle- surface modified glassy carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Sebarchievici, I., E-mail: incemc@incemc.ro [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Tăranu, B.O. [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Birdeanu, M. [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Institute of Chemistry Timisoara of Romanian Academy, M. Viteazul Ave. 24, 300223 Timisoara (Romania); Rus, S.F. [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Fagadar-Cosma, E., E-mail: efagadar@yahoo.com [Institute of Chemistry Timisoara of Romanian Academy, M. Viteazul Ave. 24, 300223 Timisoara (Romania)

    2016-12-30

    Highlights: • Mn-porphyrin/gold nanoparticle-modified glassy carbon electrodes were obtained. • AFM investigations of thin films display multilayer of triangular type architecture. • Oxidation and reduction processes of H{sub 2}O{sub 2} are diffusion controled. • There is a linear dependence between H{sub 2}O{sub 2} concentration and the currents intensity. • The modified electrodes show better electrochemical detection ability to H{sub 2}O{sub 2}. - Abstract: The main purpose of this research was to obtain manganese porphyrin/gold nanoparticle-modified glassy carbon electrodes and to use them for the detection of H{sub 2}O{sub 2}. Two sets of modified electrodes were prepared by drop-cast deposition of 5,10,15,20-tetra(4-methyl-phenyl)porphyrinato manganese(III) chloride alone and of the same Mn-porphyrin and gold-colloid solution and comparatively characterized by Raman, UV–vis, ellipsometry, AFM and TEM microscopy, XPS and cyclic voltammetry. XPS spectrum recorded for GC-MnP-nAu modified electrode displayed the characteristic signals of gold nanoparticles. The optical parameters have greater values for GC-MnP-nAu in comparison with GC-MnP, due to increasing charge transfer efficiency. The MnP-nAu film mediates the electron transfer between H{sub 2}O{sub 2} and GC, evidenced by an increase in the current intensity of the anodic peak, and facilitates the electrochemical regeneration of oxidized H{sub 2}O{sub 2} at cathodic potentials. From the cyclic voltammetry experiments a linear relationship between H{sub 2}O{sub 2} concentration vs oxidation and reduction currents was observed. The linear dependence between density of current and the square root of the scan rate indicates that the oxidation and reduction processes of H{sub 2}O{sub 2} are diffusion controlled. The GC-MnP-nAu modified electrode shows great potential as electrochemical sensor for determination of hydrogen peroxide.

  12. "Spider"-shaped porphyrins with conjugated pyridyl anchoring groups as efficient sensitizers for dye-sensitized solar cells.

    Science.gov (United States)

    Stangel, Christina; Bagaki, Anthi; Angaridis, Panagiotis A; Charalambidis, Georgios; Sharma, Ganesh D; Coutsolelos, Athanasios G

    2014-11-17

    Two novel "spider-shaped" porphyrins, meso-tetraaryl-substituted 1PV-Por and zinc-metalated 1PV-Zn-Por, bearing four oligo(p-phenylenevinylene) (oPPV) pyridyl groups with long dodecyloxy chains on the phenyl groups, have been synthesized. The presence of four pyridyl groups in both porphyrins, which allow them to act as anchoring groups upon coordination to various Lewis acid sites, the conjugated oPPV bridges, which offer the possibility of electronic communication between the porphyrin core and the pyridyl groups, and the dodecyloxy groups, which offer the advantage of high solubility in a variety of organic solvents of different polarities and could prevent porphyrin aggregation, renders porphyrins 1PV-Por and 1PV-Zn-Por very promising sensitizers for dye-sensitized solar cells (DSSCs). Photophysical measurements, together with electrochemistry experiments and density functional theory calculations, suggest that both porphyrins have frontier molecular orbital energy levels that favor electron injection and dye regeneration in DSSCs. Solar cells sensitized by 1PV-Por and 1PV-Zn-Por were fabricated, and it was found that they show power conversion efficiencies (PCEs) of 3.28 and 5.12%, respectively. Photovoltaic measurements (J-V curves) together with incident photon-to-electron conversion efficiency spectra of the two cells reveal that the higher PCE value of the DSSC based on 1PV-Zn-Por is ascribed to higher short-circuit current (Jsc), open-circuit voltage (Voc), and dye loading values. Emission spectra and electrochemistry experiments suggest a greater driving force for injection of the photogenerated electrons into the TiO2 conduction band for 1PV-Zn-Por rather than its free-base analogue. Furthermore, electrochemical impedance spectroscopy measurements prove that the utilization of 1PV-Zn-Por as a sensitizer offers a high charge recombination resistance and, therefore, leads to a longer electron lifetime.

  13. Water-soluble Manganese and Iron Mesotetrakis(carboxyl)porphyrin: DNA Binding, Oxidative Cleavage, and Cytotoxic Activities.

    Science.gov (United States)

    Shi, Lei; Jiang, Yi-Yu; Jiang, Tao; Yin, Wei; Yang, Jian-Ping; Cao, Man-Li; Fang, Yu-Qi; Liu, Hai-Yang

    2017-06-29

    Two new water-soluble metal carboxyl porphyrins, manganese (III) meso -tetrakis (carboxyl) porphyrin and iron (III) meso -tetrakis (carboxyl) porphyrin, were synthesized and characterized. Their interactions with ct-DNA were investigated by UV-Vis titration, fluorescence spectra, viscosity measurement and CD spectra. The results showed they can strongly bind to ct-DNA via outside binding mode. Electrophoresis experiments revealed that both complexes can cleave pBR322 DNA efficiently in the presence of hydrogen peroxide, albeit 2-Mn exhibited a little higher efficiency. The inhibitor tests suggest the oxidative DNA cleavage by these two complexes may involve hydroxyl radical active intermediates. Notably, 2-Mn exhibited considerable photocytotoxicity against Hep G2 cell via triggering a significant generation of ROS and causing disruption of MMP after irradiation.

  14. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

    Science.gov (United States)

    den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E; Nolte, Roeland J M; Speller, Sylvia; Amabilino, David B; De Feyter, Steven; Elemans, Johannes A A W

    2013-07-01

    Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

  15. Magnetocaloric properties of manganese(III) porphyrins bearing 2,6-di-tert-butylphenol groups

    Energy Technology Data Exchange (ETDEWEB)

    Korolev, V.V., E-mail: vvk@isc-ras.ru [G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaya str., 1, Ivanovo 153045 (Russian Federation); Lomova, T.N.; Maslennikova, A.N.; Korolev, D.V. [G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaya str., 1, Ivanovo 153045 (Russian Federation); Shpakovsky, D.B.; Zhang, Jianwei; Milaeva, E.R. [Lomonosov Moscow State University, Department of Medicinal Chemistry and Fine Organic Synthesis, Moscow 119991 (Russian Federation)

    2016-03-01

    Magnetocaloric effect (MCE) and heat capacity during the magnetization of (5,10,15,20-tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphynato) manganese (III) chloride (1), (5-(4-hydroxyphenyl)-10,15,20-tris(3,5-di-tert-butyl-4-hydroxyphenyl) porphynato) manganese (III) chloride (2), and (5-(4-palmitoyloxyphenyl)-10,15,20-tris(3,5-di-tert-butyl-4-hydroxyphenyl) porphynato) manganese (III) chloride (3) in their aqueous suspensions were determined by the microcalorimetric method over the temperature range of 278–320 K and in magnetic fields from 0 to 1 T. MCE was positive for all complexes studied, i.e. the magnetic field impression under adiabatic conditions led to an increase in temperature of the complexes suspensions. MCE increased with an increase in the magnetic field induction at all temperatures studied. Dependences of MCE on temperature had weak maxima at 298 K at all magnetic induction values. The disturbance of the intermolecular hydrogen-bonding of hydroxyl groups is one of probable reasons for such dependences type. MCE values increased under the palmitoyl substituent incorporation into one of the phenol groups at all temperatures. The heat capacity of the studied complexes rose slightly with temperature growth. Dependences of the heat capacity on temperature showed that the magnetic component of the heat capacity did not appear due to the presence of the manganese atom acting as a paramagnetic center in complexes 1, 2, and 3. The relation between the complexes structure and their magnetothermal properties was analyzed. It was justified that the changes of magnetothermal properties were caused by electronic substitution effects and, to an even greater degree, by the conditions of intermolecular hydrogen bonds formation in the paramagnetic materials. - Highlights: • The magnetocaloric effect and heat capacity of 3 manganese porphyrin were determined. • Temperature dependences of magnetocaloric effect has been studied. • The relation between the

  16. High-conductance surface-anchoring of a mechanically flexible platform-based porphyrin complex

    International Nuclear Information System (INIS)

    Hauptmann, Nadine; Buchmann, Kristof; Scheil, Katharina; Berndt, Richard; Groß, Lynn; Herrmann, Carmen; Schütt, Christian; Otte, Franziska L; Herges, Rainer

    2015-01-01

    The conductances of molecular model junctions comprising a triazatriangulenium platform with or without an ethynyl spacer and an upright Zn-porphyrin are probed with a low-temperature scanning probe microscope. The platform alone is found to be highly conductive. The ethynyl-linked Zn-porphyrin moiety reduces the conductance by three orders of magnitude and leads to an unexpected, non-monotonous variation of the force that was measured simultaneously at the tip of the microscope. Density functional theory calculations show that this variation results from an induced tilting of the porphyrin. (paper)

  17. The Addition of Manganese Porphyrins during Radiation Inhibits Prostate Cancer Growth and Simultaneously Protects Normal Prostate Tissue from Radiation Damage

    Directory of Open Access Journals (Sweden)

    Arpita Chatterjee

    2018-01-01

    Full Text Available Radiation therapy is commonly used for prostate cancer treatment; however, normal tissues can be damaged from the reactive oxygen species (ROS produced by radiation. In separate reports, we and others have shown that manganese porphyrins (MnPs, ROS scavengers, protect normal cells from radiation-induced damage but inhibit prostate cancer cell growth. However, there have been no studies demonstrating that MnPs protect normal tissues, while inhibiting tumor growth in the same model. LNCaP or PC3 cells were orthotopically implanted into athymic mice and treated with radiation (2 Gy, for 5 consecutive days in the presence or absence of MnPs. With radiation, MnPs enhanced overall life expectancy and significantly decreased the average tumor volume, as compared to the radiated alone group. MnPs enhanced lipid oxidation in tumor cells but reduced oxidative damage to normal prostate tissue adjacent to the prostate tumor in combination with radiation. Mechanistically, MnPs behave as pro-oxidants or antioxidants depending on the level of oxidative stress inside the treated cell. We found that MnPs act as pro-oxidants in prostate cancer cells, while in normal cells and tissues the MnPs act as antioxidants. For the first time, in the same in vivo model, this study reveals that MnPs enhance the tumoricidal effect of radiation and reduce oxidative damage to normal prostate tissue adjacent to the prostate tumor in the presence of radiation. This study suggests that MnPs are effective radio-protectors for radiation-mediated prostate cancer treatment.

  18. High Performance of Manganese Porphyrin Sensitized p-Type CuFe2O4 Photocathode for Solar Water Splitting to Produce Hydrogen in a Tandem Photoelectrochemical Cell

    Directory of Open Access Journals (Sweden)

    Xia Li

    2018-03-01

    Full Text Available A novel composite composed of (5, 10, 15, 20-tetraphenyl porphinato manganese sensitized p-type CuFe2O4 was developed for constructing the photocathode of a tandem photoelectrochemical (PEC cell. The prepared material was characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, X-ray photoelectron spectroscopy (XPS and UV-vis diffuse reflectance spectroscopy (DRS. Light-driven water splitting to produce hydrogen can be achieved through the PEC cell, and the results show that H2 and O2 can be collected separately at low applied bias. This work demonstrates that manganese porphyrin sensitized CuFe2O4 is an effective hybrid material for building the photocathode of a PEC cell for solar water splitting to produce H2.

  19. REGIOSELECTIVE OXIDATIONS OF EQUILENIN DERIVATIVES CATALYZED BY A RHODIUM (III) PORPHYRIN COMPLEX-CONTRAST WITH THE MANGANESE (III) PORPHYRIN. (R826653)

    Science.gov (United States)

    AbstractEquilenin acetate and dihydroequilenin acetate were oxidized with iodosobenzene and a rhodium(III) porphyrin catalyst. The selectivity of the reactions differs from that with the corresponding Mn(III) catalyst, or from that of free radical chain oxidation.

  20. Manganese

    Science.gov (United States)

    ... research suggests that taking a specific product (7-Keto Naturalean) containing manganese, 7-oxo-DHEA, L-tyrosine, ... can absorb.Milk proteinAdding milk protein to the diet might increase the amount of manganese the body ...

  1. Manganese

    International Nuclear Information System (INIS)

    Fayziev, A.R.

    2002-01-01

    Present article is devoted to manganese content in fluoride. The manganese content of some geologic deposits of Tajikistan was determined by means of chemical analysis. The mono mineral samples of fluorite of 5 geologic deposits of various mineralogical and genetic type was studied. The manganese content in fluorite of geologic deposits of various mineralogical and genetic type was defined.

  2. Isolation of an oxomanganese(V) porphyrin intermediate in the reaction of a manganese(III) porphyrin complex and H2O2 in aqueous solution.

    Science.gov (United States)

    Nam, Wonwoo; Kim, Inwoo; Lim, Mi Hee; Choi, Hye Jin; Lee, Je Seung; Jang, Ho G

    2002-05-03

    The reaction of [Mn(TF(4)TMAP)](CF(3)SO(3))(5) (TF(4)TMAP=meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H(2)O(2) (2 equiv) at pH 10.5 and 0 degrees C yielded an oxomanganese(V) porphyrin complex 1 in aqueous solution, whereas an oxomanganese(IV) porphyrin complex 2 was generated in the reactions of tert-alkyl hydroperoxides such as tert-butyl hydroperoxide and 2-methyl-1-phenyl-2-propyl hydroperoxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H(2) (18)O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF(4)TMAP)](5+) with various oxidants in the pH range 3-11, the O-O bond cleavage of hydroperoxides was found to be sensitive to the hydroperoxide substituent and the pH of the reaction solution. Whereas the O-O bond of hydroperoxides containing an electron-donating tert-alkyl group is cleaved homolytically, an electron-withdrawing substituent such as an acyl group in m-chloroperoxybenzoic acid (m-CPBA) facilitates O-O bond heterolysis. The mechanism of the O-O bond cleavage of H(2)O(2) depends on the pH of the reaction solution: O-O bond homolysis prevails at low pH and O-O bond heterolysis becomes a predominant pathway at high pH. The effect of pH on (18)O incorporation from H(2) (18)O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF(4)TMAP)](5+) and KHSO(5) in buffered H(2) (18)O solutions. A high proportion of (18)O was incorporated into the CBZ-10,11-oxide product at all pH values but this proportion was not affected significantly by the pH of the reaction solution.

  3. Manganese

    Science.gov (United States)

    Cannon, William F.; Kimball, Bryn E.; Corathers, Lisa A.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Manganese is an essential element for modern industrial societies. Its principal use is in steelmaking, where it serves as a purifying agent in iron-ore refining and as an alloy that converts iron into steel. Although the amount of manganese consumed to make a ton of steel is small, ranging from 6 to 9 kilograms, it is an irreplaceable component in the production of this fundamental material. The United States has been totally reliant on imports of manganese for many decades and will continue to be so for at least the near future. There are no domestic reserves, and although some large low-grade resources are known, they are far inferior to manganese ores readily available on the international market. World reserves of manganese are about 630 million metric tons, and annual global consumption is about 16 million metric tons. Current reserves are adequate to meet global demand for several decades. Global resources in traditional land-based deposits, including both reserves and rocks sufficiently enriched in manganese to be ores in the future, are much larger, at about 17 billion metric tons. Manganese resources in seabed deposits of ferromanganese nodules and crusts are larger than those on land and have not been fully quantified. No production from seabed deposits has yet been done, but current research and development activities are substantial and may bring parts of these seabed resources into production in the future. The advent of economically successful seabed mining could substantially alter the current scenario of manganese supply by providing a large new source of manganese in addition to traditional land-based deposits.From a purely geologic perspective, there is no global shortage of proven ores and potential new ores that could be developed from the vast tonnage of identified resources. Reserves and resources are very unevenly distributed, however. The Kalahari manganese district in South Africa contains 70 percent of the world’s identified resources

  4. Novel Manganese-Porphyrin Superoxide Dismutase-Mimetic Widens the Therapeutic Margin in a Preclinical Head and Neck Cancer Model

    Energy Technology Data Exchange (ETDEWEB)

    Ashcraft, Kathleen A. [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina (United States); Boss, Mary-Keara [Department of Molecular Biomedical Sciences, North Carolina State College of Veterinary Medicine, Raleigh, North Carolina (United States); Tovmasyan, Artak [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina (United States); Roy Choudhury, Kingshuk [Department of Biostatistics and Bioinformatics, Duke University, Durham, North Carolina (United States); Fontanella, Andrew N. [Department of Biomedical Engineering, Duke University, Durham, North Carolina (United States); Young, Kenneth H.; Palmer, Gregory M.; Birer, Samuel R.; Landon, Chelsea D.; Park, Won [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina (United States); Das, Shiva K. [Physics and Computing Division, Department of Radiation Oncology, University of North Carolina School of Medicine, Chapel Hill, North Carolina (United States); Weitner, Tin [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina (United States); Sheng, Huaxin; Warner, David S. [Department of Anesthesiology, Duke University Medical Center, Durham, North Carolina (United States); Brizel, David M. [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina (United States); Department of Surgery, Duke University Medical Center, Durham, North Carolina (United States); Spasojevic, Ivan [Department of Medicine, Duke University Medical Center, Durham, North Carolina (United States); Batinic-Haberle, Ines [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina (United States); Dewhirst, Mark W., E-mail: mark.dewhirst@duke.edu [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina (United States); Department of Biostatistics and Bioinformatics, Duke University, Durham, North Carolina (United States)

    2015-11-15

    Purpose: To test the effects of a novel Mn porphyrin oxidative stress modifier, Mn(III) meso-tetrakis(N-n-butoxyethylpyridinium-2-yl)porphyrin (MnBuOE), for its radioprotective and radiosensitizing properties in normal tissue versus tumor, respectively. Methods and Materials: Murine oral mucosa and salivary glands were treated with a range of radiation doses with or without MnBuOE to establish the dose–effect curves for mucositis and xerostomia. Radiation injury was quantified by intravital near-infrared imaging of cathepsin activity, assessment of salivation, and histologic analysis. To evaluate effects of MnBuOE on the tumor radiation response, we administered the drug as an adjuvant to fractionated radiation of FaDu xenografts. Again, a range of radiation therapy (RT) doses was administered to establish the radiation dose–effect curve. The 50% tumor control dose values with or without MnBuOE and dose-modifying factor were determined. Results: MnBuOE protected normal tissue by reducing RT-mediated mucositis, xerostomia, and fibrosis. The dose-modifying factor for protection against xerostomia was 0.77. In contrast, MnBuOE increased tumor local control rates compared with controls. The dose-modifying factor, based on the ratio of 50% tumor control dose values, was 1.3. Immunohistochemistry showed that MnBuOE-treated tumors exhibited a significant influx of M1 tumor-associated macrophages, which provides mechanistic insight into its radiosensitizing effects in tumors. Conclusions: MnBuOE widens the therapeutic margin by decreasing the dose of radiation required to control tumor, while increasing normal tissue resistance to RT-mediated injury. This is the first study to quantitatively demonstrate the magnitude of a single drug's ability to radioprotect normal tissue while radiosensitizing tumor.

  5. Anchoring alpha-manganese oxide nanocrystallites on multi-walled carbon nanotubes as electrode materials for supercapacitor

    Energy Technology Data Exchange (ETDEWEB)

    Li Li; Qin Zongyi, E-mail: phqin@dhu.edu.cn; Wang Lingfeng; Liu Hongjin; Zhu Meifang [Donghua University, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering (China)

    2010-09-15

    The partial coverage of manganese oxide (MnO{sub 2}) particles was achieved on the surfaces of multi-walled carbon nanotubes (MWCNTs) through a facile hydrothermal process. These particles were demonstrated to be alpha-manganese dioxide ({alpha}-MnO{sub 2}) nanocrystallites, and exhibited the appearance of the whisker-shaped crystals with the length of 80-100 nm. In such a configuration, the uncovered CNTs in the nanocomposite acted as a good conductive pathway and the whisker-shaped MnO{sub 2} nanocrystallites efficiently increased the contact of the electrolyte with the active materials. Thus, the highest specific capacitance of 550 F g{sup -1} was achieved using the resulting nanocomposites as the supercapacitor electrode. In addition, the enhancement of the capacity retention was observed, with the nanocomposite losing only 10% of the maximum capacity after 1,500 cycles.

  6. Anchoring alpha-manganese oxide nanocrystallites on multi-walled carbon nanotubes as electrode materials for supercapacitor

    Science.gov (United States)

    Li, Li; Qin, Zong-Yi; Wang, Ling-Feng; Liu, Hong-Jin; Zhu, Mei-Fang

    2010-09-01

    The partial coverage of manganese oxide (MnO2) particles was achieved on the surfaces of multi-walled carbon nanotubes (MWCNTs) through a facile hydrothermal process. These particles were demonstrated to be alpha-manganese dioxide (α-MnO2) nanocrystallites, and exhibited the appearance of the whisker-shaped crystals with the length of 80-100 nm. In such a configuration, the uncovered CNTs in the nanocomposite acted as a good conductive pathway and the whisker-shaped MnO2 nanocrystallites efficiently increased the contact of the electrolyte with the active materials. Thus, the highest specific capacitance of 550 F g-1 was achieved using the resulting nanocomposites as the supercapacitor electrode. In addition, the enhancement of the capacity retention was observed, with the nanocomposite losing only 10% of the maximum capacity after 1,500 cycles.

  7. One-pot synthesis of gold nanoparticles using tetradentate porphyrins

    International Nuclear Information System (INIS)

    Canitez, Fatma K.; Yavuz, Mustafa S.; Ozturk, Ramazan

    2011-01-01

    In this study, the meso-tetra (p-hydroxyphenyl) porphyrin and meso-tetra (m-hydroxyphenyl) porphyrin were coated on to gold nanoparticles (AuNPs) via thioacetate anchors which easily dissociate to form S–Au bonds. 4-tert-butyl phenyl thioacetate-AuNPs were prepared and used as a monodentate passivant to control the size of the tetradentate porphyrin-AuNPs. The porphyrin-coated AuNPs were characterized by UV–Vis, TEM, XRD, and XPS analyses. The tetradentate porphyrin-AuNPs size is within a range of 5–15 nm in diameter with exotic shapes. The plausible network formation for AuNP-p-TPP-SAc and the capping structure of the AuNP-m-TPP-SAc have been suggested.

  8. Novel polar sedimentary porphyrins

    Science.gov (United States)

    Prowse, W. G.; Maxwell, J. R.

    1989-11-01

    Two polar nickel porphyrins in Messel oil shale are shown to be the C 32 and C 30 components IIIa,b. In the sample examined, component IIIa is by far the major porphyrin alcohol and is present in an abundance similar to that of the major nickel alkyl porphyrin. These primary alcohols, which do not appear to be artifacts, are structurally related to alkyl porphyrins reported previously in Serpiano oil shale.

  9. Inverted porphyrins and expanded porphyrins: An overview

    Indian Academy of Sciences (India)

    Unknown

    More recently, synthetic porphyrins and porphyrin-like macrocycles have ... one of the meso carbons resulting in the formation of corroles; – (d) Isomeric ... spectroscopic, chemical and physical properties, which can find applications in ..... diol 55 under TFA catalysis yielding 20–28% yield of expected rubyrins 85 and 86 as.

  10. Fabrication of manganese dioxide nanoplates anchoring on biomass-derived cross-linked carbon nanosheets for high-performance asymmetric supercapacitors

    Science.gov (United States)

    Li, Yiju; Yu, Neng; Yan, Peng; Li, Yuguang; Zhou, Xuemei; Chen, Shuangling; Wang, Guiling; Wei, Tong; Fan, Zhuangjun

    2015-12-01

    In this paper, MnO2 nanoplates loading on biomass-derived cross-linked carbon nanosheets have been prepared by a two-step synthesis. At first, the cross-linked carbon nanosheets derived from willow catkin are synthesized by one-step pyrolysis and activation method, then the MnO2 anchored cross-linked carbon nanosheets is prepared via in-situ hydrothermal deposition. The asymmetric supercapacitor with terrific energy and power density is assembled by employing the MnO2 anchored cross-linked carbon nanosheets as the positive electrode and the cross-linked carbon nanosheets as the negative electrode in a 1 M Na2SO4 electrolyte. The asymmetric supercapacitor displays a high energy density of 23.6 Wh kg-1 at a power density of 188.8 W kg-1 within a wide voltage rage of 0-1.9 V. In addition, the asymmetric supercapacitor exhibits excellent cycling stability with only 1.4% capacitance loss after 10000 cycles at 1 A g-1. These discoveries open up the prospect of biomass/biowaste derived carbon-based composites for high-voltage asymmetric supercapacitors with superb energy and power density performance.

  11. Soluble porphyrin polymers

    Science.gov (United States)

    Gust, Jr., John Devens; Liddell, Paul Anthony

    2015-07-07

    Porphyrin polymers of Structure 1, where n is an integer (e.g., 1, 2, 3, 4, 5, or greater) ##STR00001## are synthesized by the method shown in FIGS. 2A and 2B. The porphyrin polymers of Structure 1 are soluble in organic solvents such as 2-MeTHF and the like, and can be synthesized in bulk (i.e., in processes other than electropolymerization). These porphyrin polymers have long excited state lifetimes, making the material suitable as an organic semiconductor for organic electronic devices including transistors and memories, as well as solar cells, sensors, light-emitting devices, and other opto-electronic devices.

  12. Porphyrins - blood test

    Science.gov (United States)

    ... page: //medlineplus.gov/ency/article/003372.htm Porphyrins blood test To use the sharing features on this page, ... blood or the urine . This article discusses the blood test. How the Test is Performed A blood sample ...

  13. Push-pull quinoidal porphyrins.

    Science.gov (United States)

    Smith, Martin J; Blake, Iain M; Clegg, William; Anderson, Harry L

    2018-05-01

    A family of push-pull quinoidal porphyrin monomers has been prepared from a meso-formyl porphyrin by bromination, thioacetal formation, palladium-catalyzed coupling with malononitrile and oxidation with DDQ. Attempts at extending this synthesis to a push-pull quinoidal/cumulenic porphyrin dimer were not successful. The crystal structures of the quinoidal porphyrins indicate that there is no significant contribution from singlet biradical or zwitterionic resonance forms. The crystal structure of an ethyne-linked porphyrin dimer shows that the torsion angle between the porphyrin units is only about 3°, in keeping with crystallographic results on related compounds, but contrasting with the torsion angle of about 35° predicted by computational studies. The free-base quinoidal porphyrin monomers form tightly π-stacked layer structures, despite their curved geometries and bulky aryl substituents.

  14. Synthetic Porphyrins and Metalloporphyrins

    Science.gov (United States)

    1976-12-10

    disease syndromes , drug metabolism and cancer. Porphyrins and metalloporphyrins such as tetraphenylporphine sulfonate and hema- toporphyrin have been found...267(1941). 34. A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour and L. Korsakoff , J. Org. Chem., 32, 476(1967). 35. H. W

  15. Synthesis and characterization of a novel meso-porphyrin and its metallo derivatives

    Directory of Open Access Journals (Sweden)

    Paulo Cesar Bega

    2014-02-01

    Full Text Available There has been a growing interest in the properties of substituted meso-tetraarylporphyrins and metallo porphyrins as catalysts for oxidation of hydrocarbons, oxygen detection, among others. This work describes the synthesis of a new porphyrin, 5,10,15,20-tetrakis(4-butoxy-3-methoxyphenylporphyrin, and its metallo complexes. Herein it was used a readily available reactant, vanillin, as starting material which was submitted to alkylation with n-bromobutane affording the synthetic precursor. The desired porphyrin was obtained by reacting the O-alkylated aldehyde with pyrrole in the presence of propionic acid (Alder-Longo method. The purified porphyrin was then subjected to the metallation process using iron (II and manganese (II salts. The synthesized compounds were characterized by IR, UV-Vis, NMR and EPR spectroscopy.

  16. Porphyrins at interfaces

    Science.gov (United States)

    Auwärter, Willi; Écija, David; Klappenberger, Florian; Barth, Johannes V.

    2015-02-01

    Porphyrins and other tetrapyrrole macrocycles possess an impressive variety of functional properties that have been exploited in natural and artificial systems. Different metal centres incorporated within the tetradentate ligand are key for achieving and regulating vital processes, including reversible axial ligation of adducts, electron transfer, light-harvesting and catalytic transformations. Tailored substituents optimize their performance, dictating their arrangement in specific environments and mediating the assembly of molecular nanoarchitectures. Here we review the current understanding of these species at well-defined interfaces, disclosing exquisite insights into their structural and chemical properties, and also discussing methods by which to manipulate their intramolecular and organizational features. The distinct characteristics arising from the interfacial confinement offer intriguing prospects for molecular science and advanced materials. We assess the role of surface interactions with respect to electronic and physicochemical characteristics, and describe in situ metallation pathways, molecular magnetism, rotation and switching. The engineering of nanostructures, organized layers, interfacial hybrid and bio-inspired systems is also addressed.

  17. Studies of interactions of porphyrins with transfer RNA by high-resolution NMR

    International Nuclear Information System (INIS)

    Birdsall, W.J.; Lehigh Univ., Bethlehem, PA; Anderson, W.R. Jr; Foster, N.

    1989-01-01

    The interactions of tetra-4N-methulpyridyl porphyrin and its zinc (II), copper (II) and manganese (III) complexes with brewer's yeast type V phenylalanine specific tRNA have been evaluated by high-resolution NMR. Differences in chemical shifts have been noted for thre proton resonances in response to the presence of small quantities of the fre base and the zinc and copper complexes. The protons giving rise to these signals are located on bases T54 and psi55, both of which are involved in the primary intraloop and interloop hydroen bonds that hold the D and TpsiC loops together in the tertiary structure. In addition, broadening of specific resonances due to hydrogen bonding protons in the D stem at low ratios of porphyrin to tRNA indicates that the association of porphyrins increases the rate of imino proton exchange. The titration of the tRNA with the manganese (III) complex did not eveal shifts or spcific broadening comparable to the other porpyrins at low ratios. The changes induced in the NMR spectrum of tNA by porphyrins define their site of interaction with the polynucleotide. This site, at the outside of the elbow-bend in the tRNA 'L', is different from the locus of binding in tRNA for other classical DNA intercalators. Furthermore, a new mode of binding may be involved that is neither intercalative nor simply electrostatic. (author). 36 refs.; 4 figs

  18. A cross-linked manganese porphyrin as highly efficient ...

    Indian Academy of Sciences (India)

    The catalyst is found to oxidize the alkenes selectively and it is not destroyed even 5% in ... the catalysts have been prepared by covalent approach. These materials are ... reagents under argon or obtained as dehydrated reagent from Merck's ...

  19. Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

    KAUST Repository

    Diev, Vyacheslav V.; Schlenker, Cody W.; Hanson, Kenneth; Zhong, Qiwen; Zimmerman, Jeramy D.; Forrest, Stephen R.; Thompson, Mark E.

    2012-01-01

    A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.

  20. Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

    KAUST Repository

    Diev, Vyacheslav V.

    2012-01-06

    A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.

  1. The Ogden Anchor.

    Science.gov (United States)

    Knudson, W E; Cerniglia, M W; Carro, A

    1998-06-01

    Many procedures performed by podiatric surgeons today require the use of a soft-tissue anchoring device. In recent years, many new anchoring devices have become available for use in the foot and ankle. The authors introduce a new soft-tissue anchoring device that has yet to be described in the podiatric literature and present two cases in which the new anchor was used.

  2. Manganese Catalyzed C–H Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Groves, John T.

    2015-06-16

    The remarkable aliphatic C–H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon–halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C–H bonds to C–Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L–MnV$=$O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn–F fluorine source, effecting carbon–fluorine bond

  3. Engineering of Porphyrin Molecules for Use as Effective Cathode Interfacial Modifiers in Organic Solar Cells of Enhanced Efficiency and Stability.

    Science.gov (United States)

    Tountas, Marinos; Verykios, Apostolis; Polydorou, Ermioni; Kaltzoglou, Andreas; Soultati, Anastasia; Balis, Nikolaos; Angaridis, Panagiotis A; Papadakis, Michael; Nikolaou, Vasilis; Auras, Florian; Palilis, Leonidas C; Tsikritzis, Dimitris; Evangelou, Evangelos K; Gardelis, Spyros; Koutsoureli, Matroni; Papaioannou, George; Petsalakis, Ioannis D; Kennou, Stella; Davazoglou, Dimitris; Argitis, Panagiotis; Falaras, Polycarpos; Coutsolelos, Athanassios G; Vasilopoulou, Maria

    2018-06-06

    In the present work, we effectively modify the TiO 2 electron transport layer of organic solar cells with an inverted architecture using appropriately engineered porphyrin molecules. The results show that the optimized porphyrin modifier bearing two carboxylic acids as the anchoring groups and a triazine electron-withdrawing spacer significantly reduces the work function of TiO 2 , thereby reducing the electron extraction barrier. Moreover, the lower surface energy of the porphyrin-modified substrate results in better physical compatibility between the latter and the photoactive blend. Upon employing porphyrin-modified TiO 2 electron transport layers in PTB7:PC 71 BM-based organic solar cells we obtained an improved average power conversion efficiency up to 8.73%. Importantly, porphyrin modification significantly increased the lifetime of the devices, which retained 80% of their initial efficiency after 500 h of storage in the dark. Because of its simplicity and efficacy, this approach should give tantalizing glimpses and generate an impact into the potential of porphyrins to facilitate electron transfer in organic solar cells and related devices.

  4. Supramolecular Allosteric Cofacial Porphyrin Complexes

    International Nuclear Information System (INIS)

    Oliveri, Christopher G.; Gianneschi, Nathan C.; Nguyen, Son Binh T.; Mirkin, Chad A.; Stern, Charlotte L.; Wawrzak, Zdzislaw; Pink, Maren

    2008-01-01

    Nature routinely uses cooperative interactions to regulate cellular activity. For years, chemists have designed synthetic systems that aim toward harnessing the reactivity common to natural biological systems. By learning how to control these interactions in situ, one begins to allow for the preparation of man-made biomimetic systems that can efficiently mimic the interactions found in Nature. To this end, we have designed a synthetic protocol for the preparation of flexible metal-directed supramolecular cofacial porphyrin complexes which are readily obtained in greater than 90% yield through the use of new hemilabile porphyrin ligands with bifunctional ether-phosphine or thioether-phosphine substituents at the 5 and 15 positions on the porphyrin ring. The resulting architectures contain two hemilabile ligand-metal domains (Rh I or Cu I sites) and two cofacially aligned porphyrins (Zn II sites), offering orthogonal functionalities and allowing these multimetallic complexes to exist in two states, 'condensed' or 'open'. Combining the ether-phosphine ligand with the appropriate Rh I or Cu I transition-metal precursors results in 'open' macrocyclic products. In contrast, reacting the thioether-phosphine ligand with RhI or CuI precursors yields condensed structures that can be converted into their 'open' macrocyclic forms via introduction of additional ancillary ligands. The change in cavity size that occurs allows these structures to function as allosteric catalysts for the acyl transfer reaction between X-pyridylcarbinol (where X = 2, 3, or 4) and 1-acetylimidazole. For 3- and 4-pyridylcarbinol, the 'open' macrocycle accelerates the acyl transfer reaction more than the condensed analogue and significantly more than the porphyrin monomer. In contrast, an allosteric effect was not observed for 2-pyridylcarbinol, which is expected to be a weaker binder and is unfavorably constrained inside the macrocyclic cavity.

  5. Respiratory Monitoring by Porphyrin Modified Quartz Crystal Microbalance Sensors

    Directory of Open Access Journals (Sweden)

    Seung-Woo Lee

    2011-01-01

    Full Text Available A respiratory monitoring system based on a quartz crystal microbalance (QCM sensor with a functional film was designed and investigated. Porphyrins 5,10,15,20-tetrakis-(4-sulfophenyl-21H,23H-porphine (TSPP and 5,10,15,20-tetrakis-(4-sulfophenyl-21H, 23H-porphine manganese (III chloride (MnTSPP used as sensitive elements were assembled with a poly(diallyldimethyl ammonium chloride (PDDA. Films were deposited on the QCM resonators using layer-by-layer method in order to develop the sensor. The developed system, in which the sensor response reflects lung movements, was able to track human respiration providing respiratory rate (RR and respiratory pattern (RP. The sensor system was tested on healthy volunteers to compare RPs and calculate RRs. The operation principle of the proposed system is based on the fast adsorption/desorption behavior of water originated from human breath into the sensor films deposited on the QCM electrode.

  6. Bis-Porphyrin Racks with Space-Separated Co-Planar Porphyrin Rings

    Directory of Open Access Journals (Sweden)

    Martin R. Johnston

    2001-03-01

    Full Text Available A porphyrin appended norbornenyl building block 8 has been isolated and coupled, using a 1,3-dipolar ACE reaction, to yield bis-porphyrin compounds in which the porphyrin moietes are angled upward relative to the norbornane backbone.

  7. Electropolymerized supramolecular tetraruthenated porphyrins applied as a voltammetric sensor

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Monize M. da; Ribeiro, Gabriel H.; Faria, Anizio M. de; Bogado, Andre L.; Dinelli, Luis R., E-mail: dinelli@pontal.ufu.br [Universidade Federal de Uberlandia (UFU), Ituiutaba, MG (Brazil). Faculdade de Ciencias Integradas do Pontal; Batista, Alzir A. [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica

    2013-11-15

    Porphyrin 5,10,15,20-Tetra(4-pyridyl)manganese(III), [Mn-TPyP(H{sub 2}O){sub 2}]PF{sub 6}, and electropolymerized supramolecular porphyrins (ESP), {l_brace}Mn-TPyP(H{sub 2}O){sub 2}[RuCl{sub 3}(dppb)]{sub 4}{r_brace}PF{sub 6} (dppb = 1,4-bis(diphenylphosphine)butane), were synthesized and characterized. A thin solid film of ESP was obtained on a glass carbon electrode surface by a cyclic voltammetry method. The peak current increased with the number of voltammetric cycles, which shows a typical behavior of the species being adsorbed on the surface of the electrode. Cyclic voltammetry was also employed for acetaminophen quantification using an ESP modified electrode. The modified electrode shows a linear relationship between the anodic peak current and the concentration of acetaminophen (in the rage 0.05 to 0.7 mmol L{sup -1}. The performance of the modified electrode was verified by the determination of acetaminophen in a commercial pharmaceutical product and the results were in good agreement with those obtained by a control HPLC method. (author)

  8. Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

    Directory of Open Access Journals (Sweden)

    Mingyan Wang

    2017-07-01

    Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

  9. Porphyrin coordination polymer nanospheres and nanorods

    Science.gov (United States)

    Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

    2012-12-04

    A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

  10. Susceptibility to anchoring effects

    Directory of Open Access Journals (Sweden)

    Todd McElroy

    2007-02-01

    Full Text Available Previous research on anchoring has shown this heuristic to be a very robust psychological phenomenon ubiquitous across many domains of human judgment and decision-making. Despite the prevalence of anchoring effects, researchers have only recently begun to investigate the underlying factors responsible for how and in what ways a person is susceptible to them. This paper examines how one such factor, the Big-Five personality trait of openness-to-experience, influences the effect of previously presented anchors on participants' judgments. Our findings indicate that participants high in openness-to-experience were significantly more influenced by anchoring cues relative to participants low in this trait. These findings were consistent across two different types of anchoring tasks providing convergent evidence for our hypothesis.

  11. A novel self-assembly with zinc porphyrin coordination polymer for enhanced photocurrent conversion in supramolecular solar cells

    International Nuclear Information System (INIS)

    Cao, Jing; Liu, Jia-Cheng; Deng, Wen-Ting; Li, Ren-Zhi; Jin, Neng-Zhi

    2013-01-01

    Graphical abstract: An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells. - Highlights: • A novel assembly with acetohydrazide porphyrin coordination polymer. • The assembly based on porphyrin is prepared as parallel sample. • Coordination polymer-based assembly shows enhanced photoelectronic behavior. • A series of different organic acid ligands as anchoring groups are prepared. - Abstract: In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO 2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO 2 electrode surface in supramolecular solar cells

  12. Computational screening of functionalized zinc porphyrins for dye sensitized solar cells

    DEFF Research Database (Denmark)

    Ørnsø, Kristian Baruël; García Lastra, Juan Maria; Thygesen, Kristian Sommer

    2013-01-01

    separation, and high output voltage. Here we demonstrate an extensive computational screening of zinc porphyrins functionalized with electron donating side groups and electron accepting anchoring groups. The trends in frontier energy levels versus side groups are analyzed and a no-loss DSSC level alignment...... quality is estimated. Out of the initial 1029 molecules, we find around 50 candidates with level alignment qualities within 5% of the optimal limit. We show that the level alignment of five zinc porphyrin dyes which were recently used in DSSCs with high efficiencies can be further improved by simple side......An efficient dye sensitized solar cell (DSSC) is one possible solution to meet the world's rapidly increasing energy demands and associated climate challenges. This requires inexpensive and stable dyes with well-positioned frontier energy levels for maximal solar absorption, efficient charge...

  13. Porphyrin-based Photocatalytic Nanolithography

    Energy Technology Data Exchange (ETDEWEB)

    Bearinger, J P; Stone, G; Dugan, L C; Dasher, B E; Stockton, C; Conway, J W; Kuenzler, T; Hubbell, J A

    2009-06-08

    Nanoarray fabrication is a multidisciplinary endeavor encompassing materials science, chemical engineering and biology. We form nanoarrays via a new technique, porphyrin-based photocatalytic nanolithography (PCNL). The nanoarrays, with controlled features as small as 200 nm, exhibit regularly ordered patterns and may be appropriate for (a) rapid and parallel proteomic screening of immobilized biomolecules, (b) protein-protein interactions and/or (c) biophysical and molecular biology studies involving spatially dictated ligand placement. We demonstrate protein immobilization utilizing nanoarrays fabricated via PCNL on silicon substrates, where the immobilized proteins are surrounded by a non-fouling polymer background.

  14. Novel drug delivery strategies for porphyrins and porphyrin precursors

    Science.gov (United States)

    Morrow, D. I. J.; Donnelly, R. F.

    2009-06-01

    superficial lesions, such as actinic keratosis. In addition, photodynamic antimicrobial chemotherapy (PACT) is attracting increasing interest for the treatment of infection. However, delivery strategies for topical PDT and PACT are still based on application of rather simplistic cream and solution formulations, with little consideration given to thermodynamics, targeting or the physicochemical properties of the active agent. Purpose-designed dosage forms for topical delivery of aminolevulinic acid or its esters include creams containing penetration enhancers and/or iron chelators, pressure sensitive patches and bioadhesive patches. Such systems aim to enhance drug delivery across the stratum corneum and keratinised debris overlying neoplastic lesions and improve subsequent protoporphyrin IX (PpIX) production. The alternative to using porphyrin precursors is the use of pre-formed photosensitisers. However, owing to their relatively high molecular weights, conventional topical application is not appropriate. Innovative strategies, such as the use of needle-free injections and microneedle arrays, bypass the stratum corneum, enabling rapid and targeted delivery not only porphyrin precursors but also pre-formed photosensitisers. This presentation will review drug delivery work published to date in the fields of PDT and PACT. In addition, the benefits of employing the latest advances in pharmaceutical technology will be highlighted.

  15. Optimizing porphyrins for dye sensitized solar cells using large-scale ab initio calculations

    DEFF Research Database (Denmark)

    Ørnsø, Kristian Baruël; Pedersen, Christian S.; García Lastra, Juan Maria

    2014-01-01

    different side and anchoring groups. Based on the calculated frontier orbital energies and optical gaps we quantify the energy level alignment with the TiO2 conduction band and different redox mediators. An analysis of the energy level-structure relationship reveals a significant structural diversity among...... the dyes with the highest level alignment quality, demonstrating the large degree of flexibility in porphyrin dye design. As a specific example of dye optimization, we show that the level alignment of the high efficiency record dye YD2-o-C8 [Yella et al., Science, 2011, 334, 629-634] can be significantly...

  16. De novo design and engineering of functional metal and porphyrin-binding protein domains

    Science.gov (United States)

    Everson, Bernard H.

    In this work, I describe an approach to the rational, iterative design and characterization of two functional cofactor-binding protein domains. First, a hybrid computational/experimental method was developed with the aim of algorithmically generating a suite of porphyrin-binding protein sequences with minimal mutual sequence information. This method was explored by generating libraries of sequences, which were then expressed and evaluated for function. One successful sequence is shown to bind a variety of porphyrin-like cofactors, and exhibits light- activated electron transfer in mixed hemin:chlorin e6 and hemin:Zn(II)-protoporphyrin IX complexes. These results imply that many sophisticated functions such as cofactor binding and electron transfer require only a very small number of residue positions in a protein sequence to be fixed. Net charge and hydrophobic content are important in determining protein solubility and stability. Accordingly, rational modifications were made to the aforementioned design procedure in order to improve its overall success rate. The effects of these modifications are explored using two `next-generation' sequence libraries, which were separately expressed and evaluated. Particular modifications to these design parameters are demonstrated to effectively double the purification success rate of the procedure. Finally, I describe the redesign of the artificial di-iron protein DF2 into CDM13, a single chain di-Manganese four-helix bundle. CDM13 acts as a functional model of natural manganese catalase, exhibiting a kcat of 0.08s-1 under steady-state conditions. The bound manganese cofactors have a reduction potential of +805 mV vs NHE, which is too high for efficient dismutation of hydrogen peroxide. These results indicate that as a high-potential manganese complex, CDM13 may represent a promising first step toward a polypeptide model of the Oxygen Evolving Complex of the photosynthetic enzyme Photosystem II.

  17. Photoexcited iron porphyrin as biomimetic catalysts

    International Nuclear Information System (INIS)

    Bartocci, C.; Maldotti, A.; Varani, G.; Consiglio Nazionale delle Ricerche, Ferrara

    1996-01-01

    Photoexcited iron porphyrins can be of some interest in both fine and industrial chemistry in view of the preparation of new efficient biomimetic catalysts, working with high selectivity under mild temperature and pressure

  18. Magnetic interactions in iron (III) porphyrin chlorides

    International Nuclear Information System (INIS)

    Ernst, J.; Subramanian, Japyesan; Fuhrhop, J.H.

    1977-01-01

    Intermolecular exchange interactions in iron(III) porphyrin chlorides (porphyrin = OEP, proto, TPP) have been studied by X-ray structure, EPR and magnetic susceptibility studies. The crystal structure of Fe(III)OEP-Cl was found to be different from that of the other two. Different types of exchange broadened EPR-spectra are obtained which are attributable to the arrangement in the crystals. The EPR results correlate well with magnetic susceptibility data. (orig.) [de

  19. Urinary porphyrin excretion in hepatitis C infection

    OpenAIRE

    Vogeser, Michael; Jacob, Karl; Zachoval, Reinhart

    1999-01-01

    A high prevalence of hepatitis C virus infection in porphyria cutanea tarda in some populations suggests a close link between viral hepatitis and alteration of porphyrin metabolism. Moreover, there is evidence of a role of porphyrinopathies in hepatocarcinogenesis. The aim of our study was to obtain data on the prevalence and patterns of heme metabolism alterations in patients with chronic hepatitis C virus infection. Urinary porphyrin excretion was prospectively studied in 100 consecutive ou...

  20. Electron injection dynamics in high-potential porphyrin photoanodes.

    Science.gov (United States)

    Milot, Rebecca L; Schmuttenmaer, Charles A

    2015-05-19

    There is a growing need to utilize carbon neutral energy sources, and it is well known that solar energy can easily satisfy all of humanity's requirements. In order to make solar energy a viable alternative to fossil fuels, the problem of intermittency must be solved. Batteries and supercapacitors are an area of active research, but they currently have relatively low energy-to-mass storage capacity. An alternative and very promising possibility is to store energy in chemical bonds, or make a solar fuel. The process of making solar fuel is not new, since photosynthesis has been occurring on earth for about 3 billion years. In order to produce any fuel, protons and electrons must be harvested from a species in its oxidized form. Photosynthesis uses the only viable source of electrons and protons on the scale needed for global energy demands: water. Because artificial photosynthesis is a lofty goal, water oxidation, which is a crucial step in the process, has been the initial focus. This Account provides an overview of how terahertz spectroscopy is used to study electron injection, highlights trends from previously published reports, and concludes with a future outlook. It begins by exploring similarities and differences between dye-sensitized solar cells (DSSCs) for producing electricity and a putative device for splitting water and producing a solar fuel. It then identifies two important problems encountered when adapting DSSC technology to water oxidation-improper energy matching between sensitizer energy levels with the potential for water oxidation and the instability of common anchoring groups in water-and discusses steps to address them. Emphasis is placed on electron injection from sensitizers to metal oxides because this process is the initial step in charge transport. Both the rate and efficiency of electron injection are analyzed on a sub-picosecond time scale using time-resolved terahertz spectroscopy (TRTS). Bio-inspired pentafluorophenyl porphyrins are

  1. Photosensitization of liposomes by porphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Grossweiner, L I; Goyal, G C

    1984-01-01

    Lipid peroxidation was photosensitized in egg phosphatidylcholine (EPC) liposomes by hematoporphyrin (HP), hematoporphyrin derivative (HpD) and uroporphyrin I (Uro-I). Photosensitization by HP was type II via singlet oxygen (/sup 1/O/sub 2/) for the monomeric and dimeric states and type I for aggregated HP. Uro-I was an efficient type II /sup 1/O/sub 2/ photosensitizer. The HpD fraction enriched in the active biological component (HpD-A) was a type II /sup 1/O/sub 2/ photosensitizer at high and low concentrations. The spectral differences between HpD-A in buffer and solubilized in small EPC liposomes are attributed to a conformation change of a key dimer constituent from a folded to a planar geometry. The implications of the results for the action mechanism in photoradiation therapy of tumors with these porphyrins are discussed. 73 references, 1 figure, 5 tables.

  2. Electron Transport through Porphyrin Molecular Junctions

    Science.gov (United States)

    Zhou, Qi

    The goal of this work is to study the properties that would affect the electron transport through a porphyrin molecular junction. This work contributes to the field of electron transport in molecular junctions in the following 3 aspects. First of all, by carrying out experiments comparing the conductance of the iron (III) porphyrin (protected) and the free base porphyrin (protected), it is confirmed that the molecular energy level broadening and shifting occurs for porphyrin molecules when coupled with the metal electrodes, and this level broadening and shifting plays an important role in the electron transport through molecular junctions. Secondly, by carrying out an in-situ deprotection of the acetyl-protected free base porphyrin molecules, it is found out that the presence of acetyl groups reduces the conductance. Thirdly, by incorporating the Matrix-assisted laser desorption/ionization (MALDI) spectrum and the in-situ deprotection prior to formation of molecular junctions, it allows a more precise understanding of the molecules involved in the formation of molecular junctions, and therefore allows an accurate analysis of the conductance histogram. The molecules are prepared by self-assembly and the junctions are formed using a Scanning Tunneling Microscopy (STM) molecular break junction technique. The porphyrin molecules are characterized by MALDI in solution before self-assembly to a gold/mica substrate. The self-assembled monolayers (SAMs) of porphyrins on gold are characterized by Ultraviolet-visible (UV-Vis) reflection spectroscopy to confirm that the molecules are attached to the substrate. The SAMs are then characterized by Angle-Resolved X-ray photoelectron spectroscopy (ARXPS) to determine the thickness and the average molecular orientation of the molecular layer. The electron transport is measured by conductance-displacement (G-S) experiments under a given bias (-0.4V). The conductance value of a single molecule is identified by a statistical analysis

  3. Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.

    Science.gov (United States)

    Melomedov, Jascha; Wünsche von Leupoldt, Anica; Meister, Michael; Laquai, Frédéric; Heinze, Katja

    2013-07-14

    New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy in combination with DFT/PCM calculations on diamagnetic neutral bis(porphyrins) 4 and on respective charged mixed-valent radicals 4(+/-). The interaction via the -C6H4-NHCO-C6H4- bridge, the site of oxidation and reduction and the lowest excited singlet state S1, is tuned by the substituents on the individual porphyrins and the metalation state.

  4. Effects of Bulky Substituents of Push-Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Higashino, Tomohiro; Kawamoto, Kyosuke; Sugiura, Kenichi; Fujimori, Yamato; Tsuji, Yukihiro; Kurotobi, Kei; Ito, Seigo; Imahori, Hiroshi

    2016-06-22

    To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.

  5. N-Annulated perylene substituted zinc–porphyrins with different linking modes and electron acceptors for dye sensitized solar cells

    KAUST Repository

    Luo, Jie

    2016-05-03

    Three new N-annulated perylene (NP) substituted porphyrin dyes WW-7-WW-9 with different linking modes and accepting groups were synthesized and applied in Co(ii)/(iii) based dye sensitized solar cells (DSCs). The bay-linked porphyrins WW-7 and WW-8 exhibited moderate power conversion efficiency (PCE = 4.4% and 4.8%, respectively), while the peri-linked porphyrin dye WW-9 showed a PCE up to 9.2% which is slightly lower than that of our reference dye WW-6. Detailed physical measurements (optical and electrochemical), DFT calculations, and photovoltaic characterizations were performed to understand how the structural changes affect their light-harvesting ability, molecular orbital profile, energy level alignment, and eventually the photovoltaic performance. It turned out that the lower efficiencies of the cells based on WW-7 and WW-8 could be ascribed to the weak π-conjugation between the bay-substituted NP and phenylethynyl substituted porphyrin unit. The introduction of a benzothiadiazole acceptor at the anchoring group has induced a significant red shift of the IPCE action spectra of WW-8 and WW-9, by about 90 nm and 50 nm as compared to that of WW-7 and WW-6, respectively. However, less efficient electron injection was observed. Our studies gave some insight into the important role of electronic interactions between different components when one designs a dye for high-efficiency DSCs. © The Royal Society of Chemistry 2016.

  6. N-Annulated perylene substituted zinc–porphyrins with different linking modes and electron acceptors for dye sensitized solar cells

    KAUST Repository

    Luo, Jie; Zhang, Jing; Huang, Kuo-Wei; Qi, Qingbiao; Dong, Shaoqiang; Zhang, Jie; Wang, Peng; Wu, Jishan

    2016-01-01

    Three new N-annulated perylene (NP) substituted porphyrin dyes WW-7-WW-9 with different linking modes and accepting groups were synthesized and applied in Co(ii)/(iii) based dye sensitized solar cells (DSCs). The bay-linked porphyrins WW-7 and WW-8 exhibited moderate power conversion efficiency (PCE = 4.4% and 4.8%, respectively), while the peri-linked porphyrin dye WW-9 showed a PCE up to 9.2% which is slightly lower than that of our reference dye WW-6. Detailed physical measurements (optical and electrochemical), DFT calculations, and photovoltaic characterizations were performed to understand how the structural changes affect their light-harvesting ability, molecular orbital profile, energy level alignment, and eventually the photovoltaic performance. It turned out that the lower efficiencies of the cells based on WW-7 and WW-8 could be ascribed to the weak π-conjugation between the bay-substituted NP and phenylethynyl substituted porphyrin unit. The introduction of a benzothiadiazole acceptor at the anchoring group has induced a significant red shift of the IPCE action spectra of WW-8 and WW-9, by about 90 nm and 50 nm as compared to that of WW-7 and WW-6, respectively. However, less efficient electron injection was observed. Our studies gave some insight into the important role of electronic interactions between different components when one designs a dye for high-efficiency DSCs. © The Royal Society of Chemistry 2016.

  7. Dualism of Sensitivity and Selectivity of Porphyrin Dimers in Electroanalysis.

    Science.gov (United States)

    Lisak, Grzegorz; Tamaki, Takashi; Ogawa, Takuji

    2017-04-04

    This work uncovers the application of porphyrin dimers for the use in electroanalysis, such as potentiometric determination of ions. It also puts in question a current perception of an occurrence of the super-Nernstian response, as a result of the possible dimerization of single porphyrins within an ion-selective membrane. To study that, four various porphyrin dimers were used as ionophores, namely, freebase-freebase, Zn-Zn, Zn-freebase, and freebase-Zn. Since the Zn-freebase and freebase-Zn porphyrin dimers carried both anion- and cation-sensitive porphyrin units, their application in ISEs was utilized in both anion- and cation-sensitive sensors. With respect to the lipophilic salt added, both porphyrins dimers were found anion- and cation-sensitive. This allowed using a single molecule as novel type of versatile ionophore (anion- and cation-selective), simply by varying the membrane composition. All anion-sensitive sensors were perchlorate-sensitive, while the cation-selective sensors were silver-sensitive. The selectivity of the sensors depended primarily on the porphyrin dimers in the ion-selective membrane. Furthermore, the selectivity of cation-sensitive dimer based sensors was found significantly superior to the ones measured for the single porphyrin unit based sensors (precursors of the porphyrin dimers). Thus, the dimerization of single porphyrins may actually be a factor to increase or modulate porphyrin selectivity. Moreover, in the case of cation-sensitive sensors, the selectivity vastly depended on the order of porphyrin units in the dimer. This opens a new approach of regulating and adjusting sensitivity and selectivity of the sensor through the application of complex porphyrin systems with more than one porphyrin units with mix sensitive porphyrins.

  8. Synthesis of borylated porphyrin and bromo- porphyrin as building blocks for light harvesting antenna molecule

    Science.gov (United States)

    Radzuan, Nuur Haziqah Mohd; Hassan, Nurul Izzaty; Bakar, Muntaz Abu

    2018-04-01

    The building blocks for synthesis of light harvesting antenna which are 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-10,20-diphenylporphyrin, 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-10,20-dihexylporphyrin and 5,10,15,20-tetra-(bromophenyl)porphyrin were synthesized. Borylated porphyrin was synthesized by Suzuki coupling reaction between A2BC bromo-porphyrin and pinacolborane. Whereas 5,10,15,20-tetra-(bromophenyl) porphyrin was synthesized by Lindsey condensation reaction between pyrrole and 4-bromobenzaldehyde. 1H-NMR, 13C-NMR spectroscopy and UV-visible spectroscopy confirmed the successful formation of all compounds.

  9. Helical chirality induction of expanded porphyrin analogues

    Indian Academy of Sciences (India)

    of this figure-eight conformation in relation to the num- ber of π-electrons attracts ... porphyrin moieties.7a–d In this context, application of ... become problematic. Lindsey .... cell. [a]. CD sign (λmax/nm). UV-vis θ/ abs. Ligand of 1st Cotton effect.

  10. Porphyrin formation and its regulation in Arthrobacter

    NARCIS (Netherlands)

    Kortstee, G.J.J.

    1969-01-01

    Porphyrins (tetrapyrroles) are the basic compounds of a number of substances functioning in living organisms as carriers of oxygen (hemoglobin), carriers of electrons (cytochromes) or as a trap for radiant energy (chlorophyll). In these active forms the tetrapyrroles contain a metal and are

  11. Photodynamic Efficiency of Porphyrins Encapsulated into Polysilsesquioxanes

    Czech Academy of Sciences Publication Activity Database

    Rychtáriková, Renata; Šabata, Stanislav; Hetflejš, Jiří; Kuncová, Gabriela

    2012-01-01

    Roč. 66, č. 4 (2012), s. 269-277 ISSN 0366-6352 R&D Projects: GA MŠk ME 892; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40720504 Keywords : porphyrin * immobilization * specific surface area Subject RIV: CC - Organic Chemistry Impact factor: 0.879, year: 2012

  12. Photoconductivity in DNA-Porphyrin Complexes

    Science.gov (United States)

    Myint, Peco; Oxford, Emma; Nyazenga, Collence; Smith, Walter; Qi, Zhengqing; Johnson, A. T.

    2015-03-01

    We have measured the photoconductivity of λ - DNA that is modified by intercalating a porphyrin compound, meso-tetrakis(N-methyl-4-pyridiniumyl)porphyrin (TMPyP), into its base stacks. Intercalation was verified by a red shift and hypochromism of the Soret absorption peak. The DNA/porphyrin strands were then deposited onto oxidized silicon substrates which had been patterned with interdigitated electrodes, and blown dry. Electrical measurements were carried out under nitrogen, using illumination from a 445 nm laser; this wavelength falls within the absorption peak of the DNA/porphyrin complexes. When initially measured under dry nitrogen, the complexes show no photoconductivity or dark conductivity. However, at relative humidities of 30% and above, we do observe dark conductivity, and also photoconductivity that grows with time. Photoconductivity gets larger at higher relative humidity. Remarkably, when the humidity is lowered again, some photoconductivity is now observed, indicating a change that persists for more than 24 hours. It may be that the humidity alters the structure of the DNA, perhaps allowing for better alignment of the bases. This work was supported by NSF Grant BMAT-1306170.

  13. Thin porphyrin composite membranes with enhanced organic solvent transport

    KAUST Repository

    Phuoc, Duong

    2018-05-01

    Extending the stability of polymeric membranes in organic solvents is important for applications in chemical and pharmaceutical industry. Thin-film composite membranes with enhanced solvent permeance are proposed, using porphyrin as a building block. Hybrid polyamide films are formed by interfacial polymerization of 5,10,15,20-(tetra-4-aminophenyl)porphyrin/m-phenylene diamine (MPD) mixtures with trimesoyl chloride. Porphyrin is a non-planar molecule, containing a heterocyclic tetrapyrrole unit. Its incorporation into a polyamide film leads to higher free volume than that of a standard polyamide film. Polyamide films derived from porphyrin and MPD amines with a fixed total amine concentration of 1wt% and various porphyrin/MPD ratios were fabricated and characterized. The porphyrin/MPD polyamide film was complexed with Cu(II), due to the binding capacity of porphyrin to metal ions. By coupling scanning transmission electron microscopy (STEM) with electron energy-loss spectroscopy (EELS), Cu mapping was obtained, revealing the distribution of porphyrin in the interfacial polymerized layer. By using porphyrin as amine-functionalized monomer a membrane with thin selective skin and enhanced solvent transport is obtained, with good dye selectivity in the nanofiltration range. For instance, an ultra-fast hexane permeance, 40-fold increased, was confirmed when using 0.5/0.5 porphyrin/MPD mixtures, instead of only MPD as amine monomer. A rejection of 94.2% Brilliant Blue R (826g/mol) in methanol was measured.

  14. Theoretical investigation of the charge-transfer properties in different meso-linked zinc porphyrins for highly efficient dye-sensitized solar cells.

    Science.gov (United States)

    Namuangruk, Supawadee; Sirithip, Kanokkorn; Rattanatwan, Rattanawelee; Keawin, Tinnagon; Kungwan, Nawee; Sudyodsuk, Taweesak; Promarak, Vinich; Surakhot, Yaowarat; Jungsuttiwong, Siriporn

    2014-06-28

    The charge transfer effect of different meso-substituted linkages on porphyrin analogue 1 (A1, B1 and C1) was theoretically investigated using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The calculated geometry parameters and natural bond orbital analysis reveal that the twisted conformation between porphyrin macrocycle and meso-substituted linkages leads to blocking of the conjugation of the conjugated backbone, and the frontier molecular orbital plot shows that the intramolecular charge transfer of A1, B1 and C1 hardly takes place. In an attempt to improve the photoinduced intramolecular charge transfer ability of the meso-linked zinc porphyrin sensitizer, a strong electron-withdrawing group (CN) was introduced into the anchoring group of analogue 1 forming analogue 2 (A2, B2 and C2). The density difference plot of A2, B2 and C2 shows that the charge transfer properties dramatically improved. The electron injection process has been performed using TDDFT; the direct charge-transfer transition in the A2-(TiO2)38 interacting system takes place; our results strongly indicated that introducing electron-withdrawing groups into the acceptor part of porphyrin dyes can fine-tune the effective conjugation length of the π-spacer and improve intramolecular charge transfer properties, consequently inducing the electron injection process from the anchoring group of the porphyrin dye to the (TiO2)38 surface which may improve the conversion efficiency of the DSSCs. Our calculated results can provide valuable information and a promising outlook for computation-aided sensitizer design with anticipated good properties in further experimental synthesis.

  15. Building-up novel coordination polymer with Zn(II) porphyrin dimer ...

    Indian Academy of Sciences (India)

    mer with porphyrin dimer. Solution structures of the complexes along with binding studies in solution between ... porphyrin polymers by self-assembly is fascinating ..... ture determination. ..... J K M 2000 In The Porphyrin Handbook Kadish K M,.

  16. Cosensitized Porphyrin System for High-Performance Solar Cells with TOF-SIMS Analysis.

    Science.gov (United States)

    Wu, Wenjun; Xiang, Huaide; Fan, Wei; Wang, Jinglin; Wang, Haifeng; Hua, Xin; Wang, Zhaohui; Long, Yitao; Tian, He; Zhu, Wei-Hong

    2017-05-17

    To date, development of organic sensitizers has been predominately focused on light harvesting, highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels, and the electron transferring process. In contrast, their adsorption mode as well as the dynamic loading behavior onto nanoporous TiO 2 is rarely considered. Herein, we have employed the time-of-flight secondary ion mass spectrometry (TOF-SIMS) to gain insight into the competitive dye adsorption mode and kinetics in the cosensitized porphyrin system. Using novel porphyrin dye FW-1 and D-A-π-A featured dye WS-5, the different bond-breaking mode in TOF-SIMS and dynamic dye-loading amount during the coadsorption process are well-compared with two different anchoring groups, such as benzoic acid and cyanoacrylic acid. With the bombardment mode in TOF-SIMS spectra, we have speculated that the cyano group grafts onto nanoporous TiO 2 as tridentate binding for the common anchoring unit of cyanoacrylic acid and confirmed it through extensive first-principles density functional theory calculation by anchoring either the carboxyl or cyano group, which shows that the cyano group can efficiently participate in the adsorption of the WS-5 molecule onto the TiO 2 nanocrystal. The grafting reinforcement interaction between the cyano group and TiO 2 in WS-5 can well-explain the rapid adsorption characteristics. A strong coordinate bond between the lone pair of electrons on the nitrogen or oxygen atom and the Lewis acid sites of TiO 2 can increase electron injection efficiencies with respect to those from the bond between the benzoic acid group and the Brønsted acid sites of the TiO 2 surface. Upon optimization of the coadsorption process with dye WS-5, the photoelectric conversion efficiency based on porphyrin dye FW-1 is increased from 6.14 to 9.72%. The study on the adsorption dynamics of organic sensitizers with TOF-SIMS analysis might provide a new venue for improvement of cosensitized solar

  17. The Holding Power of Anchors

    Indian Academy of Sciences (India)

    The efficiency of an anchor may be expressed as the ratio (holding force + weight of anchor). In dry sand .... the market at the beginning of the coming season in three sizes, namely 20, 35 and. 60 lb. These are ... Taylor frozen-flow hypothesis.

  18. Graphene oxide vs. reduced graphene oxide as carbon support in porphyrin peroxidase biomimetic nanomaterials.

    Science.gov (United States)

    Socaci, C; Pogacean, F; Biris, A R; Coros, M; Rosu, M C; Magerusan, L; Katona, G; Pruneanu, S

    2016-02-01

    The paper describes the preparation of supramolecular assemblies of tetrapyridylporphyrin (TPyP) and its metallic complexes with graphene oxide (GO) and thermally reduced graphene oxide (TRGO). The two carbon supports are introducing different characteristics in the absorption spectra of the investigated nanocomposites. Raman spectroscopy shows that the absorption of iron-tetrapyridylporphyrin is more efficient on GO than TRGO, suggesting that oxygen functionalities are involved in the non-covalent interaction between the iron-porphyrin and graphene. The biomimetic peroxidase activity is investigated and the two iron-containing composites exhibit a better catalytic activity than each component of the assembly, and their cobalt and manganese homologues, respectively. The main advantages of this work include the demonstration of graphene oxide as a very good support for graphene-based nanomaterials with peroxidase-like activity (K(M)=0.292 mM), the catalytic activity being observed even with very small amounts of porphyrins (the TPyP:graphene ratio=1:50). Its potential application in the detection of lipophilic antioxidants (vitamin E can be measured in the 10(-5)-10(-4) M range) is also shown. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. [Renal excretion of total porphyrins and hippuric acid in rats].

    Science.gov (United States)

    Gartzke, J; Burck, D

    1986-09-01

    The amounts of total porphyrins, hippuric acid and creatinine, excreted in urine by adult male Wistar rats, exhibited normal distributions for hippuric acid and creatinine, but a bimodal distribution for total porphyrins. This typical distribution of total porphyrins was still observed when creatinine was used as reference parameter. In biochemical and toxicological experiments in rats, the tested parameters should be therefore be investigated for homogeneity.

  20. Dehalogenation of lindane by a variety of porphyrins and corrins.

    OpenAIRE

    Marks, T S; Allpress, J D; Maule, A

    1989-01-01

    The dehalogenation of lindane by a range of hemoproteins, porphyrins, and corrins has been tested under reducing conditions in the presence of dithiothreitol. In addition, a series of porphyrin-metal ion complexes have been prepared and have also been screened for the capacity to dehalogenate lindane. Hemoglobin, hemin, hematin, and chlorophyll alpha all catalyzed the dehalogenation of lindane, as did all of the corrins tested. The porphyrins which did not contain metal centers--coproporphyri...

  1. Not all Anchors Weigh Equally.

    Science.gov (United States)

    Greenstein, Michael; Velazquez, Alexandra

    2017-11-01

    The anchoring bias is a reliable effect wherein a person's judgments are affected by initially presented information, but it is unknown specifically why this effect occurs. Research examining this bias suggests that elements of both numeric and semantic priming may be involved. To examine this, the present research used a phenomenon wherein people treat numeric information presented differently in Arabic numeral or verbal formats. We presented participants with one of many forms of an anchor that represented the same value (e.g., twelve hundred or 1,200). Thus, we could examine how a concept's meaning and its absolute numeric value affect anchoring. Experiments 1 and 2 showed that people respond to Arabic and verbal anchors differently. Experiment 3 showed that these differences occurred largely because people tend to think of numbers in digit format. This suggests that one's conceptual understanding of the anchored information matters more than its strict numeric value.

  2. Iron porphyrins doped sol-gel glasses: a chemometric study

    International Nuclear Information System (INIS)

    Sacco, Herica C.; Vidoto, Ednalva A.; Nascimento, Otaciro R.

    2000-01-01

    This paper describes the optimized conditions for preparation of iron porphyrin-template doped silica Fe PDS-template) obtained by the sol-gel process. The following porphyrins (Fe P) were used: Fe TFPP Cl, Fe TDCSPP(Na) 4 Cl and Fe TCPP(Na) 4 Cl. Pyridine or 4-phenylimidazole was used as template. The variables that present significant influence on iron porphyrin loading on xerogel were identified and the values that maximize the iron porphyrin loading on xerogel were established . The variables (Solvent volume, fractional factorial design in two levels, 2 5-1 type, generating 16 total experiments for each Fe P studied. (author)

  3. Iron porphyrins doped sol-gel glasses: a chemometric study

    Energy Technology Data Exchange (ETDEWEB)

    Sacco, Herica C.; Vidoto, Ednalva A.; Nascimento, Otaciro R. [Soap Paulo Univ (USP), Sao Carlos (Brazil). Inst. de Fisica; Biazzotto, Juliana C.; Serra, Osvaldo A.; Iamamoto, Yassuko [Sao Paulo Univ. (USP), Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras; Ciuffi, Katia J.; Mello, Cesar A.; Oliveira, Daniela C. de [Universidade de Franca , SP (Brazil)

    2000-07-01

    This paper describes the optimized conditions for preparation of iron porphyrin-template doped silica Fe (PDS-template) obtained by the sol-gel process. The following porphyrins (Fe P) were used: Fe TFPP Cl, Fe TDCSPP(Na){sub 4}Cl and Fe TCPP(Na){sub 4} Cl. Pyridine or 4-phenylimidazole was used as template. The variables that present significant influence on iron porphyrin loading on xerogel were identified and the values that maximize the iron porphyrin loading on xerogel were established. The variables Solvent volume, fractional factorial design in two levels, 2{sup 5-1} type, generating 16 total experiments for each Fe P studied. (author)

  4. A Study of Porphyrins in Petroleum Source Rocks

    Energy Technology Data Exchange (ETDEWEB)

    Huseby, Berit

    1997-12-31

    This thesis discusses several aspects of porphyrin geochemistry. Degradation experiments have been performed on the Messel oil shale (Eocene, Germany) to obtain information on porphyrins bound or incorporated into macromolecular structures. Thermal heating of the preextracted kerogen by hydrous pyrolysis was used to study the release of porphyrins and their temperature dependent changes during simulated diagenesis and catagenesis. Selective chemical degradation experiments were performed on the preextracted sediment to get more detailed information about porphyrins that are specifically bound to the macromolecular structures via ester bonds. From the heating experiments, in a separate study, the porphyrin nitrogen content in the generated bitumens was compared to the bulk of organic nitrogen compounds in the fraction. The bulk nitrogen contents in the generated bitumens, the water phase and the residual organic matter was recorded to establish the distribution of nitrogen between the kerogen and product phases. Porphyrins as biomarkers were examined in naturally matured Kimmeridge clay source rocks (Upper Jurassic, Norway), and the use of porphyrins as general indicators of maturity was evaluated. Underlying maturity trends in the biomarker data was investigated by Partial Least Squares analysis. Porphyrin as indicators of depositional conditions was also addressed, where the correlations between the (amounts) abundance of nickel and vanadyl porphyrins were mapped together with other descriptors that are assumed to be indicative of redox depositional conditions. 252 refs., 28 figs., 4 tabs.

  5. A Study of Porphyrins in Petroleum Source Rocks

    Energy Technology Data Exchange (ETDEWEB)

    Huseby, Berit

    1996-12-31

    This thesis discusses several aspects of porphyrin geochemistry. Degradation experiments have been performed on the Messel oil shale (Eocene, Germany) to obtain information on porphyrins bound or incorporated into macromolecular structures. Thermal heating of the preextracted kerogen by hydrous pyrolysis was used to study the release of porphyrins and their temperature dependent changes during simulated diagenesis and catagenesis. Selective chemical degradation experiments were performed on the preextracted sediment to get more detailed information about porphyrins that are specifically bound to the macromolecular structures via ester bonds. From the heating experiments, in a separate study, the porphyrin nitrogen content in the generated bitumens was compared to the bulk of organic nitrogen compounds in the fraction. The bulk nitrogen contents in the generated bitumens, the water phase and the residual organic matter was recorded to establish the distribution of nitrogen between the kerogen and product phases. Porphyrins as biomarkers were examined in naturally matured Kimmeridge clay source rocks (Upper Jurassic, Norway), and the use of porphyrins as general indicators of maturity was evaluated. Underlying maturity trends in the biomarker data was investigated by Partial Least Squares analysis. Porphyrin as indicators of depositional conditions was also addressed, where the correlations between the (amounts) abundance of nickel and vanadyl porphyrins were mapped together with other descriptors that are assumed to be indicative of redox depositional conditions. 252 refs., 28 figs., 4 tabs.

  6. A Zinc Porphyrin Sensitizer Modified with Donor and Acceptor Groups for Dye-ensitized Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    Lee, See Woo; Sarker, K. Ashis; Hong, Jong Dal [Incheon National University, Incheon (Korea, Republic of)

    2014-09-15

    In this article, we have designed and synthesized a novel donor-π-acceptor (D-π-A) type porphyrin-based sensitizer (denoted UI-5), in which a carboxyl anchoring group and a 9,9-dimethyl fluorene were introduced at the meso-positions of porphyrin ring via phenylethynyl and ethynyl bridging units, respectively. Long alkoxy chains in ortho-positions of the phenyls were supposed to reduce the degree of dye aggregation, which tends to affect electron injection yield in a photovoltaic cell. The cyclic voltammetry was employed to determine the band gap of UI-5 to be 1.41 eV based on the HOMO and LUMO energy levels, which were estimated by the onset oxidation and reduction potentials. The incident monochromatic photon-to-current conversion efficiency of the UI-5 DSSC assembled with double-layer (20 nm-sized TiO{sub 2}/400 nm-sized TiO{sub 2}) film electrodes appeared lower upon overall ranges of the excitation wavelengths, but exhibited a higher value over the NIR ranges (λ = 650-700 nm) compared to the common reference sensitizer N719. The UI-5-sensitized cell yielded a relatively poor device performance with an overall conversion efficiency of 0.74% with a short circuit photocurrent density of 3.05 mA/cm2, an open circuit voltage of 0.54 mV and a fill factor of 0.44 under the standard global air mass (AM 1.5) solar conditions. However, our report about the synthesis and the photovoltaic characteristics of a porphyrin-based sensitizer in a D-π-A structure demonstrated a significant complex relationship between the sensitizer structure and the cell performance.

  7. Manganese in silicon carbide

    Energy Technology Data Exchange (ETDEWEB)

    Linnarsson, M.K., E-mail: marga@kth.se [Royal Institute of Technology, School of Information and Communication Technology, P.O. Box E229, SE-16440 Kista-Stockhom (Sweden); Hallen, A. [Royal Institute of Technology, School of Information and Communication Technology, P.O. Box E229, SE-16440 Kista-Stockhom (Sweden)

    2012-02-15

    Structural disorder and relocation of implanted Mn in semi-insulating 4H-SiC has been studied. Subsequent heat treatment of Mn implanted samples has been performed in the temperature range 1400-2000 Degree-Sign C. The depth distribution of manganese is recorded by secondary ion mass spectrometry. Rutherford backscattering spectrometry has been employed for characterization of crystal disorder. Ocular inspection of color changes of heat-treated samples indicates that a large portion of the damage has been annealed. However, Rutherford backscattering shows that after heat treatment, most disorder from the implantation remains. Less disorder is observed in the [0 0 0 1] channel direction compared to [112{sup Macron }3] channel direction. A substantial rearrangement of manganese is observed in the implanted region. No pronounced manganese diffusion deeper into the sample is recorded.

  8. Manganese in silicon carbide

    International Nuclear Information System (INIS)

    Linnarsson, M.K.; Hallén, A.

    2012-01-01

    Structural disorder and relocation of implanted Mn in semi-insulating 4H–SiC has been studied. Subsequent heat treatment of Mn implanted samples has been performed in the temperature range 1400–2000 °C. The depth distribution of manganese is recorded by secondary ion mass spectrometry. Rutherford backscattering spectrometry has been employed for characterization of crystal disorder. Ocular inspection of color changes of heat-treated samples indicates that a large portion of the damage has been annealed. However, Rutherford backscattering shows that after heat treatment, most disorder from the implantation remains. Less disorder is observed in the [0 0 0 1] channel direction compared to [112 ¯ 3] channel direction. A substantial rearrangement of manganese is observed in the implanted region. No pronounced manganese diffusion deeper into the sample is recorded.

  9. Analysis of Anchoring Mechanism of Fully Grouted Prestressed Anchor

    Directory of Open Access Journals (Sweden)

    WEN Zhi-jie

    2014-01-01

    Full Text Available Some researchers have been carried out on analysis of the influence of the full grouted prestressed anchor shape of borehole wall on its carrying capacity. Based on the self-affine fractal feature of anchor borehole wall structural plane, the relation equation among structural plane shear strength, liquid injection pressure, tensile load and structural plane fractal dimension D was built, the instability judgment criterion of anchoring bearing strata and rock structural plane was determined, the solving equations of disintegrated rock support density were derived. Based on the experimental results, the theoretical basis of support design under the disintegrated rock condition was offered.

  10. Zinc Porphyrins Possessing Three p-Carboxyphenyl Groups: Effect of the Donor Strength of Push-Groups on the Efficiency of Dye Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Ram B. Ambre

    2016-06-01

    Full Text Available Zinc porphyrins decorated with three p-carboxyphenyl anchoring groups and various “push” substituents of varied electron-donating strengths were prepared in good yields by facile and straightforward ways. The effect of electron-donating strength of the donor molecules on the overall power conversion efficiency was evaluated with the help of photophysical, electrochemical, photovoltaic spectroscopy and quantum chemical calculations. It is observed from the photophysical and Infrared (IR spectroscopic data that multi-anchoring dyes are more stable and bind more strongly to the TiO2 surface than their one-anchor counterparts. The properties like a three-step synthesis, high overall yields, possible mass production on a gram-scale and strong binding affinities with TiO2 surfaces make them a suitable choice for commercial applications. Zn1NH3A, with electron donating and anti-aggregation characteristics, achieved the highest efficiency of 6.50%.

  11. Structures and properties of spatially distorted porphyrins

    International Nuclear Information System (INIS)

    Golubchikov, Oleg A; Kuvshinova, Elizaveta M; Pukhovskaya, Svetlana G

    2005-01-01

    The published data on the structures and properties of porphyrins with distorted aromatic macrocycles are generalised and analysed. Data on the crystal structures, spectra and kinetics of formation and dissociation of their coordination derivatives are summarised. It is demonstrated that the distortion of the planar structure of the tetrapyrrole core is one of the most efficient means of controlling spectral, physicochemical and coordination properties of these compounds.

  12. The photodynamic and non-photodynamic actions of porphyrins

    Directory of Open Access Journals (Sweden)

    S.G. Afonso

    1999-03-01

    Full Text Available Porphyrias are a family of inherited diseases, each associated with a partial defect in one of the enzymes of the heme biosynthetic pathway. In six of the eight porphyrias described, the main clinical manifestation is skin photosensitivity brought about by the action of light on porphyrins, which are deposited in the upper epidermal layer of the skin. Porphyrins absorb light energy intensively in the UV region, and to a lesser extent in the long visible bands, resulting in transitions to excited electronic states. The excited porphyrin may react directly with biological structures (type I reactions or with molecular oxygen, generating excited singlet oxygen (type II reactions. Besides this well-known photodynamic action of porphyrins, a novel light-independent effect of porphyrins has been described. Irradiation of enzymes in the presence of porphyrins mainly induces type I reactions, although type II reactions could also occur, further increasing the direct non-photodynamic effect of porphyrins on proteins and macromolecules. Conformational changes of protein structure are induced by porphyrins in the dark or under UV light, resulting in reduced enzyme activity and increased proteolytic susceptibility. The effect of porphyrins depends not only on their physico-chemical properties but also on the specific site on the protein on which they act. Porphyrin action alters the functionality of the enzymes of the heme biosynthetic pathway exacerbating the metabolic deficiencies in porphyrias. Light energy absorption by porphyrins results in the generation of oxygen reactive species, overcoming the protective cellular mechanisms and leading to molecular, cell and tissue damage, thus amplifying the porphyric picture.

  13. Manganese dipyridoxyl diphosphate:

    DEFF Research Database (Denmark)

    H, Brurok; Ardenkjær-Larsen, Jan Henrik; G, Hansson

    1999-01-01

    Manganese dipyridoxyl diphosphate (MnDPDP) is a contrast agent for magnetic resonance imaging (MRI) of the liver. Aims of the study were to examine if MnDPDP possesses superoxide dismutase (SOD) mimetic activity in vitro, and if antioxidant protection can be demonstrated in an ex vivo rat heart...

  14. Resonance Raman study on distorted symmetry of porphyrin in ...

    Indian Academy of Sciences (India)

    The resonance Raman (RR) spectra of nickel octaethyl porphyrin, Ni(OEP), ... Nickel ocatethyl porphyrin, Ni(OEP), plays a central role in studies of the molec- ..... [8] T Kitagawa and Y Ozaki, Structure and bonding (Springer-Verlag, Berlin, ... [10] R S Czernuszewicz, K A Macar, Li Xiao-Yuan, J R Kincaid and T G Spiro, J. Am.

  15. Multifunctional porphyrinic materials encapsulated into macronets with photo chemotherapeutic applications

    Energy Technology Data Exchange (ETDEWEB)

    Ion, R. -M.; Fierascu, R. -C.; Dimitriu, I. [Valahia University, Materials Science Department, Targoviste (Romania)

    2008-07-01

    Supramolecidar chemistry is expected to keep a high developing advanced of molecular devices based on multifunctional materials. Porphyrins and their analogues should play a significant role as a consequence of their catalytic, electrocatalytic, photochemical and photoelectrochemical properties. Such molecular materials contain a high porosity with large cavities and galleries that can be functionalization yielding to a desired chirality and structure. The functionalization implies inserting into macrocydic cavity, followed by auto-assembling as columnar aggregates. The obtained cavities are used as host for different molecular guests. H and J-aggregates of some porphyrins are based on the intermolecular interactions of 3-5 Kcal/mol per porphyrin face. The columnar structure formed by porphyrins has a length of 5 to 27 porphyrin unities. In this paper we focused on our own strategy based on coordination chemistry for the design and build-up of supermolecules and supra molecular structures constituted by a porphyrin (TSPPJ and a new and revolutionary method for stabilizing porphyrins (as organic part), by their incapsulation into supports with controlled porosity as macronets (as inorganic parts), obtaining some hybrids materials. Included are also their properties and potential applications. Key words: porphyrins, macronets, photochemotherapy.

  16. The effects of urea, guanidinium chloride and sorbitol on porphyrin ...

    Indian Academy of Sciences (India)

    This paper compares the inhibition effect of porphyrin aggregation in the presence of urea, guanidinium chloride (Gdn) and sorbitol by molecular dynamics simulation. It demonstrates that porphyrin aggregation increases in sorbitol, but decreases towards addition of urea and Gdn. It shows that urea, Gdn and sorbitol can ...

  17. Manganese, Metallogenium, and Martian Microfossils

    Science.gov (United States)

    Stein, L. Y.; Nealson, K. H.

    1999-01-01

    Manganese could easily be considered an abundant element in the Martian regolith, assuming that the composition of martian meteorites reflects the composition of the planet. Mineralogical analyses of 5 SNC meteorites have revealed an average manganese oxide concentration of 0.48%, relative to the 0.1% concentration of manganese found in the Earth's crust. On the Earth, the accumulation of manganese oxides in oceans, soils, rocks, sedimentary ores, fresh water systems, and hydrothermal vents can be largely attributed to microbial activity. Manganese is also a required trace nutrient for most life forms and participates in many critical enzymatic reactions such as photosynthesis. The wide-spread process of bacterial manganese cycling on Earth suggests that manganese is an important element to both geology and biology. Furthermore, there is evidence that bacteria can be fossilized within manganese ores, implying that manganese beds may be good repositories for preserved biomarkers. A particular genus of bacteria, known historically as Metallogenium, can form star-shaped manganese oxide minerals (called metallogenium) through the action of manganese oxide precipitation along its surface. Fossilized structures that resemble metallogenium have been found in Precambrian sedimentary formations and in Cretaceous-Paleogene cherts. The Cretaceous-Paleogene formations are highly enriched in manganese and have concentrations of trace elements (Fe, Zn, Cu, and Co) similar to modern-day manganese oxide deposits in marine environments. The appearance of metallogenium-like fossils associated with manganese deposits suggests that bacteria may be preserved within the minerals that they form. Additional information is contained in the original extended abstract.

  18. Porphyrin and fullerene-based artificial photosynthetic materials for photovoltaics

    International Nuclear Information System (INIS)

    Imahori, Hiroshi; Kashiwagi, Yukiyasu; Hasobe, Taku; Kimura, Makoto; Hanada, Takeshi; Nishimura, Yoshinobu; Yamazaki, Iwao; Araki, Yasuyuki; Ito, Osamu; Fukuzumi, Shunichi

    2004-01-01

    We have developed artificial photosynthetic systems in which porphyrins and fullerenes are self-assembled as building blocks into nanostructured molecular light-harvesting materials and photovoltaic devices. Multistep electron transfer strategy has been combined with our finding that porphyrin and fullerene systems have small reorganization energies, which are suitable for the construction of light energy conversion systems as well as artificial photosynthetic models. Highly efficient photosynthetic electron transfer reactions have been realized at ITO electrodes modified with self-assembled monolayers of porphyrin oligomers as well as porphyrin-fullerene linked systems. Porphyrin-modified gold nanoclusters have been found to have potential as artificial photosynthetic materials. These results provide basic information for the development of nanostructured artificial photosynthetic systems

  19. Corroles-Porphyrins: A Teamwork for Gas Sensor Arrays

    Directory of Open Access Journals (Sweden)

    Rosamaria Capuano

    2015-04-01

    Full Text Available Porphyrins provide an excellent material for chemical sensors, and they have been used for sensing species both in air and solution. In the gas phase, the broad selectivity of porphyrins is largely dependant on molecular features, such as the metal ion complexed at the core of the aromatic ring and the peripheral substituents. Although these features have been largely exploited to design gas sensor arrays, so far, little attention has been devoted to modify the sensing properties of these macrocycles by variation of the molecular aromatic ring. In this paper, the gas sensing properties of a porphyrin analog, the corrole, are studied in comparison with those of the parent porphyrin. Results show that changes in the aromatic ring have important consequences on the sensitivity and selectivity of the sensors and that porphyrins and corroles can positively cooperate to enhance the performance of sensor arrays.

  20. Measurement of urinary porphyrins and porphyrin precursors in Dutch hospital laboratories: a review of quality control over 5 years.

    NARCIS (Netherlands)

    Zuijderhoudt, F.M.; Weykamp, C.W.; Willems, J.L.

    2003-01-01

    BACKGROUND: We evaluated a quality control scheme for the measurement of urinary uroporphyrin, coproporphyrin, total urinary porphyrins and precursors of urinary porphyrins, delta-aminolevulinic acid and porphobilinogen that was performed in The Netherlands during a period of 5 years. METHODS: Six

  1. Porphyrin-magnetite nanoconjugates for biological imaging

    LENUS (Irish Health Repository)

    Nowostawska, Malgorzata

    2011-04-08

    Abstract Background The use of silica coated magnetic nanoparticles as contrast agents has resulted in the production of highly stable, non-toxic solutions that can be manipulated via an external magnetic field. As a result, the interaction of these nanocomposites with cells is of vital importance in understanding their behaviour and biocompatibility. Here we report the preparation, characterisation and potential application of new "two-in-one" magnetic fluorescent nanocomposites composed of silica-coated magnetite nanoparticles covalently linked to a porphyrin moiety. Method The experiments were performed by administering porphyrin functionalised silica-coated magnetite nanoparticles to THP-1 cells, a human acute monocytic leukaemia cell line. Cells were cultured in RPMI 1640 medium with 25 mM HEPES supplemented with heat-inactivated foetal bovine serum (FBS). Results We have synthesised, characterised and analysed in vitro, a new multimodal (magnetic and fluorescent) porphyrin magnetic nanoparticle composite (PMNC). Initial co-incubation experiments performed with THP-1 macrophage cells were promising; however the PMNC photobleached under confocal microscopy study. β-mercaptoethanol (β-ME) was employed to counteract this problem and resulted not only in enhanced fluorescence emission, but also allowed for elongated imaging and increased exposure times of the PMNC in a cellular environment. Conclusion Our experiments have demonstrated that β-ME visibly enhances the emission intensity. No deleterious effects to the cells were witnessed upon co-incubation with β-ME alone and no increases in background fluorescence were recorded. These results should present an interest for further development of in vitro biological imaging techniques.

  2. Porphyrin Protonation Studied by Magnetic Circular Dichroism

    Czech Academy of Sciences Publication Activity Database

    Štěpánek, Petr; Andrushchenko, Valery; Ruud, K.; Bouř, Petr

    2012-01-01

    Roč. 116, č. 1 (2012), s. 778-783 ISSN 1089-5639 R&D Projects: GA ČR GAP208/11/0105; GA ČR GA203/09/2037; GA ČR GAP208/10/0559; GA MŠk(CZ) LH11033 Institutional research plan: CEZ:AV0Z40550506 Keywords : magnetic circular dichroism ( MCD ) * TPPS * spectra simulations * porphyrin protonation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.771, year: 2012

  3. Valence electronic properties of porphyrin derivatives.

    Science.gov (United States)

    Stenuit, G; Castellarin-Cudia, C; Plekan, O; Feyer, V; Prince, K C; Goldoni, A; Umari, P

    2010-09-28

    We present a combined experimental and theoretical investigation of the valence electronic structure of porphyrin-derived molecules. The valence photoemission spectra of the free-base tetraphenylporphyrin and of the octaethylporphyrin molecule were measured using synchrotron radiation and compared with theoretical spectra calculated using the GW method and the density-functional method within the generalized gradient approximation. Only the GW results could reproduce the experimental data. We found that the contribution to the orbital energies due to electronic correlations has the same linear behavior in both molecules, with larger deviations in the vicinity of the HOMO level. This shows the importance of adequate treatment of electronic correlations in these organic systems.

  4. Microgravity Drill and Anchor System

    Science.gov (United States)

    Parness, Aaron; Frost, Matthew A.; King, Jonathan P.

    2013-01-01

    This work is a method to drill into a rock surface regardless of the gravitational field or orientation. The required weight-on-bit (WOB) is supplied by a self-contained anchoring mechanism. The system includes a rotary percussive coring drill, forming a complete sampling instrument usable by robot or human. This method of in situ sample acquisition using micro - spine anchoring technology enables several NASA mission concepts not currently possible with existing technology, including sampling from consolidated rock on asteroids, providing a bolt network for astronauts visiting a near-Earth asteroid, and sampling from the ceilings or vertical walls of lava tubes and cliff faces on Mars. One of the most fundamental parameters of drilling is the WOB; essentially, the load applied to the bit that allows it to cut, creating a reaction force normal to the surface. In every drilling application, there is a minimum WOB that must be maintained for the system to function properly. In microgravity (asteroids and comets), even a small WOB could not be supported conventionally by the weight of the robot or astronaut. An anchoring mechanism would be needed to resist the reactions, or the robot or astronaut would push themselves off the surface and into space. The ability of the system to anchor itself to a surface creates potential applications that reach beyond use in low gravity. The use of these anchoring mechanisms as end effectors on climbing robots has the potential of vastly expanding the scope of what is considered accessible terrain. Further, because the drill is supported by its own anchor rather than by a robotic arm, the workspace is not constrained by the reach of such an arm. Yet, if the drill is on a robotic arm, it has the benefit of not reflecting the forces of drilling back to the arm s joints. Combining the drill with the anchoring feet will create a highly mobile, highly stable, and highly reliable system. The drilling system s anchor uses hundreds of

  5. Porphyrin Interactions with Wild Type and Mutant Mouse Ferrochelatase

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Gloria C.; Franco, Ricardo; Lu, Yi; Ma, Jian-Guo; Shelnutt, John A.

    1999-05-19

    Ferrochelatase (EC 4.99.1.1), the terminal enzyme of the heme biosynthetic pathway, catalyzes Fe2+ chelation into protoporphyrin IX. Resonance Raman and W-visible absorbance spectroscopes of wild type and engineered variants of murine ferrochelatase were used to examine the proposed structural mechanism for iron insertion into protoporphyrin by ferrochelatase. The recombinant variants (i.e., H207N and E287Q) are enzymes in which the conserved amino acids histidine-207 and glutamate-287 of murine ferrochelatase were substituted with asparagine and glutamine, respectively. Both of these residues are at the active site of the enzyme as deduced from the Bacillus subtilis ferrochelatase three-dimensional structure. Addition of free base or metalated porphyrins to wild type ferrochelatase and H207N variant yields a quasi 1:1 complex, possibly a monomeric protein-bound species. In contrast, the addition of porphyrin (either free base or metalated) to E287Q is sub-stoichiometric, as this variant retains bound porphyrin in the active site during isolation and purification. The specificity of porphyrin binding is confirmed by the narrowing of the structure-sensitive resonance Raman lines and the vinyl vibrational mode. Resonance Raman spectra of free base and metalated porphyrins bound to the wild type ferrochelatase indicate a nonplanar distortion of the porphyrin macrocycle, although the magnitude of the distortion cannot be determined without first defining the specific type of deformation. Significantly, the extent of the nonplanar distortion varies in the case of H207N- and E287Q-bound porphyrins. In fact, resonance Raman spectral decomposition indicates a homogeneous ruffled distortion for the nickel protoporphyrin bound to the wild type ferrochelatase, whereas both a planar and ruffled conformations are present for the H207N-bound porphyrin. Perhaps more revealing is the unusual resonance , 3 Raman spectrum of the endogenous E287Q-bound porphyrin, which has

  6. The Holding Power of Anchors

    Indian Academy of Sciences (India)

    as the chain begins to drag along the ground; and it also serves, by lying flat on the ground, to keep the palm set at the correct angle as it buries itself. In stockless anchors there are two digging blades set on opposite sides of the shank, and hinged to it by a horizontal hinge which allows them to set themselves at the correct.

  7. Synthesis, spectroscopy and photosensitizing properties of hydroxynitrophenyl porphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Maestrin, Ana Paula J.; Tedesco, Antonio Claudio; Neri, Claudio R.; Gandini, Maria Elisa F.; Serra, Osvaldo A.; Iamamoto, Yassuko [Sao Paulo Univ., Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras. Inst. de Quimica]. E-mail: osaserra@usp.br

    2004-10-01

    The hydroxynitrophenyl porphyrins, 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrin and 5-mono(carboxyphenyl)-10,15,20-tris(2-hydroxy-5-nitrophenyl)porphyrin described in this work were prepared through Adler's method. These compounds were characterized by {sup 1}H NMR and light absorption and emission spectroscopy in the visible region. In order to demonstrate the involvement of {sup 1}O{sub 2} production, the uric (UA) acid test was carried out, which considers the decrease in the absorbance of UA at 293 nm following laser light irradiation of a solution containing UA and a photosensitizer. The results obtained demonstrate that these hydroxynitrophenyl porphyrins can be considered as promising photosensitizers in PDT. (author)

  8. Porphyrin Diacid-Polyelectrolyte Assemblies: Effective Photocatalysts in Solution

    Directory of Open Access Journals (Sweden)

    Sabine Frühbeißer

    2016-05-01

    Full Text Available Developing effective and versatile photocatalytic systems is of great potential in solar energy conversion. Here we investigate the formation of supramolecular catalysts by electrostatic self-assembly in aqueous solution: Combining positively charged porphyrins with negatively charged polyelectrolytes leads to nanoscale assemblies where, next to electrostatic interactions, π–π interactions also play an important role. Porphyrin diacid-polyelectrolyte assemblies exhibit a substantially enhanced catalytic activity for the light-driven oxidation of iodide. Aggregates with the hexavalent cationic porphyrin diacids show up to 22 times higher catalytic activity than the corresponding aggregates under neutral conditions. The catalytic activity can be increased by increasing the valency of the porphyrin and by choice of the loading ratio. The structural investigation of the supramolecular catalysts took place via atomic force microscopy and small angle neutron scattering. Hence, a new facile concept for the design of efficient and tunable self-assembled photocatalysts is presented.

  9. Thin porphyrin composite membranes with enhanced organic solvent transport

    KAUST Repository

    Phuoc, Duong; Anjum, Dalaver H.; Peinemann, Klaus-Viktor; Nunes, Suzana Pereira

    2018-01-01

    Extending the stability of polymeric membranes in organic solvents is important for applications in chemical and pharmaceutical industry. Thin-film composite membranes with enhanced solvent permeance are proposed, using porphyrin as a building block

  10. Challenging Density Functional Theory Calculations with Hemes and Porphyrins

    Science.gov (United States)

    de Visser, Sam P.; Stillman, Martin J.

    2016-01-01

    In this paper we review recent advances in computational chemistry and specifically focus on the chemical description of heme proteins and synthetic porphyrins that act as both mimics of natural processes and technological uses. These are challenging biochemical systems involved in electron transfer as well as biocatalysis processes. In recent years computational tools have improved considerably and now can reproduce experimental spectroscopic and reactivity studies within a reasonable error margin (several kcal·mol−1). This paper gives recent examples from our groups, where we investigated heme and synthetic metal-porphyrin systems. The four case studies highlight how computational modelling can correctly reproduce experimental product distributions, predicted reactivity trends and guide interpretation of electronic structures of complex systems. The case studies focus on the calculations of a variety of spectroscopic features of porphyrins and show how computational modelling gives important insight that explains the experimental spectra and can lead to the design of porphyrins with tuned properties. PMID:27070578

  11. Challenging Density Functional Theory Calculations with Hemes and Porphyrins

    Directory of Open Access Journals (Sweden)

    Sam P. de Visser

    2016-04-01

    Full Text Available In this paper we review recent advances in computational chemistry and specifically focus on the chemical description of heme proteins and synthetic porphyrins that act as both mimics of natural processes and technological uses. These are challenging biochemical systems involved in electron transfer as well as biocatalysis processes. In recent years computational tools have improved considerably and now can reproduce experimental spectroscopic and reactivity studies within a reasonable error margin (several kcal·mol−1. This paper gives recent examples from our groups, where we investigated heme and synthetic metal-porphyrin systems. The four case studies highlight how computational modelling can correctly reproduce experimental product distributions, predicted reactivity trends and guide interpretation of electronic structures of complex systems. The case studies focus on the calculations of a variety of spectroscopic features of porphyrins and show how computational modelling gives important insight that explains the experimental spectra and can lead to the design of porphyrins with tuned properties.

  12. PORPHYRIN METABOLISM AND LIVER FUNCTION IN THE BANTU

    African Journals Online (AJOL)

    method for the detection of urinary coproporphyrin, Mentz5 calculated that ... defect in porphyrin metabolism which is commonly found in the Bantu could be ..... wood,61 traces of uroporphyrin may be excreted in normal urine. As much as 5 ...

  13. Mineralogy of halloysites and their interaction with porphyrine

    Czech Academy of Sciences Publication Activity Database

    Vašutová, V.; Bezdička, Petr; Lang, Kamil; Hradil, David

    2013-01-01

    Roč. 57, č. 3 (2013), s. 243-250 ISSN 0862-5468 Institutional support: RVO:61388980 Keywords : organoclays * mineralogy * porphyrine * CEC Subject RIV: CA - Inorganic Chemistry Impact factor: 0.434, year: 2013

  14. Tetrakis(4-tert-butylphenyl) substituted and fused quinoidal porphyrins

    KAUST Repository

    Zeng, Wangdong

    2012-01-01

    4-tert-Butylphenyl-substituted and fused quinoidal porphyrins 1 and 2 are prepared for the first time. They show (1) intense one-photon absorption in the far-red/near-infrared region, (2) enhanced two-photon absorption compared with aromatic porphyrin monomers, and (3) amphoteric redox behavior. Their geometry and electronic structure are studied by DFT calculations. This journal is © 2012 The Royal Society of Chemistry.

  15. Investigation of the porphyrine role at the mechanism of radioprotection

    International Nuclear Information System (INIS)

    Demoukhamedova, S.D.; Alieva, I.N.; Aliev, D.I.

    2002-01-01

    Full text: To date, it is well known that unfavourable radioecological conditions capable effect on the oxygen transport system in an living organism, particularly, on the conformational state of hemoglobin. Underlying mechanism is more active autoxidation of Hb(O 2 )4 into met-hemoglobin. Decreasing of the oxygen binding to the heme group of protein as a result of modified effect of ionization was observed into peripheral blood of people living on the polluted territory. Porphyrin, the main component of hemoglobin has been showed a wide range radioprotector properties. So, the conformational reorganization of the porphyrin ring plays an important role at the mechanism of hemoglobin functioning. In this report the result of conformational study, quantum-chemical calculations and theoretical calculation of frequencies and intensities of normal oscillations of IR-absorption spectrum of the porphyrin molecule at the NO-binding are presented. Computational program 'LEV' was used in all carried calculations. Due to changes into IR-spectrum of different complexes, the mechanism underlying the ligand bond formation are discussed. The theoretical frequencies of normal oscillations, satisfactorily described the porphyrin experimental IR-spectrum are received. On the base of both obtained normal oscillation forms and potential energy distribution of vibrational coordinates the detailed theoretical interpretation of the porphyrin molecule vibrational spectrum as well as the analysis of the nature of each absorption band the porphyrin molecule IR-spectrum have been carried out. Porphyrin molecule force field analysis has been showed that the ring electron density is irregular. The results of this study may be used at the theoretical calculations of IR-absorption spectrum of different metallo complexes of the porphyrin

  16. Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

    Energy Technology Data Exchange (ETDEWEB)

    Jarvis, Jacqueline M.; Sudasinghe, Nilusha M.; Albrecht, Karl O.; Schmidt, Andrew J.; Hallen, Richard T.; Anderson, Daniel B.; Billing, Justin M.; Schaub, Tanner M.

    2016-10-01

    We apply Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for direct characterization of iron-porphyrins in hydrothermal liquefaction (HTL) biocrude oils derived from two algae: Tetraselmis sp. and cyanobacteria. The ironporphyrin compounds are shown to cause catalyst bed plugging during hydroprocessing due to iron deposition. Inductively-coupled plasma optical emission spectrometry (ICPOES) was utilized for iron quantitation in the plugged catalyst beds formed through hydroprocessing of the two HTL biocrudes and identifies an enrichment of iron in the upper five centimeters of the catalyst bed for Tetraselmis sp. (Fe=100,728 ppm) and cyanobacteria (Fe=115,450 ppm). Direct infusion FT-ICR MS analysis of the two HTL biocrudes with optimized instrument conditions facilitates rapid screening and identification of iron-porphyrins without prior chromatographic separation. With FT-ICR MS we identify 138 unique iron-porphyrin compounds in the two HTL biocrudes that are structurally similar to metal-porphyrins (e.g. Ni and V) observed in petroleum. No ironporphyrins are observed in the cyanobacteria HTL biocrude after hydroprocessing, which indicates that iron-porphyrin structures in the HTL biocrude are degraded during hydroprocessing. Hydrodemetallization reactions that occur through hydroprocessing of HTL biocrudes could be responsible for the decomposition of iron-porphyrin structures leading to metal deposition in the catalyst bed that result in catalyst deactivation and bed plugging, and must be addressed for effective upgrading of algal HTL biocrudes.

  17. Microwave Production of Manganese from Manganese (IV) Oxide ...

    African Journals Online (AJOL)

    Michael O. Mensah

    2015-12-02

    Dec 2, 2015 ... energy consumption occurs in the upper part of the ferromanganese furnace ... The pre-reduction of manganese ores by carbon has been investigated by Abdel ..... Awaso Bauxite Ore using Waste Pure Water. Sachets as ...

  18. Influence of substituents in meso-aryl groups of iron l-oxo porphyrins\

    Czech Academy of Sciences Publication Activity Database

    Tabor, Edyta; Poltowicz, J.; Pamin, K.; Basag, S.; Kubiak, W.

    2016-01-01

    Roč. 119, NOV 2016 (2016), s. 342-349 ISSN 0277-5387 Institutional support: RVO:61388955 Keywords : iron porphyrins * μ-Oxo porphyrins * oxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.926, year: 2016

  19. Nominal Anchors in the CIS

    OpenAIRE

    Peter M Keller; Thomas J Richardson

    2003-01-01

    Monetary policy has become increasingly important in the countries of the Commonwealth of Independent States (CIS) as fiscal adjustment and structural reforms have taken root. Inflation has been brought down to relatively low levels in almost all of these countries, raising the question of what should be the appropriate nominal anchor at this stage. Formally, almost all CIS countries have floating exchange rate regimes, yet in practice they manage their exchange rates very heavily, perhaps be...

  20. Manganese deficiency in plants

    DEFF Research Database (Denmark)

    Schmidt, Sidsel Birkelund; Jensen, Poul Erik; Husted, Søren

    2016-01-01

    Manganese (Mn) is an essential plant micronutrient with an indispensable function as a catalyst in the oxygen-evolving complex (OEC) of photosystem II (PSII). Even so, Mn deficiency frequently occurs without visual leaf symptoms, thereby masking the distribution and dimension of the problem...... restricting crop productivity in many places of the world. Hence, timely alleviation of latent Mn deficiency is a challenge in promoting plant growth and quality. We describe here the key mechanisms of Mn deficiency in plants by focusing on the impact of Mn on PSII stability and functionality. We also address...... the mechanisms underlying the differential tolerance towards Mn deficiency observed among plant genotypes, which enable Mn-efficient plants to grow on marginal land with poor Mn availability....

  1. Manganese Research Health Project (MHRP)

    Science.gov (United States)

    2009-02-01

    green nucleic acid staining further confirmed the neurotoxic effect of cadmium in this cell model (Fig 10C). Next, we examined the enzymatic activity...Quantification of Nissl bodies revealed a widespread reduction in SNpc cell numbers. Other areas of the basal ganglia were also altered by manganese as...the substantia nigra pars compacta (SNpc) following manganese treatment. Quantification of Nissl bodies revealed a widespread reduction in SNpc

  2. 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.

  3. Multi-step intramolecular excitation energy transfer in dendritic pyrene-phosphorus(V)porphyrin heptads

    International Nuclear Information System (INIS)

    Hirakawa, Kazutaka; Segawa, Hiroshi

    2016-01-01

    Dendritic heptad molecules in which four pyrenyl groups are connected at the central phosphorus atom of the edge-porphyrins of the center-to-edge type porphyrin trimers were synthesized to investigate a multi-step excitation energy transfer. As the central energy acceptor, two types porphyrins which one was phosphorus(V)tetraphenylporphyrin (H2) and another was its derivative substituted by butoxy groups at four para-position of meso-phenyl groups (H1) were used. In the photoexcited state of the pyrene units, the excitation energy transfer to the central-porphyrin unit was observed in toluene. The excitation energy transfer is considered to be through two pathways; one is a stepwise pathway through the edge-porphyrin unit and another is a direct excitation energy transfer to the central porphyrin. The direct excitation energy transfer from pyrenes to the edge-porphyrin and central-porphyrin were observed in the case for H1. From the excited state of the edge-porphyrins, the excitation energy transfer to the central-porphyrin occurs in the H1 case. In the H2 case, the excitation energy of central-porphyrin is higher than that of H1, and the electron transfer from edge-porphyrin to the central-porphyrin become predominant process. - Highlights: • Dendritic pyrene-porphyrin heptads were synthesized. • Excitation energy transfer occurs from the pyrenyl moiety to the phosphorus(V)porphyrin. • The stepwise and direct energy transfer pathways were observed. • The quantum yields of these energy transfer pathways could be determined.

  4. Multi-step intramolecular excitation energy transfer in dendritic pyrene-phosphorus(V)porphyrin heptads

    Energy Technology Data Exchange (ETDEWEB)

    Hirakawa, Kazutaka, E-mail: hirakawa.kazutaka@shizuoka.ac.jp [Applied Chemistry and Biochemical Engineering Course, Department of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, Johoku 3-5-1, Naka-ku, Hamamatsu, Shizuoka 432-8561 (Japan); Department of Optoelectronics and Nanostructure Science, Graduate School of Science and Technology, Shizuoka University, Johoku 3-5-1, Naka-ku, Hamamatsu, Shizuoka 432-8561 (Japan); Segawa, Hiroshi [Department of Multi-Disciplinary Science - General Systems Studies, Graduate School of Arts and Sciences, The University of Tokyo, Komaba 3-8-1, Meguro-ku, Tokyo 153-8904 (Japan); Research Center for Advanced Science and Technology, The University of Tokyo, Komaba 4-6-1, Meguro-ku, Tokyo 153-8904 (Japan)

    2016-11-15

    Dendritic heptad molecules in which four pyrenyl groups are connected at the central phosphorus atom of the edge-porphyrins of the center-to-edge type porphyrin trimers were synthesized to investigate a multi-step excitation energy transfer. As the central energy acceptor, two types porphyrins which one was phosphorus(V)tetraphenylporphyrin (H2) and another was its derivative substituted by butoxy groups at four para-position of meso-phenyl groups (H1) were used. In the photoexcited state of the pyrene units, the excitation energy transfer to the central-porphyrin unit was observed in toluene. The excitation energy transfer is considered to be through two pathways; one is a stepwise pathway through the edge-porphyrin unit and another is a direct excitation energy transfer to the central porphyrin. The direct excitation energy transfer from pyrenes to the edge-porphyrin and central-porphyrin were observed in the case for H1. From the excited state of the edge-porphyrins, the excitation energy transfer to the central-porphyrin occurs in the H1 case. In the H2 case, the excitation energy of central-porphyrin is higher than that of H1, and the electron transfer from edge-porphyrin to the central-porphyrin become predominant process. - Highlights: • Dendritic pyrene-porphyrin heptads were synthesized. • Excitation energy transfer occurs from the pyrenyl moiety to the phosphorus(V)porphyrin. • The stepwise and direct energy transfer pathways were observed. • The quantum yields of these energy transfer pathways could be determined.

  5. MINERALOGY OF HALLOYSITES AND THEIR INTERACTION WITH PORPHYRINE

    Directory of Open Access Journals (Sweden)

    Vašutová V.

    2013-09-01

    Full Text Available Samples representing two modifications of halloysites, dehydrated (7 Å and hydrated (10 Å forms, respectively, were examined with the aim to select suitable candidates for to be used as carriers of porphyrine photoactive molecules. The samples were analysed by powder X-ray diffraction (pXRD, infrared spectroscopy (FT-IR, and high resolution transmission electron microscopy (HRTEM. Chemical composition was also determined. For the determination of cationic exchange capacity (CEC the silver thiourea method (AgTU was used. Silver cations concentrations in the solution before and after the interaction were determined by atomic absorption spectrometry (AAS. By the interaction of two pure hydrated halloysites with porphyrine it was found that porphyrine does not intercalate the interlayer space, but it is adsorbed on the outer surface of halloysite. This interaction changed the colour of clay sample from white to green. The changes were also clearly visible on diffuse reflectance spectra (DRS.

  6. Platinum porphyrins as ionophores in polymeric membrane electrodes

    DEFF Research Database (Denmark)

    Lvova, Larisa; Verrelli, Giorgio; Nardis, Sara

    2011-01-01

    A comparative study of Pt(II)- and Pt(IV)-porphyrins as novel ionophores for anion-selective polymeric membrane electrodes is performed. Polymeric membranes of different compositions, prepared by varying plasticizers, cationic and anionic additives and Pt porphyrins, have been examined...... within the electrode membranes, while those based on Pt(IV)TPPCl2 operate via a mixed mode carrier mechanism, evidencing also a partial reduction of the starting ionophore to Pt(II)TPP. Spectrophotometric measurements of thin polymeric films indicate that no spontaneous formation of hydroxide ion bridged...... porphyrin dimers occurs in the membrane plasticized both with high or low dielectric constant plasticizer, due to a low oxophilicity of central Pt. The computational study of various anion–Pt(IV)TPPCl2 complex formation by means of semi-empirical and density functional theory (DFT) methods revealed a good...

  7. Interaction of porphyrins with CdTe quantum dots

    International Nuclear Information System (INIS)

    Zhang Xing; Liu Zhongxin; Ma Lun; Hossu, Marius; Chen Wei

    2011-01-01

    Porphyrins may be used as photosensitizers for photodynamic therapy, photocatalysts for organic pollutant dissociation, agents for medical imaging and diagnostics, applications in luminescence and electronics. The detection of porphyrins is significantly important and here the interaction of protoporphyrin-IX (PPIX) with CdTe quantum dots was studied. It was observed that the luminescence of CdTe quantum dots was quenched dramatically in the presence of PPIX. When CdTe quantum dots were embedded into silica layers, almost no quenching by PPIX was observed. This indicates that PPIX may interact and alter CdTe quantum dots and thus quench their luminescence. The oxidation of the stabilizers such as thioglycolic acid (TGA) as well as the nanoparticles by the singlet oxygen generated from PPIX is most likely responsible for the luminescence quenching. The quenching of quantum dot luminescence by porphyrins may provide a new method for photosensitizer detection.

  8. Role of complement in porphyrin-induced photosensitivity

    International Nuclear Information System (INIS)

    Lim, H.W.; Gigli, I.

    1981-01-01

    Addition of porphyrins to sera of guinea pigs in vitro, followed by irradiation with 405 nm light, resulted in dose-dependent inhibitions of hemolytic activity of complement. With guinea pig as an animal model, we also found that systemically administered porphyrins, followed by irradiation with 405 nm light, resulted in dose-dependent inhibition of CH50 in vivo. The erythrocytes from porphyrin-treated guinea pigs showed an increased susceptibility to hemolysis induced by 405 nm irradiation in vitro. Clinical changes in these animals were limited to light-exposed areas and consisted of erythema, crusting, and delayed growth of hair. Histologically, dermal edema, dilation of blood vessels, and infiltration of mononuclear and polymorphonuclear cells were observed. Guinea pigs irradiated with ultraviolet-B developed erythema, but had no alteration of their complement profiles. It is suggested that complement products may play a specific role in the pathogenesis of the cutaneous lesions of some porphyrias

  9. Extraction of manganese from electrolytic manganese residue by bioleaching.

    Science.gov (United States)

    Xin, Baoping; Chen, Bing; Duan, Ning; Zhou, Changbo

    2011-01-01

    Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. Copyright © 2010 Elsevier Ltd. All rights reserved.

  10. Theoretical study on junctions in porphyrin oligomers for nano scale devices

    International Nuclear Information System (INIS)

    Mizuseki, Hiroshi; Belosludov, Rodion V.; Farajian, Amir A.; Igarashi, Nobuaki; Kawazoe, Yoshiyuki

    2005-01-01

    A unimolecular rectifier could be built by combining two molecular sub-units that contain acceptor or donor groups. Porphyrin possesses good electron-donating properties due to its large, easily ionized, π-conjugated system. In this study, we propose that a rectifier diode could be created by combining two metal porphyrin molecules containing different metal atoms. This function would realize an effect similar to a p-n junction in a solid-state device. A Zn porphyrin-Ni porphyrin junction in a non-conjugated porphyrin system displays a localization of frontier orbitals that is similar to a rectifier function

  11. Effects of Immersion Solvent on Photovoltaic and Photophysical Properties of Porphyrin-Sensitized Solar Cells.

    Science.gov (United States)

    Hayashi, Hironobu; Higashino, Tomohiro; Kinjo, Yuriko; Fujimori, Yamato; Kurotobi, Kei; Chabera, Pavel; Sundström, Villy; Isoda, Seiji; Imahori, Hiroshi

    2015-08-26

    Memory effects in self-assembled monolayers (SAMs) of zinc porphyrin carboxylic acid on TiO2 electrodes have been demonstrated for the first time by evaluating the photovoltaic and electron transfer properties of porphyrin-sensitized solar cells prepared by using different immersion solvents sequentially. The structure of the SAM of the porphyrin on the TiO2 was maintained even after treating the porphyrin monolayer with different neat immersion solvents (memory effect), whereas it was altered by treatment with solutions containing different porphyrins (inverse memory effect). Infrared spectroscopy shows that the porphyrins in the SAM on the TiO2 could be exchanged with the same or analogous porphyrin, leading to a change in the structure of the porphyrin SAM. The memory and inverse memory effects are well correlated with a change in porphyrin geometry, mainly the tilt angle of the porphyrin along the long molecular axis from the surface normal on the TiO2, as well as with kinetics of electron transfer between the porphyrin and TiO2. Such a new structure-function relationship for DSSCs will be very useful for the rational design and optimization of photoelectrochemical and photovoltaic properties of molecular assemblies on semiconductor surfaces.

  12. Antibatic photovoltaic response in zinc-porphyrin-liked oligothiophenes

    DEFF Research Database (Denmark)

    Krebs, Frederik C; Spanggaard, H.

    2005-01-01

    -stannylchloride and subsequent palladium catalysed Stille coupling. We further synthesised 5,15-bis(3, 4', 4", 4"', 4", 4""', 4""", 4"""'-octahexyl-[2, 2'; 5', 2" 5", 2'"; 5"', 2""; 5"", 2""'; 5""', 2"""; 5""", 2"""']octithiophene-5-yl)-10, 20-bis(3, 5-ditertbutylphenyl)zinc(II)porphyrin (5) from trimethyl(3, 4', 4", 4'", 4......"", 4""', 4""", 4"""'-Octahexyl-[2, 2'; 5', 2"; 5"; 2'"; 5"', 2""; 5"", 2"'"; 5""', 2"""; 5""", 2"""']octithiophene-5-yl)stannane (3-SnMe3) and 5, 15-dibromo-10, 20-bis(3, 5-ditertbutylphenyl)zinc(II)porphyrin (6) by Stille coupling. All the products were characterised by size exclusion chromatography...

  13. Experimental testing of anchoring devices for bottom rails in partially anchored timber frame shear walls

    OpenAIRE

    Caprolu, Giuseppe

    2011-01-01

    Källsner and Girhammar have presented a new plastic design method of wood-framed shear walls at ultimate limit state. This method allows the designer to calculate the load-carrying capacity of shear walls partially anchored, where the leading stud is not anchored against the uplift.The anchorage system of shear walls is provided from anchor bolts and hold downs. Anchor bolts provide horizontal shear continuity between the bottom rail and the foundation. Hold downs are directly connected from ...

  14. Determination of manganese content in aqueous solutions

    International Nuclear Information System (INIS)

    Reeder, S.D.; Smith, J.R.

    1977-01-01

    The three analytical methods used in the hydrogen-to-manganese cross-section ratio measurement were: volumetric determination of manganese, gravimetric analysis of manganous sulfate; and densimetric determination of manganous sulfate

  15. Manganese activated phosphate glass for dosimetry

    International Nuclear Information System (INIS)

    Regulla, D.

    1975-01-01

    A measuring element comprises a metaphosphate glass doped with manganese as an activator. The manganese activated metaphosphate glass can detect and determine radiation doses in the range between milliroentgens and more than 10 megaroentgens. (auth)

  16. Anchor Bolt Position in Base Plate In Terms Of T and J Anchor Bolt

    Directory of Open Access Journals (Sweden)

    b Osman Mohamad Hairi

    2017-01-01

    Full Text Available Generally, L anchor bolt system has been used for a long period of time in construction industry as one of the distributing load structures. However, there are some weaknesses in L anchor bolt which may straighten and pullup when charged with tensile load. Current practices prefer to use other types of anchor bolt systems, such as headed studs anchor bolt system to replace the L anchor bolt design. There has been lack of studies to prove that it is more effective in terms of performance. A new T anchor bolt which was basically modified from headed studs anchor bolt was proposed in this study to compare its performance of tensile loading in concrete failure to typical L design. This study aims to determine whether the T anchor bolt system gives better performance as compared to an L anchor bolt system. The performance was rated based on tensile loading on concrete failure pattern. A pullout test was conducted on two different anchor bolt systems, namely L and T. The anchor bolt embedded depth, h in concrete were varied according to their hook or bend radius. Each sample was repeated twice. There were totally eight samples. The hook or bend radius used were 50 mm and 57.5 mm for sample L1 and L2, respectively. 90-degree bend were used on sample T1 and T2. Based on test results, it can be seen that the performance of concrete failure pattern under tensile load on both L and T anchor bolt design samples with 200 mm embedment depth was better than deeper embedment depth of 230 mm. But the L anchor bolt design gives the best results as compared to T design. Although T anchor bolt design shows higher resistance before first bond failure to the concrete sample. T anchor bolt was analysed and needed deeper embedment depth to allow formation of cone pull-out shape to acquire better performance.

  17. 21 CFR 184.1446 - Manganese chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Manganese chloride. 184.1446 Section 184.1446 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Specific Substances Affirmed as GRAS § 184.1446 Manganese chloride. (a) Manganese chloride (MnCl2·4H2O, CAS...

  18. 21 CFR 582.5446 - Manganese chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Manganese chloride. 582.5446 Section 582.5446 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5446 Manganese chloride. (a) Product. Manganese chloride. (b) Conditions of use. This...

  19. Link Anchors in Images: Is there Truth?

    NARCIS (Netherlands)

    Aly, Robin; McGuinness, Kevin; Kleppe, Martijn; Ordelman, Roeland J.F.; O'Connor, Noel; de Jong, Franciska M.G.

    2012-01-01

    While automatic linking in text collections is well understood, little is known about links in images. In this work, we investigate two aspects of anchors, the origin of a link, in images: 1) the requirements of users for such anchors, e.g. the things users would like more information on, and 2)

  20. 76 FR 30301 - Commercial Acquisition; Anchor Tenancy

    Science.gov (United States)

    2011-05-25

    ... NATIONAL AERONAUTICS AND SPACE ADMINISTRATION 48 CFR Part 1812 RIN 2700-AD64 Commercial... consistent with NASA's authority under Section 401 of the Commercial Space Competitiveness Act (CSCA) of 1992. NASA may enter into multi-year anchor tenancy contracts for commercial space goods or services. Anchor...

  1. Re(I) bridged porphyrin dyads, triads and tetrads

    Indian Academy of Sciences (India)

    DNA cleavage.4 Design strategies to develop solid-state multichromophore arrays of defined rigidity, ... lent synthetic strategies to porphyrin arrays have gen- erally proved quite limiting. The covalent synthetic ...... since retention times vary inversely with size.23 Pulsed- field-gradient NMR, which measures coefficients for.

  2. Expanded porphyrins as third order non-linear optical materials ...

    Indian Academy of Sciences (India)

    WINTEC

    function correlations ... An understanding of the structure–function corre- lations of these expanded porphyrins is an important first step for ... where χ (2) and χ (3) are the quadratic χ (2) (first- order) and χ (3) cubic (second-order) susceptibilities.

  3. Interaction of porphyrins with PAMAM dendrimers in aqueous solution

    Czech Academy of Sciences Publication Activity Database

    Kubát, Pavel; Lang, Kamil; Zelinger, Zdeněk

    2007-01-01

    Roč. 131, - (2007), s. 200-205 ISSN 0167-7322 R&D Projects: GA ČR GA203/04/0426 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40320502 Keywords : porphyrin * PAMAM dendrimer * aggragation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.982, year: 2007

  4. Synthesis of metallic nanoshells on porphyrin-stabilized emulsions

    Science.gov (United States)

    Wang, Haorong [Albuquerque, NM; Song, Yujiang [Albuquerque, NM; Shelnutt, John A [Tijeras, NM; Medforth, Craig J [Winters, CA

    2011-12-13

    Metal nanostructures formed by photocatalytic interfacial synthesis using a porphyrin-stabilized emulsion template and the method for making the nanostructures. Catalyst-seeded emulsion droplets are employed as templates for hollow-nanoshell growth. The hollow metal nanospheres may be formed with or without inclusions of other materials.

  5. Trilobolide-porphyrin conjugates: On synthesis and biological effects evaluation

    Czech Academy of Sciences Publication Activity Database

    Tomanová, P.; Rimpelová, S.; Jurášek, M.; Buděšínský, Miloš; Vejvodová, L.; Ruml, T.; Kmoníčková, E.; Drašar, P. B.

    2015-01-01

    Roč. 97, SI (2015), s. 8-12 ISSN 0039-128X Grant - others:GA ČR(CZ) GA14-04329S; GA MŠk(CZ) ED2.1.00/03.0076 Institutional support: RVO:61388963 Keywords : trilobolide * porphyrin * nitric oxide * fluorescence microscopy Subject RIV: CE - Biochemistry Impact factor: 2.513, year: 2015

  6. Porphyrin involvement in redshift fluorescence in dentin decay

    Science.gov (United States)

    Slimani, A.; Panayotov, I.; Levallois, B.; Cloitre, T.; Gergely, C.; Bec, N.; Larroque, C.; Tassery, H.; Cuisinier, F.

    2014-05-01

    The aim of this study was to evaluate the porphyrin involvement in the red fluorescence observed in dental caries with Soprolife® light-induced fluorescence camera in treatments mode (SOPRO, ACTEON Group, La Ciotat, France) and Vistacam® camera (DÜRR DENTAL AG, Bietigheim-Bissingen, Germany). The International Caries Detection and Assessment System (ICDAS) was used to rand the samples. Human teeth cross-sections, ranked from ICDAS score 0 to 6, were examined by epi-fluorescence microscopy and Confocal Raman microscopy. Comparable studies were done with Protoporphyrin IX, Porphyrin I and Pentosidine solutions. An RGB analysis of Soprolife® images was performed using ImageJ Software (1.46r, National Institutes of Health, USA). Fluorescence spectroscopy and MicroRaman spectroscopy revealed the presence of Protoporphyrin IX, in carious enamel, dentin and dental plaque. However, the presence of porphyrin I and pentosidine cannot be excluded. The results indicated that not only porphyrin were implicated in the red fluorescence, Advanced Glygation Endproducts (AGEs) of the Maillard reaction also contributed to this phenomenon.

  7. Ringstone anchors from Gujarat, west coast of India

    Digital Repository Service at National Institute of Oceanography (India)

    Gaur, A.S.; Sundaresh; Tripati, S.; Bandodkar, S.N.

    of Dwarka and Somanath have yielded several ringstone anchors along with other stone anchors such as triangular and grapnel types. The raw material used for these ring stones comprises basalt, sandstone and limestone. Earlier, these anchors were identified...

  8. Bionic catalysis of porphyrin for electrochemical detection of nucleic acids

    International Nuclear Information System (INIS)

    Li Jie; Lei Jianping; Wang Quanbo; Wang Peng; Ju Huangxian

    2012-01-01

    Highlights: ► This is the first application of bionic catalysis of porphyrin as detection probe in bioanalysis. ► Porphyrin–DNA–gold nanoparticle probe is synthesized. ► Binding model between FeTMPyP and DNA is verified. ► The detection probe shows excellent electrocatalytic behaviors toward the reduction of O 2 . ► The biosensor exhibited good performance with wide linear range and high specificity. - Abstract: A novel electrochemical strategy was designed for the detection of DNA based on the bionic catalysis of porphyrin. The detection probe was prepared via the assembly of thiolated double strand DNA (dsDNA) with gold nanoparticles (AuNPs), and then interacted with cationic iron (III) meso-tetrakis (N-methylphyridinum-4-yl) porphyrin (FeTMPyP) via groove binding along the dsDNA surface. The resulting nanocomplex was characterized with transmission electron microscopy, UV–vis absorption and circular dichroism spectroscopy. The FeTMPyP–DNA–AuNPs probe on gold electrode demonstrated the excellent electrocatalytic behaviors toward the reduction of O 2 due to the largely loading of FeTMPyP and good conductivity. Based on bionic catalysis of porphyrin for the reduction of O 2 , the resulting biosensor exhibited a good performance for the detection of DNA with a wide linear range from 1 × 10 −12 to 1 × 10 −8 mol L −1 and detection limit of 2.5 × 10 −13 mol L −1 at the signal/noise of 3. More importantly, the biosensor presented excellent ability to discriminate the perfectly complementary target and the mismatched stand. This strategy could be conveniently extended for detection of other biomolecules. To the best of our knowledge, this is the first application of bionic catalysis of porphyrin as detection probe and opens new opportunities for sensitive detection of biorecognition events.

  9. Dietary manganese in the Glasgow area

    International Nuclear Information System (INIS)

    Cross, J.D.; Dale, I.M.; Raie, R.M.

    1979-01-01

    The manganese content of the diet and human tissue (adult and infant) in the Glasgow area is established. The total manganese intake by a breast fed infant (6 μg/day) is very much lower than that of an adult (5 mg/day). This does not appear to cause any upset in the infant's metabolism and the tissue levels of both groups are similar. This indicates that the human system can obtain its required manganese from both levels of intake. Tea is the major source of manganese in the diet: tobacco, which is rich in manganese, does not contribute a significant amount when smoked. (author)

  10. Noncollinear magnetism in manganese nanostructures

    Czech Academy of Sciences Publication Activity Database

    Zelený, Martin; Šob, Mojmír; Hafner, J.

    2009-01-01

    Roč. 80, č. 14 (2009), 144414/1-144414/19 ISSN 1098-0121 R&D Projects: GA AV ČR IAA100100920; GA MŠk OC09011 Institutional research plan: CEZ:AV0Z20410507 Keywords : magnetism of nanostructures * nanowires * noncollinear magnetism * manganese Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.475, year: 2009

  11. Effect of porphyrin on photocatalytic activity of TiO2 nanoparticles toward Rhodamine B photodegradation.

    Science.gov (United States)

    Ahmed, M A; Abou-Gamra, Z M; Medien, H A A; Hamza, M A

    2017-11-01

    As known, porphyrins have central role in photosynthesis, biological oxidation and reduction and oxygen transport beside to their intensive color which qualify them to be good photosensitizers. Herein, tetra (4-carboxyphenyl) porphyrin (TCPP) was prepared by a simple one-pot synthesis to use as a visible antenna for TiO 2 nanoparticles that were prepared via a simple template-free sol-gel method. Various loading percentages of TCPP (0.05-1%) were incorporated on the surface of TiO 2 as photosensitizer for photocatalytic degradation of Rhodamine B (Rh B) dye as a primary cationic pollutant model. Among them, 0.1% TCPP-TiO 2 was the most reactive sample. It was found that the photoactivity of 0.1% TCPP-TiO 2 sample (0.5g/L) was approximately 1.5 times greater than that of pure TiO 2 (0.5g/L) toward the degradation of Rh B (1×10 -5 M) under UV-A irradiation. Transient fluorescence decay measurements showed that the life time of TiO 2 excited state has doubled after anchoring TCPP, thus the probability of electron-hole recombination has decreased. The samples were characterized by XRD, HR-TEM, DRS and N 2 adsorption-desorption isotherms. The XRD patterns confirmed the successful preparation of TiO 2 nanoparticles with average crystalline size of 25.7nm. Also, XRD patterns suggested the presence of mixed phase TiO 2 nanoparticles of 77% anatase and 23% rutile. DRS showed that the characteristic peaks of TCPP covered the whole visible range 400-700nm. HR-TEM images showed the spheroids shape of TiO 2 nanoparticles and confirmed the presence of anatase and rutile phases as suggested from XRD data. The different parameters affecting the photodegradation of Rh B dye such as catalyst dose, dye concentration and pH were studied to obtain the optimum conditions. Almost complete degradation of Rh B was obtained which confirmed by HPLC and TOC measurements. The effect of scavengers was studied to indicate the most active species. TCPP-TiO 2 gave a good response toward the

  12. Photophysical properties of novel Porphyrin-Flavin Dyads

    International Nuclear Information System (INIS)

    Stark, S.

    2001-10-01

    Photosynthesis belongs to the fundamentals of life on earth, therefore it is an important matter in natural sciences. The basic principle of photosynthesis is the transformation of solar light into chemical energy. The starting steps of photosynthesis are light-induced energy- and electron-transfer-steps with singular efficiency. One attempt to enlighten the molecular processes involved is to synthesize simpler model systems with similar properties. Important research goals are the dependencies of light-induced processes on distance and orientation of donor and acceptor. A second aim next to the clarification of the molecular conditions of photosynthesis is to create molecular light-driven machines. The most simple so-called biomimetic model system consists of an electron-donor connected to an electron-acceptor via a spacer-group. This simplest form is also referred to as dyad. Beyond dyads far more complicated compounds have been introduced consisting of several donors and/or acceptors, so-called triads, tetrads, pentads etc. Usually porphyrin serves as electron-donor. Next to chinones several other electron-acceptors are used, e.g. anthracene, pyromellitimide and fullerene. Artificial photosynthetic centers are often more stable and/or the excited states are easier to detect compared to the natural photosynthetic center. The photophysical characteristics of four dyads are reported in this work. The dyads consist of porphyrin (either free-base or zinc-metallated) and flavin, connected by different spacers. These dyads reveal photo-induced electron transfer from porphyrin to flavin and energy-transfer in the reversed direction with different efficiencies. The object of the study is the dependency of these processes on the structural features. The spacer of the dyads 1a-1c is an aromatic bridge which leads to well defined donor-acceptor distances. Because of this structure conjugation through the spacer is increased, whereas the absorption in the visible and near UV

  13. Tunable photophysical processes of porphyrin macrocycles on the surface of ZnO nanoparticles

    KAUST Repository

    Parida, Manas R.

    2015-01-23

    We investigated the impact of the molecular structure of cationic porphyrins on the degree of electrostatic interactions with zinc oxide nanoparticles (ZnO NPs) using steady-state and time-resolved fluorescence and transient absorption spectroscopy. Our results demonstrate that the number of cationic pyridinium units has a crucial impact on the photophysics of the porphyrin macrocycle. Fluorescence enhancement, relative to initial free porphyrin fluorescence, was found to be tuned from 3.4 to 1.3 times higher by reducing the number of cationic substituents on the porphyrin from 4 to 2. The resulting enhancement of the intensity of the fluorescence is attributed to the decrease in the intramolecular charge transfer (ICT) character between the porphyrin cavity and its meso substituent. The novel findings reported in this work provide an understanding of the key variables involved in nanoassembly, paving the way toward optimizing the interfacial chemistry of porphyrin-ZnO NP assembly for photodynamic therapy and energy conversion.

  14. Substituted group and side chain effects for the porphyrin and zinc(II)–porphyrin derivatives: A DFT and TD-DFT study

    International Nuclear Information System (INIS)

    Tai, Chin-Kuen; Chuang, Wen-Hua; Wang, Bo-Cheng

    2013-01-01

    The DFT/B3LYP/LANL2DZ and TD-DFT calculations have been performed to generate the optimized structures, electronic and photo-physical properties for the porphyrin and zinc(II)–porphyrin (metalloporphyrin) derivatives. The substituted group and side chain effects for these derivatives are discussed in this study. According to the calculation results, the side chain moiety extends the π-delocalization length from the porphyrin core to the side chain moiety. The substituted group with a stronger electron-donating ability increases the energy level of highest occupied molecular orbital (E HOMO ). The side chain moiety with a lower resonance energy decreases E HOMO , the energy level of the lowest unoccupied molecular orbital (E LUMO ), and the energy gap (E g ) between HOMO and LUMO in the porphyrin and zinc(II)–porphyrin derivatives. The natural bonding orbital (NBO) analysis determines the possible electron transfer mechanism from the electron-donating to -withdrawing groups (the side chain moiety) in these porphyrin derivatives. The projected density of state (PDOS) analysis shows that the electron-donating group affects the electron density distribution in both HOMO and LUMO, and the side chain moiety influence the electron density distribution in LUMO. The calculated photo-physical properties (absorption wavelengths and the related oscillator strength, f) in dichloromethane environment for porphyrin and zinc(II)–porphyrin derivatives have been simulated by using the TD-DFT method within the Polarizable Continuum Model (PCM). The present of both of the substituted group and the side chain moiety in these derivatives results in a red shift and broadening of the range of the absorption peaks of the Q/Soret band as compared to porphin. -- Highlights: • Side chain moiety extends the π-delocalization for the porphyrins. • Substituted group increases the energy of highest occupied molecular orbital. • Side chain moiety influences the Q/Soret band of

  15. Effect of Human and Bovine Serum Albumin on kinetic Chemiluminescence of Mn (III-Tetrakis (4-Sulfonatophenyl Porphyrin-Luminol-Hydrogen Peroxide System

    Directory of Open Access Journals (Sweden)

    Sayed Yahya Kazemi

    2012-01-01

    Full Text Available The present work deals with an attempt to study the effect of human and bovine serum albumin on kinetic parameters of chemiluminescence of luminol-hydrogen peroxide system catalyzed by manganese tetrasulfonatophenyl porphyrin (MnTSPP. The investigated parameters involved pseudo-first-order rise and fall rate constant for the chemiluminescence burst, maximum level intensity, time to reach maximum intensity, total light yield, and values of the intensity at maximum CL which were evaluated by nonlinear least square program KINFIT. Because of interaction of metalloporphyrin with proteins, the CL parameters are drastically affected. The systems resulted in Stern-Volmer plots with values of 3.17×105 and 3.7×105M−1 in the quencher concentration range of 1.5×10−6 to 1.5×10−5 M for human serum albumin (HSA and bovine serum albumin (BSA, respectively.

  16. Local Electric Field Effects on Rhodium-Porphyrin and NHC-Gold Catalysts

    Science.gov (United States)

    2015-01-05

    AFRL-OSR-VA-TR-2015-0023 (NII) - Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold Catalysts MATTHEW KANAN LELAND STANFORD JUNIOR UNIV...Effects on Rhodium -Porphyrin and NHC-Gold Catalysts Principal Investigator: Matthew W. Kanan Project Publications: 1. “An Electric Field–Induced Change...Stanford University Grant/Contract Title The full title of the funded effort. (NII)-Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold

  17. Dye linked conjugated homopolymers: using conjugated polymer electroluminescence to optically pump porphyrin-dye emission

    DEFF Research Database (Denmark)

    Nielsen, K.T.; Spanggaard, H.; Krebs, Frederik C

    2004-01-01

    . Electroluminescent devices of the homopolymer itself and of the zinc-porphyrin containing polymer were prepared and the nature of the electroluminescence was characterized. The homopolymer segments were found to optically pump the emission of the zinc-porphyrin dye moities. The homopolymer exhibits blue......Zinc-porphyrin dye molecules were incorporated into the backbone of a conjugated polymer material by a method, which allowed for the incorporation of only one zinc-porphyrin dye molecule into the backbone of each conjugated polymer molecule. The electronic properties of the homopolymer were...

  18. Boronated porphyrins in NCT: Results with a new potent tumor localizer

    International Nuclear Information System (INIS)

    Kahl, S.B.; Koo, M.S.; Laster, B.H.; Fairchild, R.G.

    1988-01-01

    Several chemical methods are available for the solubilization of boronated porphyrins. We have previously reported the tumor localization of nido carboranyl porphyrins in which the icosahedral carborane cages have been opened to give B 9 C 2 anions. One of these species has shown tumor boron levels of nearly 50 μg B/g when delivered by week-long subcutaneous infusions. We report here recent in vivo experiments with a new, highly water-soluble porphyrin based on the hematoporphyrin-type of compound in which aqueous solubility is achieved using the two propionic acid side chains of the ''natural'' porphyrin frame. 7 refs

  19. Peripherally Metalated Porphyrins with Applications in Catalysis, Molecular Electronics and Biomedicine.

    Science.gov (United States)

    Longevial, Jean-François; Clément, Sébastien; Wytko, Jennifer A; Ruppert, Romain; Weiss, Jean; Richeter, Sébastien

    2018-04-24

    Porphyrins are conjugated, stable chromophores with a central core that binds a variety of metal ions and an easily functionalized peripheral framework. By combining the catalytic, electronic or cytotoxic properties of selected transition metal complexes with the binding and electronic properties of porphyrins, enhanced characteristics of the ensemble are generated. This review article focuses on porphyrins bearing one or more peripheral transition metal complexes and discusses their potential applications in catalysis or biomedicine. Modulation of the electronic properties and intramolecular communication through coordination bond linkages in bis-porphyrin scaffolds is also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Anchoring effects on early autobiographical memories.

    Science.gov (United States)

    Greenberg, Daniel L; Bishara, Anthony J; Mugayar-Baldocchi, Marino A

    2017-10-01

    Studies of childhood memory typically show that our earliest memories come from between three and four years of age. This finding is not universal, however. The age estimate varies across cultures and is affected by social influences. Research from the judgments and decision-making literature suggests that these estimates might also involve a judgment under uncertainty. Therefore, they might be susceptible to less social influences such as heuristics and biases. To investigate this possibility, we conducted two experiments that used anchoring paradigms to influence participants' estimates of their age during early autobiographical memories. In Experiment 1, participants answered either a high-anchor or a low-anchor question, and were warned that the anchor was uninformative; they went on to estimate their age during their earliest autobiographical memory. In Experiment 2, we replicated Experiment 1 and extended the design to examine additional early autobiographical memories. In both experiments, participants in the low-anchor condition gave earlier age estimates than those in the high-anchor condition. These results provide new insights into the methods used to investigate autobiographical memory. Moreover, they show that reports of early autobiographical memories can be influenced by a relatively light touch - a change to a single digit in a single question.

  1. Improving performance by anchoring movement and "nerves".

    Science.gov (United States)

    Iso-Ahola, Seppo E; Dotson, Charles O; Jagodinsky, Adam E; Clark, Lily C; Smallwood, Lorraine L; Wilburn, Christopher; Weimar, Wendi H; Miller, Matthew W

    2016-10-01

    Golf's governing bodies' recent decision to ban all putting styles "anchoring one end of the club against the body" bridges an important practical problem with psychological theory. We report the first experiment testing whether anchoring provides technical and/or psychological advantage in competitive performance. Many "greats" of professional golf from Arnold Palmer and Jack Nicklaus to Tiger Woods have argued against anchoring, believing that it takes "nerves" out of competitive performance and therefore artificially levels the playing field. To shed more light on the issue, we tested participants' performance with anchored and unanchored putters under low and high pressure when controlling for the putter length. We found no statistically significant evidence for a technical advantage due to anchoring but a clear psychological advantage: participants who anchored their putters significantly outperformed unanchored counterparts under high, but not low, pressure. Results provide tentative evidence for the ban's justification from a competitive standpoint. However, before any definite conclusions can be made, more research is needed when using high-level golfers. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Spectroscopic characterization of manganese minerals.

    Science.gov (United States)

    Lakshmi Reddy, S; Padma Suvarna, K; Udayabhaska Reddy, G; Endo, Tamio; Frost, R L

    2014-01-03

    Manganese minerals ardenite, alleghanyite and leucopoenicite originated from Madhya Pradesh, India, Nagano prefecture Japan, Sussex Country and Parker Shaft Franklin, Sussex Country, New Jersey respectively are used in the present work. In these minerals manganese is the major constituent and iron if present is in traces only. An EPR study of on all of the above samples confirms the presence of Mn(II) with g around 2.0. Optical absorption spectrum of the mineral alleghanyite indicates that Mn(II) is present in two different octahedral sites and in leucophoenicite Mn(II) is also in octahedral geometry. Ardenite mineral gives only a few Mn(II) bands. NIR results of the minerals ardenite, leucophoenicite and alleghanyite are due to hydroxyl and silicate anions which confirming the formulae of the minerals. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Characterization of functionalised porphyrin films using synchrotron radiation

    International Nuclear Information System (INIS)

    Arima, V.; Matino, F.; Thompson, J.; Del Sole, R.; Mele, G.; Vasapollo, G.; Cingolani, R.; Rinaldi, R.; Blyth, R.I.R.

    2005-01-01

    Porphyrins and C 60 are strategic materials for the fabrication of nanoscale molecular devices by virtue of their optical, photo-electro-chemical and chemical properties. We have developed procedures to immobilise cobalt tetra-butyl-phenyl porphyrins (CoTBPPs) on gold surfaces via ligation to self-assembled monolayers of aromatic aminothiophenols (4-ATP). We have used synchrotron radiation photoemission and near-edge X-ray absorption, NEXAFS, to characterise such films, both in their native state, and with ligated fulleropyrrolidines N-methyl-2-(p-pyridyl)-3,4-fulleropyrrolidine (Py-C 60 ), forming charge-separation complexes which may have applications in solar cells. While photoemission spectra appear dominated by the individual CoTBPP and Py-C 60 components, we observe an apparent signature of charge separation in fulleropyrrolidine NEXAFS spectra

  4. Enhanced solar energy collection in porphyrin based photoconversion schemes

    Science.gov (United States)

    Gust, D.; Moore, T. A.

    1983-02-01

    A series of carotenoporphyrins whose conformations varied from folded (with the carotenoid (PI)-electron system stacked over that of the porphyrin) to extended (with the two chromophores widely separated) were studied. The conformations were determined by high resolution proton NMR studies. Laser flash spectroscopy revealed triplet energy transfer from porphyrin to carotenoid. Three distinct pathways for such transfer were discovered: (1) static through space transfer which does not require significant intramolecular motions; (2) dynamic through space transfer mediated by intramolecular motions; (3) triplet transfer mediated by the chemical bonds joining the chromophores. pulse radiolysis and fluorescence quenching of these ethers and related carotenoporphyrins revealed electron transfer in the systems. It is demonstrated that the natural carotenoid functions of photoprotection from singlet oxygen damage and antenna function can be mimicked by synthetic molecules, and therefore, in principle can be applied to artificial solar energy conversion systems.

  5. Characterization of functionalised porphyrin films using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Arima, V. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy)]. E-mail: valentina.arima@unile.it; Matino, F. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Thompson, J. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Del Sole, R. [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, via per Arnesano, 73100 Lecce (Italy); Mele, G. [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, via per Arnesano, 73100 Lecce (Italy); Vasapollo, G. [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, via per Arnesano, 73100 Lecce (Italy); Cingolani, R. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Rinaldi, R. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Blyth, R.I.R. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy)

    2005-07-30

    Porphyrins and C{sub 60} are strategic materials for the fabrication of nanoscale molecular devices by virtue of their optical, photo-electro-chemical and chemical properties. We have developed procedures to immobilise cobalt tetra-butyl-phenyl porphyrins (CoTBPPs) on gold surfaces via ligation to self-assembled monolayers of aromatic aminothiophenols (4-ATP). We have used synchrotron radiation photoemission and near-edge X-ray absorption, NEXAFS, to characterise such films, both in their native state, and with ligated fulleropyrrolidines N-methyl-2-(p-pyridyl)-3,4-fulleropyrrolidine (Py-C{sub 60}), forming charge-separation complexes which may have applications in solar cells. While photoemission spectra appear dominated by the individual CoTBPP and Py-C{sub 60} components, we observe an apparent signature of charge separation in fulleropyrrolidine NEXAFS spectra.

  6. Synthesis and anion binding properties of porphyrins and related compounds

    KAUST Repository

    Figueira, Flávio

    2016-12-02

    Over the last two decades the preparation of pyrrole-based receptors for anion recognition has attracted considerable attention. In this regard porphyrins, phthalocyanines and expanded porphyrins have been used as strong and selective receptors while the combination of those with different techniques and materials can boost their applicability in different applications as chemosensors and extracting systems. Improvements in the field, including the synthesis of this kind of compounds, can contribute to the development of efficient, cheap, and easy-to-prepare anion receptors. Extensive efforts have been made to improve the affinity and selectivity of these compounds and the continuous expansion of related research makes this chemistry even more promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  7. Facile Preparation of Hybrid Zinc Porphyrin Dendrimer Using Coordination Complex

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Go-Eun; Shin, Eun Ju [Sunchon National University, Suncheon (Korea, Republic of)

    2016-03-15

    Porphyrins and metalloporphyrins have been investigated extensively due to their important role in natural photosynthesis, strong absorption in visible region, good light-harvesting properties, unique photophysical and electrochemical properties, and the development of simple synthetic routes for various derivatives. Dendrimers have globular structure with branches of repeating units and wide diversity of the architecture because their size, shape, and functionalities can be tailored. Numerous dendrimers have been designed and synthesized for various applications ranging from catalyst to drug delivery. Both pyridine dendrons Py-PD and Py-AD were successfully coordinated at axial position on central zinc metal cation in zinc porphyrin dendrimers ZnP-AD, ZnP-AD2, or ZnP-AD4. Therefore, it was proven that the formation of axial coordination complex between metal-centered dendrimer and ligand-containing dendron provides another facile method for the preparation of new hybrid dendrimer.

  8. Synthesis and Spectroscopic Characterization of Two Tetrasubstituted Cationic Porphyrin Derivatives

    Directory of Open Access Journals (Sweden)

    Newton M. Barbosa Neto

    2011-07-01

    Full Text Available An imidazolium tetrasubstituted cationic porphyrin derivative (the free base and its Zn(II complex with five-membered heterocyclic groups in the meso-positions were synthesized using microwave irradiation, and the compounds obtained characterized by 1H-NMR and mass spectrometry. We observed that under microwave irradiation the yield is similar to when the synthesis is performed under conventional heating, however, the time required to prepare the porphyrins decreases enormously. In order to investigate the electronic state of these compounds, we employed UV-Vis and fluorescence spectroscopy combined with quantum chemical calculations. The results reveal the presence, in both compounds, of a large number of electronic states involving the association between the Soret and a blue-shifted band. The Soret band in both compounds also shows a considerable solvent dependence. As for emission, these compounds present low quantum yield at room temperature and no solvent influence on the fluorescence spectra was observed.

  9. Emulating porphyrins with a rippled multivacancy graphene system

    Science.gov (United States)

    Mombrú, Dominique; Faccio, Ricardo; Mombrú, Alvaro W.

    2018-04-01

    The interaction between a complex porphyrin-like system formed by an iron atom and multivacant graphene layer and O2, CO and CO2 molecules is studied, using Density Functional Theory (DFT) calculations. The multivacancy graphene system used for this study, consists in the removal of a 1,4-dimethybenzene-like moiety, in a 6 × 6 supercell. This removal and the structural optimization subsequently performed, yield to a biaxial vacancy, where the location of an iron atom embedded in it, lead to a system with resemblance to iron-porphyrin systems. This similar structure could be used to form complexes where gas molecules are allowed to interact with these iron-octavacant graphene systems. The study focuses on the structure of the system and the net magnetic moment for different gas molecules: O2, CO2 and CO. Rippling in the vacant graphene is enhanced through this interaction.

  10. The Use of Comics-Based Cases in Anchored Instruction

    Science.gov (United States)

    Kneller, Matthew F.

    2009-01-01

    The primary purpose of this research was to understand how comics fulfill the role of anchor in an anchored instruction learning environment. Anchored instruction addresses the inert knowledge problem through the use of realistic multimedia stories, or "anchors," that embed a problem and the necessary data to solve it within the narrative. In the…

  11. An earth anchor system: installation and design guide.

    Science.gov (United States)

    R.L. Copstead; D.D. Studier

    1990-01-01

    A system for anchoring the guylines and skylines of cable yarding equipment is presented. A description of three types of tipping plate anchors is given. Descriptions of the installation equipment and methods specific to each type are given. Procedures for determining the correct number of anchors to install are included, as are guidelines for installing the anchors so...

  12. Fabrication mechanism and photocatalytic activity for a novel graphene oxide hybrid functionalized with tetrakis-(4-hydroxylphenyl)porphyrin and 1-pyrenesulfonic acid

    Science.gov (United States)

    Luo, Qiang; Ge, Riyue; Kang, Shi-Zhao; Qin, Lixia; Li, Guodong; Li, Xiangqing

    2018-01-01

    A new type of nanohybrid (GO/THPP/PSA) was noncovalently constructed by anchoring 5, 10, 15, 20-tetrakis-(4-hydroxylphenyl)porphyrin (THPP) and 1-pyrenesulfonic acid hydrate (PSA) in graphene oxide (GO). The assembly mechanism of the nanohybrid was explored in detail. The results showed that THPP and PSA were attached in the GO by π-π stacking interaction and hydrogen bond. Compared with pure GO, GO/THPP or GO/PSA, the GO/THPP/PSA nanohybrid showed better photocatalytic activity for hydrogen evolution. The mechanism of electron transfer in the GO/THPP/PSA nanohybrid was investigated. It was shown that light absorption and separation of electron/hole pairs were improved dramatically due to wider light response and multi-channel electrons transfer in the hybrid. The results could initiate new ideas for constructing other graphene-based functionalized materials with high photocatalytic activity.

  13. Supramolecular Ferric Porphyrins as Cyanide Receptors in Aqueous Solution

    Science.gov (United States)

    2011-01-01

    All fundamental data about binding of the cyanide to a supramolecular complex composed of a per-O-methylated β-cyclodextrin dimer having an imidazole linker (Im3CD) and an anionic ferric porphyrin (Fe(III)TPPS) indicate that the Fe(III)TPPS/Im3CD complex is much better as an cyanide receptor in vivo than hydroxocobalamin, whose cyanide binding ability is lowered by its strong binding to serum proteins in the blood. PMID:24900285

  14. Photoinduced electron transfer within porphyrin-cyclodextrin conjugates

    Czech Academy of Sciences Publication Activity Database

    Lang, Kamil; Král, V.; Kapusta, P.; Kubát, Pavel; Vašek, P.

    2002-01-01

    Roč. 43, - (2002), s. 4919-4922 ISSN 0040-4039 R&D Projects: GA ČR GA203/99/1163; GA ČR GA203/01/0634; GA ČR GA203/02/1483 Institutional research plan: CEZ:AV0Z4032918 Keywords : porphyrin-cyclodextrin * chiral aggregate * quenching Subject RIV: CA - Inorganic Chemistry Impact factor: 2.357, year: 2002

  15. Chemistry of supramolecular systems containing porphyrins and metal complexes

    OpenAIRE

    Araki, Koiti; Toma, Henrique Eisi

    2002-01-01

    Supramolecular chemistry is expected to keep a high developing pace in the next years, giving support to the advancement of molecular devices and nanotechnology. In this sense, porphyrins and their analogues should play a significant role as a consequence of their catalytic, electrocatalytic, photochemical and photoelectrochemical properties. In this review we focused on our own strategy based on coordination chemistry for the design and build-up of supermolecules and supramolecular structure...

  16. Porphyrin-based Nanostructure-Dependent Photodynamic and Photothermal Therapies

    Science.gov (United States)

    Jin, Cheng S.

    This thesis presents the investigation of nanostructure-dependent phototherapy. We reviewed the liposomal structures for delivery of photosensitizers, and introduced a novel class of phototransducing liposomes called "porphysomes". Porphysomes are self-assembled from high packing density of pyropheophorbide alpha-conjugated phospholipids, resulting in extreme self-quenching of porphyrin fluorescence and comparable optical absorption to gold nanoparticles for high photothermal efficiency. We demonstrated this self-assembly of porphyrin-lipid conjugates converts a singlet oxygen generating mechanism (photodynamic therapy PDT activity) of porphyrin to photothermal mechanism (photothermal therapy PTT activity). The efficacy of porphysome-enhanced PTT was then evaluated on two pre-clinical animal models. We validated porphysome-enabled focal PTT to treat orthotopic prostate cancer using MRI-guided focal laser placement to closely mimic the current clinic procedure. Furthermore, porphysome-enabled fluorescence-guided transbronchial PTT of lung cancer was demonstrated in rabbit orthotopic lung cancer models, which led to the development of an ultra-minimally invasive therapy for early-stage peripheral lung cancer. On the other hand, the nanostructure-mediated conversion of PDT to PTT can be switched back by nanoparticle dissociation. By incorporating folate-conjugated phospholipids into the formulation, porphysomes were internalized into cells rapidly via folate receptor-mediated endocytosis and resulted in efficient disruption of nanostructures, which turned back on the photodynamic activity of densely packed porphyrins, making a closed loop of conversion between PDT and PTT. The multimodal imaging and therapeutic features of porphysome make it ideal for future personalized cancer treatments.

  17. Mineral resource of the month: manganese

    Science.gov (United States)

    Corathers, Lisa A.

    2012-01-01

    Manganese is a silver-colored metal resembling iron and often found in conjunction with iron. The earliest-known human use of manganese compounds was in the Stone Age, when early humans used manganese dioxide as pigments in cave paintings. In ancient Rome and Egypt, people started using it to color or remove the color from glass - a practice that continued to modern times. Today, manganese is predominantly used in metallurgical applications as an alloying addition, particularly in steel and cast iron production. Steel and cast iron together provide the largest market for manganese (historically 85 to 90 percent), but it is also alloyed with nonferrous metals such as aluminum and copper. Its importance to steel cannot be overstated, as almost all types of steel contain manganese and could not exist without it.

  18. Porphyrin doped vanadium pentoxide xerogel as electrode material

    Energy Technology Data Exchange (ETDEWEB)

    Anaissi, F.J.; Engelmann, F.M.; Araki, K.; Toma, H.E. [Sao Paulo Univ., SP (Brazil). Inst. de Quimica

    2003-04-01

    The lamellar composite material, VXG-TMPyP, obtained from the combination of cationic, water-soluble meso-(tetra-4-methyl-pyridinium)porphyrin (TMPyP) and vanadium pentoxide gel was investigated and employed as electrode modifying material. This material was isolated as a xerogel and characterized by X-ray diffraction, UV-Vis spectroscopy, cyclic voltammetry, spectro-electrochemistry and TG analysis. According to the X-ray diffraction data, the original VXG lamellar matrix framework is kept in the composite, evidencing a topotatic reaction. UV-Vis spectra indicated a strong interaction between VXG and TMPyP leading to the protonation of the porphyrin ring. In contrast with the vanadium oxide xerogel the new material is stable in water. The presence of the cationic porphyrin species in its structure turns it able to incorporate negatively charged ions, such as ferrocyanide and I{sup -}. The presence of the I{sub 2}/I{sup -} couple gives rise to a dramatic increase in the reversibility of the V{sup V/IV} process and in the charge capacity of the material. (authors)

  19. New approaches to novel boronated porphyrins for neutron capture therapy

    International Nuclear Information System (INIS)

    Kahl, S.B.

    1986-01-01

    The use of boon compounds in the treatment of human cancer is based on the unique ability of nonradioactive 10 B nuclei to absorb thermal neutrons. The prompt nuclear reactions, which occur in neutron absorption, deliver a dose of nearly 2.8 MeV only in the vicinity of boron-containing cells, since the nuclear garments produced (alpha particles and recoil lithium atoms) travel only 10 to 15 μm. The practical, clinical use of this technique to date has been limited by the authors inability to target boron-containing compounds specifically to tumor cells in amounts sufficient for therapy and in a chemical form that has an acceptable level of toxicity. Porphyrins are one important and large class of compounds that are known to accumulate in practically all tumor systems yet examined. Such site-specific accumulation is not known to be based on any currently identifiable selective transport mechanism and yet is observed for both natural and synthetic porphyrins. Tetraphenylporphine sulfonate (TPPS) has been shown by Fairchild et al. to be an ideal model compound for assessing porphyrin uptake, and suitably boronated tetraphenyl porphine might be expected to behave similarly. This report describes the synthesis, properties, and preliminary biodistribution of such compounds

  20. Antimicrobial activity of new porphyrins of synthetic and natural origin

    Science.gov (United States)

    Gyulkhandanyan, Grigor V.; Ghazaryan, Robert K.; Paronyan, Marina H.; Ulikhanyan, Ghukas I.; Gyulkhandanyan, Aram G.; Sahakyan, Lida A.

    2012-03-01

    Antimicrobial photodynamic inactivation has been successfully used against Gram (+) microorganisms, but most of the photosensitizers (PSs) on Gram (-) bacteria acts weakly. PSs are the natural or synthetic origin dyes, mainly porphyrins. We have synthesized more than 100 new cationic porphyrins and metalloporphyrins with different functional groups (hydroxyethyl, butyl, allyl, methallyl) and metals (cobalt, iron, copper, zinc, silver and other); from the nettle have also been purified pheophytin (a+b) and pheophytin (a) and have synthesized their Ag-and Zn-metalloporphyrins. It was found that in the dark (cytotoxic) mode, the most highly efficiency against microorganisms showed Agmetalloporphyrins of both types of porphyrins (synthetic and natural). Metalloporphyrin of natural origin Ag-pheophytin (a + b) is a strong antibacterial agent and causes 100% death as the Gram (+) microorganisms (St. aureus and MRSA) and the Gram (-) microorganisms (E.coli and Salmonella). It is established that for the destruction of Gram (+) and Gram (-) microorganisms in photodynamic mode cationic water-soluble synthetic metalloporphyrins, especially Zn-TBut4PyP, many times more effective than pheophytins. In vivo conditions on mice established that the best therapeutic activity against various strains of the microorganism St. aureus has the synthetic metalloporphyrin Ag-TBut4PyP. It is significantly more efficient than known drug "Chlorophyllipt" (2.5-3 times) and leads the survival rate of animals up to 50-60%.

  1. Anchors as Semantic Primes in Value Construction: An EEG Study of the Anchoring Effect.

    Directory of Open Access Journals (Sweden)

    Qingguo Ma

    Full Text Available Previous research regarding anchoring effects has demonstrated that human judgments are often assimilated to irrelevant information. Studies have demonstrated that anchors influence the economic valuation of various products and experiences; however, the cognitive explanations of this effect remain controversial, and its neural mechanisms have rarely been explored. In the current study, we conducted an electroencephalography (EEG experiment to investigate the anchoring effect on willingness to accept (WTA for an aversive hedonic experience and the role of anchors in this judgment heuristic. The behavioral results demonstrated that random numbers affect participants' WTA for listening to pieces of noise. The participants asked for higher pay after comparing their WTA with higher numbers. The EEG results indicated that anchors also influenced the neural underpinnings of the valuation process. Specifically, when a higher anchor number was drawn, larger P2 and late positive potential amplitudes were elicited, reflecting the anticipation of more intensive pain from the subsequent noise. Moreover, higher anchors induced a stronger theta band power increase compared with lower anchors when subjects listened to the noises, indicating that the participants felt more unpleasant during the actual experience of the noise. The levels of unpleasantness during both anticipation and experience were consistent with the semantic information implied by the anchors. Therefore, these data suggest that a semantic priming process underlies the anchoring effect in WTA. This study provides proof for the robustness of the anchoring effect and neural evidence of the semantic priming model. Our findings indicate that activated contextual information, even seemingly irrelevant, can be embedded in the construction of economic value in the brain.

  2. HAEM SYNTHASE AND COBALT PORPHYRIN SYNTHASE IN VARIOUS MICRO-ORGANISMS.

    Science.gov (United States)

    PORRA, R J; ROSS, B D

    1965-03-01

    1. The preparation of a crude extract of Clostridium tetanomorphum containing cobalt porphyrin synthase but little haem-synthase activity is described. 2. The properties of cobalt porphyrin synthase in the clostridial extracts is compared with the properties of a haem synthase present in crude extracts of the yeast Torulopsis utilis. 3. Cobalt porphyrin synthase in extracts of C. tetanomorphum inserts Co(2+) ions into the following dicarboxylic porphyrins in descending order of rate of insertion: meso-, deutero- and proto-porphyrins. Esterification renders meso- and deutero-porphyrins inactive as substrates. Neither the tetracarboxylic (coproporphyrin III) nor the octacarboxylic (uroporphyrin III) compounds are converted into cobalt porphyrins by the extract, but the non-enzymic incorporation of Co(2+) ions into these two porphyrins is rapid. These extracts are unable to insert Mn(2+), Zn(2+), Mg(2+) or Cu(2+) ions into mesoporphyrin. 4. Crude extracts of T. utilis readily insert both Co(2+) and Fe(2+) ions into deutero-, meso, and proto-porphyrins. Unlike the extracts of C. tetanomorphum, these preparations catalyse the insertion of Co(2+) ions into deuteroporphyrin more rapidly than into mesoporphyrin. This parallels the formation of haems by the T. utilis extract. 5. Cobalt porphyrin synthase is present in the particulate fraction of the extracts of C. tetanomorphum but requires a heat-stable factor present in the soluble fraction. This soluble factor can be replaced by GSH. 6. Cobalt porphyrin synthase in the clostridial extract is inhibited by iodoacetamide and to a smaller extent by p-chloromercuribenzoate and N-ethylmaleimide. The haem synthases of T. utilis and Micrococcus denitrificans are also inhibited by various thiol reagents.

  3. Efficient sensitization of dye-sensitized solar cells by novel triazine-bridged porphyrin-porphyrin dyads.

    Science.gov (United States)

    Zervaki, Galateia E; Roy, Mahesh S; Panda, Manas K; Angaridis, Panagiotis A; Chrissos, Emmanouel; Sharma, Ganesh D; Coutsolelos, Athanassios G

    2013-09-03

    Two novel porphyrin-porphyrin dyads, the symmetrical Zn[Porph]-Zn[Porph] (2) and unsymmetrical Zn[Porph]-H2[Porph] (4), where Zn[Porph] and H2[Porph] are the metalated and free-base forms of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, respectively, in which two porphyrin units are covalently bridged by 1,3,5-triazine, have been synthesized via the stepwise amination of cyanuric chloride. The dyads are also functionalized by a terminal carboxylic acid group of a glycine moiety attached to the triazine group. Photophysical measurements of 2 and 4 showed broaden and strengthened absorptions in their visible spectra, while electrochemistry experiments and density functional theory calculations revealed negligible interaction between the two porphyrin units in their ground states but appropriate frontier orbital energy levels for use in dye-sensitized solar cells (DSSCs). The 2- and 4-based solar cells have been fabricated and found to exhibit power conversion efficiencies (PCEs) of 3.61% and 4.46%, respectively (under an illumination intensity of 100 mW/cm(2) with TiO2 films of 10 μm thickness). The higher PCE value of the 4-based DSSC, as revealed by photovoltaic measurements (J-V curves) and incident photon-to-current conversion efficiency (IPCE) spectra of the two cells, is attributed to its enhanced short-circuit current (J(sc)) under illumination, high open-circuit voltage (V(oc)), and fill factor (FF) values. Electrochemical impedance spectra demonstrated shorter electron-transport time (τd), longer electron lifetime (τe), and high charge recombination resistance for the 4-based cell, as well as larger dye loading onto TiO2.

  4. New carbon-carbon linked amphiphilic carboranyl-porphyrins as boron neutron capture agents

    International Nuclear Information System (INIS)

    Vicente, M.G.H.; Wickramasinghe, A.; Shetty, S.J.; Smith, K.M.

    2000-01-01

    Novel amphiphilic carboranyl-porphyrins have been synthesized for Boron Neutron Capture Therapy (BNCT). These compounds have carbon-carbon bonds between the carborane residues and the porphyrin meso-phenyl groups, and contain 28-31% boron by weight . (author)

  5. A Fluorinated Cobalt(III) Porphyrin Complex for Hydroalkoxylation of Alkynes.

    Science.gov (United States)

    Ushimaru, Richiro; Nishimura, Takuho; Iwatsuki, Toshiki; Naka, Hiroshi

    2017-01-01

    A fluorinated cobalt(III) porphyrin complex [Co(TPFPP)NTf 2 ·2C 2 H 5 OH, where TPFPP=5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, Tf=CF 3 SO 2 ] promotes hydroalkoxylation of alkynes to give acetals in good to excellent yields. The acetals can be directly functionalized with nucleophiles in a one-pot procedure.

  6. Ultrafast electron injection at the cationic porphyrin-graphene interface assisted by molecular flattening

    KAUST Repository

    Aly, Shawkat Mohammede; Parida, Manas R.; Alarousu, Erkki; Mohammed, Omar F.

    2014-01-01

    The steady-state and femtosecond (fs) time-resolved data clearly demonstrate that the charge transfer (CT) process at the porphyrin-graphene carboxylate (GC) interfaces can be tuned from zero to very sufficient and ultrafast by changing the electronic structure of the meso unit and the redox properties of the porphyrin cavity. This journal is © the Partner Organisations 2014.

  7. To what extent can charge localization influence electron injection efficiency at graphene-porphyrin interfaces?

    KAUST Repository

    Parida, Manas R.

    2015-04-28

    Controlling the electron transfer process at donor- acceptor interfaces is a research direction that has not yet seen much progress. Here, with careful control of the charge localization on the porphyrin macrocycle using β -Cyclodextrin as an external cage, we are able to improve the electron injection efficiency from cationic porphyrin to graphene carboxylate by 120% . The detailed reaction mechanism is also discussed.

  8. Molecular modeling of cationic porphyrin-anthraquinone hybrids as DNA topoisomerase IIβ inhibitors.

    Science.gov (United States)

    Arba, Muhammad; Ruslin; Ihsan, Sunandar; Tri Wahyudi, Setyanto; Tjahjono, Daryono H

    2017-12-01

    Human DNA Topoisomerase II has been regarded as a promising target in anticancer drug discovery. In the present study, we designed six porphyrin-anthraquinone hybrids bearing pyrazole or pyridine group as meso substituents and evaluated their potentials as DNA Topoisomerase IIβ inhibitor. First, we investigated the binding orientation of porphyrin hybrids into DNA topoisomerase IIβ employing AutoDock 4.2 and then performed 20-ns molecular dynamics simulations to see the dynamic stability of each porphyrin-Topo IIβ complex using Amber 14. We found that the binding of porphyrin hybrids occured through intercalation and groove binding mode in addition interaction with the amino acid residues constituting the active cavity of Topo IIβ. Each porphyrin-Topo IIβ complex was stabilized during 20-ns dynamics simulations. The MM-PBSA free energy calculation shows that the binding affinities of porphyrin hybrids were modified with the number of meso substituent. Interestingly, the affinity of all porphyrin hybrids to Topo IIβ was stronger than that of native ligand (EVP), indicating the potential of the designed porphyrin to be considered in experimental research. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Career anchors and learning plan (part one

    Directory of Open Access Journals (Sweden)

    Daniela Brečko

    2006-12-01

    Full Text Available The article is divided into three parts. The first part concentrates on how important career is for an individual, organization and society. The author establishes that understanding of career has changed dramatically and does not only refer to climbing up the career ladder, but also moving off or even down the career ladder. The notion of career, as a lifelong and professional path, encompasses all aspects of human personality and their roles acquired through one's life. On basis of vast and longitudinal research, where the author has studied career anchors of individuals, it is the objective of the author to find out on basis of what grounds do the individuals decide to take certain directions in their careers and how learning contributes to such decisions. As a source the author has used Shein's theory of career anchors. Part one describes in greater detail 8 different career anchors and introduces their main features with the findings of the research, which refer to the analysis of professions (work positions and established career anchors. The author thus verifies the hypothesis that career anchors do exist in our area.

  10. Formation and thermodynamic stability of (polymer + porphyrin) supramolecular structures in aqueous solutions

    International Nuclear Information System (INIS)

    Costa, Viviana C.P. da; Hwang, Barrington J.; Eggen, Spencer E.; Wallace, Megan J.; Annunziata, Onofrio

    2014-01-01

    Highlights: • Thermodynamic stability of a (polymer + porphyrin) supramolecular structure was characterized. • Isothermal titration calorimetry provided two ways to determine reaction enthalpies. • Exothermic (polymer + porphyrin) binding competes with porphyrin self-association. • (Polymer + porphyrin) binding is entropically favored with respect to porphyrin self-association. • Spectral shifts show importance of porphyrin central hydrogens in polymer binding. - Abstract: Optical properties of porphyrins can be tuned through (polymer + porphyrin) (host + guest) binding in solution. This gives rise to the formation of supramolecular structures. In this paper, the formation, thermodynamic stability and spectroscopic properties of (polymer + porphyrin) supramolecular structures and their competition with porphyrin self-association were investigated by both isothermal titration calorimetry (ITC) and absorption spectroscopy. Specifically, reaction enthalpies and equilibrium constants were measured for meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) self-association and TPPS binding to the polymer poly(vinylpyrrolidone) (PVP, 40 kg/mol) in aqueous solutions at pH 7 and three different temperatures (12, 25 and 37 °C). ITC, compared to spectroscopic techniques, provides two independent means to determine reaction enthalpies: direct measurements and Van’t Hoff plot. This was used as a criterion to assess that (1) self-association of TPPS is limited to the formation of dimers and (2) TPPS binds to PVP in its monomeric state only. The formation of TPPS dimers and (PVP + TPPS) supramolecular structures are both enthalpically driven. However, (polymer + porphyrin) binding was found to be entropically favored compared to dimerization. Furthermore, the reaction enthalpies of these two processes significantly depend on temperature. This behavior was attributed to hydrophobic interactions. Finally, the limiting absorption spectra of monomeric, dimeric and polymer

  11. Excitation energy deactivation funnel in 3-substituted BODIPY-porphyrin conjugate

    International Nuclear Information System (INIS)

    Nguyen, Nguyen Tran; Verbelen, Bram; Leen, Volker; Waelkens, Etienne; Dehaen, Wim; Kruk, Mikalai

    2016-01-01

    BODIPYs absorb in the visible region which is complementary to that of porphyrins and therefore can be suggested as promising antenna groups to improve the light-harvesting potential of porphyrins. A boron-dipyrromethene dye was combined at the 3-position with a Zn-porphyrin to afford a conjugate. The fluorescence of the conjugate was found to originate from the BODIPY moiety independently of the excitation wavelength due to an unique set of energy transfer rates between the BODIPY and Zn-porphyrin moieties. The fluorescence intensity was shown to be tunable over a wide range using the solvent properties. This feature makes the studied BODIPY-porphyrin conjugate a promising compound for the design of new photochromic devices.

  12. Excitation energy deactivation funnel in 3-substituted BODIPY-porphyrin conjugate

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Nguyen Tran [Chemistry Department, University of Education, The University of DaNang, Ton Duc Thang 459, Da Nang (Viet Nam); Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Belgium); Verbelen, Bram; Leen, Volker [Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Belgium); Waelkens, Etienne [Department of Cellular and Molecular Medicine, KU Leuven, Herestraat 49, Box 901, 3000 Leuven (Belgium); Dehaen, Wim, E-mail: wim.dehaen@kuleuven.be [Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Belgium); Kruk, Mikalai, E-mail: m.kruk@belstu.by [Belarusian State Technological University, Physics Department, Sverdlov Str., 13a, Minsk 220006 (Belarus)

    2016-11-15

    BODIPYs absorb in the visible region which is complementary to that of porphyrins and therefore can be suggested as promising antenna groups to improve the light-harvesting potential of porphyrins. A boron-dipyrromethene dye was combined at the 3-position with a Zn-porphyrin to afford a conjugate. The fluorescence of the conjugate was found to originate from the BODIPY moiety independently of the excitation wavelength due to an unique set of energy transfer rates between the BODIPY and Zn-porphyrin moieties. The fluorescence intensity was shown to be tunable over a wide range using the solvent properties. This feature makes the studied BODIPY-porphyrin conjugate a promising compound for the design of new photochromic devices.

  13. Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

    Science.gov (United States)

    Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.

    2015-08-18

    A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

  14. 10Be in manganese nodules

    International Nuclear Information System (INIS)

    Thomas, J.; Parker, P.; Mangini, A.; Cochran, K.; Turekian, K.; Krishnaswami, S.; Sharma, P.

    1981-01-01

    10 Be (t/sub 1/2) = 1.5 MY) is(formed in the upper atmosphere by cosmic ray spallation on nitrogen and oxygen. It is transported to the earth's surface via precipitation. In the oceans it is eventually associated with solid phases depositing on the ocean floor such as manganese nodules and deep-sea sediments. One of the assumptions that is normally made in analysis of such processes is that 10 Be has been produced at a relatively uniform rate over the pat several million years. If we assume, in addition, that the initial specific concentration of 10 Be as it precipitates with a solid phase is invariant with time, then we would expect that the decrease of the 10 Be concentration as a function of depth in a deep-sea core or in a manganese nodule would provide a record of sediment accumulation rate in the former and of growth rate in the latter. The possibility of using cosmic-ray produced 10 Be for the dating of marine deposits had been proposed 25 years ago by Arnold and Goel et al. The method of analysis used by these investigators, and those subsequently pursuing the problem, was low-level β counting. Though the potential of using 10 Be for dating manganese nodules was explored more than a decade ago, only a few measurements of 10 Be in nodules exist in date. This is largely because of the 10 Be measurements in environmental samples have gained considerable momentum during the past 3 to 4 years, after the development of accelerator mass spectrometry for its determination

  15. Ultimate load capacities of expansion anchor bolts

    International Nuclear Information System (INIS)

    Czarnecki, R.M.; Manrique, M.A.; Samaddar, S.K.

    1993-01-01

    A summary of available experimental expansion anchor bolt test data is presented. These data were collected as part of programs by the nuclear industry to address generic issues related to verification of seismic adequacy of equipment in nuclear power plants. Some of the data presented are suitable for use in seismic probabilistic risk assessments. For example, mean values of ultimate strength, along with their standard deviation and coefficients of variation, for a range of most typical expansion anchor bolt sizes are presented. Effects of interaction between shear and tension, edge distance, spacing, and cracking of the concrete are presented in a manner that is more suitable for use in deterministic evaluations. Related industry programs to derive anchor bolt capacities are briefly discussed. Recommendations for areas of further investigation are also presented

  16. Anchoring Proteins as Regulators of Signaling Pathways

    Science.gov (United States)

    Perino, Alessia; Ghigo, Alessandra; Scott, John D.; Hirsch, Emilio

    2012-01-01

    Spatial and temporal organization of signal transduction is coordinated through the segregation of signaling enzymes in selected cellular compartments. This highly evolved regulatory mechanism ensures the activation of selected enzymes only in the vicinity of their target proteins. In this context, cAMP-responsive triggering of protein kinase A is modulated by a family of scaffold proteins referred to as A-kinase anchoring proteins. A-kinase anchoring proteins form the core of multiprotein complexes and enable simultaneous but segregated cAMP signaling events to occur in defined cellular compartments. In this review we will focus on the description of A-kinase anchoring protein function in the regulation of cardiac physiopathology. PMID:22859670

  17. Comparison of Suture-Based Anchors and Traditional Bioabsorbable Anchors in Foot and Ankle Surgery.

    Science.gov (United States)

    Hembree, W Chad; Tsai, Michael A; Parks, Brent G; Miller, Stuart D

    We compared the pullout strength of a suture-based anchor versus a bioabsorbable anchor in the distal fibula and calcaneus and evaluated the relationship between bone mineral density and peak load to failure. Eight paired cadaveric specimens underwent a modified Broström procedure and Achilles tendon reattachment. The fibula and calcaneus in the paired specimens received either a suture-based anchor or a bioabsorbable suture anchor. The fibular and calcaneal specimens were loaded to failure, defined as a substantial decrease in the applied load or pullout from the bone. In the fibula, the peak load to failure was significantly greater with the suture-based versus the bioabsorbable anchors (133.3 ± 41.8 N versus 76.8 ± 35.3 N; p = .002). No significant difference in load with 5 mm of displacement was found between the 2 groups. In the calcaneus, no difference in the peak load to failure was found between the 2 groups, and the peak load to failure with 5 mm of displacement was significantly lower with the suture-based than with the bioabsorbable anchors (52.2 ± 9.8 N versus 75.9 ± 12.4 N; p = .003). Bone mineral density and peak load to failure were significantly correlated in the fibula with the suture-based anchor. An innovative suture-based anchor had a greater peak load to failure compared with a bioabsorbable anchor in the fibula. In the calcaneus, the load at 5 mm of displacement was significantly lower in the suture-based than in the bioabsorbable group. The correlation findings might indicate the need for a cortical bone shelf with the suture-based anchor. Suture-based anchors could be a viable alternative to bioabsorbable anchors for certain foot and ankle procedures. Copyright © 2016 American College of Foot and Ankle Surgeons. Published by Elsevier Inc. All rights reserved.

  18. CO2 electroreduction performance of a single transition metal atom supported on porphyrin-like graphene: a computational study.

    Science.gov (United States)

    Wang, Zhongxu; Zhao, Jingxiang; Cai, Qinghai

    2017-08-30

    Searching for low-cost, efficient, and stable electrocatalysts for CO 2 electroreduction (CO 2 ER) reactions is highly desirable for the reduction of CO 2 emission and its conversion into useful products, but remains a great challenge. In this work, single transition metal atoms supported on porphyrin-like graphene catalysts, i.e., TMN 4 /graphene, acting as electrocatalysts for CO 2 reduction were explored by means of comprehensive density functional theory (DFT) computations. Our results revealed that these anchored TM atoms possess high stability due to their strong hybridization with the unsaturated N atoms of the substrate and function as the active sites. On the basis of the calculated adsorption strength of CO 2 ER intermediates, we have identified that single Co, Rh, and Ir atoms exhibit superior catalytic activity towards CO 2 reduction. In particular, CH 3 OH is the preferred product of CO 2 ER on the CoN 4 /graphene catalyst with an overpotential of 0.59 V, while the RhN 4 /graphene and IrN 4 /graphene catalysts prefer to reduce CO 2 to CH 2 O with an overpotential of 0.35 and 0.29 V, respectively. Our work may open a new avenue for the development of catalytic materials with high efficiency for CO 2 electroreduction.

  19. Monogenean anchor morphometry: systematic value, phylogenetic signal, and evolution

    Science.gov (United States)

    Soo, Oi Yoon Michelle; Tan, Wooi Boon; Lim, Lee Hong Susan

    2016-01-01

    Background. Anchors are one of the important attachment appendages for monogenean parasites. Common descent and evolutionary processes have left their mark on anchor morphometry, in the form of patterns of shape and size variation useful for systematic and evolutionary studies. When combined with morphological and molecular data, analysis of anchor morphometry can potentially answer a wide range of biological questions. Materials and Methods. We used data from anchor morphometry, body size and morphology of 13 Ligophorus (Monogenea: Ancyrocephalidae) species infecting two marine mugilid (Teleostei: Mugilidae) fish hosts: Moolgarda buchanani (Bleeker) and Liza subviridis (Valenciennes) from Malaysia. Anchor shape and size data (n = 530) were generated using methods of geometric morphometrics. We used 28S rRNA, 18S rRNA, and ITS1 sequence data to infer a maximum likelihood phylogeny. We discriminated species using principal component and cluster analysis of shape data. Adams’s Kmult was used to detect phylogenetic signal in anchor shape. Phylogeny-correlated size and shape changes were investigated using continuous character mapping and directional statistics, respectively. We assessed morphological constraints in anchor morphometry using phylogenetic regression of anchor shape against body size and anchor size. Anchor morphological integration was studied using partial least squares method. The association between copulatory organ morphology and anchor shape and size in phylomorphospace was used to test the Rohde-Hobbs hypothesis. We created monogeneaGM, a new R package that integrates analyses of monogenean anchor geometric morphometric data with morphological and phylogenetic data. Results. We discriminated 12 of the 13 Ligophorus species using anchor shape data. Significant phylogenetic signal was detected in anchor shape. Thus, we discovered new morphological characters based on anchor shaft shape, the length between the inner root point and the outer root

  20. Magnetic Circular Dichroism of Porphyrin Lanthanide M3+ Complexes

    Czech Academy of Sciences Publication Activity Database

    Andrushchenko, Valery; Padula, Daniele; Zhivotova, E.; Yamamoto, S.; Bouř, Petr

    2014-01-01

    Roč. 26, č. 10 (2014), s. 655-662 ISSN 0899-0042 R&D Projects: GA ČR GA13-03978S; GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Grant - others:GA AV ČR(CZ) M200550902 Institutional support: RVO:61388963 Keywords : magnetic circular dichroism * lanthanides * porphyrin complexes * density functional theory * sum over state computations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.886, year: 2014

  1. Polystyrene nanofiber materials modified with an externally bound porphyrin photosensitizer

    Czech Academy of Sciences Publication Activity Database

    Henke, P.; Lang, Kamil; Kubát, Pavel; Sýkora, Jan; Šlouf, Miroslav; Mosinger, Jiří

    2013-01-01

    Roč. 5, č. 9 (2013), s. 3776-3783 ISSN 1944-8244 R&D Projects: GA ČR GAP208/10/1678; GA ČR GBP208/12/G016; GA ČR GA13-12496S Institutional support: RVO:61388980 ; RVO:61388955 ; RVO:61389013 Keywords : nanofiber * porphyrin * singlet oxygen * adsorption * photooxidation * antibacterial Subject RIV: CA - Inorganic Chemistry; CD - Macromolecular Chemistry (UMCH-V); CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 5.900, year: 2013

  2. Chemical biology of Glycosylphosphatidylinositol (GPI) anchors

    Indian Academy of Sciences (India)

    Admin

    CSIR-IIIM. Chemical biology of. Glycosylphosphatidylinositol (GPI) anchors. Ram Vishwakarma. CSIR-Indian Institute of Integrative Medicine, Jammu. N ti l I tit t f I l. N. D lhi. National Institute of Immunology, New Delhi. Piramal Life Sciences Ltd, Mumbai ...

  3. Method and apparatus for dismantling mechanical anchors

    Energy Technology Data Exchange (ETDEWEB)

    Dubovskiy, Yu P; Chendev, F S; Gritsayuk, B I; Gubin, N I; Osipov, S P

    1982-01-01

    This apparatus is designed to reduce the amount of labor required to dismantle mechanical anchors while at the same time lowering expenditures for lumber. Longwall beams and timber skips are used to support the cap and any fractured rock faces. The apparatus itself has grooves, vertical guides, and a drive system to position the longwall beams.

  4. Influence of Anchoring on Burial Depth of Submarine Pipelines.

    Directory of Open Access Journals (Sweden)

    Yuan Zhuang

    Full Text Available Since the beginning of the twenty-first century, there has been widespread construction of submarine oil-gas transmission pipelines due to an increase in offshore oil exploration. Vessel anchoring operations are causing more damage to submarine pipelines due to shipping transportation also increasing. Therefore, it is essential that the influence of anchoring on the required burial depth of submarine pipelines is determined. In this paper, mathematical models for ordinary anchoring and emergency anchoring have been established to derive an anchor impact energy equation for each condition. The required effective burial depth for submarine pipelines has then been calculated via an energy absorption equation for the protection layer covering the submarine pipelines. Finally, the results of the model calculation have been verified by accident case analysis, and the impact of the anchoring height, anchoring water depth and the anchor weight on the required burial depth of submarine pipelines has been further analyzed.

  5. Stone anchors from the Okhamandal region, Gujarat Coast, India

    Digital Repository Service at National Institute of Oceanography (India)

    Sundaresh; Gaur, A.S.; Gudigar, P.; Tripati, S.; Vora, K.H.; Bandodkar, S.N.

    During marine archaeological explorations since 1983, off Dwarka, a large number of stone anchors were discovered and dated to 1400 BC, comparing with anchors found in Mediterranean waters. In recent archaeological explorations off Dwarka, Bet...

  6. Influence of Anchoring on Burial Depth of Submarine Pipelines.

    Science.gov (United States)

    Zhuang, Yuan; Li, Yang; Su, Wei

    2016-01-01

    Since the beginning of the twenty-first century, there has been widespread construction of submarine oil-gas transmission pipelines due to an increase in offshore oil exploration. Vessel anchoring operations are causing more damage to submarine pipelines due to shipping transportation also increasing. Therefore, it is essential that the influence of anchoring on the required burial depth of submarine pipelines is determined. In this paper, mathematical models for ordinary anchoring and emergency anchoring have been established to derive an anchor impact energy equation for each condition. The required effective burial depth for submarine pipelines has then been calculated via an energy absorption equation for the protection layer covering the submarine pipelines. Finally, the results of the model calculation have been verified by accident case analysis, and the impact of the anchoring height, anchoring water depth and the anchor weight on the required burial depth of submarine pipelines has been further analyzed.

  7. Manganese porphyrin immobilized on magnetic MCM-41 nanoparticles as an efficient and reusable catalyst for alkene oxidations with sodium periodate

    Science.gov (United States)

    Hajian, Robabeh; Ehsanikhah, Amin

    2018-01-01

    This study describes the immobilization of tetraphenylporphyrinatomanganese(III) chloride, (MnPor), onto imidazole functionalized MCM-41 with magnetite nanoparticle core (Fe3O4@MCM-41-Im). The resultant material (Fe3O4@MCM-41-Im@MnPor) was characterized by X-ray diffractometry (XRD), Fourier transform infra-red (FT-IR), diffuse reflectance UV-Vis spectrophotometry (DR UV-Vis), field emission scanning electron microscopy (FESEM), Inductively coupled plasma (ICP), analyzer transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) surface area. This new heterogenized catalyst was applied as an efficient catalyst for the epoxidation of a variety of cyclic and linear olefins with NaIO4 under mild conditions. The prepared catalyst can be easily recovered through the application of an external magnet, and reused several times without any significant decrease in activity and magnetic properties.

  8. The synthesis of chlorophyll-a biosynthetic precursors and methyl substituted iron porphyrins

    International Nuclear Information System (INIS)

    Matera, K.M.

    1988-01-01

    The biosynthetic intermediates were incubated in a plant system. The activity levels calculated show that magnesium 6-acrylate porphyrins and one of the magnesium 6-β-hydroxypropionate porphyrins are not intermediates. In addition, plant systems incubated with 18 O 2 were found to synthesize magnesium 2,4-divinyl pheoporphyrin-a 5 incorporated with 18 O at the 9-carbonyl oxygen. Mass spectroscopy confirmed the presence of the oxygen label, thus eliminating one of two hypothesized pathways to chlorophyll-a. An overall description is given of iron porphyrins and iron porphyrin containing proteins. The function of the propionic side chains of the heme prosthetic group during electron transport reactions will be investigated. The synthesis of a series of iron(III) hexamethyl porphyrins with increasingly longer substituents in the remaining two peripheral positions of the porphyrin is described. Models for NMR studies of iron chlorin containing enzymes are discussed. Iron(III) pyropheophorbide-a and methyl pyropheophorbide-a were synthesized in addition to 5-CD 3 , 10-CD 2 iron(III) pyropheophorbide-a and methyl pyropheophorbide-a. Together, these pyropheophorbides were used to assign NMR resonances and ultimately provide a model for other iron chlorins. The synthesis of nickel(II) anhydro-mesorhodoporphyrin from zinc(III) anhydromesorhodochlorin is described; this nickel porphyrin was used as a standard for ring current calculations of reduced nickel analogs of anhydromesorhodoporphyrin

  9. Interactions of tetracationic porphyrins with DNA and their effects on DNA cleavage

    Science.gov (United States)

    Lebedeva, Natalya Sh.; Yurina, Elena S.; Gubarev, Yury A.; Syrbu, Sergey A.

    2018-06-01

    The interaction of tetracationic porphyrins with DNA was studied using UV-Vis absorption, fluorescence spectroscopy and viscometry, and the particle sizes were determined. Аs cationic porphyrins, two isomer porphyrins, 3,3‧,3″,3‴-(5,10,15,20-Porphyrintetrayl)tetrakis(1-methylpyridinium) (TMPyP3) and 4,4‧,4″,4‴-(5,10,15,20-Porphyrintetrayl)tetrakis(1-methylpyridinium) (TMPyP4), were studied. They differ in the position of NCH3+ group in phenyl ring of the porphyrins and hence, in degree of freedom of rotation of the phenyl rings about the central macrocycle. It was found that intercalated complexes are formed at DNA/porphyrin molar ratios (R) of 2.2 and 3.9 for TMPyP3 и TMPyP4, respectively. Decreasing R up to 0.4 and 0.8 for TMPyP3 и TMPyP4, respectively, leads mainly to formation of outside complexes due to π-π stacking between the porphyrin chromophores interacting electrostatically with phosphate framework of DNA. Each type of the obtained complexes was characterized using Scatchard approach. It was ascertained that the affinity of TMPyP4 to DNA is stronger than TMPyP3, meanwhile the wedge effect of the latter is higher. The differences between the porphyrin isomers become more evident at irradiation of their complexes with DNA. It was established that irradiation of the intercalated complexes results in DNA fragmentation. In the case of TMPyP4, DNA fragments of different size are formed. The irradiation of the outside DNA/porphyrin complexes leads to cleavage of DNA (TMPyP3 and TMPyP4) and partial destruction of the complex due to photolysis of the porphyrin (TMPyP3).

  10. Recovery of manganese from manganese oxide ores in the EDTA solution

    Science.gov (United States)

    Zhang, Chao; Wang, Shuai; Cao, Zhan-fang; Zhong, Hong

    2018-04-01

    A new process has been experimentally and theoretically established for the recovery of manganese from manganese oxide ores, mainly including the reductive leaching of manganese by ethylenediaminetetraacetic acid (EDTA), EDTA recovery, and manganese electrolysis. The experimental conditions for this process were investigated. Moderate leaching environment by EDTA with the pH in the range of 5-6 is of benefit to leach manganese from some manganese oxide ores with high-content impurities, such as iron and aluminum. Most of EDTA can be recovered by acidification. A small amount of the residual EDTA in the electrolyte can prevent the generation of anode mud. In addition, trimanganese tetroxide (Mn3O4) can be obtained by the roasting of the EDTA-Mn crystallized product.

  11. AnchorDock: Blind and Flexible Anchor-Driven Peptide Docking.

    Science.gov (United States)

    Ben-Shimon, Avraham; Niv, Masha Y

    2015-05-05

    The huge conformational space stemming from the inherent flexibility of peptides is among the main obstacles to successful and efficient computational modeling of protein-peptide interactions. Current peptide docking methods typically overcome this challenge using prior knowledge from the structure of the complex. Here we introduce AnchorDock, a peptide docking approach, which automatically targets the docking search to the most relevant parts of the conformational space. This is done by precomputing the free peptide's structure and by computationally identifying anchoring spots on the protein surface. Next, a free peptide conformation undergoes anchor-driven simulated annealing molecular dynamics simulations around the predicted anchoring spots. In the challenging task of a completely blind docking test, AnchorDock produced exceptionally good results (backbone root-mean-square deviation ≤ 2.2Å, rank ≤15) for 10 of 13 unbound cases tested. The impressive performance of AnchorDock supports a molecular recognition pathway that is driven via pre-existing local structural elements. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Manganese oxide nanoparticles, methods and applications

    Science.gov (United States)

    Abruna, Hector D.; Gao, Jie; Lowe, Michael A.

    2017-08-29

    Manganese oxide nanoparticles having a chemical composition that includes Mn.sub.3O.sub.4, a sponge like morphology and a particle size from about 65 to about 95 nanometers may be formed by calcining a manganese hydroxide material at a temperature from about 200 to about 400 degrees centigrade for a time period from about 1 to about 20 hours in an oxygen containing environment. The particular manganese oxide nanoparticles with the foregoing physical features may be used within a battery component, and in particular an anode within a lithium battery to provide enhanced performance.

  13. Career Paths, Images and Anchors: A Study with Brazilian Professionals

    Science.gov (United States)

    Kilimnik, Zelia Miranda; de Oliveira, Luiz Claudio Vieira; Sant'anna, Anderson De Souza; Barros, Delba Teixeira Rodrigues

    2011-01-01

    This article analyses career anchors changes associated to images and professionals trajectories. Its main question: Do anchors careers change through time? We conducted twelve interviews involving professionals from the Administration Area, applying Schein's Career Anchors Inventory (1993). We did the same two years later. In both of them, the…

  14. In vitro and in vivo analysis of boronated porphyrins

    International Nuclear Information System (INIS)

    Edwards, Benjamin; Matthews, Kristin; Hou, Yongjin; Vicente, M.G.H.; Autry-Conwell, Susan; James, Boggan

    2000-01-01

    New series of meso-phenylporphyrins linked through carbon-carbon bonds to nido-carboranyl groups, and containing 26-31% boron by weight, have been reported. Dark toxicity, photo-toxicity, and measurements of uptake and efflux were performed using mouse, rat, and human malignant cell lines. Drug uptake and retention by log phase cells are shown by spectrophotometry (porphyrins) and ICP-MS (boron) of cellular extracts to be concentration and time dependent, and to be influenced by plasma lipoproteins. Plasma pharmacokinetics and tissues biodistribution were studied in adult male Fisher 344 rats with bilateral subcutaneous 9L tumors injected (2.2 ml, 2 mM i.v.) with carboranyl porphyrin solutions. Whole blood, brain, liver, spleen, skin and tumors were collected at 2, 8, 18, 24 and 48 hours post-injection. Blood cells were separated from plasma and stored frozen with the other tissues. Tissue boron content was determined quantitatively by ICP-MS analysis following microwave digestion of carefully weighed samples. (author)

  15. Electron transfer reactions involving porphyrins and chlorophyll a

    International Nuclear Information System (INIS)

    Neta, P.; Scherz, A.; Levanon, H.

    1979-01-01

    Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H 2 TPP), its tetracarboxy derivative (H 2 TCPP), the sodium and zinc compounds (Na 2 TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH 3 ) 2 CO - . Reduction by (CH 3 ) 2 COH was rapid in aqueous solutions but relatively slow in i-PrOH solutions. Transient spectra of the anion radicals were determined and, in the case of H 2 TCPP - ., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H 2 TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 10 7 -10 9 M -1 s -1 which depend on the pH and the quinone reduction potential. Reactions of Na 2 TPP - ., ZnTPP - ., and Chl a - . with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 10 9 M -1 s -1 . The spectral changes associated with these electron-transfer reactions as observed over a period of approx. 1 ms indicated, in some cases, the formation of an intermediate complex [P...Q - .]. 8 figures, 2 tables

  16. Experimental Research on Destruction Mode and Anchoring Performance of Carbon Fiber Phyllostachys pubescens Anchor Rod with Different Forms

    Directory of Open Access Journals (Sweden)

    Wang Yulan

    2018-01-01

    Full Text Available The anchoring technology is extensively applied in reinforcing protection of the earth relics. Now that no specification is available for different new anchor rods in earth relics protection due to diversified destruction modes of earth relics and complexity of engineering technology conditions, it is urgent to guide reinforcing design and construction with a complete detailed anchor rod research document. With the new carbon fiber Phyllostachys pubescens anchor rod as the research object, six lots of in situ tests are designed to, respectively, study the destruction mode and anchoring performance of the carbon fiber Phyllostachys pubescens anchor rod under different anchor length L, anchor rod diameter D, bore diameter H, grouting material S, rib spacing R, and inclination angle A in this paper. By studying load shift curve experiment in drawing of the anchor rod, the destruction mode and ultimate bearing capacity of the carbon fiber Phyllostachys pubescens anchor rod in different experiment lots are obtained, and the concept of permitted application value N in anchor rod design is proposed. By studying strain distribution characteristics of anchor rods in experimental lots along the length direction under action of the permitted application value N and combining the existing destruction mode and ultimate bearing capacity, this paper analyzes influences of L, D, H, S, R, and A on anchoring effect of the carbon fiber Phyllostachys pubescens anchor rod; gives the reasonable value range of L, D, H, and R when the carbon fiber Phyllostachys pubescens anchor rod is used for reinforcing design of the earth relics; and provides favorable experiment basis for reinforcing design of the earth relics based on the carbon fiber Phyllostachys pubescens anchor rod.

  17. Three manganese oxide-rich marine sediments harbor similar communities of acetate-oxidizing manganese-reducing bacteria

    OpenAIRE

    Vandieken, Verona; Pester, Michael; Finke, Niko; Hyun, Jung-Ho; Friedrich, Michael W; Loy, Alexander; Thamdrup, Bo

    2012-01-01

    Dissimilatory manganese reduction dominates anaerobic carbon oxidation in marine sediments with high manganese oxide concentrations, but the microorganisms responsible for this process are largely unknown. In this study, the acetate-utilizing manganese-reducing microbiota in geographically well-separated, manganese oxide-rich sediments from Gullmar Fjord (Sweden), Skagerrak (Norway) and Ulleung Basin (Korea) were analyzed by 16S rRNA-stable isotope probing (SIP). Manganese reduction was the p...

  18. Manganese Oxidation by Bacteria: Biogeochemical Aspects

    Digital Repository Service at National Institute of Oceanography (India)

    Sujith, P.P.; LokaBharathi, P.A.

    Manganese is an essential trace metal that is not as readily oxidizable like iron. Several bacterial groups posses the ability to oxidize Mn effectively competing with chemical oxidation. The oxides of Mn are the strongest of the oxidants, next...

  19. Manganese(II) chelate contrast media

    International Nuclear Information System (INIS)

    Rocklage, S.M.; Quay, S.C.

    1994-01-01

    New chelate forming compounds for use as contrast media in NMR imaging are described. Especially mentioned are manganese(II) ion chelates of N,N' dipyridoxaldiamine, N,N' diacetic acid, and salts and esters thereof. 1 fig

  20. 21 CFR 73.2775 - Manganese violet.

    Science.gov (United States)

    2010-04-01

    .... Mercury (as Hg), not more than 1 part per million. Total color, based on Mn content in “as is” sample, not less than 93 percent. (c) Uses and restrictions. Manganese violet is safe for use in coloring cosmetics...

  1. Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution.

    Science.gov (United States)

    Lei, Di; Zheng, Qianwen; Wang, Yili; Wang, Hongjie

    2015-02-01

    A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH2-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu2+ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N2 adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH2-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu2+ on NH2-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH2-Mn-SBA-15 for Cu2+ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu2+ by NH2-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu2+. The NH2-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH2-Mn-SBA-15 could be regenerated by acid treatment without altering its properties. Copyright © 2014. Published by Elsevier B.V.

  2. Comparative Study on Different Slot Forms of Prestressed Anchor Blocks

    Science.gov (United States)

    Fan, Rong; Si, Jianhui; Jian, Zheng

    2018-03-01

    In this paper, two models of prestressed pier, rectangular cavity anchor block and arch hollow anchor block are established. The ABAQUS software was used to calculate the stress of the surface of the neck of the pier and the cavity of the anchor block, through comparative analysis. The results show that compared with the rectangular cavity anchor block, the stress of the pier and the cavity can be effectively reduced when the arch hole is used, and the amount of prestressed anchor can be reduced, so as to obtain obvious economic benefits.

  3. Personality traits in persons with manganese poisoning

    Energy Technology Data Exchange (ETDEWEB)

    Platonov, A A

    1976-10-01

    Results of studies with the Minnesota Multiphasic Personality Inventory (MMPI) in 3 groups of arc welders with various degrees of manganese poisoning (22 symptom-free, 23 with functional disturbances, 55 with organic symptoms) and 50 controls were discussed. There was a close relation between the severity of the poisoning and quantitative and qualitative personality changes. Personality tests are considered a useful addition to the clinical diagnosis of chronic manganese poisoning.

  4. Composite materials formed with anchored nanostructures

    Science.gov (United States)

    Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

    2015-03-10

    A method of forming nano-structure composite materials that have a binder material and a nanostructure fiber material is described. A precursor material may be formed using a mixture of at least one metal powder and anchored nanostructure materials. The metal powder mixture may be (a) Ni powder and (b) NiAl powder. The anchored nanostructure materials may comprise (i) NiAl powder as a support material and (ii) carbon nanotubes attached to nanoparticles adjacent to a surface of the support material. The process of forming nano-structure composite materials typically involves sintering the mixture under vacuum in a die. When Ni and NiAl are used in the metal powder mixture Ni.sub.3Al may form as the binder material after sintering. The mixture is sintered until it consolidates to form the nano-structure composite material.

  5. A scale distortion theory of anchoring.

    Science.gov (United States)

    Frederick, Shane W; Mochon, Daniel

    2012-02-01

    We propose that anchoring is often best interpreted as a scaling effect--that the anchor changes how the response scale is used, not how the focal stimulus is perceived. Of importance, we maintain that this holds true even for so-called objective scales (e.g., pounds, calories, meters, etc.). In support of this theory of scale distortion, we show that prior exposure to a numeric standard changes respondents' use of that specific response scale but does not generalize to conceptually affiliated judgments rendered on similar scales. Our findings highlight the necessity of distinguishing response language effects from representational effects in places where the need for that distinction has often been assumed away.

  6. Electrochromic mirror using viologen-anchored nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Han Na [Electronics and Telecommunications Research Institute, Nature-mimic I/O interface Research Section, 218 Gajeong-roYuseong-gu, Daejeon 305-700 (Korea, Republic of); University of Science and Technology, Advanced Device Technology, 217 Gajeong-roYuseong-gu, Daejeon 305-350 (Korea, Republic of); Cho, Seong M.; Ah, Chil Seong; Song, Juhee; Ryu, Hojun; Kim, Yong Hae [Electronics and Telecommunications Research Institute, Nature-mimic I/O interface Research Section, 218 Gajeong-roYuseong-gu, Daejeon 305-700 (Korea, Republic of); Kim, Tae-Youb, E-mail: youby@etri.re.kr [Electronics and Telecommunications Research Institute, Nature-mimic I/O interface Research Section, 218 Gajeong-roYuseong-gu, Daejeon 305-700 (Korea, Republic of); University of Science and Technology, Advanced Device Technology, 217 Gajeong-roYuseong-gu, Daejeon 305-350 (Korea, Republic of)

    2016-10-15

    Highlights: • Three types of ECM device were fabricated using viologen-anchored ECDs. • The devices were investigated according to their optical structures. • The anti-reflection material affects the reflectance and the coloration efficiency. • The device design of ECMs is a crucial factor for clear reflected images. - Abstract: Electrochromic mirrors (ECMs) that are used in automobile mirrors need to have high reflectance, a high contrast ratio, and a clear image. In particular, it is critical that distortions of clear images are minimized for safety. Therefore, an ECM is fabricated using viologen-anchored nanoparticles and a magnesium fluoride (MgF{sub 2}) layer with an anti-reflection function. The ECM has approximately 30.42% in the reflectance dynamic range and 125 cm{sup 2}/C high coloration efficiency.

  7. Autonomic function in manganese alloy workers

    Energy Technology Data Exchange (ETDEWEB)

    Barrington, W.W.; Angle, C.R.; Willcockson, N.K.; Padula, M.A. [Univ. of Nebraska Medical Center, Omaha, NE (United States); Korn, T.

    1998-07-01

    The observation of orthostatic hypotension in an index case of manganese toxicity lead to this prospective attempt to evaluate cardiovascular autonomic function and cognitive and emotional neurotoxicity in eight manganese alloy welders and machinists. The subjects consisted of a convenience sample consisting of an index case of manganese dementia, his four co-workers in a frog shop for gouging, welding, and grinding repair of high manganese railway track and a convenience sample of three mild steel welders with lesser manganese exposure also referred because of cognitive or autonomic symptoms. Frog shop air manganese samples 9.6--10 years before and 1.2--3.4 years after the diagnosis of the index case exceeded 1.0 mg/m{sup 3} in 29% and 0.2 mg/m{sup 3} in 62%. Twenty-four-hour electrocardiographic (Holter) monitoring was used to determine the temporal variability of the heartrate (RR{prime} interval) and the rates of change at low frequency and high frequency. MMPI and MCMI personality assessment and short-term memory, figure copy, controlled oral word association, and symbol digit tests were used.

  8. Magnesium and manganese content of halophilic bacteria

    International Nuclear Information System (INIS)

    de Medicis, E.; Paquette, J.; Gauthier, J.J.; Shapcott, D.

    1986-01-01

    Magnesium and manganese contents were measured by atomic absorption spectrophotometry in bacteria of several halophilic levels, in Vibrio costicola, a moderately halophilic eubacterium growing in 1 M NaCl, Halobacterium volcanii, a halophilic archaebacterium growing in 2.5 NaCl, Halobacterium cutirubrum, an extremely halophilic archaebacterium growing in 4 M NaCl, and Escherichia coli, a nonhalophilic eubacterium growing in 0.17 M NaCl. Magnesium and manganese contents varied with the growth phase, being maximal at the early log phase. Magnesium and manganese molalities in cell water were shown to increase with the halophilic character of the logarithmically growing bacteria, from 30 mmol of Mg per kg of cell water and 0.37 mmol of Mn per kg of cell water for E. coli to 102 mmol of Mg per kg of cell water and 1.6 mmol of Mn per kg of cell water for H cutirubrum. The intracellular concentrations of manganese were determined independently by a radioactive tracer technique in V. costicola and H. volcanii. The values obtained by 54 Mn loading represented about 70% of the values obtained by atomic absorption. The increase of magnesium and manganese contents associated with the halophilic character of the bacteria suggests that manganese and magnesium play a role in haloadaptation

  9. Anchoring in a novel bimanual coordination pattern.

    Science.gov (United States)

    Maslovat, Dana; Lam, Melanie Y; Brunke, Kirstin M; Chua, Romeo; Franks, Ian M

    2009-02-01

    Anchoring in cyclical movements has been defined as regions of reduced spatial or temporal variability [Beek, P. J. (1989). Juggling dynamics. PhD thesis. Amsterdam: Free University Press] that are typically found at movement reversal points. For in-phase and anti-phase movements, synchronizing reversal points with a metronome pulse has resulted in decreased anchor point variability and increased pattern stability [Byblow, W. D., Carson, R. G., & Goodman, D. (1994). Expressions of asymmetries and anchoring in bimanual coordination. Human Movement Science, 13, 3-28; Fink, P. W., Foo, P., Jirsa, V. K., & Kelso, J. A. S. (2000). Local and global stabilization of coordination by sensory information. Experimental Brain Research, 134, 9-20]. The present experiment examined anchoring during acquisition, retention, and transfer of a 90 degrees phase-offset continuous bimanual coordination pattern (whereby the right limb lags the left limb by one quarter cycle), involving horizontal flexion about the elbow. Three metronome synchronization strategies were imposed: participants either synchronized maximal flexion of the right arm (i.e., single metronome), both flexion and extension of the right arm (i.e., double metronome within-limb), or flexion of each arm (i.e., double metronome between-limb) to an auditory metronome. In contrast to simpler in-phase and anti-phase movements, synchronization of additional reversal points to the metronome did not reduce reversal point variability or increase pattern stability. Furthermore, practicing under different metronome synchronization strategies did not appear to have a significant effect on the rate of acquisition of the pattern.

  10. Consistency Anchor Formalization and Correctness Proofs

    OpenAIRE

    Miguel, Correia; Bessani, Alysson

    2014-01-01

    This is report contains the formal proofs for the techniques for increasing the consistency of cloud storage as presented in "Bessani et al. SCFS: A Cloud-backed File System. Proc. of the 2014 USENIX Annual Technical Conference. June 2014." The consistency anchor technique allows one to increase the consistency provided by eventually consistent cloud storage services like Amazon S3. This technique has been used in the SCFS (Shared Cloud File System) cloud-backed file system for solving rea...

  11. Porphyrin metabolisms in human skin commensal Propionibacterium acnes bacteria: potential application to monitor human radiation risk.

    Science.gov (United States)

    Shu, M; Kuo, S; Wang, Y; Jiang, Y; Liu, Y-T; Gallo, R L; Huang, C-M

    2013-01-01

    Propionibacterium acnes (P. acnes), a Gram-positive anaerobic bacterium, is a commensal organism in human skin. Like human cells, the bacteria produce porphyrins, which exhibit fluorescence properties and make bacteria visible with a Wood's lamp. In this review, we compare the porphyrin biosynthesis in humans and P. acnes. Also, since P. acnes living on the surface of skin receive the same radiation exposure as humans, we envision that the changes in porphyrin profiles (the absorption spectra and/or metabolism) of P. acnes by radiation may mirror the response of human cells to radiation. The porphyrin profiles of P. acnes may be a more accurate reflection of radiation risk to the patient than other biodosimeters/biomarkers such as gene up-/down-regulation, which may be non-specific due to patient related factors such as autoimmune diseases. Lastly, we discuss the challenges and possible solutions for using the P. acnes response to predict the radiation risk.

  12. Thermodynamics of complex formation of natural iron(III)porphyrins with neutral ligands

    International Nuclear Information System (INIS)

    Lebedeva, Nataliya Sh.; Yakubov, Sergey P.; Vyugin, Anatoly I.; Parfenyuk, Elena V.

    2003-01-01

    Calorimetric titrations in benzene and chloroform at 298.15 K have been performed to give the complexes stability constants and the thermodynamic parameters for the complex formation of nature iron(III)porphyrins with pyridine. Stoichimetry of the complexes formed has been determined. It has been found that the thermodynamic parameters obtained depend on nature of peripheral substituents of the porphyrins. The estimation of the influence of Cl - and Ac - ions on the processes studied has been carried out. Using thermodynamic analysis method, the crystallsolvates of nature iron(III)porphyrins with benzene have been studied. Stoichiometry, thermal and energetic stability of the π-π-complexes formed have been determined. The data obtained have been used to the estimate solvent effect on the thermodynamic parameters of axial coordination of pyridine on the iron(III)porphyrins in benzene

  13. Functionalized porphyrin conjugate thin films deposited by matrix assisted pulsed laser evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Iordache, S. [University of Bucharest, 3Nano-SAE Research Center, PO Box MG-38, Bucharest-Magurele (Romania); Cristescu, R., E-mail: rodica.cristescu@inflpr.ro [National Institute for Lasers, Plasma and Radiation Physics, Lasers Department, P.O. Box MG-36, Bucharest-Magurele (Romania); Popescu, A.C.; Popescu, C.E.; Dorcioman, G.; Mihailescu, I.N. [National Institute for Lasers, Plasma and Radiation Physics, Lasers Department, P.O. Box MG-36, Bucharest-Magurele (Romania); Ciucu, A.A. [University of Bucharest, Faculty of Chemistry, Bucharest (Romania); Balan, A.; Stamatin, I. [University of Bucharest, 3Nano-SAE Research Center, PO Box MG-38, Bucharest-Magurele (Romania); Fagadar-Cosma, E. [Institute of Chemistry Timisoara of Romanian Academy, M. Viteazul Ave. 24, 300223-Timisoara (Romania); Chrisey, D.B. [Tulane University, Departments of Physics and Biomedical Engineering, New Orleans, LA 70118 (United States)

    2013-08-01

    We report on the deposition of nanostructured porphyrin-base, 5(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin thin films by matrix assisted pulsed laser evaporation onto silicon substrates with screen-printed electrodes. AFM investigations have shown that at 400 mJ/cm{sup 2} fluence a topographical transition takes place from the platelet-like stacking porphyrin-based nanostructures in a perpendicular arrangement to a quasi-parallel one both relative to the substrate surface. Raman spectroscopy has shown that the chemical structure of the deposited thin films is preserved for fluences within the range of 200–300 mJ/cm{sup 2}. Cyclic voltammograms have demonstrated that the free porphyrin is appropriate as a single mediator for glucose in a specific case of screen-printed electrodes, suggesting potential for designing a new class of biosensors.

  14. A New Synthesis of Porphyrins with Extended Conjugation and their Photophysics

    National Research Council Canada - National Science Library

    Ono, Noboru

    2005-01-01

    .... These molecules useful non-linear optical and optoelectronic properties. The contractor used a synthesis method based on the retro Diels-Alder reaction of porphyrins fused with bicyclo[2.2.2]octadiene units...

  15. A panchromatic anthracene-fused porphyrin sensitizer for dye-sensitized solar cells

    KAUST Repository

    Ball, James M.; Davis, Nicola K. S.; Wilkinson, James D.; Kirkpatrick, James; Teuscher, Joë l; Gunning, Robert; Anderson, Harry L.; Snaith, Henry J.

    2012-01-01

    The development of ruthenium-free sensitizers which absorb light over a broad range of the solar spectrum is important for improving the power conversion efficiency of dye-sensitized solar cells. Here we study three chemically tailored porphyrin

  16. Biodistribution, toxicity and efficacy of a boronated porphyrin for boron neutron capture therapy

    International Nuclear Information System (INIS)

    Miura, Michiko; Micca, P.; Fairchild, R.; Slatkin, D.; Gabel, D.

    1992-01-01

    Boron-containing porphyrins may be useful for boron neutron capture therapy (BNCT) in the treatment of brain tumors. Porphyrins have been shown to accumulate in tumor tissue and to be essentially excluded from normal brain. However, problems of toxicity may prevent some boron-containing porphyrins from being considered for BNCT. The authors have synthesized the boronated porphyrin 2,4-bis-vinyl-o-nidocarboranyl-deuteroporphyrin IX (VCDP). Preliminary studies in tumor-bearing mice showed considerable uptake of boron at a total dose of 150 μg/gbw with low mortality. They now report that a total dose to mice of ∼ 275 μg VCDP/gbw administered in multiple intraperitoneal (ip) injections can provide 40-50μg B per gram of tumor with acceptable toxicity. Toxicity experiments and a preliminary trial of BNCT in mice given such doses are also reported

  17. Distribution of exogenous porphyrins in vivo; implications for neutron capture therapy

    International Nuclear Information System (INIS)

    Fairchild, R.G.; Gabel, D.; Hillman, M.; Watts, K.

    1982-01-01

    Endogenous porphyrins (HpD) are already in clinical use for phototherapy, in which red light is used to stimulate a cytotoxic response in tumors. The evident success, at least with superficial cancers, gives biological evidence of selective concentrations of porphyrins in tumors adequate for therapy. The authors have investigated, in addition, the biodistribution of a synthetic porphyrin (tetraphenylporphinesulfonate, or TPPS) in seven different animal tumor models. Their data, as well as those of others, indicate abundant accumulations of TPPS in tumor. If boronated analogs behave in the same way, boron concentrations would be up to 10 times that needed for therapy. Utilization of such porphyrin analogs in the neutron capture therapy (NCT) procedure is similar in concept to phototherapy currently being used clinically, with the distinct advantage of deeper tissue penetration produced by the activating neutrons

  18. 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.

  19. Electrocatalytic miRNA Detection Using Cobalt Porphyrin-Modified Reduced Graphene Oxide

    Directory of Open Access Journals (Sweden)

    Camille De Souza

    2014-06-01

    Full Text Available Metalated porphyrins have been described to bind nucleic acids. Additionally, cobalt porphyrins present catalytic properties towards oxygen reduction. In this work, a carboxylic acid-functionalized cobalt porphyrin was physisorbed on reduced graphene oxide, then immobilized on glassy carbon electrodes. The carboxylic groups were used to covalently graft amino-terminated oligonucleotide probes which are complementary to a short microRNA target. It was shown that the catalytic oxygen electroreduction on cobalt porphyrin increases upon hybridization of miRNA strand (“signal-on” response. Current changes are amplified compared to non-catalytic amperometric system. Apart from oxygen, no added reagent is necessary. A limit of detection in the sub-nanomolar range was reached. This approach has never been described in the literature.

  20. Electrical characteristic of spin coated Fe-Porphyrin on Cu substrates

    Energy Technology Data Exchange (ETDEWEB)

    Utari, E-mail: utari@ugm.ac.id [Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Sebelas Maret, Jl. Ir. Sutami 36A Kentingan Surakarta 57126 (Indonesia); Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Bulaksumur BLS 21 Yogyakarta 55281 (Indonesia); Kusumandari,; Purnama, Budi, E-mail: bpurnama@mipa.uns.ac.id [Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Sebelas Maret, Jl. Ir. Sutami 36A Kentingan Surakarta 57126 (Indonesia); Mudasir [Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Bulaksumur BLS 21 Yogyakarta 55281 (Indonesia); Abraha, Kamsul [Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Bulaksumur BLS 21 Yogyakarta 55281 (Indonesia)

    2016-06-17

    This paper describes the electrical-characteristics of Fe-Porphyrin thin films on Cu substrates. The thin layer samples used were deposited by spin coating methods on Cu-substrates at room temperature with and without induced magnetic field in the plane direction of the surface films. Fe-porphyrin was dissolved in chloroform and mixed with a magnetic stirrer for 60 min at a rotational speed of 200 rpm. The experimental results show that the mobility carrier charge of the Fe-Porphyrin layer with induced magnetic field during deposition has lower value than that without induced magnetic field case. The decrease of the mobility can be attribute to the change of the surface morphology in Fe-porphyrin films by means of increase in the nano-granular/nano-molecular size caused by the induce magnetic field.

  1. Acid-base and coordination properties of Meso-substituted porphyrins in nonaqueous solutions

    Science.gov (United States)

    Pukhovskaya, S. G.; Nam, Dao Tkhe; Fien, Chan Ding; Domanina, E. N.; Ivanova, Yu. B.; Semeikin, A. S.

    2017-09-01

    Acid-base and coordination properties of alkyl and aryl meso-substituted porphyrins are studied spectrophotometrically in nonaqueous solutions. It is found that the nature of the substituent greatly affects the basicity of ligands for porphyrins characterized by a flat structure of macrocycle. The electronic effects of substituents have a much weaker influence on the kinetics of complexing. These effects could be due to the opposite orientation of some factors: an increase in the basicity and stability of the N-H bonds of porphyrin reaction centers. Dissociation constants p K b of the cationic forms of meso-substituted derivatives of porphyrin are measured. The values of p K b are in good agreement with classic concepts of the nature of substituents, particularly those indirectly included in the macrocycle through phenyl buffer rings.

  2. Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework

    KAUST Repository

    Chen, Chen; Joshi, Trinity; Li, Huifang; Chavez, Anton D.; Pedramrazi, Zahra; Liu, Pei-Nian; Li, Hong; Dichtel, William R.; Bredas, Jean-Luc; Crommie, Michael F.

    2017-01-01

    We have characterized the local electronic structure of a porphyrin-containing single-layer covalent organic framework (COF) exhibiting a square lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde

  3. Career anchors and career resilience: Supplementary constructs?

    Directory of Open Access Journals (Sweden)

    L. J. Van Vuuren

    2000-06-01

    Full Text Available Previously the authors reported on a study in which an attempt was made at defining and measuring the construct career resilience (Fourie & Van Vuuren, 1998. The present article continues this investigation by reporting on the relationship between career resilience and career anchors, as defined in Scheins (1975; 1978; 1990; 1992 career anchor model. The aim of the study was to determine whether career anchor patterning could potentially inhibit or facilitate individuals' levels of career resilience. The "Career Resilience Questionnaire" (CRQ (Fourie & Van Vuuren, 1998 together with Scheins (1990 "Career Orientations Inventory" (COI were administered to 352 skilled employees. The findings regarding the statistical relationship between the two constructs are discussed. Opsomming Loopbaanankers en loopbaangehardheid: supplementere konstrukte? In n vorige publikasie van Fourie en Van Vuuren (1998 is die bevindinge aangaande die afbakening en meting van die konstruk, loopbaangehardheid, gerapporteer. In die huidige artikel word die ondersoek voortgesit met 'n beskrywing van die verwantskap tussen loopbaangehardheid en loopbaanankers, soos gedefinieer in die loopbaanankermodel van Schein (1975; 1978; 1990; 1992. Die doel met die studie was om te bepaal of die mate van loopbaanankerontplooiing individuele vlakke van loopbaangehardheid potensieel fasiliteer ofinhibeer. Die "Career Resilience Questionnaire" (CRQ (Fourie & Van Vuuren, 1998 is tesame met die "Career Orientation Inventory" (COI (Schein, 1990 op 352 geskoolde werknemers geadministreer. Die bevindinge betreffende die statistiese verwantskap tussen die twee konstrukte word bespreek.

  4. The Analysis Stability of Anchor Retaining Wall

    International Nuclear Information System (INIS)

    Benamara, F. Z.; Belabed, L

    2011-01-01

    The construction of anchored retaining walls reach every day in the field of Civil Engineering especially in public works. Their dimensioning and stability are the axes of research for geotechnical. The rule is to reduce the active forces of the slide and increase the effective normal stress on the rupture surface. So that, we anchored tied-back (constituted by steel cables) in the stable ground located under the failure surface and we apply at the top a traction force. This effort can be distributed over the ground surface by means of small plates or massive reinforced concrete. The study of the stability of anchored retaining wall was also performed by using software GEO4. Many cases can be solved using analytical solutions available in the group GEO4 program, but for our standard model solution studied analytically proved unsatisfactory so we used a numerical analysis based on the method of finite element in this program. The results obtained by numerical study were interpreted to identify the precision numerical predictions. Moreover these methods were useful and economics in the realization of reinforced slopes by tied-buck. (author)

  5. Spectral properties of porphyrins in the systems with layered silicates

    International Nuclear Information System (INIS)

    Ceklovsky, A.

    2009-03-01

    This work is focused on investigation of hybrid materials based on layered silicates, representing host inorganic component, and porphyrin dyes as organic guest. Aqueous colloidal dispersions, as well as thin solid films of layered silicate/porphyrin systems were studied. Modification of photophysical properties, such as absorption and fluorescence of molecules, adsorbed or incorporated in layered silicate hosts, were studied mainly to spread the knowledge about the environments suitable for incorporating aromatic compounds, providing photoactive properties of potential technological interest. TMPyP cations interact with the surfaces of layered silicates via electrostatic interactions. The extent of dye adsorption on colloidal particles of the silicates is influenced by the CEC values and swelling ability of silicates. Interaction of porphyrins with layered silicate hosts leads to significant changes of dye spectral properties. One of the key parameters that has a crucial impact on this interaction is the layer charge of silicate template. Other factors influence the resulting spectral properties of hybrid systems, such as the method of hybrid material preparation, the material's type (colloid, film), and the modification of the silicate host. Molecular orientation studies using linearly-polarized spectroscopies in VIS and IR regions revealed that TMPyP molecules were oriented in almost parallel fashion with respect to the silicate surface plane. Slightly higher values of the orientation angle of TMPyP transition moment were observed for the TMPyP/FHT system. Thus, flattening of the guest TMPyP molecules is the next important factor (mainly in the systems with lower layer charge), influencing its spectral properties upon the interaction with layered silicates. Fluorescence was effectively quenched in the systems based on solid films prepared from the high concentration of the dye (10-3 mol.dm-3). The quenching is most probably related to the structure of the

  6. Porphyrin molecules boost the sensitivity of epitaxial graphene for NH3 detection

    Science.gov (United States)

    Iezhokin, I.; den Boer, D.; Offermans, P.; Ridene, M.; Elemans, J. A. A. W.; Adriaans, G. P.; Flipse, C. F. J.

    2017-02-01

    The sensitivity of quasi-free standing epitaxial graphene for NH3 detection is strongly enhanced by chemical functionalization with cobalt porphyrins resulting in a detection limit well below 100 ppb. Hybridization between NH3 and cobalt porphyrins induces a charge transfer to graphene and results in a shift of the graphene Fermi-level as detected by Hall measurements and theoretically explained by electronic structure calculations.

  7. N-annulated perylene fused porphyrins with enhanced near-IR absorption and emission

    KAUST Repository

    Jiao, Chongjun

    2010-09-17

    N-Annulated perylene fused porphyrins 1 and 2 were synthesized by oxidative dehydrogenation using a Sc(OTf)3/DDQ system. These newly synthesized hybrid molecules are highly soluble in organic solvents and exhibit remarkably intense near-IR absorption, as well as detectable photoluminescence quantum yields, all of which are comparable to or even exceed those of either meso-β doubly linked porphyrin dimer/trimer or bis/tri-N-annulated rylenes. © 2010 American Chemical Society.

  8. Comparative VOCs sensing performance for conducting polymer and porphyrin functionalized carbon nanotubes based sensors

    Science.gov (United States)

    Datta, Kunal; Rushi, Arti; Ghosh, Prasanta; Shirsat, Mahendra

    2018-05-01

    We report sensors for detection of ethyl alcohol, a prominent volatile organic compound (VOC). Single walled carbon nanotubes were selected as main sensing backbone. As efficiency of sensor is dependent upon the choice of sensing materials, the performances of conducting polymer and porphyrin based sensors were compared. Chemiresistive sensing modality was adopted to observe the performance of sensors. It has been found that porphyrin based sensor shows higher affinity towards ethyl alcohol.

  9. Self-organization of porphyrin units induced by magnetic field during sol-gel polymerization.

    Science.gov (United States)

    Lerouge, Frédéric; Cerveau, Geneviève; Corriu, Robert J P; Stern, Christine; Guilard, Roger

    2007-04-21

    The use of a magnetic field as a controlling factor during the hydrolysis-polycondensation of porphyrin precursors substituted by Si(OR)(3) groups, induces a self-organization of porphyrin moieties due to the stacking of these units in the hybrid material and this study also confirms the effect of the magnetic field in the nano- and micrometric organization during the kinetically controlled polycondensation process.

  10. Pt(II) porphyrin modified TiO{sub 2} composites as photocatalysts for efficient 4-NP degradation

    Energy Technology Data Exchange (ETDEWEB)

    Mingyue, Duan [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xian, Shaanxi 710069 (China); Li Jun, E-mail: junli@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xian, Shaanxi 710069 (China); Min, Li [Datang Wujiang Gas Turbine Power Limited Liability Company, Jiangsu 215214 (China); Zengqi, Zhang; Chen, Wang [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xian, Shaanxi 710069 (China)

    2012-05-01

    Three Pt(II) porphyrins 5,10,15,20-tetra-[2 or 3 or 4-(3-phenoxy)propoxy]phenyl porphyrin]platinum(II) (1-3) were synthesized and characterized spectroscopically. The corresponding Pt(II) porphyrins-TiO{sub 2} composites were then prepared and characterized by means of FT-IR and diffused reflectance spectra, X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of Pt(II) porphyrins-TiO{sub 2} catalyst was investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under irradiation with Xenon lamp. The results indicated that Pt(II) porphyrins greatly enhanced the photocatalytic efficiency of bare TiO{sub 2} in photodegrading the 4-NP, and the distinct space tropisms of peripheral substituents in meso-sites of porphyrin ring led to different results.

  11. Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and 1O2 generation

    International Nuclear Information System (INIS)

    Pan, Jie; Jiang, Lijun; Chan, Chi-Fai; Tsoi, Tik-Hung; Shiu, Kwok-Keung; Kwong, Daniel W.J.; Wong, Wing-Tak; Wong, Wai-Kwok; Wong, Ka-Leung

    2017-01-01

    Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

  12. Robotic Ankle for Omnidirectional Rock Anchors

    Science.gov (United States)

    Parness, Aaron; Frost, Matthew; Thatte, Nitish

    2013-01-01

    Future robotic exploration of near-Earth asteroids and the vertical and inverted rock walls of lava caves and cliff faces on Mars and other planetary bodies would require a method of gripping their rocky surfaces to allow mobility without gravitational assistance. In order to successfully navigate this terrain and drill for samples, the grippers must be able to produce anchoring forces in excess of 100 N. Additionally, the grippers must be able to support the inertial forces of a moving robot, as well gravitational forces for demonstrations on Earth. One possible solution would be to use microspine arrays to anchor to rock surfaces and provide the necessary load-bearing abilities for robotic exploration of asteroids. Microspine arrays comprise dozens of small steel hooks supported on individual suspensions. When these arrays are dragged along a rock surface, the steel hooks engage with asperities and holes on the surface. The suspensions allow for individual hooks to engage with asperities while the remaining hooks continue to drag along the surface. This ensures that the maximum possible number of hooks engage with the surface, thereby increasing the load-bearing abilities of the gripper. Using the microspine array grippers described above as the end-effectors of a robot would allow it to traverse terrain previously unreachable by traditional wheeled robots. Furthermore, microspine-gripping robots that can perch on cliffs or rocky walls could enable a new class of persistent surveillance devices for military applications. In order to interface these microspine grippers with a legged robot, an ankle is needed that can robotically actuate the gripper, as well as allow it to conform to the large-scale irregularities in the rock. The anchor serves three main purposes: deploy and release the anchor, conform to roughness or misalignment with the surface, and cancel out any moments about the anchor that could cause unintentional detachment. The ankle design contains a

  13. Reduced graphene oxide and porphyrin. An interactive affair in 2-D.

    Science.gov (United States)

    Wojcik, Aleksandra; Kamat, Prashant V

    2010-11-23

    Photoexcited cationic 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP) undergoes charge-transfer interaction with chemically reduced graphene oxide (RGO). Formation of the ground-state TMPyP-RGO complex in solution is marked by the red-shift of the porphyrin absorption band. This complexation was analyzed by Benesi-Hildebrand plot. Porphyrin fluorescence lifetime reduced from 5 to 1 ns upon complexation with RGO, indicating excited-state interaction between singlet excited porphyrin and RGO. Femtosecond transient absorption measurements carried out with TMPyP adsorbed on RGO film revealed fast decay of the singlet excited state, followed by the formation of a longer-living product with an absorption maximum around 515 nm indicating the formation of a porphyrin radical cation. The ability of TMPyP-RGO to undergo photoinduced charge separation was further confirmed from the photoelectrochemical measurements. TMPyP-RGO coated conducting glass electrodes are capable of generating photocurrent under visible excitation. These results are indicative of the electron transfer between photoexcited porphyrin and RGO. The role of graphene in accepting and shuttling electrons in light-harvesting assemblies is discussed.

  14. Real-time porphyrin detection in plaque and caries: a case study

    Science.gov (United States)

    Timoshchuk, Mari-Alina I.; Ridge, Jeremy S.; Rugg, Amanda L.; Nelson, Leonard Y.; Kim, Amy S.; Seibel, Eric J.

    2015-02-01

    An ultrathin scanning fiber endoscope, originally developed for cancer diagnosis, was used in a case study to locate plaque and caries. The imaging system incorporated software mitigation of background auto-fluorescence (AF). In conventional fluorescence imaging, varying AF across a tooth surface can mask low-level porphyrin signals. Laser-induced auto-fluorescence signals of dental tissue excited using a 405-nm laser typically produce fluorescence over a wavelength range extending from 440-nm to 750-nm. Anaerobic bacterial metabolism produces various porphyrin species (eg. protoporphyrin IX) that are located in carious enamel, dentin, gingivitis sites, and plaque. In our case study, these porphyrin deposits remained as long as one day after prophylaxis. Imaging the tooth surface using 405-nm excitation and subtracting the natural AF enhances the image contrast of low-level porphyrin deposits, which would otherwise be masked by the high background AF. In a case study, healthy tissues as well as sites of early and advanced caries formations were scanned for visual and quantitative signs of red fluorescence associated with porphyrin species using a background mitigation algorithm. Initial findings show increasing amplitudes of red fluorescence as caries severity increases from early to late stages. Sites of plaque accumulation also displayed red fluorescence similar to that found in carious dental tissue. The use of real-time background mitigation of natural dental AF can enhance the detection of low porphyrin concentrations that are indicators of early stage caries formation.

  15. Photoluminescence and dynamics of excitation relaxation in graphene oxide-porphyrin nanorods composite

    International Nuclear Information System (INIS)

    Khenfouch, M.; Wéry, J.; Baïtoul, M.; Maaza, M.

    2014-01-01

    Generally, porphyrin nanostructured materials are known by playing many roles such as photoconductors, photovoltaics and capable of light induced charging. Also their combination with acceptors like graphene, the rising two dimension material, added exciting physical and chemical properties. In this work, Morphology, optical absorption and photoluminescence properties were investigated in order to elucidate the interaction between the few layered graphene oxide (FGO) and pophyrin nanorods. Reporting on the photoluminescence (PL) of both porphyrin nanorods and FGO/porphyrin nanorods composite, synthesized via a self-assembly method, we have experimentally demonstrated the generation of a new photoluminescence band giving rise to a white light. This luminescence was studied by the analysis of its origins and dynamics which show a huge change of exciton life time found to be longer after the interaction with graphene oxide (GO) sheets. -- Highlights: • We prepared FGO-porphyrin nanorods composite via a simple chemical method. • Luminescence properties were studied presenting the absorption, photoluminescence and dynamics measurements. • These results show the emission of a white light which we studied its emissions origins. • TEM images show FGO sheets decorated with porphyrin nanorods. • FGO had like effect an increase of the exciton lifetime in porphyrin nanorods

  16. Uncharged water-soluble porphyrin tweezers as a supramolecular sensor for α-amino acids

    International Nuclear Information System (INIS)

    Villari, Valentina; Mineo, Placido; Micali, Norberto; Angelini, Nicola; Vitalini, Daniele; Scamporrino, Emilio

    2007-01-01

    The binding between uncharged cobalt porphyrin tweezers and L-amino acids in aqueous solutions is studied by means of UV-vis and circular dichroism spectroscopy. By varying the length of the aliphatic bridge between the two porphyrin units, the number of cobalt ions in the porphyrin cores and the pH of the solution, the chirality induction phenomenon has been investigated. The binding of the amino acid to the porphyrin seems to occur via a coordination mechanism between the metal and the nitrogen of the amino group; the steric, hydrophobic and π-π interactions operate to stabilize the complexes. The chirogenesis displays an opposite behaviour in the presence of aromatic guests with respect to the non-aromatic ones. Moreover, the UV-vis and the induced circular dichroism spectral changes suggest that the amino acid arrangement in the tweezers is determined by many factors, so that, unlike in organic solvent, the porphyrin tweezers in aqueous solution allow for two different arrangements of the same aromatic amino acid. The experimental findings indicate that the porphyrins tweezers reported in the paper are promising in opening perspectives toward their application as a selective molecular sensor in aqueous solutions directly

  17. Fluorescence quenching behaviour of uric acid interacting with water-soluble cationic porphyrin

    International Nuclear Information System (INIS)

    Makarska-Bialokoz, Magdalena; Borowski, Piotr

    2015-01-01

    The process of association between 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate (H 2 TTMePP) and uric acid as well as its sodium salt has been studied in aqueous NaOH solution analysing its absorption and steady-state fluorescence spectra. The fluorescence quenching effect observed during interactions porphyrin-uric acid compounds points at the fractional accessibility of the fluorophore for the quencher. The association and fluorescence quenching constants are of the order of magnitude of 10 5 mol −1 . The fluorescence lifetimes and the quantum yields of the porphyrin anionic form were established. The results demonstrate that uric acid and its sodium salt can interact with H 2 TTMePP at basic pH and through formation of stacking complexes are able to quench its ability to emission. - Highlights: • Association study of water soluble cationic porphyrin with uric acid. • Porphyrin absorption spectra undergo the bathochromic and hypochromic effects. • Uric acid interacts with porphyrin in inhibiting manner, quenching its emission. • Fluorescence quenching effect testifies for the partial inactivation of a porphyrin. • The association and fluorescence quenching constants were calculated

  18. Fluorescence quenching behaviour of uric acid interacting with water-soluble cationic porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Makarska-Bialokoz, Magdalena, E-mail: makarska@hektor.umcs.lublin.pl [Department of Inorganic Chemistry, Maria Curie-Sklodowska University M. C. Sklodowska Sq. 2, 20-031 Lublin (Poland); Borowski, Piotr [Faculty of Chemistry, Maria Curie-Sklodowska University M. C. Sklodowska Sq. 3, 20-031 Lublin (Poland)

    2015-04-15

    The process of association between 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate (H{sub 2}TTMePP) and uric acid as well as its sodium salt has been studied in aqueous NaOH solution analysing its absorption and steady-state fluorescence spectra. The fluorescence quenching effect observed during interactions porphyrin-uric acid compounds points at the fractional accessibility of the fluorophore for the quencher. The association and fluorescence quenching constants are of the order of magnitude of 10{sup 5} mol{sup −1}. The fluorescence lifetimes and the quantum yields of the porphyrin anionic form were established. The results demonstrate that uric acid and its sodium salt can interact with H{sub 2}TTMePP at basic pH and through formation of stacking complexes are able to quench its ability to emission. - Highlights: • Association study of water soluble cationic porphyrin with uric acid. • Porphyrin absorption spectra undergo the bathochromic and hypochromic effects. • Uric acid interacts with porphyrin in inhibiting manner, quenching its emission. • Fluorescence quenching effect testifies for the partial inactivation of a porphyrin. • The association and fluorescence quenching constants were calculated.

  19. Dehalogenation of chloroalkanes by nickel(i) porphyrin derivatives, a computational study.

    Science.gov (United States)

    Szatkowski, L; Hall, M B

    2016-11-14

    The nickel(i) octaethylisobacteriochlorin anion ([OEiBCh-Ni (I) ] - ) is commonly used as a synthetic model of cofactor F 430 from Methyl-Coenzyme M Reductase. In this regard, experimental studies show that [OEiBCh-Ni (I) ] - can catalyze dehalogenation of aliphatic halides in DMF solution by a highly efficient S N 2 reaction. To better understand this process, we constructed theoretical models of the dehalogenation of chloromethane by a simple nickel(i) isobacteriochlorin anion and compared its reactivity with that of similar Ni (I) complexes with other porphyrin-derived ligands: porphyrin, chlorin, bactreriochlorin, hexahydroporphyrin and octahydroporphyrin. Our calculations predict that all of the porphyrin derivative's model reactions proceed through low-spin complexes. Relative to the energy of the separate reactants the theoretical activation energies (free-energy barriers with solvation corrections) for the dehalogenation of chloromethane are similar for all of the porphyrin derivatives and range for the different functionals from 10-15 kcal mol -1 for B3LYP to 5-10 kcal mol -1 for M06-L and to 13-18 kcal mol -1 for ωB97X-D. The relative free energies of the products of the dehalogenation step, L-Ni-Me adducts, have a range from -5 to -40 kcal mol -1 for all functionals; generally becoming more negative with increasing saturation of the porphyrin ligand. Moreover, no significant differences in the theoretical chlorine kinetic isotope effect were discernable with change of porphyrin ligand.

  20. Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

    KAUST Repository

    Anderson, Carly E.

    2013-09-18

    Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

    KAUST Repository

    Anderson, Carly E.; Vagin, Sergei I.; Hammann, Markus; Zimmermann, Leander; Rieger, Bernhard

    2013-01-01

    Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Structural and Molecular Characterization of meso-Substituted Zinc Porphyrins: A DFT Supported Study

    Directory of Open Access Journals (Sweden)

    Giuseppe Mele

    2011-12-01

    Full Text Available Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrin's central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral data were reported and analyzed in context of the individual molecular features introduced by the meso substituents into the porphyrin moiety base. Raw experimental spectral data, including 1H- and 13C-NMR, UV-Vis, FTIR, XRD, and other relevant physicochemical details have been provided for a specially chosen reference zinc porphyrin functionalized by tert-butylphenyl groups.

  3. Photoluminescence and dynamics of excitation relaxation in graphene oxide-porphyrin nanorods composite

    Energy Technology Data Exchange (ETDEWEB)

    Khenfouch, M., E-mail: khenfouch@yahoo.fr [University Sidi Mohamed Ben Abdellah, Faculty of Sciences Dhar el Mahraz, Laboratory of Solid State Physics, Group of Polymers and Nanomaterials, BP 1796 Atlas, Fez 30 000 (Morocco); iThemba LABS-National Research Foundation of South Africa, Old Faure Road, PO Box 722, Somerset West 7129, Western Cape Province (South Africa); UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Wéry, J. [Institut des Matériaux Jean Rouxel, Nantes, 2 rue de la Houssinière, BP 32229, 44322 Nantes, Cedex 3 (France); Baïtoul, M., E-mail: baitoul@yahoo.fr [University Sidi Mohamed Ben Abdellah, Faculty of Sciences Dhar el Mahraz, Laboratory of Solid State Physics, Group of Polymers and Nanomaterials, BP 1796 Atlas, Fez 30 000 (Morocco); Maaza, M. [iThemba LABS-National Research Foundation of South Africa, Old Faure Road, PO Box 722, Somerset West 7129, Western Cape Province (South Africa); UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa)

    2014-01-15

    Generally, porphyrin nanostructured materials are known by playing many roles such as photoconductors, photovoltaics and capable of light induced charging. Also their combination with acceptors like graphene, the rising two dimension material, added exciting physical and chemical properties. In this work, Morphology, optical absorption and photoluminescence properties were investigated in order to elucidate the interaction between the few layered graphene oxide (FGO) and pophyrin nanorods. Reporting on the photoluminescence (PL) of both porphyrin nanorods and FGO/porphyrin nanorods composite, synthesized via a self-assembly method, we have experimentally demonstrated the generation of a new photoluminescence band giving rise to a white light. This luminescence was studied by the analysis of its origins and dynamics which show a huge change of exciton life time found to be longer after the interaction with graphene oxide (GO) sheets. -- Highlights: • We prepared FGO-porphyrin nanorods composite via a simple chemical method. • Luminescence properties were studied presenting the absorption, photoluminescence and dynamics measurements. • These results show the emission of a white light which we studied its emissions origins. • TEM images show FGO sheets decorated with porphyrin nanorods. • FGO had like effect an increase of the exciton lifetime in porphyrin nanorods.

  4. π -Plasmon model for carbon nano structures: Application to porphyrin

    International Nuclear Information System (INIS)

    Ha, Dao Thu; Anh, Chu Thuy; Nga, Do Thi; Thanh, Le Minh; Van, Tran Thi Thanh; Viet, Nguyen Ai

    2016-01-01

    In traditional concept, the optical properties of semiconductors and semimetals near their fundamental optical band gaps are attributed to single excitations (such electron-hole pairs, excitons...). In our earlier article, we proposed the collective mechanism of π -plasmons for optical properties of low dimensional carbon nano structures. A simple way to calculate the peak positions of UV-vis absorption spectra was pointed out and gave a good agreement with experimental data. In this work we analyze different schemas to calculate the UV-vis absorption peaks. A new parameter k which characterizes the dependence of schema on geometry and number of carbon sites is defined. As an example, the case of porphyrin was investigated. (paper)

  5. Leaching of manganese from electrolytic manganese residue by electro-reduction.

    Science.gov (United States)

    Shu, Jiancheng; Liu, Renlong; Liu, Zuohua; Chen, Hongliang; Tao, Changyuan

    2017-08-01

    In this study, an improved process for leaching manganese from electrolytic manganese residue (EMR) by electro-reduction was developed. The mechanisms of the electro-reduction leaching were investigated through X-ray diffraction, scanning electron microscopy, X-ray fluorescence, and Brunauer Emmett Teller. The results show that the electric field could change the surface charge distribution of EMR particles, and the high-valent manganese can be reduced by electric field. The leaching efficient of manganese reached 84.1% under the optimal leaching condition: 9.2 wt% H 2 SO 4 , current density of 25 mA/cm 2 , solid-to-liquid ratio of 1:5, and leaching time for 1 h. It is 37.9% higher than that attained without an electric field. Meanwhile, the manganese content in EMR decreased from 2.57% to 0.48%.

  6. Effect of manganese on neonatal rat: manganese concentration and enzymatic alterations in brain

    Energy Technology Data Exchange (ETDEWEB)

    Seth, P K; Husain, R; Mushtaq, M; Chandra, S V

    1977-01-01

    Suckling rats were exposed for 15 and 30 days to manganese through the milk of nursing dams receiving 15 mg MnCl/sub 2/.4H/sub 2/O/kg/day orally and after which the neurological manifestations of metal poisoning were studied. No significant differences in the growth rate, developmental landmarks and walking movements were observed between the control and manganese-exposed pups. The metal concentration was significantly increased in the brain of manganese-fed pups at 15 days and exhibited a further three-fold increase over the control, at 30 days. The accumulation of the metal in the brain of manganese-exposed nursing dams was comparatively much less. A significant decrease in succinic dehydrogenase, adenosine triphosphatase, adenosine deaminase, acetylcholine esterase and an increase in monoamine oxidase activity was observed in the brain of experimental pups and dams. The results suggest that the developing brain may also be susceptible to manganese.

  7. Old age and gender influence the pharmacokinetics of inhaled manganese sulfate and manganese phosphate in rats

    International Nuclear Information System (INIS)

    Dorman, David C.; McManus, Brian E.; Marshall, Marianne W.; James, R. Arden; Struve, Melanie F.

    2004-01-01

    In this study, we examined whether gender or age influences the pharmacokinetics of manganese sulfate (MnSO 4 ) or manganese phosphate (as the mineral form hureaulite). Young male and female rats and aged male rats (16 months old) were exposed 6 h day -1 for 5 days week -1 to air, MnSO 4 (at 0.01, 0.1, or 0.5 mg Mn m -3 ), or hureaulite (0.1 mg Mn m -3 ). Tissue manganese concentrations were determined in all groups at the end of the 90-day exposure and 45 days later. Tissue manganese concentrations were also determined in young male rats following 32 exposure days and 91 days after the 90-day exposure. Intravenous 54 Mn tracer studies were also performed in all groups immediately after the 90-day inhalation to assess whole-body manganese clearance rates. Gender and age did not affect manganese delivery to the striatum, a known target site for neurotoxicity in humans, but did influence manganese concentrations in other tissues. End-of-exposure olfactory bulb, lung, and blood manganese concentrations were higher in young male rats than in female or aged male rats and may reflect a portal-of-entry effect. Old male rats had higher testis but lower pancreas manganese concentrations when compared with young males. Young male and female rats exposed to MnSO 4 at 0.5 mg Mn m -3 had increased 54 Mn clearance rates when compared with air-exposed controls, while senescent males did not develop higher 54 Mn clearance rates. Data from this study should prove useful in developing dosimetry models for manganese that consider age or gender as potential sensitivity factors

  8. Dynamic performance of concrete undercut anchors for Nuclear Power Plants

    Energy Technology Data Exchange (ETDEWEB)

    Mahrenholtz, Christoph, E-mail: christoph@mahrenholtz.net; Eligehausen, Rolf

    2013-12-15

    Graphical abstract: - Highlights: • Behavior of undercut anchors under dynamic actions simulating earthquakes. • First high frequency load and crack cycling tests on installed concrete anchors ever. • Comprehensive review of anchor qualification for Nuclear Power Plants. - Abstract: Post-installed anchors are widely used for structural and nonstructural connections to concrete. In many countries, concrete anchors used for Nuclear Power Plants have to be qualified to ensure reliable behavior even under extreme conditions. The tests required for qualification of concrete anchors are carried out at quasi-static loading rates well below the rates to be expected for dynamic actions deriving from earthquakes, airplane impacts or explosions. To investigate potentially beneficial effects of high loading rates and cycling frequencies, performance tests on installed undercut anchors were conducted. After introductory notes on anchor technology and a comprehensive literature review, this paper discusses the qualification of anchors for Nuclear Power Plants and the testing carried out to quantify experimentally the effects of dynamic actions on the load–displacement behavior of undercut anchors.

  9. Single-step electron transfer on the nanometer scale: ultra-fast charge shift in strongly coupled zinc porphyrin-gold porphyrin dyads.

    Science.gov (United States)

    Fortage, Jérôme; Boixel, Julien; Blart, Errol; Hammarström, Leif; Becker, Hans Christian; Odobel, Fabrice

    2008-01-01

    The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II)-gold(III) bisporphyrin dyads (ZnP--S--AuP(+)) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert-(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45 A. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state (.+)ZnP--S--AuP(.), whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2 ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (tau=2.3 ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnP--AuP(+) dyads linked via meso-phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical

  10. Metal-porphyrin interactions. V. Kinetics of cyanide addition to a water soluble iron porphyrin dimer(1)

    Energy Technology Data Exchange (ETDEWEB)

    Hambright, P; Rishnamurthy, M K

    1975-01-01

    The kinetics of cyanide addition to the water-soluble oxybridged iron dimer of tetra (p-sulophenyl) porphin indicate that HCN is the reactant. The rate law is of the form: Rate = (3.8 +- 0.2) x 10/sup 4/ (Fe dimer) (HCN)/(1 + (3.1 +- 0.3) x 10/sup 10/ (H/sup +/)) at 25/sup 0/ ..mu.. = 0.7 (NaNO/sub 3/). The cyano iron dimer dissociates into dicyano iron monomers by two pathways, one first order in (H/sup +/), and one proportional to (H/sup +/)(CN/sup -/)/sup 2/. The mechanism of this dimer reaction is compared to iron porphyrin monomer systems.

  11. Globally sustainable manganese metal production and use.

    Science.gov (United States)

    Hagelstein, Karen

    2009-09-01

    The "cradle to grave" concept of managing chemicals and wastes has been a descriptive analogy of proper environmental stewardship since the 1970s. The concept incorporates environmentally sustainable product choices-such as metal alloys utilized steel products which civilization is dependent upon. Manganese consumption is related to the increasing production of raw steel and upgrading ferroalloys. Nonferrous applications of manganese include production of dry-cell batteries, plant fertilizer components, animal feed and colorant for bricks. The manganese ore (high grade 35% manganese) production world wide is about 6 million ton/year and electrolytic manganese metal demand is about 0.7 million ton/year. The total manganese demand is consumed globally by industries including construction (23%), machinery (14%), and transportation (11%). Manganese is recycled within scrap of iron and steel, a small amount is recycled within aluminum used beverage cans. Recycling rate is 37% and efficiency is estimated as 53% [Roskill Metals and Minerals Reports, January 13, 2005. Manganese Report: rapid rise in output caused by Chinese crude steel production. Available from: http://www.roskill.com/reports/manganese.]. Environmentally sustainable management choices include identifying raw material chemistry, utilizing clean production processes, minimizing waste generation, recycling materials, controlling occupational exposures, and collecting representative environmental data. This paper will discuss two electrolytically produced manganese metals, the metal production differences, and environmental impacts cited to date. The two electrolytic manganese processes differ due to the addition of sulfur dioxide or selenium dioxide. Adverse environmental impacts due to use of selenium dioxide methodology include increased water consumption and order of magnitude greater solid waste generation per ton of metal processed. The use of high grade manganese ores in the electrolytic process also

  12. Photodynamic inactivation of Candida albicans sensitized by tri- and tetra-cationic porphyrin derivatives.

    Science.gov (United States)

    Cormick, M Paula; Alvarez, M Gabriela; Rovera, Marisa; Durantini, Edgardo N

    2009-04-01

    The photodynamic action of 5-(4-trifluorophenyl)-10,15,20-tris(4-trimethylammoniumphenyl)porphyrin iodide (TFAP(3+)) and 5,10,15,20-tetra(4-N,N,N-trimethylammonium phenyl)porphyrin p-tosylate (TMAP(4+)) has been studied in vitro on Candida albicans. The results of these cationic porphyrins were compared with those of 5,10,15,20-tetra(4-sulphonatophenyl)porphyrin (TPPS(4-)), which characterizes an anionic sensitizer. In vitro investigations show that these cationic porphyrins are rapidly bound to C. albicans cells, reaching a value of approximately 1.4 nmol/10(6) cells, when the cellular suspensions were incubated with 5 microM sensitizer for 30 min. In contrast, TPPS(4-) is poorly uptaken by yeast cells. The fluorescence spectra of these sensitizers into the cells confirm this behaviour. The amount of porphyrin binds to cells is dependent on both sensitizer concentrations (1-5 microM) and cells densities (10(6)-10(8) cells/mL). Photosensitized inactivation of C. albicans cellular suspensions increases with sensitizer concentration, causing a approximately 5 log decrease of cell survival, when the cultures are treated with 5 microM of cationic porphyrin and irradiated for 30 min. However, the photocytotoxicity decreases with an increase in the cell density, according to its low binding to cells. Under these conditions, the photodynamic activity of TFAP(3+) is quite similar to that produced by TMAP(4+), whereas no important inactivation effect was found for TPPS(4)(-). The high photodynamic activity of cationic porphyrins was confirmed by growth delay experiments. Thus, C. albicans cell growth was not detected in the presence of 5 microM TFAP(3+). Photodynamic inactivation capacities of these sensitizers were also evaluated on C. albicans cells growing in colonies on agar surfaces. Cationic porphyrins produce a growth delay of C. albicans colonies and viability of cells was not observed after 3 h irradiation, indicating a complete inactivation of yeast cells

  13. Photogeochemical reactions of manganese under anoxic conditions

    Science.gov (United States)

    Liu, W.; Yee, N.; Piotrowiak, P.; Falkowski, P. G.

    2017-12-01

    Photogeochemistry describes reactions involving light and naturally occurring chemical species. These reactions often involve a photo-induced electron transfer that does not occur in the absence of light. Although photogeochemical reactions have been known for decades, they are often ignored in geochemical models. In particular, reactions caused by UV radiation during an ozone free early Earth could have influenced the available oxidation states of manganese. Manganese is one of the most abundant transition metals in the crust and is important in both biology and geology. For example, the presence of manganese (VI) oxides in the geologic record has been used as a proxy for oxygenic photosynthesis; however, we suggest that the high oxidation state of Mn can be produced abiotically by photochemical reactions. Aqueous solutions of manganese (II) as well as suspensions of rhodochrosite (MnCO3) were irradiated under anoxic condition using a 450 W mercury lamp and custom built quartz reaction vessels. The photoreaction of the homogeneous solution of Mn(II) produced H2 gas and akhtenskite (ɛ-MnO2) as the solid product . This product is different than the previously identified birnessite. The irradiation of rhodochrosite suspensions also produced H2 gas and resulted in both a spectral shift as well as morphology changes of the mineral particles in the SEM images. These reactions offer alternative, abiotic pathways for the formation of manganese oxides.

  14. Starting point anchoring effects in choice experiments

    DEFF Research Database (Denmark)

    Ladenburg, Jacob; Olsen, Søren Bøye

    of preferences in Choice Experiments resembles the Dichotomous Choice format, there is reason to suspect that Choice Experiments are equally vulnerable to anchoring bias. Employing different sets of price levels in a so-called Instruction Choice Set presented prior to the actual choice sets, the present study...... subjectivity in the present study is gender dependent, pointing towards, that female respondents are prone to be affected by the price levels employed. Male respondents, on the other hand, are not sensitive towards these prices levels. Overall, this implicates that female respondents, when employing a low......-priced Instruction Choice Set, tend to express lower willingness-to-pay than when higher prices are employed....

  15. The bone-anchored hearing aid

    DEFF Research Database (Denmark)

    Foghsgaard, Søren

    2014-01-01

    The bone-anchored hearing aid (Baha) was introduced in 1977 by Tjellström and colleagues and has now been used clinically for over 30 years. Generally, the outcomes are good, and several studies have shown improved audiological- and quality of life outcomes. The principle of the Baha is, that sou...... vibrations are led directly to the inner ear via the mastoid bone, bypassing the middle ear. This is achieved via an osseointegrated implant and a skin-penetrating abutment. Studies report high success rates and a majority of complications as typically minor in nature....

  16. Stone anchors from Minicoy Island, Lakshadweep, India

    Digital Repository Service at National Institute of Oceanography (India)

    Tripati, S.

    and Ali Rajas of Kerala. It appears that the mainland had contact with these islands during the early centuries of the Christian era, if not earlier (Sila Tripati, 1999). Though Islam came to Lakshadweep after the 11th and 12th centuries AD..., stitches, ropes and even sails (Hourani, 1995). With the passage of time the maritime contacts between the people of Lakshadweep and Arabs became closer, as demonstrated by the discovery of an Indo- 3 Arabian stone anchor in the Jama Mosque on Minicoy...

  17. ANCHORING IN THE POLITICAL AND ECONOMIC MARKETING

    Directory of Open Access Journals (Sweden)

    Tatyana L. Shklyar

    2015-01-01

    Full Text Available The main purpose of marketing, both ineconomy and in politics is to attract themaximum number of customers or voters, maximizing customer satisfaction and ,ideally, improve the quality of life.The author, in various aspects, thetechnology of anchoring used in NLP, to attract customers and voters, both in the economy and in politics.In different examples demonstrate theoverall impact on the psychology of the consumer. Separating policy and the economy, marketers are missing something. The author proposes to look at how psychologicalanchors affect these two, at fi rst glance, different vector.

  18. Adsorption phenomena and anchoring energy in nematic liquid crystals

    CERN Document Server

    Barbero, Giovanni

    2005-01-01

    Despite the large quantity of phenomenological information concerning the bulk properties of nematic phase liquid crystals, little is understood about the origin of the surface energy, particularly the surface, interfacial, and anchoring properties of liquid crystals that affect the performance of liquid crystal devices. Self-contained and unique, Adsorption Phenomena and Anchoring Energy in Nematic Liquid Crystals provides an account of new and established results spanning three decades of research into the problems of anchoring energy and adsorption phenomena in liquid crystals.The book contains a detailed discussion of the origin and possible sources of anchoring energy in nematic liquid crystals, emphasizing the dielectric contribution to the anchoring energy in particular. Beginning with fundamental surface and anchoring properties of liquid crystals and the definition of the nematic phase, the authors explain how selective ion adsorption, dielectric energy density, thickness dependence, and bias voltage...

  19. Manganese and acute paranoid psychosis: a case report

    NARCIS (Netherlands)

    Verhoeven, W.M.A.; Egger, J.I.M.; Kuijpers, H.J.H.

    2011-01-01

    Introduction Manganese regulates many enzymes and is essential for normal development and body function. Chronic manganese intoxication has an insidious and progressive course and usually starts with complaints of headache, fatigue, sleep disturbances, irritability and emotional instability. Later,

  20. Manganese and acute paranoid psychosis: A case report

    NARCIS (Netherlands)

    W.M.A. Verhoeven (Wim); J.I.M. Egger (Jos); H.J. Kuijpers (Harold)

    2011-01-01

    textabstractIntroduction: Manganese regulates many enzymes and is essential for normal development and body function. Chronic manganese intoxication has an insidious and progressive course and usually starts with complaints of headache, fatigue, sleep disturbances, irritability and emotional

  1. Investigation of suction anchor pullout capacity under undrained conditions

    OpenAIRE

    Jarand, Pollestad

    2015-01-01

    Master's thesis in Offshore technology Floating units are dependent on reliable mooring systems to ensure safety during marine operations. Suction anchors have proved to be a technologically viable and cost-effective concept. They are capable of precision installation, re-use, and provide large resistive capacity. This thesis investigates load capacity and failure modes of suction anchors subjected to vertical, horizontal (lateral), and incline loading. Suction anchor design co...

  2. Fluorescence spectroscopic studies on substituted porphyrins in homogeneous solvents and cationic micellar medium

    International Nuclear Information System (INIS)

    Phukan, Smritakshi; Mishra, Bhupendra; Chandra Shekar, K.P.; Kumar, Anil; Kumar, Dalip; Mitra, Sivaprasad

    2013-01-01

    Steady state and time-resolved fluorescence properties of porphyrin appended 1,3,4-oxadiazoles and thiazoles were described in homogeneous medium as well as in presence of cationic surfactant cetyltrimethylammonium bromide (CTAB). The electron withdrawing substituent on the porphyrin moiety in both the cases make a donor–spacer–acceptor type of intramolecular photoinduced electron transfer (PET) system resulting substantial quenching in porphyrin fluorescence due to partial energy migration towards the acceptor in the excited state. The increase in fluorescence yield as well as appreciable difference in fluorescence decay behavior in aqueous buffer solution of pH 4.2 from that in chloroform solution is believed due to partial protonation of the porphyrin ring. All the investigated systems show preferential binding into the interfacial region of the micellar sub-domain with varying degree of penetration depending on the nature of the substituent. Almost 2–4 fold increase in fluorescence yield for the probes is explained on the basis of restricted flexibility and corresponding decrease in total nonradiative rate inside the micellar interface layer. - Highlights: ► Synthesis and detail fluorescence studies of a series of porphyrin appended 1,3,4-oxadiazoles and thiazoles. ► Comparison of homogeneous solvent study with that in CTAB. ► Substantial porphyrin fluorescence quenching in donor–spacer–acceptor type system. ► Preferential binding of the substituted porphyrins in micellar sub-domain. ► Appreciable increase in fluorescence yield in micellar interface layer is due to decrease in total nonradiative rate.

  3. Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds.

    Science.gov (United States)

    Bari, Sara E; Amorebieta, Valentín T; Gutiérrez, María M; Olabe, José A; Doctorovich, Fabio

    2010-01-01

    The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([Fe(III)(TEPyP)](5+)), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([Fe(III)(TPPS)](3-)), and microperoxidase 11 ([Fe(III)(MP11)]) were studied for different [Fe(III)(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N(2) and N(2)O were found as gaseous, nitrogen-containing oxidation products, while NH(3) was the unique reduced species detected. Different N(2)/N(2)O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [Fe(III)(TEPyP)](5+) and [Fe(III)(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [Fe(III)(TPPS)](3-) led to the well characterized soluble intermediate, [Fe(II)(TPPS)NO](4-). Free-radical formation was only evidenced for [Fe(III)(TEPyP)](5+), as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the Fe(II)/Fe(III) redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO(2)(-) revealed either that no HAO-like activity was operative under our reaction conditions, or that NO(2)(-), if formed, was consumed in the reaction milieu.

  4. Silver manganese oxide electrodes for lithium batteries

    Science.gov (United States)

    Thackeray, Michael M.; Vaughey, John T.; Dees, Dennis W.

    2006-05-09

    This invention relates to electrodes for non-aqueous lithium cells and batteries with silver manganese oxide positive electrodes, denoted AgxMnOy, in which x and y are such that the manganese ions in the charged or partially charged electrodes cells have an average oxidation state greater than 3.5. The silver manganese oxide electrodes optionally contain silver powder and/or silver foil to assist in current collection at the electrodes and to improve the power capability of the cells or batteries. The invention relates also to a method for preparing AgxMnOy electrodes by decomposition of a permanganate salt, such as AgMnO4, or by the decomposition of KMnO4 or LiMnO4 in the presence of a silver salt.

  5. Testing methods of steel wi re ropes at the anchor

    Directory of Open Access Journals (Sweden)

    Stanislav Kropuch

    2012-12-01

    Full Text Available The present paper introduces an application of the acoustic andthermographic method in the defectoscopic testing of immobilesteel wire ropes at the most critical point, the anchor. Firstmeasurements and their results by these new defectoscopic methodsare shown. In defectoscopic tests at the anchor, the widelyused magnetic method gives unreliable results, and therefore presentsa problem for steel wire defectoscopy. Application of the two new methods in the steel wire defectoscopy at the anchor point will enableincreased safety measures at the anchor of steel wire ropes in bridge, roof, tower and aerial cable lift constructions.

  6. Manganese (II) induces chemical hypoxia by inhibiting HIF-prolyl hydroxylase: Implication in manganese-induced pulmonary inflammation

    International Nuclear Information System (INIS)

    Han, Jeongoh; Lee, Jong-Suk; Choi, Daekyu; Lee, Youna; Hong, Sungchae; Choi, Jungyun; Han, Songyi; Ko, Yujin; Kim, Jung-Ae; Mi Kim, Young; Jung, Yunjin

    2009-01-01

    Manganese (II), a transition metal, causes pulmonary inflammation upon environmental or occupational inhalation in excess. We investigated a potential molecular mechanism underlying manganese-induced pulmonary inflammation. Manganese (II) delayed HIF-1α protein disappearance, which occurred by inhibiting HIF-prolyl hydroxylase (HPH), the key enzyme for HIF-1α hydroxylation and subsequent von Hippel-Lindau(VHL)-dependent HIF-1α degradation. HPH inhibition by manganese (II) was neutralized significantly by elevated dose of iron. Consistent with this, the induction of cellular HIF-1α protein by manganese (II) was abolished by pretreatment with iron. Manganese (II) induced the HIF-1 target gene involved in pulmonary inflammation, vascular endothelial growth factor (VEGF), in lung carcinoma cell lines. The induction of VEGF was dependent on HIF-1. Manganese-induced VEGF promoted tube formation of HUVEC. Taken together, these data suggest that HIF-1 may be a potential mediator of manganese-induced pulmonary inflammation

  7. End-anchored polymers in good solvents from the single chain limit to high anchoring densities.

    Science.gov (United States)

    Whitmore, Mark D; Grest, Gary S; Douglas, Jack F; Kent, Michael S; Suo, Tongchuan

    2016-11-07

    An increasing number of applications utilize grafted polymer layers to alter the interfacial properties of solid substrates, motivating refinement in our theoretical understanding of such layers. To assess existing theoretical models of them, we have investigated end-anchored polymer layers over a wide range of grafting densities, σ, ranging from a single chain to high anchoring density limits, chain lengths ranging over two orders of magnitude, for very good and marginally good solvent conditions. We compare Monte Carlo and molecular dynamics simulations, numerical self-consistent field calculations, and experimental measurements of the average layer thickness, h, with renormalization group theory, the Alexander-de Gennes mushroom theory, and the classical brush theory. Our simulations clearly indicate that appreciable inter-chain interactions exist at all simulated areal anchoring densities so that there is no mushroom regime in which the layer thickness is independent of σ. Moreover, we find that there is no high coverage regime in which h follows the predicted scaling, h ∼ Nσ 1/3 , for classical polymer brushes either. Given that no completely adequate analytic theory seems to exist that spans wide ranges of N and σ, we applied scaling arguments for h as a function of a suitably defined reduced anchoring density, defined in terms of the solution radius of gyration of the polymer chains and N. We find that such a scaling approach enables a smooth, unified description of h in very good solvents over the full range of anchoring density and chain lengths, although this type of data reduction does not apply to marginal solvent quality conditions.

  8. Manganese exposure in foundry furnacemen and scrap recycling workers

    DEFF Research Database (Denmark)

    Lander, F; Kristiansen, J; Lauritsen, Jens

    1999-01-01

    Cast iron products are alloyed with small quantities of manganese, and foundry furnacemen are potentially exposed to manganese during tapping and handling of smelts. Manganese is a neurotoxic substance that accumulates in the central nervous system, where it may cause a neurological disorder...

  9. Manganese phospate physical chemistry and surface properties

    International Nuclear Information System (INIS)

    Najera R, N.; Romero G, E. T.

    2008-01-01

    This paper presents the methodology for the manganese phosphate (III) synthesis (MnP0 4 H 2 0) from manganese chloride. The physicochemical characterization was carried out by: X-ray diffraction, scanning electron microscopy, infrared analysis and thermal gravimetric analysis. The surface characterization is obtained through the determination of surface area, point of zero charge and kinetics of moisture. As a phosphate compound of a metal with low oxidation state is a promising compound for removal pollutants from water and soil, can be used for the potential construction of containment barriers for radioactive wastes. (Author)

  10. Porphyrin Based Near Infrared-Absorbing Materials for Organic Photovoltaics

    Science.gov (United States)

    Zhong, Qiwen

    photosynthesis. Photosynthesis uses light from the sun to drive a series of chemical reactions. Most natural photosynthetic systems utilize chlorophylls to absorb light energy and carry out photochemical charge separation that stores energy in the form of chemical bonds. The sun produces a broad spectrum of light output that ranges from gamma rays to radio waves. The entire visible range of light (400-700 nm) and some wavelengths in the NIR (700-1000 nm), are highly active in driving photosynthesis. Although the most familiar chlorophyll-containing organisms, such as plants, algae and cyanobacteria, cannot use light longer than 700 nm, anoxygenic bacterium containing bacteriochlorophylls can use the NIR part of the solar spectrum. No organism is known to utilize light of wavelength longer than about 1000 nm for photosynthesis. NIR light has a very low-energy content in each photon, so that large numbers of these low-energy photons would have to be used to drive the chemical reactions of photosynthesis. This is thermodynamically possible but would require a fundamentally different molecular mechanism that is more akin to a heat engine than to photochemistry. Early work on developing light absorbing materials for OPVs was inspired by photosynthesis in which light is absorbed by chlorophyll. Structurally related to chlorophyll is the porphyrin family, which has accordingly drawn much interest as the potential light absorbing component in OPV applications. In this dissertation, the design and detail studies of several porphyrin-based NIR absorbing materials, including pi--extended perylenyl porphryins and pyrazole-containing carbaporphyrins, as well as porphyrin modified single-walled carbon nanotube hybrids, will be presented, dedicating efforts to develop novel and application-oriented materials for efficient utilization of sustainable solar energy.

  11. Testing and modeling of cyclically loaded rock anchors

    Directory of Open Access Journals (Sweden)

    Joar Tistel

    2017-12-01

    Full Text Available The Norwegian Public Roads Administration (NPRA is planning for an upgrade of the E39 highway route at the westcoast of Norway. Fixed links shall replace ferries at seven fjord crossings. Wide spans and large depths at the crossings combined with challenging subsea topography and environmental loads call for an extension of existing practice. A variety of bridge concepts are evaluated in the feasibility study. The structures will experience significant loads from deadweight, traffic and environment. Anchoring of these forces is thus one of the challenges met in the project. Large-size subsea rock anchors are considered a viable alternative. These can be used for anchoring of floating structures but also with the purpose of increasing capacity of fixed structures. This paper presents first a thorough study of factors affecting rock anchor bond capacity. Laboratory testing of rock anchors subjected to cyclic loading is thereafter presented. Finally, the paper presents a model predicting the capacity of a rock anchor segment, in terms of a ribbed bar, subjected to a cyclic load history. The research assumes a failure mode occurring in the interface between the rock anchor and the surrounding grout. The constitutive behavior of the bonding interface is investigated for anchors subjected to cyclic one-way tensile loads. The model utilizes the static bond capacity curve as a basis, defining the ultimate bond τbu and the slip s1 at τbu. A limited number of input parameters are required to apply the model. The model defines the bond-slip behavior with the belonging rock anchor capacity depending on the cyclic load level (τmax cy/τbu, the cyclic load ratio (R = τmin cy/τmax cy, and the number of load cycles (N. The constitutive model is intended to model short anchor lengths representing an incremental length of a complete rock anchor.

  12. Synthesis and characterization of a novel series of meso (nitrophenyl and meso (carboxyphenyl substituted porphyrins

    Directory of Open Access Journals (Sweden)

    Schiavon Marco A.

    2000-01-01

    Full Text Available The anionic 5,10,15-tris(4-carboxyphenyl, 20-mono(2-nitrophenyl porphyrin (1, 5,10(or 15-bis(4-carboxyphenyl, 15(or 10,20-bis(2-nitrophenylporphyrin (2 and 5-mono(4-carboxyphenyl, 10,15,20-tris(2-nitrophenylporphyrin (3 were sinthesized directly by reaction of pyrrole with substituted benzaldehydes in nitrobenzene/propionic acid media. The benzaldehydes molar ratio was controlled to optimize the synthesis and purification of the desired porphyrins. This new series of porphyrins was characterised by TLC, mass spectrometry (FAB MS, ¹H NMR, UV/Vis, IR and electrochemistry. 5,10,15,20-Tetrakis(4-carboxyphenylporphyrin (4 and 5,10,15,20-Tetrakis(2-nitrophenylporphyrin (5 were also characterised for comparative purposes, completing the series The electrochemical reduction was investigated for the free base and corresponding iron(III porphyrins on glassy carbon and mercury electrodes. The reduction potentials showed the expected dependence on the number of electron-withdrawing nitro groups present on the porphyrin ring providing additional evidences for the characterisation of the synthesised compounds.

  13. A panchromatic anthracene-fused porphyrin sensitizer for dye-sensitized solar cells

    KAUST Repository

    Ball, James M.

    2012-01-01

    The development of ruthenium-free sensitizers which absorb light over a broad range of the solar spectrum is important for improving the power conversion efficiency of dye-sensitized solar cells. Here we study three chemically tailored porphyrin-based dyes. We show that by fusing the porphyrin core to an anthracene unit, we can extend the conjugation length and lower the optical gap, shifting the absorption spectrum into the near-infrared (NIR). All three dyes were tested in dye-sensitized solar cells, using both titanium dioxide and tin dioxide as the electron-transport material. Solar cells incorporating the anthracene-fused porphyrin dye exhibit photocurrent collection at wavelengths up to about 1100 nm, which is the longest reported for a porphyrin-based system. Despite extending the photon absorption bandwidth, device efficiency is found to be low, which is a common property of cells based on porphyrin dyes with NIR absorption. We show that in the present case the efficiency is reduced by inefficient electron injection into the oxide, as opposed to dye regeneration, and highlight some important design considerations for panchromatic sensitizers. © 2012 The Royal Society of Chemistry.

  14. Emission properties of porphyrin compounds in new polymeric PS:CBP host

    Science.gov (United States)

    Jafari, Mohammad Reza; Bahrami, Bahram

    2015-06-01

    In this study, a device with fundamental structure of ITO/PEDOT:PSS (60 nm)/PS:CBP (70 nm)/Al (150 nm) was fabricated. The electroluminescence spectrum of device designated a red shift rather than PS:CBP photoluminescence spectra. It can be suggested that the electroplex emission occurs at PS:CBP interface. By following this step, red light-emitting devices using porphyrin compounds as a red dopant in a new host material PS:CBP with a configuration of ITO/PEDOT:PSS (60 nm)/PS:CBP:porphyrin compounds(70 nm)/Al (150 nm) have been fabricated and investigated. The electroluminescent spectra of the porphyrin compounds were red-shifted as compared with the PS:CBP blend. OLED devices based on doping 3,4PtTPP and TPPNO2 in PS:CBP showed purer red emission compared with ZnTPP and CoTPP doped devices. We believe that the electroluminescence performance of OLED devices based on porphyrin compounds depends on overlaps between the absorption of the porphyrin compounds and the emission of PS:CBP.

  15. Reduction reactions of water soluble cyano-cobalt(III)-porphyrins: Metal versus ligand centered processes

    International Nuclear Information System (INIS)

    Mosseri, S.; Neta, P.; Harriman, A.; Hambright, P.

    1990-01-01

    Reduction reactions of dicyano-cobalt(III)-porphyrins [potential in vivo cyanide scavenger drugs] were studied by radiolytic and electrochemical methods using the water soluble tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP). For [(CN)2CoIIITPPS]-, reduction occurs stepwise to the CoII, CoI, and finally to the phlorin anion. This behavior is similar to that of the cobalt porphyrins in the absence of cyanide, except that the cyanide ligand shifts the reduction potentials to much more negative values. On the other hand, under radiolytic conditions, [(CN)2CoIIITMPyP]- is reduced on the porphyrin macrocycle by one electron to give the CoIII pi-radical anion, which disproportionates into the initial complex and the two-electron ring reduced CoIII phlorin. The radical anion is also formed by intramolecular electron transfer subsequent to the reaction of CoIITMPyP and cyanide. The results are compared with the chemistry of Vitamin B-12

  16. Mechanistic aspects of the photodynamic inactivation of Candida albicans induced by cationic porphyrin derivatives.

    Science.gov (United States)

    Quiroga, Ezequiel D; Cormick, M Paula; Pons, Patricia; Alvarez, M Gabriela; Durantini, Edgardo N

    2012-12-01

    Photodynamic inactivation of Candida albicans produced by 5-(4-trifluorophenyl)-10,15,20-tris(4-N,N,N-trimethylammoniumphenyl)porphyrin (TFAP(3+)), 5,10,15,20-tetrakis(4-N,N,N-trimethylammoniumphenyl)porphyrin (TMAP(4+)) and 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (TMPyP(4+)) was investigated to obtain insight about the mechanism of cellular damage. In solution, absorption spectroscopic studies showed that these cationic porphyrins interact strongly with calf thymus DNA. The electrophoretic analysis indicated that photocleavage of DNA induced by TFAP(3+) took place after long irradiation periods (>5 h). In contrast, TMAP(4+) produced a marked reduction in DNA band after 1 h irradiation. In C. albicans, these cationic porphyrins produced a ∼3.5 log decrease in survival when the cell suspensions (10(7) cells/mL) were incubated with 5 μM photosensitizer and irradiated for 30 min with visible light (fluence 162 J/cm(2)). After this treatment, modifications of genomic DNA isolated from C. albicans cells were not found by electrophoresis. Furthermore, transmission electron microscopy showed structural changes with appearance of low density areas into the cells and irregularities in cell barriers. However, the photodamage to the cell envelope was insufficient to cause the release of intracellular biopolymers. Therefore, modifications in the cytoplasmic biomolecules and alteration in the cell barriers could be mainly involved in C. albicans photoinactivation. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  17. Detection of a weak ring current in a nonaromatic porphyrin nanoring using magnetic circular dichroism.

    Science.gov (United States)

    Kowalska, Patrycja; Peeks, Martin D; Roliński, Tomasz; Anderson, Harry L; Waluk, Jacek

    2017-12-13

    We compare the absorption and magnetic circular dichroism (MCD) spectra of a series of porphyrin oligomers - dimer, tetramer, and hexamer - bound in a linear or cyclic fashion. The MCD signal is extremely weak for low energy transitions in the linear oligomers, but it is amplified when the cyclic porphyrin hexamer binds a template, restricting rotational freedom. The appearance of Faraday A terms in the MCD spectra demonstrates the presence of a magnetic moment, and thus, uncompensated electronic current. The value of the excited state magnetic moment estimated from the A term is very low compared with those of monomeric porphyrins, which confirms the nonaromatic character of the cyclic array and the lack of a global ring current in the ground state of the neutral nanoring. DFT calculations predict the absorption and MCD patterns reasonably well, but fail to reproduce the MCD sign inversion observed in substituted monomeric zinc porphyrins ("soft" chromophores). Interestingly, a correct sign pattern is predicted by INDO/S calculations. Analysis of the MCD spectra of the monomeric porphyrin unit allowed us to distinguish between two close-lying lowest energy transitions, which some previous assignments placed further apart. The present results prove the usefulness of MCD not only for deconvolution and assignment of electronic transitions, but also as a sensitive tool for detecting electronic ring currents.

  18. Stepwise π-extension of meso-alkylidenyl porphyrins through sequential 1,3-dipolar cycloaddition and redox reactions.

    Science.gov (United States)

    Park, Dowoo; Jeong, Seung Doo; Ishida, Masatoshi; Lee, Chang-Hee

    2014-08-25

    Several regioselectively π-extended, pyrrole fused porphyrinoids have been synthesized by the 1,3-dipolar cycloaddition of meso-alkylidene-(benzi)porphyrins. Pd(II) complexes gave oxidation resistant, bis-pyrrole fused adducts. The repeated 1,3-dipolar cycloaddition followed by oxidation-reduction of pentaphyrin analogs afforded π-extended porphyrin analogs.

  19. Syntheses and biological evaluation of F-18 and I-123 labeled porphyrins as potential tumor imaging agents

    Energy Technology Data Exchange (ETDEWEB)

    Lee, J. H.; Ji, D. Y. [Inha University, Incheon (Korea, Republic of); Moon, B. S.; Lee, T. S.; Lee, D. H.; Lee, K. C.; Ahn, G. I.; Yang, S. D.; Choi, C. W.; Jun, K. S. [KIRAMS, Seoul (Korea, Republic of)

    2005-07-01

    Photofrin has currently been approved for general use by licensing authorities to treatment for solid tumor and cancer using photodynamic therapy (PDT) that treat to photochemical effect induced by light. Recently, meso-tetra(3-hydroxyphenyl)porphyrin has been developed as one of best tumor localizer and also shown a favorable tissue distribution. We have studied to develop I-123 labeled meso-tetra(3-methoxyphenyl)porphyrins for tumor imaging. We have studied to develop iodine-123 labeled meso-tetra(3-carboxymethoxy phenyl)porphyrin for tumor imaging agent. The radioiodinated porphyrin compound was obtained by the iodination reaction of tin precursor (50 ig) of porphyrin with Na-123I (200 {mu}L, 100-200 mCi), in the presence of peracetic acid (40 {mu}L) in ethanol. Iodine-123 labeled porphyrin derivative was obtained in 20-30% radiochemical yield and purified by HPLC at 2 mL/min using EtOH/water gradient condition and the fraction at 24-26 min was collected and characterized to desired compound by co injection with cold porphyrin analogue. Total time was around 120 min. The in vitro and in vivo of I-123 labeled porphyrin derivative is under studying.

  20. Syntheses and biological evaluation of F-18 and I-123 labeled porphyrins as potential tumor imaging agents

    International Nuclear Information System (INIS)

    Lee, J. H.; Ji, D. Y.; Moon, B. S.; Lee, T. S.; Lee, D. H.; Lee, K. C.; Ahn, G. I.; Yang, S. D.; Choi, C. W.; Jun, K. S.

    2005-01-01

    Photofrin has currently been approved for general use by licensing authorities to treatment for solid tumor and cancer using photodynamic therapy (PDT) that treat to photochemical effect induced by light. Recently, meso-tetra(3-hydroxyphenyl)porphyrin has been developed as one of best tumor localizer and also shown a favorable tissue distribution. We have studied to develop I-123 labeled meso-tetra(3-methoxyphenyl)porphyrins for tumor imaging. We have studied to develop iodine-123 labeled meso-tetra(3-carboxymethoxy phenyl)porphyrin for tumor imaging agent. The radioiodinated porphyrin compound was obtained by the iodination reaction of tin precursor (50 ig) of porphyrin with Na-123I (200 μL, 100-200 mCi), in the presence of peracetic acid (40 μL) in ethanol. Iodine-123 labeled porphyrin derivative was obtained in 20-30% radiochemical yield and purified by HPLC at 2 mL/min using EtOH/water gradient condition and the fraction at 24-26 min was collected and characterized to desired compound by co injection with cold porphyrin analogue. Total time was around 120 min. The in vitro and in vivo of I-123 labeled porphyrin derivative is under studying

  1. Porphyrins from Messel oil shale (Eocene, Germany): Structure elucidation, geochemical and biological significance, and distribution as a function of depth

    Energy Technology Data Exchange (ETDEWEB)

    Ocampo, R.; Bauder, C.; Callot, H.J.; Albrecht, P. (Univ. Louis Pasteur, Strasbourg (France))

    1992-02-01

    The extraction and isolation procedures of twenty nickel porphyrins (seven alkylporphyrins, thirteen carboxylic acids) from lacustrine Messel shale (Eocene, Germany), as well as the unequivocal structural assignments (obtained using 200 and 400 MHz nuclear magnetic resonance (NMR), nuclear Overhauser effect, mass spectrometry, and total or partial synthesis of six reference compounds) are described. Ten porphyrins could be specifically correlated with biological precursors: algal chlorophyll c (4), bacteriochlorophylls d (3), and heme (3), while the remaining ones may arise from several chlorophylls. The structures of these fossil pigments mostly confirm the classical Treibs scheme,' including the origin of some porphyrins from nonchlorophyll sources. They also show that, even in a very immature sediment, deep modifications occur, including, in particular, extensive degradation of chlorophyll E ring. The composition of the porphyrin fractions of Messel oil shale was also studied as a function of depth. A porphyrin acids/alkylporphyrins ratio varying from 0.35 to 24.8 demonstrated that the apparent homogeneity of the shale is not reflected on the molecular scale. This was confirmed when the abundance of the twenty individual porphyrins of known structure was measured along the core. Significant correlations between individual porphyrins were found: fossils of bacteriochlorophylls d, homolog pairs of porphyrins (3-H/3-ethyl), etc.

  2. Porphyrins from Messel oil shale (Eocene, Germany): Structure elucidation, geochemical and biological significance, and distribution as a function of depth

    Science.gov (United States)

    Ocampo, Rubén; Bauder, Claude; Callot, Henry J.; Albrecht, Pierre

    1992-02-01

    The extraction and isolation procedures of twenty nickel porphyrins (seven alkylporphyrins, thirteen carboxylic acids) from lacustrine Messel shale (Eocene, Germany), as well as the unequivocal structural assignments (obtained using 200 and 400 MHz nuclear magnetic resonance (NMR), nuclear Overhauser effect, mass spectrometry and total or partial synthesis of six reference compounds) are described. Ten porphyrins could be specifically correlated with biological precursors: algal chlorophyll c (4), bacteriochlorophylls d (3) and heme (3), while the remaining ones may arise from several chlorophylls. The structures of these fossil pigments mostly confirm the classical "Treibs scheme," including the origin of some porphyrins from nonchlorophyll sources. They also show that, even in a very immature sediment, deep modifications occur, including, in particular, extensive degradation of chlorophyll E ring. The composition of the porphyrin fractions of Messel oil shale was also studied as a function of depth. A porphyrin acids/alkylporphyrins ratio varying from 0.35 to 24.8 demonstrated that the apparent homogeneity of the shale is not reflected on the molecular scale. This was confirmed when the abundance of the twenty individual porphyrins of known structure was measured along the core. Significant correlations between individual porphyrins were found: fossils of bacteriochlorophylls d, homolog pairs of porphyrins (3-H/3-ethyl), etc.

  3. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries

    International Nuclear Information System (INIS)

    Sun, Shanshan; Miao, He; Xue, Yejian; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2016-01-01

    In this paper, the hybrid catalysts of manganese oxide decorated by silver nanoparticles (Ag-MnO x ) are fully investigated and show the excellent oxygen reduction reaction (ORR) activity. The Ag-MnO 2 is synthesized by a facile strategy of the electroless plating of silver on the manganese oxide. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the ORR activities of the catalysts are systematically investigated by the rotating disk electrode (RDE) and aluminum-air battery technologies. The Ag nanoparticles with the diameters at about 10 nm are anchored on the surface of α-MnO 2 and a strong interaction between Ag and MnO 2 components in the hybrid catalyst are confirmed. The electrochemical tests show that the activity and stability of the 50%Ag-MnO 2 composite catalyst (the mass ratio of Ag/MnO 2 is 1:1) toward ORR are greatly enhanced comparing with single Ag or MnO 2 catalyst. Moreover, the peak power density of the aluminum-air battery with 50%Ag-MnO 2 can reach 204 mW cm −2 .

  4. High-performance symmetric electrochemical capacitor based on graphene foam and nanostructured manganese oxide

    Directory of Open Access Journals (Sweden)

    Abdulhakeem Bello

    2013-08-01

    Full Text Available We have fabricated a symmetric electrochemical capacitor with high energy and power densities based on a composite of graphene foam (GF with ∼80 wt% of manganese oxide (MnO2 deposited by hydrothermal synthesis. Raman spectroscopy and X-ray diffraction measurements showed the presence of nanocrystalline MnO2 on the GF, while scanning and transmission electron microscopies showed needle-like manganese oxide coated and anchored onto the surface of graphene. Electrochemical measurements of the composite electrode gave a specific capacitance of 240 Fg−1 at a current density of 0.1 Ag−1 for symmetric supercapacitors using a two-electrode configuration. A maximum energy density of 8.3 Whkg−1 was obtained, with power density of 20 kWkg−1 and no capacitance loss after 1000 cycles. GF is an excellent support for pseudo-capacitive oxide materials such as MnO2, and the composite electrode provided a high energy density due to a combination of double-layer and redox capacitance mechanisms.

  5. Effect of manganese on neonatal rat: manganese distribution in vital organs

    Energy Technology Data Exchange (ETDEWEB)

    Husain, R; Mushtaq, M; Seth, P K; Chandra, S V

    1976-01-01

    At present very little is known about the effect of manganese on the early stage of life, though the metal poisoning in adult humans and experimental animals has been known for quite some time. The possibility of the exposure of the general public to the deleterious effects of the metal through the environmental contamination resulting from its increasing industrial applications, and the use of Methyl Cyclopentadienyl Manganese Tricarbonyl (MMT) in gasoline and motor fuel, points to the need for such an information. Our recent studies in this direction have shown that manganese exposed nursing dams can transfer significant amounts of the metal via maternal milk of their sucklings and the brain of the latter exhibited marked enzymatic alterations. The present communication deals with the distribution of manganese in the vital organs of rat pups nursing on mothers receiving the metal orally.

  6. An action spectrum for blue and near ultraviolet inactivation of Propionibacterium acnes; with emphasis on a possible porphyrin photosensitization

    International Nuclear Information System (INIS)

    Kjeldstad, B.; Johnsson, A.

    1986-01-01

    Propionibacterium acnes (P. acnes), grown on Eagles medium with different pH, were irradiated with monochromatic light in the range 320 to 440 nm. Different pH leads to different porphyrin concentrations in the cells. The light sensitivity of the bacteria was estimated from the reduction in their ability to form colonies after radiation. The sensitivity was highest for the lowest wavelength (320 nm), and decreased continuously with increasing wavelength up to 380 nm. In the region between 380 and 440 nm there was a second maximum (at 415 nm) which corresponds to the maximum absorption of the fluorescing porphyrins in P. acnes. The sensitivity to 415 nm light was found to be dependent on the endogenous porphyrin concentration in the cells, while the sensitivity to 320 nm radiation was independent of the amount of porphyrin present. These results indicate that porphyrins produced by the bacteria are important for the light sensitivity of these bacteria. (author)

  7. Highly Efficient Cooperative Catalysis by Co III (Porphyrin) Pairs in Interpenetrating Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Zekai; Zhang, Zhi-Ming; Chen, Yu-Sheng; Lin, Wenbin (UC); (Xiamen)

    2016-12-02

    A series of porous twofold interpenetrated In-CoIII(porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent CoIII(porphyrins) in the two networks parallel to each other with a distance of about 8.8 Å, an ideal distance for the simultaneous activation of both substrates in alkyne hydration reactions. As a result, the In-CoIII(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated CoIII(porphyrin) centers, thus highlighting the potential application of MOFs in cooperative catalysis.

  8. Synthesis and properties of 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl] porphyrin and its metal complexes

    Directory of Open Access Journals (Sweden)

    Lian Wenhui

    2012-01-01

    Full Text Available A novel 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl]porphyrin and its transition metal complexes are reported in this paper. Their molecular structures were characterized by elemental analysis, IR spectra, 1HNMR spectra and UV-Vis spectra. Their spectroscopic properties were studied by Raman spectra, fluorescence spectra and X-ray photoelectron spectra (XPS. The fluorescence quantum yields have been measured at room temperature. The fluorescence intensity of porphyrin ligand was stronger than that of the complexes. In Raman spectra, there was much difference between porphyrin ligand and its metal complexes due to changes of the symmetry of porphyrin plane. In the XPS spectra, the replacement of the free-base protons by a metal ion to form the metalloporphyrin increases the symmetry of the molecule also introduces an electron with-drawing group into the center of the porphyrin ligand which increases the N1s binding energy.

  9. Evidence for porphyrins bound, via ester bonds, to the Messel oil shale kerogen by selective chemical degradation experiments

    Science.gov (United States)

    Huseby, B.; Ocampo, R.

    1997-09-01

    High amounts of nickel mono- and di-acid porphyrins were released from Messel oil shale kerogen (Eocene, Germany) by selective chemical degradation (acid and base hydrolysis). The released porphyrin fractions were quantified (UV-vis) and their constituents isolated and characterized at the molecular level (UV-vis, MS, NMR). The mono-acid porphyrin fraction released contained four compounds of similar abundance which arise from an obvious chlorophyll or bacteriochlorophyll precursor. The di-acid porphyrin fraction was, however, dominated by far by one compound, mesoporphyrin IX, which must have originated from heme-like precursors (heme, cytochromes, etc.). These results show unambigously that the released mono- and di-acid porphyrins were linked to the macromolecular kerogen network via ester bonds and suggest that precursor heme-like pigments could be selectively and/or more readily incorporated into the macromolecular kerogen network than precursor chlorophylls and bacteriochlorophylls.

  10. Thermodynamic Properties of Manganese and Molybdenum

    International Nuclear Information System (INIS)

    Desai, P.D.

    1987-01-01

    This work reviews and discusses the data on the various thermodynamic properties of manganese and molybdenum available through March 1985. These include heat capacity, enthalpy, enthalpy of transitions and melting, vapor pressure, and enthalpy of vaporization. The existing data have been critically evaluated and analyzed. The recommended values for the heat capacity, enthalpy, entropy, and Gibbs energy function from 0.5 to 2400 K for manganese and from 0.4 to 5000 K for molybdenum have been generated, as have heat capacity values for supercooled β-Mn and for γ-Mn below 298.15 K. The recommended values for vapor pressure cover the temperature range from 298.15 to 2400 K for manganese and from 298.15 to 5000 K for molybdenum. These values are referred to temperatures based on IPTS-1968. The uncertainties in the recommended values of the heat capacity range from +-3% to +-5% for manganese and from +-1.5% to +-3% for molybdenum

  11. Iron and manganese deposits in Uruguay

    International Nuclear Information System (INIS)

    Alvarado, B.

    1959-01-01

    This report is the results of the study carried out for the United Nations expert which the main object was: the study of the information available about iron and manganese formation in Uruguay, as well as the main researching deposit to determinate economical possibilities in the exportation.

  12. Crystallization and spectroscopic studies of manganese malonate

    Indian Academy of Sciences (India)

    Administrator

    ... and its esters are important intermediates in syntheses of vitamins B1 and B6, barbitu- ... been a subject of interest because of the importance of such interactions in a ... The d-values of the Bragg peaks in the XRD. Figure 1. (a) Manganese ...

  13. Treating electrolytic manganese residue with alkaline additives for stabilizing manganese and removing ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Changbo; Wang, Jiwei [Chinese Research Academy of Environmental Sciences, Beijing (China); Wang, Nanfang [Hunan Institute of Engineering, Xiangtan (China)

    2013-11-15

    Electrolytic manganese residue (EMR) from the electrolytic manganese industry is a solid waste containing mainly calcium sulfate dihydrate and quartzite. It is impossible to directly use the EMR as a building material due to some contaminants such as soluble manganese, ammonia nitrogen and other toxic substances. To immobilize the contaminants and reduce their release into the environment, treating EMR using alkaline additives for stabilizing manganese and removing ammonia was investigated. The physical and chemical characteristics of the original EMR were characterized by XRFS, XRD, and SEM. Leaching test of the original EMR shows that the risks to the environment are the high content of soluble manganese and ammonia nitrogen. The influence of various alkaline additives, solidifying reaction time, and other solidifying reaction conditions such as outdoor ventilation and sunlight, and rain flow on the efficiencies of Mn{sup 2+} solidification and ammonia nitrogen removal was investigated. The results show that with mass ratio of CaO to residue 1 : 8, when the solidifying reaction was carried out indoors for 4 h with no rain flow, the highest efficiencies of Mn{sup 2+} solidification and ammonia nitrogen removal (99.98% and 99.21%) are obtained. Leaching test shows that the concentration and emission of manganese and ammonia nitrogen of the treated EMR meets the requirements of the Chinese government legislation (GB8978-1996)

  14. Treating electrolytic manganese residue with alkaline additives for stabilizing manganese and removing ammonia

    International Nuclear Information System (INIS)

    Zhou, Changbo; Wang, Jiwei; Wang, Nanfang

    2013-01-01

    Electrolytic manganese residue (EMR) from the electrolytic manganese industry is a solid waste containing mainly calcium sulfate dihydrate and quartzite. It is impossible to directly use the EMR as a building material due to some contaminants such as soluble manganese, ammonia nitrogen and other toxic substances. To immobilize the contaminants and reduce their release into the environment, treating EMR using alkaline additives for stabilizing manganese and removing ammonia was investigated. The physical and chemical characteristics of the original EMR were characterized by XRFS, XRD, and SEM. Leaching test of the original EMR shows that the risks to the environment are the high content of soluble manganese and ammonia nitrogen. The influence of various alkaline additives, solidifying reaction time, and other solidifying reaction conditions such as outdoor ventilation and sunlight, and rain flow on the efficiencies of Mn"2"+ solidification and ammonia nitrogen removal was investigated. The results show that with mass ratio of CaO to residue 1 : 8, when the solidifying reaction was carried out indoors for 4 h with no rain flow, the highest efficiencies of Mn"2"+ solidification and ammonia nitrogen removal (99.98% and 99.21%) are obtained. Leaching test shows that the concentration and emission of manganese and ammonia nitrogen of the treated EMR meets the requirements of the Chinese government legislation (GB8978-1996)

  15. Career anchors and values from different career management perspectives

    Directory of Open Access Journals (Sweden)

    Rodrigo Cunha da Silva

    2016-06-01

    Full Text Available Purpose – To analyze the relationships between career anchors and young Generation Y professionals’ values, from the career concept perspective. Design/methodology/approach – Research concerning the proposed objective was carried out through quantitative research involving 189 Business Administration majors from a Catholic university in São Paulo, Brazil. We used two instruments to identify the career anchors and values of respondents: Schein (1990 and Schwartz (1994, respectively. We used statistical techniques to explore the relationships between career anchors and values. Findings – Among the results, mention should be made to the statistical relationships found between analyzed career anchors and values. It is also important to stress that, although the Lifestyle career anchor was predominantly present in the conglomerate division, this anchor was the predominant characteristic in the differentiation of the smaller group of respondents, the new career group. The General Management Career Anchor, which presents a lower incidence, is the predominant characteristic of the larger group, referring to organizational careers. As well as the Lifestyle career anchor, the Hedonism value was predominant among respondents. Originality/value – The need to consider the following was found: Generation Y presents generational characteristics that drive people management to propose work structures that offer activities to generate learning, pleasure, self-fulfillment and conciliation between work and personal life.

  16. Software Note: Using BILOG for Fixed-Anchor Item Calibration

    Science.gov (United States)

    DeMars, Christine E.; Jurich, Daniel P.

    2012-01-01

    The nonequivalent groups anchor test (NEAT) design is often used to scale item parameters from two different test forms. A subset of items, called the anchor items or common items, are administered as part of both test forms. These items are used to adjust the item calibrations for any differences in the ability distributions of the groups taking…

  17. Stone anchors of India: Findings, classification and significance.

    Digital Repository Service at National Institute of Oceanography (India)

    Tripati, S.

    Various types of stone anchors have been observed during inshore and offshore explorations along the east and west coasts of India. The earliest stone anchors of India have been recorded from the Harappan sites (3rd millennium BC), but their shape...

  18. Anchor stabilization of trapped particle modes in mirror machines

    International Nuclear Information System (INIS)

    Berk, H.L.; Roslyakov, G.V.

    1986-07-01

    It is shown that for trapped particle modes in tandem mirrors, the pressure of the passing particles in the anchor region introduces a stabilizing term proportional to the sum of the anchor's field line curvature and total diamagnetic pressure. The theory is applied to the proposed gas dynamic trap experiment

  19. Career Anchors: Results of an Organisational Study in the UK.

    Science.gov (United States)

    Yarnall, Jane

    1998-01-01

    Career anchors of 374 British employees were identified using Schein's questionnaire. Age, gender, and length of service had no significant effect on distribution of anchors. Job level had some relationship. The information could be used to determine appropriate career-development strategies. (SK)

  20. Anchor stabilization of trapped particle modes in mirror machines

    International Nuclear Information System (INIS)

    Berk, H.L.; Roslyakov, G.V.

    1986-04-01

    It is shown that for trapped particle modes in tandem mirrors, the pressure of the passing particles in the anchor region introduces a stabilizing term proportional to the sum of the anchor's field line curvature and total diamagnetic pressure. The theory is applied to the proposed gas dynamic trap experiment

  1. Understanding Rasch Measurement: Partial Credit Model and Pivot Anchoring.

    Science.gov (United States)

    Bode, Rita K.

    2001-01-01

    Describes the Rasch measurement partial credit model, what it is, how it differs from other Rasch models, and when and how to use it. Also describes the calibration of instruments with increasingly complex items. Explains pivot anchoring and illustrates its use and describes the effect of pivot anchoring on step calibrations, item hierarchy, and…

  2. 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.

  3. Improved sensitivity of a graphene FET biosensor using porphyrin linkers

    Science.gov (United States)

    Kawata, Takuya; Ono, Takao; Kanai, Yasushi; Ohno, Yasuhide; Maehashi, Kenzo; Inoue, Koichi; Matsumoto, Kazuhiko

    2018-06-01

    Graphene FET (G-FET) biosensors have considerable potential due to the superior characteristics of graphene. Realizing this potential requires judicious choice of the linker molecule connecting the target-specific receptor molecule to the graphene surface, yet there are few reports comparing linker molecules for G-FET biosensors. In this study, tetrakis(4-carboxyphenyl)porphyrin (TCPP) was used as a linker for surface modification of a G-FET and the properties of the device were compared to those of a G-FET device modified with the conventional linker 1-pyrenebutanoic acid succinimidyl ester (PBASE). TCPP modification resulted in a higher density of receptor immunoglobulin E (IgE) aptamer molecules on the G-FET. The detection limit of the target IgE was enhanced from 13 nM for the PBASE-modified G-FET to 2.2 nM for the TCPP-modified G-FET, suggesting that the TCPP linker is a powerful candidate for G-FET modification.

  4. Relativistic effects in iron-, ruthenium-, and osmium porphyrins

    International Nuclear Information System (INIS)

    Liao Mengsheng; Scheiner, Steve

    2002-01-01

    Nonrelativistic and relativistic DFT calculations are performed on four-coordinate metal porphyrins MP and their six-coordinate adducts MP(py) 2 and MP(py)(CO) (py=pyridine) with M=Fe, Ru, and Os. The electronic structures of the MPs are investigated by considering all possible low-lying states with different configurations of nd-electrons. FeP and OsP have a 3 A 2g ground state, while this state is nearly degenerate with 3 E g for RuP. Without relativistic corrections, the ground states of both RuP and OsP would be 3 E g . For the six-coordinate adducts with py and CO, the strong-field axial ligands raise the energy of the M d z 2 -orbital, thereby making the M II ion diamagnetic. The calculated redox properties of MP(py) 2 and MP(py)(CO) are in agreement with experiment. The difference between RuP(py)(CO) and OsP(py)(CO), in terms of site of oxidation, is due to relativistic effects

  5. Quinone-fused porphyrins as contrast agents for photoacoustic imaging

    KAUST Repository

    Banala, Srinivas

    2017-06-27

    Photoacoustic (PA) imaging is an emerging non-invasive diagnostic modality with many potential clinical applications in oncology, rheumatology and the cardiovascular field. For this purpose, there is a high demand for exogenous contrast agents with high absorption coefficients in the optical window for tissue imaging, i.e. the near infrared (NIR) range between 680 and 950 nm. We herein report the photoacoustic properties of quinone-fused porphyrins inserted with different transition metals as new highly promising candidates. These dyes exhibit intense NIR absorption, a lack of fluorescence emission, and PA sensitivity in concentrations below 3 nmol mL. In this context, the highest PA signal was obtained with a Zn(ii) inserted dye. Furthermore, this dye was stable in blood serum and free thiol solution and exhibited negligible cell toxicity. Additionally, the Zn(ii) probe could be detected with an up to 3.2 fold higher PA intensity compared to the clinically most commonly used PA agent, ICG. Thus, further exploration of the \\'quinone-fusing\\' approach to other chromophores may be an efficient way to generate highly potent PA agents that do not fluoresce and shift their absorption into the NIR range.

  6. The coordination and atom transfer chemistry of titanium porphyrin complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hays, James Allen [Iowa State Univ., Ames, IA (United States)

    1993-11-05

    Preparation, characterization, and reactivity of (η2- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The η2- alkyne complexes are prepared by reaction of (TTP)TiCl2 with LiAlH4 in presence of alkyne. Structure of (OEP)Ti(η2-Ph-C≡C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline)2 was also determined by XRD. Reaction of (TTP)Ti=O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl2 is reacted with (OEP)Ti=O.

  7. Test Score Equating Using Discrete Anchor Items versus Passage-Based Anchor Items: A Case Study Using "SAT"® Data. Research Report. ETS RR-14-14

    Science.gov (United States)

    Liu, Jinghua; Zu, Jiyun; Curley, Edward; Carey, Jill

    2014-01-01

    The purpose of this study is to investigate the impact of discrete anchor items versus passage-based anchor items on observed score equating using empirical data.This study compares an "SAT"® critical reading anchor that contains more discrete items proportionally, compared to the total tests to be equated, to another anchor that…

  8. Pipe supports and anchors - LMFBR applications

    International Nuclear Information System (INIS)

    Anderson, M.J.

    1983-06-01

    Pipe design and support design can not be treated as separate disciplines. A coordinated design approach is required if LMFBR pipe system adequacy is to be achieved at a reasonable cost. It is particularly important that system designers understand and consider those factors which influence support train flexibility and thus the pipe system dynamic stress levels. The system approach must not stop with the design phase but should continue thru the erection and acceptance test procedures. The factors that should be considered in the design of LMFBR pipe supports and anchors are described. The various pipe support train elements are described together with guidance on analysis, design and application aspects. Post erection acceptance and verification test procedures are then discussed

  9. Anchoring submersible ultrasonic receivers in river channels with stable substrate

    Science.gov (United States)

    Bettoli, Phillip William; Scholten, G.D.; Hubbs, D.

    2010-01-01

    We developed an anchoring system for submersible ultrasonic receivers (SURs) that we placed on the bottom of the riverine reaches of three main-stem reservoirs in the upper Tennessee River. Each anchor consisted of a steel tube (8.9 x 35.6 cm) welded vertically to a round plate of steel (5.1 x 40.6 cm). All seven SURs and their 57-kg anchors were successfully deployed and retrieved three times over 547 d by a dive team employing surface air-breathing equipment and a davit-equipped boat. All of the anchors and their SURs remained stationary over two consecutive winters on the hard-bottom, thalweg sites where they were deployed. The SUR and its anchor at the most downriver site experienced flows that exceeded 2,100 m(3)/s and mean water column velocities of about 0.9 m/s.

  10. Biased calculations: Numeric anchors influence answers to math equations

    Directory of Open Access Journals (Sweden)

    Andrew R. Smith

    2011-02-01

    Full Text Available People must often perform calculations in order to produce a numeric estimate (e.g., a grocery-store shopper estimating the total price of his or her shopping cart contents. The current studies were designed to test whether estimates based on calculations are influenced by comparisons with irrelevant anchors. Previous research has demonstrated that estimates across a wide range of contexts assimilate toward anchors, but none has examined estimates based on calculations. In two studies, we had participants compare the answers to math problems with anchors. In both studies, participants' estimates assimilated toward the anchor values. This effect was moderated by time limit such that the anchoring effects were larger when the participants' ability to engage in calculations was limited by a restrictive time limit.

  11. Porphyrin-phospholipid interaction and ring metallation depending on the phospholipid polar head type.

    Science.gov (United States)

    Ramos, Ana P; Pavani, Christiane; Iamamoto, Yassuko; Zaniquelli, Maria E D

    2010-10-01

    The interaction between a hydrophobically modified 5,10,15,20-tetrakis(4-N-tetradecyl-pyridyl) porphyrin and three phospholipids: two negatively charged, DMPA (the sodium salt of dimyristoyl-sn-glycero-phosphatidyl acid) and DMPG (the sodium salt of 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)]) and a zwitterionic DMPC (dimyristoyl-sn-glycero-phosphatidylcholine), were studied by means of surface pressure isotherms and spectroscopic methods. The interaction results in partial or total metallation of the porphyrin with zinc ions in the presence of negatively charged phospholipids, as attested by UV-vis and luminescence spectroscopy of the transferred films. In the presence of the zwitterionic phospholipid no insertion of zinc ion in the porphyrin ring is detected. These results are relevant for the understanding of photosensitizer-lipid-carrier binding for use in photodynamic therapy. Copyright 2010 Elsevier Inc. All rights reserved.

  12. Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction

    DEFF Research Database (Denmark)

    Bagger, Alexander; Ju, Wen; Varela, Ana Sofia

    2017-01-01

    Currently, no catalysts are completely selective for the electrochemical CO2 Reduction Reaction (CO2RR). Based on trends in density functional theory calculations of reaction intermediates we find that the single metal site in a porphyrine-like structure has a simple advantage of limiting...... the competing Hydrogen Evolution Reaction (HER). The single metal site in a porphyrine-like structure requires an ontop site binding of hydrogen, compared to the hollow site binding of hydrogen on a metal catalyst surface. The difference in binding site structure gives a fundamental energy-shift in the scaling...... relation of ∼0.3eV between the COOH* vs. H* intermediate (CO2RR vs. HER). As a result, porphyrine-like catalysts have the advantage over metal catalyst of suppressing HER and enhancing CO2RR selectivity....

  13. Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

    Science.gov (United States)

    Huang, Guan; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

    2017-04-01

    This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O2. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

  14. NANOSTRUCTURED TiO2 SENSITIZED WITH PORPHYRINS FOR SOLAR WATER-SPLITTING

    Directory of Open Access Journals (Sweden)

    MARCELA-CORINA ROŞU

    2011-03-01

    Full Text Available Nanostructured TiO2 sensitized with porphyrins for Solar water-splitting.The production of hydrogen from water using solar light is very promising for generations of an ecologically pure carrier contributing to a clean, sustainable and renewable energy system. The selection of specific photocatalyst material for hydrogen production in photoelectrochemical cells (PECs is based on some important characteristics of semiconductor, such as photo-corrosion and chemical corrosion stability, photocatalytic potential, high sensitivity for UV-visible light. In the present paper, different nanocrystalline TiO2 photoanodes have been prepared via wet-chemical techniques followed by annealing treatment and sensitized with porphyrins and supramolecular complexes of porphyrins. The so obtained photocatalysts were characterized with UV-VIS absorption spectroscopy and spectrofluorimetry. The purpose of these experiments is to show if the prepared materials possess the necessary photocatalytic characteristics and if they can be used with success in H2 production from water decomposition in PECs.

  15. New porphyrin-polyoxometalate hybrid materials: synthesis, characterization and investigation of catalytic activity in acetylation reactions.

    Science.gov (United States)

    Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

    2012-10-14

    New hybrid complexes based on covalent interaction between 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatozinc(II) and 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatotin(IV) chloride, and a Lindqvist-type polyoxometalate, Mo(6)O(19)(2-), were prepared. These new porphyrin-polyoxometalate hybrid materials were characterized by (1)H NMR, FT IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided several spectral data for synthesis of these compounds. Cyclic voltammetry showed the influence of the polyoxometalate on the redox process of the porphyrin ring. The catalytic activity of tin(IV)porphyrin-hexamolybdate hybrid material was investigated in the acetylation of alcohols and phenols with acetic anhydride. The reusability of this catalyst was also investigated.

  16. Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

    Science.gov (United States)

    Yamazaki, Shin-ichi; Yamada, Yusuke; Takeda, Sahori; Goto, Midori; Ioroi, Tsutomu; Siroma, Zyun; Yasuda, Kazuaki

    2010-08-21

    Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.

  17. Soil manganese enrichment from industrial inputs: a gastropod perspective.

    Directory of Open Access Journals (Sweden)

    Despina-Maria Bordean

    Full Text Available Manganese is one of the most abundant metal in natural environments and serves as an essential microelement for all living systems. However, the enrichment of soil with manganese resulting from industrial inputs may threaten terrestrial ecosystems. Several studies have demonstrated harmful effects of manganese exposure by cutaneous contact and/or by soil ingestion to a wide range of soil invertebrates. The link between soil manganese and land snails has never been made although these invertebrates routinely come in contact with the upper soil horizons through cutaneous contact, egg-laying, and feeding activities in soil. Therefore, we have investigated the direct transfer of manganese from soils to snails and assessed its toxicity at background concentrations in the soil. Juvenile Cantareus aspersus snails were caged under semi-field conditions and exposed first, for a period of 30 days, to a series of soil manganese concentrations, and then, for a second period of 30 days, to soils with higher manganese concentrations. Manganese levels were measured in the snail hepatopancreas, foot, and shell. The snail survival and shell growth were used to assess the lethal and sublethal effects of manganese exposure. The transfer of manganese from soil to snails occurred independently of food ingestion, but had no consistent effect on either the snail survival or shell growth. The hepatopancreas was the best biomarker of manganese exposure, whereas the shell did not serve as a long-term sink for this metal. The kinetics of manganese retention in the hepatopancreas of snails previously exposed to manganese-spiked soils was significantly influenced by a new exposure event. The results of this study reveal the importance of land snails for manganese cycling in terrestrial biotopes and suggest that the direct transfer from soils to snails should be considered when precisely assessing the impact of anthropogenic Mn releases on soil ecosystems.

  18. Grapnel stone anchors from Saurashtra: Remnants of Indo-Arab trade on the Indian coast

    Digital Repository Service at National Institute of Oceanography (India)

    Gaur, A.S.; Sundaresh; Tripati, S.

    Stone anchors have been used as a primary source of information on ancient navigation by marine archaeologists since long. These anchors used by ancient mariners are often noticed underwater at various places across the world. Stone anchors are also...

  19. Effects of accuracy motivation and anchoring on metacomprehension judgment and accuracy.

    Science.gov (United States)

    Zhao, Qin

    2012-01-01

    The current research investigates how accuracy motivation impacts anchoring and adjustment in metacomprehension judgment and how accuracy motivation and anchoring affect metacomprehension accuracy. Participants were randomly assigned to one of six conditions produced by the between-subjects factorial design involving accuracy motivation (incentive or no) and peer performance anchor (95%, 55%, or no). Two studies showed that accuracy motivation did not impact anchoring bias, but the adjustment-from-anchor process occurred. Accuracy incentive increased anchor-judgment gap for the 95% anchor but not for the 55% anchor, which induced less certainty about the direction of adjustment. The findings offer support to the integrative theory of anchoring. Additionally, the two studies revealed a "power struggle" between accuracy motivation and anchoring in influencing metacomprehension accuracy. Accuracy motivation could improve metacomprehension accuracy in spite of anchoring effect, but if anchoring effect is too strong, it could overpower the motivation effect. The implications of the findings were discussed.

  20. Containment liner plate anchors and steel embedments test results

    International Nuclear Information System (INIS)

    Chang-Lo, P.L.; Johnson, T.E.; Pfeifer, B.W.

    1977-01-01

    This paper summarizes test data on shear load and deformation capabilities for liner plate line anchors and structural steel embedments in reinforced and prestressed concrete nuclear containments. Reinforced and prestressed nuclear containments designed and constructed in the United States are lined with a minimum of 0.64 cm steel plate. The liner plates are anchored by the use of either studs or structural members (line anchors) which usually run in the vertical direction. This paper will only address line anchors. Static load versus displacement test data is necessary to assure that the design is adequate for the maximum loads. The test program for the liner anchors had the following major objectives: determine load versus displacement data for a variety of anchors considering structural tees and small beams with different weld configurations, from the preceding tests, determine which anchors would lead to an economical and extremely safe design and test these anchors for cyclic loads resulting from thermal fluctuations. Various concrete embeds in the containment and other structures are subjected to loads such as pipe rupture which results in shear. Since many of the loads are transient by nature, it is necessary to know the load-displacement relationship so that the energy absorption can be determined. The test program for the embeds had the following objectives: determine load-displacement relationship for various size anchors from 6.5 cm 2 to 26 cm 2 with maximum capacities of approximately 650 kN; determine the effect of various anchor width-to-thickness ratios for the same shear area

  1. Metal-porphyrin interactions. VI. The reactivities of several ferric porphyrin monomers with cyanide compared with ligand reactions of iron and cobalt porphyrins reconstituted with proteins. [25/sup 0/

    Energy Technology Data Exchange (ETDEWEB)

    Hambright, P. (Howard Univ., Washington, DC); Chock, P.B.

    1975-01-01

    A study of the hydrolysis and kinetics and equilibrium behavior of cyanide addition to the monomeric iron(III) complexes of meso, proto and deuteroporphyrin-IX in 2 percent sodium lauryl sulfate--0.1 M tetramethyl ammonium bromide, 25/sup 0/ is reported. The reactivity parameters are compared to reactions of the same Co(II) and Fe(II) porphyrin types reconstituted to myoglobins and hemoglobins.

  2. 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.

  3. Iron(II) porphyrins induced conversion of nitrite into nitric oxide: A computational study.

    Science.gov (United States)

    Zhang, Ting Ting; Liu, Yong Dong; Zhong, Ru Gang

    2015-09-01

    Nitrite reduction to nitric oxide by heme proteins was reported as a protective mechanism to hypoxic injury in mammalian physiology. In this study, the pathways of nitrite reduction to nitric oxide mediated by iron(II) porphyrin (P) complexes, which were generally recognized as models for heme proteins, were investigated by using density functional theory (DFT). In view of two type isomers of combination of nitrite and Fe(II)(P), N-nitro- and O-nitrito-Fe(II)-porphyrin complexes, and two binding sites of proton to the different O atoms of nitrite moiety, four main pathways for the conversion of nitrite into nitric oxide mediated by iron(II) porphyrins were proposed. The results indicate that the pathway of N-bound Fe(II)(P)(NO2) isomer into Fe(III)(P)(NO) and water is similar to that of O-bound isomer into nitric oxide and Fe(III)(P)(OH) in both thermodynamical and dynamical aspects. Based on the initial computational studies of five-coordinate nitrite complexes, the conversion of nitrite into NO mediated by Fe(II)(P)(L) complexes with 14 kinds of proximal ligands was also investigated. Generally, the same conclusion that the pathways of N-bound isomers are similar to those of O-bound isomer was obtained for iron(II) porphyrin with ligands. Different effects of ligands on the reduction reactions were also found. It is notable that the negative proximal ligands can improve reactive abilities of N-nitro-iron(II) porphyrins in the conversion of nitrite into nitric oxide compared to neutral ligands. The findings will be helpful to expand our understanding of the mechanism of nitrite reduction to nitric oxide by iron(II) porphyrins. Copyright © 2015 Elsevier Inc. All rights reserved.

  4. Cutaneous porphyrins exhibit anti-stokes fluorescence that is detectable in sebum (Conference Presentation)

    Science.gov (United States)

    Tian, Giselle; Zeng, Haishan; Zhao, Jianhua; Wu, Zhenguo; Al Jasser, Mohammed; Lui, Harvey; Mclean, David I.

    2016-02-01

    Porphyrins produced by Propionibacterium acnes represent the principal fluorophore associated with acne, and appear as orange-red luminescence under the Wood's lamp. Assessment of acne based on Wood's lamp (UV) or visible light illumination is limited by photon penetration depth and has limited sensitivity for earlier stage lesions. Inducing fluorescence with near infrared (NIR) excitation may provide an alternative way to assess porphyrin-related skin disorders. We discovered that under 785 nm CW laser excitation PpIX powder exhibits fluorescence emission in the shorter wavelength range of 600-715 nm with an intensity that is linearly dependent on the excitation power. We attribute this shorter wavelength emission to anti-Stokes fluorescence. Similar anti-Stokes fluorescence was also detected focally in all skin-derived samples containing porphyrins. Regular (Stokes) fluorescence was present under UV and visible light excitation on ex vivo nasal skin and sebum from uninflamed acne, but not on nose surface smears or sebum from inflamed acne. Co-registered CW laser-excited anti-Stokes fluorescence and fs laser-excited multi-photon fluorescence images of PpIX powder showed similar features. In the skin samples because of the anti-Stokes effect, the NIR-induced fluorescence was presumably specific for porphyrins since there appeared to be no anti-Stokes emission signals from other typical skin fluorophores such as lipids, keratins and collagen. Anti-Stokes fluorescence under NIR CW excitation is more sensitive and specific for porphyrin detection than UV- or visible light-excited regular fluorescence and fs laser-excited multi-photon fluorescence. This approach also has higher image contrast compared to NIR fs laser-based multi-photon fluorescence imaging. The anti-Stokes fluorescence of porphyrins within sebum could potentially be applied to detecting and targeting acne lesions for treatment via fluorescence image guidance.

  5. Biomechanical comparison of traditional anchors to all-suture anchors in a double-row rotator cuff repair cadaver model.

    Science.gov (United States)

    Goschka, Andrew M; Hafer, Jason S; Reynolds, Kirk A; Aberle, Nicholas S; Baldini, Todd H; Hawkins, Monica J; McCarty, Eric C

    2015-10-01

    To further reduce the invasiveness of arthroscopic rotator cuff repair surgery the all-suture anchor has been developed. The all-suture anchor requires less bone removal and reduces the potential of loose body complications. The all-suture anchor must also have adequate biomechanical strength for the repair to heal. The hypothesis is there is no significant difference in the biomechanical performance of supraspinatus repairs using an all-suture anchor when compared to traditional solid-body suture anchors. Using nine shoulders per group, the supraspinatus tendon was dissected from the greater tuberosity. The four different double row repairs tested were (medial row/lateral row): A: ICONIX2/ICONIX2; B: ICONIX2/Stryker ReelX 3.9mm; C: ICONIX2/Stryker ReelX 4.5mm; D: Arthrex BioComposite CorkScrew FT 4.5mm/Arthrex BioComposite SwiveLock 4.75mm. The ICONIX2 was the only all-suture anchor tested. Tendons underwent cyclic loading from 10 to 100N for 500 cycles, followed by load-to-failure. Data was collected at cycles 5, 100, 200, 300, 400, and 500. One-way ANOVA analysis was used to assess significance (P≤0.05). The anchor combinations tested did not differ significantly in anterior (P>0.4) or posterior (P>0.3) gap formation, construct stiffness (P>0.7), ultimate load (P=0.06), or load to 5mm gap formation (P=0.84). The all-suture anchor demonstrated comparable biomechanical performance in multiple double-row anchor combinations to a combination of traditional solid-body anchors. Thus it may be an attractive option to further reduce the invasiveness of rotator cuff repairs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. A simple route to synthesize manganese germanate nanorods

    International Nuclear Information System (INIS)

    Pei, L.Z.; Yang, Y.; Yuan, C.Z.; Duan Taike; Zhang Qianfeng

    2011-01-01

    Manganese germanate nanorods have been synthesized by a simple route using germanium dioxide and manganese acetate as the source materials. X-ray diffraction observation shows that the nanorods are composed of orthorhombic and monoclinic manganese germanate phases. Scanning electron microscopy and transmission electron microscopy observations display that the manganese germanate nanorods have flat tips with the length of longer than 10 micrometers and diameter of 60-350 nm, respectively. The role of the growth conditions on the formation of the manganese germanate nanorods shows that the proper selection and combination of the growth conditions are the key factor for controlling the formation of the manganese germanate nanorods. The photoluminescence spectrum of the manganese germanate nanorods exhibits four fluorescence emission peaks centered at 422 nm, 472 nm, 487 nm and 530 nm showing the application potential for the optical devices. - Research Highlights: → Manganese germanate nanorods have been synthesized by simple hydrothermal process. → The formation of manganese germanate nanorods can be controlled by growth conditions. → Manganese germanate nanorods exhibit good PL emission ability for optical device.

  7. Manganese binding proteins in human and cow's milk

    International Nuclear Information System (INIS)

    Loennerdal, B.; Keen, C.L.; Hurley, L.S.

    1985-01-01

    Manganese nutrition in the neonatal period is poorly understood, due in part to a lack of information on the amount of manganese in infant foods and its bioavailability. Since the molecular localization of an element in foods is one determinant of its subsequent bioavailability, a study was made of the binding of manganese in human and cow's milk. An extrinsic label of 54 Mn was shown to equilibrate isotopically with native manganese in milks and formulas. Milk samples were separated into fat, casein and whey by ultracentrifugation. In human milk, the major part (71%) of manganese was found in whey, 11% in casein and 18% in the lipid fraction. In contrast, in cow's milk, 32% of total manganese was in whey, 67% in casein and 1% in lipid. Within the human whey fraction, most of the manganese was bound to lactoferrin, while in cow's whey, manganese was mostly complexed to ligands with molecular weights less than 200. The distribution of manganese in formulas was closer to that of human milk than of cow's milk. The bioavailability of manganese associated with lactoferrin, casein and low molecular weight complexes needs to be assessed

  8. Spin selection at organic spinterface by anchoring group

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhao; Qiu, Shuai; Miao, Yuan-yuan; Ren, Jun-feng; Wang, Chuan-kui [School of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); Hu, Gui-chao, E-mail: hgc@sdnu.edu.cn [School of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); Institute of Theoretical Physics, Technische Universität Dresden, 01062 Dresden (Germany)

    2017-07-01

    Highlights: • The sign of interfacial spin polarization can be selected by using different anchoring groups. • A sp{sup 3}-d or sp-d hybridization may occur and induce spin polarization when the anchoring group changes. • Interfacial spin polarization depends on both the type of the outer orbital of the anchoring atom as well as its energy. - Abstract: Control of organic interfacial spin polarization is crucial in organic spintronics. Based on ab initio theory, here we proposed a spin selection at organic interface via anchoring group by adsorbing an organic molecule onto Ni(111) surface. The results demonstrate that either a positive or negative interfacial spin polarization may be obtained by choosing different anchoring groups. The orbital analysis via the projected density of states shows that the interfacial spin polarization is sensitive to the hybridization of the outer orbital of the anchoring atom as well as its energy relative to the d orbital of the ferromagnetic atom. The work indicates a feasible way to realize spin selection at the organic spinterface by anchoring group.

  9. Anchorage Behaviors of Frictional Tieback Anchors in Silty Sand

    Science.gov (United States)

    Hsu, Shih-Tsung; Hsiao, Wen-Ta; Chen, Ke-Ting; Hu, Wen-Chi; Wu, Ssu-Yi

    2017-06-01

    Soil anchors are extensively used in geotechnical applications, most commonly serve as tieback walls in deep excavations. To investigate the anchorage mechanisms of this tieback anchor, a constitutive model that considers both strain hardening and softening and volume dilatancy entitled SHASOVOD model, and FLAC3D software are used to perform 3-D numerical analyses. The results from field anchor tests are compared with those calculated by numerical analyses to enhance the applicability of the numerical method. After the calibration, this research carried out the parameter studies by numerical analyses. The numerical results reveal that whether the yield of soil around an anchor develops to ground surface and/or touches the diaphragm wall depending on the overburden depth H and the embedded depth Z of an anchor, this study suggests the minimum overburden and embedded depths to avoid the yield of soils develop to ground surface and/or touch the diaphragm wall. When the embedded depth, overburden depth or fixed length of an anchor increases, the anchorage capacity also increases. Increasing fixed length should be the optimum method to increase the anchorage capacity for fixed length less than 20m. However, when the fixed length of an anchor exceeds 30 m, the increasing rate of anchorage capacity per fixed length decreases, and progressive yield occurs obviously between the fixed length and surrounding soil.

  10. Physical studies of porphyrin-infiltrated opal crystals

    Energy Technology Data Exchange (ETDEWEB)

    Sabataityte, J. [Semiconductor Physics Institute, Gostauto 11, LT 01108 Vilnius (Lithuania)], E-mail: julija@pfi.lt; Simkiene, I.; Babonas, G.-J.; Reza, A. [Semiconductor Physics Institute, Gostauto 11, LT 01108 Vilnius (Lithuania); Baran, M.; Szymczak, R. [Institute of Physics, PAN, PL 02668, Warsaw (Poland); Vaisnoras, R.; Rasteniene, L. [Vilnius Pedagogical University, LT 08106, Vilnius (Lithuania); Golubev, V.; Kurdyukov, D. [Ioffe Physico-Technical Institute RAS, 194021, St. Petersburg (Russian Federation)

    2007-09-15

    Artificial opals made of silica spheres and infiltrated with aqueous solution of iron porphyrin (FeTPPS) possessing the absorption band in a visible spectral range were studied. The structural, optical and magnetic properties of composite structures were investigated. Bulk samples of opal structure were obtained by sedimentation technique from colloidal solution of SiO{sub 2} spheres of diameter 240 and 245 nm. The structure of the samples was examined by atomic force microscopy. The properties of photonic crystals were demonstrated by optical measurements in transmission and reflection modes. The stop band was observed in the region 510-550 nm. In samples annealed at 900 deg. C the width of the stop band increased to {approx} 70 nm. Aqueous solutions of FeTPPS of concentration {approx} 1.0 mM and various pH-values were used for infiltration. The infiltration has led to a change of photonic characteristics, position of the stop band and dependence on light incidence angle. The absorption bands typical of FeTPPS were observed in the vicinity of the stop band. The photonic properties of infiltrated opal structures were determined to depend on the acidity of aqueous solution, which was used in technological procedure. Magnetic properties of FeTPPS-infiltrated opal samples, which have been studied at 5-300 K in magnetic fields up to 5 T, were discussed. From magnetic measurements it followed that magnetic Fe-Fe interactions have practically vanished in hybrid samples and Fe centers should be treated as isolated ones.

  11. Physical studies of porphyrin-infiltrated opal crystals

    International Nuclear Information System (INIS)

    Sabataityte, J.; Simkiene, I.; Babonas, G.-J.; Reza, A.; Baran, M.; Szymczak, R.; Vaisnoras, R.; Rasteniene, L.; Golubev, V.; Kurdyukov, D.

    2007-01-01

    Artificial opals made of silica spheres and infiltrated with aqueous solution of iron porphyrin (FeTPPS) possessing the absorption band in a visible spectral range were studied. The structural, optical and magnetic properties of composite structures were investigated. Bulk samples of opal structure were obtained by sedimentation technique from colloidal solution of SiO 2 spheres of diameter 240 and 245 nm. The structure of the samples was examined by atomic force microscopy. The properties of photonic crystals were demonstrated by optical measurements in transmission and reflection modes. The stop band was observed in the region 510-550 nm. In samples annealed at 900 deg. C the width of the stop band increased to ∼ 70 nm. Aqueous solutions of FeTPPS of concentration ∼ 1.0 mM and various pH-values were used for infiltration. The infiltration has led to a change of photonic characteristics, position of the stop band and dependence on light incidence angle. The absorption bands typical of FeTPPS were observed in the vicinity of the stop band. The photonic properties of infiltrated opal structures were determined to depend on the acidity of aqueous solution, which was used in technological procedure. Magnetic properties of FeTPPS-infiltrated opal samples, which have been studied at 5-300 K in magnetic fields up to 5 T, were discussed. From magnetic measurements it followed that magnetic Fe-Fe interactions have practically vanished in hybrid samples and Fe centers should be treated as isolated ones

  12. A Porphyrin Based Potentiometric Sensor for Zn2+ Determination

    Directory of Open Access Journals (Sweden)

    H. Lang

    2003-07-01

    Full Text Available PVC based membranes of disodium salt of porphyrin 3,7,12,17-tetramethyl-8, 13-divinyl 2,18-porphine dipropionic acid (I as ionophore with sodium tetra phenyl borate (NaTPB as anion excluder and dibutyl phthalate (DBP, dioctyl phthalate (DOP, dibutyl butyl phosphonate (DBBP, tris(2- ethyl hexylphosphate (TEP, tri-n-butylphosphate (TBP and 1- chloronaphthalene (CN as plasticizing solvent mediators were prepared and constructed for determination of Zn(II. The PVC based membrane of (I with DBBP as plasticizer and having anion excluder, NaTPB in the ratio PVC: I: NaTPB: DBBP (150: 10: 2: 200 gave the best results in terms of working concentration range (1.3×10-5-1.0 ×10-1M with a Nernstian slope (30.0 mV/decade of activity. The useful pH range of the sensor is 3.0 –7.4, beyond which a drift in potential was observed. The response time of the sensor is 10s and the lifetime was about 2 months during which it could be used without any measurable divergence. It had good stability and reproducibility. The membrane worked satisfactorily in non-aqueous medium up to 40% (v/v non-aqueous content. The selectivity coefficient values indicate that the electrode is highly selective for Zn2+ over a number of other cations except Na+ and Cd2+. Although Na+ and Cd2+ are likely to cause some interference, they would not interfere if present at the concentrations < 1 ×10-5 and < 5 ×10-5 M, respectively. The electrode has been used as an indicator electrode to determine the end point in the potentiometric titration of Zn2+ with EDTA.

  13. Ruthenium porphyrin-induced photodamage in bladder cancer cells.

    Science.gov (United States)

    Bogoeva, Vanya; Siksjø, Monica; Sæterbø, Kristin G; Melø, Thor Bernt; Bjørkøy, Astrid; Lindgren, Mikael; Gederaas, Odrun A

    2016-06-01

    Photodynamic therapy (PDT) is a noninvasive treatment for solid malignant and flat tumors. Light activated sensitizers catalyze photochemical reactions that produce reactive oxygen species which can cause cancer cell death. In this work we investigated the photophysical properties of the photosensitizer ruthenium(II) porphyrin (RuP), along with its PDT efficiency onto rat bladder cancer cells (AY27). Optical spectroscopy verified that RuP is capable to activate singlet oxygen via blue and red absorption bands and inter system crossing (ISC) to the triplet state. In vitro experiments on AY27 indicated increased photo-toxicity of RuP (20μM, 18h incubation) after cell illumination (at 435nm), as a function of blue light exposure. Cell survival fraction was significantly reduced to 14% after illumination of 20μM RuP with 15.6J/cm(2), whereas the "dark toxicity" of 20μM RuP was 17%. Structural and morphological changes of cells were observed, due to RuP accumulation, as well as light-dependent cell death was recorded by confocal microscopy. Flow cytometry verified that PDT-RuP (50μM) triggered significant photo-induced cellular destruction with a photoxicity of (93%±0.9%). Interestingly, the present investigation of RuP-PDT showed that the dominating mode of cell death is necrosis. RuP "dark toxicity" compared to the conventional chemotherapeutic drug cisplatin was higher, both evaluated by the MTT assay (24h). In conclusion, the present investigation shows that RuP with or without photoactivation induces cell death of bladder cancer cells. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Modified Kidner procedure utilizing a Mitek bone anchor.

    Science.gov (United States)

    Dawson, D M; Julsrud, M E; Erdmann, B B; Jacobs, P M; Ringstrom, J B

    1998-01-01

    The recent development of small bone suture anchors has created several potential applications in reconstructive surgery of the foot. Mitek bone anchors are simple to insert, require less aggressive dissection and surgical time than reefing of the redundant posterior tibial tendon, and are a reliable method of tendon-to-bone fixation. Mitek bone anchors are an excellent technique for the treatment of redundant tibialis posterior tendon following a modified Kidner procedure. In modified Kidner procedures involving an excessively large os tibiale externum, Mitek anchoring of the redundant tibialis posterior tendon to the navicular bone is an excellent means for secure plication of the posterior tibial tendon in cases involving intraoperative tendon laxity. A description of the Mitek Anchor System and technique of application in a modified Kinder procedure is presented. The purpose of this study was to describe patient satisfaction and long-term clinical outcomes of the modified Kinder procedure with and without the Mitek bone anchoring system. A retrospective study of the modified Kinder procedure was performed with 13 patients being evaluated, seven with Mitek anchoring and six without. The University of Maryland 100-point Painful Foot Center Scoring System was modified to be more specific to the modified Kinder procedure for assessment of subjective long-term results. Patient overall satisfaction was rated good to excellent by 85.6% of patients in the Mitek group and by 100% of patients in the non-Mitek group. Use of the Mitek anchor allowed for quicker postoperative recovery to resumption of ambulation without assistive devices (average of 3 weeks vs. 4.42 weeks) and a quicker return to pain-free ambulation in normal shoegear (average of 4 weeks vs. 6 weeks). Mitek anchoring of the tibialis posterior tendon, theoretically, increases medial arch support as evidenced by 14% of the Mitek group and 67% of the non-Mitek group requiring postoperative orthotics.

  15. Quantifying Heuristic Bias: Anchoring, Availability, and Representativeness.

    Science.gov (United States)

    Richie, Megan; Josephson, S Andrew

    2018-01-01

    Construct: Authors examined whether a new vignette-based instrument could isolate and quantify heuristic bias. Heuristics are cognitive shortcuts that may introduce bias and contribute to error. There is no standardized instrument available to quantify heuristic bias in clinical decision making, limiting future study of educational interventions designed to improve calibration of medical decisions. This study presents validity data to support a vignette-based instrument quantifying bias due to the anchoring, availability, and representativeness heuristics. Participants completed questionnaires requiring assignment of probabilities to potential outcomes of medical and nonmedical scenarios. The instrument randomly presented scenarios in one of two versions: Version A, encouraging heuristic bias, and Version B, worded neutrally. The primary outcome was the difference in probability judgments for Version A versus Version B scenario options. Of 167 participants recruited, 139 enrolled. Participants assigned significantly higher mean probability values to Version A scenario options (M = 9.56, SD = 3.75) than Version B (M = 8.98, SD = 3.76), t(1801) = 3.27, p = .001. This result remained significant analyzing medical scenarios alone (Version A, M = 9.41, SD = 3.92; Version B, M = 8.86, SD = 4.09), t(1204) = 2.36, p = .02. Analyzing medical scenarios by heuristic revealed a significant difference between Version A and B for availability (Version A, M = 6.52, SD = 3.32; Version B, M = 5.52, SD = 3.05), t(404) = 3.04, p = .003, and representativeness (Version A, M = 11.45, SD = 3.12; Version B, M = 10.67, SD = 3.71), t(396) = 2.28, p = .02, but not anchoring. Stratifying by training level, students maintained a significant difference between Version A and B medical scenarios (Version A, M = 9.83, SD = 3.75; Version B, M = 9.00, SD = 3.98), t(465) = 2.29, p = .02, but not residents or attendings. Stratifying by heuristic and training level, availability maintained

  16. Mn2+ anchored CdS polymer nanocomposites: An efficient alternative for Mn2+ doped CdS nanoparticles

    International Nuclear Information System (INIS)

    Saikia, Bhaskar Jyoti; Nath, Bikash Chandra; Borah, Chandramika; Dolui, Swapan Kumar

    2015-01-01

    A chelating bi-functional polymer brushes was prepared via atom transfer radical polymerization using grafting-from methodology. Mn 2+ -anchored CdS-polymer nanocomposites were synthesized using this graft copolymer by simple chelation method resulting in emission at about 620 nm which originates from the fluorescence of manganese ions embedded on the surface of CdS nanoparticles. This method provides an efficient straightforward substitute of Mn 2+ dopped CdS nanoparticles. Optical properties of the composites were investigated which indicates that simple Mn 2+ chelation and subsequent binding of CdS in a polymer matrix can have similar effect in the luminescence property as those synthesized via complex doping methods. Moreover this methodology can be applied for synthesis of any metal anchored nanocomposites proficiently and cost effectively in large-scale production. - Highlights: • A chelating bifunctional copolymer brush was synthesized via ATRP. • CdS nanoparticles and Mn 2+ were coupled with the bifunctional polymer. • Composites showed emission properties similar to Mn 2+ doped CdS nanoparticles. • Side chain length of the polymers also affect the emission properties of the composites.

  17. Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines.

    Science.gov (United States)

    Bettini, Simona; Maglie, Emanuela; Pagano, Rosanna; Borovkov, Victor; Inoue, Yoshihisa; Valli, Ludovico; Giancane, Gabriele

    2015-01-01

    Cu,H2-bis-porphyrin (Cu,H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir-Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase) to a surface plasmon resonance (SPR) substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

  18. Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines

    Directory of Open Access Journals (Sweden)

    Simona Bettini

    2015-11-01

    Full Text Available Cu,H2-bis-porphyrin (Cu,H2-Por2, in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir–Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase to a surface plasmon resonance (SPR substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

  19. Characterization of Sumbawa manganese ore and recovery of manganese sulfate as leaching products

    Science.gov (United States)

    Kusumaningrum, Retno; Rahmani, Siti Astari; Widayatno, Wahyu Bambang; Wismogroho, Agus Sukarto; Nugroho, Dwi Wahyu; Maulana, Syahrizal; Rochman, Nurul Taufiqu; Amal, M. Ikhlasul

    2018-05-01

    The aims of this research were to study the leaching process of manganese ore which originated from Sumbawa, Indonesia and its characterization. A high grade Indonesian manganese ore from Sumbawa, West of Nusa Tenggara was characterized by X-Ray Fluorescence (XRF). The result showed composition of 78.8 % Mn, 17.77% Fe and the rest were trace elements such as Si, Co, Ti, Zn, V and Zr contents. X-Ray Diffraction analysis showed that the manganese ore was consisted of pyrolusite (MnO2), rhodonite (MnSiO3), rhodochrosite (MnCO3) and hematite (Fe2O3). Manganese ore was also analyzed by thermal analysis to observe their thermal decomposition character. In this study, sulphuric acid (H2SO4, 6 M) was deployed as leaching agent. The leaching process was performed at 90 °C for two hours with the addition of NH4OH to control pH. Recovery percentage of leaching process yielded of 87 % Mn extracted. The crystallization process result at heating temperature of 200 °C was confirmed by XRD as manganese sulfate.

  20. Hydrometallurgical Process and Kinetics of Leaching Manganese from Semi-Oxidized Manganese Ores with Sucrose

    Directory of Open Access Journals (Sweden)

    Yuhong Wang

    2017-02-01

    Full Text Available The extraction of manganese from a semi-oxidized manganese ore was investigated with sucrose as the reducing agent in dilute sulfuric acid medium. The kinetics of leaching manganese from the complex ore containing MnCO3 and MnO2 was also investigated. The effects of sucrose and sulfuric acid concentrations, leaching temperature and reaction time on the total Mn (TMn, MnO2 and MnCO3 leaching were investigated. Results showed that MnCO3 could more easily react with hydrogen ions than MnO2 in ores, and MnO2 decomposition could be advantageous for MnCO3 leaching. The leaching efficiencies of 91.8% for total Mn, 91.4% for MnO2 and 96.9% for MnCO3 were obtained under the following optimized conditions: 0.035 mol/L sucrose concentration, 5 mol/L sulfuric acid concentration, 60 min of reaction time and 363.2 K of leaching temperature. In addition, it was found that the leaching process of semi-oxidized manganese ore follows the shrinking core model and the leaching rate was controlled by chemical reaction and diffusion. The apparent activation energy of the total manganese, MnO2, and MnCO3 leaching were 40.83, 40.59, and 53.33 kJ·mol−1, respectively.

  1. Considerations on the design of through-wall anchors

    International Nuclear Information System (INIS)

    Ricklefs, Ulf

    2012-01-01

    Connections to existing buildings are often the most difficult planning challenge for the realization of construction measures in case of piping system replacements in nuclear power plants. This is due to restricted space or limited load reserves of the building structure. Usually the realization of support connections to the existing buildings is achieved by anchor bolts. But in critical cases the preferred alternative solution uses through-wall anchors. Up to now uniform assessment thresholds are not available, no technical guidelines or regulations for construction variants exist. Through-wall anchors allow significantly higher load capacities for tensile and shear loads but require enhanced planning and realization efforts.

  2. Bioleaching of a manganese and silver Ore

    International Nuclear Information System (INIS)

    Porro, S.; Tedesco, P.H.; La Plata

    1990-01-01

    The bioleaching with a strain of Thiobacillus thiooxidans of the ore of Farallon Negro (Catamarca, Argentina) was studied in order to estimate its application to the solution and recovery of the manganese, and to improve the silver extraction. The State company which works the mine has not yet found an economical process to extract the manganese and has only reached a 30% efficiency in the recovery of silver by cianuration. The effects of pulp density variations and the addition of different quantities of FeS were analysed looking for the best working conditions. 74 μm (mesh Tyler 200) of ore particles were used because that is the size used in this plant for the cianuration process. (Author)

  3. Arsenic removal by manganese greensand filters

    Energy Technology Data Exchange (ETDEWEB)

    Phommavong, T. [Saskatchewan Environment, Regina (Canada); Viraraghavan, T. [Univ. of Regina, Saskatchewan (Canada). Faculty of Engineering

    1994-12-31

    Some of the small communities in Saskatchewan are expected to have difficulty complying with the new maximum acceptable concentration (MAC) of 25 {micro}g/L for arsenic. A test column was set up in the laboratory to study the removal of arsenic from the potable water using oxidation with KMnO{sub 4}, followed by manganese greensand filtration. Tests were run using water from the tap having a background arsenic concentration of <0.5 {micro}g/L and iron concentration in the range of 0.02 to 0.77 mg/L. The test water was spiked with arsenic and iron. Results showed that 61 % to 98% of arsenic can be removed from the potable water by oxidation with KMnO{sub 4} followed by manganese greensand filtration.

  4. Iron and manganese removal from drinking water

    OpenAIRE

    Pascu, Daniela-Elena; Neagu (Pascu), Mihaela; Alina Traistaru, Gina; Nechifor, Aurelia Cristina; Raluca Miron, Alexandra

    2016-01-01

    The purpose of the present study is to find a suitable method for removal of iron and manganese from ground water, considering both local economical and environmental aspects. Ground water is a highly important source of drinking water in Romania. Ground water is naturally pure from bacteria at a 25 m depth or more. However, solved metals may occur and if the levels are too high, the water is not drinkable. Different processes, such as electrochemical and combined electrochemical-adsorption m...

  5. Manganese concentration in human saliva using NAA

    Energy Technology Data Exchange (ETDEWEB)

    Lewgoy, Hugo R., E-mail: hugorl@usp.br [Universidade Bandeirante Anhanguera (UNIBAN), Sao Paulo, SP (Brazil); Zamboni, Cibele B.; Medeiros, Ilca M.M.A.; Medeiros, Jose A.G. de [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2013-07-01

    In this investigation the Manganese levels in human whole saliva were determined using Neutron Activation Analysis (NAA) technique for the proposition of an indicative interval. The measurements were performed considering gender and lifestyle factors of Brazilian inhabitants (non-smokers, non-drinkers and no history of toxicological exposure). The results emphasize that the indicative interval is statistically different by gender. These data are useful for identifying or preventing some diseases in the Brazilian population. (author)

  6. Manganese concentration in human saliva using NAA

    International Nuclear Information System (INIS)

    Lewgoy, Hugo R.; Zamboni, Cibele B.; Medeiros, Ilca M.M.A.; Medeiros, Jose A.G. de

    2013-01-01

    In this investigation the Manganese levels in human whole saliva were determined using Neutron Activation Analysis (NAA) technique for the proposition of an indicative interval. The measurements were performed considering gender and lifestyle factors of Brazilian inhabitants (non-smokers, non-drinkers and no history of toxicological exposure). The results emphasize that the indicative interval is statistically different by gender. These data are useful for identifying or preventing some diseases in the Brazilian population. (author)

  7. Configuration of an inelastic flexible anchored cable

    Directory of Open Access Journals (Sweden)

    T. P. Dreyer

    1992-07-01

    Full Text Available Consider an inelastic, perfectly flexible cable with given external forces acting on the total length of the cable. The one end-point is fixed in the origin and the other end-point is anchored at a given point (a;b;c in space. The resulting configuration of the cable in space can be modelled by a system of non-linear differential equations. In this article it is shown that this continuous model of the cable can always be solved in terms of an integral. In the special case of a constant (i.e. independent of the position on the cable external force per unit length the solution is given explicitly in terms of three constants that describe the tension at the origin. These three constants are determined by the boundary values a, b and c at the other end-point, and must be calculated in general by a numerical procedure from the three resulting simultaneous non-linear equations. A few applications of this method are shown.

  8. Manganese contents of soils as determined by activation analysis

    International Nuclear Information System (INIS)

    El-Kholi, A.F.; Hamdy, A.A.; Al Metwally, A.I.; El-Damaty, A.H.

    1976-01-01

    The object of this investigation is to determine total manganese by means of neutron activation analysis and evaluate this technique in comparison with the corresponding data obtained by conventional chemical analysis. Data obtained revealed that the values of total manganese in calcareous soils obtained by both chemical analysis and that by neutron activation analysis were similar. Therefore, activation analysis could be recommended as a quick laboratory, less tedious, and time consuming method for the determination of Mn content in both soils and plants than the conventional chemical techniques due to its great specificity, sensitivity and simplicity. Statistical analysis showed that there is a significant correlation at 5% probability level between manganese content in Soybean plant and total manganese determined by activation and chemical analysis giving the evidence that in the case of those highly calcareous soils of low total manganese content this fraction has to be considered as far as available soil manganese is concerned

  9. Manganese deposition in drinking water distribution systems.

    Science.gov (United States)

    Gerke, Tammie L; Little, Brenda J; Barry Maynard, J

    2016-01-15

    This study provides a physicochemical assessment of manganese deposits on brass and lead components from two fully operational drinking water distributions systems. One of the systems was maintained with chlorine; the other, with secondary chloramine disinfection. Synchrotron-based in-situ micro X-ray adsorption near edge structure was used to assess the mineralogy. In-situ micro X-ray fluorescence mapping was used to demonstrate the spatial relationships between manganese and potentially toxic adsorbed metal ions. The Mn deposits ranged in thickness from 0.01 to 400 μm. They were composed primarily of Mn oxides/oxhydroxides, birnessite (Mn(3+) and Mn(4+)) and hollandite (Mn(2+) and Mn(4+)), and a Mn silicate, braunite (Mn(2+) and Mn(4+)), in varying proportions. Iron, chromium, and strontium, in addition to the alloying elements lead and copper, were co-located within manganese deposits. With the exception of iron, all are related to specific health issues and are of concern to the U.S. Environmental Protection Agency (U.S. EPA). The specific properties of Mn deposits, i.e., adsorption of metals ions, oxidation of metal ions and resuspension are discussed with respect to their influence on drinking water quality. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Manganese-enhanced magnetic resonance imaging (MEMRI).

    Science.gov (United States)

    Koretsky, Alan P; Silva, Afonso C

    2004-12-01

    Manganese ion (Mn2+) is an essential metal that participates as a cofactor in a number of critical biological functions, such as electron transport, detoxification of free radicals and synthesis of neurotransmitters. Mn2+ can enter excitable cells using some of the same transport systems as Ca2+ and it can bind to a number of intracellular sites because it has high affinity for Ca2+ and Mg2+ binding sites on proteins and nucleic acids. Paramagnetic forms of manganese ions are potent MRI relaxation agents. Indeed, Mn2+ was the first contrast agent proposed for use in MRI. Recently, there has been renewed interest in combining the strong MRI relaxation effects of Mn2+ with its unique biology, in order to further expand the already broad assortment of useful information that can be measured by MRI. Such an approach has been continuously developed in the past several years to provide unique tissue contrast, to assess tissue viability, to act as a surrogate marker of calcium influx into cells and to trace neuronal connections. This special issue of NMR in Biomedicine on manganese-enhanced MRI (MEMRI) is aimed at providing the readers of this journal with an extensive review of some of the most prominent applications of MEMRI in biological systems. Written by several of the leaders in the field, the reviews and original research articles featured in this special issue are likely to offer an exciting and inspiring view of the broad range of applications of MEMRI. Copyright 2004 John Wiley & Sons, Ltd.

  11. Manganese and the II system in photosynthesis

    International Nuclear Information System (INIS)

    Joyard, Jacques

    1971-01-01

    The evolution during greening of some components of system II of photosynthesis has been followed in plastids extracted from Zea mays grown in the dark. Manganese studies were done by means of neutron activation, electron spin resonance (ESR) was also used in some experiments. Oxygen evolution of isolated plastids was followed by polarography (with a membrane electrode). The evolution of manganese/carotenoids ratio can be divided in three parts. During the first hour of greening, the increase shows an input of Mn in the plastids; then, whereas carotenoids content of those plastids presents no changes, Mn is released in the medium; at last, carotenoids synthesis is parallel to Mn fixation in the plastids, the ratio being constant after 24 hours of greening. From various measurements on chloroplastic manganese, it is shown that the development of system II can be divided in two main phases: during the first one (that is during the first day of light) the components are not yet bound together but the relations become more and more strong. Then, during the last period of the development, the organisation of system II is complete and the transformations of the plastids are parallel to the raise of their activity. (author) [fr

  12. Physical origin of third order non-linear optical response of porphyrin nanorods

    International Nuclear Information System (INIS)

    Mongwaketsi, N.; Khamlich, S.; Pranaitis, M.; Sahraoui, B.; Khammar, F.; Garab, G.; Sparrow, R.; Maaza, M.

    2012-01-01

    The non-linear optical properties of porphyrin nanorods were studied using Z-scan, Second and Third harmonic generation techniques. We investigated in details the heteroaggregate behaviour formation of [H 4 TPPS 4 ] 2- and [SnTPyP] 2+ mixture by means of the UV-VIS spectroscopy and aggregates structure and morphology by transmission electron microscopy. The porphyrin nanorods under investigation were synthesized by self assembly and molecular recognition method. They have been optimized in view of future application in the construction of the light harvesting system. The focus of this study was geared towards understanding the influence of the type of solvent used on these porphyrins nanorods using spectroscopic and microscopic techniques. Highlights: ► We synthesized porphyrin nanorods by self assembly and molecular recognition method. ► TEM images confirmed solid cylindrical shapes. ► UV-VIS spectroscopy showed the decrease in the absorbance peaks of the precursors. ► The enhanced third-order nonlinearities were observed.

  13. Synthesis, characterization, and nonlinear optical properties of graphene oxide functionalized with tetra-amino porphyrin

    Science.gov (United States)

    Yamuna, R.; Ramakrishnan, S.; Dhara, Keerthy; Devi, R.; Kothurkar, Nikhil K.; Kirubha, E.; Palanisamy, P. K.

    2013-01-01

    The synthesis of a porphyrin-graphene oxide hybrid (GO-TAP) was carried out by covalently functionalizing graphene oxide (GO) with 5,10,15,20 mesotetra (4-aminophenyl) porphyrin (TAP) through an amide linkage. The GO-TAP hybrid has been characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-visible spectroscopy. The peak intensity of the Soret band of the material was suppressed compared to neat TAP. This indicates a strong interaction between the electronic energy level of TAP and GO in the GO-TAP hybrid. The functionalization of GO with TAP significantly improved its solubility and dispersion stability in organic solvents. Scanning electron micrographs reveal that the hybrid was found to be similar to the unmodified GO but slightly more wrinkled. Transmission electron micrographs also demonstrate that GO sheet in the hybrid is more wrinkled with some dark spot due to functionalization. Atomic force microscopy results also reveal that the TAP functionalization increases the thickness of GO sheet to 2.0-3.0 nm from 1.2 to 1.8 nm. We observed improved nonlinear optical and optical limiting properties for the hybrid compared to both graphene oxide and porphyrin. GO-TAP shows fluorescence quenching compared with porphyrin, indicating excellent electron and/or energy transfer to GO from TAP. Thermogravimetric analysis confirms that the GO-TAP hybrid has outstanding thermal stability.

  14. Controlled electropolymerisation of a carbazole-functionalised iron porphyrin electrocatalyst for CO2 reduction

    DEFF Research Database (Denmark)

    Hu, Xinming; Salmi, Zakaria; Lillethorup, Mie

    2016-01-01

    Using a one-step electropolymerisation procedure, CO2 absorbing microporous carbazole-functionalised films of iron porphyrins are prepared in a controlled manner. The electrocatalytic reduction of CO2 for these films is investigated to elucidate their efficiency and the origin of their ultimate...

  15. N-annulated perylene fused porphyrins with enhanced near-IR absorption and emission

    KAUST Repository

    Jiao, Chongjun; Huang, Kuo-Wei; Guan, Zhenping; Xu, Qinghua; Wu, Jishan

    2010-01-01

    -IR absorption, as well as detectable photoluminescence quantum yields, all of which are comparable to or even exceed those of either meso-β doubly linked porphyrin dimer/trimer or bis/tri-N-annulated rylenes. © 2010 American Chemical Society.

  16. Aspects of investigating scrambling in the synthesis of porphyrins Different analytical methods

    DEFF Research Database (Denmark)

    Nielsen, C.B.; Krebs, Frederik C

    2005-01-01

    Herein, we discuss the analyses and quantification of the different components in porphyrin mixtures, prepared from p-anisaidehyde, p-tolualdehyde, and 5-(4-bromophenyl)-dipyrromethane with acid catalysis, using NMR and HPLC. The advantages and disadvantages of these analytical methods are emphas...

  17. Redox tuning of cytochrome b562 through facile metal porphyrin substitution

    DEFF Research Database (Denmark)

    Della Pia, Eduardo Antonio; Chi, Qijin; Elliott, Martin

    2012-01-01

    The biologically and nanotechnologically important heme protein cytochrome b562 was reconstructed with zinc and copper porphyrins, leading to significant changes in the spectral, redox and electron transfer properties. The Cu form shifts the redox potential by +300 mV and exhibits high electron t...

  18. Spectral Sensitization of TiO2 Substrates by Monolayers of Porphyrin Heterodimers

    NARCIS (Netherlands)

    Koehorst, R.B.M.; Boschloo, G.K.; Savenije, T.J.; Goossens, A.; Schaafsma, T.J.

    2000-01-01

    Photoelectrochemical cells have been constructed by depositing monolayers of oriented covalently linked zinc/free base porphyrin heterodimers onto ~30 nm nonporous layers of TiO2 on ITO, deposited by metal-organic chemical vapor deposition (MO-CVD), and onto ~100 nm porous, nanostructured TiO2

  19. New ZnO@Cardanol Porphyrin Composite Nanomaterials with Enhanced Photocatalytic Capability under Solar Light Irradiation

    Directory of Open Access Journals (Sweden)

    Viviane Gomes Pereira Ribeiro

    2017-09-01

    Full Text Available This work describes the synthesis, characterization, and photocatalytic activity of new composite nanomaterials based on ZnO nanostructures impregnated by lipophlilic porphyrins derived from cashew nut shell liquid (CNSL. The obtained nanomaterials were characterized by X-ray diffraction (XRD, UV-Vis diffuse reflectance spectroscopy (DRS, Fourier transform infrared spectroscopy (FT-IR, transmission electron microscopy (TEM, and steady-state photoluminescence spectra (PL. The results confirm nanostructures showing average diameter of 55 nm and an improved absorption in the visible region. Further, the FTIR analysis proved the existence of non-covalent interactions between the porphyrin molecules and ZnO. The photocatalytic activity of prepared photocatalysts was investigated by degradation of rhodamine B (RhB in aqueous solution under visible light irradiation and natural sunlight. It was demonstrated that the photocatalytic activity increases in the presence of the porphyrins and, also, depends on the irradiation source. The development of composite photocatalysts based on porphyrins derived from CNSL provides an alternative approach to eliminate efficiently toxic wastes from water under ambient conditions.

  20. Optical acetylcholine sensor based on free base porphyrin as a chromoionophore.

    Science.gov (United States)

    Mroczkiewicz, Monika; Pietrzak, Mariusz; Górski, Łukasz; Malinowska, Elżbieta

    2011-09-21

    In this work, the possibility of application of free base porphyrin as a lipophilic pH chromoionophore for the preparation of optical cation-selective sensors was investigated. The properties of polymeric membranes, containing porphyrins of different structures, namely tetraphenylporphyrin (TPP) and octaethylporphyrin (OEP), were compared. Changes in equilibrium between protonated and deprotonated form of porphyrin, resulting from variations in ACh concentration, were evaluated. The influence of various factors (kind and quantity of anionic additive and porphyrin in the membrane phase, pH of sample solution) on initial equilibrium was studied. The best membrane composition was chosen as: TPP 3 wt.%, KTFPB 175 mol.% relative to ionophore, PVC:o-NPOE (1 : 4) and measuring buffer solution: 0.05 M MES, pH 4.5. Selectivity, response stability, reversibility and repeatability tests were carried out for chosen sensor. Developed sensor allowed for the determination of a model analyte, acetylcholine, at the concentration range of 10(-5) to 10(-2) M, both in stationary and flow-injection system. Sensor response was reversible and repeatable in the mentioned concentration range.

  1. Spherical porphyrin sensor array based on encoded colloidal crystal beads for VOC vapor detection.

    Science.gov (United States)

    Xu, Hua; Cao, Kai-Di; Ding, Hai-Bo; Zhong, Qi-Feng; Gu, Hong-Cheng; Xie, Zhuo-Ying; Zhao, Yuan-Jin; Gu, Zhong-Ze

    2012-12-01

    A spherical porphyrin sensor array using colloidal crystal beads (CCBs) as the encoding microcarriers has been developed for VOC vapor detection. Six different porphyrins were coated onto the CCBs with distinctive encoded reflection peaks via physical adsorption and the sensor array was fabricated by placing the prepared porphyrin-modified CCBs together. The change in fluorescence color of the porphyrin-modified CCBs array serves as the detection signal for discriminating between different VOC vapors and the reflection peak of the CCBs serves as the encoding signal to distinguish between different sensors. It was demonstrated that the VOC vapors detection using the prepared sensor array showed excellent discrimination: not only could the compounds from the different chemical classes be easily differentiated (e.g., alcohol vs acids vs ketones) but similar compounds from the same chemical family (e.g., methanol vs ethanol) and the same compound with different concentration ((e.g., Sat. ethanol vs 60 ppm ethanol vs 10 ppm ethanol) could also be distinguished. The detection reproducibility and the humidity effect were also investigated. The present spherical sensor array, with its simple preparation, rapid response, high sensitivity, reproducibility, and humidity insensitivity, and especially with stable and high-throughput encoding, is promising for real applications in artificial olfactory systems.

  2. Chiral memory via chiral amplification and selective depolymerization of porphyrin aggregates

    NARCIS (Netherlands)

    Helmich, F.A.; Lee, C.C.; Schenning, A.P.H.J.; Meijer, E.W.

    2010-01-01

    Chiral memory at the supramolecular level is obtained via a new approach using chiral Zn porphrins and achiral Cu porphyrins. In a "sergeant-and-soldiers" experiment, the Zn "sergeant" transfers its own chirality to Cu "soldiers" and, after chiral amplification, the "sergeant" is removed from the

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

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Samec, Zdeněk

    2012-01-01

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

  4. Porphyrin metabolism in lymphocytes of miners exposed to diesel exhaust at oil shale mine.

    NARCIS (Netherlands)

    Muzyka, V.; Scheepers, P.T.J.; Bogovski, S.; Lang, I.; Schmidt, N.; Ryazanov, V.; Veidebaum, T.

    2004-01-01

    The present study was carried out on the evaluation and application of new biomarkers for populations exposed to occupational diesel exhaust at oil shale mines. Since not only genotoxic effects may play an important role in the generation of tumors, the level of porphyrin metabolism was proposed as

  5. Synthesis and photophysical properties of phosphorus(V) porphyrins functionalized with axial carbazolylvinylnaphthalimides.

    Science.gov (United States)

    Zhan, Yong; Cao, Kaiyu; Wang, Chenguang; Jia, Junhui; Xue, Pengchong; Liu, Xingliang; Duan, Xuemei; Lu, Ran

    2012-11-21

    We have synthesized new D-A-D type phosphorus(V) porphyrin derivatives and functionalized with axial carbazolylvinylnaphthalimide units. The absorption bands of the obtained phosphorus(V) porphyrins were in the range 250-640 nm with high molar absorption coefficients, meaning strong light-harvesting abilities. Notably, it is found that the devices based on phosphorus(V) porphyrins with a configuration structure of [ITO/PEDOT : PSS/organic active film/LiF/Al] give an incident-photon-to-current conversion efficiency (IPCE) response. The maximal IPCE value reaches 2.76% for the device based on compound , which is much higher than that of 0.20% for compound . The reason might be due to the low oxidation potential and the strong light-harvesting ability of the enlarged conjugation of the axial units in compound . Therefore, we deduced that photo-induced electron transfer happened in phosphorus(V) porphyrins bearing axial conjugated donor units, which would make them good candidates for photovoltaic materials that could be applied in solar cells.

  6. Synthesis and photobactericidal properties of a neutral porphyrin grafted onto lignocellulosic fibers

    Energy Technology Data Exchange (ETDEWEB)

    Nzambe Ta keki, Jean Kerim; Ouk, Tan-Sothéa [Laboratoire de chimie des substances naturelles, Université de Limoges, 123 avenue Albert Thomas, 87060 Limoges (France); Zerrouki, Rachida [Laboratoire de chimie des substances naturelles, Université de Limoges, 123 avenue Albert Thomas, 87060 Limoges (France); Centre de Recherche sur les Matériaux Lignocellulosiques, Université du Québec à Trois-Rivières, 3351 boul. des Forges, C.P. 500, Trois-Rivières, QC G9A 5H7 (Canada); Faugeras, Pierre-Antoine; Sol, Vincent [Laboratoire de chimie des substances naturelles, Université de Limoges, 123 avenue Albert Thomas, 87060 Limoges (France); Brouillette, François [Centre de Recherche sur les Matériaux Lignocellulosiques, Université du Québec à Trois-Rivières, 3351 boul. des Forges, C.P. 500, Trois-Rivières, QC G9A 5H7 (Canada)

    2016-05-01

    Photodynamic antimicrobial chemotherapy (PACT), as one of the promising alternative antimicrobial treatment, has received great attention in recent years. In this work, a new antimicrobial material has been elaborated by grafting a neutral porphyrin, the metallated 5-(4-azidophenyl)-10,15,20-triphenylporphyrin, onto lignocellulosic fibers by using the Copper (I)-Catalyzed Alkyne-Azide 1,3-dipolar Cycloaddition (CuAAC) reaction. The cross-linked porphyrin-Kraft pulp material was characterized by infrared and by XPS spectroscopy analyses, which proved the covalent linkage between the porphyrin and propargylated Kraft pulp fibers. The antimicrobial activity of this material was tested under visible light irradiation with a low light dose (9.5 J/cm{sup 2}) against Staphylococcus aureus and Pseudomonas aeruginosa. The two bacterial strains deposited on the resulting photosensitizing Kraft pulp are efficiently killed after illumination. Such materials could find applications in industrial, household and medical environments as an alternative to overcome the widespread microbial multiresistance to classical treatments. - Highlights: • Elaboration of new antimicrobial paper • Grafting of porphyrin on lignocellulosic fibers using click chemistry • Modification of Kraft pulp fibers, using water as solvent.

  7. Photokinetic and ultrastructural studies on porphyrin photosensitization of HeLa cells

    International Nuclear Information System (INIS)

    Milanesi, Carla; Sorgato, Fiorella; Jori, Giulio

    1989-01-01

    Liposome-bound haematoporphyrin or haematoporphyrin dimethylester, as well as haematoporphyrin dissolved in phosphate-buffered saline, were added to HeLa cell monolayers at a dose of 1 μg of porphyrin per 10 5 cells. After 2 min or 20 min incubation liposome-bound porphyrins were accumulated by cells in an about two-fold larger amount than the water-dissolved haematoporphyrin. This caused a more efficient photosensitization of HeLa cells by liposome-delivered porphyrins upon illumination with 366 nm light. Ultrastructural studies of HeLa cells, which had been incubated in a physiological medium for 24 h after the end of irradiation, showed that liposomal porphyrins induce an early and extensive endocytoplasmic damage, leading to mitochondrial swelling and vesiculation; changes of permeability of the cytoplasmic membrane are also evident, especially in the case of haematoporphyrin dimethylester. On the other hand, water-dissolved haematoporphyrin predominantly photosensitizes damage of the plasma membrane. The different pattern of cell photodamage probably reflects a different subcellular distribution of the photosensitizing drugs. (author)

  8. New ZnO@Cardanol Porphyrin Composite Nanomaterials with Enhanced Photocatalytic Capability under Solar Light Irradiation

    Science.gov (United States)

    Ribeiro, Viviane Gomes Pereira; Marcelo, Ana Maria Pereira; da Silva, Kássia Teixeira; da Silva, Fernando Luiz Firmino; Mota, João Paulo Ferreira; do Nascimento, João Paulo Costa; Sombra, Antonio Sérgio Bezerra; Clemente, Claudenilson da Silva; Mazzetto, Selma Elaine

    2017-01-01

    This work describes the synthesis, characterization, and photocatalytic activity of new composite nanomaterials based on ZnO nanostructures impregnated by lipophlilic porphyrins derived from cashew nut shell liquid (CNSL). The obtained nanomaterials were characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and steady-state photoluminescence spectra (PL). The results confirm nanostructures showing average diameter of 55 nm and an improved absorption in the visible region. Further, the FTIR analysis proved the existence of non-covalent interactions between the porphyrin molecules and ZnO. The photocatalytic activity of prepared photocatalysts was investigated by degradation of rhodamine B (RhB) in aqueous solution under visible light irradiation and natural sunlight. It was demonstrated that the photocatalytic activity increases in the presence of the porphyrins and, also, depends on the irradiation source. The development of composite photocatalysts based on porphyrins derived from CNSL provides an alternative approach to eliminate efficiently toxic wastes from water under ambient conditions. PMID:28934117

  9. RAFT Synthesis and Self-Assembly of Free-Base Porphyrin Cored Star Polymers

    Directory of Open Access Journals (Sweden)

    Lin Wu

    2011-01-01

    Full Text Available Reversible addition fragmentation chain transfer (RAFT synthesis and self-assembly of free-base porphyrin cored star polymers are reported. The polymerization, in the presence of a free-base porphyrin cored chain transfer agent (CTA-FBP, produced porphyrin star polymers with controlled molecular weights and narrow polydispersities for a number of monomers including N, N-dimethylacrylamide (DMA and styrene (St. Well-defined amphiphilic star block copolymers, P-(PS-PDMA4 and P-(PDMA-PS4 (P: porphyrin, were also prepared and used for self-assembly studies. In methanol, a selective solvent for PDMA, spherical micelles were observed for both block copolymers as characterized by TEM. UV-vis studies suggested star-like micelles were formed from P-(PS-PDMA4, while P-(PDMA-PS4 aggregated into flower-like micelles. Spectrophotometric titrations indicated that the optical response of these two micelles to external ions was a function of micellar structures. These structure-related properties will be used for micelle studies and functional material development in the future.

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

    Czech Academy of Sciences Publication Activity Database

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

    2012-01-01

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

  11. Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Vanin, Marco; Karamad, Mohammedreza

    2013-01-01

    Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center of the po......Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center...... instead of CO2. Volcano plots were constructed on the basis of scaling relations of reaction intermediates, and from these plots the reaction steps with the highest overpotentials were deduced. The Rh-porphyrin-like functionalized graphene was identified as the most active catalyst for producing methanol...... from CO, featuring an overpotential of 0.22 V. Additionally, we have also examined the hydrogen evolution and oxidation reaction, and in their case, too, Rh-porphyrin turned out to be the best catalyst with an overpotential of 0.15 V. © 2013 American Chemical Society....

  12. NO2-induced synthesis of nitrato-iron(III) porphyrin with diverse ...

    Indian Academy of Sciences (India)

    found serendipitously in the reaction of [Fe(4-Me-TPP)Cl] with nitrous acid, which ... Nitric oxide and its derivatives nitrite and nitrate ion ... oxide.2 Nitrate is produced in heme proteins from oxi- ... and nitrogen assimilation.4 Iron nitrate(III) porphyrins ... one-pot method.15 ... of the compound was determined based on the lack.

  13. Mg-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments

    Czech Academy of Sciences Publication Activity Database

    Kovář, P.; Pospíšil, M.; Káfuňková, Eva; Lang, Kamil; Kovanda, F.

    2010-01-01

    Roč. 16, č. 2 (2010), s. 223-233 ISSN 1610-2940 R&D Projects: GA ČR(CZ) GA203/06/1244; GA AV ČR KAN100500651 Institutional research plan: CEZ:AV0Z40320502 Keywords : layered double hydroxide * porphyrin * molecular simulations Subject RIV: CA - Inorganic Chemistry Impact factor: 1.871, year: 2010

  14. Transforming a Targeted Porphyrin Theranostic Agent into a PET Imaging Probe for Cancer

    Directory of Open Access Journals (Sweden)

    Jiyun Shi, Tracy W.B. Liu, Juan Chen, David Green, David Jaffray, Brian C. Wilson, Fan Wang, Gang Zheng

    2011-01-01

    Full Text Available Porphyrin based photosensitizers are useful agents for photodynamic therapy (PDT and fluorescence imaging of cancer. Porphyrins are also excellent metal chelators forming highly stable metallo-complexes making them efficient delivery vehicles for radioisotopes. Here we investigated the possibility of incorporating 64Cu into a porphyrin-peptide-folate (PPF probe developed previously as folate receptor (FR targeted fluorescent/PDT agent, and evaluated the potential of turning the resulting 64Cu-PPF into a positron emission tomography (PET probe for cancer imaging. Noninvasive PET imaging followed by radioassay evaluated the tumor accumulation, pharmacokinetics and biodistribution of 64Cu-PPF. 64Cu-PPF uptake in FR-positive tumors was visible on small-animal PET images with high tumor-to-muscle ratio (8.88 ± 3.60 observed after 24 h. Competitive blocking studies confirmed the FR-mediated tracer uptake by the tumor. The ease of efficient 64Cu-radiolabeling of PPF while retaining its favorable biodistribution, pharmacokinetics and selective tumor uptake, provides a robust strategy to transform tumor-targeted porphyrin-based photosensitizers into PET imaging probes.

  15. Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex

    KAUST Repository

    Aly, Shawkat Mohammede

    2014-10-02

    Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

  16. Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework

    KAUST Repository

    Chen, Chen

    2017-12-20

    We have characterized the local electronic structure of a porphyrin-containing single-layer covalent organic framework (COF) exhibiting a square lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMA) and 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) onto a Au(111) surface in ultrahigh vacuum followed by annealing to facilitate Schiff-base condensations between monomers. Scanning tunneling spectroscopy (STS) experiments conducted on isolated TAPP precursor molecules and the covalently linked COF networks yield similar transport (HOMO-LUMO) gaps of 1.85 ± 0.05 eV and 1.98 ± 0.04 eV, respectively. The COF orbital energy alignment, however, undergoes a significant downward shift compared to isolated TAPP molecules due to the electron-withdrawing nature of the imine bond formed during COF synthesis. Direct imaging of the COF local density of states (LDOS) via dI/dV mapping reveals that the COF HOMO and LUMO states are localized mainly on the porphyrin cores and that the HOMO displays reduced symmetry. DFT calculations reproduce the imine-induced negative shift in orbital energies and reveal that the origin of the reduced COF wave function symmetry is a saddle-like structure adopted by the porphyrin macrocycle due to its interactions with the Au(111) substrate.

  17. Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Guan, E-mail: huangg66@126.com; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

    2017-04-30

    Graphical abstract: A biomimetic catalyst of iron-tetrakis(4-sulfonatophenyl)porphyrin immobilized on powdered chitosan achieves efficient cyclohexane oxidation with high ketone and alcohol yields. - Highlights: • Fe (TPPS)/pd-CTS is an excellent catalyst for cyclohexane oxidation. • Amino ligation alters the electron cloud density around the iron cation. • Amino coordination likely reduces the activation energy of Fe (TPPS). • The catalyst achieved 22.9 mol% yields of cyclohexanone and cyclohexanol. - Abstract: This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O{sub 2}. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

  18. ALA-based fluorescent diagnosis of malignant oral lesions in the presence of bacterial porphyrin formation

    Science.gov (United States)

    Schleier, P.; Berndt, A.; Zinner, K.; Zenk, W.; Dietel, W.; Pfister, W.

    2006-02-01

    The aminolevulinic acid (5-ALA) -based fluorescence diagnosis has been found to be promising for an early detection and demarcation of superficial oral squamous cell carcinomas (OSCC). This method has previously demonstrated high sensitivity, however this clinical trial showed a specificity of approximately 62 %. This specificity was mainly restricted by tumor detection in the oral cavity in the presence of bacteria. After topical ALA application in the mouth of patients with previously diagnosed OSSC, red fluorescent areas were observed which did not correlate to confirm histological findings. Swabs and plaque samples were taken from 44 patients and cultivated microbiologically. Fluorescence was investigated (OMA-system) from 32 different bacteria strains found naturally in the oral cavity. After ALA incubation, 30 of 32 strains were found to synthesize fluorescent porphyrins, mainly Protoporphyrin IX. Also multiple fluorescent spectra were obtained having peak wavelengths of 636 nm and around 618 nm - 620 nm indicating synthesis of different porphyrins, such as the lipophylic Protoporphyrin IX (PpIX) and hydrophylic porphyrins (water soluble porphyrins, wsp). Of the 32 fluorescent bacterial strains, 18 produced wsp, often in combination with PpIX, and 5 produced solely wsp. These results clarify that ALA-based fluorescence diagnosis without consideration or suppression of bacteria fluorescence may lead to false-positive findings. It is necessary to suppress bacteria fluorescence with suitable antiseptics before starting the procedure. In this study, when specific antiseptic pre-treatment was performed bacterial associated fluorescence was significantly reduced.

  19. Exciplex-exciplex energy transfer and annihilation in solid films of porphyrin-fullerene dyads

    NARCIS (Netherlands)

    Lehtivuori, Heli; Lemmetyinen, Helge; Tkachenko, Nikolai V.

    2006-01-01

    Exciplex-exciplex annihilation was observed for the first time in porphyrin-fullerene molecular films. The films were prepared using Langmuir-Blodgett and drop casting methods. The exciplex-exciplex interactions were studied using femtosecond pump-probe method. The exciplex-exciplex annihilation can

  20. Synthesis and biological evaluation of porphyrin-polyamine conjugates as potential agents in photodynamic therapy

    International Nuclear Information System (INIS)

    Lamarche, Francois

    2004-01-01

    The synthesis of photosensitizers that specifically recognize tumoral cells constitutes a challenging step in the field of photodynamic therapy. To this end, we designed a new class of porphyrins linked to natural polyamines (spermidine, spermine). As a first step, we synthesized para and ortho-carboxy-propyl-oxy-phenyl-tritolyl-porphyrins bearing spermidine or spermine. Then, we designed two precursors, N4-aminobutyl-spermidine-Boc2 and N4-aminobutyl-spermine-Boc3. These derivatives have been fixed on carboxy-porphyrins, protoporphyrin IX and chlorin e6. These new compounds have been characterized by MALDI spectrometry, UV-Visible and 1 H NMR spectroscopy. They have been found to produce singlet oxygen. Biological activity study of these photosensitizers has been realized on K562 cell line, irradiated with fluorescent bulbs. In vitro tests of these porphyrins have shown their photo-cytotoxic activity and protoporphyrins-polyamines have been able to trigger early apoptotic events. Finally, preliminary results obtained with chlorin e6-polyamines, irradiated with red light, seem to show that these structures are good candidates for an application in PDT. (author) [fr

  1. Porphyrins and pheomelanins contribute to the reddish juvenal plumage of black-shouldered kites.

    Science.gov (United States)

    Negro, Juan J; Bortolotti, Gary R; Mateo, Rafael; García, Isabel M

    2009-07-01

    Porphyrins are a widespread group of pigments in nature, but, contrary to melanins and carotenoids, their occurrence as plumage colorants seems to be anecdotal and their function, if any, is unknown. Using thin-layer chromatography and high pressure liquid chromatography, we have found coproporphyrin III, the same porphyrin type previously reported in owls, in the plumage of nestling black-shouldered kites (Elanus caeruleus). The first plumage grown at the nest in this species includes reddish-brown contour feathers in the upperparts, and particularly in the breast area, which fade during the weeks-long post-fledging period to become either gray or white consistent with the definitive adult plumage. In these reddish feathers, we have also found small amounts of pheomelanins and traces of eumelanin. The contribution of each pigment to the final colour perceived by birds or other animals is unknown. In white and grey feathers of the same species no porphyrin was found, and only traces of eumelanin were detected in the grey ones. The fact that the reddish feathers are only found in the juvenal plumage, when individuals are vulnerable in an open nest, leads us to hypothesize a camouflage role for this ephemeral plumage. As porphyrins are involved, although not exclusively, we can for the first time ascribe them a function in the plumage of birds.

  2. Unusual near-white electroluminescence of light emitting diodes based on saddle-shaped porphyrins.

    Science.gov (United States)

    Shahroosvand, Hashem; Zakavi, Saeed; Sousaraei, Ahmad; Mohajerani, Ezeddin; Mahmoudi, Malek

    2015-05-14

    In contrast to the red electroluminescence emission frequently observed in porphyrins based OLED devices, the present devices exhibit a nearly white emission with greenish yellow, yellowish green and blue green hues in the case of Fe(II)(TCPPBr6) (TCPPBr6 = β-hexabromo-meso-tetrakis-(4-phenyl carboxyl) porphyrinato), Zn(II)(TPPBr6) and Co(II)(TPPBr6), respectively.

  3. Biosynthesis of porphyrins and immune status of children and teenagers exposed to irradiation in low doses

    International Nuclear Information System (INIS)

    Grubina, L.A.; Shavrova, Ye.N.; Vorontsova, T.V.; Vinnik, L.M.; Kuchinskaya, E.A.; Khmelevskaya, L.A.

    1999-01-01

    Immunological indices and porphyrins levels were studied in children of various ages living on the radionuclide contaminated territories. A reliable reduction of medium levels of proto- and coproporphyrins in erythrocytes of children and teenagers with the thyroid gland pathologies from radio contaminated regions was revealed. The lowest level of porphyrins was observed in children with thyroid neoplasm. The state of immune system of children with thyroid pathology was characterized by decreasing content of T-lymphocytes production and by stimulation of B-lymphocytes generation despite of the type of thyroid gland disease. Maximal changes of both porphyrins metabolism and T- and B-immune system were registered in children from the Stolin District of the Brest Region with increasing amount of incorporated cesium 137. It could be due to the complex of radio ecological factors. In another investigated groups a correlation between the immune parameters and porphyrins level from the one hand and the level of radionuclide contamination or absorbed amount of cesium 137 in organism from the other hand was not obtained

  4. Photoinduced electron transfer and photocurrent in multicomponent organic molecular films containing oriented porphyrin-fullerene dyad

    NARCIS (Netherlands)

    Kaunisto, Kimmo; Vuorinen, Tommi; Vahasalo, Heidi; Chukharev, Vladimir; Tkachenko, Nikolai V.; Efimov, Alexander; Tolkki, Antti; Lehtivuori, Heli; Lemmetyinen, Helge

    2008-01-01

    Layers of poly(3-hexylthiophene), PHT, phenyl vinyl thiophene, PVT3, poly(p-phenylene-2,3′-bis(3,2′-diphenyl)-quinoxaline-7-7′- diyl), PPQ, and covalently linked porphyrin-fullerene donor-acceptor dyad, P-F, were deposited as various multilayer films, which then were used to study photoinduced

  5. Experimental Determination of Activation Energy of Nucleophilic Aromatic Substitution on Porphyrins

    Science.gov (United States)

    Rizvi, Waqar; Khwaja, Emaad; Siddiqui, Saim; Bhupathiraju, N. V. S. Dinesh K.; Drain, Charles Michael

    2018-01-01

    A physical organic chemistry experiment is described for second-year college students. Students performed nucleophilic aromatic substitution (NAS) reactions on 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (TPPF[subscript 20]) using three different nucleophiles. Substitution occurs preferentially at the 4-position ("para")…

  6. Metabolism of manganese, iron, copper, and selenium in calves

    International Nuclear Information System (INIS)

    Ho, S.Y.

    1981-01-01

    Sixteen male Holstein calves were used to study manganese and iron metabolism. The calves were fed one of the following diets for 18 days: control, control + iron, control + manganese, and control + iron and manganese. All calves were dosed orally with manganese-54. Tissue concentrations of manganese, iron and manganese-54 were determined. Small intestinal iron was lower in calves fed the high manganese diet than in controls. Tissue manganese-54 was lower in calves fed a high manganese diet. Fecal manganese content increased in calves fed both high manganese and high manganese-high iron diets. Serum total iron was not affected by the dietary treatments. To study the effects of high dietary levels of copper and selenium on the intracellular distributions of these two elements in liver and kidney cytosol, calves were fed one of four diets for 15 days. These were 0 and 100 ppM supplemental copper and 0 and 1 ppM added selenium. The control diet containing 0.1 ppM of selenium and 15 ppM of copper. All calves were orally dosed 48 hrs prior to sacrifice with selenium-75. A high copper diet increased copper concentrations in all intracellular liver fractions and most kidney fractions. Only the effects in the liver were significant. Less copper was found in the mitochondria fractions in liver and kidney of calves fed a high selenium diet. Three major copper-binding protein peaks were separated from the soluble fractions of calf liver and kidney. Peak 1 appeared to be the major copper-binding protein in liver and kidney cytosol of copper-loaded animals. Added selenium alone or in combination with copper accentuated the copper accumulation in this peak. Most of selenium-75 was recovered in the same peak as the copper. The results of this experiment indicated that the large molecular proteins in liver and kidney cytosol of calves play an important role in copper and selenium-75 metabolism

  7. Modeling Manganese Sorption and Surface Oxidation During Filtration

    OpenAIRE

    Bierlein, Kevin Andrew

    2012-01-01

    Soluble manganese (Mn) is a common contaminant in drinking water sources. High levels of Mn can lead to aesthetic water quality problems, necessitating removal of Mn during treatment to minimize consumer complaints. Mn may be removed during granular media filtration by the â natural greensand effect,â in which soluble Mn adsorbs to manganese oxide-coated (MnOx(s)) media and is then oxidized by chlorine, forming more manganese oxide. This research builds on a previous model developed by Mer...

  8. Tapping the biotechnological potential of insect microbial symbionts: new insecticidal porphyrins.

    Science.gov (United States)

    Martinez, Ana Flávia Canovas; de Almeida, Luís Gustavo; Moraes, Luiz Alberto Beraldo; Cônsoli, Fernando Luís

    2017-06-27

    The demand for sustainable agricultural practices and the limited progress toward newer and safer chemicals for use in pest control maintain the impetus for research and identification of new natural molecules. Natural molecules are preferable to synthetic organic molecules because they are biodegradable, have low toxicity, are often selective and can be applied at low concentrations. Microbes are one source of natural insecticides, and microbial insect symbionts have attracted attention as a source of new bioactive molecules because these microbes are exposed to various selection pressures in their association with insects. Analytical techniques must be used to isolate and characterize new compounds, and sensitive analytical tools such as mass spectrometry and high-resolution chromatography are required to identify the least-abundant molecules. We used classical fermentation techniques combined with tandem mass spectrometry to prospect for insecticidal substances produced by the ant symbiont Streptomyces caniferus. Crude extracts from this bacterium showed low biological activity (less than 10% mortality) against the larval stage of the fall armyworm Spodoptera frugiperda. Because of the complexity of the crude extract, we used fractionation-guided bioassays to investigate if the low toxicity was related to the relative abundance of the active molecule, leading to the isolation of porphyrins as active molecules. Porphyrins are a class of photoactive molecules with a broad range of bioactivity, including insecticidal. The active fraction, containing a mixture of porphyrins, induced up to 100% larval mortality (LD 50  = 37.7 μg.cm -2 ). Tandem mass-spectrometry analyses provided structural information for two new porphyrin structures. Data on the availability of porphyrins in 67 other crude extracts of ant ectosymbionts were also obtained with ion-monitoring experiments. Insect-associated bacterial symbionts are a rich source of bioactive compounds. Exploring

  9. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    Science.gov (United States)

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. The anchoring bias reflects rational use of cognitive resources.

    Science.gov (United States)

    Lieder, Falk; Griffiths, Thomas L; M Huys, Quentin J; Goodman, Noah D

    2018-02-01

    Cognitive biases, such as the anchoring bias, pose a serious challenge to rational accounts of human cognition. We investigate whether rational theories can meet this challenge by taking into account the mind's bounded cognitive resources. We asked what reasoning under uncertainty would look like if people made rational use of their finite time and limited cognitive resources. To answer this question, we applied a mathematical theory of bounded rationality to the problem of numerical estimation. Our analysis led to a rational process model that can be interpreted in terms of anchoring-and-adjustment. This model provided a unifying explanation for ten anchoring phenomena including the differential effect of accuracy motivation on the bias towards provided versus self-generated anchors. Our results illustrate the potential of resource-rational analysis to provide formal theories that can unify a wide range of empirical results and reconcile the impressive capacities of the human mind with its apparently irrational cognitive biases.

  11. Correlation of Persistence, Initiative and Career Anchors Categories of Students

    Directory of Open Access Journals (Sweden)

    I A Novikova

    2008-03-01

    Full Text Available The article is devoted to the analysis of the results of comparative empirical study of persistence, initiative and Career Anchors categories of the students on the basis of the systemic-functional approach.

  12. Anchored but not internalized: shape dependent endocytosis of nanodiamond

    Science.gov (United States)

    Zhang, Bokai; Feng, Xi; Yin, Hang; Ge, Zhenpeng; Wang, Yanhuan; Chu, Zhiqin; Raabova, Helena; Vavra, Jan; Cigler, Petr; Liu, Renbao; Wang, Yi; Li, Quan

    2017-04-01

    Nanoparticle-cell interactions begin with the cellular uptake of the nanoparticles, a process that eventually determines their cellular fate. In the present work, we show that the morphological features of nanodiamonds (NDs) affect both the anchoring and internalization stages of their endocytosis. While a prickly ND (with sharp edges/corners) has no trouble of anchoring onto the plasma membrane, it suffers from difficult internalization afterwards. In comparison, the internalization of a round ND (obtained by selective etching of the prickly ND) is not limited by its lower anchoring amount and presents a much higher endocytosis amount. Molecular dynamics simulation and continuum modelling results suggest that the observed difference in the anchoring of round and prickly NDs likely results from the reduced contact surface area with the cell membrane of the former, while the energy penalty associated with membrane curvature generation, which is lower for a round ND, may explain its higher probability of the subsequent internalization.

  13. Interaction of cationic porphyrins with DNA: Importance of the number and position of the charges and minimum structural requirements for intercalation

    International Nuclear Information System (INIS)

    Sari, M.A.; Battioni, J.P.; Dupre, D.; Mansuy, D.; Le Pecq, J.B.

    1990-01-01

    Thirty-three porphyrins or metalloporphyrins corresponding to the general formula [meso-[N-methyl-4(or 3 or 2)-pyridiniumyl] n (aryl) 4-n porphyrin]M (M = H 2 , Cu II , or ClFe III ), with n = 2-4, have been synthesized and characterized by UV-visible and 1 H NMR spectroscopy and mass spectrometry. These porphyrins differ not only in the number (2-4) and position of their cationic charges but also in the steric requirements to reach even temporarily a completely planar geometry. Interaction of these porphyrins or metalloporphyrins with calf thymus DNA has been studied and their apparent affinity binding constants have been determined by use of a competition method with ethidium bromide which was applicable not only for all the free base porphyrins but also for their copper (II) or iron (III) complexes. Whatever their mode of binding may be, their apparent affinity binding constants were relatively high and a linear decrease of log K app with the number of porphyrin charges was observed. Studies of porphyrin-DNA interactions by UV and fluorescence spectroscopy, viscosimetry, and fluorescence energy transfer experiments showed that not only the tetracationic meso-tetrakis[N-methyl-4(or 3)-pyridiniumyl]porphyrins, which both involved four freely rotating meso-aryl groups, but also the corresponding tri- and dicationic porphyrins were able to intercalate into calf thymus DNA. These results show that only half of the porphyrin ring is necessary for intercalation to occur

  14. Nanostructured manganese oxide thin films as electrode material for supercapacitors

    Science.gov (United States)

    Xia, Hui; Lai, Man On; Lu, Li

    2011-01-01

    Electrochemical capacitors, also called supercapacitors, are alternative energy storage devices, particularly for applications requiring high power densities. Recently, manganese oxides have been extensively evaluated as electrode materials for supercapacitors due to their low cost, environmental benignity, and promising supercapacitive performance. In order to maximize the utilization of manganese oxides as the electrode material for the supercapacitors and improve their supercapacitive performance, the nanostructured manganese oxides have therefore been developed. This paper reviews the synthesis of the nanostructured manganese oxide thin films by different methods and the supercapacitive performance of different nanostructures.

  15. Development of a Behaviorally Anchored Rating Scale for Leadership

    Science.gov (United States)

    2018-01-01

    Research Product 2018-06 Development of a Behaviorally Anchored Rating Scale for Leadership Tatiana H. Toumbeva Krista L...anchored Rating Scale for Leadership 5a. CONTRACT NUMBER W5J9CQ-11-D-0004 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 62278 6...observer- based behavioral measure to help instructors more reliably and accurately evaluate the development of leadership attributes and competencies

  16. Talar anchor placement for modified Brostrom lateral ankle stabilization procedure.

    Science.gov (United States)

    Angirasa, Arush K; Barrett, Michael J

    2008-01-01

    The modified Brostrom procedure has been a proven procedure with excellent utility in the treatment of lateral ankle instability within limitation. Multiple variations of the original technique have been described in the literature to date. Included in these variations are differences in anchor placement, suture technique, or both. In this research study, we propose placing a bone screw anchor into the lateral shoulder of the talus rather than the typical placement at the lateral malleolus for anatomic reconstruction of the lateral ankle ligaments.

  17. Reduction of lateral loads in abutments using ground anchors

    OpenAIRE

    Laefer, Debra F.; Truong-Hong, Linh; Le, Khanh Ba

    2013-01-01

    In bridge design, economically addressing large, lateral earth pressures on bridge abutments is a major challenge. Traditional approaches employ enlargement of the abutment components to resist these pressures. This approach results in higher construction costs. As an alternative, a formal approach using ground anchors to resist lateral soil pressure on bridge abutments is proposed herein. The ground anchors are designed to minimise lateral forces at the pile cap base. Design examples for hig...

  18. Environmental conditions during the Frasnian-Fammenian mass extinction inferred from chlorophyll-derived porphyrin biomarkers.

    Science.gov (United States)

    Uveges, B. T.; Junium, C. K.; Cohen, P. A.; Boyer, D.

    2014-12-01

    The widespread mass extinction that occurred across the Frasnian- Fammenian (F-F) boundary was one of the largest losses of biodiversity in Earth's history. The F-F extinction interval is expressed in western New York State by two organic rich black shale intervals known as the Upper and Lower Kellwasser events. These shale intervals are well preserved, thermally immature, and are well constrained in age by conodont biostratigraphy, and thus provide an exceptional opportunity to study the organic material originating from the F-F boundary. In order to test hypotheses about the cause(s) and consequences of the FF biotic crisis, a broader knowledge of the organic carbon sources is needed, and a characterization of the marine primary producer communities will assist in this endeavor. One such avenue is through the study of chlorophyll-derived biomarkers (porphyrins). The organic extracts of powdered shale samples from the Kellwasser horizons were analyzed using HPLC/LC-MSn and diode array UV-Vis spectroscopy. Preliminary data from the Kellwasser intervals reveal only one porphyrin, with a mass (M+H) of 600. The UV-Vis absorbance spectrum (Soret = 405nm, α = 533nm, β = 570nm) of the metallated compound is consistent with that of a vanadyl porphyrin with a free-base (M+H) of 535. Collision-induced mass spectra displays mass losses of 43 and 57 daltons, which are consistent with an extended alkyl chain at the C-8 position. Extended alkyl chains at C-8 are exclusively associated with porphyrins derived from bacteriochlorophyll c, d or e. The presence of bacterioporphyrins is congruous with the episodic presence of anoxic and sulfidic conditions in the photic zone. What is surprising is that a bacteriochlorophyll- derived porphyrin is the most abundant in these sequences, and their study may help to elucidate the conditions surrounding the F-F mass extinction, and further constrain the fluctuations in marine oxygen content in the Upper Devonian Appalachian Basin.

  19. Adsorption characteristics of a cationic porphyrin on nanoclay at various pH.

    Science.gov (United States)

    Rice, Zachary; Bergkvist, Magnus

    2009-07-15

    Natural and synthetic porphyrin derivatives offer a range of applications including enzymatic catalysis, photosensitizers for light harvesting and chemical reactions, and molecular electronics. They exhibit unique optical spectra dominated by the presence of Soret and Q-band structures whose position and shape offer a straightforward method to characterize porphyrins in various surroundings. In many applications it is often beneficial to have porphyrins adsorbed onto a solid matrix. Applications of porphyrin-clay complexes extend to numerous biological applications including pharmaceutical drug delivery, cosmetics, and agricultural applications and thus a full understanding of porphyrin-clay surface interactions are essential. Here we investigated the adsorption behavior of meso-tetra(4-N,N,N-trimethylanilinium) porphine (TMAP) onto sodium containing, natural montmorillonite clay (Cloisite Na(+)) in characteristic biological buffers over a range of pHs (approximately 2-9). Spectroscopic analyses show a linear absorption response at acidic and basic pHs but a slight deviation at intermediate pHs. Absorption spectra for TMAP on clay showed distinct red shifts of the Soret and Q-bands compared to free TMAP for all buffer conditions indicating core pi-electron delocalization into the substituent rings. At intermediate pHs, a gradual transition between protonated/deprotonated states were seen, presumably due to higher H(+) concentration at the surface than in bulk. Results indicate TMAP adsorption to clay occurs in a monolayer fashion at low/high pH while slightly acidic/neutral pH possibly rearrange on the surface and/or form aggregates. AFM images of clay saturated with TMAP are reported and show single isolated clay sheets without aggregation, similar to clay without TMAP.

  20. Gadolinium-porphyrins: new potential magnetic resonance imaging contrast agents for melanoma detection

    Directory of Open Access Journals (Sweden)

    Daryoush Shahbazi-Gahrouei

    2006-11-01

    Full Text Available BACKGROUND: Two new porphyrin-based magnetic resonance imaging (MRI contrast agents, Gd-hematoporphyrin (Gd-H and Gd-tetra-carboranylmethoxyphenyl-porphyrin (Gd-TCP were synthesized and tested in nude mice with human melanoma (MM-138 xenografts as new melanoma contrast agents. METHODS: Subcutaneous xenografts of human melanoma cells (MM-138 were studied in 30 (five groups of six nude mice. The effect of different contrast agents (Gd-TCP, Gd-H, GdCl3 and Gd-DTPA on proton relaxation times was measured in tumors and other organs. T1 values, signal enhancement and the Gd concentration for different contrast agent solutions were also investigated. RESULTS: The porphyrin agents showed higher relaxivity compared to the clincal agent, Gd-DTPA. A significant 16% and 21% modification in T1 relaxation time of the water in human melanoma tumors grafted in the nude mice was revealed 24 hours after injection of Gd-TCP and Gd-H, respectively. The percentage of injected Gd localized to the tumor measured by inductively coupled plasma atomic emission spectrometry (ICP-AES was approximately 21% for Gd-TCP and 28% for Gd-H which were higher than that of Gd-DTPA (10%. CONCLUSIONS: The high concentration of Gd in the tumor is indicative of a selective retention of the compounds and indicates that Gd-TCP and Gd-H are promising MR imaging contrast agents for melanoma detection. Gd-porphyrins have considerable promise for further diagnostic applications in magnetic resonance imaging. KEY WORDS: MRI, porphyrin-based contrast agent, hematoporphyrin, melanoma.

  1. A comparison of lateral ankle ligament suture anchor strength.

    Science.gov (United States)

    Barber, F Alan; Herbert, Morley A; Crates, John M

    2013-06-01

    Lateral ankle ligament repairs increasingly use suture anchors instead of bone tunnels. Our purpose was to compare the biomechanical properties of a knotted and knotless suture anchor appropriate for a lateral ankle ligament reconstruction. In porcine distal fibulae, 10 samples of 2 different PEEK anchors were inserted. The attached sutures were cyclically loaded between 10N and 60N for 200 cycles. A destructive pull was performed and failure loads, cyclic displacement, stiffness, and failure mode recorded. PushLock 2.5 anchors failed before 200 cycles. PushLock 100 cycle displacement was less than Morphix 2.5 displacement (panchors completing 200 cycles was 86.5N (PushLock) and 252.1N (Morphix) (panchor breaking and suture breakage. The knotted Morphix demonstrated more displacement and greater failure strength than the knotless PushLock. The PushLock failed consistently with suture breaking. The Morphix anchor failed both by anchor breaking and by suture breaking. Copyright © 2012 European Foot and Ankle Society. Published by Elsevier Ltd. All rights reserved.

  2. Peptide-Mediated Liposome Fusion: The Effect of Anchor Positioning

    Directory of Open Access Journals (Sweden)

    Niek S. A. Crone

    2018-01-01

    Full Text Available A minimal model system for membrane fusion, comprising two complementary peptides dubbed “E” and “K” joined to a cholesterol anchor via a polyethyleneglycol spacer, has previously been developed in our group. This system promotes the fusion of large unilamellar vesicles and facilitates liposome-cell fusion both in vitro and in vivo. Whilst several aspects of the system have previously been investigated to provide an insight as to how fusion is facilitated, anchor positioning has not yet been considered. In this study, the effects of placing the anchor at either the N-terminus or in the center of the peptide are investigated using a combination of circular dichroism spectroscopy, dynamic light scattering, and fluorescence assays. It was discovered that anchoring the “K” peptide in the center of the sequence had no effect on its structure, its ability to interact with membranes, or its ability to promote fusion, whereas anchoring the ‘E’ peptide in the middle of the sequence dramatically decreases fusion efficiency. We postulate that anchoring the ‘E’ peptide in the middle of the sequence disrupts its ability to form homodimers with peptides on the same membrane, leading to aggregation and content leakage.

  3. Extreme electronic modulation of the cofacial porphyrin structural motif.

    Science.gov (United States)

    Fletcher, James T; Therien, Michael J

    2002-04-24

    The synthesis, electrochemistry, and optical spectroscopy of an extensive series of cofacial bis[(porphinato)zinc(II)] compounds are reported. These species were synthesized using sequential palladium-catalyzed cross-coupling and cobalt-mediated [2+2+2] cycloaddition reactions. This modular methodology enables facile control of the nature of macrocycle-to-macrocycle connectivity and allows unprecedented modulation of the redox properties of face-to-face porphyrin species. We report the synthesis of 5,6-bis[(5',5''-10',20'-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (1), 5,6-bis[(2'-5',10',15',20'-tetraphenylporphinato)zinc(II)]indane (2), 5-([2'-5',10',15',20'-tetraphenylporphinato]zinc(II))-6-[(5"-10'',20''-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (3), 5-([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(5' '-10' ',20' '-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (4), 5-(2'-5',10',15',20'-[tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(2''-5'',10'',15'',20''-tetraphenylporphinato)zinc(II)]indane (5), 5,6-bis([2'-5',15'-diphenyl-10',20'-(trifluoromethyl)porphinato]zinc(II))indane (6), and 5,6-bis([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))indane (7); 4-7 define the first examples of cofacial bis[(porphinato)metal] compounds in which sigma-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a beta-to-beta linkage topology. Cyclic voltammetric studies show that the electrochemically determined HOMO and LUMO energy levels of these cofacial bis(porphinato) complexes can be lowered by 780 and 945 mV, respectively, relative to the archetypal members of this class of compounds; importantly, these orbital energy levels can be modulated over well-defined increments throughout these wide potentiometric domains. Analyses of these cofacial bis

  4. LDL Receptors as Gateways for Intracellular Porphyrin Uptake

    International Nuclear Information System (INIS)

    Novick, S.; Laster, B.; Quastel, M.

    2004-01-01

    Boronated compounds are currently being studied for possible use in Boron Neutron Capture Therapy (BNCT). We found that one of these agents, BOPP (tetrakis-carborane-carboxylate, esters of 2,4-bis (a,b- dihydroxyethyl) deuteroporphyrin IX), could also be labeled with indium (In-BOPP) and, therefore, could also be used potentially to transport high Z atoms into tumor cell DNA for AET (Auger Electron Therapy). In order to assess the uptake of these agents into cells, the role of the LDL receptor in the intracellular accumulation of BOPP and In-BOPP was investigated. Pre-incubation of V-79 Chinese hamster cells in medium containing delipidized fetal bovine serum (FBS) markedly increased the subsequent uptake of intracellular boron transported by both BOPP and In-BOPP when compared with cells that had been pre-incubated with medium containing 10% normal FBS (lipidized). The increased uptake was characterized by elevated levels of receptor, and greater affinity was shown for both BOPP and In-BOPP, although less marked with the latter. Positive cooperativity was demonstrated by sigmoid saturation curves, Scatchard analysis and Hill plots. Increasing the amount of LDL in the incubation medium had a relatively small effect on the total accumulation of either indium or boron atoms inside the cell. Furthermore, chemical acetylation of LDL did not decrease the intracellular uptake of either boron or indium transported by BOPP or In-BOPP. It is thus concluded that BOPP and In-BOPP preferentially enter the cells directly by way of the LDL receptor and that only a small fraction of these molecules are transported into the cells indirectly using serum LDLs as their carriers. These data suggest a novel way of bringing greater amounts of boron and indium (and perhaps other agents) into tissues. Porphyrins can be used to transport different agents into tumor cells because they are tumor affinic molecules. Tumors express a higher number of LDL receptors than do most normal tissues

  5. On the Robustness of Anchoring Effects in WTP and WTA Experiments

    OpenAIRE

    Drew Fudenberg; David K Levine; Zacharias Maniadis

    2010-01-01

    We reexamine the effects of the anchoring manipulation of Ariely, Loewenstein, and Prelec (2003) on the evaluation of common market goods and find very weak anchoring effects. We perform the same manipulation on the evaluation of binary lotteries, and find no anchoring effects at all. This suggests limits on the robustness of anchoring effects. (JEL C91, D12, D44)

  6. The Effect of Mini and Midi Anchor Tests on Test Equating

    Science.gov (United States)

    Arikan, Çigdem Akin

    2018-01-01

    The main purpose of this study is to compare the test forms to the midi anchor test and the mini anchor test performance based on item response theory. The research was conducted with using simulated data which were generated based on Rasch model. In order to equate two test forms the anchor item nonequivalent groups (internal anchor test) was…

  7. Pyramidal anchor stone from Baga waters of Goa, west coast of India

    Digital Repository Service at National Institute of Oceanography (India)

    Tripati, S.

    . Pyramidal anchor stones have an apex hole which goes up to the round hole, however Goa anchor stone has no such perforation, but, instead has a rectangular cutting on the apex. The anchor stone is compared with Greek pyramidal anchor stones, and probably...

  8. Failure Capacity Evaluation for Anchor System of NPP Facilities by using a Shaking Table Test

    International Nuclear Information System (INIS)

    Kwon, Hyung O; Jung, Min Ki; Park, Jin Wan; Lim, Ji Hoon

    2010-02-01

    This study investigate the destructive influence of crack locations on the anchor performance to evaluate the seismic performance of NPP equipment anchored on damaged concrete. For this purpose, small-scale specimens were fabricated according to the following three cases: 1) with a non-damaged anchor; 2) with cracks running through the anchor; and 3) with cracks along the expected corn-shape fracture away from the anchor. The result verified with the finite element method is as follows: In the first and second cases that is, with a non-damaged anchor and with cracks running through the anchor destruction occurred at the anchor steel. In the third case that is, with cracks around the anchor, a 30% decline in the seismic performance was identified. This result indicates that evaluation of seismic performance and relevant reinforcement are required when cracks occur away from the anchor along the expected destructive surface

  9. Use of the ROC anchor in foot and ankle surgery. A retrospective study.

    Science.gov (United States)

    Kuwada, G T

    1999-05-01

    A retrospective study was conducted on the use of the ROC (Radial Osteo Compression) soft-tissue anchor in foot and ankle surgery. This article describes how the anchor is deployed, problematic aspects of using the anchor, and complications and success rates associated with the anchor in ankle stabilizations, posterior tibial tendon reconstruction, peroneus brevis tendon reconstruction after fracture of the base of the fifth metatarsal, and detachment and reattachment of the Achilles tendon. The ROC anchor consists of the anchor with nonabsorbable suture attached to the shaft, the deployment handle, and drill bits. The anchor and shaft are snapped into the deployment handle and inserted into the drill hole. Compression of the trigger deploys the anchor into the hole. The ROC anchor was found to be reliable, useful, and relatively easy to deploy, with outcomes similar to those of other soft-tissue anchors.

  10. Assembly of individual TiO2-C60/porphyrin hybrid nanoparticles for enhancement of photoconversion efficiency

    International Nuclear Information System (INIS)

    Jang, Jae Kwon; Park, Se Ho; Song, Hyunjoon; Park, Joon T; Kim, Chulwoo; Ko, Jaejung; Seo, Won Seok

    2011-01-01

    Rational organization of porphyrin and C 60 on the electrode surface in photovoltaic structures is essential to yield high quantum efficiency. In the present work, individual TiO 2 nanoparticles were modified by introducing C 60 and porphyrin units on the surface, and then electrophoretically deposited on an ITO/SnO 2 electrode. The morphology of the photoactive layer on the electrode was significantly different from that of the layer produced as a result of separate deposition of C 60 and porphyrin. The maximum incident photon to current efficiency of the resulting electrode approached 88% at 410 nm, which is the highest value among molecule-based photovoltaic cells reported to date. This indicates that molecular assembly of the C 60 and porphyrin units on the individual nanoparticles through strong chemical attachment is a key factor in improving effective electron transfer between the photoactive units and the electrodes.

  11. Battery recycling: recovery of manganese in the form of electrolytic manganese dioxide

    International Nuclear Information System (INIS)

    Roriz, Elizabeth Rodrigues Rangel; Von Krüge, Paulo; Espinosa, Denise Crocce Romano; Tenorio, Jorge Alberto Soares

    2010-01-01

    This work seeks to verify the possibility of using depleted batteries as a source of manganese applying the electrolytic process, considering the growing demand for products containing manganese in their composition. It was used an electrolyte solution containing the metal ions: Ca (270mg / L), Ni (3000 mg / L), Co (630 mg / L), Mn (115.300 mg / L) , Ti (400 mg / L) and Pb (20 mg / L) in concentrated sulfuric acid. The production of electrolytic manganese dioxide (EMD) was performed through galvanization using a stabilized source that monitored the potential of the working electrode. It was used an electrode of lead and two counter electrodes of graphite at a temperature of 98 deg C (± 2 deg C) and current density of 1.69A.dm"-"2. The material obtained was analyzed through the process of X-ray fluorescence spectrometry and X-ray diffraction. The results indicated that it is possible to obtain electrolytic manganese dioxide with a purity of about 94% and that the main allotropic variety obtained under the conditions of the experiment was the ε-MnO_2. (author)

  12. Controlled intracellular generation of reactive oxygen species in human mesenchymal stem cells using porphyrin conjugated nanoparticles

    Science.gov (United States)

    Lavado, Andrea S.; Chauhan, Veeren M.; Alhaj Zen, Amer; Giuntini, Francesca; Jones, D. Rhodri E.; Boyle, Ross W.; Beeby, Andrew; Chan, Weng C.; Aylott, Jonathan W.

    2015-08-01

    Nanoparticles capable of generating controlled amounts of intracellular reactive oxygen species (ROS), that advance the study of oxidative stress and cellular communication, were synthesized by functionalizing polyacrylamide nanoparticles with zinc(ii) porphyrin photosensitisers. Controlled ROS production was demonstrated in human mesenchymal stem cells (hMSCs) through (1) production of nanoparticles functionalized with varying percentages of Zn(ii) porphyrin and (2) modulating the number of doses of excitation light to internalized nanoparticles. hMSCs challenged with nanoparticles functionalized with increasing percentages of Zn(ii) porphyrin and high numbers of irradiations of excitation light were found to generate greater amounts of ROS. A novel dye, which is transformed into fluorescent 7-hydroxy-4-trifluoromethyl-coumarin in the presence of hydrogen peroxide, provided an indirect indicator for cumulative ROS production. The mitochondrial membrane potential was monitored to investigate the destructive effect of increased intracellular ROS production. Flow cytometric analysis of nanoparticle treated hMSCs suggested irradiation with excitation light signalled controlled apoptotic cell death, rather than uncontrolled necrotic cell death. Increased intracellular ROS production did not induce phenotypic changes in hMSC subcultures.Nanoparticles capable of generating controlled amounts of intracellular reactive oxygen species (ROS), that advance the study of oxidative stress and cellular communication, were synthesized by functionalizing polyacrylamide nanoparticles with zinc(ii) porphyrin photosensitisers. Controlled ROS production was demonstrated in human mesenchymal stem cells (hMSCs) through (1) production of nanoparticles functionalized with varying percentages of Zn(ii) porphyrin and (2) modulating the number of doses of excitation light to internalized nanoparticles. hMSCs challenged with nanoparticles functionalized with increasing percentages of Zn

  13. Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and {sup 1}O{sub 2} generation

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Jie; Jiang, Lijun; Chan, Chi-Fai [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Tsoi, Tik-Hung [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Shiu, Kwok-Keung; Kwong, Daniel W.J. [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Wong, Wai-Kwok, E-mail: wkwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

    2017-04-15

    Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

  14. Three manganese oxide-rich marine sediments harbor similar communities of acetate-oxidizing manganese-reducing bacteria.

    Science.gov (United States)

    Vandieken, Verona; Pester, Michael; Finke, Niko; Hyun, Jung-Ho; Friedrich, Michael W; Loy, Alexander; Thamdrup, Bo

    2012-11-01

    Dissimilatory manganese reduction dominates anaerobic carbon oxidation in marine sediments with high manganese oxide concentrations, but the microorganisms responsible for this process are largely unknown. In this study, the acetate-utilizing manganese-reducing microbiota in geographically well-separated, manganese oxide-rich sediments from Gullmar Fjord (Sweden), Skagerrak (Norway) and Ulleung Basin (Korea) were analyzed by 16S rRNA-stable isotope probing (SIP). Manganese reduction was the prevailing terminal electron-accepting process in anoxic incubations of surface sediments, and even the addition of acetate stimulated neither iron nor sulfate reduction. The three geographically distinct sediments harbored surprisingly similar communities of acetate-utilizing manganese-reducing bacteria: 16S rRNA of members of the genera Colwellia and Arcobacter and of novel genera within the Oceanospirillaceae and Alteromonadales were detected in heavy RNA-SIP fractions from these three sediments. Most probable number (MPN) analysis yielded up to 10(6) acetate-utilizing manganese-reducing cells cm(-3) in Gullmar Fjord sediment. A 16S rRNA gene clone library that was established from the highest MPN dilutions was dominated by sequences of Colwellia and Arcobacter species and members of the Oceanospirillaceae, supporting the obtained RNA-SIP results. In conclusion, these findings strongly suggest that (i) acetate-dependent manganese reduction in manganese oxide-rich sediments is catalyzed by members of taxa (Arcobacter, Colwellia and Oceanospirillaceae) previously not known to possess this physiological function, (ii) similar acetate-utilizing manganese reducers thrive in geographically distinct regions and (iii) the identified manganese reducers differ greatly from the extensively explored iron reducers in marine sediments.

  15. Long-lived, charge-shift states in heterometallic, porphyrin-based dendrimers formed via click chemistry.

    Science.gov (United States)

    Le Pleux, Loïc; Pellegrin, Yann; Blart, Errol; Odobel, Fabrice; Harriman, Anthony

    2011-05-26

    A series of multiporphyrin clusters has been synthesized and characterized in which there exists a logical gradient for either energy or electron transfer between the porphyrins. A central free-base porphyrin (FbP), for example, is equipped with peripheral zinc(II) porphyrins (ZnP) which act as ancillary light harvesters and transfer excitation energy to the FbP under visible light illumination. Additional energy-transfer steps occur at the triplet level, and the series is expanded by including magnesium(II) porphyrins and/or tin(IV) porphyrins as chromophores. Light-induced electron transfer is made possible by incorporating a gold(III) porphyrin (AuP(+)) into the array. Although interesting by themselves, these clusters serve as control compounds by which to understand the photophysical processes occurring within a three-stage dendrimer comprising an AuP(+) core, a second layer formed from four FbP units, and an outer layer containing 12 ZnP residues. Here, illumination into a peripheral ZnP leads to highly efficient electronic energy transfer to FbP, followed by charge transfer to the central AuP(+). Charge recombination within the resultant charge-shift state is intercepted by secondary hole transfer to the ZnP, which occurs with a quantum yield of around 20%. The final charge-shift state survives for some microseconds in fluid solution at room temperature.

  16. Synthesis and characterization of a new class of glycosylated porphyrins bearing the RGD moiety and their application in photodynamic therapy

    International Nuclear Information System (INIS)

    Chaleix, Vincent

    2003-01-01

    The use of porphyrins and analogues as photosensitisers together with visible light is a new treatment of tumors (photodynamic therapy, PDT). Carbohydrate-substituted porphyrins are in this domain very promising compounds. In addition, it is known that endothelial cells of the neo-vascularisation in tumors express αVβ3 integrin. Extracellular domains of this transmembrane glycoprotein are able to bind components of the extracellular matrix (ECM) and more precisely the sequence Arg-Gly-Asp. With the aim of their utilization in photodynamic therapy of cancers, we describe the synthesis and characterization (UV-Visible, mass, NMR) of new glucosylated porphyrins bearing the RGD moiety. The first synthesised compounds were derived from tritolyl and tri-glucosyl-aryl-porphyrins where the peptidic moiety is linked to the phenyl group by a spacer arm by means of a solid phase reaction.. The second series consists of glucosylated porphyrin derivatives bearing a cyclical unsaturated pentapeptide including RGD sequence, obtained by ring closing metathesis in solid phase. We have also synthesized a dimer in which the two glucosylated porphyrins are linked by the RGD sequence. These compounds produced 1 O 2 and photo-cyto-toxicities against K562 leukemia cell line were favourably compared to Photofrin II R . Due to their sensitising abilities, these compounds are of considerable interest for photodynamic therapy. (author) [fr

  17. Proof of concept for molecular velcro based on the attractive interaction between porphyrin and pyridine containing copolymers

    Directory of Open Access Journals (Sweden)

    M. Sievers

    2018-06-01

    Full Text Available In this short communication, we investigated the synthesis and mixing of porphyrin and pyridine functionalized copolymers as a proof of concept for a velcro-like interaction. A functionalized porphyrin monomer with one polymerizable side chain was synthesized following a rational synthetic pathway. Subsequent copolymerization and careful removal of residual free porphyrin led to poly(n-butyl acrylate-co-5,10,15-triphenyl-20-(3-vinylphenylporphyrin. The immobilized porphyrin was transformed into the corresponding zinc(II complex, which is capable of the coordinative binding of one pyridine moiety. Complete metallation was proven by absorption spectroscopy. 4-Vinylpyridine was immobilized by copolymerization with n-butyl acrylate, too. Via controlled radical polymerization conditions, the molecular weight of poly(n-butyl acrylate-co-4-vinylpyridine was limited to one tenth of the molecular weight of the porphyrin containing copolymer. This large difference in the molecular weight easily allowed identifying the polymers in the mixture of both. With the help of diffusion ordered nuclear magnetic resonance spectroscopy, the complete and temperature-stable precipitation of the porphyrin containing copolymer was observed, proving the expected attractive interaction and supramolecular network formation.

  18. Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa

    Directory of Open Access Journals (Sweden)

    Nhi-Thi Pham

    2015-07-01

    Full Text Available We compared antioxidant responses and regulation of porphyrin metabolism in rice plants treated with oxyfluorfen (OF or methyl viologen (MV. Plants treated with MV exhibited not only greater increases in conductivity and malondialdehyde but also a greater decline in Fv/Fm, compared to plants treated with OF. MV-treated plants had greater increases in activities of superoxide dismutase (SOD and catalase (CAT as well as transcript levels of SODA and CATA than OF-treated plants after 28 h of the treatments, whereas increases in ascorbate peroxidase (APX activity and transcript levels of APXA and APXB were greater in OF-treated plants. Both OF- and MV-treated plants resulted in not only down-regulation of most genes involved in porphyrin biosynthesis but also disappearance of Mg-porphyrins during the late stage of photooxidative stress. By contrast, up-regulation of heme oxygenase 2 (HO2 is possibly part of an efficient antioxidant response to compensate photooxidative damage in both treatments. Our data show that down-regulated biosynthesis and degradation dynamics of porphyrin intermediates have important roles in photoprotection of plants from perturbed porphyrin biosynthesis and photosynthetic electron transport. This study suggests that porphyrin scavenging as well as strong antioxidative activities are required for mitigating reactive oxygen species (ROS production under photooxidative stress caused by OF and MV.

  19. Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa.

    Science.gov (United States)

    Pham, Nhi-Thi; Kim, Jin-Gil; Jung, Sunyo

    2015-07-21

    We compared antioxidant responses and regulation of porphyrin metabolism in rice plants treated with oxyfluorfen (OF) or methyl viologen (MV). Plants treated with MV exhibited not only greater increases in conductivity and malondialdehyde but also a greater decline in Fv/Fm, compared to plants treated with OF. MV-treated plants had greater increases in activities of superoxide dismutase (SOD) and catalase (CAT) as well as transcript levels of SODA and CATA than OF-treated plants after 28 h of the treatments, whereas increases in ascorbate peroxidase (APX) activity and transcript levels of APXA and APXB were greater in OF-treated plants. Both OF- and MV-treated plants resulted in not only down-regulation of most genes involved in porphyrin biosynthesis but also disappearance of Mg-porphyrins during the late stage of photooxidative stress. By contrast, up-regulation of heme oxygenase 2 (HO2) is possibly part of an efficient antioxidant response to compensate photooxidative damage in both treatments. Our data show that down-regulated biosynthesis and degradation dynamics of porphyrin intermediates have important roles in photoprotection of plants from perturbed porphyrin biosynthesis and photosynthetic electron transport. This study suggests that porphyrin scavenging as well as strong antioxidative activities are required for mitigating reactive oxygen species (ROS) production under photooxidative stress caused by OF and MV.

  20. Synthesis and characterization of monomeric manganese(II) and ...

    African Journals Online (AJOL)

    The geometry at the manganese center is seven-coordinate, and is best described as a capped trigonal pyramid with the water molecule forming the cap and the six nitrogen atoms of the tpen ligand occupying the pyramidal sites. The manganese atom and the water molecule lie on a crystallographic twofold axis.

  1. Adsorptive removal of manganese, arsenic and iron from groundwater

    NARCIS (Netherlands)

    Buamah, R.

    2009-01-01

    Arsenic, manganese and iron in drinking water at concentrations exceeding recommended guideline values pose health risks and aesthetic defects. Batch and pilot experiments on manganese adsorption equilibrium and kinetics using iron-oxide coated sand (IOCS), Aquamandix and other media have been

  2. Gastroprotective Properties of Manganese Chloride on Acetic Acid

    African Journals Online (AJOL)

    Dr Olaleye

    Drugs with multiple mechanisms of protective action may be effective in minimizing ... that Manganese had dose and treatment duration dependent effect on healing of ulcerated stomach. .... The stomach was bathed with normal saline ..... Arnaud, J., and Favier, A. (1995): "Copper, iron, manganese ... Experimental Toxic.

  3. Behavior of manganese ion in basic medium: consequence for the ...

    African Journals Online (AJOL)

    Dr. J. T. Ekanem

    2006-01-25

    Jan 25, 2006 ... adding manganese chloride or manganese sulfate to sodium hydroxyde or sodium carbonate in aqueous ... carbonate (1 M). The release of p- nitrophenoxide anion (pNP) was quantified at. 420 nm using a spectrophotometer (Spectronic. Genesis 5). .... These curves were bell-type with an ascending.

  4. Bioconcentration of manganese and iron in Panaeoloideae Sing

    NARCIS (Netherlands)

    Stijve, T.; Blake, C.

    1994-01-01

    According to literature, the manganese content of most basidiomycetes fluctuates between 10 and 60 mg/kg, whereas the iron levels range from 100-500 mg/kg (both expressed on dry weight). The present authors report that bioconcentration of manganese is a distinguishing feature of the Panaeoloideae,

  5. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Barium calcium manganese strontium... Specific Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium calcium...

  6. Characterization and concentration of manganese ore waste

    International Nuclear Information System (INIS)

    Lima, Rosa Malena Fernandes; Pereira, Eder Esper; Reis, Erica Linhares; Silva, Glaucia Regina da

    2010-01-01

    In this work is presented the tests results of characterization and concentration by gravity and flotation methods carried out with a manganese sample waste. By optical microscopy, SEM/EDS and X-ray diffractometry were identified the Mn minerals spessartite (20%), tephroite (15%), rhodonite (5%), rhodochrosite and carbonates minerals (29%), opaque minerals and others (16%), micaceus minerals (6%) and quartz (4%). It was obtained Mn metallurgical recovery of 58% with Mn concentrate contents varying from 30 to 32.5%. The concentrates SiO_2 contents of flotation were until 1.5% smaller than those contents of gravity method concentrates. (author)

  7. Manganese accumulation in the brain: MR imaging

    Energy Technology Data Exchange (ETDEWEB)

    Uchino, A.; Nomiyama, K.; Takase, Y.; Nakazono, T.; Nojiri, J.; Kudo, S. [Saga Medical School, Department of Radiology, Saga (Japan); Noguchi, T. [Kyushu University, Department of Clinical Radiology, Graduate School of Medicine, Fukuoka (Japan)

    2007-09-15

    Manganese (Mn) accumulation in the brain is detected as symmetrical high signal intensity in the globus pallidi on T1-weighted MR images without an abnormal signal on T2-weighted images. In this review, we present several cases of Mn accumulation in the brain due to acquired or congenital diseases of the abdomen including hepatic cirrhosis with a portosystemic shunt, congenital biliary atresia, primary biliary cirrhosis, congenital intrahepatic portosystemic shunt without liver dysfunction, Rendu-Osler-Weber syndrome with a diffuse intrahepatic portosystemic shunt, and patent ductus venosus. Other causes of Mn accumulation in the brain are Mn overload from total parenteral nutrition and welding-related Mn intoxication. (orig.)

  8. [Study on the aggregation behavior of cationic porphyrins and their interaction with ctDNA].

    Science.gov (United States)

    Ma, Hong-Min; Chen, Xin; Sun, Shu-Ting; Zhang, Li-Na; Wu, Dan; Zhu, Pei-Hua; Li, Yan; Du, Bin; Wei, Qin

    2009-02-01

    Interest in the interaction between cationic porphyrins, particularly derivatives of meso-tetra(N-methylpyridinium-4-yl) porphyrin(TMPyP), and DNA abounds because they are versatile DNA-binding agents that could find application in photodynamic therapy, cancer detection, artificial nucleases, virus inhibition and so on. The interaction of two water-soluble cationic porphyrins, meso-tetrakis(4-N, N, N-trimethylanilinium) porphyrin (TMAP) and 5-phenyl-10,15,20-tris[4-(N-methyl) pyridinium]porphyrin (TriMPyP), with calf thymus DNA (ctDNA) was studied by UV-Vis absorption spectroscopy, fluorescence spectroscopy and resonance light scattering technique. TriMPyP forms aggregate in water due to the molecular asymmetry while TMAP exists as monomers. At lower concentrations of ctDNA (R > 1, R = c(TMAP)/c(DNA) base pair), the interaction of TMAP with DNA leads to significant hypochromicity and bathochromic shift of absorption spectra. And the fluorescence of TMAP was quenched while it showed enhanced resonance light scattering signals. But the extent of enhancement of resonance light scattering signals is very small, so the aggregate of TMAP is not very high. These observations indicate the self-stacking of TMAP along the DNA surface. At higher concentrations of ctDNA (R TMAP association with DNA is via outside binding which is accompanied with hyperchromic effect and fluorescence enhancement while the resonance light scattering signals is reduced. DNA addition decreases the fluorescence intensity of TriMPyP and it shifts the peak to the higher wavelengths (red shift). The interaction with DNA promotes the aggregation of TriMPyP and no simple outside binding is observed even at higher concentrations of ctDNA. The steric effect of molecular distortion constrains the intercalation or further binding to DNA. The effect of ionic strength on the interaction was investigated at two DNA concentrations, 1.2 and 24.0 micromol x L(-1), for TMAP. The Interactions of both porphyrins

  9. Alternative irradiation system for efficiency manganese bath determination

    Energy Technology Data Exchange (ETDEWEB)

    Passos Leite, Sandro, E-mail: sandro@ird.gov.b [Programa de Engenharia Nuclear/COPPE, Universidade Federal do Rio de Janeiro, Ilha do Fundao, Caixa Postal 68509, 21945-970, Rio de Janeiro, RJ (Brazil); Wagner Pereira, Walsan, E-mail: walsan@ird.gov.b [Instituto de Radioprotecao e Dosimetria LNMRI/IRD/CNEN, Av. Salvador Allende, s/no, Recreio dos Bandeirantes, CEP: 22780-160, Rio de Janeiro (Brazil); Xavier da Silva, Ademir, E-mail: ademir@con.ufrj.b [Programa de Engenharia Nuclear/COPPE, Universidade Federal do Rio de Janeiro, Ilha do Fundao, Caixa Postal 68509, 21945-970, Rio de Janeiro, RJ (Brazil); Simoes da Fonseca, Evaldo, E-mail: evaldo@ird.gov.b [Instituto de Radioprotecao e Dosimetria LNMRI/IRD/CNEN, Av. Salvador Allende, s/no, Recreio dos Bandeirantes, CEP: 22780-160, Rio de Janeiro (Brazil); Souza Patrao, Karla Cristina de, E-mail: karla@ird.gov.b [Instituto de Radioprotecao e Dosimetria LNMRI/IRD/CNEN, Av. Salvador Allende, s/no, Recreio dos Bandeirantes, CEP: 22780-160, Rio de Janeiro (Brazil)

    2010-12-15

    An alternative irradiation system, which works with a radionuclide neutron source and manganese sulphate solution volume have been proposed for efficiency determination of a Manganese Bath System (MBS). This irradiation system was designed by simulation with MCNP5 code, considering a californium neutron source in several manganese sulphate volumes and different neutron reflectors. Although its solution specific activity are less than those in nuclear reactors, the simulation results have showed that the irradiation system proposed takes a manganese neutron capture increase up to 200 times when it compared to manganese neutron capture from a MBS whose diameter is about 100 cm. That becomes possible to use those samples for some of the absolute specific activity measuring methods.

  10. Assessing tether anchor labeling and usability in pickup trucks.

    Science.gov (United States)

    Klinich, Kathleen D; Manary, Miriam A; Malik, Laura A; Flannagan, Carol A; Jermakian, Jessica S

    2018-04-03

    The objective of this study was to investigate vehicle factors associated with child restraint tether use and misuse in pickup trucks and evaluate 4 labeling interventions designed to educate consumers on proper tether use. Volunteer testing was performed with 24 subjects and 4 different pickup trucks. Each subject performed 8 child restraint installations among the 4 pickups using 2 forward-facing restraints: a Britax Marathon G4.1 and an Evenflo Triumph. Vehicles were selected to represent 4 different implementations of tether anchors among pickups: plastic loop routers (Chevrolet Silverado), webbing routers (Ram), back wall anchors (Nissan Frontier), and webbing routers plus metal anchors (Toyota Tundra). Interventions included a diagram label, Quick Response (QR) Code linked to video instruction, coordinating text label, and contrasting text tag. Subjects used the child restraint tether in 93% of trials. However, tether use was completely correct in only 9% of trials. An installation was considered functional if the subject attached the tether to a tether anchor and had a tight installation (ignoring routing and head restraint position); 28% of subjects achieved a functional installation. The most common installation error was attaching the tether hook to the anchor/router directly behind the child restraint (near the top of the seatback) rather than placing the tether through the router and attaching it to the anchor in the adjacent seating position. The Nissan Frontier, with the anchor located on the back wall of the cab, had the highest rate of correct installations but also had the highest rate of attaching the tether to components other than the tether anchor (seat adjustor, child restraint storage hook, around head restraint). None of the labeling interventions had a significant effect on correct installation; not a single subject scanned the QR Code to access the video instruction. Subjects with the most successful installations spent extensive time

  11. Diffusion abnormalities of the globi pallidi in manganese neurotoxicity

    Energy Technology Data Exchange (ETDEWEB)

    McKinney, Alexander M.; Filice, Ross W.; Teksam, Mehmet; Casey, Sean; Truwit, Charles; Clark, H. Brent; Woon, Carolyn; Liu, Hai Ying [Department of Radiology, Medical School, Box 292, 420 Delaware Street S.E., 55455, Minneapolis, MN (United States)

    2004-04-01

    Manganese is an essential trace metal required for normal central nervous system function, which is toxic when in excess amounts in serum. Manganese neurotoxicity has been demonstrated in patients with chronic liver/biliary failure where an inability to excrete manganese via the biliary system causes increased serum levels, and in patients on total parenteral nutrition (TPN), occupational/inhalational exposure, or other source of excess exogenous manganese. Manganese has been well described in the literature to deposit selectively in the globi pallidi and to induce focal neurotoxicity. We present a case of a 53-year-old woman who presented for a brain MR 3 weeks after liver transplant due to progressively decreasing level of consciousness. The patient had severe liver failure by liver function tests and bilirubin levels, and had also been receiving TPN since the transplant. The MR demonstrated symmetric hyperintensity on T1-weighted images in the globi pallidi. Apparent diffusion coefficient (ADC) map indicated restricted diffusion in the globi pallidi bilaterally. The patient eventually succumbed to systemic aspergillosis 3 days after the MR. The serum manganese level was 195 mcg/l (micrograms per liter) on postmortem exam (over 20 times the upper limits of normal). The patient was presumed to have suffered from manganese neurotoxicity since elevated serum manganese levels have been shown in the literature to correlate with hyperintensity on T1-weighted images, neurotoxicity symptoms, and focal concentration of manganese in the globi pallidi. Neuropathologic sectioning of the globi pallidi at autopsy was also consistent with manganese neurotoxicity. (orig.)

  12. Simplified design of flexible expansion anchored plates for nuclear structures

    International Nuclear Information System (INIS)

    Mehta, N.K.; Hingorani, N.V.; Longlais, T.G.; Sargent and Lundy, Chicago, IL)

    1984-01-01

    In nuclear power plant construction, expansion anchored plates are used to support pipe, cable tray and HVAC duct hangers, and various structural elements. The expansion anchored plates provide flexibility in the installation of field-routed lines where cast-in-place embedments are not available. General design requirements for expansion anchored plate assemblies are given in ACI 349, Appendix B (1). The manufacturers recommend installation procedures for their products. Recent field testing in response to NRC Bulletin 79-02 (2) indicates that anchors, installed in accordance with manufacturer's recommended procedures, perform satisfactorily under static and dynamic loading conditions. Finite element analysis is a useful tool to correctly analyze the expansion anchored plates subject to axial tension and biaxial moments, but it becomes expensive and time-consuming to apply this tool for a large number of plates. It is, therefore, advantageous to use a simplified method, even though it may be more conservative as compared to the exact method of analysis. This paper presents a design method referred to as the modified rigid plate analysis approach to simplify both the initial design and the review of as-built conditions

  13. Reduction of ripening time of full-scale manganese removal filters with manganese oxide-coated media

    NARCIS (Netherlands)

    Bruins, J.H.; Petrusevski, B.; Slokar, Y.M.; Huysman, K.; Joris, K.; Kruithof, J.C.; Kennedy, M.D.

    2015-01-01

    Effective manganese removal by conventional aeration-filtration with virgin filter media requires a long ripening time. The aim of this study was to assess the potential of manganese oxide-coated media to shorten the ripening time of filters with virgin media, under practical conditions. A full

  14. Communication: Charge-transfer rate constants in zinc-porphyrin-porphyrin-derived dyads: A Fermi golden rule first-principles-based study

    International Nuclear Information System (INIS)

    Manna, Arun K.; Dunietz, Barry D.

    2014-01-01

    We investigate photoinduced charge transfer (CT) processes within dyads consisting of porphyrin derivatives in which one ring ligates a Zn metal center and where the rings vary by their degree of conjugation. Using a first-principles approach, we show that molecular-scale means can tune CT rates through stabilization affected by the polar environment. Such means of CT tuning are important for achieving high efficiency optoelectronic applications using organic semiconducting materials. Our fully quantum mechanical scheme is necessary for reliably modeling the CT process across different regimes, in contrast to the pervading semi-classical Marcus picture that grossly underestimates transfer in the far-inverted regime

  15. Ferromagnetic properties of manganese doped iron silicide

    Science.gov (United States)

    Ruiz-Reyes, Angel; Fonseca, Luis F.; Sabirianov, Renat

    We report the synthesis of high quality Iron silicide (FeSi) nanowires via Chemical Vapor Deposition (CVD). The materials exhibits excellent magnetic response at room temperature, especially when doped with manganese showing values of 2.0 X 10-04 emu for the FexMnySi nanowires. SEM and TEM characterization indicates that the synthesized nanowires have a diameter of approximately 80nm. MFM measurements present a clear description of the magnetic domains when the nanowires are doped with manganese. Electron Diffraction and XRD measurements confirms that the nanowires are single crystal forming a simple cubic structure with space group P213. First-principle calculations were performed on (111) FeSi surface using the Vienna ab initio simulation package (VASP). The exchange correlations were treated under the Ceperley-Alder (CA) local density approximation (LDA). The Brillouin Zone was sampled with 8x8x1 k-point grid. A total magnetic moment of about 10 μB was obtained for three different surface configuration in which the Iron atom nearest to the surface present the higher magnetization. To study the effect of Mn doping, Fe atom was replaced for a Mn. Stronger magnetization is presented when the Mn atom is close to the surface. The exchange coupling constant have been evaluated calculating the energy difference between the ferromagnetic and anti-ferromagnetic configurations.

  16. Iron and manganese removal from drinking water

    Directory of Open Access Journals (Sweden)

    Daniela-Elena Pascu

    2016-04-01

    Full Text Available The purpose of the present study is to find a suitable method for removal of iron and manganese from ground water, considering bothlocal economical and environmental aspects. Ground water is a highly important source of drinking water in Romania. Ground water is naturally pure from bacteria at a 25 m depth or more. However, solved metals may occur and if the levels are too high, the water is not drinkable. Different processes, such as electrochemical and combined electrochemical-adsorption methods have been applied to determine metals content in accordance to reports of National Water Agency from Romania (ANAR. Every water source contains dissolved or particulate compounds. The concentrations of these compounds can affect health, productivity, compliance requirements, or serviceability and cannot be economically removed by conventional filtration means. In this study, we made a comparison between the electrochemical and adsorption methods (using membranes. Both methods have been used to evaluate the efficiency of iron and manganese removal at various times and temperatures. We used two membrane types: composite and cellulose, respectively. Different approaches, including lowering the initial current density and increasing the initial pH were applied. Reaction kinetics was achieved using mathematical models: Jura and Temkin.

  17. In vitro enzyme-mimic activity and in vivo therapeutic potential of HSJ-0017, a novel Mn porphyrin-based antioxidant enzyme mimic.

    Science.gov (United States)

    Li, Bao-qiu; Dong, Xin; Li, Na; Gao, Ji-you; Yuan, Qiang; Fang, Shi-hong; Gong, Xian-chang; Wang, Shu-juan; Wang, Feng-shan

    2014-10-01

    Manganese (III) 5, 10, 15, 20-tetrakis [3-(2-(2-methoxy)-ethoxy) ethoxy] phenyl porphyrin chloride, designated HSJ-0017, is a novel antioxidant enzyme mimic. The aim of the present study was to investigate the enzyme-mimic activity and the therapeutic potential of HSJ-0017 in free radical-related diseases. Superoxide dismutase (SOD) mimic activity was measured by the nitroblue tetrazolium chloride monohydrate reduction assay. Catalase (CAT) mimic activity was measured based on the decomposition of hydrogen peroxide. The antitumor, radioprotective and chemoprotective effects of HSJ-0017 were evaluated in H22 or S180 tumor-bearing Kunming mice. The anti-inflammatory and hepatoprotective effects were, respectively, evaluated in histamine-induced edema model and CCl4-induced hepatic damage model in Wistar rats. HSJ-0017 over a concentration range of 0.001-10 µmol/L significantly inhibited the generation of superoxide anion. Significant hydrogen peroxide scavenging activity was observed when the concentration of HSJ-0017 was higher than 0.01 µmol/L. HSJ-0017 at a dose of 3.0 mg/kg exhibited significant antitumor effect on S180 tumor xenografts, whereas no significant antitumor effect was observed in H22 tumor xenografts. HSJ-0017 at a dose of 3.0 mg/kg enhanced the antitumor effects of radiotherapy and chemotherapy, and reduced their toxicity. However, HSJ-0017 counteracted the antitumor effects of radiotherapy when administered simultaneously with radiotherapy. HSJ-0017 showed significant anti-inflammatory and hepatoprotective effects. Our results demonstrate that HSJ-0017 exhibits antioxidant, antitumor, anti-inflammatory, radioprotective, chemoprotective, and hepatoprotective effects. It is a potent dual SOD/CAT mimic. © 2014 by the Society for Experimental Biology and Medicine.

  18. Biological removal of iron and manganese in rapid sand filters - Process understanding of iron and manganese removal

    DEFF Research Database (Denmark)

    Lin, Katie

    to precipitation and corrosion. Manganese and iron can either be removed physico-chemically or biologically or combined. The physico-chemical oxidation and precipitation of manganese can theoretically be achieved by aeration, but this process is slow unless pH is raised far above neutral, making the removal...... of manganese by simple aeration and precipitation under normal drinking water treatment conditions insignificant. Manganese may also be oxidized autocatalytically. Iron is usually easier to remove. First, iron is rapidly chemically oxidized by oxygen at neutral pH followed by precipitation and filtration......-filter, where iron is removed. Step 2: Filtration in an after-filter where e.g. ammonium and manganese is removed. The treatment relies on microbial processes and may present an alternative, greener and more sustainable approach for drinking water production spending less chemicals and energy than chemical (e...

  19. Porphyrin synthesized from cashew nut shell liquid as part of a novel superparamagnetic fluorescence nanosystem

    Energy Technology Data Exchange (ETDEWEB)

    Clemente, C. S.; Ribeiro, V. G. P.; Sousa, J. E. A.; Maia, F. J. N.; Barreto, A. C. H. [Universidade Federal do Ceara, Laboratorio de Produtos e Tecnologia em Processos (LPT) (Brazil); Andrade, N. F. [Universidade Federal do Ceara, Departamento de Fisica (Brazil); Denardin, J. C. [Universidad de Santiago de Chile (USACH), Departamento de Fisica (Chile); Mele, G. [Universita del Salento, Dipartimento di Ingegneria dell' Innovazione (Italy); Carbone, L. [NNL, Istituto Nanoscienze UOS Lecce (Italy); Mazzetto, S. E. [Universidade Federal do Ceara, Laboratorio de Produtos e Tecnologia em Processos (LPT) (Brazil); Fechine, P. B. A., E-mail: fechine@ufc.br [Universidade Federal do Ceara (UFC), Grupo de Quimica de Materiais Avancados (GQMAT), Departamento de Quimica Analitica e Fisico-Quimica (Brazil)

    2013-06-15

    Magnetic Fe{sub 3}O{sub 4} nanoparticles with average size approximately 11 nm were first oleic acid coated to interact with the meso-porphyrin derivative from CNSL. This procedure produced a novel superparamagnetic fluorescent nanosystem (SFN) linked by van der Waals interactions. This system was characterized by transmission electron microscope, infrared spectroscopy, thermogravimetric analysis, magnetic measurements, UV-Vis absorption, and fluorescence emission measurements. These results showed that SFN has good thermal stability, excellent magnetization, and nanosized dimensions ({approx}13 nm). It exhibited emission peaks at 668 and 725 nm with a maximum emission at 467 nm of excitation wavelength. The type of interaction between porphyrin and magnetic nanoparticles allowed to obtain a material with interesting optical properties which might be used as an imaging agent for contrast in cells as well as heterogeneous photocatalysis.

  20. A supramolecular miktoarm star polymer based on porphyrin metal complexation in water.

    Science.gov (United States)

    Hou, Zhanyao; Dehaen, Wim; Lyskawa, Joël; Woisel, Patrice; Hoogenboom, Richard

    2017-07-25

    A novel supramolecular miktoarm star polymer was successfully constructed in water from a pyridine end-decorated polymer (Py-PmDEGA) and a metalloporphyrin based star polymer (ZnTPP-(PEG) 4 ) via metal-ligand coordination. The Py-PmDEGA moiety was prepared via a combination of reversible addition-fragmentation chain transfer polymerization (RAFT) and subsequent aminolysis and Michael addition reactions to introduce the pyridine end-group. The ZnTPP(PEG) 4 star-polymer was synthesized by the reaction between tetrakis(p-hydroxyphenyl)porphyrin and toluenesulfonyl-PEG, followed by insertion of a zinc ion into the porphyrin core. The formation of a well-defined supramolecular AB 4 -type miktoarm star polymer was unambiguously demonstrated via UV-Vis spectroscopic titration, isothermal titration calorimetry (ITC) and diffusion ordered NMR spectroscopy (DOSY).

  1. Tunneling electron induced molecular electroluminescence from individual porphyrin J-aggregates

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Qiushi; Zhang, Chao; Zhang, Yang, E-mail: zhyangnano@ustc.edu.cn, E-mail: zcdong@ustc.edu.cn; Zhang, Yao; Liao, Yuan; Dong, Zhenchao, E-mail: zhyangnano@ustc.edu.cn, E-mail: zcdong@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2015-07-27

    We investigate molecular electroluminescence from individual tubular porphyrin J-aggregates on Au(111) by tunneling electron excitations in an ultrahigh-vacuum scanning tunneling microscope (STM). High-resolution STM images suggest a spiral tubular structure for the porphyrin J-aggregate with highly ordered “brickwork”-like arrangements. Such aggregated nanotube is found to behave like a self-decoupled molecular architecture and shows red-shifted electroluminescence characteristics of J-aggregates originated from the delocalized excitons. The positions of the emission peaks are found to shift slightly depending on the excitation sites, which, together with the changes in the observed spectral profiles with vibronic progressions, suggest a limited exciton coherence number within several molecules. The J-aggregate electroluminescence is also found unipolar, occurring only at negative sample voltages, which is presumably related to the junction asymmetry in the context of molecular excitations via the carrier injection mechanism.

  2. Mitochondria-targeted cationic porphyrin-triphenylamine hybrids for enhanced two-photon photodynamic therapy.

    Science.gov (United States)

    Hammerer, Fabien; Poyer, Florent; Fourmois, Laura; Chen, Su; Garcia, Guillaume; Teulade-Fichou, Marie-Paule; Maillard, Philippe; Mahuteau-Betzer, Florence

    2018-01-01

    The proof of concept for two-photon activated photodynamic therapy has already been achieved for cancer treatment but the efficiency of this approach still heavily relies on the availability of photosensitizers combining high two-photon absorption and biocompatibility. In this line we recently reported on a series of porphyrin-triphenylamine hybrids which exhibit high singlet oxygen production quantum yield as well as high two-photon absorption cross-sections but with a very poor cellular internalization. We present herein new photosensitizers of the same porphyrin-triphenylamine hybrid series but bearing cationic charges which led to strongly enhanced water solubility and thus cellular penetration. In addition the new compounds have been found localized in mitochondria that are preferential target organelles for photodynamic therapy. Altogether the strongly improved properties of the new series combined with their specific mitochondrial localization lead to a significantly enhanced two-photon activated photodynamic therapy efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Effects of radiation and porphyrin on mitosis and chromosomes in human hematopoietic cell lines

    International Nuclear Information System (INIS)

    Tan, J.C.; Huang, C.C.; Fiel, R.J.

    1976-01-01

    The effect on mitosis of a human hematopoietic cell line RPMI-1788 treated with a metal chelate (Zn ++ ) of meso-tetra (p-carboxyphenyl) porphine (Zn-TCPP) alone at various concentrations or in combination with gamma-irradiation at various doses were studied. The results showed that both Zn-TCPP and radiation were effective in interfering with normal mitosis and that the effect of radiation was relatively more effective. Data also suggest interacting effects between Zn-TCPP and gamma-irradiation. At low doses of radiation, Zn-TCPP potentiated the effect of radiation. The reverse seemed to be true at a high dose of radiation. The effects of two porphyrins (Zn-TCPP and hematoporphyrin) and radiation on chromosomes were also studied. Chromosomal aberrations characteristic of radiation were observed. The porphyrins were found not to be effective chromosome-breaking agents under the experimental conditions tested

  4. Balancing Exchange Mixing in Density-Functional Approximations for Iron Porphyrin.

    Science.gov (United States)

    Berryman, Victoria E J; Boyd, Russell J; Johnson, Erin R

    2015-07-14

    Predicting the correct ground-state multiplicity for iron(II) porphyrin, a high-spin quintet, remains a significant challenge for electronic-structure methods, including commonly employed density functionals. An even greater challenge for these methods is correctly predicting favorable binding of O2 to iron(II) porphyrin, due to the open-shell singlet character of the adduct. In this work, the performance of a modest set of contemporary density-functional approximations is assessed and the results interpreted using Bader delocalization indices. It is found that inclusion of greater proportions of Hartree-Fock exchange, in hybrid or range-separated hybrid functionals, has opposing effects; it improves the ability of the functional to identify the ground state but is detrimental to predicting favorable dioxygen binding. Because of the uncomplementary nature of these properties, accurate prediction of both the relative spin-state energies and the O2 binding enthalpy eludes conventional density-functional approximations.

  5. Radiolabeled porphyrin versus gallium-67 citrate for the detection of human melanoma in athymic mice

    International Nuclear Information System (INIS)

    Maric, N.; Chan, S. Ming; Hoffer, P.B.; Duray, P.

    1987-01-01

    We performed the biodistribution and imaging studies of 111 In and 67 Ga labeled tetra(4-N-methylpyridyl) porphine, (T4NMPYP), and compared it to that of 67 Ga citrate in athymic mice bearing a human melanoma xenograft. The biodistribution results of both 111 In and 67 Ga labeled T4NMPYP (3, 6, 24, and 48 hours) were similar but differed from that of 67 Ga citrate (48 hours). The optimum tumor uptake of both radiolabeled porphyrins was at 6 hours postinjection and was lower than the tumor uptake of 67 Ga citrate at 48 hours postinjection. Kidney was the only organ showing higher uptake of radiolabeled porphyrin compared to that of 67 Ga citrate. The imaging studies performed with 111 In T4NMPYP and 67 Ga citrate correspond to the biodistribution results. Osteomyelitis present in one mouse showed good localization of 111 In T4NMPYP. 15 refs., 3 figs., 5 tabs

  6. Porphyrin-sensitized solar cells: systematic molecular optimization, coadsorption and cosensitization.

    Science.gov (United States)

    Song, Heli; Liu, Qingyun; Xie, Yongshu

    2018-02-15

    As a promising low-cost solar energy conversion technique, dye-sensitized solar cells have undergone spectacular development since 1991. For practical applications, improvement of power conversion efficiency has always been one of the major research topics. Porphyrins are outstanding sensitizers endowed with strong sunlight harvesting ability in the visible region and multiple reaction sites available for functionalization. However, judicious molecular design in consideration of light-harvest, energy levels, operational dynamics, adsorption geometry and suppression of back reactions is specifically required for achieving excellent photovoltaic performance. This feature article highlights some of the recently developed porphyrin sensitizers, especially focusing on the systematic dye structure optimization approach in combination with coadsorption and cosensitization methods in pursuing higher efficiencies. Herein, we expect to provide more insights into the structure-performance correlation and molecular engineering strategies in a stepwise manner.

  7. Diagnostic use of blood porphyrin and radiographic changes in lead exposure in goats

    International Nuclear Information System (INIS)

    Swarup, D.; Maiti, S.K.; Dwivedi, S.K.

    1990-01-01

    Blood porphyrin, hematological examination and radiographic changes were evaluated for the detection of lead intoxication in goats given daily po doses of 10, 15 and 20 mg lead acetate (5.43, 8.15 and 10.86 mg lead)/kg body weight for 30, 30 and 31 days, or a total of 91 days. Blood porphyrin was found a sensitive indicator with direct correlation (r = 0.976) to blood lead concentration. Basophilic stippling was not seen in the lead-exposed goats. Radiopaque bands developed at the distal metaphysis of the radius in 7 of the 12 lead-exposed goats at day 30. The usefulness of this sign for the diagnosis of lead exposure in goats requires further investigation

  8. Effect of ferrocene-substituted porphyrin RL-91 on Candida albicans biofilm formation.

    Science.gov (United States)

    Lippert, Rainer; Vojnovic, Sandra; Mitrovic, Aleksandra; Jux, Norbert; Ivanović-Burmazović, Ivana; Vasiljevic, Branka; Stankovic, Nada

    2014-08-01

    Ferrocene-substituted porphyrin RL-91 exhibits antifungal activity against opportune human pathogen Candida albicans. RL-91 efficiently inhibits growth of both planktonic C. albicans cells and cells within biofilms without photoactivation. The minimal inhibitory concentration for plankton form (PMIC) was established to be 100 μg/mL and the same concentration killed 80% of sessile cells in the mature biofilm (SMIC80). Furthermore PMIC of RL-91 efficiently prevents C. albicans biofilm formation. RL-91 is cytotoxic for human fibroblasts in vitro in concentration of 10 μg/mL, however it does not cause hemolysis in concentrations of up to 50 μg/mL. These findings open possibility for application of RL-91 as an antifungal agent for external antibiofilm treatment of medical devices as well as a scaffold for further development of porphyrin based systemic antifungals. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Anchoring effect on first passage process in Taiwan financial market

    Science.gov (United States)

    Liu, Hsing; Liao, Chi-Yo; Ko, Jing-Yuan; Lih, Jiann-Shing

    2017-07-01

    Empirical analysis of the price fluctuations of financial markets has received extensive attention because a substantial amount of financial market data has been collected and because of advances in data-mining techniques. Price fluctuation trends can help investors to make informed trading decisions, but such decisions may also be affected by a psychological factors-the anchoring effect. This study explores the intraday price time series of Taiwan futures, and applies diffusion model and quantitative methods to analyze the relationship between the anchoring effect and price fluctuations during first passage process. Our results indicate that power-law scaling and anomalous diffusion for stock price fluctuations are related to the anchoring effect. Moreover, microscopic price fluctuations before switching point in first passage process correspond with long-term price fluctuations of Taiwan's stock market. We find that microscopic trends could provide useful information for understanding macroscopic trends in stock markets.

  10. Effect of zinc insertion and hydrophobicity on the membrane interactions and PDT activity of porphyrin photosensitizers.

    Science.gov (United States)

    Pavani, Christiane; Uchoa, Adjaci F; Oliveira, Carla S; Iamamoto, Yassuko; Baptista, Maurício S

    2009-02-01

    A series of photosensitizers (PS), which are meso-substituted tetra-cationic porphyrins, was synthesized in order to study the role of amphiphilicity and zinc insertion in photodynamic therapy (PDT) efficacy. Several properties of the PS were evaluated and compared within the series including photophysical properties (absorption spectra, fluorescence quantum yield Phif, and singlet oxygen quantum yield PhiDelta), uptake by vesicles, mitochondria and HeLa cells, dark and phototoxicity in HeLa cells. The photophysical properties of all compounds are quite similar (Phifporphyrin ring result in higher vesicle and cell uptake. Binding in mitochondria is dependent on the PS lipophilicity and on the electrochemical membrane potential, i.e., in uncoupled mitochondria PS binding decreases by up to 53%. The porphyrin substituted with octyl groups (TC8PyP) is the compound that is most enriched in mitochondria, and its zinc derivative (ZnTC8PyP) has the highest global uptake. The stronger membrane interaction of the zinc-substituted porphyrins is attributed to a complexing effect with phosphate groups of the phospholipids. Zinc insertion was also shown to decrease the interaction with isolated mitochondria and with the mitochondria of HeLa cells, an effect that has been explained by the particular characteristics of the mitochondrial internal membrane. Phototoxicity was shown to increase proportionally with membrane binding efficiency, which is attributed to favorable membrane interactions which allow more efficient membrane photooxidation. For this series of compounds, photodynamic efficiency is directly proportional to the membrane binding and cell uptake, but it is not totally related to mitochondrial targeting.

  11. Ion pair recognition by Zn-porphyrin/crown ether conjugates: visible sensing of sodium cyanide.

    Science.gov (United States)

    Kim, Yeon-Hwan; Hong, Jong-In

    2002-03-07

    Synthesis and complexation behavior of ditopic neutral receptors composed of both a Lewis-acidic binding site (zinc porphyrin moiety) and a Lewis-basic binding site (crown ether moiety) are reported; the receptors bound only NaCN in a ditopic fashion with a color change, and in contrast other sodium salts bound to the receptors in a monotopic fashion without a color change.

  12. Designing Porphyrinic Covalent Organic Frameworks for the Photodynamic Inactivation of Bacteria

    Czech Academy of Sciences Publication Activity Database

    Hynek, Jan; Zelenka, J.; Rathouský, Jiří; Kubát, Pavel; Ruml, T.; Demel, Jan; Lang, Kamil

    2018-01-01

    Roč. 10, č. 10 (2018), s. 8527-8535 ISSN 1944-8244 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : antibacterial coating * biofilm * covalent organic framework * photodynamic * porphyrin * singlet oxygen Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) OBOR OECD: Inorganic and nuclear chemistry; Physical chemistry (UFCH-W) Impact factor: 7.504, year: 2016

  13. Thiacalix[4]arene–porphyrin conjugates with high selectivity towards fullerene C70

    Czech Academy of Sciences Publication Activity Database

    Kundrát, O.; Káš, M.; Tkadlecová, M.; Lang, Kamil; Cvačka, Josef; Stibor, I.; Lhoták, P.

    2007-01-01

    Roč. 48, č. 38 (2007), s. 6620-6623 ISSN 0040-4039 R&D Projects: GA MŠk ME 857 Grant - others:GA MŠk(CZ) OC 134 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40550506 Keywords : porphyrin * thiacalixarenes * derivatives Subject RIV: CA - Inorganic Chemistry Impact factor: 2.615, year: 2007

  14. Enhanced magneto-optical SPR platform for amine sensing based on Zn porphyrin dimers

    OpenAIRE

    Manera, M. G.; Ferreiro-Vila, E.; Garcia-Martin, J. M.; Cebollada, A.; Garcia-Martin, A.; Giancane, G.; Valli, L.; Rella, R.

    2013-01-01

    Ethane-bridged Zn porphyrins dimers (ZnPP) have been deposited by Langmuir-Schäfer (LS) deposition technique onto proper transducer layers for surface plasmon resonance (SPR) and magneto-optical surface plasmon resonance (MO-SPR) characterization techniques performed in controlled atmosphere. This last tool has emerged as a novel and very performing sensing technique using as transducer layers a combination of noble and magnetic layers deposited onto glass substrates. A magnetic actuation all...

  15. Response of the oral mucosa to porphyrin mediated boron neutron capture therapy

    International Nuclear Information System (INIS)

    Morris, G.M.

    2003-01-01

    Pre-clinical studies are now in progress to develop boron neutron capture therapy (BNCT) modalities for the treatment of head and neck carcinomas. BNCT is a bimodal therapy which involves the administration of a boron-10 enriched compound, that accumulates preferentially in tumours, prior to irradiation with low energy neutrons. These neutrons are captured by boron-10 atoms to produce a highly localised radiation exposure. More recently, it has been demonstrated that various boronated porphyrins can target a variety of tumours. Of the porphyrins evaluated to date, copper tetracarboranylphenyl porphyrin (CuTCPH) is a strong candidate for potential clinical evaluation. It has extremely high specificity for a variety of tumour models. Therapeutic efficacy of CuTCPH mediated BNCT has been demonstrated in pre-clinical studies using the murine EMT-6 carcinoma model. In the present investigation the response of the oral mucosa to CuTCPH mediated boron neutron capture (BNC) irradiation was assessed using a standard rat model (ventral tongue). Single exposure irradiation was carried out on the thermal neutron beam at the Brookhaven Medical Research Reactor, at 3 days after the final injection of the boronated porphyrin. The impact of CuTCPH mediated BNC irradiation on oral mucosa at therapeutically effective exposure times, assessed using the ventral tongue model, was minimal. This was primarily due to the fact that blood boron levels (from CuTCPH) were very low at the time of irradiation. Analysis of the dose-effect data for CuTCPH gave a compound biological effectiveness (CBE) factor of 2.5. It can be concluded that, although, the CBE factor (calculated using blood boron concentrations) was relatively high, CuTCPH mediated BNC irradiation should not cause significant damage at clinically relevant radiation doses. This is because blood boron levels would be very low at the time of irradiation

  16. Nanoparticles with Embedded Porphyrin Photosensitizers for Photooxidation Reactions and Continuous Oxygen Sensing

    Czech Academy of Sciences Publication Activity Database

    Kubát, Pavel; Henke, P.; Berzediová, V.; Štěpánek, M.; Lang, Kamil; Mosinger, Jiří

    2017-01-01

    Roč. 9, č. 41 (2017), s. 36229-36238 ISSN 1944-8244 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388955 ; RVO:61388980 Keywords : photooxidation * polystyrene nanoparticles * porphyrins Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) OBOR OECD: Physical chemistry; Inorganic and nuclear chemistry (UACH-T) Impact factor: 7.504, year: 2016

  17. Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

    KAUST Repository

    Fathalla, Maher; Strutt, Nathan; Srinivasan, Sampath; Katsiev, Khabiboulakh; Hartlieb, Karel J.; Bakr, Osman; Stoddart, J. Fraser

    2015-01-01

    A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

  18. C-84 Selective Porphyrin Macrocycle with an Adaptable Cavity Constructed Through Alkyne Metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C. X.; Long, H.; Zhang, W.

    2012-06-21

    A bisporphyrin macrocycle was constructed from a porphyrin-based diyne monomer in one step through alkyne metathesis. The fullerene binding studies (C{sub 60}, C{sub 70} and C{sub 84}) showed the highest binding affinity of the macrocycle for C{sub 84}, which is in great contrast to its bisporphyrin four-armed cage analogue that showed the strongest binding with C{sub 70}.

  19. Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

    KAUST Repository

    Fathalla, Maher

    2015-05-18

    A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

  20. Nanoparticles with Embedded Porphyrin Photosensitizers for Photooxidation Reactions and Continuous Oxygen Sensing

    Czech Academy of Sciences Publication Activity Database

    Kubát, Pavel; Henke, P.; Berzediová, V.; Štěpánek, M.; Lang, Kamil; Mosinger, Jiří

    2017-01-01

    Roč. 9, č. 41 (2017), s. 36229-36238 ISSN 1944-8244 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388955 ; RVO:61388980 Keywords : photooxidation * polystyrene nanoparticles * porphyrins Subject RIV: CF - Physical ; Theoretical Chemistry ; CA - Inorganic Chemistry (UACH-T) OBOR OECD: Physical chemistry ; Inorganic and nuclear chemistry (UACH-T) Impact factor: 7.504, year: 2016

  1. Glycol porphyrin derivatives and temoporfin elicit resistance to photodynamic therapy by different mechanisms

    Czech Academy of Sciences Publication Activity Database

    Králová, Jarmila; Kolář, Michal; Kahle, Michal; Truksa, Jaroslav; Lettlová, Sandra; Balusiková, K.; Bartůněk, Petr

    2017-01-01

    Roč. 7, Mar 15 (2017), č. článku 44497. ISSN 2045-2322 R&D Projects: GA MŠk LO1220 Institutional support: RVO:68378050 ; RVO:86652036 Keywords : Glycol porphyrin derivates * chemotherapy * cancer * multidrug resistance Subject RIV: EB - Genetics ; Molecular Biology; EB - Genetics ; Molecular Biology (BTO-N) OBOR OECD: Biochemistry and molecular biology; Biochemistry and molecular biology (BTO-N) Impact factor: 4.259, year: 2016

  2. Supramolecular tetracluster-cobalt porphyrin: a four-electron transfer catalyst for dioxygen reduction

    International Nuclear Information System (INIS)

    Winnischofer, Herbert; Otake, Vesper Yoshiyuki; Dovidauskas, Sergio; Nakamura, Marcelo; Toma, Henrique Eisi; Araki, Koiti

    2004-01-01

    Electrocatalysis by CoTCP {CoTCP meso-tetrakis(4-pyridyl)porphynatocobalt(III)} coordinated to four [Ru 3 (μ 3 -O)(μ 2 -CH 3 CO 2 ) 6 (py) 2 ] + complexes in the four-electron reduction of dioxygen, has been unequivocally demonstrated in this work by using two types of electrostatically assembled films of CoTCP and anionic zinc or free-base meso-tetrakis(4-sulfonatophenyl)porphyrins (ZnTPPS or H 2 TPPS), as well as, by employing different electrode materials. An enhanced electrocatalytic activity has been observed, in spite of the fact that the typical bis-coordination of dioxygen to two cobalt porphyrin sites is precluded in such CoTCP/ZnTPPS or CoTCP/H 2 TPPS bilayered films. In addition, negligible ring currents have been observed in ring-disk voltammetry measurements, yielding straight Levich and Koutecky-Levich plots, whose slopes approached the theoretical 4e - curve in air, or in O 2 saturated solutions (pH 3-5). The use of gold instead of glassy carbon (GC) electrodes has not also significantly perturbed the mechanism. By ruling out any influence from the electrode materials, a well known critical point in the catalysis by cobalt porphyrins, the results have shown that CoTCP is acting as a four-electron transfer catalyst for dioxygen reduction. Also, by excluding the possibility of bis-coordination of dioxygen, it was shown that the electronic and supramolecular effects exerted by the peripheral ruthenium cluster complexes should be triggering the four-electron catalytic activity of the cobalt porphyrin center

  3. Interaction of porphyrin and sapphyrin macrocycles with nucleobases and nucleosides. Spectroscopic, quantum chemical and chromatographic investigation

    Czech Academy of Sciences Publication Activity Database

    Záruba, K.; Tománková, Z.; Sýkora, D.; Charvátová, J.; Kavenová, I.; Bouř, Petr; Matějka, P.; Fähnrich, J.; Volka, K.; Král, V.

    2001-01-01

    Roč. 437, - (2001), s. 39-53 ISSN 0003-2670 R&D Projects: GA ČR GA203/01/0031; GA MŠk VS97135; GA ČR GV301/98/K042 Grant - others:HHMI(US) 75195-541101 Institutional research plan: CEZ:AV0Z4055905 Keywords : HPLC * porphyrin Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.073, year: 2001

  4. Facile one-pot synthesis of porphyrin based porous polymer networks (PPNs) as biomimetic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zou, LF; Feng, DW; Liu, TF; Chen, YP; Fordham, S; Yuan, S; Tian, J; Zhou, HC

    2015-01-01

    Stable porphyrin based porous polymer networks, PPN-23 and PPN-24, have been synthesized through a facile one-pot approach by the aromatic substitution reactions of pyrrole and aldehydes. PPN-24(Fe) shows high catalytic efficiency as a biomimetic catalyst in the oxidation reaction of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) in the presence of H2O2.

  5. Porphyrin-layered double hydroxide/polymer composites as novel ecological photoactive surfaces

    Czech Academy of Sciences Publication Activity Database

    Káfuňková, Eva; Lang, Kamil; Kubát, Pavel; Klementová, Mariana; Mosinger, Jiří; Šlouf, Miroslav; Troutier-Thuilliez, A. L.; Leroux, F.; Verney, V.; Taviot-Guého, Ch.

    2010-01-01

    Roč. 20, č. 42 (2010), s. 9423-9432 ISSN 0959-9428 R&D Projects: GA ČR GAP207/10/1447 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503; CEZ:AV0Z40500505 Keywords : porphyrins * nanoparticles * hydroxide/polymer composites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.101, year: 2010

  6. Spectroscopic evidence of xanthine compounds fluorescence quenching effect on water-soluble porphyrins

    Science.gov (United States)

    Makarska-Bialokoz, Magdalena

    2015-02-01

    The formation of π-stacked complexes between water-soluble porphyrins: 4,4‧,4″,4″‧-(21H,23H-porphine-5,10,15,20-tetrayl)tetrakis-(benzoic acid) (H2TCPP), 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphine (H2TPPS4), 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate (H2TTMePP), 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine tetra-p-tosylate (H2TMePyP), the Cu(II) complexes of H2TTMePP and H2TMePyP, as well as chlorophyll a with xanthine, theophylline (1,3-dimethylxanthine) and theobromine (3,7-dimethylxanthine) has been studied analysing their absorption and steady-state fluorescence spectra in aqueous (or acetone in case of chlorophyll a) solution. During titration by the compounds from xanthine group the bathochromic effect in the porphyrin absorption spectra as well as the hypochromicity of the porphyrin Soret maximum can be noticed. The fluorescence quenching effect observed during interactions in the systems examined suggests the process of static quenching. The association and fluorescence quenching constants are of the order of magnitude of 103 - 102 mol-1. The results obtained show that xanthine and its derivatives can quench the fluorescence of the porphyrins according to the number of methyl groups in the molecule of quencher.

  7. Endogenous and exogenous porphyrins as photosensitizers in the Hep-2 human carcinoma cell line.

    Science.gov (United States)

    Alvarez, M G; Milanesio, M; Rivarola, V; Durantini, E; Batlle, A; Fukuda, H

    2009-07-01

    The photodynamic activity of three photosensitizers (PS): AL-induced PPIX, the porphyrin derivative 5-(4-trimethylammoniumphenyl)-10, 5, 20-tris (2,4,6- trimethoxyphenyl) porphyrin (CP) and the molecular dyad porphyrin-C(60) (P-C(60)), the last two incorporated into liposomal vesicles, was evaluated on Hep-2 human larynx carcinoma cell line. ALA-induced accumulation of the endogenous PS PPIX, reached saturation values between 5 and 24 h incubation time; the maximal PPIX content was 5.7 nmol/106 cells. The same intracellular level was accumulated when the cationic porphyrin CP was used, while the amount of P-C(60) attained was 1.5 nmol/106 cells. Under violet-blue exciting light, the fluorescence of PPIX and P-C(60) was found in the cytoplasm showing a granular appearance indicating lysosomal localization. CP was mainly detected as a filamentous pattern characteristic of mitochondrial localization. No dark cytotoxicity was observed using 1mM ALA, 5 microM CP and 1 microM P-C(60) after 24 h incubation. Cell morphology was analyzed using Hoechst-33258, toluidine blue staining, TUNEL assay and DNA fragmentation, 24 h after irradiation with 54 J/cm2. When photosensitized with ALA and P-C(60), chromatine condensation characteristic of apoptotic cell death was found; instead, 58 % of necrotic cells were observed with CP. The results show that in the Hep-2 cells, of the three PS analyzed, the molecular dyad P-C(60) was more efficient than CP and PPIX, and confirm that PDT can induce different mechanisms of cell death depending on the PS and the irradiation dose.

  8. Two-photon excitation of porphyrin-functionalized porous silicon nanoparticles for photodynamic therapy.

    Science.gov (United States)

    Secret, Emilie; Maynadier, Marie; Gallud, Audrey; Chaix, Arnaud; Bouffard, Elise; Gary-Bobo, Magali; Marcotte, Nathalie; Mongin, Olivier; El Cheikh, Khaled; Hugues, Vincent; Auffan, Mélanie; Frochot, Céline; Morère, Alain; Maillard, Philippe; Blanchard-Desce, Mireille; Sailor, Michael J; Garcia, Marcel; Durand, Jean-Olivier; Cunin, Frédérique

    2014-12-03

    Porous silicon nanoparticles (pSiNPs) act as a sensitizer for the 2-photon excitation of a pendant porphyrin using NIR laser light, for imaging and photodynamic therapy. Mannose-functionalized pSiNPs can be vectorized to MCF-7 human breast cancer cells through a mannose receptor-mediated endocytosis mechanism to provide a 3-fold enhancement of the 2-photon PDT effect. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Perylene anhydride fused porphyrins as near-infrared sensitizers for dye-sensitized solar cells

    KAUST Repository

    Jiao, Chongjun

    2011-07-15

    Two perylene anhydride fused porphyrins 1 and 2 have been synthesized and employed successfully in dye-sensitized solar cells (DSCs). Both compounds showed broad incident monochromatic photon-to-current conversion efficiency spectra covering the entire visible spectral region and even extending into the near-infrared (NIR) region up to 1000 nm, which is impressive for ruthenium-free dyes in DSCs. © 2011 American Chemical Society.

  10. Determination of semi-empirical relationship between the manganese and hydrogen atoms ratio, physical density and concentration in an aqueous solution of manganese sulphate

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues Bittencourt, Guilherme, E-mail: bittencourt@ird.gov.b [Instituto de Radioprotecao e Dosimetria LNMRI/IRD/CNEN, Av. Salvador Allende, s/n Recreio dos Bandeirantes, CEP 22780-160, Rio de Janeiro, RJ (Brazil); Souza Patrao, Karla Cristina de, E-mail: karla@ird.gov.b [Instituto de Radioprotecao e Dosimetria LNMRI/IRD/CNEN, Av. Salvador Allende, s/n Recreio dos Bandeirantes, CEP 22780-160, Rio de Janeiro, RJ (Brazil); Passos Leite, Sandro, E-mail: sandro@ird.gov.b [Programa de Engenharia Nuclear/COPPE, Universidade Federal do Rio de Janeiro, Ilha do Fundao, Caixa Postal 68509, 21945-970, Rio de Janeiro, RJ (Brazil); Wagner Pereira, Walsan, E-mail: walsan@ird.gov.b [Instituto de Radioprotecao e Dosimetria LNMRI/IRD/CNEN, Av. Salvador Allende, s/n Recreio dos Bandeirantes, CEP 22780-160, Rio de Janeiro, RJ (Brazil); Simoes da Fonseca, Evaldo, E-mail: evaldo@ird.gov.b [Instituto de Radioprotecao e Dosimetria LNMRI/IRD/CNEN, Av. Salvador Allende, s/n Recreio dos Bandeirantes, CEP 22780-160, Rio de Janeiro, RJ (Brazil)

    2010-12-15

    The Manganese sulphate solution has been used for neutron metrology through the method of Manganese Bath. This method uses physical parameters of manganese sulphate solution to obtain its corrections. This work established a functional relationship, using the gravimetric method, between those physical parameters: density, concentration and hydrogen to manganese ratio. Comparisons were done between manganese sulphate solution concentration from the Manganese Bath system of Laboratory of Metrology of Ionising Radiation and estimated values from the functional relationship obtained, showing percentage difference of less than 0.1%. This result demonstrates the usefulness in the correlation of the physical values of the solution to the MB.

  11. Synthesis, reactivity, and properties of N-fused porphyrin rhenium(I) tricarbonyl complexes.

    Science.gov (United States)

    Toganoh, Motoki; Ikeda, Shinya; Furuta, Hiroyuki

    2007-11-12

    The thermal reactions of N-fused tetraarylporphyrins or N-confused tetraarylporphyrins with Re2(CO)10 gave the rhenium(I) tricarbonyl complexes bearing N-fused porphyrinato ligands (4) in moderate to good yields. The rhenium complexes 4 are characterized by mass, IR, 1H, and 13C NMR spectroscopy, and the structures of tetraphenylporphynato complex 4a and its nitro derivative 15 are determined by X-ray single crystal analysis. The rhenium complexes 4 show excellent stability against heat, light, acids, bases, and oxidants. The aromatic substitution reactions of 4 proceed without a loss of the center metal to give the nitro (15), formyl (16), benzoyl (17), and cyano derivatives (19), regioselectively. In the electrochemical measurements for 4, one reversible oxidation wave and two reversible reduction waves are observed. Their redox potentials imply narrow HOMO-LUMO band gaps of 4 and are consistent with their electronic absorption spectra, in which the absorption edges exceed 1000 nm. Theoretical study reveals that the HOMO and LUMO of the rhenium complexes are exclusively composed of the N-fused porphyrin skeleton. Protonation of 4 takes place at the 21-position regioselectively, reflecting the high coefficient of the C21 atom in the HOMO orbital. The skeletal rearrangement reaction from N-confused porphyrin Re(I) complex (8) to N-fused porphyrin Re(I) complex (4) is suggested from the mechanistic study as well as DFT calculations.

  12. Synthesis, characterization, and nonlinear optical properties of graphene oxide functionalized with tetra-amino porphyrin

    International Nuclear Information System (INIS)

    Yamuna, R.; Ramakrishnan, S.; Dhara, Keerthy; Devi, R.; Kothurkar, Nikhil K.; Kirubha, E.; Palanisamy, P. K.

    2013-01-01

    The synthesis of a porphyrin–graphene oxide hybrid (GO–TAP) was carried out by covalently functionalizing graphene oxide (GO) with 5,10,15,20 mesotetra (4-aminophenyl) porphyrin (TAP) through an amide linkage. The GO–TAP hybrid has been characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV–visible spectroscopy. The peak intensity of the Soret band of the material was suppressed compared to neat TAP. This indicates a strong interaction between the electronic energy level of TAP and GO in the GO–TAP hybrid. The functionalization of GO with TAP significantly improved its solubility and dispersion stability in organic solvents. Scanning electron micrographs reveal that the hybrid was found to be similar to the unmodified GO but slightly more wrinkled. Transmission electron micrographs also demonstrate that GO sheet in the hybrid is more wrinkled with some dark spot due to functionalization. Atomic force microscopy results also reveal that the TAP functionalization increases the thickness of GO sheet to 2.0–3.0 nm from 1.2 to 1.8 nm. We observed improved nonlinear optical and optical limiting properties for the hybrid compared to both graphene oxide and porphyrin. GO–TAP shows fluorescence quenching compared with porphyrin, indicating excellent electron and/or energy transfer to GO from TAP. Thermogravimetric analysis confirms that the GO–TAP hybrid has outstanding thermal stability.

  13. Role of electrostatic complementarity between perylenediimide and porphyrin in highly stabilized GNA

    Energy Technology Data Exchange (ETDEWEB)

    Xiang, Yonggang [Department of Chemistry, College of Science, Huazhong Agricultural University, Wuhan 430070 (China); Zhang, Qingye [Agricultural Bioinformatics Key Laboratory of Hubei Province, College of Informatics Huazhong Agricultural University, Wuhan 430070 (China); Li, Zibiao, E-mail: lizb@imre.a-star.edu.sg [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Chen, Hao, E-mail: hchenhao@mail.hzau.edu.cn [Department of Chemistry, College of Science, Huazhong Agricultural University, Wuhan 430070 (China)

    2017-01-01

    Relatively electron-deficient perylenediimide (PDI) and relatively electron-rich porphyrin (Por) were introduced into the middle of 16-mer glycol nucleic acid (GNA), and up to five consecutive chromophores were arranged in the zipper-like interstrand alternating fashion. Remarkable variation for the CD spectra ascribed to chromophores was observed, and bathochromic shift in the UV/Vis absorption region of chromophores occurred upon duplex formation. Interestingly, zipper-like heteroaggregates of chromophores inside had marvelous positive effects on the stabilization of the duplex, T{sub m} of Por-PDI-Por sandwich-type modified GNA duplex was increased by 24 °C in comparison with three A-T base pairs, moreover, Por-PDI-Por-PDI-Por interstrand modified GNA duplex was even stabilized by 25 °C in replacement of five A-T base pairs. The specificity of high duplex stability might be driven by the strong hydrophobic electrostatic complementarity between PDI and Por face-centered stacking. - Highlights: • Electrostatic complementarity between relatively electron-deficient perylenediimide and relatively electron-rich porphyrin • Zipper-like heteroaggregates of perylenediimide and porphyrin could stablize the GNA duplex significantly. • Chromophores can lead to remarkable variation for the CD spectra and bathochromic shift occurred upon duplex formation.

  14. Controlled intracellular generation of reactive oxygen species in human mesenchymal stem cells using porphyrin conjugated nanoparticles.

    Science.gov (United States)

    Lavado, Andrea S; Chauhan, Veeren M; Zen, Amer Alhaj; Giuntini, Francesca; Jones, D Rhodri E; Boyle, Ross W; Beeby, Andrew; Chan, Weng C; Aylott, Jonathan W

    2015-09-14

    Nanoparticles capable of generating controlled amounts of intracellular reactive oxygen species (ROS), that advance the study of oxidative stress and cellular communication, were synthesized by functionalizing polyacrylamide nanoparticles with zinc(II) porphyrin photosensitisers. Controlled ROS production was demonstrated in human mesenchymal stem cells (hMSCs) through (1) production of nanoparticles functionalized with varying percentages of Zn(II) porphyrin and (2) modulating the number of doses of excitation light to internalized nanoparticles. hMSCs challenged with nanoparticles functionalized with increasing percentages of Zn(II) porphyrin and high numbers of irradiations of excitation light were found to generate greater amounts of ROS. A novel dye, which is transformed into fluorescent 7-hydroxy-4-trifluoromethyl-coumarin in the presence of hydrogen peroxide, provided an indirect indicator for cumulative ROS production. The mitochondrial membrane potential was monitored to investigate the destructive effect of increased intracellular ROS production. Flow cytometric analysis of nanoparticle treated hMSCs suggested irradiation with excitation light signalled controlled apoptotic cell death, rather than uncontrolled necrotic cell death. Increased intracellular ROS production did not induce phenotypic changes in hMSC subcultures.

  15. XAFS Debye-Waller Factors Temperature-Dependent Expressions for Fe+2-Porphyrin Complexes

    Science.gov (United States)

    Dimakis, Nicholas; Bunker, Grant

    2007-02-01

    We present an efficient and accurate method for directly calculating single and multiple scattering X-ray absorption fine structure (XAFS) thermal Debye-Waller factors for Fe+2 -porphiryn complexes. The number of multiple scattering Debye-Waller factors on metal porphyrin centers exceeds the number of available parameters that XAFS experimental data can support during fitting with simulated spectra. Using the Density Functional Theory (DFT) under the hybrid functional of X3LYP, phonon normal mode spectrum properties are used to express the mean square variation of the half-scattering path length for a Fe+2 -porphiryn complex as a function of temperature for the most important single and multiple scattering paths of the complex thus virtually eliminating them from the fitting procedure. Modeled calculations are compared with corresponding values obtained from DFT-built and optimized Fe+2 -porphyrin bis-histidine structure as well as from experimental XAFS spectra previously reported. An excellent agreement between calculated and reference Debye-Waller factors for Fe+2-porphyrins is obtained.

  16. Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

    International Nuclear Information System (INIS)

    Viana, A.S.; Leupold, S.; Montforts, F.-P.; Abrantes, L.M.

    2005-01-01

    A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 x 10 -10 mol cm -2 and a thickness of 13 A, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water

  17. In vivo photoacoustic tumor tomography using a quinoline-annulated porphyrin as NIR molecular contrast agent.

    Science.gov (United States)

    Luciano, Michael; Erfanzadeh, Mohsen; Zhou, Feifei; Zhu, Hua; Bornhütter, Tobias; Röder, Beate; Zhu, Quing; Brückner, Christian

    2017-01-25

    The synthesis and photophysical properties of a tetra-PEG-modified and freely water-soluble quinoline-annulated porphyrin are described. We previously demonstrated the ability of quinoline-annulated porphyrins to act as an in vitro NIR photoacoustic imaging (PAI) contrast agent. The solubility of the quinoline-annulated porphyrin derivative in serum now allowed the assessment of the efficacy of the PEGylated derivative as an in vivo NIR contrast agent for the PAI of an implanted tumor in a mouse model. A multi-fold contrast enhancement when compared to the benchmark dye ICG could be shown, a finding that could be traced to its photophysical properties (short triplet lifetimes, low fluorescence and singlet oxygen sensitization quantum yields). A NIR excitation wavelength of 790 nm could be used, fully taking advantage of the optical window of tissue. Rapid renal clearance of the dye was observed. Its straight-forward synthesis, optical properties with the possibility for further optical fine-tuning, nontoxicity, favorable elimination rates, and contrast enhancement make this a promising PAI contrast agent. The ability to conjugate the PAI chromophore with a fluorescent tag using a facile and general conjugation strategy was also demonstrated.

  18. 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

  19. Light-activated nanotube–porphyrin conjugates as effective antiviral agents

    International Nuclear Information System (INIS)

    Banerjee, Indrani; Douaisi, Marc P; Mondal, Dhananjoy; Kane, Ravi S

    2012-01-01

    Porphyrins have been used for photodynamic therapy (PDT) against a wide range of targets like bacteria, viruses and tumor cells. In this work, we report porphyrin-conjugated multi-walled carbon nanotubes (NT-P) as potent antiviral agents. Specifically, we used Protoporphyrin IX (PPIX), which we attached to acid-functionalized multi-walled carbon nanotubes (MWNTs). We decided to use carbon nanotubes as scaffolds because of their ease of recovery from a solution through filtration. In the presence of visible light, NT-P was found to significantly reduce the ability of Influenza A virus to infect mammalian cells. NT-P may be used effectively against influenza viruses with little or no chance of them developing resistance to the treatment. Furthermore, NT-P can be easily recovered through filtration which offers a facile strategy to reuse the active porphyrin moiety to its fullest extent. Thus NT-P conjugates represent a new approach for preparing ex vivo reusable antiviral agents. (paper)

  20. Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

    Science.gov (United States)

    Rebelo, Susana L H; Silva, André M N; Medforth, Craig J; Freire, Cristina

    2016-04-12

    Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H₂TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H₂TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.