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.

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

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.

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

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.

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.

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

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.

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...

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.

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.

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)

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.

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.

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.

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.

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.

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...

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.

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.

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.

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.

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

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.

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.

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.

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

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.

The photodynamic and non-photodynamic actions of porphyrins

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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.

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

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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%.

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.

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.

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.

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.

Respiratory Monitoring by Porphyrin Modified Quartz Crystal Microbalance Sensors

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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.

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

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.

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

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.

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

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.

Corroles-Porphyrins: A Teamwork for Gas Sensor Arrays

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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.

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.

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.

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.

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)

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,.

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.

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

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

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.

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)

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.

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.

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.

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.

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.

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)

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

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

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 ...

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.

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

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.

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.

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

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.

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.

[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.

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.

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

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...

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.

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

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.

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.

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.

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.

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

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...

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.

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.

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.

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.

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.

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.

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

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.

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

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).

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.

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

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

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.

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.

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.

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.

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

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.

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.

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...

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

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.

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 ...

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.

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

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 ...

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

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.

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.

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.

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.

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.

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

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.

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...

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

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.

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.

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.

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.

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

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.

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

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.

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

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)

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.

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.

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

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.

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.

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%.

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)

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.

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.

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.

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

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)

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.

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

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)

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.

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.

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.

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-Co^III(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 Co^III(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-Co^III(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated Co^III(porphyrin) centers, thus highlighting the potential application of MOFs in cooperative catalysis.

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

Analysis of Anchoring Mechanism of Fully Grouted Prestressed Anchor

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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.

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

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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.

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...

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.

Susceptibility to anchoring effects

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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.

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.

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.

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.

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.

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

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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.

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.

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...

RAFT Synthesis and Self-Assembly of Free-Base Porphyrin Cored Star Polymers

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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.

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.

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.

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.

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.

New porphyrins bearing positively charged peripheral groups linked by a sulfonamide group to meso-tetraphenylporphyrin: interactions with calf thymus DNA.

Science.gov (United States)

Manono, Janet; Marzilli, Patricia A; Marzilli, Luigi G

2009-07-06

New water-soluble cationic meso-tetraarylporphyrins (TArP, Ar = 4-C(6)H(4)) and some metal derivatives have been synthesized and characterized. One main goal was to assess if N-methylpyridinium (N-Mepy) groups must be directly attached to the porphyrin core for intercalative binding of porphyrins to DNA. The new porphyrins have the general formula, [T(R(2)R(1)NSO(2)Ar)P]X(4/8) (R(1) = CH(3) or H and R(2) = N-Mepy-n-CH(2) with n = 2, 3, or 4; or R(1) = R(2) = Et(3)NCH(2)CH(2)). Interactions of selected porphyrins and metalloporphyrins (Cu(II), Zn(II)) with calf thymus DNA were investigated by visible circular dichroism (CD), absorption, and fluorescence spectroscopies. The DNA-induced changes in the porphyrin Soret region (a positive induced CD feature and, at high DNA concentration, increases in the Soret band and fluorescence intensities) indicate that the new porphyrins interact with DNA in an outside, non-self-stacking binding mode. Several new metalloporphyrins did not increase DNA solution viscosity and thus do not intercalate, confirming the conclusion drawn from spectroscopic studies. Porphyrins known to intercalate typically bear two or more N-Mepy groups directly attached to the porphyrin ring, such as the prototypical meso-tetra(N-Mepy)porphyrin tetracation (TMpyP(4)). The distances between the nitrogens of the N-Mepy group are estimated to be approximately 11 A (cis) and 16 A (trans) for the relatively rigid TMpyP(4). For the new flexible porphyrin, [T(N-Mepy-4-CH(2)(CH(3))NSO(2)Ar)P]Cl(4), the distances between the nitrogens are estimated to be able to span the range from approximately 9 to approximately 25 A. Thus, the N-Mepy groups in the new porphyrins can adopt the same spacing as in known intercalators such as TMpyP(4). The absence of intercalation by the new porphyrins indicates that the propensity for the N-Mepy group to facilitate DNA intercalation of cationic porphyrins requires direct attachment of N-Mepy groups to the porphyrin core.

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

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.

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.

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....

Solvent effects on the fluorescence and effective three-photon absorption of a Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin

Science.gov (United States)

Wan, Yong; Xue, Yuxiong; Sheng, Ning; Rui, Guanghao; Lv, Changgui; He, Jun; Gu, Bing; Cui, Yiping

2018-06-01

The fluorescence and effective three-photon absorption (3PA) properties of Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin] (labeled Zn(II)-porphyrin) dissolved in three different polar solvents were systematically investigated. The electrochemical and photophysical properties of Zn(II)-porphyrin were investigated by 1H NMR spectra, IR spectra, mass spectroscopy, and electronic absorption spectra. The fluorescence emission of Zn(II)-porphyrin in three different solvents excited at the wavelengths of 420 nm (Soret band) and 550 nm (Q-band) were analyzed. By performing Z-scan experiments with femtosecond laser pulses at a wavelength of 800 nm, the effective 3PA process of Zn(II)-porphyrin in three different solvents was observed and the underlying mechanism was discussed in detail. It is found that the fluorescence spectra slightly depend on the polarity of the solvent. Interestingly, the effective 3PA properties of Zn(II)-porphyrin strongly depend on the solvent polarity. The lower the solvent polarity is, the larger effective 3PA cross-section is. Low polar solvents are beneficial to applications of Zn(II)-porphyrin in optical limiting, photodynamic therapy, etc.

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

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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 ...

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

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

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei

2015-02-05

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei; Salmeia, Khalifah A.; Vagin, Sergei I.; Rieger, Bernhard

2015-01-01

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

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.

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.

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.

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.

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.

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 .

Mechanistic insight of the photodynamic effect induced by tri- and tetra-cationic porphyrins on Candida albicans cells.

Science.gov (United States)

Cormick, M Paula; Quiroga, Ezequiel D; Bertolotti, Sonia G; Alvarez, M Gabriela; Durantini, Edgardo N

2011-10-01

The photodynamic mechanism of action induced 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 on Candida albicans cells. These cationic porphyrins are effective photosensitizers, producing a ~5 log decrease of cell survival when the cultures are incubated with 5 μM photosensitizer and irradiated for 30 min with visible light. Studies under anoxic conditions indicated that oxygen is necessary for the mechanism of action of photodynamic inactivation of this yeast. Furthermore, photoinactivation of C. albicans cells was negligible in the presence of 100 mM azide ion, whereas the photocytotoxicity induced by these porphyrins increased in D(2)O. In contrast, the addition of 100 mM mannitol produced a negligible effect on the cellular phototoxicity. On the other hand, in vitro direct observation of singlet molecular oxygen, O(2)((1)Δ(g)) phosphorescence at 1270 nm was analyzed using C. albicans in D(2)O. A shorter lifetime of O(2)((1)Δ(g)) was found in yeast cellular suspensions. These cationic porphyrins bind strongly to C. albicans cells and the O(2)((1)Δ(g)) generated inside the cells is rapidly quenched by the biomolecules of the cellular microenvironment. Therefore, the results indicate that these cationic porphyrins appear to act as photosensitizers mainly via the intermediacy of O(2)((1)Δ(g)). This journal is © The Royal Society of Chemistry and Owner Societies 2011

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.

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.

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

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

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.

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.

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.

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

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 ...

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.

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)

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)

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.

First Example of a Lipophilic Porphyrin-Cardanol Hybrid Embedded in a Cardanol-Based Micellar Nanodispersion

Directory of Open Access Journals (Sweden)

Giuseppe Vasapollo

2012-10-01

Full Text Available Cardanol is a natural and renewable organic raw material obtained as the major chemical component by vacuum distillation of cashew nut shell liquid. In this work a new sustainable procedure for producing cardanol-based micellar nanodispersions having an embedded lipophilic porphyrin itself peripherally functionalized with cardanol substituents (porphyrin-cardanol hybrid has been described for the first time. In particular, cardanol acts as the solvent of the cardanol hybrid porphyrin and cholesterol as well as being the main component of the nanodispersions. In this way a “green” micellar nanodispersion, in which a high percentage of the micellar system is derived from renewable “functional” molecules, has been produced.

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.

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.

XAFS Debye-Waller Factors Temperature-Dependent Expressions for Fe+2-Porphyrin Complexes

International Nuclear Information System (INIS)

Dimakis, Nicholas; Bunker, Grant

2007-01-01

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

Studies of alkyl porphyrin distributions in organic-rich sediments using LC-MS

International Nuclear Information System (INIS)

Eckardt, C.B.; Carter, J.F.; Keely, B.J.; Maxwell, J.R.; Kilpatrick, G.

1992-01-01

In recent years, structure elucidation of a wide variety of sedimentary tetrapyrroles has provided clear molecular evidence for the presence of primary photosynthetic communities in palaeo water columns. The reported structures indicate an origin from algal chlorophylls c for certain components, while an origin from photosynthetic bacteria is apparent from the carbon skeletons of other components. In particular, the structures of ≤C 34 porphyrin carboxylic acids in the Eocene Messel shale indicate an origin from Chloroblum bacteria. Since such bacteria are strict anaerobes, the presence of these species is evidence for anoxic conditions extending into the photic zone of Messel lake. By analogy, the presence in the more widely-occurring alkyl porphyrin distributions of components >C 33 would also suggest a Chlorobium chlorophyll origin. Hence, in this paper, the authors studied by LC-MS, the distributions of alkyl porphyrins in selected sediments and searched for the presence of such components, in order to determine photic zone anoxia in the respective palaeo environments

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.

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.

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.

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.

Remarkable fluorescence enhancement versus complex formation of cationic porphyrins on the surface of ZnO nanoparticles

KAUST Repository

Aly, Shawkat Mohammede

2014-06-12

Fluorescence enhancement of organic fluorophores shows tremendous potential to improve image contrast in fluorescence-based bioimaging. Here, we present an experimental study of the interaction of two cationic porphyrins, meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride (TMPyP) and meso-tetrakis(4-N,N,N-trimethylanilinium)porphyrin chloride (TMAP), with cationic surfactant-stabilized zinc oxide nanoparticles (ZnO NPs) based on several steady-state and time-resolved techniques. We show the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic porphyrins. For TMPyP, we observe a sixfold increase in the fluorescence intensity of TMPyP upon addition of ZnO NPs. Our experimental results indicate that the electrostatic binding of TMPyP with the surface of ZnO NPs increases the symmetry of the porphyrin macrocycle. This electronic communication hinders the rotational relaxation of the meso unit and/or decreases the intramolecular CT character between the cavity and the meso substituent of the porphyrin, resulting in the enhancement of the intensity of the fluorescence. For TMAP, on the other hand, the different type and nature of the positive charge resulting in the development of the CT band arise from the interaction with the surface of ZnO NPs. This observation is confirmed by the femtosecond transient absorption spectroscopy, which provides clear spectroscopic signatures of photoinduced electron transfer from TMAP to ZnO NPs. © 2014 American Chemical Society.

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.

Porphyrins as Corrosion Inhibitors for N80 Steel in 3.5% NaCl Solution: Electrochemical, Quantum Chemical, QSAR and Monte Carlo Simulations Studies

Directory of Open Access Journals (Sweden)

Ambrish Singh

2015-08-01

Full Text Available The inhibition of the corrosion of N80 steel in 3.5 wt. % NaCl solution saturated with CO2 by four porphyrins, namely 5,10,15,20-tetrakis(4-hydroxyphenyl-21H,23H-porphyrin (HPTB, 5,10,15,20-tetra(4-pyridyl-21H,23H-porphyrin (T4PP, 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayltetrakis(benzoic acid (THP and 5,10,15,20-tetraphenyl-21H,23H-porphyrin (TPP was studied using electrochemical impedance spectroscopy (EIS, potentiodynamic polarization, scanning electrochemical microscopy (SECM and scanning electron microscopy (SEM techniques. The results showed that the inhibition efficiency, η% increases with increasing concentration of the inhibitors. The EIS results revealed that the N80 steel surface with adsorbed porphyrins exhibited non-ideal capacitive behaviour with reduced charge transfer activity. Potentiodynamic polarization measurements indicated that the studied porphyrins acted as mixed type inhibitors. The SECM results confirmed the adsorption of the porphyrins on N80 steel thereby forming a relatively insulated surface. The SEM also confirmed the formation of protective films of the porphyrins on N80 steel surface thereby protecting the surface from direct acid attack. Quantum chemical calculations, quantitative structure activity relationship (QSAR were also carried out on the studied porphyrins and the results showed that the corrosion inhibition performances of the porphyrins could be related to their EHOMO, ELUMO, ω, and μ values. Monte Carlo simulation studies showed that THP has the highest adsorption energy, while T4PP has the least adsorption energy in agreement with the values of σ from quantum chemical calculations.

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)

Broad hexagonal columnar mesophases formation in bioinspired transition-metal complexes of simple fatty acid meta-octaester derivatives of meso-tetraphenyl porphyrins.

Science.gov (United States)

Wu, Bin; Chen, Keyang; Deng, Yuchen; Chen, Jian; Liu, Chengjie; Cheng, Rongshi; Chen, Dongzhong

2015-02-23

A series of meta-substituted fatty acid octaester derivatives and their transition-metal complexes of meso- tetraphenyl porphyrins (TPP-8OOCR, with R = C(n-1)H(2n-1), n = 8, 12, or 16) have been prepared through very simple synthesis protocols. The thermotropic phase behavior and the liquid crystalline (LC) organization structures of the synthesized porphyrin derivatives were systematically investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable-temperature small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) techniques. The shorter octanoic acid ester substituted porphyrin (C8-TPP) did not show liquid crystallinity and its metal porphyrins exhibited an uncommon columnar mesophase. The lauric acid octaester (C12-TPP) and the palmitic acid octaester (C16-TPP) series porphyrins generated hexagonal columnar mesophase Colh. Moreover, the metal porphyrins C12-TPPM and C16-TPPM with M = Zn, Cu, or Ni, exhibited well-organized Colh mesophases of broad LC temperature ranges increasing in the order of TPPNiacid octaester porphyrins and their metal complexes very attractive for variant applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

A novel chlorine derivative of Meso-tris(pentafluorophenyl)-4-pyridyl porphyrin: synthesis, photophysics and photochemical properties

Energy Technology Data Exchange (ETDEWEB)

Maestrin, Ana Paula J.; Ribeiro, Anderson O.; Tedesco, Antonio Claudio; Neri, Claudio R.; Vinhado, Fabio S.; Serra, Osvaldo A.; Martins, Patricia R.; Iamamoto, Yassuko [Sao Paulo Univ., Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras. Inst. de Quimica]. E-mail: oaserra@ffclrp.usp.br; Silva, Ana Margarida G.; Tome, Augusto C.; Neves, Maria G.P.M.S.; Cavaleiro, Jose A.S. [Universidade de Aveiro (Portugal). Dept. de Quimica]. E-mail: jcavaleiro@dq.ua.pt

2004-12-01

Photodynamic therapy (PDT) is based on the accumulation of a photosensitizer, such as a porphyrin or a chlorine, in a malignant tissue after its administration. Chlorins exhibit photophysical properties similar to those of the porphyrin macrocycles, but with intensified and red-shifted Q bands, making chlorine-containing systems even better candidates for PDT. In this contribution, we report the synthesis of 5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)porphyrin, (2) and its transformation to the novel chlorine derivatives 4, (5,10,20-tris(pentafluorophenyl)-15-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo [3,4-b]porphyrin and 5, (5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo[3,4-b]porphyrin) by 1,3-dipolar cycloaddition with an azomethine ylide. The new products have been characterized by UV-Vis, {sup 1}H NMR and FAB-MS. The photophysics, photochemical and photobleaching properties of chlorine 4 have been evaluated. Its quantum yield of photobleaching ({phi}{sub Pb}, mol Einstein{sup -1}) was 0.047{+-}0.014. In order to demonstrate the production of {sup 1}O{sub 2} when 4 is used as a photosensitizer, uric acid tests have been carried out. The results indicate that chlorine 4 can be considered a promising photosensitizer in PDT. (author)

A novel chlorine derivative of Meso-tris(pentafluorophenyl)-4-pyridyl porphyrin: synthesis, photophysics and photochemical properties

International Nuclear Information System (INIS)

Maestrin, Ana Paula J.; Ribeiro, Anderson O.; Tedesco, Antonio Claudio; Neri, Claudio R.; Vinhado, Fabio S.; Serra, Osvaldo A.; Martins, Patricia R.; Iamamoto, Yassuko; Silva, Ana Margarida G.; Tome, Augusto C.; Neves, Maria G.P.M.S.; Cavaleiro, Jose A.S.

2004-01-01

Photodynamic therapy (PDT) is based on the accumulation of a photosensitizer, such as a porphyrin or a chlorine, in a malignant tissue after its administration. Chlorins exhibit photophysical properties similar to those of the porphyrin macrocycles, but with intensified and red-shifted Q bands, making chlorine-containing systems even better candidates for PDT. In this contribution, we report the synthesis of 5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)porphyrin, (2) and its transformation to the novel chlorine derivatives 4, (5,10,20-tris(pentafluorophenyl)-15-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo [3,4-b]porphyrin and 5, (5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo[3,4-b]porphyrin) by 1,3-dipolar cycloaddition with an azomethine ylide. The new products have been characterized by UV-Vis, 1 H NMR and FAB-MS. The photophysics, photochemical and photobleaching properties of chlorine 4 have been evaluated. Its quantum yield of photobleaching (φ Pb , mol Einstein -1 ) was 0.047±0.014. In order to demonstrate the production of 1 O 2 when 4 is used as a photosensitizer, uric acid tests have been carried out. The results indicate that chlorine 4 can be considered a promising photosensitizer in PDT. (author)

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.

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.

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

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.

Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance

Science.gov (United States)

Wang, Aijian; Yu, Wang; Huang, Zhipeng; Zhou, Feng; Song, Jingbao; Song, Yinglin; Long, Lingliang; Cifuentes, Marie P.; Humphrey, Mark G.; Zhang, Long; Shao, Jianda; Zhang, Chi

2016-03-01

Reduced graphene oxide (RGO)-porphyrin (TPP) nanohybrids (RGO-TPP 1 and RGO-TPP 2) were prepared by two synthetic routes that involve functionalization of the RGO using diazonium salts. The microscopic structures, morphology, photophysical properties and nonlinear optical performance of the resultant RGO-TPP nanohybrids were investigated. The covalent bonding of the porphyrin-functionalized-RGO nanohybrid materials was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin units to the surface of the RGO by diazotization significantly improves the solubility and ease of processing of these RGO-based nanohybrid materials. Ultraviolet/visible absorption and steady-state fluorescence studies indicate considerable π-π interactions and effective photo-induced electron and/or energy transfer between the porphyrin moieties and the extended π-system of RGO. The nonlinear optical properties of RGO-TPP 1 and RGO-TPP 2 were investigated by open-aperture Z-scan measurements at 532 nm with both 4 ns and 21 ps laser pulses, the results showing that the chemical nanohybrids exhibit improved nonlinear optical properties compared to those of the benchmark material C60, and the constituent RGO or porphyrins.

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

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.

[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

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.

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)

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

Science.gov (United States)

Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

2014-01-01

The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

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....

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

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.

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.

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.

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.

Obstruction of photoinduced electron transfer from excited porphyrin to graphene oxide: a fluorescence turn-on sensing platform for iron (III ions.

Directory of Open Access Journals (Sweden)

Zhong De Liu

Full Text Available A comparative research of the assembly of different porphyrin molecules on graphene oxide (GO and reduced graphene oxide (RGO was carried out, respectively. Despite the cationic porphyrin molecules can be assembled onto the surfaces of graphene sheets, including GO and RGO, to form complexes through electrostatic and π-π stacking interactions, the more obvious fluorescence quenching and the larger red-shift of the Soret band of porphyrin molecule in RGO-bound states were observed than those in GO-bound states, due to the difference of molecular flattening in degree. Further, more interesting finding was that the complexes formed between cationic porphyrin and GO, rather than RGO sheets, can facilitate the incorporation of iron (III ions into the porphyrin moieties, due to the presence of the oxygen-contained groups at the basal plane of GO sheets served as auxiliary coordination units, which can high-efficiently obstruct the electron transfer from excited porphyrin to GO sheets and result in the occurrence of fluorescence restoration. Thus, a fluorescence sensing platform has been developed for iron (III ions detection in this contribution by using the porphyrin/GO nanohybrids as an optical probe, and our present one exhibited rapid and sensitive responses and high selectivity toward iron (III ions.

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.

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)

Influence of aqueous media properties on aggregation and solubility of four structurally related meso-porphyrin photosensitizers evaluated by spectrophotometric measurements.

Science.gov (United States)

Sobczyński, J; Tønnesen, H H; Kristensen, S

2013-02-01

Porphyrin photosensitizers tend to aggregate in aqueous solutions even in the micromolar concentration range. This is a challenge during formulation of e.g., parenteral preparations for photodynamic cancer therapy, or preparations for local or topical administration in antimicrobial photodynamic therapy. Monomerization is essential to achieve biocompatible drug formulations of high bioavailability and physiological response (i.e., photoreactivity) and low toxicity. The aggregation and solubilization of four structurally related meso-tetraphenyl porphyrin photosensitizers with nonionic (4-hydroxy), anionic (4-sulphonate; 4-carboxy) and cationic (4-trimethylanilinium) substituents were evaluated in various vehicles by use of UV-Vis spectroscopy. Substituents, overall charge and charge distribution influenced the pKa-values and interaction of the porphyrins with different solvents, excipients and impurities. Modification of medium polarity and solubilization by the nonionic surfactant Tween 80 adjusted the acid-base equilibria and increased the solubility by reduction of porphyrin aggregation. The selected porphyrins were sensitive towards ionic strength, temperature and inorganic impurities to various extents. The results will be further used during development of parenteral and topical formulations of porphyrin photosensitizers for use in photodynamic therapy of cancer and bacterial infections.

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...

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.

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.

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.

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.

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

Shedding lights on the flexible-armed porphyrins: Human telomeric G4 DNA interaction and cell photocytotoxicity research.

Science.gov (United States)

Sun, Xiang-Yu; Zhao, Ping; Jin, Shu-Fang; Liu, Min-Chao; Wang, Xia-Hong; Huang, Yu-Min; Cheng, Zhen-Feng; Yan, Si-Qi; Li, Yan-Yu; Chen, Ya-Qing; Zhong, Yan-Mei

2017-08-01

DNA polymorphism exerts a fascination on a large scientific community. Without crystallographic structural data, clarification of the binding modes between G-quadruplex (G4) and ligand (complex) is a challenging job. In the present work, three porphyrin compounds with different flexible carbon chains (arms) were designed, synthesized and characterized. Their binding, folding and stabilizing abilities to human telomeric G4 DNA structures were comparatively researched. Positive charges at the end of the flexible carbon chains seem to be favorable for the DNA-porphyrin interactions, which were evidenced by the spectral results and further confirmed by the molecular docking calculations. Biological function analysis demonstrated that these porphyrins show no substantial inhibition to Hela, A549 and BEL 7402 cancer cell lines under dark while exhibit broad inhibition under visible light. This significantly enhanced photocytotoxicity relative to the dark control is an essential property of photochemotherapeutic agents. The feature of the flexible arms emerges as critical influencing factors in the cell photocytotoxicity. Moreover, an ROS-mediated mitochondrial dysfunction pathway was suggested for the cell apoptosis induced by these flexible-armed porphyrins. It is found that the porphyrins with positive charges located at the end of the flexible arms represent an exciting opportunity for photochemotherapeutic anti-cancer drug design. Copyright © 2017. Published by Elsevier B.V.

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.

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

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.

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.

Charge-transfer state and large first hyperpolarizability constant in a highly electronically coupled zinc and gold porphyrin dyad.

Science.gov (United States)

Fortage, Jérôme; Scarpaci, Annabelle; Viau, Lydie; Pellegrin, Yann; Blart, Errol; Falkenström, Magnus; Hammarström, Leif; Asselberghs, Inge; Kellens, Ruben; Libaers, Wim; Clays, Koen; Eng, Mattias P; Odobel, Fabrice

2009-09-14

We report the synthesis and the characterizations of a novel dyad composed of a zinc porphyrin (ZnP) linked to a gold porphyrin (AuP) through an ethynyl spacer. The UV/Vis absorption spectrum and the electrochemical properties clearly reveal that this dyad exhibits a strong electronic coupling in the ground state as evidenced by shifted redox potentials and the appearance of an intense charge-transfer band localized at lambda = 739 nm in dichloromethane. A spectroelectrochemical study of the dyad along with the parent homometallic system (i.e., ZnP-ZnP and AuP-AuP) was undertaken to determine the spectra of the reduced and oxidized porphyrin units. Femtosecond transient absorption spectroscopic analysis showed that the photoexcitation of the heterometallic dyad leads to an ultrafast formation of a charge-separated state ((+)ZnP-AuP(*)) that displays a particularly long lifetime (tau = 4 ns in toluene) for such a short separation distance. The molecular orbitals of the dyad were determined by DFT quantum-chemical calculations. This theoretical study confirms that the observed intense band at lambda = 739 nm corresponds to an interporphyrin charge-transfer transition from the HOMO orbital localized on the zinc porphyrin to LUMO orbitals localized on the gold porphyrin. Finally, a Hyper-Rayleigh scattering study shows that the dyad possesses a large first molecular hyperpolarizability coefficient (beta = 2100x10(-30) esu at lambda = 1064 nm), thus highlighting the valuable nonlinear optical properties of this new type of push-pull porphyrin system.

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

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

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%.

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...

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

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.

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.

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...

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.

χ{sup (3)} measurements of axial ligand modified high valent tin(IV) porphyrins using degenarete four wave mixing at 532nm

Energy Technology Data Exchange (ETDEWEB)

Narendran, N. K. Siji, E-mail: sijinarendran@gmail.com; Chandrasekharan, K. [Laser and nonlinear optics laboratory, Department of Physics, National Institute of Technology Calicut, Calicut-673601, Kerala (India); Soman, Rahul; Arunkumar, Chellaiah [Bioinorganic materials laboratory, Department of Chemistry, National Institute of Technology Calicut, Calicut-673601, Kerala (India); Sudheesh, P. [Department of Physics, VTM NSS College, Dhanuvachapuram, Thiruvananthapuram (India)

2014-10-15

Porphyrins and metalloporphyrins are unique class of molecules for Nonlinear Optical applications because of their unique structure of altering the central metal atom, large extended π-system, high thermal stability, tunable shape, symmetry and synthetic versatility Here, we report χ{sup (3)} Measurements of a simple phenyl porphyrins and its highvalent tin(IV) porphyrins with Bromination characterized by UV-Visible spectroscopic method. In this study, we employed the Degenerate Four Wave Mixing technique using forward Boxcar geometry with an Nd:YAG nano second pulsed laser as source and it was found that the tin(IV) porphyrin with Bromination exhibits good χ{sup (3)} value and figure of merit.

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

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.

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.

Facile N...N coupling of manganese(V) imido species.

Science.gov (United States)

Yiu, Shek-Man; Lam, William W Y; Ho, Chi-Ming; Lau, Tai-Chu

2007-01-31

(Salen)manganese(V) nitrido species are activated by electrophiles such as trifluoroacetic anhydride (TFAA) or trifluoroacetic acid (TFA) to produce N2. Mechanistic studies suggest that the manganese(V) nitrido species first react with TFAA or TFA to produce an imido species, which then undergoes N...N coupling. It is proposed that the resulting manganese(III) mu-diazene species decomposes via internal redox to give N2 and manganese(II). The manganese(II) species is then rapidly oxidized by manganese(V) imide to give manganese(III) and CF3CONH2 (for TFAA) or NH3 (for TFA).

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...

Porphyrin-containing polyaspartamide gadolinium complexes as potential magnetic resonance imaging contrast agents.

Science.gov (United States)

Yan, Guo-Ping; Li, Zhen; Xu, Wei; Zhou, Cheng-Kai; Yang, Lian; Zhang, Qiao; Li, Liang; Liu, Fan; Han, Lin; Ge, Yuan-Xing; Guo, Jun-Fang

2011-04-04

Porphyrin-containing polyaspartamide ligands (APTSPP-PHEA-DTPA) were synthesized by the incorporation of diethylenetriaminepentaacetic acid (DTPA) and 5-(4'-aminophenyl)-10,15,20-tris(4'-sulfonatophenyl) porphyrin, trisodium salt (APTSPP) into poly-α,β-[N-(2-hydroxyethyl)-l-aspartamide] (PHEA). These ligands were further reacted with gadolinium chloride to produce macromolecule-gadolinium complexes (APTSPP-PHEA-DTPA-Gd). Experimental data of (1)H NMR, IR, UV and elemental analysis evidenced the formation of the polyaspartamide ligands and gadolinium complexes. In vitro and in vivo property tests indicated that APTSPP-PHEA-DTPA-Gd possessed noticeably higher relaxation effectiveness, less toxicity to HeLa cells, and significantly higher enhanced signal intensities (SI) of the VX2 carcinoma in rabbits with lower injection dose requirement than that of Gd-DTPA. Moreover, APTSPP-PHEA-DTPA-Gd was found to greatly enhance the contrast of MR images of the VX2 carcinoma, providing prolonged intravascular duration, and distinguished the VX2 carcinoma and normal tissues in rabbits according to MR image signal enhancements. These porphyrin-containing polyaspartamide gadolinium complexes can be used as the candidates of contrast agents for targeted MRI to tumors. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

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

Spectroscopic studies on the interaction of a water-soluble cationic porphyrin with proteins

Science.gov (United States)

Ma, Hong-Min; Chen, Xin; Zhang, Nuo; Han, Yan-Yan; Wu, Dan; Du, Bin; Wei, Qin

2009-04-01

The interaction of a water-soluble cationic porphyrin, meso-tetrakis (4- N, N, N-trimethylanilinium) porphyrin (TMAP), with two proteins, bovine serum albumin (BSA) and human serum albumin (HSA), was studied by UV-vis absorption spectroscopy, fluorescence spectroscopy, fluorescence anisotropy and synchronous fluorescence spectroscopy at neutral aqueous solutions. Free base TMAP bound to proteins as monomers and no aggregation was observed. The binding of TMAP quenched the fluorescence of the protein. On the contrary, the fluorescence of TMAP was enhanced and the fluorescence anisotropy increased due to the binding. The direct static binding mechanism could account for the quenching by TMAP and the binding constants were calculated. TMAP showed a higher quenching efficiency and binding constant of HSA than BSA. The binding of TMAP had no obvious effect on the molecular conformation of the protein. There was only one binding site for TMAP and it was located on the surface of the protein molecule. Electrostatic force played an important role in the binding due to the opposite charges on porphyrin and the proteins.

Correlation between airborne manganese concentration at the workstations in the iron foundry and manganese concentration in workers’ blood

Directory of Open Access Journals (Sweden)

Seyedtaghi Mirmohammadi

2017-08-01

Full Text Available Background: Manganese (Mn used as raw material for melting process in the ferrous foundry is considered as hazardous neurotoxic substance because it accumulates in the central nervous system and may cause neurological disorders. The furnace-men and melting department workers are potentially exposed to manganese particles or fume in the workplace. The objective of the research has been to investigate the sources and levels of manganese exposure in the foundry by correlation of blood-manganese (B-Mn and air-manganese (air-Mn measurement. Material and Methods: Air-Mn and Mn of blood serum were measured involving workers who worked in a big-sized foundry during 1 year. The standard method of the Occupational Safety and Health Administration (OSHA ID-121 was used for air and blood assessment and atomic absorption spectroscopy (AAS was carried out for air and blood sample analysis. Results: The air sampling results have revealed that there is a high exposure to manganese (4.5 mg/m3 in the workplace as compared to the National Institute for Occupational Safety and Health’s (NIOSH time weighted average (the reference time-weighted average (TWA = 1 mg/m3. The average blood serum Mn concentration was 2.745 μg/l for subjects working for shorter than 3 months and 274.85 μg/l for subjects working 3–12 months. Conclusions: Against the research hypothesis there was no correlation between the air-Mn concentration and the B-Mn (serum level of manganese in the serum of the exposed subjects. It may be due to short time of air sampling of manganese airborne particles, and a real-time monitoring of airborne manganese particles is suggested for any future study. Med Pr 2017;68(4:449–458

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)

New Activity of a Protein from Canavalia ensiformis

Directory of Open Access Journals (Sweden)

Vanya Petkova BOGOEVA

2014-06-01

Full Text Available Concanavalin A is a legume lectin which preferentially agglutinates transformed cells and shows antitumor effects on human breast carcinoma cells in vitro and in vivo. It is considered as a new potential antineoplastic agent targeting apoptosis, autophagy, and anti-angiogenesis in preclinical or clinical trials for cancer therapeutics, which has recently become the object of intensive study. In the present investigation, we show the capacity of the lectin to bind manganese, gold, iron, and zinc porphyrins: all potential anticancer agents. The interaction of the legume lectin with the studied compounds has been investigated by tryptophan fluorescence, showing conformational changes within the quaternary and tertiary structures of the protein. The binding of Con A with manganese, gold, and iron porphyrins, as well as adenine, was studied by fluorescence quenching. In contrast, the interaction of Con A with zinc porphyrin caused an increase in Trp fluorescence and a red shift of 10 nm of the emission maximum position. However, the binding of Con A to iron porphyrin was accompanied by a 5 nm blue shift of the emission maximum, and a kD of 0.95 ± 0.13 μM was calculated, respectively. The sigmoidal shape of the curve showed cooperative interactions, which indicated the presence of more than one class of binding site within the Con A molecule for iron porphyrin, confirmed by the Hill slope (h = 1.89±0.46. We have found that the legume lectin interacts with porphyrins and adenine with an affinity (0.14–1.89 μM similar to that of the non-legume lectin, wheat germ agglutinin. In conclusion, the protein Con A shows new binding activity towards porphyrins with anticancer activities and could find prospective application as a drug delivery molecule that specifically targets cancer cells.

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

Body burden of hexachlorobenzene in suckling rats and its effects on various organs and on liver porphyrin accumulation

Energy Technology Data Exchange (ETDEWEB)

Mendoza, C E; Grant, D L; Shields, J B

1975-01-01

The hexachlorobenzene (HCB) and porphyrin accumulation in the organs of 18-day-old Wistar rats, whose mothers were fed a diet containing 80 ppM HCB, were studied. Among the organs examined, the highest HCB residue was in the liver greater than kidney greater than or equal to lung greater than brain greater than spleen greater than heart. The porphyrin level in the liver of the HCB-treated group was approximately 2.5 fold greater than that in the control liver. About equal porphyrin concentrations were found in the male and female pups. The analysis of variance indicated the liver weight was significantly increased by the HCB-treatment. On the contrary, the weights of the kidney, brain, spleen, and heart were significantly reduced. Sex did not influence the organ weight except that of the brain. The results suggested that accumulation of HCB in different organs and porphyrin in the liver of suckling Wistar rats was about equal for the males and females.

HepG2 human hepatocarcinomas cells sensitization by endogenous porphyrins

Science.gov (United States)

Vonarx-Coinsmann, Veronique; Foultier, Marie-Therese; de Brito, Leonor X.; Morlet, Laurent; Patrice, Thierry

1995-03-01

We assessed the ability of the human hepatocarcinoma cell line HepG2 to synthesize PpIX in vitro from exogenous ALA and analyzed ALA-induced toxicity and phototoxicity on this cell line. ALA induced a slight dose-dependent dark toxicity, with 79 and 66% cell survival respectively for ALA 50 and 100 mg/ml after 3-h incubation. Whereas the same treatment followed by laser irradiation (l equals 632 nm, 25 J/sq cm) induced dose-dependent phototoxicity, with 54 and 19% cell survival 24 h after PDT. Whatever the incubation time with ALA, a 3-h delay before light exposure was found optimal to reach a maximal phototoxicity. Photoproducts induced by porphyrin light irradiation absorbed light in the red spectral region at longer wavelengths than did the original porphyrins. The possible enhancement of PDT effects after ALA HepG2 cell incubation was investigated by irradiating cells successively with red light (l equals 632 nm) and light (l equals 650 nm). Total fluence was kept constant at 25 J/sq cm. Phototoxicity was lower when cells were irradiated for increased periods of l equals 650 nm light than with l equals 632 nm light alone. Any photoproducts involved had either a short life or were poorly photoreactive. HepG2 cells, synthesizing enzymes and precursors of endogenous porphyrin synthesis, represent a good in vitro model for experiments using ALA-PpIX-PDT.

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.

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.

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.

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.

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.

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.

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.

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.

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...

Cooperative effects in CdSe/ZnS-PEGOH quantum dot luminescence quenching by a water soluble porphyrin

International Nuclear Information System (INIS)

Borissevitch, I.E.; Parra, G.G.; Zagidullin, V.E.; Lukashev, E.P.; Knox, P.P.; Paschenko, V.Z.; Rubin, A.B.

2013-01-01

In this work we report on the study of the interaction of CdSe/ZnS-PEGOH 570 Quantum Dot (QD) with negatively charged meso-tetrakis(p-sulfonato-phenyl)porphyrin (TPPS 4 ) using optical absorption and fluorescence spectroscopies accompanied with time resolved “single photon counting” and dynamic and resonance light scattering techniques. In the steady-state experiments the QD luminescence quenching by TPPS 4 was well approximated by a square law. In the time-resolved experiments we observed a typical multi-exponential luminescence decay curve, successfully fitted by a bi-exponential approximation. At QD interaction with porphyrin the time quenching of both components was described by a linear Stern–Volmer dependence. The discrepancy between Stern–Volmer dependences in the steady-state and time resolved experiments may be due to formation of mixed m(TPPS 4 )+n(QD) complexes, in which one TPPS 4 molecule can quench several excited QDs. This idea is in accordance with the dynamic and resonance light scattering data, which demonstrate an increase of the scattering particle size at the TPPS 4 addition to QD solutions. - Highlights: ► Quantum Dot luminescence quenching by TPPS porphyrin was studied in water solutions. ► The size of particles in QD solutions possessed increase at the TPPS4 addition. ► Quenching of the QD luminescence by TPPS4 is realized in contact QD–porphyrin complexes. ► The formation of mixed quantum dot–porphyrin aggregates takes place.

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

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...

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.

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

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.

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

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

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

Perturbations in DNA structure upon interaction with porphyrins revealed by chemical probes, DNA footprinting and molecular modelling.

Science.gov (United States)

Ford, K G; Neidle, S

1995-06-01

The interactions of several porphyrins with a 74 base-pair DNA sequence have been examined by footprinting and chemical protection methods. Tetra-(4-N-methyl-(pyridyl)) porphyrin (TMPy), two of its metal complexes and tetra-(4-trimethylanilinium) porphyrin (TMAP) bind to closely similar AT-rich sequences. The three TMPy ligands produce modest changes in DNA structure and base accessibility on binding, in contrast to the large-scale conformational changes observed with TMAP. Molecular modelling studies have been performed on TMPy and TMAP bound in the AT-rich minor groove of an oligonucleotide. These have shown that significant structural change is needed to accommodate the bulky trimethyl substituent groups of TMAP, in contrast to the facile minor groove fit of TMPy.

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 ...

Restoration of growth by manganese in a mutant strain of Escherichia coli lacking most known iron and manganese uptake systems

DEFF Research Database (Denmark)

Taudte, Nadine; German, Nadezhda; Zhu, Yong-Guan

2016-01-01

The interplay of manganese and iron homeostasis and oxidative stress in Escherichia coli can give important insights into survival of bacteria in the phagosome and under differing iron or manganese bioavailabilities. Here, we characterized a mutant strain devoid of all know iron/manganese-uptake ......The interplay of manganese and iron homeostasis and oxidative stress in Escherichia coli can give important insights into survival of bacteria in the phagosome and under differing iron or manganese bioavailabilities. Here, we characterized a mutant strain devoid of all know iron...

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.

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.

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.

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.

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.

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.

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.

Electron transfer between a zinc porphyrin photo-sensitized in the visible, and various acceptors, in aqueous and micellar solutions

International Nuclear Information System (INIS)

Le Roux, Dominique

1983-01-01

This research thesis addresses the study of reactions occurring during the transformation of solar energy in chemical energy, and more precisely the search for photochemical systems allowing the dissociation of water into hydrogen and oxygen. In this study on water photolysis, the author chose to use a porphyrin soluble in water, the zinc tetra-meta-N-methylpyridinium porphyrin, as one of its isomer provided a good efficiency in hydrogen formation. Before reporting the study of electron photo-transfer, the author reports the study of photo-physical and photochemical properties of this porphyrin. Then, in the case of a well known electron acceptor (methyl viologen), he studied the influence of Coulomb effects on the kinetics of direct electron transfer, and on the kinetics of recombination of formed species. He also studied the influence of organised systems (cationic micelles) on these reactions when using a viologen with long chains. He finally reports the study of reactions of the triplet state of this porphyrin with metallic complexes

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

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)

Aggregation and metal-complexation behaviour of THPP porphyrin in ethanol/water solutions as function of pH

Science.gov (United States)

Zannotti, Marco; Giovannetti, Rita; Minofar, Babak; Řeha, David; Plačková, Lydie; D'Amato, Chiara A.; Rommozzi, Elena; Dudko, Hanna V.; Kari, Nuerguli; Minicucci, Marco

2018-03-01

The effect of pH change on 5,10,15,20-Tetrakis(4-hydroxyphenyl)-21H,23H-porphine (THPP) with its aggregation as function of water-ethanol mixture was studied with UV-vis, fluorescence, Raman and computational analysis. In neutral pH, THPP was present as free-base and, increasing the water amount, aggregation occurred with the formation of H- and J-aggregates. The aggregation constant and the concentration of dimers were calculated, other information about the dimer aggregation were evaluated by computational study. In acidic pH, by the insertions of two hydrogens in the porphyrin rings, the porphyrin changed its geometry with a ring deformation confirmed by red-shifted spectrum and quenching in fluorescence; at this low pH, increasing the water amount, the acidic form (THPPH2)2 + resulted more stable due to a polar environment with stronger interaction by hydrogen bonding. In basic pH, reached by NH4OH, THPP porphyrin was able to react with alkali metals in order to form sitting-atop complex (M2THPP) confirmed by the typical absorption spectrum of metallo-porphyrin, Raman spectroscopy and by computational analysis.

N-Annulated perylene-substituted and fused porphyrin dimers with intense near-infrared one-photon and two-photon absorption

KAUST Repository

Luo, Jie

2015-01-21

Fusion of two N-annulated perylene (NP) units with a fused porphyrin dimer along the S0-S1 electronic transition moment axis has resulted in new near-infrared (NIR) dyes 1a/1b with very intense absorption (ε>1.3×105M-1cm-1) beyond 1250nm. Both compounds displayed moderate NIR fluorescence with fluorescence quantum yields of 4.4×10-6 and 6.0×10-6 for 1a and 1b, respectively. The NP-substituted porphyrin dimers 2a/2b have also been obtained by controlled oxidative coupling and cyclodehydrogenation, and they showed superimposed absorptions of the fused porphyrin dimer and the NP chromophore. The excited-state dynamics of all of these compounds have been studied by femtosecond transient absorption measurements, which revealed porphyrin dimer-like behaviour. These new chromophores also exhibited good nonlinear optical susceptibility with large two-photon absorption cross-sections in the NIR region due to extended π-conjugation. Time-dependent density functional theory calculations have been performed to aid our understanding of their electronic structures and absorption spectra.

Trace Oxygen Sensitive Material Based on Two Porphyrin Derivatives in a Heterodimeric Complex

Directory of Open Access Journals (Sweden)

Eugenia Fagadar-Cosma

2017-10-01

Full Text Available The successful preparation of a novel dimer complex formed between 5,10,15,20-tetrakis(3,4-dimethoxyphenyl-porphyrin Fe(III chloride and (5,10,15,20-tetraphenylporphinato dichlorophosphorus(V chloride using the well-known reactivity of the P–X bond is reported. The obtained complex was characterized by UV-vis, Fourier transform infrared spectroscopy (FT-IR, fluorescence, 1H-NMR, 13C-NMR, and 31P-NMR spectroscopic techniques and also by additional Heteronuclear Single Quantum Coherence (HSQC and Heteronuclear Multiple Bond Correlation (HMBC experiments in order to correctly assign the NMR signals. Scanning electron microscopy (SEM and EDX quantifications completed the characterizations. This novel porphyrin dimer complex demonstrated fluorescence sensing of H2O2 in water for low oxygen concentrations in the range of 40–90 µM proving medical relevance for early diagnosis of diseases such as Alzheimer’s, Parkinson’s, Huntington’s, and even cancer because higher concentrations of H2O2 than 50 μM are consideredcytotoxic for life. Due to its optical properties, this novel metalloporphyrin–porphyrin based complex is expected to show PDT and bactericidal activity under visible-light irradiation.

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…

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.

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.

Molecular-structure control of ultrafast electron injection at cationic porphyrin-CdTe quantum dot interfaces

KAUST Repository

Aly, Shawkat Mohammede

2015-03-05

Charge transfer (CT) at donor (D)/acceptor (A) interfaces is central to the functioning of photovoltaic and light-emitting devices. Understanding and controlling this process on the molecular level has been proven to be crucial for optimizing the performance of many energy-challenge relevant devices. Here, we report the experimental observations of controlled on/off ultrafast electron transfer (ET) at cationic porphyrin-CdTe quantum dot (QD) interfaces using femto- and nanosecond broad-band transient absorption (TA) spectroscopy. The time-resolved data demonstrate how one can turn on/off the electron injection from porphyrin to the CdTe QDs. With careful control of the molecular structure, we are able to tune the electron injection at the porphyrin-CdTe QD interface from zero to very efficient and ultrafast. In addition, our data demonstrate that the ET process occurs within our temporal resolution of 120 fs, which is one of the fastest times recorded for organic photovoltaics. © 2015 American Chemical Society.

Synthesis, optical and electrochemical properties of Zn-porphyrin for dye sensitized solar cell applications

Energy Technology Data Exchange (ETDEWEB)

Kotteswaran, S.; Pandian, M. Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in [SSN Research Centre, SSN College of Engineering, Chennai-603110, Tamilnadu (India)

2016-05-23

Zn-Porphyrin dye has been synthesized by the reaction between aldehydes and pyrrole. The dye structure was confirmed by {sup 1}H NMR, {sup 13}C NMR spectrum. The functional group of the dye molecule was confirmed by FTIR spectrum. The UV-Vis-NIR absorption spectrum of Zn-Porphyrin in DMF solution was recorded in spectrophotometer. The UV-Vis NIR spectrum of dye exhibits a strong Soret band and Q-band. Cyclic Voltammograms were obtained with three electrode systems: Pt as counter electrode, saturated calomel used as a reference electrode and glassy carbon as working electrode at a scan rate of 100 mV/s. The curves recorded the oxidation of 0.5 mM compound Zn-Porphyrin in a dichloromethane solution containing 0.1M TBAP as supporting electrolyte, reveal two successive quasi reversible redox couples with the first anodic and cathodic peak potentials of -0.2 V and -1 V. The second anodic and cathodic peak potentials are 0.82 V and 0.01 V respectively.

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.

Cooperative effects in CdSe/ZnS-PEGOH quantum dot luminescence quenching by a water soluble porphyrin

Energy Technology Data Exchange (ETDEWEB)

Borissevitch, I.E., E-mail: iourib@ffclrp.usp.br [Departamento de Fisica, Faculdade de Filosofia Ciencia e Letras de Ribeirao Preto, Universidade de Sao Paulo, Av. Bandeirantes 3900, Ribeirao Preto, SP (Brazil); Parra, G.G. [Departamento de Fisica, Faculdade de Filosofia Ciencia e Letras de Ribeirao Preto, Universidade de Sao Paulo, Av. Bandeirantes 3900, Ribeirao Preto, SP (Brazil); Zagidullin, V.E.; Lukashev, E.P.; Knox, P.P.; Paschenko, V.Z.; Rubin, A.B. [Department of Biophysics, Faculty of Biology, M.V. Lomonosov Moscow State University, Vorobyovy Gory, 119991 Moscow (Russian Federation)

2013-02-15

In this work we report on the study of the interaction of CdSe/ZnS-PEGOH 570 Quantum Dot (QD) with negatively charged meso-tetrakis(p-sulfonato-phenyl)porphyrin (TPPS{sub 4}) using optical absorption and fluorescence spectroscopies accompanied with time resolved 'single photon counting' and dynamic and resonance light scattering techniques. In the steady-state experiments the QD luminescence quenching by TPPS{sub 4} was well approximated by a square law. In the time-resolved experiments we observed a typical multi-exponential luminescence decay curve, successfully fitted by a bi-exponential approximation. At QD interaction with porphyrin the time quenching of both components was described by a linear Stern-Volmer dependence. The discrepancy between Stern-Volmer dependences in the steady-state and time resolved experiments may be due to formation of mixed m(TPPS{sub 4})+n(QD) complexes, in which one TPPS{sub 4} molecule can quench several excited QDs. This idea is in accordance with the dynamic and resonance light scattering data, which demonstrate an increase of the scattering particle size at the TPPS{sub 4} addition to QD solutions. - Highlights: Black-Right-Pointing-Pointer Quantum Dot luminescence quenching by TPPS porphyrin was studied in water solutions. Black-Right-Pointing-Pointer The size of particles in QD solutions possessed increase at the TPPS4 addition. Black-Right-Pointing-Pointer Quenching of the QD luminescence by TPPS4 is realized in contact QD-porphyrin complexes. Black-Right-Pointing-Pointer The formation of mixed quantum dot-porphyrin aggregates takes place.

Saddle-shaped porphyrins for dye-sensitized solar cells: new insight into the relationship between nonplanarity and photovoltaic properties.

Science.gov (United States)

Shahroosvand, Hashem; Zakavi, Saeed; Sousaraei, Ahmad; Eskandari, Mortaza

2015-03-07

We report on the theoretical and experimental studies of the new dye-sensitized solar cells functionalized with 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin zinc(II) complexes bearing 2- and 8-bromo substituents at the β positions. In agreement with the results of TD-DFT calculations, the absorption maxima of di- and octa-brominated Zn(II) complexes, ZnTCPPBr2 and ZnTCPPBr8, exhibited large red-shift compared to that of the non-brominated free base porphyrin (H2TCPP). Furthermore, DFT calculations showed that the higher stabilization of the LUMO levels relative to the HOMO ones makes the HOMO-LUMO gap of the brominated Zn-porphyrins models smaller compared to that of the nonbrominated counterparts, which explains the red shifts of the Soret and Q bands of the brominated compounds. Solar cells containing the new saddle-shaped Zn(II) porphyrins were subjected to analysis in a photovoltaic calibration laboratory to determine their solar to electric energy conversion. In this regard, we found that the overall conversion efficiency of ZnTCPPBr8 adsorbed on TiO2 nanocrystalline films was 5 times as large as that of ZnTCPPBr2 adsorbed on the same films. The effect of the increasing number of Br groups on the photovoltaic performance of the complexes was compared to the results of computational methods using ab initio DFT molecular dynamics simulations and quantum dynamics calculations of electronic relaxation to investigate the interfacial electron transfer (IET) in TCPPBrx/TiO2-anatase nanostructures. Better IET in ZnTCPPBr8 compared to ZnTCPPBr2, and in H2TCPP was evaluated from interfacial electron transfer (IET) simulations. The IET results indicate that electron injection in ZnTCPPBr8-TiO2 (τ = 25 fs) can be up to 5 orders of magnitude faster than ZnTCPPBr2-TiO2 (τ = 125 fs). Both experimental and theoretical results demonstrate that the increase of the number of bromo-substituents at the β-pyrrole positions of the porphyrin macrocycle created a new class of

Reversible formation of high-valent-iron-oxo-porphyrin intermediate in heme-based catalysis: revisiting the kinetic model for horseradish peroxidase.

NARCIS (Netherlands)

Haandel, van M.J.H.; Primus, J.L.; Teunis, C.; Boersma, M.G.; Osman, A.M.; Veeger, C.; Rietjens, I.M.C.M.

1998-01-01

Many heme-containing biocatalysts exert their catalytic action through the initial formation of so-called high-valent-iron-oxo porphyrin intermediates. For horseradish peroxidase the initial intermediate formed has been identified as a high-valent-iron-oxo porphyrin π-radical cation, called compound

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.

Perturbations in the Photosynthetic Pigment Status Result in Photooxidation-Induced Crosstalk between Carotenoid and Porphyrin Biosynthetic Pathways

Directory of Open Access Journals (Sweden)

Joon-Heum Park

2017-11-01

Full Text Available Possible crosstalk between the carotenoid and porphyrin biosynthetic pathways under photooxidative conditions was investigated by using their biosynthetic inhibitors, norflurazon (NF and oxyfluorfen (OF. High levels of protoporphyrin IX (Proto IX accumulated in rice plants treated with OF, whereas Proto IX decreased in plants treated with NF. Both NF and OF treatments resulted in greater decreases in MgProto IX, MgProto IX methyl ester, and protochlorophyllide. Activities and transcript levels of most porphyrin biosynthetic enzymes, particularly in the Mg-porphyrin branch, were greatly down-regulated in NF and OF plants. In contrast, the transcript levels of GSA, PPO1, and CHLD as well as FC2 and HO2 were up-regulated in NF-treated plants, while only moderate increases in FC2 and HO2 were observed in the early stage of OF treatment. Phytoene, antheraxanthin, and zeaxanthin showed high accumulation in NF-treated plants, whereas other carotenoid intermediates greatly decreased. Transcript levels of carotenoid biosynthetic genes, PSY1 and PDS, decreased in response to NF and OF, whereas plants in the later stage of NF treatment exhibited up-regulation of BCH and VDE as well as recovery of PDS. However, perturbed porphyrin biosynthesis by OF did not noticeably influence levels of carotenoid metabolites, regardless of the strong down-regulation of carotenoid biosynthetic genes. Both NF and OF plants appeared to provide enhanced protection against photooxidative damage, not only by scavenging of Mg-porphyrins, but also by up-regulating FC2, HO2, and Fe-chelatase, particularly with increased levels of zeaxanthin via up-regulation of BCH and VDE in NF plants. On the other hand, the up-regulation of GSA, PPO1, and CHLD under inhibition of carotenogenic flux may be derived from the necessity to recover impaired chloroplast biogenesis during photooxidative stress. Our study demonstrates that perturbations in carotenoid and porphyrin biosynthesis coordinate

Perturbations in the Photosynthetic Pigment Status Result in Photooxidation-Induced Crosstalk between Carotenoid and Porphyrin Biosynthetic Pathways.

Science.gov (United States)

Park, Joon-Heum; Tran, Lien H; Jung, Sunyo

2017-01-01

Possible crosstalk between the carotenoid and porphyrin biosynthetic pathways under photooxidative conditions was investigated by using their biosynthetic inhibitors, norflurazon (NF) and oxyfluorfen (OF). High levels of protoporphyrin IX (Proto IX) accumulated in rice plants treated with OF, whereas Proto IX decreased in plants treated with NF. Both NF and OF treatments resulted in greater decreases in MgProto IX, MgProto IX methyl ester, and protochlorophyllide. Activities and transcript levels of most porphyrin biosynthetic enzymes, particularly in the Mg-porphyrin branch, were greatly down-regulated in NF and OF plants. In contrast, the transcript levels of GSA, PPO1 , and CHLD as well as FC2 and HO2 were up-regulated in NF-treated plants, while only moderate increases in FC2 and HO2 were observed in the early stage of OF treatment. Phytoene, antheraxanthin, and zeaxanthin showed high accumulation in NF-treated plants, whereas other carotenoid intermediates greatly decreased. Transcript levels of carotenoid biosynthetic genes, PSY1 and PDS , decreased in response to NF and OF, whereas plants in the later stage of NF treatment exhibited up-regulation of BCH and VDE as well as recovery of PDS . However, perturbed porphyrin biosynthesis by OF did not noticeably influence levels of carotenoid metabolites, regardless of the strong down-regulation of carotenoid biosynthetic genes. Both NF and OF plants appeared to provide enhanced protection against photooxidative damage, not only by scavenging of Mg - porphyrins, but also by up-regulating FC2, HO2 , and Fe-chelatase, particularly with increased levels of zeaxanthin via up-regulation of BCH and VDE in NF plants. On the other hand, the up-regulation of GSA, PPO1 , and CHLD under inhibition of carotenogenic flux may be derived from the necessity to recover impaired chloroplast biogenesis during photooxidative stress. Our study demonstrates that perturbations in carotenoid and porphyrin biosynthesis coordinate the

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

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.

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.

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).

Visible light-driven O2 reduction by a porphyrin-laccase system.

Science.gov (United States)

Lazarides, Theodore; Sazanovich, Igor V; Simaan, A Jalila; Kafentzi, Maria Chrisanthi; Delor, Milan; Mekmouche, Yasmina; Faure, Bruno; Réglier, Marius; Weinstein, Julia A; Coutsolelos, Athanassios G; Tron, Thierry

2013-02-27

Several recent studies have shown that the combination of photosensitizers with metalloenzymes can support a light-driven multielectron reduction of molecules such as CO(2) or HCN. Here we show that the association of the zinc tetramethylpyridinium porphyrin (ZnTMPyP(4+)) photosensitizer with the multicopper oxidase (MCO) laccase allows to link the oxidation of an organic molecule to the four electrons reduction of dioxygen into water. The enzyme is photoreduced within minutes with porphyrin/enzyme ratio as low as 1:40. With a 1:1 ratio, the dioxygen consumption rate is 1.7 μmol L(-1) s(-1). Flash photolysis experiments support the formation of the triplet excited state of ZnTMPyP(4+) which reduces the enzyme to form a radical cation of the porphyrin with a k(ET) ≈ 10(7) s(-1) M(-1). The long-lived triplet excited state of the ZnTMPyP(4+) (τ(0) = 0.72 ms) accounts for a substantial electron-transfer quantum yield, φ(ET) = 0.35. Consequently, the enzyme-dependent photo-oxidation of the electron donor occurs with a turnover of 8 min(-1) for the one-electron oxidation process, thereby supporting the suitability of such enzyme/sensitizer hybrid systems for aerobic photodriven transformations on substrates. This study is the first example of a phorphyrin-sensitized four-electron reduction of an enzyme of the MCO family, leading to photoreduction of dioxygen into water.

GUN4-Porphyrin Complexes Bind the ChlH/GUN5 Subunit of Mg-Chelatase and Promote Chlorophyll Biosynthesis in Arabidopsis[W

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Adhikari, Neil D.; Froehlich, John E.; Strand, Deserah D.; Buck, Stephanie M.; Kramer, David M.; Larkin, Robert M.

2011-01-01

The GENOMES UNCOUPLED4 (GUN4) protein stimulates chlorophyll biosynthesis by activating Mg-chelatase, the enzyme that commits protoporphyrin IX to chlorophyll biosynthesis. This stimulation depends on GUN4 binding the ChlH subunit of Mg-chelatase and the porphyrin substrate and product of Mg-chelatase. After binding porphyrins, GUN4 associates more stably with chloroplast membranes and was proposed to promote interactions between ChlH and chloroplast membranes—the site of Mg-chelatase activity. GUN4 was also proposed to attenuate the production of reactive oxygen species (ROS) by binding and shielding light-exposed porphyrins from collisions with O2. To test these proposals, we first engineered Arabidopsis thaliana plants that express only porphyrin binding–deficient forms of GUN4. Using these transgenic plants and particular mutants, we found that the porphyrin binding activity of GUN4 and Mg-chelatase contribute to the accumulation of chlorophyll, GUN4, and Mg-chelatase subunits. Also, we found that the porphyrin binding activity of GUN4 and Mg-chelatase affect the associations of GUN4 and ChlH with chloroplast membranes and have various effects on the expression of ROS-inducible genes. Based on our findings, we conclude that ChlH and GUN4 use distinct mechanisms to associate with chloroplast membranes and that mutant alleles of GUN4 and Mg-chelatase genes cause sensitivity to intense light by a mechanism that is potentially complex. PMID:21467578

Synthesis and Spectroscopic Characterization of Two Tetrasubstituted Cationic Porphyrin Derivatives

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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.

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

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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.

Studies on the mechanical behavior of rock anchors. ; Results of in-situ pull-out tests. Rock anchor no rikigaku kyodo ni kansuru kenkyu. ; Gen prime ichi shiken ni okeru anchor no kyodo

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Arimoto, K.; Ebisu, S.; Nakagawa, M.; Usui, M.; Someya, T.; Machida, N. (Okumura Corp., Tokyo (Japan))

1991-10-31

The rock anchor method is planned to apply to some permanent structures but since this method was developed for temporary structures, the clarification of the transferring mechanism of force from an anchor to a rockmass, the fracture mechanism and the development of the dynamic model have not been established. This paper arranged the data obtained by a full-scale, in-situ pulling out test of a rock anchor as the first step to understand the dynamic behavior and analyzed by paying attetion to the modulus of deformation of the rockmass where the anchor was embedded to elucidate the affecting degree of rockmass modulus of deformation, the embedded length and the tendon diameter on the dynamic behavior of the anchor. The rock anchor behavior could be expressed accurately by applying a theoretical solution derived by the balancing condition of forces at the boundary face. Especially, when the rockmass is uniform and the fracture occurrs at the interface between the tendon and grout, this approach can express the fracture with the accuracy similar to that made by the finite element method. 6 refs., 11 figs.,1 tab.

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.

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

Statistical Optimization of Synthesis of Manganese Carbonates Nanoparticles by Precipitation Methods

International Nuclear Information System (INIS)

Javidan, A.; Rahimi-Nasrabadi, M.; Davoudi, A.A.

2011-01-01

In this study, an orthogonal array design (OAD), OA9, was employed as a statistical experimental method for the controllable, simple and fast synthesis of manganese carbonate nanoparticle. Ultrafine manganese carbonate nanoparticles were synthesized by a precipitation method involving the addition of manganese ion solution to the carbonate reagent. The effects of reaction conditions, for example, manganese and carbonate concentrations, flow rate of reagent addition and temperature, on the diameter of the synthesized manganese carbonate nanoparticle were investigated. The effects of these factors on the width of the manganese carbonate nanoparticle were quantitatively evaluated by the analysis of variance (ANOVA). The results showed that manganese carbonate nanoparticle can be synthesized by controlling the manganese concentration, flow rate and temperature. Finally, the optimum conditions for the synthesis of manganese carbonate nanoparticle by this simple and fast method were proposed. The results of ANOVA showed that 0.001 mol/ L manganese ion and carbonate reagents concentrations, 2.5 mL/ min flow rate for the addition of the manganese reagent to the carbonate solution and 0 degree Celsius temperature are the optimum conditions for producing manganese carbonate nanoparticle with 75 ± 25 nm width. (author)

Modified Kidner procedure utilizing a Mitek bone anchor.

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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.

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

Editorial Commentary: All-Suture Anchors, Foam Blocks, and Biomechanical Testing.

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Brand, Jefferson C

2017-06-01

Barber's biomechanical work is well known to Arthroscopy's readers as thorough, comprehensive, and inclusive of new designs as they become available. In "All-Suture Anchors: Biomechanical Analysis of Pullout Strength, Displacement, and Failure Mode," the latest iteration, Barber and Herbert test all-suture anchors in both porcine femurs and biphasic foam. While we await in vivo clinical trials that compare all-suture anchors to currently used anchors, Barber and Herbert have provided data to inform anchor choice, and using their biomechanical data at time zero from all-suture anchor trials in an animal model, we can determine the anchors' feasibility for human clinical investigations. Copyright © 2017 Arthroscopy Association of North America. Published by Elsevier Inc. All rights reserved.

Diffusion abnormalities of the globi pallidi in manganese neurotoxicity

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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.)

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.

Visible light photocatalytic disinfection of E. coli with TiO_2–graphene nanocomposite sensitized with tetrakis(4-carboxyphenyl)porphyrin

International Nuclear Information System (INIS)

Rahimi, Rahmatollah; Zargari, Solmaz; Yousefi, Azam; Yaghoubi Berijani, Marzieh; Ghaffarinejad, Ali; Morsali, Ali

2015-01-01

Graphical abstract: TiO_2–graphene nanocomposites with different content of graphene were synthesized via a facile one-step solvothermal method. Photoelectrochemical responses of prepared photocatalysts were measured to determine the optimum content of graphene in TG nanocomposites. The results show that the TG nanocomposite with 3% of graphene has the highest photoactivity. This compound was sensitized with tetrakis(4-carboxyphenyl)porphyrin (TGP). The prepared photocatalysts were used for photocatalytic disinfection of E. coli. The results showed that the photocatalytic disinfection of the TG nanocomposite was increased after sensitization with porphyrin. The enhanced photocatalytic performance could be attributed to the synergistic effect between TiO_2, graphene and porphyrin sensitizer in the TGP photocatalyst. - Highlights: • TiO_2–graphene nanocomposites (TG) were synthesized with different content of graphene. • The TG nanocomposite with different content of graphene was sensitized with porphyrin (TGP). • The disinfection of E. coli using TGP was investigated in the visible light. • Porphyrin sensitizer increases effectively the photocatalytic disinfection efficiency of TGP. - Abstract: The present research deals with the development of a new heterogeneous photocatalysis system for disinfection of bacteria from wastewater by using TiO_2–graphene (TG) nanocomposite sensitized with tetrakis(4-carboxyphenyl)porphyrin (TCPP). The disinfection of wastewater using this photocatalyst is not reported in the literature yet. All the synthesized materials were thoroughly characterized by Raman, XRD, DRS, BET, and SEM analysis. The optimum content of graphene in the TiO_2–graphene nanocomposite was determined by photocurrent responses of prepared photocatalysts. Subsequently, the photocurrent measurements demonstrate that the TiO_2–graphene nanocomposite with 3% graphene content has higher photoactivity. Furthermore, sensitization of the TiO_2�

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

Electrochemical synthesis of novel {pi}-extended phenoxazine derivatives of porphyrincatecholes

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Osati, Samira; Davarani, Saied Saeed Hosseiny [Department of Chemistry, Faculty of Science, Shahid Beheshti University, G.C, Evin, 1983963113 Tehran (Iran, Islamic Republic of); Safari, Nasser, E-mail: n-safari@cc.sbu.ac.ir [Department of Chemistry, Faculty of Science, Shahid Beheshti University, G.C, Evin, 1983963113 Tehran (Iran, Islamic Republic of); Banitaba, Mohammad Hossein [Department of Chemistry, Faculty of Science, Shahid Beheshti University, G.C, Evin, 1983963113 Tehran (Iran, Islamic Republic of)

2011-10-30

Three new functionalized phenoxazine-catechol porphyrins 7a-c have been synthesized by a green one-pot method and structurally characterized by spectroscopic analysis. The electro-oxidation of 5,10,15,20-tetrakis(2,3-dihydroxyphenyl) porphyrins(1a-c) with four catechol units in the presence of 2-aminophenol 8 as bidentate nucleophile has been done and phenoxazine rings have been formed by intermolecular and intramolecular Michael addition reactions. Spectroscopic characterization and voltammetry results have allowed us to propose four independent ECEC mechanisms for the electrochemical oxidation pathway. The functionalization of the porphyrins affected their photophysical properties. Expansion of the UV-vis spectrum range and the decrease of the fluorescence intensity of the products would support the energy transfer between the porphyrin core excited states to the four substitutions as the electron acceptor subunits. SEM images indicate that this method produces regularly shaped manganese porphyrin nano-particles 7c that possess a cubic nano structure.

Hydrogen bond controlled adduct formation of meso-tetra(4-sulfonatophenyl)porphyrin with protic acids: a UV-vis spectroscopic study.

Science.gov (United States)

Zakavi, Saeed; Rahiminezhad, Hajar; Alizadeh, Robabeh

2010-12-01

Interaction of meso-tetra(4-sulfonatophenyl)porphyrin (H2tppS4) with weak and strong protic acid have been studied by UV-vis spectroscopy in water, dichloromethane and methanol. Different shifts of the Soret and Q(0,0) bands in the three solvents, the aggregation of diprotonated species and the stability of porphyrin-acid adducts in the solution, may be explained by the inter- and intramolecular hydrogen bonds. Whilst, the addition of excess amounts of tetra-n-butylammonium chloride to H2tppS4(Cl)2 in dichloromethane has little to no effect on the UV-vis spectrum of the dication, gradual addition of tetra-n-butylammonium hydrogen sulfate to the dichloromethane solution of H2tppS4(H2SO4)2 leads to the degradation of adducts and the release of porphryin. The results of this study clearly show the crucial role played by hydrogen bonds between the porphyrin diprotonated species and the counter ion in the stability of porphyrin diacids in solution. Copyright © 2010 Elsevier B.V. All rights reserved.

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

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

Science.gov (United States)

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

2018-01-24

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

Properties of halogenated and sulfonated porphyrins relevant for the selection of photosensitizers in anticancer and antimicrobial therapies.

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Barbara Pucelik

Full Text Available The impact of substituents on the photochemical and biological properties of tetraphenylporphyrin-based photosensitizers for photodynamic therapy of cancer (PDT as well as photodynamic inactivation of microorganisms (PDI was examined. Spectroscopic and physicochemical properties were related with therapeutic efficacy in PDT of cancer and PDI of microbial cells in vitro. Less polar halogenated, sulfonamide porphyrins were most readily taken up by cells compared to hydrophilic and anionic porphyrins. The uptake and PDT of a hydrophilic porphyrin was significantly enhanced with incorporation in polymeric micelles (Pluronic L121. Photodynamic inactivation studies were performed against Gram-positive (S. aureus, E. faecalis, Gram-negative bacteria (E. coli, P. aeruginosa, S. marcescens and fungal yeast (C. albicans. We observed a 6 logs reduction of S. aureus after irradiation (10 J/cm2 in the presence of 20 μM of hydrophilic porphyrin, but this was not improved with incorporation in Pluronic L121. A 2-3 logs reduction was obtained for E. coli using similar doses, and a decrease of 3-4 logs was achieved for C. albicans. Rational substitution of tetraphenylporphyrins improves their photodynamic properties and informs on strategies to obtain photosensitizers for efficient PDT and PDI. However, the design of the photosensitizers must be accompanied by the development of tailored drug formulations.

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.

Charge Carrier Dynamics and pH Effect on Optical Properties of Anionic and Cationic Porphyrin-Graphene Oxide Composites

Science.gov (United States)

Bajjou, O.; Bakour, A.; Khenfouch, M.; Baitoul, M.; Mothudi, B.; Maaza, M.; Faulques, E.

2018-02-01

Composites of graphene oxide (GO) functionalized with Sn(V) tetrakis (4-pyridyl)porphyrin (SnTPyP2+) and meso-tetrakis(4-phenylsulfonic acid)porphyrin (H4TPPS4 2- ) were prepared at different pH values.Successful synthesis of water-soluble stable suspension of GO-SnTPyP2+ and GO-H4TPPS4 2-was confirmed using various spectroscopic techniques, including scanning electronic microscopy (SEM), Raman spectroscopy, and ultraviolet-visible (UV-Vis) absorption. Variation of the pH was found to strongly influence the optical properties of the GO-SnTPyP2+ and GO-H4TPPS4 2-composites, as demonstrated by the UV-Vis absorption results. Steady-state photoluminescence (PL) and time-resolved PL (TRPL) results for both composites showed PL quenching and decrease in the exciton mean lifetime, suggesting strong excited-state interactions between the different components. Moreover, charge carrier dynamics study revealed that insertion of GO into both porphyrin derivatives led to faster mean lifetime for excitons with a slight advantage in the case of the cationic porphyrin-GO composite, making it a better choice for charge separation applications thanks to the higher efficiency of charge/energy transfer interactions.

Efficacies of manganese chloride and Ca-DTPA for the elimination of incorporated manganese-54 in mice

International Nuclear Information System (INIS)

Sato, Itaru; Matsusaka, Naonori; Shinagawa, Kunihiro; Kobayashi, Haruo; Nishimura, Yoshikazu.

1993-01-01

Efficacies of manganese chloride and Ca-DTPA (calcium diethylenetriaminepentaacetic acid) for the elimination of incorporated 54 Mn were investigated in mice. Each mouse was given an intraperitoneal injection of 54 Mn and initial whole-body radioactivity was measured immediately. Manganese chloride (10 mg-Mn/kg) or Ca-DTPA (10 or 100 mg/kg) was injected intraperitoneally once or repeatedly at various times after 54 Mn injection. Efficacies for elimination were estimated by measuring the whole body retention of 54 Mn for 14 or 21 days. A single injection of manganese chloride eliminated more than 80% of the incorporated 54 Mn when it was injected within 24 h after the injection of 54 Mn. Although the efficacy was decreased with the passage of time after the injection of 54 Mn, about 50% was still eliminated after 14 days. Repeated injection of this agent raised the efficacy, but the second or later injection was less effective than the first injection. Ca-DTPA eliminated the incorporated 54 Mn by 57% for 100 mg/kg and by 19% for 10 mg/kg when it was injected after 3 h. But after 6 h or later, Ca-DTPA had little efficacy. These results indicate that manganese chloride is very effective to eliminate the 54 Mn from accidentally contaminated persons and the efficacy of Ca-DTPA is less than that of manganese chloride. (author)

Thallium and manganese complexes involved in the luminescence emission of potassium-bearing aluminosilicates

Energy Technology Data Exchange (ETDEWEB)

Gomez-Gonzalez, Miguel A., E-mail: miguel.gomez@mncn.csic.es [Museo Nacional de Ciencias Naturales, CSIC, Jose Gutierrez Abascal 2, Madrid E-28006 (Spain); Garcia-Guinea, Javier, E-mail: guinea@mncn.csic.es [Museo Nacional de Ciencias Naturales, CSIC, Jose Gutierrez Abascal 2, Madrid E-28006 (Spain); Garrido, Fernando, E-mail: fernando.garrido@mncn.csic.es [Museo Nacional de Ciencias Naturales, CSIC, Jose Gutierrez Abascal 2, Madrid E-28006 (Spain); Townsend, Peter D., E-mail: pdtownsend@gmail.com [School of Science and Technology, University of Sussex, Brighton BN1 9QH (United Kingdom); Marco, Jose-Francisco, E-mail: jfmarco@iqfr.csic.es [Instituto de Química-Física Rocasolano, CSIC, Calle Serrano 119, Madrid E-28006 (Spain)

2015-03-15

coordinated Mn{sup 2+}. Moscovite samples display spectral CL bands at 285 and 560 nm but only when the electron-beam is directed along the (0 1 0) orientation and not along the (0 0 1) orientation. The Tl{sup +} versus K{sup +} cation isomorphism anchors the luminogenous hydrous thallium–manganese complexes to the potassium-bearing aluminosilicate surfaces under analyses. The CL emission bands at 285 and 560 nm of these complexes together with the EDS detection of thallium are a fast analytical measurement detecting the presence of thallium in further studies involving this toxic element. - Highlights: • Different K-aluminosilicates with thallium and manganese display similar CL spectra. • Cathodoluminescence bands at 285 and 560 nm are associated with Tl{sup 1+} and Mn{sup 2+}. • K-feldspar, quartz and moscovite with CL 285 nm peak have accesorial Tl{sup 1+} by EDS. • Moscovites exhibit 285 nm CL bands along (0 1 0) orientation but not along (0 0 1). • Surficial Tl{sup +} in K{sup +} sites are anchors for hydrous Tl{sup 1+}/Mn{sup 2+} complexes and clusters.

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...

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

Failure of manganese to protect from Shiga toxin.

Directory of Open Access Journals (Sweden)

Marsha A Gaston

Full Text Available Shiga toxin (Stx, the main virulence factor of Shiga toxin producing Escherichia coli, is a major public health threat, causing hemorrhagic colitis and hemolytic uremic syndrome. Currently, there are no approved therapeutics for these infections; however manganese has been reported to provide protection from the Stx1 variant isolated from Shigella dysenteriae (Stx1-S both in vitro and in vivo. We investigated the efficacy of manganese protection from Stx1-S and the more potent Stx2a isoform, using experimental systems well-established for studying Stx: in vitro responses of Vero monkey kidney cells, and in vivo toxicity to CD-1 outbred mice. Manganese treatment at the reported therapeutic concentration was toxic to Vero cells in culture and to CD-1 mice. At lower manganese concentrations that were better tolerated, we observed no protection from Stx1-S or Stx2a toxicity. The ability of manganese to prevent the effects of Stx may be particular to certain cell lines, mouse strains, or may only be manifested at high, potentially toxic manganese concentrations.

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

Outcomes of the modified Brostrom procedure using suture anchors for chronic lateral ankle instability--a prospective, randomized comparison between single and double suture anchors.

Science.gov (United States)

Cho, Byung-Ki; Kim, Yong-Min; Kim, Dong-Soo; Choi, Eui-Sung; Shon, Hyun-Chul; Park, Kyoung-Jin

2013-01-01

The present prospective, randomized study was conducted to compare the clinical outcomes of the modified Brostrom procedure using single and double suture anchors for chronic lateral ankle instability. A total of 50 patients were followed up for more than 2 years after undergoing the modified Brostrom procedure. Of the 50 procedures, 25 each were performed using single and double suture anchors by 1 surgeon. The Karlsson scale had improved significantly to 89.8 points and 90.6 points in the single and double anchor groups, respectively. Using the Sefton grading system, 23 cases (92%) in the single anchor group and 22 (88%) in the double anchor group achieved satisfactory results. The talar tilt angle and anterior talar translation on stress radiographs using the Telos device had improved significantly to an average of 5.7° and 4.6 mm in the single anchor group and 4.5° and 4.3 mm in the double anchor group, respectively. The double anchor technique was superior with respect to the postoperative talar tilt. The single and double suture anchor techniques produced similar clinical and functional outcomes, with the exception of talar tilt as a reference of mechanical stability. The modified Brostrom procedure using both single and double suture anchors appears to be an effective treatment method for chronic lateral ankle instability. Copyright © 2013 American College of Foot and Ankle Surgeons. Published by Elsevier Inc. All rights reserved.

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.

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

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.

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

The study of cellulosic fabrics impregnated with porphyrin compounds for use as photo-bactericidal polymers

Energy Technology Data Exchange (ETDEWEB)

Rahimi, Rahmatollah, E-mail: rahimi_rah@iust.ac.ir [Bioinorganic Chemistry Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114 (Iran, Islamic Republic of); Fayyaz, Fatemeh [Bioinorganic Chemistry Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114 (Iran, Islamic Republic of); Rassa, Mehdi [Department of Biology, Faculty of Science, University of Guilan, Rasht (Iran, Islamic Republic of)

2016-02-01

In the present work, we report on the preparation of cellulosic fabrics bearing two types of photo-sensitizers in order to prepare efficient polymeric materials for antimicrobial applications. The obtained porphyrin-grafted cellulosic fabrics were characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, diffuse reflectance UV–Vis (DRUV) spectroscopy, thermo-gravimetric analysis (TG) and scanning electron microscopy (SEM). Antimicrobial activity of the prepared porphyrin-cellulose was tested under visible light irradiation against Staphylococcus aureus, Pseudomunas aeroginosa and Escherichia coli. In addition, the effect of two parameters on photo-bactericidal activity of treated fibers was studied: illumination time and concentration of photosensitizers (PS). - Highlights: • Cellulosic fabrics were impregnated with various concentrations of porphyrins (TAPP and its zinc ion complex). • The products were characterized by ATR-FTIR, DRUV, SEM and TG. • The photo-antibacterial activity of products was determined against S. aureus, P. aeroginosa and E. coli. • The effect of two parameters were studied on photoinactivation of treated fibers: illumination time and concentration of PS.

THE STATE OF MANGANESE IN THE PHOTOSYNTHETIC APPARATUS. I. EXAFS STUDIES ON CHLOROPLASTS AND di-u-oxo BRIDGED di-MANGANESE MODEL COMPOUNDS

Energy Technology Data Exchange (ETDEWEB)

Kirby, J. A.; Robertson, A. S.; Smith, J. P.; Thompson, A. C.; Thompson, A. C.; Klein, M. P.

1980-11-01

Extended X-ray Absorption Fine Structure (EXAFS) studies on the manganese contained in spinach chloroplasts and on certain di-u-oxo bridged manganese dimers of the form (X{sub 2}Mn)O{sub 2}(MnX{sub 2} (X=2,2'-bypyridine and 1,10-phenanthroline) are reported. From these studies, the manganese associated with photosynthetic oxygen evolution is suggested to occur as a bridged transition metal dimer with most likely another manganese. Extensive details on the analysis are included.

Understanding the low uptake of bone-anchored hearing aids: a review.

Science.gov (United States)

Powell, R; Wearden, A; Pardesi, S M; Green, K

2017-03-01

Bone-anchored hearing aids improve hearing for patients for whom conventional behind-the-ear aids are problematic. However, uptake of bone-anchored hearing aids is low and it is important to understand why this is the case. A narrative review was conducted. Studies examining why people accept or decline bone-anchored hearing aids and satisfaction levels of people with bone-anchored hearing aids were reviewed. Reasons for declining bone-anchored hearing aids included limited perceived benefits, concerns about surgery, aesthetic concerns and treatment cost. No studies providing in-depth analysis of the reasons for declining or accepting bone-anchored hearing aids were identified. Studies of patient satisfaction showed that most participants reported benefits with bone-anchored hearing aids. However, most studies used cross-sectional and/or retrospective designs and only included people with bone-anchored hearing aids. Important avenues for further research are in-depth qualitative research designed to fully understand the decision-making process for bone-anchored hearing aids and rigorous quantitative research comparing satisfaction of people who receive bone-anchored hearing aids with those who receive alternative (or no) treatments.

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.

Self-tapping ability of carbon fibre reinforced polyetheretherketone suture anchors.

Science.gov (United States)

Feerick, Emer M; Wilson, Joanne; Jarman-Smith, Marcus; Ó'Brádaigh, Conchur M; McGarry, J Patrick

2014-10-01

An experimental and computational investigation of the self-tapping ability of carbon fibre reinforced polyetheretherketone (CFR-PEEK) has been conducted. Six CFR-PEEK suture anchor designs were investigated using PEEK-OPTIMA® Reinforced, a medical grade of CFR-PEEK. Experimental tests were conducted to investigate the maximum axial force and torque required for self-taping insertion of each anchor design. Additional experimental tests were conducted for some anchor designs using pilot holes. Computational simulations were conducted to determine the maximum stress in each anchor design at various stages of insertion. Simulations also were performed to investigate the effect of wall thickness in the anchor head. The maximum axial force required to insert a self-tapping CFR-PEEK suture anchor did not exceed 150 N for any anchor design. The maximum torque required to insert a self-tapping CFR-PEEK suture anchor did not exceed 0.8 Nm. Computational simulations reveal significant stress concentrations in the region of the anchor tip, demonstrating that a re-design of the tip geometry should be performed to avoid fracture during self-tapping, as observed in the experimental component of this study. This study demonstrates the ability of PEEK-OPTIMA Reinforced suture anchors to self-tap polyurethane foam bone analogue. This provides motivation to further investigate the self-tapping ability of CFR-PEEK suture anchors in animal/cadaveric bone. An optimised design for CFR-PEEK suture anchors offers the advantages of radiolucency, and mechanical properties similar to bone with the ability to self-tap. This may have positive implications for reducing surgery times and the associated costs with the procedure. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Structural implications of the C-terminal tail in the catalytic and stability properties of manganese peroxidases from ligninolytic fungi

Energy Technology Data Exchange (ETDEWEB)

Fernández-Fueyo, Elena [CSIC, Ramiro de Maeztu 9, 28040 Madrid (Spain); Acebes, Sandra [Barcelona Supercomputing Center, Jordi Girona 29, 08034 Barcelona (Spain); Ruiz-Dueñas, Francisco J.; Martínez, María Jesús; Romero, Antonio; Medrano, Francisco Javier, E-mail: fjmedrano@cib.csic.es [CSIC, Ramiro de Maeztu 9, 28040 Madrid (Spain); Guallar, Victor, E-mail: fjmedrano@cib.csic.es [Barcelona Supercomputing Center, Jordi Girona 29, 08034 Barcelona (Spain); ICREA, Passeig Lluís Companys 23, 08010 Barcelona (Spain); Martínez, Angel T., E-mail: fjmedrano@cib.csic.es [CSIC, Ramiro de Maeztu 9, 28040 Madrid (Spain)

2014-12-01

The variable C-terminal tail of manganese peroxidases, a group of enzymes involved in lignin degradation, is implicated in their catalytic and stability properties, as shown by new crystal structures, molecular-simulation and directed-mutagenesis data. Based on this structural–functional evaluation, short and long/extralong manganese peroxidase subfamilies have been accepted; the latter are characterized by exceptional stability, while it is shown for the first time that the former are able to oxidize other substrates at the same site where manganese(II) is oxidized. The genome of Ceriporiopsis subvermispora includes 13 manganese peroxidase (MnP) genes representative of the three subfamilies described in ligninolytic fungi, which share an Mn{sup 2+}-oxidation site and have varying lengths of the C-terminal tail. Short, long and extralong MnPs were heterologously expressed and biochemically characterized, and the first structure of an extralong MnP was solved. Its C-terminal tail surrounds the haem-propionate access channel, contributing to Mn{sup 2+} oxidation by the internal propionate, but prevents the oxidation of 2, 2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS), which is only oxidized by short MnPs and by shortened-tail variants from site-directed mutagenesis. The tail, which is anchored by numerous contacts, not only affects the catalytic properties of long/extralong MnPs but is also associated with their high acidic stability. Cd{sup 2+} binds at the Mn{sup 2+}-oxidation site and competitively inhibits oxidation of both Mn{sup 2+} and ABTS. Moreover, mutations blocking the haem-propionate channel prevent substrate oxidation. This agrees with molecular simulations that position ABTS at an electron-transfer distance from the haem propionates of an in silico shortened-tail form, while it cannot reach this position in the extralong MnP crystal structure. Only small differences exist between the long and the extralong MnPs, which do not justify their

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

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.

Anomalous carrier life-time relaxation mediated by head group interaction in surface anchored MnSe quantum dots conjugated with albumin proteins

Energy Technology Data Exchange (ETDEWEB)

Sarma, Runjun; Mohanta, Dambarudhar, E-mail: best@tezu.ernet.in

2017-02-01

We report on the radiative emission decay dynamics of a less known, γ-phase manganese selenide quantum dot system (MnSe QDs) subjected to bio-functionalization. A short-ligand thioglycolic acid (TGA), and a long-chain sodium dodecyl sulfate (SDS) surfactants were used as surface anchors prior bioconjugation with albumin proteins (BSA). Time resolved photoluminescence (TR-PL) spectra of the QDs have revealed bi-exponential decay trends with the fast (τ{sub 1}) and slow (τ{sub 2}) decay parameters assigned to the core state recombination and surface trapped excitons; respectively. The average lifetime (τ{sub avg}) was found to get shortened from a value of ∼0.87 ns–0.72 ns in unconjugated and BSA conjugated MnSe-TGA QDs; respectively. Conversely, MnSe-SDS QDs with BSA conjugation exhibited nearly four-fold enhancement of τ{sub avg} with respect to its unconjugated counterpart. Moreover, a considerable amount of Förster resonance energy transfer (FRET) was found to occur from the TGA coated MnSe QDs to BSA and with an ensuing efficiency of ∼61%. The origin of anomalous carrier life-time relaxation features has also been encountered through a simplified model as regards head group interaction experienced by the MnSe QDs with different surfactant types. Exploiting luminescence decay characteristics of a magneto-fluorescent candidate could find immense scope in diverse biological applications including assays, labeling and imaging. - Highlights: • Surface anchored manganese selenide quantum dots (MnSe QDs) have been synthesized via a physico-chemical reduction route. • Time resolved luminescence spectra of the QDs have displayed bi-exponential decay trend. • Thioglycolic acid (TGA) coated QDs exhibited shorter lifetime as compared to sodium dodecyl sulfo-succinate (SDS) coated ones. • Upon BSA conjugation, the average life time is four-fold enhanced in MnSe-SDS QDs. • An efficient FRET process has been revealed in BSA conjugated TGA coated MnSe QDs.

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…

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...

On Moderator Detection in Anchoring Research: Implications of Ignoring Estimate Direction

Directory of Open Access Journals (Sweden)

Nathan N. Cheek

2018-05-01

Full Text Available Anchoring, whereby judgments assimilate to previously considered standards, is one of the most reliable effects in psychology. In the last decade, researchers have become increasingly interested in identifying moderators of anchoring effects. We argue that a drawback of traditional moderator analyses in the standard anchoring paradigm is that they ignore estimate direction—whether participants’ estimates are higher or lower than the anchor value. We suggest that failing to consider estimate direction can sometimes obscure moderation in anchoring tasks, and discuss three potential analytic solutions that take estimate direction into account. Understanding moderators of anchoring effects is essential for a basic understanding of anchoring and for applied research on reducing the influence of anchoring in real-world judgments. Considering estimate direction reduces the risk of failing to detect moderation.

Visible light photocatalytic disinfection of E. coli with TiO{sub 2}–graphene nanocomposite sensitized with tetrakis(4-carboxyphenyl)porphyrin

Energy Technology Data Exchange (ETDEWEB)

Rahimi, Rahmatollah, E-mail: rahimi_rah@iust.ac.ir [Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114 (Iran, Islamic Republic of); Zargari, Solmaz [Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114 (Iran, Islamic Republic of); Yousefi, Azam [School of Chemical Engineering, Iran University of Science and Technology, Tehran 16846-13114 (Iran, Islamic Republic of); Yaghoubi Berijani, Marzieh; Ghaffarinejad, Ali [Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114 (Iran, Islamic Republic of); Morsali, Ali [Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran 14115-175 (Iran, Islamic Republic of)

2015-11-15

Graphical abstract: TiO{sub 2}–graphene nanocomposites with different content of graphene were synthesized via a facile one-step solvothermal method. Photoelectrochemical responses of prepared photocatalysts were measured to determine the optimum content of graphene in TG nanocomposites. The results show that the TG nanocomposite with 3% of graphene has the highest photoactivity. This compound was sensitized with tetrakis(4-carboxyphenyl)porphyrin (TGP). The prepared photocatalysts were used for photocatalytic disinfection of E. coli. The results showed that the photocatalytic disinfection of the TG nanocomposite was increased after sensitization with porphyrin. The enhanced photocatalytic performance could be attributed to the synergistic effect between TiO{sub 2}, graphene and porphyrin sensitizer in the TGP photocatalyst. - Highlights: • TiO{sub 2}–graphene nanocomposites (TG) were synthesized with different content of graphene. • The TG nanocomposite with different content of graphene was sensitized with porphyrin (TGP). • The disinfection of E. coli using TGP was investigated in the visible light. • Porphyrin sensitizer increases effectively the photocatalytic disinfection efficiency of TGP. - Abstract: The present research deals with the development of a new heterogeneous photocatalysis system for disinfection of bacteria from wastewater by using TiO{sub 2}–graphene (TG) nanocomposite sensitized with tetrakis(4-carboxyphenyl)porphyrin (TCPP). The disinfection of wastewater using this photocatalyst is not reported in the literature yet. All the synthesized materials were thoroughly characterized by Raman, XRD, DRS, BET, and SEM analysis. The optimum content of graphene in the TiO{sub 2}–graphene nanocomposite was determined by photocurrent responses of prepared photocatalysts. Subsequently, the photocurrent measurements demonstrate that the TiO{sub 2}–graphene nanocomposite with 3% graphene content has higher photoactivity. Furthermore

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.

Status and Role of Manganese in the Environment

Directory of Open Access Journals (Sweden)

RK Kamble

2014-09-01

Full Text Available Manganese is the second most abundant heavy metal, and in frequency list of elements it occupies 12th place. The Earth’s core contains about 1.5% manganese. According to Indian Standards for Drinking water (IS 10500:2012 manganese concentration in drinking water is 0.1 ppm (acceptable limit and 0.3 ppm as permissible limit. An attempt has been made to record the presence of manganese in different environmental matrices such as air, water, soil, food, its effects on plants, animals including human beings. DOI: http://dx.doi.org/10.3126/ije.v3i3.11081 International Journal of Environment Vol.3(3 2014: 222-234

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.

Efficient solar cells sensitized by porphyrins with an extended conjugation framework and a carbazole donor: from molecular design to cosensitization.

Science.gov (United States)

Wang, Yueqiang; Chen, Bin; Wu, Wenjun; Li, Xin; Zhu, Weihong; Tian, He; Xie, Yongshu

2014-09-26

Porphyrin dyes containing the carbazole electron donor have been designed and optimized by wrapping the porphyrin framework, introducing an additional ethynylene bridge to extend the wavelength range of light absorption, and further suppression of the dye aggregation by introducing additional alkoxy chains. Application of a cosensitization approach results in improved current density (Jsc) and open-circuit voltage (Voc) values, thus achieving the highest cell efficiency of 10.45%. This work provides an effective combined strategy of molecular design and cosensitization for developing efficient dye-sensitized solar cells (DSSCs). In addition, carbazole has been demonstrated to be a promising donor for porphyrin sensitizers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manganese and acute paranoid psychosis: a case report

Directory of Open Access Journals (Sweden)

Egger Jos I

2011-04-01

Full Text Available Abstract 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, several organ systems may be affected and, due to neurotoxicity, an atypical parkinsonian syndrome may emerge. With regard to neuropsychiatry, an array of symptoms may develop up to 30 years after intoxication, of which gait and speech abnormalities, cognitive and motor slowing, mood changes and hallucinations are the most common. Psychotic phenomena are rarely reported. Case presentation We describe the case of a 49-year-old Caucasian man working as a welder who was referred to our facility for evaluation of acute paranoid psychotic behavior. Our patient's medical history made no mention of any somatic complaints or psychiatric symptoms, and he had been involved in a professional career as a metalworker. On magnetic resonance imaging scanning of his brain, a bilateral hyperdensity of the globus pallidus, suggestive for manganese intoxication, was found. His manganese serum level was 52 to 97 nmol/L (range: 7 to 20 nmol/L. A diagnosis of organic psychotic disorder due to manganese overexposure was made. His psychotic symptoms disappeared within two weeks of treatment with low-dose risperidone. At three months later, serum manganese was decreased to slightly elevated levels and the magnetic resonance imaging T1 signal intensity was reduced. No signs of Parkinsonism were found and a definite diagnosis of manganese-induced apathy syndrome was made. Conclusion Although neuropsychiatric and neurological symptoms caused by (chronic manganese exposure have been reported frequently in the past, in the present day the disorder is rarely diagnosed. In this report we stress that manganese intoxication can still occur, in our case in a confined

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

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

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.

Electrochemical behavior of meso-substituted iron porphyrins in alkaline aqueous media

Science.gov (United States)

Berezina, N. M.; Bazanov, M. I.; Maksimova, A. A.; Semeikin, A. S.

2017-12-01

The effect meso-substitution in iron porphyrin complexes has on their redox behavior in alkaline aqueous solutions is studied via cyclic voltammetry. The voltammetric features of the reduction of iron pyridylporphyrins suggest that the sites of electron transfer lie at the ligand, the metal ion, and the pyridyl moieties. The electron transfer reactions between the different forms of these compounds, including the oxygen reduction reaction they mediate, are outlined to show the sequence and potential ranges in which they occur in alkaline aqueous media. Under our experimental conditions, the iron porphyrins exist as μ-oxo dimmers whose activity for the electrocatalytic reduction of oxygen displays a considerable dependence on the nature of the substitutents and nitrogen isomerization (for pyridylporphyrins) and grows in the order (Fe( ms-Ph)4P)2O, (Fe[ ms-(Py-3)Ph3]P)2O, (Fe[ ms-(Py-4)4]P)2O, and (Fe[ ms-(Py-3)4]P)2O.

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.

Method for the quantification of vanadyl porphyrins in fractions of crude oils by High Performance Liquid Chromatography-Flow Injection-Inductively Coupled Plasma Mass Spectrometry

Science.gov (United States)

Wandekoken, Flávia G.; Duyck, Christiane B.; Fonseca, Teresa C. O.; Saint'Pierre, Tatiana D.

2016-05-01

High performance liquid chromatography hyphenated by flow injection to inductively coupled plasma mass spectrometry (HPLC-FI-ICP-MS) was used to investigate V linked to porphyrins present in fractions of crude oil. First, the crude oil sample was submitted to fractionation by preparative liquid chromatography with UV detection, at the porphyrin Soret band wavelength (400 nm). The obtained porphyrin fractions were then separated in a 250 mm single column, in the HPLC, and eluted with different mobile phases (methanol or methanol:toluene (80:20; v:v)). The quantification of V-porphyrins in the fractions eluted from HPLC was carried out by online measuring the 51V isotope in the ICP-MS, against vanadyl octaethylporphine standard solutions (VO-OEP), prepared in the same solvent as the mobile phase, and injected post-column directly into the plasma. A 20 μg L- 1 Ge in methanol was used as internal standard for minimizing non-spectral interference, such as short-term variations due to injection. The mathematical treatment of the signal based on Fast Fourier Transform smoothing algorithm was employed to improve the precision. The concentrations of V as V-porphyrins were between 2.7 and 11 mg kg- 1 in the fractions, which were close to the total concentration of V in the porphyrin fractions of the studied crude oil.

Manganese oxide-based materials as electrochemical supercapacitor electrodes.

Science.gov (United States)

Wei, Weifeng; Cui, Xinwei; Chen, Weixing; Ivey, Douglas G

2011-03-01

Electrochemical supercapacitors (ECs), characteristic of high power and reasonably high energy densities, have become a versatile solution to various emerging energy applications. This critical review describes some materials science aspects on manganese oxide-based materials for these applications, primarily including the strategic design and fabrication of these electrode materials. Nanostructurization, chemical modification and incorporation with high surface area, conductive nanoarchitectures are the three major strategies in the development of high-performance manganese oxide-based electrodes for EC applications. Numerous works reviewed herein have shown enhanced electrochemical performance in the manganese oxide-based electrode materials. However, many fundamental questions remain unanswered, particularly with respect to characterization and understanding of electron transfer and atomic transport of the electrochemical interface processes within the manganese oxide-based electrodes. In order to fully exploit the potential of manganese oxide-based electrode materials, an unambiguous appreciation of these basic questions and optimization of synthesis parameters and material properties are critical for the further development of EC devices (233 references).

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...

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")…

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.

Development of Gd(III) porphyrin-conjugated chitosan nanoparticles as contrast agents for magnetic resonance imaging

Energy Technology Data Exchange (ETDEWEB)

Jahanbin, Tania [Université Paul Sabatier, Toulouse III, INSERM U825, CHU Purpan, 31059 Toulouse Cedex 9 (France); Sauriat-Dorizon, Hélène [Institut de Chimie Moléculaire et des Matériaux d' Orsay, UMR CNRS 8182, ECBB, Université Paris-Sud, 91405 Orsay (France); Spearman, Peter [Faculty of Science, Engineering and Computing, University of Kingston, Penrhyn Road Kingston upon Thames Surrey KT1 2EE, London (United Kingdom); Benderbous, Soraya, E-mail: soraya.benderbous@univ-tlse3.fr [Université Paul Sabatier, Toulouse III, INSERM U825, CHU Purpan, 31059 Toulouse Cedex 9 (France); Korri-Youssoufi, Hafsa, E-mail: hafsa.korri-youssoufi@u-psud.fr [Institut de Chimie Moléculaire et des Matériaux d' Orsay, UMR CNRS 8182, ECBB, Université Paris-Sud, 91405 Orsay (France)

2015-07-01

A novel magnetic resonance imaging (MRI) contrast agent based on gadolinium meso-tetrakis(4-pyridyl)porphyrin [Gd(TPyP)] conjugated with chitosan nanoparticles has been developed. The chitosan nanoparticles were synthesized following an ionic gelation method and the conditions optimized to generate small nanoparticles (CNs) with a narrow size distribution of 35–65 nm. The gadolinium meso-tetrakis(4-pyridyl)porphyrin [Gd(TPyP)] was loaded into chitosan nanoparticles by passive adsorption. The interaction of chitosan with Gd(TPyP) has been examined by UV–visible, Fourier transform infrared spectroscopies (FT-IR) and inductively coupled plasma mass spectrometry (ICP-MS), which indicate the successful association of Gd(TPyP) without any structural distortion throughout the chitosan nanoparticles. The potential of Gd(TPyP)-CNs as MRI contrast agent has been investigated by magnetic resonance imaging (MRI) in-vitro. Relaxivities of Gd(TPyP)-CNs obtained from T{sub 1}-weighted images, increased with Gd concentration and attained an optimum r{sub 1} of 38.35 mM{sup −1} s{sup −1}, which is 12-fold higher compared to commercial Gd-DOTA (~ 4 mM{sup −1} s{sup −1} at 3T). The combination of such strong MRI contrast with the known properties of porphyrins in photodynamic therapy and biocompatibility of chitosan, presents a new perspective in using these compounds in cancer theranostics. - Highlights: • Synthesis of chitosan nanoparticles with small size • Study of loading properties with gadolinium porphyrins • In vitro properties of the conjugated complex as contrast agent for MRI imaging • Comparison of MRI properties with commercial contrast agent Gd-DOTA.

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

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.

Effects of dietary manganese contents on 54Mn metabolism in mice

International Nuclear Information System (INIS)

Sato, I.; Matsusaka, N.; Kobayashi, H.; Nishimura, Y.

1996-01-01

Several parameters of 54 Mn metabolism were noted in mice maintained on diets with manganese contents of 80 to 8000 mg/kg. Excretion of 54 Mn was promoted as the dietary manganese contents increased. Clearance of 54 Mn from the liver, kidneys, pancreas, and spleen was markedly accelerated by feeding mice a high-manganese diet, but clearance from the muscles, femurs, and brain was relatively insensitive to the dietary manganese. Manganese concentrations in the tissue were regulated homoestatically upto the dietary manganese content of 2400 mg/kg, but marked accumulations of manganese occurred when mice were given 8000 mg/kg diet. No toxic symptoms were found up to the 2400 mg/kg diet, but consumption of the 8000 mg/kg diet was less than for other diets. These results suggest that an oral intake of excess manganese is effective for promoting the excretion of 54 Mn from a body contaminated with this isotope. (author)

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.

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...

Theoretical study of a neutral, doubly protonated, and doubly deprotonated porphyrin dithiolate used as a molecular switch

International Nuclear Information System (INIS)

Girard, Yvan; Kondo, Masakazu; Yoshizawa, Kazunari

2006-01-01

The zero-bias conductance of the neutral, doubly protonated, and doubly deprotonated porphyrin molecules used as molecular junctions between gold electrodes is investigated by using a Green's function formalism combined with density functional theory calculations. The probability for an electron to scatter through the porphyrin is predicted to be significantly increased by the protonation or the deprotonation, and the molecule could be used as a switch controlled by the pH. The shapes and energies of the frontier orbitals are used to rationalize these results

Post-installed concrete anchors in nuclear power plants: Performance and qualification

International Nuclear Information System (INIS)

Mahrenholtz, Philipp; Eligehausen, Rolf

2015-01-01

Graphical abstract: - Highlights: • Review of qualification and design regulations for anchors in nuclear power plants. • First complete set of nuclear anchor load–displacement data and its evaluation ever. • Demonstration of robust test behavior of a qualified post-installed anchor product. - Abstract: In nuclear power plants (NPPs), post-installed anchors are widely used for structural and non-structural connections to concrete. In many countries, anchor products employed for safety relevant applications have to be approved by the authorities. For the high safety standards in force for NPPs, special requirements have to be met to allow for extreme design situations. This paper presents an experimental test program conducted to evaluate the performance of anchors according to the German Guideline for Anchorages in Nuclear Power Plants and Nuclear Technology Installations (DIBt KKW Leitfaden, 2010). After a brief introduction to anchor behavior and the regulative context, the results of tension and shear tests carried out on undercut anchors are discussed. Robust load capacities and relatively small displacements determined for demanding load and crack cycling tests demonstrated the suitability of anchors qualified according to a state-of-the-art qualification guideline

Permanganate-based synthesis of manganese oxide nanoparticles in ferritin

Science.gov (United States)

Olsen, Cameron R.; Smith, Trevor J.; Embley, Jacob S.; Maxfield, Jake H.; Hansen, Kameron R.; Peterson, J. Ryan; Henrichsen, Andrew M.; Erickson, Stephen D.; Buck, David C.; Colton, John S.; Watt, Richard K.

2017-05-01

This paper investigates the comproportionation reaction of MnII with {{{{MnO}}}4}- as a route for manganese oxide nanoparticle synthesis in the protein ferritin. We report that {{{{MnO}}}4}- serves as the electron acceptor and reacts with MnII in the presence of apoferritin to form manganese oxide cores inside the protein shell. Manganese loading into ferritin was studied under acidic, neutral, and basic conditions and the ratios of MnII and permanganate were varied at each pH. The manganese-containing ferritin samples were characterized by transmission electron microscopy, UV/Vis absorption, and by measuring the band gap energies for each sample. Manganese cores were deposited inside ferritin under both the acidic and basic conditions. All resulting manganese ferritin samples were found to be indirect band gap materials with band gap energies ranging from 1.01 to 1.34 eV. An increased UV/Vis absorption around 370 nm was observed for samples formed under acidic conditions, suggestive of MnO2 formation inside ferritin.

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...

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.

Constrained Active Learning for Anchor Link Prediction Across Multiple Heterogeneous Social Networks.

Science.gov (United States)

Zhu, Junxing; Zhang, Jiawei; Wu, Quanyuan; Jia, Yan; Zhou, Bin; Wei, Xiaokai; Yu, Philip S

2017-08-03

Nowadays, people are usually involved in multiple heterogeneous social networks simultaneously. Discovering the anchor links between the accounts owned by the same users across different social networks is crucial for many important inter-network applications, e.g., cross-network link transfer and cross-network recommendation. Many different supervised models have been proposed to predict anchor links so far, but they are effective only when the labeled anchor links are abundant. However, in real scenarios, such a requirement can hardly be met and most anchor links are unlabeled, since manually labeling the inter-network anchor links is quite costly and tedious. To overcome such a problem and utilize the numerous unlabeled anchor links in model building, in this paper, we introduce the active learning based anchor link prediction problem. Different from the traditional active learning problems, due to the one-to-one constraint on anchor links, if an unlabeled anchor link a = ( u , v ) is identified as positive (i.e., existing), all the other unlabeled anchor links incident to account u or account v will be negative (i.e., non-existing) automatically. Viewed in such a perspective, asking for the labels of potential positive anchor links in the unlabeled set will be rewarding in the active anchor link prediction problem. Various novel anchor link information gain measures are defined in this paper, based on which several constraint active anchor link prediction methods are introduced. Extensive experiments have been done on real-world social network datasets to compare the performance of these methods with state-of-art anchor link prediction methods. The experimental results show that the proposed Mean-entropy-based Constrained Active Learning (MC) method can outperform other methods with significant advantages.

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.

Mercury distribution characteristics in primary manganese smelting plants

International Nuclear Information System (INIS)

Back, Seung-Ki; Sung, Jin-Ho; Moon, Young-Hoon; Kim, Young-Hee; Seok, Kwang-Seol; Song, Geum-Ju; Seo, Yong-Chil

2017-01-01

The mercury (Hg) distribution characteristics were investigated in three primary manganese smelting plants in Korea for the assessment of anthropogenic Hg released. Input and output materials were sampled from each process, and Hg concentrations in the samples were analyzed. Among the input materials, the most mercury was found in the manganese ore (83.1–99.7%) and mercury was mainly released through fly ash or off gas, depending on the condition of off gas cleaning system. As off gas temperature decreases, proportion and concentration of emitted gaseous elemental mercury (Hg 0 ) in off gas decreases. Based on mass balance study from these three plants and national manganese production data, the total amount of mercury released from those Korean plants was estimated to 644 kg/yr. About half of it was emitted into the air while the rest was released to waste as fly ash. With the results of this investigation, national inventory for Hg emission and release could be updated for the response to Minamata Convention on Mercury. - Graphical abstract: 1. Lack of data on mercury (Hg) distribution in manganese smelters. 2. Mass distribution of Hg released from 3 plants (as normalized values) were made as follows by measurements. 3. Information of distribution of Hg in Manganese smelters would be used for emission in to air and releases to other streams for the nation and globe in UNEP mercury report. - Highlights: • The mass balance study by on-site measurement from primary manganese smelting plants was made at first time in the world. • Hg distribution and main input and release pathways of Hg from primary manganese smelting plants could be found as the first time. • Gas temperature in bag filter affects Hg behavior and speciation changes in APCDs. • National inventory of Hg emssion has been updated with new data. - Mercury distribution in manganese smelting plant was investigated as the first measurements at commercial plants in the world. National Hg release

Synthesis and characterization of a new porphyrin-polyoxometalate hybrid material and investigation of its catalytic activity.

Science.gov (United States)

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

2012-03-14

In the present work, the preparation of a new organic-inorganic hybrid material in which tetrakis(p-aminophenylporphyrin) is covalently linked to a Lindqvist structure of polyoxometalate, is reported. This new porphyrin-polyoxometalate hybrid material was characterized by (1)H NMR, FT-IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided spectral data of the synthesis of this compound. Cyclic voltammetry showed the influence of the porphyrin on the redox process of the polyoxometalate. The catalytic activity of this hybrid material was investigated in the alkene epoxidation with NaIO(4).

MS2 bacteriophage as a delivery vessel of porphyrins for photodynamic therapy

Science.gov (United States)

Cohen, Brian A.; Kaloyeros, Alain E.; Bergkvist, Magnus

2011-02-01

Challenges associated with photodynamic therapy (PDT) include the packaging and site-specific delivery of therapeutic agents to the tissue of interest. Nanoscale encapsulation of PDT agents inside targeted virus capsids is a novel concept for packaging and site-specific targeting. The icosahedral MS2 bacteriophage is one potential candidate for such a packaging-system. MS2 has a porous capsid with an exterior diameter of ~28 nm where the pores allow small molecules access to the capsid interior. Furthermore, MS2 presents suitable residues on the exterior capsid for conjugation of targeting ligands. Initial work by the present investigators has successfully demonstrated RNA-based self-packaging of a heterocyclic PDT agent (meso-tetrakis(para-N-trimethylanilinium)porphine, TMAP) into the MS2 capsid. Packaging photoactive compounds in confined spaces could result in energy transfer between the molecules upon photoactivation, which could in turn reduce the production of radical oxygen species (ROS). ROS are key components in photodynamic therapy, and a reduced production could negatively impact the efficacy of PDT treatment. Here, findings are presented from an investigation of ROS generation of TMAP encapsulated within the MS2 capsid compared to free TMAP in solution. Monitoring of ROS production upon photoactivation via a specific singlet oxygen assay revealed the impact on ROS generation between packaged porphyrins as compared to free porphyrin in an aqueous solution. Follow on work will study the ability of MS2-packaged porphyrins to generate ROS in vitro and subsequent cytotoxic effects on cells in culture.

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)

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…

Occupational neurotoxicology due to heavy metals-especially manganese poisoning

International Nuclear Information System (INIS)

Inoue, Naohide

2007-01-01

The most hazardous manganese exposures occur in mining and smelting of ore. Recently, the poisoning has been frequently reported to be associated with welding. In occupational exposure, manganese is absorbed mainly by inhalation. Manganese preferentially accumulates in tissues rich in mitochondria. It also penetrates the blood brain barrior and accumulate in the basal ganglia, especially the globus pallidus, but also the striatum. Manganese poisoning is clinically characterized by the central nervous system involvement including psychiatric symptomes, extrapyramidal signs, and less frequently other neurological manifestations. Psychiatric symptomes are well described in the manganese miners and incrude sleep disturbance, disorientation, emotional lability, compulsive acts, hallucinations, illusions, and delusions. The main characteristic manifestations usually begin shortly after the appearance of these psychiatric symptomes. The latter neurological signs are progressive bradykinesia, dystonia, and disturbance of gait. Bradykinesia is one of the most important findings. There is a remarkable slowing of both active and passive movements of the extremities. Micrographia is frequently observed and a characteristic finding. The patients may show some symmetrical tremor, which usually not so marked. The dystonic posture of the limbs is often accompanied by painfull cramps. This attitudal hypertonia has a tendency to decrease or disappear in the supine position and to increase in orthostation. Cog-wheel rigidity is also elisited on the passive movement of all extremities. Gait disturbance is also characteristic in this poisoning. In the severe cases, cook gait has been reported. The patient uses small steps, but has a tendency to elevate the heels and to rotate them outward. He progress without pressing on the flat of his feet, but only upon the metatarsophalangeal articulations, mainly of the fourth and fifth toes. Increased signal in T1-weighted image in the basal

A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

Science.gov (United States)

Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

2005-05-04

A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

Anti-sigma factor YlaD regulates transcriptional activity of sigma factor YlaC and sporulation via manganese-dependent redox-sensing molecular switch in Bacillus subtilis.

Science.gov (United States)

Kwak, Min-Kyu; Ryu, Han-Bong; Song, Sung-Hyun; Lee, Jin-Won; Kang, Sa-Ouk

2018-05-14

YlaD, a membrane-anchored anti-sigma factor of Bacillus subtilis , contains a HX 3 CXXC motif that functions as a redox-sensing domain and belongs to one of the zinc-coordinated anti-sigma factor families. Despite previously showing that the YlaC transcription is controlled by YlaD, experimental evidence of how the YlaC-YlaD interaction is affected by active cysteines and/or metal ions is lacking. Here, we showed that the P yla promoter is autoregulated solely by YlaC. Moreover, reduced YlaD contained zinc and iron, while oxidized YlaD did not. Cysteine substitution in YlaD led to changes in its secondary structure; Cys3 had important structural functions in YlaD, and its mutation caused dissociation from YlaC, indicating the essential requirement of a HX 3 CXXC motif for regulating interactions of YlaC with YlaD. Analyses of the far-UV CD spectrum and metal content revealed that the addition of Mn ions to Zn-YlaD changed its secondary structure and that iron was substituted for manganese. The ylaC gene expression using βGlu activity from P yla : gusA was observed at the late-exponential and early-stationary phase and the ylaC -overexpressing mutant constitutively expressed gene transcripts of clpP and sigH , an important alternative sigma factor regulated by ClpXP. Collectively, our data demonstrated that YlaD senses redox changes and elicits increase in manganese ion concentrations and that, in turn, YlaD-mediated transcriptional activity of YlaC regulates sporulation initiation under oxidative stress and manganese-substituted conditions by regulating clpP gene transcripts. This is the first report of the involvement of oxidative stress-responsive B. subtilis extracytoplasmic function sigma factors during sporulation via a manganese-dependent redox-sensing molecular switch. ©2018 The Author(s).

Effect of diphenyl ether herbicides and oxadiazon on porphyrin biosynthesis in mouse liver, rat primary hepatocyte culture and HepG2 cells.

Science.gov (United States)

Krijt, J; van Holsteijn, I; Hassing, I; Vokurka, M; Blaauboer, B J

1993-01-01

The effects of the herbicides fomesafen, oxyfluorfen, oxadiazon and fluazifop-butyl on porphyrin accumulation in mouse liver, rat primary hepatocyte culture and HepG2 cells were investigated. Ten days of herbicide feeding (0.25% in the diet) increased the liver porphyrins in male C57B1/6J mice from 1.4 +/- 0.6 to 4.8 +/- 2.1 (fomesafen) 16.9 +2- 2.9 (oxyfluorfen) and 25.9 +/- 3.1 (oxadiazon) nmol/g wet weight, respectively. Fluazifop-butyl had no effect on liver porphyrin metabolism. Fomesafen, oxyfluorfen and oxadiazon increased the cellular porphyrin content of rat hepatocytes after 24 h of incubation (control, 3.2 pmol/mg protein, fomesafen, oxyfluorfen and oxadiazon at 0.125 mM concentration 51.5, 54.3 and 44.0 pmol/mg protein, respectively). The porphyrin content of HepG2 cells increased from 1.6 to 18.2, 10.6 and 9.2 pmol/mg protein after 24 h incubation with the three herbicides. Fluazifop-butyl increased hepatic cytochrome P450 levels and ethoxy- and pentoxyresorufin O-dealkylase (EROD and PROD) activity, oxyfluorfen increased PROD activity. Peroxisomal palmitoyl CoA oxidation increased after fomesafen and fluazifop treatment to about 500% of control values both in mouse liver and rat hepatocytes. Both rat hepatocytes and HepG2 cells can be used as a test system for the porphyrogenic potential of photobleaching herbicides.

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.

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...

Aquatic environmental risk assessment of manganese processing industries.

Science.gov (United States)

Marks, Becky; Peters, Adam; McGough, Doreen

2017-01-01

An environmental risk assessment (ERA) has been conducted for sites producing and processing manganese and its inorganic compounds, focussing on potential risks to freshwater. A site specific questionnaire was used to collect information. Sites fall into three broad categories: mining sites, refining sites, and sites producing chemicals and pigments. Waste disposal is principally carried out by the treatment of liquid wastes to separate solids for disposal off-site with a consented wastewater discharge, or disposal on-site using evaporation or settlement ponds in order to maintain the waste materials in a suitable manner following site closure. The main source of emissions from refining and alloying sites is from the treatment of emissions to air using wet scrubber air filters. There is also the potential for fugitive environmental emissions of manganese from stockpiles of raw material held on-site. Data provided from the questionnaires were both site-specific and also commercially sensitive. Therefore, this paper has undertaken the manganese exposure assessment, using a probabilistic approach to reflect the distribution of emissions of manganese and also to maintain the confidentiality of site specific data. An inverse correlation was observed between the total annual tonnage of manganese processed at the site and the emission factor, such that sites processing larger quantities resulted in lower emissions of manganese per tonne processed. The hazard assessment determined a Predicted No Effect Concentration (PNEC) for freshwater using a species sensitivity distribution approach, resulting in a freshwater PNEC of 0.075mgL -1 for soluble manganese. Based on the exposure data and the freshwater PNEC derived for this study, the distributions of risk characterisation ratios using the probabilistic approach indicates that two thirds of manganese processing sites would not be expected to pose a potential risk to the local aquatic environment due to wastewater emissions

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

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

Molecular Structure and Electronic Properties of Porphyrin-Thiophene-Perylene Using Quantum Chemical Calculation

Directory of Open Access Journals (Sweden)

Tatiya Chokbunpiam

2010-01-01

Full Text Available This study aimed to design a new series of compounds consisting of a porphyrin macrocycle linked to a perylene unit via a thiophenic bridge. The structural and electronic properties of the molecules, and the effects of mono- and di-substituents R on C3 and R′ on C4 of the thiophene ring were investigated using a quantum calculation approach. The results from the method validation revealed that using the density functional theory approach at B3LYP/6–31G(d data set was the optimal one, considering the accuracy attained and maintaining the computer time required within tractable limits. The results from the B3LYP/6–31G(d approach indicated that significant changes of the torsion angle between the molecular planes of the porphyrin and perylene rings, compared to that of the unsubstituted derivatives, were found in the di-substituted systems bearing R = R′ = −OCH3 and −NH2, and in a mono-substituted system having R = −H and R′=−NH2. The symmetric di-substitution does not provide a significantly lower HOMO-LUMO energy gap (ΔEg. Noticeable decreases in ΔEg were found only with the substitution patterns of: R, R′ = −OCH3, −H; −OH, −H; −N(CH32, −H; −H, −NH2. UV-visible spectra of all derivatives exhibited characteristic absorption maxima of the free bases of porphyrin and perylene.

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

Removal of Iron and Manganese in Groundwater using Natural Biosorbent

Science.gov (United States)

Baharudin, F.; Tadza, M. Y. Mohd; Imran, S. N. Mohd; Jani, J.

2018-04-01

This study was conducted to measure and compare the concentration of iron, manganese and hardness of the river and groundwater and to determine the effectiveness of iron and manganese removal by using natural biosorbent which is banana peels. The samples of river and groundwater were collected at riverbank filtration site at Jenderam Hilir, Dengkil. Based on the water quality investigation, the concentration of iron and manganese in the samples of groundwater have exceeded the drinking water quality standard which are 0.3 mg/L for iron and 0.1 mg/L for manganese. The removal process of the iron and manganese in the groundwater was done by using 2, 4 and 8 grams of banana peels activated carbon. It is found that with higher amount of activated banana peels, the removal of iron and manganese is more effective. The ranges of percentage of iron and manganese removal are between 82.25% to 90.84% and 98.79% to 99.43% respectively. From the result, banana peels activated carbon can be concluded as a one of the most effective low-cost adsorbent for groundwater treatment.

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)

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…

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.

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

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...

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...

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.

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...

Mutational analysis of the glycosylphosphatidylinositol (GPI) anchor pathway demonstrates that GPI-anchored proteins are required for cell wall biogenesis and normal hyphal growth in Neurospora crassa.

Science.gov (United States)

Bowman, Shaun M; Piwowar, Amy; Al Dabbous, Mash'el; Vierula, John; Free, Stephen J

2006-03-01

Using mutational and proteomic approaches, we have demonstrated the importance of the glycosylphosphatidylinositol (GPI) anchor pathway for cell wall synthesis and integrity and for the overall morphology of the filamentous fungus Neurospora crassa. Mutants affected in the gpig-1, gpip-1, gpip-2, gpip-3, and gpit-1 genes, which encode components of the N. crassa GPI anchor biosynthetic pathway, have been characterized. GPI anchor mutants exhibit colonial morphologies, significantly reduced rates of growth, altered hyphal growth patterns, considerable cellular lysis, and an abnormal "cell-within-a-cell" phenotype. The mutants are deficient in the production of GPI-anchored proteins, verifying the requirement of each altered gene for the process of GPI-anchoring. The mutant cell walls are abnormally weak, contain reduced amounts of protein, and have an altered carbohydrate composition. The mutant cell walls lack a number of GPI-anchored proteins, putatively involved in cell wall biogenesis and remodeling. From these studies, we conclude that the GPI anchor pathway is critical for proper cell wall structure and function in N. crassa.

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.

Antitumor effects evaluation of a novel porphyrin derivative in photodynamic therapy.

Science.gov (United States)

Li, Jian-Wei; Wu, Zhong-Ming; Magetic, Davor; Zhang, Li-Jun; Chen, Zhi-Long

2015-12-01

In this paper, the antitumor activity of a novel porphyrin-based photosensitizer 5,10,15,20-tetrakis[(5-diethylamino)pentyl] porphyrin (TDPP) was reported in vitro and in vivo. The photophysical and cellular properties of TDPP were investigated. The singlet oxygen generation quantum yield of TDPP was detected; it showed a high singlet oxygen quantum yield of 0.52. The intracellular distribution of photosensitizer was detected with laser scanning confocal microscopy. The efficiency of TDPP-photodynamic therapy (PDT) in vitro was analyzed by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay and in situ trypan blue exclusion test. Treated with a 630-nm laser, TDPP can kill cultured human esophageal cancer cell line (Eca-109) cells and reduce the growth of Eca-109 xenograft tumors significantly in BABL/c nude mice. And histopathological study was also used to confirm the antitumor effect. It has the perspective to be developed as a new antitumor drug in photodynamic therapy and deserves further investigation.

Efficiency of Dinucleosides as the Backbone to Pre-Organize Multi-Porphyrins and Enhance Their Stability as Sandwich Type Complexes with DABCO

Directory of Open Access Journals (Sweden)

Sonja Merkaš

2017-07-01

Full Text Available Flexible linkers such as uridine or 2′-deoxyuridine pre-organize bis-porphyrins in a face-to-face conformation, thus forming stable sandwich complexes with a bidentate base such as 1,4-diazabicyclo[2.2.2]octane (DABCO. Increased stability can be even greater when a dinucleotide linker is used. Such pre-organization increases the association constant by one to two orders of magnitude when compared to the association constant of DABCO with a reference porphyrin. Comparison with rigid tweezers shows a better efficiency of nucleosidic dimers. Thus, the choice of rigid spacers is not the only way to pre-organize bis-porphyrins, and well-chosen nucleosidic linkers offer an interesting option for the synthesis of such devices.

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.

Effect of amino acid ligands on the structure of iron porphyrins and their ability to bind oxygen.

Science.gov (United States)

Berryman, Victoria E J; Baker, Matthew G; Boyd, Russell J

2014-06-26

Density functional theory is used to study a series of model iron porphyrins in the gas phase. In the first part of this study, three range-separated hybrid density functionals developed by Chai and Head-Gordon were assessed; ωB97, ωB97X, and ωB97XD. The effects of including full Hartree-Fock exchange at long-range and dispersion corrections are reported with respect to the geometries and binding energies of oxygen to the iron porphyrin systems. The functionals all correctly predict the quintet ground state for the deoxy-iron porphyrins, where typically hybrid functionals fail and predict a triplet ground state. Including dispersion in ωB97XD is shown to give the best results for the O2 binding energy and geometrical parameters. The second part of the study employs ωB97XD to study iron porphine systems with different amino acids in the axial position. Geometrical parameters are reported and compared to experimental data, where available. Binding energies of the systems with oxygen are also reported and discussed.

Investigation of cobalt porphyrin doped polymer membrane films for the optical sensing of imidazole and its derivatives

Directory of Open Access Journals (Sweden)

Yueyang Tan

2015-03-01

Full Text Available A cobalt(II porphyrin was successfully incorporated into polymer membranes for the optical sensing of imidazole and its derivatives. This research has led to a better understanding of the behavior of Co(II porphyrin in solution and in polymeric membranes. In aprotic dichloromethane (DCM, the Co(II tetraphenylporphyrin (CoTPP and Co(II octaethylporphyrin (CoOEP show a sensitive response to imidazole due to the strong ligation of the N-3 on the imidazole ring to the Co(II center, which induces an absorbance change to the Soret band. However, when doped in polymeric films, only the CoTPP exhibits moderate sensitivity towards aqueous imidazole, histamine and histidine. This weakened coordination ability of CoTPP towards imidazole in the polymer films may be due to the coordination of the plasticizer, the impurities from the THF and polymer matrix at the Co(II center. The selectivity of the polymer films towards imidazole over common anions is high. Lifetime of the cobalt(II porphyrin incorporated polymer film was relatively short.

Water Soluble Cationic Porphyrin Sensor for Detection of Hg2+, Pb2+, Cd2+, and Cu2+

Directory of Open Access Journals (Sweden)

Matibur Zamadar

2016-01-01

Full Text Available Here we report the sensing properties of the aqueous solution of meso-tetra(N-methyl-4-pyridylporphine tetrachloride (1 for simultaneous detection of toxic metal ions by using UV-vis spectroscopy. Cationic porphyrin 1 displayed different electronic absorptions in UV-vis region upon interacting with Hg2+, Pb2+, Cd2+, and Cu2+ ions in neutral water solution at room temperature. Quite interestingly, the porphyrin 1 showed that it can function as a single optical chemical sensor and/or metal ion receptor capable of detecting two or more toxic metal ions, particularly Hg2+, Pb2+, and Cd2+ ions coexisting in a water sample. Porphyrin 1 in an aqueous solution provides a unique UV-vis sensing system for the determination of Cd2+ in the presence of larger metal ions such as Hg2+, or Pb2+. Finally, the examination of the sensing properties of 1 demonstrated that it can operate as a Cu2+ ion selective sensor via metal displacement from the 1-Hg2+, 1-Pb2+, and 1-Cd2+.

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.

Porphyrin lipid nanoparticles for enhanced photothermal therapy in a patient-derived orthotopic pancreas xenograft cancer model

Science.gov (United States)

MacLaughlin, Christina M.; Ding, Lili; Jin, Cheng; Cao, Pingjiang; Siddiqui, Iram; Hwang, David M.; Chen, Juan; Wilson, Brian C.; Zheng, Gang; Hedley, David W.

2016-03-01

Local disease control is a major problem in the treatment of pancreatic cancer, because curative-intent surgery is only possible in a minority of patients, and radiotherapy cannot be delivered in curative doses. Despite the promise of photothermal therapy (PTT) for ablation of pancreatic tumors, this approach remains under investigated. Using photothermal sensitizers in combination with laser light for PTT can result in more efficient conversion of light energy to heat, and confinement of thermal destruction to the tumor, thus sparing adjacent organs and vasculature. Porphyrins have been previously employed as photosensitizers for PDT and PTT, however their incorporation in to "porphysomes", lipid-based nanoparticles each containing ~80,000 porphyrins through conjugation of pyropheophorbide to phospholipids, carries two distinct advantages: 1) high-density porphyrin packing imparts the nanoparticles with enhanced photonic properties for imaging and phototherapy; 2) the enhanced permeability and retention effect may be exploited for optimal delivery of porphysomes to the tumor region thus high payload porphyrin delivery. The feasibility of porphysome-enhanced PTT for pancreatic cancer treatment was investigated using a patient-derived orthotopic pancreas xenograft tumor model. Uptake of porphysomes at the orthotopic tumor site was validated using ex vivo fluorescence imaging of intact organs of interest. The accumulation of porphysomes in orthotopic tumor microstructure was also confirmed by fluorescence imaging of excised tissue slices. PTT progress was monitored as changes in tumor surface temperature using IR optical imaging. Histological analyses were conducted to examine microstructure changes in tissue morphology, and the viability of remaining tumor tissues following exposure to heat. These studies may also provide insight as to the contribution of heat sink in application of thermal therapies to highly vascularized pancreatic tumors.

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

Preparation and performance of manganese-oxide-coated zeolite for the removal of manganese-contamination in groundwater.

Science.gov (United States)

Lyu, Cong; Yang, Xuejiao; Zhang, Shengyu; Zhang, Qihui; Su, Xiaosi

2017-12-29

A promising and easily prepared catalytic filler media, manganese-oxide-coated zeolite (MOCZ), for the removal of Mn (II) contamination in groundwater was studied. The optimal condition for MOCZ preparation was given as follows: acid activation of zeolite with 5% HCl mass percent for 12 h, then soaking of acid-activated zeolite with 7% KMnO 4 mass percent for 8 h, and finally calcination at 300°C for 5 h. Acid activation significantly enlarged the specific surface area of the zeolite (>79 m 2  g -1 ), subsequently enhancing the coating of manganese oxides onto the surface of the zeolite. This was further supported by the manganese-to-zeolite ratio (γ Mn ) and Energy dispersive analysis-mapping. The γ Mn was over 12.26 mg Mn g -1 zeolite, representing more active sites for the adsorption and catalytic-oxidation of Mn (II). As such, great performance of Mn (II) removal by MOCZ was obtained in the filter experiment. An estimated 98-100% removal efficiency of Mn (II) was achieved in a greatly short startup time (only 2 h). During the filtration process, newborn flocculent manganese oxides with a mixed-valence of manganese (Mn (II) and Mn (IV)) were generated on the MOCZ surface, further facilitating the adsorption and catalytic-oxidation of Mn (II). The filter with MOCZ as adsorbent had a great performance on the Mn (II) removal in a wide range of hydraulic retention time (HRT) (4-40 min), particularly in a short HRT. Besides, the filter prolonged the filtration period (60 days), which would significantly reduce the frequency of backwash. Thus, it could be concluded that MOCZ prepared in this study showed a good performance in terms of Mn (II) removal in waterworks, especially small waterworks in the villages/towns.

[ALLELES C282Y AND H63D HFE GENE, INSULIN RESISTANCE AND SUSCEPTIBILITY TO DISTURBANCE OF PORPHYRIN METABOLISM IN NON-ALCOHOLIC FATTY LIVER DISEASE].