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Sample records for cationic meso-substituted porphyrins

  1. Electrochemical Behavior of meso-Substituted Porphyrins: The Role of Cation Radicals to the Half-Wave Oxidation Potential Splitting.

    Science.gov (United States)

    Tran, Thai T H; Chang, Yan-Ru; Hoang, Tuan K A; Kuo, Ming-Yu; Su, Yuhlong O

    2016-07-21

    In this study, the electrochemical behavior of free base and zinc meso-substituted porphyrins is examined by cyclic voltammetry (CV) and density functional theory (DFT). The results show that the half-wave oxidation potential splitting of the two oxidation states (ΔE= second E1/2 - first E1/2) of tetraphenylporphyrin (H2TPP) and its zinc complex (ZnTPP) are higher than those of porphyrins and their zinc complexes with meso-substituted five-membered heterocylic rings. The ΔE values follow the trend of TPP > T(3'-thienyl)P > T(3'-furyl)P > T(2'-thienyl)P for both meso-porphyrins and their respective zinc complexes. By employing DFT calculations, we have found that the trend of ΔE values is consistent with that of highest spin density (HSD) distribution and HOMO-LUMO energy gaps of cationic radicals as well as the π-conjugation between central porphyrin and meso-substituted rings. Also, they exhibit the better resonance between the porphyrin ring with meso-substituted rings as moving from porphyrins and their zinc complexes with phenyl rings to five-membered heterocyclic rings. A good agreement between calculated and experimental results indicates that cationic radicals, especially their spin density distribution, do play an important role in half-wave oxidation potential splitting of meso-porphyrins and their zinc complexes. PMID:27379447

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

    OpenAIRE

    Giuseppe Mele; Małgorzata A. Broda; Krzysztof Ejsmont; Gabriela Dyrda; Rudolf Słota

    2011-01-01

    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 repr...

  3. 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.

  4. Synthesis and characterization of new meso-substituted unsymmetrical metalloporphyrins

    Indian Academy of Sciences (India)

    Babasaheeb P Bandgar; Pradip B Gujarathi

    2008-03-01

    The synthesis and characterization of new meso-substituted unsymmetrical metalloporphyrins has been described. A new modified Adler method was used for the synthesis of two unsymmetrical porphyrins. Reactions of these unsymmetrical porphyrins with metal acetates afforded the corresponding metalloporphyrins in high yields with excellent purity. These porphyrins and their metal derivatives were characterized by spectroscopic methods. However, the copper complexes were further studied by ESR spectra and zinc complex by fluorescence spectrum.

  5. Modulation of Group I Ribozyme Activity by Cationic Porphyrins

    Directory of Open Access Journals (Sweden)

    Shigeyoshi Matsumura

    2015-03-01

    Full Text Available The effects of cationic porphyrins on the catalytic activities of four group I ribozymes were investigated. A cationic porphyrin possessing four pyridinium moieties (pPyP inhibited two group IC3 ribozymes (Syn Rz and Azo Rz and a group IC1 ribozyme (Tet Rz. In the case of a group IA2 ribozyme (Td Rz, however, pPyP served not only as an inhibitor but also as an activator, and the effects of pPyP were dependent on its concentration. To analyze the structural and electronic factors determining the effects of pPyP on group I ribozymes, three cationic porphyrins (pPyNCP, pPyF4P, and TMPyP were also examined. As interactions between small organic molecules and nucleic acids are attractive and important issues in biochemistry and biotechnology, this study contributes to the development of porphyrin-based molecules that can modulate functions of structured RNA molecules.

  6. meso-Substituted bisanthenes as soluble and stable near-infrared dyes

    KAUST Repository

    Li, Jinling

    2010-02-05

    (Chemical Equation Presented) Three meso-substituted bisanthenes, 4-6, were prepared in a short synthetic route from the bisanthenequinone. They exhibit largely improved stability and solubility in comparison to the parent bisanthene. All of these compounds also show near-infrared (NIR) absorption and emission with high to moderate fluorescence quantum yields. Amphoteric redox behavior was observed for 4-6 by cyclic voltammetry, and these compounds can be reversibly oxidized and reduced into respective cationic and anionic species by both electrochemical and chemical processes. In addition, compound 5 adopts a herringbone π-stacking motif in the single crystal. © 2010 American Chemical Society.

  7. Porphyrin Analogues of a Trityl Cation and Anion.

    Science.gov (United States)

    Kato, Kenichi; Kim, Woojae; Kim, Dongho; Yorimitsu, Hideki; Osuka, Atsuhiro

    2016-05-17

    Porphyrin-stabilized meso- or β-carbocations were generated upon treatment of the corresponding bis(4-tert-butylphenyl)porphyrinylcarbinols with trifluoroacetic acid (TFA). Bis(4-tert-butylphenyl)porphyrinylcarbinols were treated with TFA to generate the corresponding carbocations stabilized by a meso- or β-porphyrinyl group. The meso-porphyrinylmethyl carbocation displayed more effective charge delocalization with decreasing aromaticity compared with the β-porphyrinylmethyl carbocation. A propeller-like porphyrin trimer, tris(β-porphyrinyl)carbinol, was also synthesized and converted to the corresponding cation that displayed a more intensified absorption reaching over the NIR region. meso-Porphyrinylmethyl carbanion was generated as a stable species upon deprotonation of bis(4-tert-butylphenyl)(meso-porphyrinyl)methane with potassium bis(trimethylsilyl)amide (KHMDS) and [18]crown-6, whereas β-porphyrinylmethyl anions were highly unstable. PMID:26991021

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

    Directory of Open Access Journals (Sweden)

    Newton M. Barbosa Neto

    2011-07-01

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

  9. Multi-triphenylamine-substituted porphyrin-fullerene conjugates as charge stabilizing "antenna-reaction center" mimics.

    Science.gov (United States)

    D'Souza, Francis; Gadde, Suresh; Islam, D-M Shafiqul; Wijesinghe, Channa A; Schumacher, Amy L; Zandler, Melvin E; Araki, Yasuyaki; Ito, Osamu

    2007-09-01

    A new concept of charge stabilization via delocalization of the pi-cation radical species over the donor macrocycle substituents in a relatively simple donor-acceptor bearing multimodular conjugates is reported. The newly synthesized multimodular systems were composed of three covalently linked triphenylamine entities at the meso position of the porphyrin ring and one fulleropyrrolidine at the fourth meso position. The triphenylamine entities were expected to act as energy transferring antenna units and to enhance the electron donating ability of both free-base and zinc(II) porphyrin derivatives of these pentads. Appreciable electronic interactions between the meso-substituted triphenylamine entities and the porphyrin pi-system were observed, and as a consequence, these moieties acted together as an electron-donor while the fullerene moiety acted as an electron-acceptor in the multimodular conjugates. In agreement with the spectral and electrochemical results, the computational studies performed by the DFT B3LYP/3-21G(*) method revealed delocalization of the frontier highest occupied molecular orbital (HOMO) over the triphenylamine entities in addition to the porphyrin macrocycle. Free-energy calculations suggested that the light-induced processes from the singlet excited state of porphyrins are exothermic in the investigated multimodular conjugates. The occurrence of photoinduced charge-separation and charge-recombination processes was confirmed by the combination of time-resolved fluorescence and nanosecond transient absorption spectral measurements. Charge-separated states, on the order of a few microseconds, were observed as a result of the delocalization of the pi-cation radical species over the porphyrin macrocycle and the meso-substituted triphenylamine entities. The present study successfully demonstrates a novel approach of charge-stabilization in donor-acceptor multimodular conjugates. PMID:17608464

  10. One-electron oxidation of nickel porphyrins. Effect of structure and medium on formation of nickel(III) porphyrin or nickel(II) porphyrin π-radical cation

    International Nuclear Information System (INIS)

    The oxidation of several nickel(II) porphyrins by various radicals has been studied by pulse radiolysis in different media (Cl2sm-bullet- and Br2sm-bullet- in aqueous systems, Br atoms in organic solvents, and peroxyl radicals in organic and aqueous/organic systems). Photochemical oxidation was also examined in some cases. The absorption spectrum of the oxidation product was monitored within several microseconds after the pulse. Two types of differential spectra were observed, a broad absorption at 640-700 nm ascribed to the π-radical cation, or a sharp absorption at 560-580 nm ascribed to nickel(III) porphyrin. NiIITPP (tetraphenylporphyrin) in several organic solvents, protic and aprotic, was oxidized to NiIIITPP. The addition of 10% water as cosolvent or 0.1 M of electrolyte changed the route of oxidation to give the radical cation NiIITPPsm-bullet+. On the other hand, NiIITSPP (tetrakis(4-sulfonatophenyl)porphyrin), which has four negative charges, was oxidized on the porphyrin ligand by all the radicals examined, in water and in several organic solvents. NiIIbis(N-methyl-4-pyridyl)diphenylporphyrin, with a charge of +2, and NiII tris(4-sulfonatophenyl)(N-methyl-4-pyridyl)porphyrin, with an overall charge of -2, were oxidized on the ligand in aqueous solution but on the metal in organic solvents. These and other results led to the conclusion that most radicals react with NiIIP by an inner-sphere mechanism to bind onto the metal and give the NiIIIP form. However, when the porphyrin is sufficiently charged to repel the axially bound anion, and/or when the medium enhances the separation of this anion from the metal, the result is oxidation of the porphyrin π-system. In all cases, however, the one-electron-oxidation products, whether NiIIPsm-bullet+ or NiIIIP, decay to yield two-electron ring oxidation products

  11. Fluorescence quenching effect of guanine interacting with water-soluble cationic porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Makarska-Bialokoz, Magdalena, E-mail: makarska@hektor.umcs.lublin.pl

    2014-03-15

    The process of association between 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate (H{sub 2}TTMePP) and guanine has been studied both in NaOH solution and TRIS buffer analysing its absorption and steady-state fluorescence spectra. The fluorescence quenching effect observed during interactions porphyrin-guanine 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 monoanion form were established. The results demonstrate that guanine can interact with H{sub 2}TTMePP at basic pH and through formation of stacking complexes is able to quench its ability to emission. -- Highlights: • Association study of water soluble cationic porphyrin with guanine. • Porphyrin absorption spectra undergo the bathochromic and hypochromic effects. • Guanine interacts with porphyrin in inhibiting manner, quenching its emission. • Fluorescence quenching process is static with fractional accessibility of porphyrin. • The association and fluorescence quenching constants were calculated.

  12. 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.

  13. 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. PMID:23142673

  14. In vitro photodynamic inactivation of conidia of the phytopathogenic fungus Colletotrichum graminicola with cationic porphyrins.

    Science.gov (United States)

    Vandresen, Camila Chevonica; Gonçalves, Alan Guilherme; Ducatti, Diogo Ricardo Bazan; Murakami, Fabio Seigi; Noseda, Miguel Daniel; Duarte, Maria Eugenia Rabello; Barreira, Sandra Mara Woranovicz

    2016-05-11

    Photodynamic inactivation (PDI) is an efficient approach for the elimination of a series of microorganisms; however, PDI involving phytopathogenic filamentous fungi is scarce in the literature. In the present study, we have demonstrated the photoinactivating properties of five cationic meso-(1-methyl-4-pyridinio)porphyrins on conidia of the phytopathogen Colletotrichum graminicola. For this purpose, photophysical properties (photostability and (1)O2 singlet production) of the porphyrins under study were first evaluated. PDI assays were then performed with a fluence of 30, 60, 90 and 120 J cm(-2) and varying the porphyrin concentration from 1 to 25 μmol L(-1). Considering the lowest concentration that enabled the best photoinactivation, with the respective lowest effective irradiation time, the meso-(1-methyl-4-pyridinio)porphyrins herein studied could be ranked as follows: triple-charged 4 (1 μmol L(-1) with a fluence of 30 J cm(-2)) > double-charged-trans2 (1 μmol L(-1) with 60 J cm(-2)) > tetra-charged 5 (15 μmol L(-1) with 90 J cm(-2)) > mono-charged 1 (25 μmol L(-1) with 120 J cm(-2)). Double-charged-cis-porphyrin 3 inactivated C. graminicola conidia in the absence of light. Evaluation of the porphyrin binding to the conidia and fluorescence microscopic analysis were also performed, which were in agreement with the PDI results. In conclusion, the cationic porphyrins herein studied were considered efficient photosensitizers to inactivate C. graminicola conidia. The amount and position of positive charges are related to the compounds' amphiphilicity and therefore to their photodynamic activity. PMID:27109559

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

    International Nuclear Information System (INIS)

    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.

  16. Quantum chemical investigation of a dinuclear iridium porphyrin and its dipositive π-cation biradical

    International Nuclear Information System (INIS)

    Quantum chemical calculations at both HF/6-31G and B3LYP/6-31G levels have been performed on a dinuclear iridium porphyrin and its dipositive π-cation biradical. The dimer consists of two units of an iridium octaethylporphyrin (OEP) ring with an axial chlorine and a bridging ligand, 1,2-bis(diphenylphosphino)ethane (dppe), and has the formula of [(OEP)IrCl]2dppe. Geometric parameters and 1H nuclear magnetic resonance from the theoretical calculations and the X-ray crystallographic determinations have been compared for the neutral dimer. With few exceptions, the optimized geometric parameters, in general, agree well with X-ray crystallographic analysis. However, comparisons between the theoretical calculations and the experimental values reveal that some of the calculated bond lengths are more reasonable for a specific type of bond than those observed. The calculated 1H chemical shifts are in good agreement with values obtained from experiment. In addition, theoretical calculations on the structure of the dipositive π-cation biradical, {[(OEP ·)IrCl]2dppe}2+, have been conducted. Unlike other cofacial π-cation dimers, the bond length alternation around the central 16-membered C12N4 ring is not predicted to exist in this dipositive π-cation biradical. The natural population analysis of the neutral and the biradical dimers at both levels suggests that the bonding between the iridium and the porphyrin is more covalent than ionic

  17. Study on the synthesis and antimicrobial activity of novel cationic porphyrins

    Institute of Scientific and Technical Information of China (English)

    Ke Gui Yu; Dong Hong Li; Cheng He Zhou; Jun Lin Diao

    2009-01-01

    A novel series of quaternary ammonium cationic derivatives based on tetrapyridyl-porphyrin was synthesized.All the compounds were evaluated for their in vitro antibacterial activities against S.aureus,E.coli and P aeruginosa,and antifunga activities against C. albicans.where microorganisms were exposed and unexposed to the irradiation.The results revealed that some of these compounds,especially,3a and 4a displayed satisfactory antibacterial activity against Gram-positive bacteria S. aureus and moderate antifungal activity against C. albicans.Unfortunately.Gram-negative bacteria P. aeruginasa was resistant to all compounds.The antimicrobial activity was found to be sensitive to the functional groups attached on the aromatic ring and the complex metal in the porphyrin ring,and decreased with the increase of electron-withdrawing capability of the functional groups.These preliminary results suggested that the remarkable antibacterial efficiency against S.aureus makes these substances promising antimicrobial agents.

  18. Sewage bacteriophage inactivation by cationic porphyrins: influence of light parameters.

    Science.gov (United States)

    Costa, Liliana; Carvalho, Carla M B; Faustino, Maria A F; Neves, Maria G P M S; Tomé, João P C; Tomé, Augusto C; Cavaleiro, José A S; Cunha, Angela; Almeida, Adelaide

    2010-08-01

    Photodynamic therapy has been used to inactivate microorganisms through the use of targeted photosensitizers. Although the photoinactivation of microorganisms has already been studied under different conditions, a systematic evaluation of irradiation characteristics is still limited. The goal of this study was to test how the light dose, fluence rate and irradiation source affect the viral photoinactivation of a T4-like sewage bacteriophage. The experiments were carried out using white PAR light delivered by fluorescent PAR lamps (40 W m(-2)), sun light (600 W m(-2)) and an halogen lamp (40-1690 W m(-2)). Phage suspensions and two cationic photosensitizers (Tetra-Py(+)-Me, Tri-Py(+)-Me-PF) at concentrations of 0.5, 1.0 and 5.0 microM were used. The results showed that the efficacy of the bacteriophage photoinactivation is correlated not only with the sensitizer and its concentration but also with the light source, energy dose and fluence rate applied. Both photosensitizers at 5.0 microM were able to inactivate the T4-like phage to the limit of detection for each light source and fluence rate. However, depending of the light parameters, different irradiation times are required. The efficiency of photoinactivation is dependent on the spectral emission distribution of the light sources used. Considering the same light source and a fixed light dose applied at different fluence rates, phage inactivation was significantly higher when low fluence rates were used. In this way, the light source, fluence rate and total light dose play an important role in the effectiveness of the antimicrobial photodynamic therapy and should always be considered when establishing an optimal antimicrobial protocol. PMID:20563346

  19. Self-Assemblies of Cationic Porphyrins with Functionalized Water-Soluble Single-Walled Carbon Nanotubes

    Czech Academy of Sciences Publication Activity Database

    Kubát, Pavel; Lang, Kamil; Janda, Pavel; Frank, O.; Matulková, Irena; Sýkora, Jan; Civiš, Svatopluk; Hof, Martin; Kavan, Ladislav

    2009-01-01

    Roč. 9, č. 10 (2009), s. 5795-5802. ISSN 1533-4880 R&D Projects: GA ČR GA203/07/1424; GA ČR(CZ) GA203/06/1244; GA AV ČR KAN100500652; GA AV ČR IAA400400804; GA AV ČR KAN200100801; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40320502 Keywords : cationic porphyrin * carbon nanotubes * fluorescence spectroscopy * FTIR * Raman spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.435, year: 2009

  20. Graphene Oxide Nanofiltration Membranes Stabilized by Cationic Porphyrin for High Salt Rejection.

    Science.gov (United States)

    Xu, Xiao-Ling; Lin, Fu-Wen; Du, Yong; Zhang, Xi; Wu, Jian; Xu, Zhi-Kang

    2016-05-25

    Swelling has great influences on the structure stability and separation performance of graphene oxide laminate membranes (GOLMs) for water desalination and purification. Herein, we report cross-linked GOLMs from GO assembled with cationic tetrakis(1-methyl-pyridinium-4-yl)porphyrin (TMPyP) by a vacuum-assisted strategy. The concave nonoxide regions (G regions) of GO are used as cross-linking sites for the first time to precisely control the channel size for water permeation and salt ion retention. Channels around 1 nm are constructed by modulating the assembly ratio of TMPyP/GO, and these cross-linked GOLMs show high salt rejection. PMID:27158976

  1. Synergistic enhancement of tolerance mechanisms in response to photoactivation of cationic tetra (N-methylpyridyl) porphyrins in tomato plantlets.

    Science.gov (United States)

    Guillaumot, Damien; Issawi, Mohammad; Da Silva, Anne; Leroy-Lhez, Stephanie; Sol, Vincent; Riou, Catherine

    2016-03-01

    Antimicrobial photodynamic treatment (APDT) is largely used in medical domain and could be envisaged as a farming practice against crop pathogens such as bacteria and fungi that generate drops in agricultural yields. Thus, as a prerequisite for this potential application, we studied the effect of water-soluble anionic (TPPS and Zn-TPPS) and cationic (TMPyP and Zn-TMPyP) porphyrins tested on tomato (Solanum lycopersicum) plantlets grown in vitro under a 16 h photoperiod. First of all, under dark conditions, none of the four porphyrins inhibited germination and induced cytotoxic effects on tomato plantlets as etiolated development was not altered. The consequences of porphyrin long-term photoactivation (14 days) were thus studied on in vitro-grown tomato plantlets at phenotypic and molecular levels. Cationic porphyrins especially Zn-TMPyP were the most efficient photosensitizers and dramatically altered growth without killing plantlets. Indeed, tomato plantlets were rescued after cationic porphyrins treatment. To gain insight, the different molecular ways implied in the plantlet tolerance to photoactivated Zn-TMPyP, lipid peroxidation, antioxidative molecules (total thiols, proline, ascorbate), and ROS detoxification enzymes were evaluated. In parallel to an increase in lipid peroxidation and hydrogen peroxide production, antioxidative molecules and enzymes (guaiacol peroxidase, catalase, and superoxide dismutase) were up-regulated in root apparatus in response to photoactivated Zn-TMPyP. This study showed that tomato plantlets could overcome the pressure triggered by photoactivated cationic porphyrin by activating antioxidative molecule and enzyme arsenal and confining Zn-TMPyP into cell wall and/or apoplasm, suggesting that APDT directed against tomato pathogens could be envisaged in the future. PMID:26854612

  2. Supramolecular porphyrin-fullerene via 'two-point' binding strategy: axial-coordination and cation-crown ether complexation.

    Science.gov (United States)

    D'Souza, Francis; Chitta, Raghu; Gadde, Suresh; Zandler, Melvin E; Sandanayaka, Atula S D; Araki, Yasuyuki; Ito, Osamu

    2005-03-14

    A highly stable porphyrin-fullerene conjugate with defined distance and orientation, was formed using a newly developed 'two-point' binding strategy involving axial-coordination and cation-crown ether complexation; photochemical studies performed in benzonitrile revealed efficient charge separation and slow charge-recombination in the supramolecular complex. PMID:15742051

  3. 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.

  4. Self-assemblies of cationic porphyrins with functionalized water-soluble single-walled carbon nanotubes.

    Science.gov (United States)

    Kubát, Pavel; Lang, Kamil; Jandal, Pavel; Frank, Ota; Matulková, Irena; Sýkora, Jan; Civis, Svatopluk; Hof, Martin; Kavan, Ladislav

    2009-10-01

    5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin, 5,10,15,20-tetrakis(2-N-methylpyridyl)porphyrin, and 5,10,15,20-tetrakis(4-trimethylammoniophenyl)porphyrin form self-assemblies with single-walled carbon nanotubes (SWNT) functionalized by polyaminobenzene sulfonic acid. Both steady-state and time-resolved emission studies revealed efficient quenching of the excited singlet states of the porphyrins. Atomic force microscopy, fluorescence confocal microscopy, and fluorescence lifetime imaging allowed the visualization of individual bundles of SWNTs and the differentiation of porphyrin molecules at specific binding sites of SWNT. PMID:19908455

  5. Synthesis of magnetite-porphyrin nanocomposite and its application as a novel magnetic adsorbent for removing heavy cations

    International Nuclear Information System (INIS)

    Graphical abstract: Magnetite-porphyrin nanocomposite (MPNC) as a novel magnetic adsorbent for removing heavy cations was synthesized. - Highlights: • Nanosized Fe3O4 was prepared by hydrothermal reaction of iron salt in alkaline media. • The synthesized magnetite and nanocomposite had soft ferromagnetic property. • Magnetic nanocomposite as a novel magnetic adsorbent for heavy cations was prepared. • Satisfactory separation from solutions in the order of Pb2+ > Cd2+ > Hg2+ was obtained. - Abstract: Magnetite-porphyrin nanocomposite (MPNC) was synthesized as a novel magnetic adsorbent for removing heavy cations. Firstly, we prepared nano-sized magnetite using a simple hydrothermal route. The synthesis of nanoscaled magnetite was carried out through reaction between iron source and various amines. In this paper, we studied effective parameters in controlling shape and size of nanoscaled magnetite. These parameters were presence of alkaline, reaction time, kind of amine and iron salt. Morphology, particle size and magnetic properties of the nanoscaled magnetite were obtained by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier transform infrared (FT-IR), diffuse reflectance spectra (DRS) and vibrating sample magnetometer (VSM). Our study showed that the synthesized magnetite from reaction between FeSO4 and hydrazinum hydrate has spherical shape. The synthesized magnetite was a nanosized compound and used for preparation of magnetite-porphyrin nanocomposite. The synthesized magnetite-porphyrin hybrid material had magnetic property and was used as magnetic adsorbent for removing heavy cations of water. Satisfactory separation from solutions in the order of Pb2+ > Cd2+ > Hg2+ was obtained

  6. 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)

    Thirty-three porphyrins or metalloporphyrins corresponding to the general formula [meso-[N-methyl-4(or 3 or 2)-pyridiniumyl]n(aryl)4-nporphyrin]M (M = H2, CuII, or ClFeIII), with n = 2-4, have been synthesized and characterized by UV-visible and 1H 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 Kapp 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

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

    KAUST Repository

    Aly, Shawkat Mohammede

    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.

  8. Metal cation sensing material based on the assembly of meso-terakis(4-N,N,N-trimethylamiophenyl) porphyrin and mesoporous molecular sieve MCM-41

    Institute of Scientific and Technical Information of China (English)

    ZHANG Huidong; SUN Yinghui; ZHANG Ping; YE Kaiqi; ZHANG Jingying; WANG Yue

    2005-01-01

    The metal cation sensing material was prepared by entrapment of a water-soluble porphyrin compound, mesoterakis(4-N,N,N-trimethylamiophenyl) porphyrin (TTMAPP), in mesoporous molecular sieve MCM-41. The powder X-ray diffraction (XRD) spectra results demonstrated that after the introduction of TTMAPP, the ordered channel arrangement of MCM-41 remained. The assembly material, TTMAPP/MCM-41, exhibited a typical absorption feature of porphyrin compound. Emission spectrum study revealed that the introduction of zinc (II) cation resulted in the formation of a new emission peak at 600 nm for TTMAPP/MCM-41, while the presence of copper (II) cation at low concentration led to that the luminescent intensity of TTMAPP/MCM-41 was obviously reduced by 68.42%. The experiment results demonstrated that TTMAPP/MCM-41 is a cation sensing materials with good performance.

  9. Meso-functionalized octamethoxyporphyrins: A new class of nonasubstituted porphyrins

    Indian Academy of Sciences (India)

    Pradeepta K Panda; V Krishnan

    2005-03-01

    Octamethoxyporphyrin containing multiple-donor substituents has been functionalized for the first time. A large number of its mono-meso-substituted derivatives with substituents such as nitro, amino, N-methylamino, formyl, hydroxymethyl, oxime, cyano and carboxy functional groups have been synthesized and characterized. They form a new class of nonasubstituted porphyrins. Crystallographic studies on the cyano derivative show that the -C N group is in conjugation with the prophyrin -system. The calculated optical transition energies and the electron densities on the imino nitrogens of the synthesised porphyrins using AMI calculations correlate well with the experimentally observed data. Mesosubstituted porphyrins are found to be essentially planar.

  10. Synthesis and characterization of some heteroleptic copper(II) complexes based on meso-substituted dipyrrins

    Indian Academy of Sciences (India)

    Rakesh Kumar Gupta; Mahendra Yadav; Rampal Pandey; Daya Shankar Pandey

    2011-11-01

    The syntheses and characterizations of meso-substituted dipyrrins, 5-(4-imidazol-1-yl-phenyl)-dipyrromethene (4-impdpm), 5-(4-nitro-imidazol-1-yl-phenyl)-dipyrromethene, (4-nimpdpm), 5-(4-benzimidazol-1-yl-phenyl)-dipyrromethene (4-bimp-dpm) and heteroleptic complexes [Cu3(4-impdpm)2(hfacac)4] 1, [Cu(4-nimpdpm)(acac)] 2, [Cu(4-nimpdpm)(hfacac)] 3, [{Cu(4-bimpdpm)(acac)}] 4 and [{Cu(4-bimpdpm)-(hfacac)}] 5, imparting acetylacetonato (acac) and hexafluoroacetylacetonato (hfacac) groups as co-ligand have been described. The dipyrrins and complexes 1-5 have been characterized by elemental analyses and spectral (IR ESI-MS, NMR, electronic absorption and emission) studies. Crystal structures of 1, 3 and 4 have been authenticated by X-ray single crystal analyses. The reaction between 4-impdpm and Cu(hfacac)2 gave a trimetallic complex, under analogous conditions 4-nimpdpm and 4-bimpdpm reacted with Cu(acac)2 and Cu(hfacac)2·2H2O to afford mononuclear (2, 3) and 1D polymeric (4, 5) complexes.

  11. 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.

  12. 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+.

  13. Actinide bis(porphyrinate) π-radical cations and dications, including the x-ray crystal structure of [(TPP)2Th][SbCl6

    International Nuclear Information System (INIS)

    The chemistry of actinide porphyrin complexes remains in large part undeveloped. The authors report here the first synthesis, isolation, and detailed characterization of several actinide bis-porphyrin sandwich complexes, including the neutral, π-radical monocation, and π-radical dication complexes, [(TPP)2M]/sup n+/, where M = Th(IV) or U(IV) and n = 0, 1, or 2. In addition, the x-ray crystal structure of both the neutral Th complex and its oxidized π-radical cation, [(TPP)2Th][SbCl60, have been solved. These complexes are among the very first π-radical cations where close interaction between two porphyrins occurs. Moreover, these complexes belong to an unusual class of actinide complexes where redox processes can occur in near proximity to the f-element

  14. Thin films of layered silicates with photochemically-active porphyrin cations

    Czech Academy of Sciences Publication Activity Database

    Čeklovský, A.; Bujdák, J.; Lang, Kamil

    Bratislava : Institute of Inorganic Chemistry, Slovak Academy of Sciences, 2008. s. 23. ISBN 978-80-224-1019-9. [Conference on Solid State Chemistry /8./. 06.06.2008-11.06.2008, Bratislava] Institutional research plan: CEZ:AV0Z40320502 Keywords : porphyrin Subject RIV: CA - Inorganic Chemistry

  15. Synthesis of Meso-Substituted Subphthalocyanine-Subporphyrin Hybrids: Boron SubTriBenzoDiAzaPorphyrins (SubTBDAPs)

    OpenAIRE

    Remiro Buenamanana, Sonia; Diaz-Moscoso, Alejandro; Hughes, David; Bochmann, Manfred; Graham J. Tizzard; Coles, Simon J.; Cammidge, Andy

    2015-01-01

    The first syntheses of hybrid structures that lie between subphthalocyanines and subporphyrins are reported. The versatile single-step synthetic method uses a preformed aminoisoindolene to provide the bridging methine unit and its substituent while trialkoxyborates simultaneously act as Lewis acid, template, and provider of the apical substituent. The selection of each component therefore allows for the controlled formation of diverse, differentially functionalized systems. The new hybrids ar...

  16. Light-induced aggregation of cationic porphyrins and its consequences on photochemical behaviour

    Czech Academy of Sciences Publication Activity Database

    Mosinger, Jiří; Lang, Kamil; Kubát, Pavel

    Bad Hofgastein : EPA , 2006, s. 25-25. [Central European Conference on Photochemistry. Bad Hohgastein (AT), 05.03.2006-09.03.2006] R&D Projects: GA ČR GA203/04/0426; GA ČR(CZ) GA203/06/1244 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : porphyrin Subject RIV: CA - Inorganic Chemistry

  17. Quantum confinement-tunable intersystem crossing and the triplet state lifetime of cationic porphyrin-CdTe quantum dot nano-assemblies

    KAUST Repository

    Ahmed, Ghada H.

    2015-01-01

    Here, we report a ground-state interaction between the positively charged cationic porphyrin and the negatively charged carboxylate groups of the thiol ligands on the surface of CdTe quantum dots (QDs), leading to the formation of a stable nanoassembly between the two components. Our time-resolved data clearly demonstrate that we can dramatically tune the intersystem crossing (ISC) and the triplet state lifetime of porphyrin by changing the size of the QDs in the nanoassembly. © 2015 The Royal Society of Chemistry.

  18. PORPHYRINS WITH 1,4-BENZODIAZEPINE SUBSTITUENTS

    OpenAIRE

    Pavlovskaya, T. V.; Ishkov, Yu. V.; Mazepa, A. V.; Pavlovsky, V. І.

    2016-01-01

    The interaction of the derivatives of meso-substituted porphyrins with Взаємодією похідних лезо-заміщених порфіринів з гідразидом 7-bromo-2-oxo-5-phenyl-2,3-dihydrobenzo[e][1, 4]diazepin-1-yl)-acetic acid hydrazide lead to range of new compounds - potential antitumor agents.

  19. An efficient solvent-free synthesis of meso-substituted dipyrromethanes using SnCl2•2H2O catalysis

    Directory of Open Access Journals (Sweden)

    Kabeer Ahmed Shaikh

    2012-07-01

    Full Text Available Highly rapid and simple methodology has been developed for the quantitative synthesis of meso-substituted dipyrromethanes from lowest pyrrole/aldehyde ratio. The method was carried out by using SnCl2•2H2O as a catalyst under solvent free condition. The method is environmentally friendly, easy to workup, and gives excellent yield of the products.

  20. Two-Step, One-Flask Synthesis of a Meso-Substituted Phlorin.

    Science.gov (United States)

    Kim, Dongjoon; Chun, Hao-Jung; Donnelly, Christopher C; Geier, G Richard

    2016-06-17

    A two-step, one-flask reaction of pyrrole with pentafluorobenzaldehyde and acetone was investigated to determine the potential for a streamlined synthesis of a phlorin and/or 5-isocorrole as an alternative to stepwise, dipyrromethanecarbinol routes. Analytical-scale reactions were performed examining the effect of reactant concentration, reactant ratio, acid catalyst (TFA or BF3·OEt2), concentration of acid catalyst, oxidant quantity, and reaction time on the distribution of phlorin and 5-isocorrole as well as three additional porphyrinoids (porphodimethene, porphyrin, and corrole). Phlorin was observed ubiquitously in yields up to 20-26%, whereas 5-isocorrole was not detected. Promising reaction conditions for the one-flask synthesis of the phlorin were performed on a preparative scale. The best reaction condition afforded the phlorin in an isolated yield of 20-21% (249-268 mg). Preliminary attempts to extend the methodology to the preparation of phlorins derived from other ketones resulted in a low yield of phlorin from acetophenone (5%) and no detectable phlorin from benzophenone. The discovery of reaction conditions for the two-step, one-flask synthesis of a phlorin provides easier access to this interesting compound, and provides encouragement for the further study of reactions of pyrrole with an aldehyde and a ketone. PMID:27231965

  1. Interfacial Self-Assembly of Water-Soluble Cationic Porphyrins for the Reduction of Oxygen to Water

    OpenAIRE

    Olaya, Astrid J.; Schaming, Delphine; Brevet, Pierre-Francois; Nagatani, Hirohisa; Xu, Hai-jun; Meyer, Michel; Girault, Hubert H.

    2012-01-01

    Meet at the border: Assembly of the water-soluble cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP]4+ at soft interfaces is enhanced and stabilized by its interfacial interaction with the lipophilic anion (C6F5)4B−. The supramolecular structure thus formed (see picture) provides excellent catalytic activity in the four-electron reduction of oxygen.

  2. Interfacial self-assembly of water-soluble cationic porphyrins for the reduction of oxygen to water.

    Science.gov (United States)

    Olaya, Astrid J; Schaming, Delphine; Brevet, Pierre-Francois; Nagatani, Hirohisa; Xu, Hai-Jun; Meyer, Michel; Girault, Hubert H

    2012-06-25

    Meet at the border: Assembly of the water-soluble cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP](4+) at soft interfaces is enhanced and stabilized by its interfacial interaction with the lipophilic anion (C(6)F(5))(4)B(-). The supramolecular structure thus formed provides excellent catalytic activity in the four-electron reduction of oxygen. PMID:22615211

  3. Transient formation of the oxo-iron(IV) porphyrin radical cation during the reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin with hydrogen peroxide in aqueous solution.

    Science.gov (United States)

    Saha, Tapan Kumar; Karmaker, Subarna; Tamagake, Keietsu

    2003-01-01

    The reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin (Fe(III)TMPyP) with hydrogen peroxide (H(2)O(2)) and the catalytic activity of the reaction intermediates on the luminescent peroxidation of luminol in aqueous solution were studied by using a double-mixing stopped-flow system. The observed luminescence intensities showed biphasic decay depending on the conditions. The initial flashlight decayed within flashlight appeared during the formation of the oxo-iron(IV) porphyrin, TMPyPFe(IV) = O, which is responsible for the sustained emission. The absorption spectra 0.0-0.5 s did not reproduce well by a simple combination of the two spectra of Fe(III)TMPyP and TMPyPFe(IV) = O, indicating that transient species was formed at the initial stage. Addition of uric acid (UA) caused a significant delay in the initiation of the luminol emission as well as in the formation of the TMPyPFe(IV) = O. Both of them were completely diminished in the presence of UA equimolar with H(2)O(2), while mannitol had no effect at all. The delay of the light emission as well as the appearance of TMPyPFe(IV) = O was directly proportional to the [UA](0) but other kinetic profiles were not changed significantly. Based on these observations and the kinetic analysis, we confirmed the involvement of the oxo-iron(IV) porphyrin radical cation, (TMPyP)(.+)Fe(IV) = O, as an obligatory intermediate in the rate-determining step of the overall reaction, Fe(III)TMPyP + H(2)O(2) --> TMPyPFe(IV) = O, with a rate constant of k = 4.3 x 10(4)/mol/L/s. The rate constants for the reaction between the (TMPyP)(.+)Fe(IV) = O and luminol, and between the TMPyPFe(IV) = O and luminol were estimated to be 3.6 x 10(6)/mol/L/s and 1.31 x 10(4)/mol/L/s, respectively. PMID:12701092

  4. Strati-bis porphyrins: a promising gauge for study of photo-induced electron transfer. Final summary report

    Energy Technology Data Exchange (ETDEWEB)

    Mauzerall, D.

    1982-02-01

    The synthesis of a new series of strati-bisporphyrins (sbPs) is reported. The synthesis via the preparation of the first amide-linked sbP, tetra-meso-(m,m' (N-benzyl benzamide)) strati-bisporphyrin, III. This highly symmetric and well defined staked porphyrin dimer of two meso-substituted tetra phenyl porphyrins joined at the meta positions of all eight phenyl groups by four methyl formamide linkages, -CH/sub 2/NHCO-. This sbP is being prepared by the de-novo coupling procedure where a second porphyrin ring is constructed upon an initial porphyrin ring by way of the internal condensation of a porphyrin tetraaldehyde with four pyrrole molecules. This is the same general scheme which was successfully used in the synthesis of the first sbP system which had ester linkages. The necessary porphyrin tetraaldehyde for this new amide-linked dimer has already been synthesized. The porphyrin, tetraaldehyde, T-meso (m-N-benzyl(m'-formyl)benzamide) porphyrin, II, was prepared by the acylation of a porphyrin tetraamine with m-chlorocarbonyl benzaldehyde. The porphyrin tetraamine, tetra-meso-(m-aminomethyl-phenyl porphyrin, I, was prepared by the condensation of the shiff-base polymer of m-amino-methyl benzaldehyde with pyrrole in the usual way. The most effective synthetic scheme for the sbP III begins with the preparation of the essential benzaldehydes 5 and 9 by the bromination of commercially available toluene derivatives. The fluorescence and other photophysical properties of these molecules will be studied as purified samples are prepared. 3 figures. (DMC)

  5. Porphyrin Tests

    Science.gov (United States)

    ... attack Table adapted from: "Iron and porphyrin metabolism," Clinical Chemistry: Theory, Analysis and Correlation , courtesy of William E. ... For Health Professionals ©2001 - by American Association for Clinical Chemistry • Contact Us | Terms of Use | Privacy We comply ...

  6. Fabrication of optochemical and electrochemical sensors using thin films of porphyrin and phthalocyanine derivatives

    Indian Academy of Sciences (India)

    Palanisamy Kalimuthu; Arumugam Sivanesan; S Abraham John

    2012-11-01

    This paper describes the fabrication of thin films of porphyrin and metallophthalocyanine derivatives on different substrates for the optochemical detection of HCl gas and electrochemical determination of L-cysteine (CySH). Solid state gas sensor for HCl gas was fabricated by coating meso-substituted porphyrin derivatives on glass slide and examined optochemical sensing of HCl gas. The concentration of gaseous HCl was monitored from the changes in the absorbance of Soret band. Among the different porphyrin derivatives, meso-tetramesitylporphyrin (MTMP) coated film showed excellent sensitivity towards HCl and achieved a detection limit of 0.03 ppm HCl. Further, we have studied the self-assembly of 1,8,15,22-tetraaminometallophthalocyanine (4-MTAPc; M = Co and Ni) from DMF on GC electrode. The CVs for the self-assembled monolayers (SAMs) of 4-CoIITAPc and 44-NiIITAPc show two pairs of well-defined redox couple corresponding to metal and ring. Using the 4-CoIITAPc SAM modified electrode, sensitive and selective detection of L-cysteine was demonstrated. Further, the SAM modified electrode also successfully separates the oxidation potentials of AA and CySH with a peak separation of 320mV.

  7. Self-Assembly of Porphyrin J-Aggregates

    Science.gov (United States)

    Snitka, Valentinas; Rackaitis, Mindaugas; Navickaite, Gintare

    2006-03-01

    The porphyrin nanotubes were built by ionic self-assembly of two oppositely charged porphyrins in aqueous solution. The porphyrins in the acid aqueous solution self-assemble into J-aggregates, wheels or other structures. The electrostatic forces between these porphyrin blocks contribute to the formation of porphyrin aggregates in the form of nanotubes, enhance the structural stability of these nanostructures. The nanotubes were composed mixing aqueous solutions of the two porphyrins - anionic Meso-tetra(4- sulfonatophrnyl)porhine dihydrochloride (TPPS4) and cationic Meso-tetra(4-pyridyl)porphine (T4MPyP). The porphyrin nanotubes obtained are hollow structures with the length of 300 nm and diameter 50 nm. Photocatalytic porphyrins are used to reduce metal complexes from aqueous solution and to control the deposition of Au from AuHCl4 and Au nanoparticles colloid solutions onto porphyrin nanotubes. Porphyrin nanotubes are shown to reduce metal complexes and deposit the metal selectively onto the inner or outer surface of the tubes, leading to nanotube-metal composite structures.

  8. Photophysics of the porphyrins; unusual fluorescence of europium porphyrin complex entrapped in sol-gel silica matrix

    International Nuclear Information System (INIS)

    In this paper, the study on encapsulation of water-soluble cationic porphyrins: methyl-pyridyl porphyrin (H2TMePyP) and its Eu(III) complex in the monolith gels prepared by sol-gel method are reported. The samples doped with the porphyrins were prepared by tetraethoxysilane (TEOS) hydrolysis and condensation. Their absorption and emission spectroscopic properties in comparison with the spectra of the same compounds in various solvents are investigated. The spectra of metal complex were compared with those of free-base porphyrin. The strong fluorescence of europium porphyrin in the silica matrix is observed under excitation in Q-band (530 nm), while at the same time emission neither free-base porphyrin nor europium chloride does not occur. It can be explained by the strong interaction of the Eu(III)TMePyP(acac) with the silica

  9. Photophysics of the porphyrins; unusual fluorescence of europium porphyrin complex entrapped in sol-gel silica matrix

    Energy Technology Data Exchange (ETDEWEB)

    Dargiewicz-Nowicka, J.; Makarska, M.; Villegas, M.A.; Legendziewicz, J.; Radzki, St

    2004-10-20

    In this paper, the study on encapsulation of water-soluble cationic porphyrins: methyl-pyridyl porphyrin (H{sub 2}TMePyP) and its Eu(III) complex in the monolith gels prepared by sol-gel method are reported. The samples doped with the porphyrins were prepared by tetraethoxysilane (TEOS) hydrolysis and condensation. Their absorption and emission spectroscopic properties in comparison with the spectra of the same compounds in various solvents are investigated. The spectra of metal complex were compared with those of free-base porphyrin. The strong fluorescence of europium porphyrin in the silica matrix is observed under excitation in Q-band (530 nm), while at the same time emission neither free-base porphyrin nor europium chloride does not occur. It can be explained by the strong interaction of the Eu(III)TMePyP(acac) with the silica.

  10. Kinetics of electron transfer from cobalt(II) porphyrins to various metalloporphyrin pi-radical cations in irradiated carbon tetrachloride solutions

    International Nuclear Information System (INIS)

    One-electron oxidation of a series of metallotetraphenylporphyrins (M-TPP) was studied by pulse radiolysis in CCl4 solutions. The resultant pi-radical cations were found to oxidize Co/sup II/TPP to Co/sup III/TPP with rate constants of the order of 105 M-1 s-1, much slower than the diffusion-controlled rates despite the high free energies of these reactions. In the presence of pyridine these electron-transfer reactions were much faster (107-108 M-1 s-1), suggesting that pyridine, as an axial ligand, facilitates the electron transfer between metalloporphyrins. 20 references, 1 table

  11. 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.

  12. Inverted porphyrins and expanded porphyrins: An overview

    Indian Academy of Sciences (India)

    S K Pushpan; S Venkatraman; V G Anand; J Sankar; H Rath; T K Chandrashekar

    2002-08-01

    Porphyrins and metallopophyrins have attracted the attention of chemists for the past 100 years or more owing to their widespread involvement in biology. More recently, synthetic porphyrins and porphyrin-like macrocycles have attracted the attention of researchers due to their diverse applications as sensitizers for photodynamic therapy, MRI contrasting agents, and complexing agents for larger metal ions and also for their anion binding abilities. The number of -electrons in the porphyrin ring can be increased either by increasing the number of conjugated double bonds between the pyrrole rings or by increasing the number of heterocyclic rings. Thus, 22 sapphyrins, 26 rubyrins, 30 heptaphyrins, 34 octaphyrins and higher cyclic polypyrrole analogues containing 40, 48, 64, 80 and 96 systems have recently been reported in the literature. These macrocycles show rich structural diversity where normal and different kinds of inverted structures have been identified. In this review, an attempt has been made to collect the literature of the inverted porphyrins and expanded porphyrins reported until December 2001. Since the meso aryl expanded porphyrins have tendency to form both inverted and non-inverted structures more emphasis has been given to meso aryl expanded porphyrins.

  13. 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 by potenti......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...... correlation between calculated and measured ionophore selectivity....

  14. Synthesis of porphyrin nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Hongyou; Bai, Feng

    2014-10-28

    The present disclosure generally relates to self-assembly methods for generating porphyrin nanostructures. For example, in one embodiment a method is provided that includes preparing a porphyrin solution and a surfactant solution. The porphyrin solution is then mixed with the surfactant solution at a concentration sufficient for confinement of the porphyrin molecules by the surfactant molecules. In some embodiments, the concentration of the surfactant is at or above its critical micelle concentration (CMC), which allows the surfactant to template the growth of the nanostructure over time. The size and morphology of the nanostructures may be affected by the type of porphyrin molecules used, the type of surfactant used, the concentration of the porphyrin and surfactant the pH of the mixture of the solutions, and the order of adding the reagents to the mixture, to name a few variables.

  15. Fullerene - Porphyrin constructs

    OpenAIRE

    Boyd, PDW; Reed, CA

    2005-01-01

    Porphyrins and fullerenes are spontaneously attracted to each other. This new supramolecular recognition element can be used to construct discrete host-guest complexes, as well as ordered arrays of interleaved porphyrins and fullerenes. The fullerene-porphyrin interaction underlies successful Chromatographic separations of fullerenes, and there are promising applications in the areas of porous framework solids and photovoltaic devices. © 2005 American Chemical Society.

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

    KAUST Repository

    Mohammed, Omar F.

    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.

  17. 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.

  18. 1,1’,1’’,1’’’-[Porphyrin-5,10,15,20-tetrayltetrakis(3,1-phenylenemethylene]tetraquinolinium Tetrabromide

    Directory of Open Access Journals (Sweden)

    Satoshi Fujii

    2010-11-01

    Full Text Available Cationic porphyrins interact strongly with guanine quadruplex DNA (G-quadruplex. We herein report the preparation of a cationic porphyrin bearing quinolinium side arms, 1,1’,1’’,1’’’-[porphyrin-5,10,15,20-tetrayltetrakis(3,1-phenylenemethylene]­tetra­quinolinium tetrabromide (mQu, as a potential G-quadruplex ligand.

  19. 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.

  20. Radioactively labelled porphyrin derivatives

    International Nuclear Information System (INIS)

    Radioactive labelling of guanidine bearing tetraphenylporphyrin and Dy-texaphyrin with 166Ho and 90Y is described. UV-VIS absorption spectrometry was used to describe porphyrin and texaphyrin, including their behaviour over a wide pH range. This technique also provided preliminary information about the complexation of holmium and yttrium with porphyrin and texaphyrin. The labelling yield of the macrocyclic molecules depends on the pH of the reaction mixture, metal-to-ligand ratio and time of incubation. The optimum reaction conditions for the formation of radioactive complexes of porphyrin and texaphyrin were determined by thin layer chromatography combined with beta activity measurement. The ability of porphyrin derivatives to bind anions was also examined. Our experiments were focused on perrhenate ion (ReO4-) because radiopharmaceuticals labeled with 186Re and 188Re play an important role in the therapy of many tumorous diseases. The possibility of using the ReO4- anion directly for labeling without reduction to a lower oxidation state can simplify considerably the preparation of the radiotherapeutic pharmaceuticals. Neither UV-Vis spectrometry nor TLC gave evidence of any incorporation of the ReO4- anion into the porphyrin ring

  1. Photoinduced Charge Separation in Porphyrin Ion Pairs.

    Science.gov (United States)

    Natali, Mirco; Scandola, Franco

    2016-03-10

    Ion pairs between porphyrin-type compounds have been successfully employed for spectral sensitization of semiconductor surfaces and for the preparation of collective binary ionic materials for photonic and (photo)catalytic applications. The understanding of the photophysical processes occurring within ion-paired porphyrin dimers is thus of remarkable importance for the optimization and improvement of such systems. Herein the ion-pair species formed between ZnTMePyP(4+) (Zn1) or H2TMePyP(4+) (H21) and ZnTPPS(4-) (Zn2) or H2TPPS(4-) (H22) in a variety of solvent mixtures are characterized and their photophysics thoroughly investigated by time-resolved techniques. In all the systems studied, very fast and efficient photoinduced charge separation is observed, with the cationic porphyrin being reduced and the anionic one oxidized. Interestingly, despite the very short charge separation distance, the lifetime for charge recombination, depending on the energy gap, can extend into the nanosecond time domain, showing great potential for the utilization of this molecular design within energy conversion schemes. PMID:26905260

  2. Lanthanide porphyrin complexes

    International Nuclear Information System (INIS)

    The review summarizes literature data and results of the author's research on the synthesis, properties and possible fields of practical application of lanthanide porphyrin complexes. Emphasis is given to the application of luminescence properties of lanthanide derivatives in medicine. The bibliography includes 108 references.

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

    OpenAIRE

    Eugenia Fagadar-Cosma; Vlad Chiriac; Elena Maria Pica; Luminita Nica; Liviu Calin Bolundut; Vasile Ostafe; Stela Pruneanu; Florina Pogacean; Liliana Olenic; Dana Vlascici

    2010-01-01

    Two manganese(III) porphyrins: manganese(III) tetraphenylporphyrin chloride and manganese(III)-tetrakis(3-hydroxyphenyl)porphyrin chloride were tested as ionophores for the construction of new diclofenac−selective electrodes. The electroactive material was incorporated either in PVC or a sol−gel matrix. The effect of different plasticizers and additives (anionic and cationic) on the potentiometric response was studied. The best results were obtained for the PVC membrane plasticized with dioct...

  4. 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.

  5. Molecular Simulations of Porphyrins and Heme Proteins

    Energy Technology Data Exchange (ETDEWEB)

    SHELNUTT,JOHN A.

    2000-01-18

    An overview of the use of classical mechanical molecular simulations of porphyrins, hydroporphyrins, and heme proteins is given. The topics cover molecular mechanics calculations of structures and conformer energies of porphyrins, energies of barriers for interconversion between stable conformers, molecular dynamics of porphyrins and heme proteins, and normal-coordinate structural analysis of experimental and calculated porphyrin structures. Molecular mechanics and dynamics are currently a fertile area of research on porphyrins. In the future, other computational methods such as Monte Carlo simulations, which have yet to be applied to porphyrins, will come into use and open new avenues of research into molecular simulations of porphyrins.

  6. 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)

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

    International Nuclear Information System (INIS)

    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 O2. ► 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 O2 due to the largely loading of FeTMPyP and good conductivity. Based on bionic catalysis of porphyrin for the reduction of O2, 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.

  8. Electrochemical Generation of Porphyrin-Porphyrin and Porphyrin-C60 Polymeric Photoactive Organic Heterojunctions

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Photoactive organic-organic interfaces were formed by electrochemical synthesis. • Zn(II), free base porphyrin and C60 films were used to form donor-aceptor bilayers. • Photoinduced electron transfer between the interfaces were analyzed by SPV. • The heterojunctions were able to produce photoinduced charge separated states. - Abstract: Photoactive organic-organic interfaces are formed by electrochemical synthesis. The generation of porphyrin/porphyrin and porphyrin/C60 heterojunctions over indium tin oxide electrodes by successive electropolymerization steps is described. Functionalized C60 buckminsterfullerene holding a carbazol residue and porphyrins containing carbazol and phenylamino moieties are able to form electrodeposited layers by cyclic voltammetry. Photoinduced electron transfer between Zn(II), free base porphyrins and C60 films were analyzed by both, light modulated surface photovoltage spectroscopy and laser induced transient photovoltage. The results showed that the electrochemical generated polymeric heterojunctions are able to produce photoinduced charge separated states, which could present a potential application in the design and construction of organic optoelectronic devices

  9. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO2+) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO2+; therefore, cation-cation complexes indicate something unique about AnO2+ cations compared to actinide cations in general. The first cation-cation complex, NpO2+·UO22+, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO2+ species, the cation-cation complexes of NpO2+ have been studied most extensively while the other actinides have not. The only PuO2+ cation-cation complexes that have been studied are with Fe3+ and Cr3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO2+·UO22+, NpO2+·Th4+, PuO2+·UO22+, and PuO2+·Th4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M-1

  10. Structural study of a manganese(II) 'picket-fence' porphyrin complex.

    Science.gov (United States)

    Yu, Qiang; Li, Xiangjun; Liu, Diansheng; Li, Jianfeng

    2015-07-01

    'Picket-fence' porphyrin compounds are used in the investigation of interactions of hemes with dioxygen, carbon monoxide, nitric monoxide and imidazole ligands. (Cryptand-222)potassium chlorido[meso-tetra(α,α,α,α-o-pivalamidophenyl)porphyrinato]manganese tetrahydrofuran monosolvate (cryptand-222 is 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane), [K(C18H36N2O6)][Mn(C64H64N8O4)Cl]·C4H8O or [K(222)][Mn(TpivPP)Cl]·THF [systematic name for TpivPP: 5,10,15,20-tetrakis(2-tert-butanamidophenyl)porphyrin], is a five-coordinate high-spin manganese(II) picket-fence porphyrin complex. It crystallizes with a potassium cation chelated inside a cryptand-222 molecule; the average K-O and K-N distances are 2.83 (4) and 2.995 (13) Å, respectively. All four protecting tert-butyl pickets of the porphyrin are ordered. The porphyrin plane is nearly planar, as indicated by the atomic displacements and the dihedral angles between the mean planes of the pyrrole rings and the 24-atom mean plane. The axial chloride ligand is located inside the molecular cavity on the hindered porphyrin side and the Mn-Cl bond is tilted slightly off the normal to the porphyrin plane by 3.68 (2)°. The out-of-plane displacement of the metal centre relative to the 24-atom mean plane (Δ24) is 0.7013 (4) Å, indicating a noticeable porphyrin core doming. PMID:26146391

  11. Design, syntheses, and studies of supramolecular porphyrin-fullerene conjugates, using bis-18-crown-6 appended porphyrins and pyridine or alkyl ammonium functionalized fullerenes.

    Science.gov (United States)

    D'Souza, Francis; Chitta, Raghu; Gadde, Suresh; McCarty, Amy L; Karr, Paul A; Zandler, Melvin E; Sandanayaka, Atula S D; Araki, Yasuyaki; Ito, Osamu

    2006-03-30

    Photoinduced electron-transfer processes in cis and trans functionalized bis-18-crown-6 porphyrin self-assembled with fullerene functionalized with pyridine or alkylammonium cation entities are reported. The structural integrity of the newly formed supramolecular conjugates was accomplished by optical absorption and emission, electron spray ionization mass, electrochemistry, and semiempirical PM3 calculations. A 1:2 stoichiometry of the supramolecular porphyrin:fullerene conjugates was deduced from these studies. The conjugates revealed stable "two-point"' binding involving metal-ligand coordination and alkylammonium cation-crown ether binding or only the latter type of binding depending upon the functionality of the fullerene and metal ion in the porphyrin cavity. The effect of the variation on free energy changes of charge separation and the charge recombination was achieved by varying the metal ion in the porphyrin cavity. The charge-separation rates (k(CS)) determined from the picosecond time-resolved emission studies were generally higher for the cis bis-crown functionalized porphyrins than those of the corresponding trans ones. A comparison of the k(CS) values reported earlier for 1:1 porphyrin-fullerene conjugates with a similar self-assembly mechanism suggested that employing a higher number of acceptor entities improves the electron-transfer rates. The calculated charge-recombination rates (k(CR)) were 2-3 orders of magnitude smaller than the k(CS) values, suggesting the occurrence of the charge recombination process in the Marcus inverted region. The lifetimes of the radical ion pair (tau(RIP)) ranged between 46 and 233 ns indicating charge stabilization in the studied conjugates. PMID:16553397

  12. Fluorinated Dodecaphenylporphyrins: Synthetic and Electrochemical Studies Including the First Evidence of Intramolecular Electron Transfer Between an Fe(II) Porphyrin -Anion Radical and an Fe(I) Porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    D' Souza, F.; Forsyth, T.P.; Fukuzumi, S.; Kadish, K.M.; Krattinger, B.; Lin, M.; Medforth, C.J.; Nakanishi, I.; Nurco, D.J.; Shelnutt, J.A.; Smith, K.M.; Van Caemelbecke, E.

    1998-10-19

    Dodecaphenylporphyrins with varying degrees of fluorination of the peripheral phenyl rings (FXDPPS) were synthesized as model compounds for studying electronic effects in nonplan~ porphyrins, and detailed electrochemical studies of the chloroiron(HI) complexes of these compounds were undertaken. The series of porphyrins, represented as FeDPPCl and as FeFXDPPCl where x = 4, 8 (two isomers), 12, 20,28 or 36, could be reversibly oxidized by two electrons in dichloromethane to give n-cation radicals and n-dications. All of the compounds investigated could also be reduced by three electrons in benzonitrile or pyridine. In benzonitrile, three reversible reductions were observed for the unfluorinated compound FeDPPC1, whereas the FeFXDPPCl complexes generally exhibited irreversible first and second reductions which were coupled to chemical reactions. The chemical reaction associated with the first reduction involved a loss of the chloride ion after generation of Fe FXDPPC1. The second chemical reaction involved a novel intramolecular electron transfer between the initially generated Fe(H) porphyrin n-anion radical and the final Fe(I) porphyrin reduction product. In pyridine, three reversible one electron reductions were observed with the second reduction affording stable Fe(II) porphyrin o - anion radicals for ail of the complexes investigated.

  13. Porphyrin/calixarene self-assemblies in aqueous solution

    Czech Academy of Sciences Publication Activity Database

    Kubát, Pavel; Lang, Kamil; Lhoták, P.; Janda, Pavel; Sýkora, Jan; Matějíček, P.; Hof, Martin; Procházka, K.; Zelinger, Zdeněk

    2008-01-01

    Roč. 198, č. 1 (2008), s. 18-25. ISSN 1010-6030 R&D Projects: GA ČR GA203/07/1424; GA ČR(CZ) GA203/06/1244; GA AV ČR KAN100500652; GA MŠk(CZ) LC06063 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40320502 Keywords : cationic porphyrin * calix[4]arene * thiacalix[4]arene Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.362, year: 2008

  14. 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.

  15. Chemistry of porphyrin-appended cellulose strands with a helical structure: spectroscopy, electrochemistry, and in situ circular dichroism spectroelectrochemistry.

    Science.gov (United States)

    Redl, F X; Lutz, M; Daub, J

    2001-12-17

    Around 100 porphyrin units have been selectively linked at C(6)-O to a cellulose (Avicel). The properties of the metal-free and zincated porphyrin-celluloses 2 and Zn-2 have been determined by optical and electrochemical methods. Circular dichroism indicates a helical arrangement of the porphyrin units and reveals intra-chain coupling reminiscent, in the broadest sense, of strands of nucleic acids. Cyclic voltammetry and spectroelectrochemistry have been used to characterize the radical ions and dianions. The electrochromism of the oxidation of cellulose 2 to porphyrin radical cations of 2 has been employed for both molecular switching and the transduction of an electrochemical input into chiroptical signal expression. PMID:11822435

  16. Measurement of nitric oxide in single cells and tissue using a porphyrinic microsensor.

    Science.gov (United States)

    Malinski, T; Huk, I

    2001-05-01

    This unit describes the preparation and applications of porphyrinic sensors for quantitative measurement of nitric oxide (NO) in single cells and in tissues. The determination of NO is based on the electrochemical oxidation of NO on a carbon fiber electrode covered with a thin layer of a conducting polymeric metalloporphyrin catalyst, overlaid with another thin film of Nafion, a cation exchange material. The electric current generated during NO oxidation on the surface of the polymeric porphyrin is linearly proportional to the concentration of NO, so this current is used as an analytical signal which can be measured in either the amperometric or the voltammetric mode. Both methods provide a quantitative signal. This unit describes the electrochemical setup for measurement of NO in single cells and tissue. Support protocols describe porphyrin synthesis, sensor preparation, and sensor calibration. PMID:18428525

  17. Application of an Optical Biosensor to Study the Interaction between Porphyrins and Wheat Germ Agglutinin

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    An optical biosensor with a stirred cuvette has been used to monitor the interaction of immobilized wheat germ agglutinin (WGA) with two water-soluble cationic porphyrins. The association constants (Ka) of the free base porphyrin and its Zn(Ⅱ) complex form were 2.66 and 27.31×105 L/mol at 20 ℃ respectively. The interactions of the free base porphyrin were further investigated at temperatures between 15 ℃ and 37 ℃. The thermodynamics parameters, changes in free energy, enthalpy and entropy, were -31.23, 22.92, 54.15 kJ/mol respectively. The heat capacity change was -355.53 J·mol-1·K-1. The binding was driven by entropic contribution, and showed strong enthalpy-entropy compensation. It was governed primarily by hydrophobic forces.

  18. Quantitative vibrational dynamics of iron in nitrosyl porphyrins.

    Science.gov (United States)

    Leu, Bogdan M; Zgierski, Marek Z; Wyllie, Graeme R A; Scheidt, W Robert; Sturhahn, Wolfgang; Alp, E Ercan; Durbin, Stephen M; Sage, J Timothy

    2004-04-01

    We use quantitative experimental and theoretical approaches to characterize the vibrational dynamics of the Fe atom in porphyrins designed to model heme protein active sites. Nuclear resonance vibrational spectroscopy (NRVS) yields frequencies, amplitudes, and directions for 57Fe vibrations in a series of ferrous nitrosyl porphyrins, which provide a benchmark for evaluation of quantum chemical vibrational calculations. Detailed normal mode predictions result from DFT calculations on ferrous nitrosyl tetraphenylporphyrin Fe(TPP)(NO), its cation [Fe(TPP)(NO)]+, and ferrous nitrosyl porphine Fe(P)(NO). Differing functionals lead to significant variability in the predicted Fe-NO bond length and frequency for Fe(TPP)(NO). Otherwise, quantitative comparison of calculated and measured Fe dynamics on an absolute scale reveals good overall agreement, suggesting that DFT calculations provide a reliable guide to the character of observed Fe vibrational modes. These include a series of modes involving Fe motion in the plane of the porphyrin, which are rarely identified using infrared and Raman spectroscopies. The NO binding geometry breaks the four-fold symmetry of the Fe environment, and the resulting frequency splittings of the in-plane modes predicted for Fe(TPP)(NO) agree with observations. In contrast to expectations of a simple three-body model, mode energy remains localized on the FeNO fragment for only two modes, an N-O stretch and a mode with mixed Fe-NO stretch and FeNO bend character. Bending of the FeNO unit also contributes to several of the in-plane modes, but no primary FeNO bending mode is identified for Fe(TPP)(NO). Vibrations associated with hindered rotation of the NO and heme doming are predicted at low frequencies, where Fe motion perpendicular to the heme is identified experimentally at 73 and 128 cm-1. Identification of the latter two modes is a crucial first step toward quantifying the reactive energetics of Fe porphyrins and heme proteins. PMID

  19. Layered silicate films with photochemically active porphyrin cations

    Czech Academy of Sciences Publication Activity Database

    Čeklovský, A.; Czímerová, A.; Lang, Kamil; Bujdák, J.

    2009-01-01

    Roč. 81, č. 8 (2009), s. 1385-1396. ISSN 0033-4545 R&D Projects: GA AV ČR KAN100500651; GA ČR(CZ) GA203/06/1244 Grant ostatní: GA(SK) VEGA2/6180/27 Institutional research plan: CEZ:AV0Z40320502 Keywords : clay minerals * layer charge * smectites Subject RIV: CA - Inorganic Chemistry Impact factor: 2.289, year: 2009

  20. Supramolecular Allosteric Cofacial Porphyrin Complexes

    International Nuclear Information System (INIS)

    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 (RhI or CuI sites) and two cofacially aligned porphyrins (ZnII 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 RhI or CuI 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.

  1. Supramolecular Allosteric Cofacial Porphyrin Complexes

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-12

    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{sup I} or Cu{sup I} sites) and two cofacially aligned porphyrins (Zn{sup 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{sup I} or Cu{sup 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

  2. A charge-stabilizing, multimodular, ferrocene-bis(triphenylamine)-zinc-porphyrin-fullerene polyad.

    Science.gov (United States)

    Wijesinghe, Channa A; El-Khouly, Mohamed E; Zandler, Melvin E; Fukuzumi, Shunichi; D'Souza, Francis

    2013-07-15

    A novel multimodular donor-acceptor polyad featuring zinc porphyrin, fullerene, ferrocene, and triphenylamine entities was designed, synthesized, and studied as a charge-stabilizing, photosynthetic-antenna/reaction-center mimic. The ferrocene and fullerene entities, covalently linked to the porphyrin ring, were distantly separated to accomplish the charge-separation/hole-migration events leading to the creation of a long-lived charge-separated state. The geometry and electronic structures of the newly synthesized compound was deduced by B3LYP/3-21G(*) optimization, while the energy levels for different photochemical events was established using data from the optical absorption and emission, and electrochemical studies. Excitation of the triphenylamine entities revealed singlet-singlet energy transfer to the appended zinc porphyrin. As predicted from the energy levels, photoinduced electron transfer from both the singlet and triplet excited states of the zinc porphyrin to fullerene followed by subsequent hole migration involving ferrocene was witnessed from the transient absorption studies. The charge-separated state persisted for about 8.5 μs and was governed by the distance between the final charge-transfer product, that is, a species involving a ferrocenium cation and a fullerene radical anion, with additional influence from the charge-stabilizing triphenylamine entities located on the zinc-porphyrin macrocycle. PMID:23754703

  3. Dual-sensing porphyrin-containing copolymer nanosensor as full-spectrum colorimeter and ultra-sensitive thermometer.

    Science.gov (United States)

    Yan, Qiang; Yuan, Jinying; Kang, Yan; Cai, Zhinan; Zhou, Lilin; Yin, Yingwu

    2010-04-28

    A porphyrin-containing copolymer has dual-sensing in response to metal ions and temperature as a novel nanosensor. Triggered by ions, the sensor exhibits full-color tunable behavior as a cationic detector and colorimeter. Responding to temperature, the sensor displays an "isothermal" thermochromic point as an ultra-sensitive thermometer. PMID:20369181

  4. 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.

  5. The Antimicrobial Activity of Porphyrin Attached Polymers

    Science.gov (United States)

    Thompson, Lesley

    2008-03-01

    We are interested in testing the antimicrobial activity of a porphyrin that is attached to a polymer. The porphyrin (5-(4-carboxyphenyl)-10,15,20-tris-(4-pryridyl)) was synthesized from methyl 4-formyl benzoate, 4-pyridinecarboxaldehyde, and pyrrole and attached to a copolymer of polystyrene/poly(vinyl benzyl chloride), which was synthesized by free radical polymerization. The antimicrobial activity of the polymer-attached porphyrin was then determined for gram-negative E. Coli grown to 0.80 OD. In this procedure, glass slides were coated with polymer-attached porphyrin via dip-coating, and the E. Coli bacteria were plated in Luria Broth media. The plates were subsequently exposed to light overnight before they were incubated as porphyrins act as photo-sensitizers when irradiated with light. The polymer-attached porphyrin did exhibit antimicrobial activity and parameters that affect its efficiency will be discussed.

  6. 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.

  7. Porphyrin Microparticles for Biological and Biomedical Applications

    Science.gov (United States)

    Huynh, Elizabeth

    Lipids are one of the critical building blocks of life, forming the plasma membrane of cells. In addition, porphyrins also play an equally important role in life, for example, through carrying oxygen in blood. The importance of both these components is evident through the biological and biomedical applications of supramolecular structures generated from lipids and porphyrins. This thesis investigates new porphyrin microparticles based on porphyrin-lipid architecture and their potential applications in biology and medicine. In Chapter 1, a background on lipid and porphyrin-based supramolecular structures is presented and design considerations for generating multifunctional agents. Chapter 2 describes the generation of a monolayer porphyrin microparticle as a dual-modal ultrasound and photoacoustic contrast agent and subsequently, a trimodal ultrasound, photoacoustic and fluorescence contrast agent. Chapter 3 examines the optical and morphological response of these multimodality ultrasound-based contrast agents to low frequency, high duty cycle ultrasound that causes the porphyrin microparticles to convertinto nanoparticles. Chapter 4 examines the generation of bilayer micrometer-sized porphyrin vesicles and their properties. Chapter 5 presents a brief summary and potential future directions. Although these microscale structures are similar in structure, the applications of these structures greatly differ with potential applications in biology and also imaging and therapy of disease. This thesis aims to explore and demonstrate the potential of new simplified, supramolecular structures based on one main building block, porphyrin-lipid.

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

    Indian Academy of Sciences (India)

    M Yedukondalu; M Ravikanth

    2011-03-01

    Porphyrin rings containing two meso-pyridyl groups either in cis or trans fashion can be used to construct Re(I) bridged multiporphyrin assemblies. The cis-dipyridyl porphyrins with various porphyrin cores such as N4, N3O, N3S, N2S2 have been used to react with Re(CO)5Cl in THF at refluxing temperature and constructed planar Re(I) bridged porphyrin dyads containing either one type of porphyrin subunit or two types of porphyrin subunits. The trans-dipyridyl porphyrins have been used to construct Re(I) bridged porphyrin squares. The porphyrin dyads have been explored for singlet-singlet energy transfer studies and porphyrin squares have been used for catalysis, chemical sensing, molecular sieving and photocurrent production studies. An overview of synthesis of Re(I) bridged porphyrin dyads, triads and tetrads and their interesting photophysical properties are highlighted in this paper.

  9. NO2-induced synthesis of nitrato-iron(III) porphyrin with diverse coordination mode and the formation of isoporphyrin

    Indian Academy of Sciences (India)

    Jagannath Bhuyan; Sabyasachi Sarkar

    2013-07-01

    Two nitrato-iron(III) porphyrinates [Fe(4-Me-TPP)(NO3)] 1 and [Fe(4-OMe-TPP)(NO3)] 2 are reported. Interestingly, [Fe(4-Me-TPP)(NO3)] 1 has nitrate ion coordinated as monodentate (by single oxygen atom), while [Fe(4-OMe-TPP)(NO3)] 2 has nitrate coordination through bidentate mode. Compound 1 was found serendipitously in the reaction of [Fe(4-Me-TPP)Cl] with nitrous acid, which was performed for the synthesis of nitro-iron(III) porphyrin, [Fe(4-Me-TPP)NO2]. The compound 2 was synthesized by passing NO2 gas through a solution of [Fe(4-OMe-TPP)]2O. Upon passing NO2 gas through a solution of a -oxo-dimer, [Fe(4-Me-TPP)]2O also produces 1. It is interesting that in more electron-rich porphyrin 2, binding of the nitrate in a symmetrical bidentate way while in less electron-rich porphyrin 1, binding of the anion is unidentate by a terminal oxygen atom. However, it is expected that the energy difference between the monodentate and bidentate coordination mode is very small and the interchange between these coordination is possible. Upon passing NO2 gas through a solution of -oxo-dimeric iron(III) porphyrin, the nitrato-iron(III) porphyrin forms first, that later gets oxidized to -cation radical to yield hydroxy-isoporphyrin in the presence of trace amount of water. These nitrato-iron(III) porphyrinates in moist air slowly converted back to their respective -oxo-dimeric iron(III) porphyrins.

  10. Porphyrin-Based Nanostructures for Photocatalytic Applications

    OpenAIRE

    Yingzhi Chen; Aoxiang Li; Zheng-Hong Huang; Lu-Ning Wang; Feiyu Kang

    2016-01-01

    Well-defined organic nanostructures with controllable size and morphology are increasingly exploited in optoelectronic devices. As promising building blocks, porphyrins have demonstrated great potentials in visible-light photocatalytic applications, because of their electrical, optical and catalytic properties. From this perspective, we have summarized the recent significant advances on the design and photocatalytic applications of porphyrin-based nanostructures. The rational strategies, such...

  11. Ultrafast reorganization of the hole charge created upon outer-valence ionization of porphyrins

    International Nuclear Information System (INIS)

    Highlights: ► Ultrafast electron dynamics following ionization of porphyrins is studied. ► Ionization spectra of the free-base porphyrin and Mg(II) porphyrin are analyzed. ► Hole charge created upon ionization spreads over the molecule in only few femtoseconds. ► This redistribution of the charge may predetermine the nuclear dynamics that follow. - Abstract: Based on elaborated ab initio calculations we first study the ionization spectra of the free-base porphyrin (H2-P) and Mg(II) porphyrin (Mg-P). Then we investigate the ultrafast electron dynamics following outer-valence ionization of these systems which constitutes the highlight of this paper. It is shown that the electron correlation effects are very strong in these systems giving rise to pronounced shake-down satellites in the outer-valence part of the ionization spectra. We show that due to these strong correlation effects the removal of an electron from the 3b1g orbital of H2-P and Mg-P leads to an ultrafast reorganization of the electronic cloud. After being initially localized on the B and D pyrrole rings, the hole charge created upon ionization spreads throughout the molecule in only few femtoseconds. In both systems the electron dynamics triggered by the ionization represent alternating ultrafast delocalizations and localizations of the charge. The results may also give a hint on the nuclear dynamics in the free-base and Mg(II) porphyrin radical cations that will follow the ultrafast charge migration.

  12. Electrochemical and Spectroelectrochemical Study of A4 and A2B2 Pyrene Dendronized Porphyrins

    International Nuclear Information System (INIS)

    The electrochemical behaviour of two free-base pyrene dendronized porphyrins, Por-(Py2G1)2, Por-(Py2G1)4, and their zinc metallated forms, Zn-Por-(Py2G1)2 and Zn-Por-(Py2G1)4, has been studied by cyclic voltammetry in CH2Cl2. The investigated compounds exhibit several oxidation processes. The study of five model molecules, equivalent to the nuclei and branches of the dendrimer, allowed the assignment of the different oxidation processes. The first oxidation, centered on the porphyrin ring, was also studied by in situ UV-vis spectroelectrochemistry in CH2Cl2 and THF for all the dendrimers. The electrooxidation in the thin layer spectroelectrochemical cell of the two free-base dendritic molecules shows spectral changes that suggest the formation of porphyrin diprotonated species, both in THF and CH2Cl2. Even though the electrochemical and spectroscopic characteristics of the solutions after exhaustive electrolysis in THF were consistent with the formation of these protonated species; in CH2Cl2, a paramagnetic species was obtained, and no further evidence of the formation of diprotonated species could be found. Two-electrons per molecule were consumed during the electrolysis in THF and only one-electron in CH2Cl2, the starting porphyrin was not regenerated by counterelectrolysis in any case. It was demonstrated that irradiation of the porphyrin itself accounts for the observed evolution of the UV–vis spectra in CH2Cl2. For the Zn dendronized porphyrins, the oxidation was a clean one-electron transfer, giving rise to the radical cation, subsequent reductive electrolysis regenerates the initial product

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

    International Nuclear Information System (INIS)

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

  14. Design and studies on supramolecular ferrocene-porphyrin-fullerene constructs for generating long-lived charge separated states.

    Science.gov (United States)

    D'Souza, Francis; Chitta, Raghu; Gadde, Suresh; Islam, D-M Shafiqul; Schumacher, Amy L; Zandler, Melvin E; Araki, Yasuyuki; Ito, Osamu

    2006-12-21

    Supramolecular ferrocene-porphyrin-fullerene constructs, in which covalently linked ferrocene-porphyrin-crown ether compounds were self-assembled with alkylammonium cation functionalized fullerenes, have been designed to achieve stepwise electron transfer and hole shift to generate long-lived charge separated states. The adopted crown ether-alkylammonium cation binding strategy resulted in stable conjugates as revealed by computational studies performed by the DFT B3LYP/3-21G(*) method in addition to the binding constants obtained from fluorescence quenching studies. The free-energy changes for charge-separation and charge-recombination were varied by the choice of different metal ions in the porphyrin cavity. Free-energy calculations suggested that the light-induced electron-transfer processes from the singlet excited state of porphyrins to be exothermic in all of the investigated supramolecular dyads and triads. Photoinduced charge-separation and charge-recombination processes have been confirmed by the combination of the time-resolved fluorescence and nanosecond transient absorption spectral measurements. In case of the triads, the charge-recombination processes of the radical anion of the fullerene moiety take place in two steps, viz., a direct charge recombination from the porphyrin cation radical and a slower step involving distant charge recombination from the ferrocene cation moiety. The rates of charge recombination for the second route were found to be an order of magnitude slower than the former route, thus fulfilling the condition for charge migration to generate long-lived charge-separated states in supramolecular systems. PMID:17165968

  15. Porphyrin-Based Photocatalytic Lithography

    Energy Technology Data Exchange (ETDEWEB)

    Bearinger, J; Stone, G; Christian, A; Dugan, L; Hiddessen, A; Wu, K J; Wu, L; Hamilton, J; Stockton, C; Hubbell, J

    2007-10-15

    Photocatalytic lithography is an emerging technique that couples light with coated mask materials in order to pattern surface chemistry. We excite porphyrins to create radical species that photocatalytically oxidize, and thereby pattern, chemistries in the local vicinity. The technique advantageously does not necessitate mass transport or specified substrates, it is fast and robust and the wavelength of light does not limit the resolution of patterned features. We have patterned proteins and cells in order to demonstrate the utility of photocatalytic lithography in life science applications.

  16. 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.

  17. Water exchange rates of water-soluble manganese(III) porphyrins of therapeutical potential.

    Science.gov (United States)

    Budimir, Ana; Kalmár, József; Fábián, István; Lente, Gábor; Bányai, István; Batinić-Haberle, Ines; Birus, Mladen

    2010-05-14

    The activation parameters and the rate constants of the water-exchange reactions of Mn(III)TE-2-PyP(5+) (meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin) as cationic, Mn(III)TnHex-2-PyP(5+) (meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin) as sterically shielded cationic, and Mn(III)TSPP(3-) (meso-tetrakis(4-sulfonatophenyl)porphyrin) as anionic manganese(iii) porphyrins were determined from the temperature dependence of (17)O NMR relaxation rates. The rate constants at 298 K were obtained as 4.12 x 10(6) s(-1), 5.73 x 10(6) s(-1), and 2.74 x 10(7) s(-1), respectively. On the basis of the determined entropies of activation, an interchange-dissociative mechanism (I(d)) was proposed for the cationic complexes (DeltaS(double dagger) = approximately 0 J mol(-1) K(-1)) whereas a limiting dissociative mechanism (D) was proposed for Mn(III)TSPP(3-) complex (DeltaS(double dagger) = +79 J mol(-1) K(-1)). The obtained water exchange rate of Mn(III)TSPP(3-) corresponded well to the previously assumed value used by Koenig et al. (S. H. Koenig, R. D. Brown and M. Spiller, Magn. Reson. Med., 1987, 4, 52-260) to simulate the (1)H NMRD curves, therefore the measured value supports the theory developed for explaining the anomalous relaxivity of Mn(III)TSPP(3-) complex. A magnitude of the obtained water-exchange rate constants further confirms the suggested inner sphere electron transfer mechanism for the reactions of the two positively charged Mn(iii) porphyrins with the various biologically important oxygen and nitrogen reactive species. Due to the high biological and clinical relevance of the reactions that occur at the metal site of the studied Mn(iii) porphyrins, the determination of water exchange rates advanced our insight into their efficacy and mechanism of action, and in turn should impact their further development for both diagnostic (imaging) and therapeutic purposes. PMID:20422097

  18. A new micro/nanoencapsulated porphyrin formulation for PDT treatment.

    Science.gov (United States)

    Deda, Daiana K; Uchoa, Adjaci F; Caritá, Eduardo; Baptista, Maurício S; Toma, Henrique E; Araki, Koiti

    2009-07-01

    The highly hydrophobic 5,10,15-triphenyl-20-(3-N-methylpyridinium-yl)porphyrin (3MMe) cationic species was synthesized, characterized and encapsulated in marine atelocollagen/xanthane gum microcapsules by the coacervation method. Further reduction in the capsule size, from several microns down to about 300-400 nm, was carried out successfully by ultrasonic processing in the presence of up to 1.6% Tween 20 surfactant, without affecting the distribution of 3MMe in the oily core. The resulting cream-like product exhibited enhanced photodynamic activity but negligible cytotoxicity towards HeLa cells. The polymeric micro/nanocapsule formulation was found to be about 4 times more phototoxic than the respective phosphatidylcholine lipidic emulsion, demonstrating high potentiality for photodynamic therapy applications. PMID:19409465

  19. Tetra-anionic porphyrin loading onto ZnO nanoneedles: A hybrid covalent/non covalent approach

    Energy Technology Data Exchange (ETDEWEB)

    Di Mauro, Alessandro; Smecca, Emanuele [Dipartimento di Scienze Chimiche and INSTM UdR Catania, Università di Catania, Viale Andrea Doria 6, 95100 Catania (Italy); D' Urso, Alessandro [Dipartimento di Scienze Chimiche, Università di Catania, Viale Andrea Doria 6, 95100 Catania (Italy); Condorelli, Guglielmo G. [Dipartimento di Scienze Chimiche and INSTM UdR Catania, Università di Catania, Viale Andrea Doria 6, 95100 Catania (Italy); Fragalà, Maria Elena, E-mail: me.fragala@unict.it [Dipartimento di Scienze Chimiche and INSTM UdR Catania, Università di Catania, Viale Andrea Doria 6, 95100 Catania (Italy)

    2014-02-14

    A stepwise surface functionalization procedure, based on hybrid covalent and non-covalent approach is herein proposed to anchor tetra-anionic meso-tetrakis(4-sulfonatophenyl)porphyrin on ZnO nanorods. Carboxyalkylphosphonic acids have been proven effective to form stable self-assembled monolayers through the surface grafting of –PO{sub 3}H{sub 2} headgroups. The exposed carboxylic functionalities are suitable for the successful grafting of cationic poly-L-lysine that drives, in water, the non-covalent anchoring of the anionic porphyrin. A stepwise surface characterization, provided by X-ray photoelectron spectroscopy, elucidates the multilayers deposition and surface composition after each process step, thus, giving interesting insights on the chemical speciation of the exposed functionalities. UV–vis spectroscopy confirms the role of ZnO morphology to increase the porphyrin loading onto the investigated surfaces. The proposed approach is effective to achieve deposition of anionic porphyrins on ZnO nanostructures and combines the robustness of covalent functionalization with the versatility and full reversibility of the non-covalent strategies. - Highlights: • ZnO nanoneedles are covalently functionalized with carboxyalkylphosphonic acids. • Polylysine drives non-covalent loading of H{sub 2}TPPS on ZnO nanoneedles. • XPS stepwise analysis provides information on surface composition and termination. • ZnO nanostructuration increases the surface porphyrin loading.

  20. Porphyrins as Catalysts in Scalable Organic Reactions.

    Science.gov (United States)

    Barona-Castaño, Juan C; Carmona-Vargas, Christian C; Brocksom, Timothy J; de Oliveira, Kleber T

    2016-01-01

    Catalysis is a topic of continuous interest since it was discovered in chemistry centuries ago. Aiming at the advance of reactions for efficient processes, a number of approaches have been developed over the last 180 years, and more recently, porphyrins occupy an important role in this field. Porphyrins and metalloporphyrins are fascinating compounds which are involved in a number of synthetic transformations of great interest for industry and academy. The aim of this review is to cover the most recent progress in reactions catalysed by porphyrins in scalable procedures, thus presenting the state of the art in reactions of epoxidation, sulfoxidation, oxidation of alcohols to carbonyl compounds and C-H functionalization. In addition, the use of porphyrins as photocatalysts in continuous flow processes is covered. PMID:27005601

  1. Porphyrin-Based Nanostructures for Photocatalytic Applications

    Directory of Open Access Journals (Sweden)

    Yingzhi Chen

    2016-03-01

    Full Text Available Well-defined organic nanostructures with controllable size and morphology are increasingly exploited in optoelectronic devices. As promising building blocks, porphyrins have demonstrated great potentials in visible-light photocatalytic applications, because of their electrical, optical and catalytic properties. From this perspective, we have summarized the recent significant advances on the design and photocatalytic applications of porphyrin-based nanostructures. The rational strategies, such as texture or crystal modification and interfacial heterostructuring, are described. The applications of the porphyrin-based nanostructures in photocatalytic pollutant degradation and hydrogen evolution are presented. Finally, the ongoing challenges and opportunities for the future development of porphyrin nanostructures in high-quality nanodevices are also proposed.

  2. 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...

  3. Porphyrin-loaded nanoparticles for cancer theranostics

    Science.gov (United States)

    Zhou, Yiming; Liang, Xiaolong; Dai, Zhifei

    2016-06-01

    Porphyrins have been used as pioneering theranostic agents not only for the photodynamic therapy, sonodynamic therapy and radiotherapy of cancer, but also for diagnostic fluorescence imaging, magnetic resonance imaging and photoacoustic imaging. A variety of porphyrins have been developed but very few of them have actually been employed in clinical trials due to their poor selectivity to tumorous tissue and high accumulation rates in the skin. In addition, most porphyrin molecules are hydrophobic and form aggregates in aqueous media. Nevertheless, the use of nanoparticles as porphyrin carriers shows great promise to overcome these shortcomings. Encapsulating or attaching porphyrins to nanoparticles makes them more suitable for tissue delivery because we can create materials with a conveniently specific tissue lifetime, specific targeting, immune tolerance, and hydrophilicity as well as other characteristics through rational design. In addition, various functional components (e.g. for targeting, imaging or therapeutic functions) can be easily introduced into a single nanoparticle platform for cancer theranostics. This review presents the current state of knowledge on porphyrin-loaded nanoparticles for the interwined imaging and therapy of cancer. The future trends and limitations of prophyrin-loaded nanoparticles are also outlined.

  4. Ion induced dissociation of tetraphenyl iron(III) porphyrin chloride and electron-capture induced dissociation of protoporphyrin IX ions

    International Nuclear Information System (INIS)

    We performed experiments concerning the fragmentation of different porphyrin molecules. Multi-ionisation and ion-induced fragmentation of FeTPPCl''q''+ (q = 1 to 4) have been studied in slow collisions with multiply charged ions. We have shown also electron-capture induced dissociation of protoporphyrin cations, where two electrons in two successive have been captured in order to convert it to the corresponding even-electron anions. All fragmentation processes are discussed in terms of charge mobility.

  5. Functionalised DNA - introducing and applying a versatile porphyrin molecular ruler

    OpenAIRE

    Burns, Jonathan

    2012-01-01

    Porphyrin moieties were rigidly attached to DNA to generate an accurate molecular ruler. Molecular ruler analysis was conducted using steady-state fluorescence, circular dichroism and small angle X-ray scattering spectroscopic techniques, in an attempt to analyse the FRET, exciton coupling and scattering intensity between different porphyrin-porphyrin labelled DNA combinations. A 21-mer test sequence was labelled with a porphyrin in one position on one strand, and seven different positions on...

  6. Excitation transfer and luminescence in porphyrin-carbon nanotube complexes

    OpenAIRE

    Magadur, Gurvan; Lauret, Jean-Sébastien; Alain-Rizzo, Valérie; C. Voisin; Roussignol, Ph.; Deleporte, Emmanuelle; Delaire, Jacques,

    2007-01-01

    Functionalization of carbon nanotubes with hydrosoluble porphyrins (TPPS) is achieved by "$\\pi$-stacking". The porphyrin/nanotube interaction is studied by means of optical absorption, photoluminescence and photoluminescence excitation spectroscopies. The main absorption line of the porphyrins adsorbed on nanotubes exhibits a 120 meV red shift, which we ascribe to a flattening of the molecule in order to optimize $\\pi-\\pi$ interactions. The porphyrin-nanotube complex shows a strong quenching ...

  7. Clay induced aggregation of a tetra-cationic metalloporphyrin in Layer by Layer self assembled film

    Science.gov (United States)

    Banik, Soma; Bhattacharjee, J.; Hussain, S. A.; Bhattacharjee, D.

    2015-12-01

    Porphyrins have a general tendency to form aggregates in ultrathin films. Also electrostatic adsorption of cationic porphyrins onto anionic nano clay platelets results in the flattening of porphyrin moieties. The flattening is evidenced by the red-shifting of Soret band with respect to the aqueous solution. In the present communication, we have studied the clay induced aggregation behaviour of a tetra-cationic metalloporphyrin Manganese (III) 5, 10, 15, 20-tetra (4 pyridyl)-21 H, 23 H-porphine chloride tetrakis (methochloride) (MnTMPyP) in Layer-by-Layer (LbL) self assembled film. The adsorption of dye molecules onto nano clay platelets resulted in the flattening of the meso substituent groups of the dye chromophore. In Layer-by-Layer ultrathin film, the flattened porphyrin molecules tagged nano clay platelets were further associated to form porphyrin aggregates. This has been clearly demonstrated from the UV-vis absorption spectroscopic studies. Atomic Force Microscopic (AFM) studies gave visual evidence of the association of organo-clay hybrid molecules in the LbL film.

  8. Urinary porphyrin excretion in hepatitis C infection.

    Science.gov (United States)

    Vogeser, M; Jacob, K; Zachoval, R

    1999-08-01

    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 outpatients with chronic hepatitis C infection without signs of photosensitivity, using an ion-pair high-performance liquid chromatography method. Increased total porphyrin excretion was found in 41 patients, with predominant excretion of coproporphyrins (whole study group: mean 146 microg/g creatinine, interquartile range 76-186; normal coproporphyrin, heptacarboxyporphyrin III increased) but the total porphyrin excretion was only slightly elevated in this case. In the whole group, total urinary porphyrin excretion correlated well with serum bilirubin and was inversely correlated with albumin and thrombin time. In conclusion, secondary coproporphyrinuria occurs frequently in heptatitis C infection, whereas in Germany, preclinical porphyria cutanea tarda seems to be rare in these patients. PMID:10536928

  9. Quantum confinement-tunable intersystem crossing and the triplet state lifetime of cationic porphyrin–CdTe quantum dot nano-assemblies

    KAUST Repository

    Ahmed, Ghada H.

    2015-03-27

    Here, we report a ground-state interaction between the positively charged cationic porphyrin and the negatively charged carboxylate groups of the thiol ligands on the surface of CdTe quantum dots (QDs), leading to the formation of a stable nanoassembly between the two components. Our time-resolved data clearly demonstrate that we can dramatically tune the intersystem crossing (ISC) and the triplet state lifetime of porphyrin by changing the size of the QDs in the nanoassembly.

  10. Synthesis, characterization and fluorescence turn-on behavior of new porphyrin analogue: meta-benziporphodimethenes.

    Science.gov (United States)

    Sharma, Ravi Kumar; Gajanan, Lale Kiran; Mehata, Mohan Singh; Hussain, Firasat; Kumar, Anil

    2016-12-01

    New fluorescence switch-on meso-substituted free base meta-benziporphodimethenes were synthesized, characterized via acid catalyzed condensation reaction and metallated with Zn(2+). Their photophysical properties were also studied. The fluorescence spectra analysis demonstrates substituent's independent behaviour on emitting λmax. The average Stokes shift of 33nm was observed. Crystal structure of 8 was obtained and gave expected perturbed geometry. PMID:27337052

  11. Resonance Raman study on distorted symmetry of porphyrin in nickel octaethyl porphyrin

    Indian Academy of Sciences (India)

    S Tewari; R Das; A Chakraborty; Ramendu Bhattacharjee

    2004-11-01

    The resonance Raman (RR) spectra of nickel octaethyl porphyrin, Ni(OEP), in CH2Cl2 (solvent) at different excitations such as 514.5, 488.0, 441.6 and 406.7 nm are recorded and analysed. The results of the theory of distortion-induced RR intensity is applied to the observed spectra to determine the excited electronic state symmetry of porphyrin in Ni(OEP). It is concluded that the porphyrin molecule (D4h structure) attains a non-polar distorted structure of D2 symmetry rather than S4 symmetry in CH2Cl2 solution.

  12. Porphyrin electrode films prepared by electrooxidation of metalloprotoporphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Macor, K.A.; Spiro, T.G.

    1983-08-24

    Electrooxidation in organic solvents of the dimethyl esters of several metalloprotoporphyrins (PP) (Ni/sup II/PP, Zn/sup II/PP, Co/sup II/PP, (Fe/sup III/PP)Cl, (Fe/sup III/PP)/sub 2/O, and (Cr/sup III/PP)/sub 2/O) leads to the deposition of thick (approx. 1000 monolayer equivalents), electroactive porphyrin films, which have been characterized by cyclic voltammetry and absorption spectroscopy on transparent SnO/sub 2/ electrodes. The films are stable toward organic solvents and aqueous acids and bases, but are removed by treatment with hot concentrated acids. The resonance Raman spectrum of the NiPP film indicates that one of the two vinyl groups is saturated on most of the porphyrin units. Deposition continues for some minutes after the current is interrupted. This evidence is consistent with a mechanism involving electroinitiated cationic vinyl polymerization. No film is formed if the metal, rather than the ring, is oxidized. Thus the first oxidation step of Co/sup II/PP, to (Co/sup III/PP)/sup +/, does not support film formation (although the potential is as high as for ring oxidation in ZnPP), but the second step, to (Co/sup III/PP)/sup 2 +/, does. Lack of film formation for (Mn/sup III/PP)Cl and (Cr/sup IV/PP)O suggests metal, rather than ring oxidation, to Mn/sup IV/ and Cr/sup V/. However, (CrPP)/sub 2/O oxidation does produce a film, suggesting ring oxidation, analogous to (FePP)/sub 2/O, which also produces a film. However, while (CrPP)/sub 2/O is incorporated intact into the film, the (FePP)/sub 2/O film contains monomer units. Incorporation of other metal ions can be accomplished by soaking a ZnPP-coated electrode in H/sub 2/SO/sub 4/ followed by contact wtih a solution of the metal dihalide in refluxing DMF. The porphyrin sites are accessible to small ions, as shown by chloride coordination of ZnPP film upon soaking in chloride solution. 49 references, 13 figures, 1 table.

  13. Vibrational study of magnesium complexes and porphyrins

    International Nuclear Information System (INIS)

    In the course of chlorophyll investigations by vibrational spectroscopy, the magnesium complex Mg(NH3)6Cl2 was studied by infrared and Raman techniques and two porphyrin molecules, by resonance Raman scattering. For the hexa-ammine magnesium chloride, all vibrations predicted by group theory (internal and external vibrations) were observed; ligand orientations gives- the complex ion a D3d point group symmetry. Five isotopically substituted compounds were studied and a force constant calculation showed that the Mg-N bond has a value higher than most of those calculated for other divalent hexa-ammine metal ions. Two porphyrins were studied: the prophine and the meso-porphyrin IX dimethyl-ester.' Unexpected variations of vibrational bands intensities and depolarization ratios were recorded on changing the excitation wavelength. Three resonance levels were tentatively attributed to the presence of pure electronic transitions in band IV of the absorption spectra of these compounds. (author)

  14. [Analysis of porphyrin photosensitizers using HPLC method].

    Science.gov (United States)

    Jia, Min-ge; Wu, Hai-yan; Sun, Li-li; Yao, Chun-suo; Zhang, Shao-liang; Li, Ya-wei; Fang, Qi-cheng

    2015-08-01

    Photodynamic therapy (PDT), because of its good targeting, minimal invasion, and safety, is becoming a very active area in cancer prevention and treatment, in which the photosensitizers have proved to be the core element for PDT. We developed a new HPLC method for analyzing porphyrin photosensitizers using Shiseido Capcell PAK C18 (150 mm x 4.6 mm, 5 µm) as the column at 30 °C, methanol-1% aqueous solution of acetic acid as the mobile phase in a flow rate of 1.0 mL · min(-1) in a gradient elution mode, and the detection wavelength at 380 nm. This method, showing good specificity, precision, accuracy and robusty via methodology validations, can be applied to the purity test and assay of porphyrin photosensitizers, and has played a key guide role in the R&D of the new porphyrin photosensitizer--sinoporphyrin sodium. PMID:26669003

  15. Blood porphyrin luminescence and tumor growth correlation

    Science.gov (United States)

    Courrol, Lilia Coronato; Silva, Flávia Rodrigues de Oliveira; Bellini, Maria Helena; Mansano, Ronaldo Domingues; Schor, Nestor; Vieira, Nilson Dias, Jr.

    2007-02-01

    Fluorescence technique appears very important for the diagnosis of cancer. Fluorescence detection has advantages over other light-based investigation methods: high sensitivity, high speed, and safety. Renal cell carcinoma (RCC) accounts for approximately 3% of new cancer incidence and mortality in the United States. Unfortunately many RCC masses remain asymptomatic and nonpalpable until they are advanced. Diagnosis and localization of early carcinoma play an important role in the prevention and curative treatment of RCC. Certain drugs or chemicals such as porphyrin derivatives accumulate substantially more in tumors than normal tissues. The autofluorescence of blood porphyrin of healthy and tumor induced male SCID mice was analyzed using fluorescence and excitation spectroscopy. A significant contrast between normal and tumor blood could be established. Blood porphyrin fluorophore showed enhanced fluorescence band (around 630 nm) in function of the tumor growth. This indicates that either the autofluorescence intensity of the blood fluorescence may provide a good parameter for the "first approximation" characterization of the tumor stage.

  16. Excitation transfer and luminescence in porphyrin-carbon nanotube complexes

    CERN Document Server

    Magadur, G; Alain-Rizzo, V; Voisin, C; Roussignol, Ph; Deleporte, E; Delaire, J A

    2007-01-01

    Functionalization of carbon nanotubes with hydrosoluble porphyrins (TPPS) is achieved by "$\\pi$-stacking". The porphyrin/nanotube interaction is studied by means of optical absorption, photoluminescence and photoluminescence excitation spectroscopies. The main absorption line of the porphyrins adsorbed on nanotubes exhibits a 120 meV red shift, which we ascribe to a flattening of the molecule in order to optimize $\\pi-\\pi$ interactions. The porphyrin-nanotube complex shows a strong quenching of the TPPS emission while the photoluminescence intensity of the nanotubes is enhanced when the excitation laser is in resonance with the porphyrin absorption band. This reveals an efficient excitation transfer from the TPPS to the carbon nanotube.

  17. Optical properties of porphyrin: graphene oxide composites

    Science.gov (United States)

    Harsha Vardhan Reddy, M.; Al-Shammari, Rusul M.; Al-Attar, Nebras; Lopez, Sergio; Keyes, Tia E.; Rice, James H.

    2014-08-01

    In this work we aim to (via a non-invasive functionalization approach) tune and alter the intrinsic features of optically "transparent" graphene, by integrating water-soluble porphyrin aggregates. We explore the potential to combine porphyrin aggregates and graphene oxide to assess the advantages of such as a composite compared to the individual systems. We apply a range of optical spectroscopy methods including photo-absorption, fluorescence assess ground-state and excited state interactions. Our studies show that comparing resonant Raman scattering with optical transmission and fluorescence microscopy that the presence of influences the microscopic structures of the resulting composites.

  18. Functionalization of diameter-sorted semiconductive SWCNTs with photosensitizing porphyrins: syntheses and photoinduced electron transfer.

    Science.gov (United States)

    Das, Sushanta K; Sandanayaka, Atula S D; Subbaiyan, Navaneetha K; Zandler, Melvin E; Ito, Osamu; D'Souza, Francis

    2012-09-01

    Covalent functionalization of diameter sorted SWCNTs with porphyrins (MP), and photochemistry to establish nanotube diameter-dependent charge separation efficiencies are reported. The MP-SWCNT(n,m) [M=2H or Zn, and (n,m)=(7,6) or (6,5)] nanohybrids are characterized by a variety of spectroscopic, thermogravimetric, TEM imaging techniques, and also by DFT MO calculations. The thermogravimetric, Raman and fluorescence studies reveal the presence of a moderate number of porphyrins on the SWCNT surface. The MO results suggest charge separation (CS) via the excited state of MP. Time-resolved fluorescence studies reveal quenching of the singlet excited state of the MP with SWCNT(n,m), giving the rate constants of charge separation (k(CS)) in the range of (4-5)×10(9) s(-1). Nanosecond transient absorption measurements confirm the charge-separated radical cation and the radical anion as [MP(.+)-SWCNT(.-)] with their characteristic absorption bands in the visible and near-IR regions. The charge separated states persist for about 70-100 ns thus giving an opportunity to utilize them to build photoelectrochemical cells, which allowed us to derive the structure-reactivity relationship between the nature of porphyrin and diameter of the employed nanotubes. PMID:22807374

  19. Development and evaluation of a 166Holmium labelled porphyrin complex as a possible therapeutic agent

    International Nuclear Information System (INIS)

    Porphyrins are interesting derivatives with low toxicity, tumor avidity and rapid wash-out suggested as potential radiopharmaceuticals in radiolabeled form. In this work, [166Ho] labeled 5,10,15,20-tetrakis(phenyl) porphyrin ([166Ho]-TPP) was prepared using [166Ho]HoCl3 and 5,10,15,20-tetrakis(phenyl)porphyrin (H2TPP) for 12 h at 50 deg C (radiochemical purity: >95 ± 2 % ITLC, >99 ± 0.5 % HPLC, specific activity: 0.9-1.1 GBq/mmol). Stability of the complex was checked in final formulation and human serum for 48 h. The partition coefficient was calculated for the compound (log P = 2.01). The biodistribution of the labeled compound in vital organs of wild-type rats was studied using scarification studies and SPECT. A detailed comparative pharmacokinetic study performed for 166Ho cation and [166Ho]-TPP performed up to 24 h. The complex is mostly washed out from the circulation through kidneys and in less extends from the liver. The kidney:blood, kidney:liver and kidney:muscle ratios 4 h post injection were 14, 3.6 and 7.38 respectively. (author)

  20. Highly ordered surface structure of large-scale porphyrin aggregates assembled from protonated TPP and water

    Science.gov (United States)

    Udal'tsov, Alexander V.; Bolshakova, Anastasia V.; Vos, Johannes G.

    2014-05-01

    Large-scale aggregates assembled from protonated meso-tetraphenylporphine (TPP) dimers and water have been investigated by IR and resonance Raman spectroscopy and also by scanning electron microscopy (SEM). It was found that the properties of water confined in the aggregates depend on the physical state of the support. When the aggregates were deposited on a solid CaF2 plate, they showed properties consistent with a quasi-crystalline structure. But when the aggregates were dispersed in oil, their IR characteristics were different; the vibration bands of the confined water were like those of water in liquid state. A doublet at about 1000 cm-1, components of which have been attributed to specific vibrations of H3O+ and H2O bound in the structure of water-porphyrin dimeric complex, was found in IR and resonance Raman spectra (λex = 441.6 nm) of protonated TPP aggregates. This doublet indicates the hydrogen ion involving in the vibrational system of water-porphyrin dimeric complex with hydrogen bonding by similar way as in so-called Zundel cation. The resonance Raman spectrum shows evidence for proton sharing between protonated water dimer and N groups of the pyrrole rings. SEM results indicate that the large-scale aggregates of the protonated porphyrin possess highly ordered structure, are only observed when using extremely pure water.

  1. Spectroscopic Studies on Binding of Porphyrin-Phenazine Conjugate to Four-Stranded Poly(G).

    Science.gov (United States)

    Ryazanova, Olga; Zozulya, Victor; Voloshin, Igor; Dubey, Larysa; Dubey, Igor; Karachevtsev, Victor

    2015-07-01

    Binding of a novel cationic porphyrin-imidazophenazine conjugate, TMPyP(3+)-ImPzn, to four-stranded poly(G) was investigated in aqueous solutions of neutral pH under near physiological ionic conditions using absorption, polarized fluorescent spectroscopy and fluorescence titration techniques. In absence of the polymer the conjugate folds into stable internal heterodimer with stacking between the porphyrin and phenazine chromophores. Binding of TMPyP(3+)-ImPzn to poly(G) is realized by two competing ways. At low polymer-to-dye ratio (P/D self-stacking is predominant. It is accompanied by heterodimer dissociation and distancing of phenazine moieties from the polymer. This binding mode is characterized by strong quenching of the conjugate fluorescence. Increase of P/D results in the disintegration of the porphyrin stacks and redistribution of the bound conjugate molecules along the polymer chain. At P/D > 10 another binding mode becomes dominant, embedding of TMPyP(3+)-ImPzn heterodimers into poly(G) groove as a whole is occurred. PMID:26076929

  2. Porphyrin-Metalation-Mediated Tuning of Photoredox Catalytic Properties in Metal–Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Jacob A.; Luo, Jian; Zhang, Xu; Chen, Yu-Sheng; Morton, Martha D.; Echeverría, Elena; Torres, Fernand E.; Zhang, Jian

    2015-09-04

    Photoredox catalytic activation of organic molecules via single-electron transfer processes has proven to be a mild and efficient synthetic methodology. However, the heavy reliance on expensive ruthenium and iridium complexes limits their applications for scale-up synthesis. To this end, photoactive metal–organic frameworks (MOFs) exhibit unique advantages as novel heterogeneous photocatalytic systems, yet their utilization toward organic transformations has been limited. Here we describe the preparation and synthetic applications of four isostructural porphyrinic MOFs, namely, UNLPF-10a, -10b, -11, and -12, which are composed of free base, InIII-, SnIVCl2-, and SnIV-porphyrin building blocks, respectively. We demonstrate that the metalation with high valent metal cations (InIII and SnIV) significantly modifies the electronic structure of porphyrin macrocycle and provides a highly oxidative photoexcited state that can undergo efficient reductive quenching processes to facilitate organic reactions. In particular, UNLPF-12 exhibits both outstanding photostability and efficient photocatalytic activities toward a range of important organic transformations including aerobic hydroxylation of arylboronic acids, amine coupling, and the Mannich reaction.

  3. Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

    Science.gov (United States)

    Tian, Yongming; M. Beavers, Christine; Busani, Tito; Martin, Kathleen E.; Jacobsen, John L.; Mercado, Brandon Q.; Swartzentruber, Brian S.; van Swol, Frank; Medforth, Craig J.; Shelnutt, John A.

    2012-02-01

    Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(ii) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(iv) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room temperature preparation of the nanosheets has provided the first X-ray crystal structure of a cooperative binary ionic (CBI) solid. The unit cell contains one and one-half molecules of aquo-ZnTPPS4- (an electron donor) and three half molecules of dihydroxy-SnTNMePyP4+ (an electron acceptor). Charge balance in the solid is reached without any non-porphyrinic ions, as previously determined for other CBI nanomaterials by non-crystallographic means. The crystal structure reveals a complicated molecular arrangement with slipped π-π stacking only occurring in isolated dimers of one of the symmetrically unique zinc porphyrins. Consistent with the crystal structure, UV-visible J-aggregate bands indicative of exciton delocalization and extended π-π stacking are not observed. XRD measurements show that the structure of the Zn/Sn nanosheets is distinct from that of Zn/Sn four-leaf clover-like CBI solids reported previously. In contrast with the Zn/Sn clovers that do exhibit J-aggregate bands and are photoconductive, the nanosheets are not photoconductive. Even so, the nanosheets act as light-harvesting structures in an artificial photosynthesis system capable of reducing water to hydrogen but not as efficiently as the Zn/Sn clovers.Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(ii) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(iv) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room

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

    International Nuclear Information System (INIS)

    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

  5. 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

  6. Metallic nanoshells on porphyrin-stabilized emulsions

    Science.gov (United States)

    Wang, Haorong; Song, Yujiang; Shelnutt, John A; Medforth, Craig J

    2013-10-29

    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.

  7. Langmuir Blodgett films of porphyrins and phthalocyanines

    CERN Document Server

    Portus, D

    2002-01-01

    Phthalocyanines and porphyrins have been studied for many years as bulk, thick and thin films. Their use in Langmuir and Langmuir-Blodgett films is governed by their peripheral substituents. These can enhance or reduce their ability to form 'quality' ultra-thin films. There are a number of potential and current applications for thin films of porphyrins and phthalocyanines, which include CD-R discs and gas-sensors. It is the latter that this PhD has focussed on. Ultra-thin films of phthalocyanines, porphyrins and a porphyrin/phthalocyanine hybrid dye were deposited onto glass microscope slides, gold-coated glass microscope slides and quartz crystals. These assemblies were then characterised using Ultraviolet-Visible spectroscopy, pressure-area isotherms, surface plasmon resonance and a quartz crystal microbalance to try and determine the nature of the molecules on the surface of the substrate. The thin films were exposed to chlorine gas and the change in their absorption spectrum and (in some cases) their surf...

  8. Fluorescence and Thermostability of Nanometer Porphyrin Trimer

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A nanometer porphyrin trimer was firstly synthesized with 1,3-dibromopropane as a bridge-linked agent and the fluorescence property and thermostability were studied. The results show that the fluorescence property and thermostability of the trimer are different from those of monoporphyrin. The effects of the molecule structure on the optical property and the thermostability were also studied in detail.

  9. Porphyrin Composite Materials for Fullerene Separation

    Czech Academy of Sciences Publication Activity Database

    Šabata, Stanislav; Kuncová, Gabriela; Hetflejš, Jiří; Lhoták, P.; Slavíček, J.

    - : -, 2011, 64 /P9/. ISBN N. [Zing Nanomaterials Conference 2011. Xcaret (MX), 28.11.2011-02.12.2011] R&D Projects: GA ČR GA203/09/0691 Institutional research plan: CEZ:AV0Z40720504 Keywords : silica gel * composite materials * porphyrin Subject RIV: CC - Organic Chemistry

  10. Synthesis and characterization of ether-linked porphyrins

    Directory of Open Access Journals (Sweden)

    Radchada Buntem

    2009-07-01

    Full Text Available The ether-linked porphyrin dimers in this research work were prepared from coupling reaction between suitableporphyrin precursors and linkers in the presence of potassium carbonate. The structures of all synthesized compounds werecharacterized by spectroscopic methods. The UV/Visible absorption maxima and extinction coefficients did not show any significant difference among these porphyrin dimers. This indicates that the length of the linker did not affect the absorption property of the dimers. However, different metal ions bonding to the porphyrin moiety affect the different absorption maxima of the porphyrin dimers. It was also found that the position of the linker on the phenyl ring of porphyrin does not affect the visible absorption pattern or the proton chemical shifts of the porphyrin core as found in the case of Zn2(metaC-dimer (13(compared with the data obtained for Zn2C2-dimer (3.

  11. Substituent effects of iron porphyrins: Structural, kinetic, and theoretical studies

    International Nuclear Information System (INIS)

    Substituent effects of iron porphyrin complexes on the structures and kinetic processes have been examined for the first time. Basing on the premise that iron porphyrin is functional analogous to heme, a series of iron porphyrin derivatives bearing different substituents at the meso positions of the corrole ring are investigated as to their electrochemistry, the relationships among the electron transfer (ET) processes, their structures, and orbital energies. The good coherence between the experiment and theory indicates that the ET rate can be accelerated when electron-donating substituents are introduced to the iron porphyrin ring. Finally, the implications of the results are discussed in the influence of stability of iron porphyrin complexes on the ability to carry molecular oxygen, which may suggest it possible to dominate the biological activity of heme by selecting the appropriate substituents to iron porphyrin ring.

  12. Substituent effects of iron porphyrins: Structural, kinetic, and theoretical studies

    Energy Technology Data Exchange (ETDEWEB)

    Lu Xiaoquan, E-mail: luxq@nwnu.edu.c [Key Laboratory of Bioelectrochemistry and Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070 (China); Ma Junying; Sun Ruiping; Nan Mina; Meng Fanfu; Du Jie; Wang Xiaoyan; Shang Hui [Key Laboratory of Bioelectrochemistry and Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070 (China)

    2010-12-15

    Substituent effects of iron porphyrin complexes on the structures and kinetic processes have been examined for the first time. Basing on the premise that iron porphyrin is functional analogous to heme, a series of iron porphyrin derivatives bearing different substituents at the meso positions of the corrole ring are investigated as to their electrochemistry, the relationships among the electron transfer (ET) processes, their structures, and orbital energies. The good coherence between the experiment and theory indicates that the ET rate can be accelerated when electron-donating substituents are introduced to the iron porphyrin ring. Finally, the implications of the results are discussed in the influence of stability of iron porphyrin complexes on the ability to carry molecular oxygen, which may suggest it possible to dominate the biological activity of heme by selecting the appropriate substituents to iron porphyrin ring.

  13. A facile fluorescent chemosensor based on a water-soluble porphyrin for Mo(6+) in aqueous solution.

    Science.gov (United States)

    Feng, Guodong; Mi, Hongyu; Fei, Qiang; Shan, Hongyan; Wang, Baojun; Xu, Hui; Li, Guanghua; Chen, Fei; Huan, Yanfu

    2016-10-01

    A novel water-soluble porphyrin (5,10,15,20-tetra(3-ethoxy-4-hydroxy-5-sulfonate) phenylporphyrin, H2TEHPPS) was synthesized. H2TEHPPS exhibited high sensitivity and selectivity towards Mo(6+). The enhanced fluorescence response of H2TEHPPS after titration with Mo(6+) in aqueous solution at pH3.5 was attributed to the formation of an inclusion complex between the porphyrin ring and Mo(6+), which R(2)=0.999 from 10 to 1000μgL(-1), providing a detection limit of 1.5μgL(-1). The fluorescence response of H2TEHPPS towards Mo(6+) showed excellent selectivity over other transition metal cations. PMID:27262661

  14. Porphyrin-Embedded Silicate Materials for Detection of Hydrocarbon Solvents

    OpenAIRE

    Mansoor Nasir; Brian J. Melde; Malanoski, Anthony P.; Johnson, Brandy J; Paul T. Charles; Anderson, Nicole E.; Deschamps, Jeffrey R.

    2011-01-01

    The development of porphyrin-embedded mesoporous organosilicate materials for application to the detection of volatile hydrocarbon solvents is described. Design of the receptor and optical indicator construct begins with parallel selection of the porphyrin indicator and design of the mesoporous sorbent. For the porphyrin indicator, high binding affinity and strong changes in spectrophotometric character upon target interaction are desired. The sorbent should provide high target binding capaci...

  15. 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.

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

    International Nuclear Information System (INIS)

    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)4Cl 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, 25-1 type, generating 16 total experiments for each Fe P studied. (author)

  17. 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)

  18. Immobilization of Porphyrins in Poly(hydroxymethylsiloxane)

    Czech Academy of Sciences Publication Activity Database

    Šabata, Stanislav; Hetflejš, Jiří; Rychtáriková, Renata; Kuncová, Gabriela; Lang, Kamil; Kubát, Pavel

    2009-01-01

    Roč. 63, č. 4 (2009), s. 438-444. ISSN 0366-6352 R&D Projects: GA ČR(CZ) GA203/06/1244; GA MŠk OC 121 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : poly(hydroxymethylsiloxane) * fluorescence spectra * porphyrin Subject RIV: CC - Organic Chemistry Impact factor: 0.791, year: 2009

  19. Molecular magnetic materials based on porphyrin macrocyles

    OpenAIRE

    ÖNAL, Emel

    2014-01-01

    The preparation of Molecule-Based Magnets is based on the assembling carriers of magnetic moment. These may be the metal ions only with diamagnetic linkers or the metal ions connected through open-shell organic molecule. The building of novel Molecule-Based Magnets architectures following the metal-radical approach relies on the design of innovative open-shell organic molecular blocks. In this regard, we focus our strategy on the synthesis of porphyrins incorporating free radicals. Indeed, po...

  20. Synthesis, antinociceptive and anti-inflammatory effects of porphyrins.

    Science.gov (United States)

    Alonso-Castro, Angel Josabad; Zapata-Morales, Juan Ramón; Hernández-Munive, Abigail; Campos-Xolalpa, Nimsi; Pérez-Gutiérrez, Salud; Pérez-González, Cuauhtémoc

    2015-05-15

    Porphyrins are natural compounds with several biological activities. We report the synthesis and the evaluation of the anti-inflammatory and antinociceptive effects of 4 porphyrins: 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetra(4'-fluorophenyl)porphyrin (TpFPP), 5,10,15,20-tetra(4'-chlorophenyl)porphyrin (TpClPP), and 5,10,15,20-tetra(4'-bromophenyl)porphyrin (TpBrPP). The in vitro anti-inflammatory effects were evaluated on heat-induced hemolysis. The antinociceptive effects were evaluated using the hot plate and formalin tests. The in vivo anti-inflammatory assays were tested on the acute and chronic TPA (12-O-tetradecanoylphorbol 13-acetate) method to induce ear edema. The anti-arthritic effects were evaluated using carrageenan kaolin induced arthritis (CKIA). All porphyrins inhibited hemolysis with similar potency than naproxen (NPX). In the antinociceptive tests, all porphyrins tested at 200mg/kg showed similar effects compared to 100mg/kg NPX. In the in vivo anti-inflammatory acute assay, only three porphyrins (TPP, TpFPP and TpBrPP) decreased inflammation with similar activity than 2mg/ear indomethacin (IND). Further anti-inflammatory experiments were carried out with TPP, TpFPP and TpBrPP. In the in vivo anti-inflammatory chronic assay, porphyrins decreased inflammation with similar activity than 8mg/kg IND. Porphyrins tested at 200mg/kg showed anti-arthritic effects. The antinociceptive, anti-inflammatory and arthritic activities of porphyrins suggest that these compounds might be a good alternative for the treatment of inflammatory diseases. PMID:25863493

  1. A moderate distortion of the `picket-fence' porphyrin (cryptand-222)potassium chlorido[meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinato]ferrate(II) n-hexane monosolvate.

    Science.gov (United States)

    Yu, Qiang; Liu, Diansheng; Li, Xiangjun; Li, Jianfeng

    2015-10-01

    As representative porphyrin model compounds, the structures of `picket-fence' porphyrins have been studied intensively. The title solvated complex salt {systematic name: (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium(I) [5,10,15,20-tetrakis(2-tert-butanamidophenyl)porphyrinato]iron(II) n-hexane monosolvate}, [K(C18H36N2O6)][Fe(C64H64N8O4)Cl]·C6H14 or [K(222)][Fe(TpivPP)Cl]·C6H14 [222 is cryptand-222 or 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, and TpivPP is meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinate(2-)], [K(222)][Fe(TpivPP)Cl]·C6H14, is a five-coordinate high-spin iron(II) picket-fence porphyrin complex. It crystallizes with a potassium cation chelated inside a cryptand-222 molecule; the average K-O and K-N distances are 2.81 (2) and 3.05 (2) Å, respectively. One of the protecting tert-butyl pickets is disordered. The porphyrin plane presents a moderately ruffled distortion, as suggested by the atomic displacements. The axial chloride ligand is located inside the molecular cavity on the hindered porphyrin side and the Fe-Cl bond is tilted slightly off the normal to the porphyrin plane by 4.1°. The out-of-plane displacement of the metal centre relative to the 24-atom mean plane (Δ24) is 0.62 Å, indicating a noticeable doming of the porphyrin core. PMID:26422211

  2. Porphyrin architectures tailored for studies of molecular information storage.

    Science.gov (United States)

    Carcel, Carole M; Laha, Joydev K; Loewe, Robert S; Thamyongkit, Patchanita; Schweikart, Karl-Heinz; Misra, Veena; Bocian, David F; Lindsey, Jonathan S

    2004-10-01

    A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Zinc porphyrins tethered to Au(111) or Si(100) provide a benchmark for studies of information storage. Three sets of porphyrins have been synthesized for studies of the interplay of molecular design and charge-storage properties: (1) A set of porphyrins is described for probing the effect of surface attachment atom on electron-transfer kinetics. Each porphyrin bears a meso-CH2X group for surface attachment where X = OH, SAc, or SeAc. (2) A set of porphyrins is described for studying the effect of surface-charge density in monolayers. Each porphyrin bears a benzyl alcohol for surface attachment and three nonlinking meso substituents of a controlled degree of bulkiness. (3) A set of porphyrins is described that enables investigation of on-chip patterning of the electrolyte. Each porphyrin bears a formyl group distal to the surface attachment group for subsequent derivatization with a molecular entity that comprises the electrolyte. Taken together, this collection of molecules enables a variety of studies to elucidate design issues in molecular-based information storage. PMID:15387598

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

    International Nuclear Information System (INIS)

    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

  4. Structural features of vanadyl porphyrins of petroleum of West Kazakhstan

    Energy Technology Data Exchange (ETDEWEB)

    Bakirova, S.F.; Kotova, A.V.; Yag' yaeva, S.; Fedorova, N.V.; Nadirov, N.K.

    1984-01-01

    During the past 10 to 15 years studies have been published concerning petroleum porphyrins in which a description was given of the composition and structure of porphyrins of petroleums found in various regions abroad and in the Soviet Union - West Siberia, the Kama region, Tajikistan. Porphyrin structure has been established using electron and IR spectroscopy, nuclear and paramagnetic resonance, mass-spectrometry (low and high resolution), these techniques enabled the form of the main nucleus and its peripheral substituents to be established and yielded information concerning the molar mass values and the number of carbon atoms in alkyl chains. Methods developed in the Tomsk Institute of Petroleum Chemistry, USSR Academy of Sciences were used in this study, which involve the following operations: (1) extraction of porphyrins from petroleum using dimethylformamide; (2) chromatographic purification of the separated porphyrins elution from columns packed with aluminas of different activities by organic solvents and their mixtures, in order of increasing polarities; (3) mass-spectrometric examination of the purified vanadyl-porphyrin samples. The composition of porphyrins and the ratio of etioporphyrins and desoxophylloerythro-etioporphyrins was deduced from the electron spectra obtained from the purified porphyrin samples separated from petroleums.

  5. The composition of petroleum porphyrines from Western Kazakhstan

    Energy Technology Data Exchange (ETDEWEB)

    Bakirova, S.F.; Benkovskiy, V.G.; Kotova, A.V.; Serebrennikova, O.V.

    1984-01-01

    A high content of vanadium porphyrines in a number of oils, which is associated with their bedding conditions and the characteristics of the starting organic matter (OV) and is characteristic for oils from Western Kazakhstan, is noted. The molecular composition is studied of vanadyl porphyrines which were isolated from oils using extractive chromatographic methods and were studied using low resolution mass spectrometry (in a MAT-311 instrument) and through analytical fine layer chromatography. It is discovered that 90 to 95 percent of all the vanadyl porphyrines consist of homologs of ethioporphyrine (the M series) and desoxophylloerythroethioporphyrines (the M-2 series). Only in a single case (the Karazhanbas deposit) are there up to 30 percent compounds of the M-6 series. The ratio of M-2 to M and the content of nonpolar porphyrines (in percent), which are chromatographically identified, were used as the characteristics. The chromatographic mobility is basically determined by the molecular mass, that is, by the number of methylene groups in the lateral substituents of the porphyrine ring. A comparison of the number of nonpolar porphyrines with the oil bedding depth shows a regular increase in the volume of these compounds with a reduction in the bedding depth; the presence in the oil of less than 50 percent nonpolar porphyrines (the Pribrezhnyy, Severnyy Buzachi and Kalamkas deposits) and the absence of polar porphyrines confirms the assumption about the intermediate stage of the migratory path of the oil and about its flow from the deep layers into the overlying sediments of the persalt complex.

  6. Post-synthetic modification of porphyrin-encapsulating metal-organic materials by cooperative addition of inorganic salts to enhance CO 2/CH 4 selectivity

    KAUST Repository

    Zhang, ZhenJie

    2012-08-21

    Keeping MOM: Reaction of biphenyl-3,4\\',5-tricarboxylate and Cd(NO 3) 2 in the presence of meso-tetra(N-methyl-4-pyridyl) porphine tetratosylate afforded porph@MOM-11, a microporous metal-organic material (MOM) that encapsulates cationic porphyrins and solvent in alternating open channels. Porph@MOM-11 has cation and anion binding sites that facilitate cooperative addition of inorganic salts (such as M +Cl -) in a stoichiometric fashion. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Porphyrin-Embedded Silicate Materials for Detection of Hydrocarbon Solvents

    Directory of Open Access Journals (Sweden)

    Mansoor Nasir

    2011-01-01

    Full Text Available The development of porphyrin-embedded mesoporous organosilicate materials for application to the detection of volatile hydrocarbon solvents is described. Design of the receptor and optical indicator construct begins with parallel selection of the porphyrin indicator and design of the mesoporous sorbent. For the porphyrin indicator, high binding affinity and strong changes in spectrophotometric character upon target interaction are desired. The sorbent should provide high target binding capacity and rapid binding kinetics. A number of porphyrin/metalloporphyrin variants and organosilicate sorbents were evaluated to determine the characteristics of their interaction with the targets, benzene, toluene, and hexane. The selected porphyrin candidates were covalently immobilized within a benzene-bridged sorbent. This construct was applied to the detection of targets using both fluorescence- and reflectance-based protocols. The use of red, green, and blue (RGB color values from the constructs in a highly simplified detection scheme is described.

  8. Preparation and characterization of monosubstituted porphyrins immobilized on nanosilica

    Indian Academy of Sciences (India)

    Ebrahim Ahmadi; Ali Ramazani; Asemeh Mashhadi-Malekzadeh; Zahra Hamdi; Zahra Mohamadnia

    2014-08-01

    Three kinds of heteroaldehydes, -(3-triethoxysilylpropyl)-4-formyl benzamide (TPHA/SiO2), were prepared by the reaction of terephthalaldehydic acid with different silica supports such as hexagonal SBA-15, spherical SBA-15 and amorphous SiO2 for comparison purposes. Anchoring of this aldehyde to different supports allows the synthesis of mono-substituted porphyrins without the production of di-, tri- and tetra-substituted porphyrin side products. The exclusion of the aforementioned side products during the synthesis of monosubstituted porphyrins greatly reduced the complexity during purification of the product. Absorption spectrophotometry was performed on silica gel immobilizing porphyrin (CPTTP), free base tetraphenylporphyrin (H2TPP) and heteroaldehydes (TPHA/SiO2) using UV–Visible instrument and confirmed the presence of porphyrin on the structure of CPTTP.

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

    Directory of Open Access Journals (Sweden)

    Rosamaria Capuano

    2015-04-01

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

  10. Photochemistry of porphyrins: a model for the origin of photosynthesis

    Science.gov (United States)

    Mercer-Smith, J. A.; Mauzerall, D. C.

    1984-01-01

    A series of porphyrins and catalysts has been prepared as a model for the origin of photosynthesis on the primordial earth. These compounds have been used to test the hypotheses that (1) the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis, and (2) the proto-photosythetic function of biogenetic porphyrins (biosynthetic chlorophyll precursors) was the oxidation of organic molecules by photoexcited porphyrins with the attendant emission of molecular hydrogen. This paper describes experiments in which photoexcited biogenetic porphyrins oxidize ethylenediamine tetraacetic acid (EDTA). The concomitant reduction of protons to hydrogen gas occurs in the presence of a colloidal platinum catalyst. The addition of methyl viologen, a one-electron shuttle, increases the amount of molecular hydrogen generated during long irradiations and the quantum yield of hydrogen production. When the porphyrin and catalyst are held in association by molecular complexes, the increased efficiency of electron transfer produces higher yields of hydrogen gas.

  11. Surface Morphology and Optical Properties of 3 Porphyrin/Au and Au/Porphyrin/Au Systems

    Czech Academy of Sciences Publication Activity Database

    Kalachyova, Y.; Lyutakov, O.; Solovyev, Andrey; Slepička, P.; Švorčík, V.

    2013-01-01

    Roč. 8, DEC 27 (2013), s. 547. ISSN 1931-7573 Grant ostatní: GA ČR(CZ) GPP108/11/P840; GA ČR(CZ) GAP108/12/1168 Institutional support: RVO:67985858 Keywords : nanostructures * gold * porphyrin * luminescence * enhancement * surface morphology Subject RIV: JJ - Other Materials Impact factor: 2.524, year: 2012

  12. 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.

  13. 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

  14. Porphyrin metabolism in some malignant diseases.

    OpenAIRE

    el-Sharabasy, M. M.; el-Waseef, A. M.; Hafez, M. M.; Salim, S. A.

    1992-01-01

    Porphyrin metabolism was studied in 21 children of both sexes suffering from acute lymphoblastic leukaemia (ALL) and 34 adult patients of different ages and sexes suffering from ALL (n = 14), non-Hodgkin's lymphoma (NHL), n = 14, or Hodgkin's disease (HD), n = 6. In addition, two groups of healthy children (n = 14), and adults (n = 17) were studied for comparison. It was apparent from this study that the activity of uroporphyrinogen-1-synthetase (URO-1-S, E.C. 4.3.1.8) was highly significantl...

  15. Theoretical study of conjugated porphyrin polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Lynge, T.B.; Kristensen, P.K.; Johansen, P.M.

    The optical gap of conjugated triply linked porphyrin chains is exceptionally low (similar to 0.5 eV). Hence, such chains are candidates for organic infrared detectors and solar cells harvesting the infrared part of the solar spectrum. However, a low exciton binding energy is required for these...... applications. From a theoretical analysis of excitons in long metalloporphyrin chains, we demonstrate that the binding energy is much lower than in usual conjugated polymers. Our calculated absorption spectra are in good agreement with measurements. (c) 2004 Elsevier B.V. All rights reserved....

  16. Theoretical DFT study of phosphorescence from porphyrins

    International Nuclear Information System (INIS)

    Geometrical structure of free-base porphin (H2P) and Mg- and Zn-porphyrins together with their vibrational frequencies and vibronic intensities in phosphorescence are investigated by density functions theory (DFT) with the standard B3LYP functional. These molecules have a closed-shell singlet ground state (S0) and low-lying triplet (T1) excited states of ππ* type. The S0-T1 transition probability and radiative lifetime of phosphorescence (τ p) of these molecules are calculated by time-dependent DFT utilizing quadratic response functions for account of spin-orbit coupling (SOC) and electric-dipole transition moments including displacements along active vibrational modes. The infrared and Raman spectra in the ground singlet and first excited triplet states are also studied for proper assignment of vibronic patterns. The long radiative lifetime of free-base porphin phosphorescence (τ p ∼ 360 s at low temperature limit, 4.2 K) gets considerably shorter for the metalloporphyrins. An order of magnitude reduction of τ p is predicted for Mg-porphyrin but no change of phosphorescence polarization is found. A forty times enhancement of the radiative phosphorescence rate constant is obtained for Zn-porphyrin in comparison with the H2P molecule which is accompanied by a strong change of polarization and spin-sublevel radiative activity. A strong vibronic activity of free-base porphin phosphorescence is found for the b2g mode at 430 cm-1, while the 679 and 715 cm-1 vibronic bands of b3g symmetry are less active. These and other out-of-plane vibrations produce considerable changes in the radiative constants of different spin sublevels of the triplet state; they also promote the S1 → T1 intersystem crossing. Among the in-plane vibrations the ag mode at 1614 cm-1 is found very active; it produces a long progression in the phosphorescence spectrum. The time-dependent DFT calculations explain the effects of the transition metal atom on phosphorescence of porphyrins and

  17. Manganese(III) porphyrin-based potentiometric sensors for diclofenac assay in pharmaceutical preparations.

    Science.gov (United States)

    Vlascici, Dana; Pruneanu, Stela; Olenic, Liliana; Pogacean, Florina; Ostafe, Vasile; Chiriac, Vlad; Pica, Elena Maria; Bolundut, Liviu Calin; Nica, Luminita; Fagadar-Cosma, Eugenia

    2010-01-01

    Two manganese(III) porphyrins: manganese(III) tetraphenylporphyrin chloride and manganese(III)-tetrakis(3-hydroxyphenyl)porphyrin chloride were tested as ionophores for the construction of new diclofenac-selective electrodes. The electroactive material was incorporated either in PVC or a sol-gel matrix. The effect of different plasticizers and additives (anionic and cationic) on the potentiometric response was studied. The best results were obtained for the PVC membrane plasticized with dioctylphtalate and having sodium tetraphenylborate as a lipophilic anionic additive incorporated. The sensor response was linear in the concentration range 3 × 10(-6) - 1 × 10(-2) M with a slope of -59.7 mV/dec diclofenac, a detection limit of 1.5 × 10(-6) M and very good selectivity coefficients. It was used for the determination of diclofenac in pharmaceutical preparations, by direct potentiometry. The results were compared with those obtained by the HPLC reference method and a good agreement was found between the two methods. PMID:22163384

  18. Porphyrin-functionalized gold nanoparticles for selective electrochemical detection of peroxyacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Li Jie; Tu Wenwen [Key Laboratory of Analytical Chemistry for Life Science (Ministry of Education of China), Department of Chemistry, Nanjing University, Nanjing 210093 (China); Lei Jianping, E-mail: jpl@nju.edu.c [Key Laboratory of Analytical Chemistry for Life Science (Ministry of Education of China), Department of Chemistry, Nanjing University, Nanjing 210093 (China); Tang Sheng [Key Laboratory of Analytical Chemistry for Life Science (Ministry of Education of China), Department of Chemistry, Nanjing University, Nanjing 210093 (China); Ju Huangxian, E-mail: hxju@nju.edu.c [Key Laboratory of Analytical Chemistry for Life Science (Ministry of Education of China), Department of Chemistry, Nanjing University, Nanjing 210093 (China)

    2011-03-30

    Two layers of cationic iron(III) meso-tetrakis (N-methylpyridinum-4-yl)porphyrin (FeTMPyP) and anionic gold nanoparticles (GNPs) were alternately assembled on a poly(diallyldimethylammonium chloride)-wrapped carbon nanotube (PDDA-CNT)-modified electrode via electrostatic interactions. The porphyrin-functionalized gold nanoparticles were characterized by scanning electron microscopy and UV-vis absorption spectrometry. The (FeTMPyP-GNP){sub 2}/PDDA-CNT modified electrode showed two stable and well-defined peaks at -0.112 V and -0.154 V, which were attributed to the GNP-accelerated redox process of Fe(III)TMPyP/Fe(II)TMPyP. The modified electrode possessed excellent electrocatalytic behavior for the reduction of peroxyacetic acid (PAA). The resulting biosensor exhibited a fast amperometric response to PAA ({approx}3 s), with a wide linear range from 2.5 x 10{sup -6} M to 1.05 x 10{sup -3} M and a detection limit of 0.5 {mu}M at a signal-to-noise ratio of 3. More importantly, H{sub 2}O{sub 2} did not interfere with the detection. Thus, this biosensor enabled highly sensitive detection of PAA without removing H{sub 2}O{sub 2} and showed a promising potential in practical applications.

  19. A Porphyrin Based Potentiometric Sensor for Zn2+ Determination

    Directory of Open Access Journals (Sweden)

    H. Lang

    2003-07-01

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

  20. Porphyrins as Theranostic Agents from Prehistoric to Modern Times

    Directory of Open Access Journals (Sweden)

    Yumiao Zhang, Jonathan F. Lovell

    2012-01-01

    Full Text Available Long before humans roamed the planet, porphyrins in blood were serving not only as indispensable oxygen carriers, but also as the bright red contrast agent that unmistakably indicates injury sites. They have proven valuable as whole body imaging modalities have emerged, with endogenous hemoglobin porphyrins being used for new approaches such as functional magnetic resonance imaging and photoacoustic imaging. With the capability for both near infrared fluorescence imaging and phototherapy, porphyrins were the first exogenous agents that were employed with intrinsic multimodal theranostic character. Porphyrins have been used as tumor-specific diagnostic fluorescence imaging agents since 1924, as positron emission agents since 1951, and as magnetic resonance (MR contrast agents since 1987. Exogenous porphyrins remain in clinical use for photodynamic therapy. Because they can chelate a wide range of metals, exogenous porphyrins have demonstrated potential for use in radiotherapy and multimodal imaging modalities. Going forward, intrinsic porphyrin biocompatibility and multimodality will keep new applications of this class of molecules at the forefront of theranostic research.

  1. Effect of axial ligation or pi-pi-type interactions on photochemical charge stabilization in "two-point" bound supramolecular porphyrin-fullerene conjugates.

    Science.gov (United States)

    D'Souza, Francis; Chitta, Raghu; Gadde, Suresh; Zandler, Melvin E; McCarty, Amy L; Sandanayaka, Atula S D; Araki, Yasuyaki; Ito, Osamu

    2005-07-18

    Two types of structurally well-defined, self-assembled zinc porphyrin-fullerene conjugates were formed by "two-point" binding strategies to probe the effect of axial ligation or pi-pi-type interactions on the photochemical charge stabilization in the supramolecular dyads. To achieve this, meso-tetraphenylporphyrin was functionalized to possess one or four [18]crown-6 moieties at different locations on the porphyrin macrocycle while fullerene was functionalized to possess an alkyl ammonium cation, and a pyridine or phenyl entities. As a result of the crown ether-ammonium cation complexation, and zinc-pyridine coordination or pi-pi-type interactions, stable zinc porphyrin-fullerene conjugates with defined distance and orientation were formed. Evidence for the zinc-pyridine complexation or pi-pi-type interactions was obtained from the spectral and computational studies. Steady-state and time-resolved emission studies revealed efficient quenching of the zinc-porphyrin singlet excited state in these dyads, and the measured rates of charge separation, k(CS) were found to be slightly better in the case of the dyads held by axial coordination and crown ether-cation complexation. Nanosecond transient absorption studies provided evidence for the electron transfer reactions, and these studies also revealed charge stabilization in these dyads. The lifetimes of the radical ion pairs were found to depend upon the type of porphyrins utilized to form the dyads, that is, porphyrin possessing the crown ether moiety at the ortho position of one of the phenyl rings yielded prolonged charge stabilized states. Addition of pyridine to the supramolecular dyads eliminated the zinc-pyridine coordination or pi-pi-type interactions of the "two-point" bound systems due to the formation of a new zinc-pyridine axial bond thus giving a unique opportunity to probe the effect of axial coordination or pi-pi interactions on k(CS) and k(CR). Under these conditions, the measured electron transfer rates

  2. Biosynthetic porphyrins and the origin of photosynthesis

    Science.gov (United States)

    Mauzerall, D.; Ley, A.; Mercer-Smith, J. A.

    1986-01-01

    Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

  3. Petroleum porphyrins as electrocatalysts for cathodic oxygen reduction

    International Nuclear Information System (INIS)

    This paper examines the possibilities for obtaining active catalysts for cathodic oxygen reduction by subjecting concentrates of vanadyl porphyrins (VONP) extracted from crude oils with dimethylformamide and then purified chromatographically on aluminum oxide and silica gel to pyrolysis on carbon. Data obtained with synthetic vanadyl tetra(nmethoxyphenyl)porphyrin (VOTMPP) are reported for comparison. It is shown that VONP-1 and VONP-3 containing more than 80 wt.% of VONP are sufficiently active catalysts for O2 reduction in alkaline solution. The lower activity of VONP-2 is evidently due to its higher impurity content. Natural vanadyl porphyrins promise to be useful as electrocatalysts of the oxygen reaction in alkaline media

  4. Real-time observation of ultrafast electron injection at graphene–Zn porphyrin interfaces

    KAUST Repository

    Masih, Dilshad

    2015-02-25

    We report on the ultrafast interfacial electron transfer ( ET) between zinc( II) porphyrin ( ZnTMPyP) and negatively charged graphene carboxylate ( GC) using state- of- the- art femtosecond laser spectroscopy with broadband capabilities. The steady- state interaction between GC and ZnTMPyP results in a red- shifted absorption spectrum, providing a clear indication for the binding affinity between ZnTMPyP and GC via electrostatic and p- p stacking interactions. Ultrafast transient absorption ( TA) spectra in the absence and presence of three different GC concentrations reveal ( i) the ultrafast formation of singlet excited ZnTMPyP*, which partially relaxes into a long- lived triplet state, and ( ii) ET from the singlet excited ZnTMPyP* to GC, forming ZnTMPyP + and GC , as indicated by a spectral feature at 650- 750 nm, which is attributed to a ZnTMPyP radical cation resulting from the ET process.

  5. Zinc-porphyrins functionalized with redox-active metal peripherals: enhancement of dπ-pπ interaction leading to unique assembly and redox-triggered remote switching of fluorescence.

    Science.gov (United States)

    Murai, Masahito; Sugimoto, Manabu; Akita, Munetaka

    2013-12-01

    Novel porphyrin-MCp*(dppe) conjugates with the acetylene linker, por-C≡CMCp*(dppe) (por = (5,15-diarylporphinato)zinc(II), Cp* = η(5)-C5Me5, dppe = 1,2-bis(diphenylphosphino)ethane; M/aryl = Fe/phenyl (1), Fe/3,5-di-tert-butylphenyl (2), Ru/phenyl (3)), are synthesized. Absorption and fluorescence spectroscopic studies combined with electrochemical investigations reveal strong interactions between the porphyrin moieties and the electron-donating MCp*(dppe) fragments. Oxidation of the porphyrin core of the iron conjugate 1 generates the dication radical 1(2+), which is spontaneously associated with its mono-cationic counterpart 1(+) to form the stable π-radical trication dimer [1(2)](3+), whereas complexes 2 and 3 undergo simple oxidation without forming such dimers. Furthermore, intramolecular charge transfer between the porphyrin rings and the MCp*(dppe) fragments causes the appearance of a charge transfer absorption band in the visible region. It is also found that fluorescence derived from the porphyrin rings is quenched upon oxidation via intramolecular photoinduced electron transfer from the MCp*(dppe) moieties to the porphyrin chromophores in the excited states. The emission is recovered by subsequent reduction of the MCp*(dppe) fragments. Thus, the fluorescence from the porphyrin moieties is switched off and on upon oxidation and subsequent reduction, respectively. The iron acetylide complex 1 can assemble with nitrogen-donors including pyridine and DABCO as well as a π-acceptor, naphthalenediimide, to provide the nano-sized stacking structures which are detected by NMR. PMID:24008592

  6. 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

  7. Quantitative vibrational dynamics of iron in nitrosyl porphyrins

    OpenAIRE

    Leu, B. M.; Zgierski, M. Z.; Wyllie, G. R. A.; Scheidt, W. R.; Sturhahn, W.; Alp, E. E.; Durbin, S. M.; Sage, J. T.

    2004-01-01

    We use quantitative experimental and theoretical approaches to characterize the vibrational dynamics of the Fe atom in porphyrins designed to model heme protein active sites. Nuclear resonance vibrational spectroscopy (NRVS) yields frequencies, amplitudes, and directions for 57Fe vibrations in a series of ferrous nitrosyl porphyrins, which provide a benchmark for evaluation of quantum chemical vibrational calculations. Detailed normal mode predictions result from DFT calculations on ferrous n...

  8. 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.

  9. Synthesis, Electrochemistry, and Photophysics of Aza-BODIPY Porphyrin Dyes.

    Science.gov (United States)

    Pascal, Simon; Bucher, Léo; Desbois, Nicolas; Bucher, Christophe; Andraud, Chantal; Gros, Claude P

    2016-03-24

    The synthesis of dyad and triad aza-BODIPY-porphyrin systems in two steps starting from an aryl-substituted aza-BODIPY chromophore is described. The properties of the resulting aza-BODIPY-porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination. PMID:26938146

  10. Progress on research of radioisotope-labeled porphyrin derivatives

    International Nuclear Information System (INIS)

    Porphyrin derivatives can be taken up by tumor cells and accumulated there for a long time. Since 1960's, radioactive isotope-labeled porphyrins have been under extensive researches around the world. The progress of labeled porphyrins with various radioactive isotopes includes 3H, 11C, 123I, 131I, 99mTc, 188Re, 117,113mSn, 153Sm, 109Pd, 111In, 57Co, 58Co, 65Zn, 64,67Cu, 90Y, 166Ho is reviewed here. Among them, we studied the labeling conditions, chemical and biochemical properties of 188Re-labeled, 117,113mSn-labeled and 153Sm-labeled T3,4CPP and TPPS4. We also studied the bio-distribution of 188Re-labeled T3,4CPP and TPPS4 in mice with transplanted liver tumor and melanoma. Other researches in porphyrins which could affect the research of radioisotope-labeled porphyrins are introduced in the end. This review could provide a reference for design of better radioisotope-labeled porphyrins. (authors)

  11. Pd-porphyrin functionalized ionic liquid-modified mesoporous SBA-15: An efficient and recyclable catalyst for solvent-free Heck reaction

    International Nuclear Information System (INIS)

    The Pd-porphyrin functionalized ionic liquid could be covalently anchored in the channels of mesoporous SBA-15 through ion-pair electrostatic interaction between imidazolium-cationic and Pd-porphyrin-anionic moieties. Such modified SBA-15 materials were prepared successfully via a post-synthesis (surface sol-gel polymerization) or a one-pot sol-gel procedure, which were characterized by powder X-ray diffraction, UV-visible spectroscopy, Fourier transform infrared spectroscopy, N2 sorption, elemental analysis, and transmission electron microscopy. The modified SBA-15 materials are efficient and recyclable catalysts for cross-coupling of aryl iodides or activated aryl bromides with ethyl acrylate without activity loss and Pd leaching even after 9 runs.

  12. Pd-porphyrin functionalized ionic liquid-modified mesoporous SBA-15: An efficient and recyclable catalyst for solvent-free Heck reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jing; Zhao, Guo-Feng [Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Chemistry Department, East China Normal University, Shanghai 200062 (China); Popovic, Zora [General and Inorganic Laboratory, Chemistry Department, University of Zagreb, HR-10000 Zagreb (Croatia); Lu, Yong [Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Chemistry Department, East China Normal University, Shanghai 200062 (China); Liu, Ye, E-mail: yliu@chem.ecnu.edu.cn [Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Chemistry Department, East China Normal University, Shanghai 200062 (China)

    2010-11-15

    The Pd-porphyrin functionalized ionic liquid could be covalently anchored in the channels of mesoporous SBA-15 through ion-pair electrostatic interaction between imidazolium-cationic and Pd-porphyrin-anionic moieties. Such modified SBA-15 materials were prepared successfully via a post-synthesis (surface sol-gel polymerization) or a one-pot sol-gel procedure, which were characterized by powder X-ray diffraction, UV-visible spectroscopy, Fourier transform infrared spectroscopy, N{sub 2} sorption, elemental analysis, and transmission electron microscopy. The modified SBA-15 materials are efficient and recyclable catalysts for cross-coupling of aryl iodides or activated aryl bromides with ethyl acrylate without activity loss and Pd leaching even after 9 runs.

  13. Helical chirality induction of expanded porphyrin analogues

    Indian Academy of Sciences (India)

    Jun-Ichiro Setsune

    2012-11-01

    Expanded porphyrin analogues with unique figure-eight conformation were prepared by way of useful pyrrole intermediates such as bis(azafulvene)s and 2-borylpyrrole. Supramolecular chirogenesis of cyclooctapyrrole O1 with 32-cycloconjugation was successfully applied to determine absolute configuration of chiral carboxylic acids. Dinuclear CuII complex of cyclooctapyrrole O2 with interrupted -conjugation was resolved by HPLC into enantiomers and their helical handedness was determined by theoretical simulation of their CD spectral pattern. Enantioselective induction of helicity in the metal helicate formation in the presence of a chiral promoter was demonstrated by using ()-(+)-1-(1-phenyl)ethylamine that favoured , helicity. Dinuclear CoII complexes of cyclotetrapyrroletetrapyridine O3 were found to be substitution labile and pick up amino acid anions in water. Those amino acid complexes of O3Co2 were rendered to adopt a particular unidirectional helical conformation preferentially depending on the ligated amino acid anion.

  14. Porphyrin studies in TCDD-exposed workers

    Energy Technology Data Exchange (ETDEWEB)

    Jung, D. (Inst. fuer Arbeits- und Sozialmedizin der Univ. Mainz (Germany)); Konietzko, J. (Inst. fuer Arbeits- und Sozialmedizin der Univ. Mainz (Germany)); Reill-Konietzko, G. (Inst. fuer Arbeits- und Sozialmedizin der Univ. Mainz (Germany)); Muttray, A. (Inst. fuer Arbeits- und Sozialmedizin der Univ. Mainz (Germany)); Zimmermann-Hoelz, H.J. (Ciba-Geigy Marienberg GmbH, Lampertheim (Germany)); Doss, M. (Abt. fuer Klinische Biochemie, Fachbereich Humanmedizin, Philippsuniversitaet Marburg (Germany)); Beck, H. (Bundesgesundheitsamt, Berlin (Germany)); Edler, L. (Deutsches Krebsforschungszentrum Heidelberg, Biostatistik (Germany)); Kopp-Schneider, A. (Deutsches Krebsforschungszentrum Heidelberg, Biostatistik (Germany))

    1994-09-01

    2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) has been shown to inhibit uroporphyrinogen decarboxylase activity resulting in chronic hepatic porphyria. From a cross-sectional study of 170 workers in chemical industry 68 showed elevated coproporphyrin levels, interpreted as secondary coproporphyrinuria. Three persons suffered from chronic hepatic porphyria in subclinical stages. None of the workers showed an overt porphyria cutanea tarda. A low-grade zinc protoporphyrinemia was observed in three persons. Forty-three of the 170 workers were evaluable for investigating the effect of TCDD on porphyrin levels. No significant correlation was found between TCDD concentration in adipose tissue and the level of uroporphyrin and coproporphyrin. The influence of a chloracne history is described. (orig.)

  15. Heptaphyrins: Expanded porphyrins with seven heterocyclic rings

    Indian Academy of Sciences (India)

    Venkataramanarao G Anand; Simi K Pushpan; Sundararaman Venkatraman; Tavarekere K Chandrashekar

    2003-10-01

    Expanded porphyrins containing seven pyrrole/heterocyclic rings linked in a cyclic fashion are termed heptaphyrins. The number of -electrons in heptaphyrins depends on the number of meso carbon bridges used to link the heterocyclic rings, accordingly heptaphyrins with 28-electrons and 30 -electrons are reported to date. Both condensation reactions of the appropriate precursors and acid-catalysed oxidative coupling reactions have been utilized to synthesise the heptaphyrins. The 30 heptaphyrins exhibit rich structural diversity where some of the heterocyclic rings in the macrocycle undergo a 180° ring flipping. An overview of the synthetic methods employed for the synthesis of heptaphyrins, their spectroscopic properties, structural behaviour and aromatic properties are highlighted in this paper.

  16. Potassium ion controlled switching of intra- to intermolecular electron transfer in crown ether appended free-base porphyrin-fullerene donor-acceptor systems.

    Science.gov (United States)

    D'Souza, Francis; Chitta, Raghu; Gadde, Suresh; Zandler, Melvin E; McCarty, Amy L; Sandanayaka, Atula S D; Araki, Yasuyaki; Ito, Osamu

    2006-04-01

    Photoinduced electron transfer in intramolecularly interacting free-base porphyrin bearing one or four 18-crown-6 ether units at different positions of the porphyrin macrocycle periphery and pristine fullerene was investigated in polar benzonitrile and nonpolar o-dichlorobenzene and toluene solvents. Owing to the presence of two modes of binding, stable dyads were obtained in which the binding constants, K, were found to range between 4.2 x 10(3) and 10.4 x 10(3) M(-1) from fluorescence quenching data depending upon the location and number of crown ether entities on the porphyrin macrocycle and the solvent. Computational studies using the B3LYP/3-21G() method were employed to arrive at the geometry and electronic structure of the intramolecular dyads. The energetics of the redox states of the dyads were established from cyclic voltammetric studies. Under the intramolecular conditions, both the steady-state and time-resolved emission studies revealed efficient quenching of the singlet excited free-base porphyrin in these dyads, and the measured rates of charge separation, k(CS), were found to be in the 10(8)-10(9) s(-1) range. Nanosecond transient absorption studies were performed to characterize the electron-transfer products and to evaluate the charge-recombination rates. Shifting of the electron-transfer pathway from the intra- to intermolecular route was achieved by complexing potassium ions to the crown ether cavity(ies) in benzonitrile. This cation complexation weakened the intramolecular interactions between fullerene and the crown ether appended free-base porphyrin supramolecules, and under these conditions, intermolecular type interactions were mainly observed. Reversible inter- to intramolecular electron transfer was also accomplished by extracting the potassium ions of the complex with the addition of 18-crown-6. The present study nicely demonstrates the application of supramolecular methodology to control the excited-state electron-transfer path in donor

  17. A porous covalent porphyrin framework with exceptional uptake capacity of saturated hydrocarbons oil spill cleanup

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xi-Sen; Liu, Jian; Bonefont, Jean M.; Yuan, Da-Qiang; Thallapally, Praveen K.; Ma, Shengqian

    2013-01-21

    Yamamoto homo-coupling reaction of tetra(4-bromophenyl)porphyrin afforded a porous covalent porphyrin framework, PCPF-1, which features strong hydrophobicity and oleophilicity and demonstrates exceptional adsorptive capacities for saturated hydrocarbons and gasoline.

  18. Noncovalent functionalization of single-walled carbon nanotubes with porphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Bassiouk, María; Basiuk, Vladimir A. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Basiuk, Elena V., E-mail: elenagd@unam.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Álvarez-Zauco, Edgar [Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Martínez-Herrera, Melchor [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Rojas-Aguilar, Aaron [Centro de Investigación y de Estudios Avanzados, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional 2508, San Pedro Zacatenco, 07360 México D.F. (Mexico); Puente-Lee, Iván [Facultad de Química, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico)

    2013-06-15

    The covalent and noncovalent interactions of porphyrins and related tetraazamacrocyclic compounds with single-walled carbon nanotubes (SWNTs) is a subject of increasing research effort, directed toward the design of novel hybrid nanomaterials combining unique electronic and optical properties of both molecular species. In this report, we used different experimental techniques as well as molecular mechanics (MM) calculations to analyze the adsorption of meso-tetraphenylporphine (or 5,10,15,20-tetraphenyl-21H,23H-porphine, H{sub 2}TPP) and its complexes with Ni(II) and Co(II) (NiTPP and CoTPP, respectively), as well as hemin (a natural porphyrin), onto the surface of SWNTs. Altogether, the results suggested that all four porphyrin species noncovalently interact with SWNTs, forming hybrid nanomaterials. Nevertheless, of all four porphyrin species, the strongest interaction with SWNTs occurs in the case of CoTPP, which is able to intercalate and considerably disperse SWNT bundles, and therefore absorb onto the surface of individual SWNTs. In contrast, NiTPP, CoTPP and hemin, due to a weaker interaction, are unable to do so and therefore are only capable to adsorb onto the surface of SWNT bundles. According to the scanning tunneling microscopy (STM) imaging and MM results, the adsorption of CoTPP onto SWNT sidewalls results in the formation of porphyrin arrays in the shape of long-period interacting helixes with variable periodicity, possibly due to different diameters and chiralities of SWNTs present in the samples. Since the remaining porphyrin species were found to adsorb onto the surface of SWNT bundles, the precise geometry of the corresponding porphyrin/SWNT complexes is difficult to characterize.

  19. Noncovalent functionalization of single-walled carbon nanotubes with porphyrins

    International Nuclear Information System (INIS)

    The covalent and noncovalent interactions of porphyrins and related tetraazamacrocyclic compounds with single-walled carbon nanotubes (SWNTs) is a subject of increasing research effort, directed toward the design of novel hybrid nanomaterials combining unique electronic and optical properties of both molecular species. In this report, we used different experimental techniques as well as molecular mechanics (MM) calculations to analyze the adsorption of meso-tetraphenylporphine (or 5,10,15,20-tetraphenyl-21H,23H-porphine, H2TPP) and its complexes with Ni(II) and Co(II) (NiTPP and CoTPP, respectively), as well as hemin (a natural porphyrin), onto the surface of SWNTs. Altogether, the results suggested that all four porphyrin species noncovalently interact with SWNTs, forming hybrid nanomaterials. Nevertheless, of all four porphyrin species, the strongest interaction with SWNTs occurs in the case of CoTPP, which is able to intercalate and considerably disperse SWNT bundles, and therefore absorb onto the surface of individual SWNTs. In contrast, NiTPP, CoTPP and hemin, due to a weaker interaction, are unable to do so and therefore are only capable to adsorb onto the surface of SWNT bundles. According to the scanning tunneling microscopy (STM) imaging and MM results, the adsorption of CoTPP onto SWNT sidewalls results in the formation of porphyrin arrays in the shape of long-period interacting helixes with variable periodicity, possibly due to different diameters and chiralities of SWNTs present in the samples. Since the remaining porphyrin species were found to adsorb onto the surface of SWNT bundles, the precise geometry of the corresponding porphyrin/SWNT complexes is difficult to characterize.

  20. Synthesis and Characterization of One-dimensional and Two-Dimensional Porphyrin Polymers* (Ⅰ)

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@Porphyrin polymers are of interest in relation to conductive materials[1, 2], catalysts for photosynthetic charge separation[3], or the fundamental features in biological systems[4]. There have been many versatile studies about them[5,6]. The one-dimensional “Shish Kebab” porphyrin polymers synthesized with a new method different from those reported and Schiff base porphyrin polymers with two-dimensional nano-structure have provided a new field of study. The present paper covers highly ordered porphyrin polymers.

  1. Synthesis and catalytic activities of porphyrin-based PCP pincer complexes.

    OpenAIRE

    Fujimoto, Keisuke; Yoneda, Tomoki; Yorimitsu, Hideki; Osuka, Atsuhiro

    2013-01-01

    2,18-Bis(diphenylphosphino)porphyrins undergo peripheral cyclometalation with group 10 transition-metal salts to afford the corresponding porphyrin-based PCP pincer complexes. The porphyrinic plane and the PCP-pincer unit are apparently coplanar, with small strain. The catalytic activities of the porphyrin-based pincer complexes at the periphery were investigated in the allylation of benzaldehyde with allylstannane and in the 1,4-reduction of chalcone to discover the electronic interplay betw...

  2. Photoinduced oxidation of a water-soluble manganese(III) porphyrin

    OpenAIRE

    Maliyackel, Anthony C.; Otvos, John W.; Spreer, Larry O.; Calvin, Melvin

    1986-01-01

    The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2′-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and t...

  3. Probing the origin of fluorescence quenching of a graphene-porphyrin hybrid material

    Directory of Open Access Journals (Sweden)

    Huijser Annemarie

    2013-03-01

    Full Text Available We report transient absorption spectroscopic studies on the hybrid material composed of porphyrin molecules covalently attached to graphene for investigating the mechanism underlying the reported fluorescence quenching of porphyrin in the hybrid [1]. Excited state dynamics of pure graphene suspension and porphyrin have also been studied as reference samples. A fast excited state decay was observed in the hybrid.

  4. Synthesis and Purification of Porphyrin-Schiff Base Using Ethyl Vanillin

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A novel porphyrin-Schiff base was synthesized via the condensation of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin and ethyl vanillin. After analyzing the level of purification of the porphyrin-Schiff base, it was successfully separated. This porphyrin-Schiff base was characterized by using UV-Vis, IR, 1 H NMR and MS spectroscopy.

  5. Synthesis of Metal Porphyrins Tailed with Salicylic Acid and their Interaction with Bovine Serum Albumin

    Institute of Scientific and Technical Information of China (English)

    Tao JIA; Kai WANG; Yi Mei ZHAO; Zao Ying LI

    2004-01-01

    A synthetic method of porphyrins tailed with salicylic substituents is described. Reaction of bromoalkoxyphenyl porphyrin 1 with salicylic acid gave porphyrins 2~5. These new compounds were confirmed by 1H NMR, IR, UV-vis, MS and elemental analysis, and observed their interaction with bovine serum albumin (BSA) in fluorescence spectrum.

  6. Porphyrin-anthraquinone dyads: Synthesis, spectroscopy and photochemistry

    Indian Academy of Sciences (India)

    P Prashanth Kumar; G Premaladha; Bhaskar G Maiya

    2005-03-01

    Free-base (H2L2), copper(II) (CuL2) and zinc(II) (ZnL2) derivatives of a porphyrin-anthraquinone conjugate with an azomethine group separating the two photoactive subunits have been synthesized and characterized by mass (FAB), IR, UV-visible, 1H NMR and ESR spectroscopic techniques and also by cyclic and differential pulse voltammetric methods. Analysis of the data reveals that the spectral and electrochemical properties of the individual chromophoric entities are retained and that there is no specific - interaction between the porphyrin and anthraquinone subunits. H2L2 and ZnL2 are shown to exhibit substantial quenching (88-97%) of the porphyrin fluorescence compared to their corresponding monomeric analogues. An intramolecular electron-transfer mechanism is proposed for the substantial decrease in fluorescence in both derivatives. The fluorescence decays of porphyrin-anthraquinone conjugates are fit to 2/3 exponentials and indicate that multiple orientations of the porphyrin and anthraquinone groups contribute to the electron-transfer event. These results are in good agreement with steady-state fluorescence results. From the time-resolved fluorescence data, the electron-transfer rate constants are calculated, indicating ET values in the range of 1.1 × 109 to 9.9 × 1010 s-1 that are dependent upon the solvent.

  7. Fluorescence spectroscopy for endogenous porphyrins in human facial skin

    Science.gov (United States)

    Seo, I.; Tseng, S. H.; Cula, G. O.; Bargo, P. R.; Kollias, N.

    2009-02-01

    The activity of certain bacteria in skin is known to correlate to the presence of porphyrins. In particular the presence of coproporphyrin produced by P.acnes inside plugged pores has been correlated to acne vulgaris. Another porphyrin encountered in skin is protoporphyrin IX, which is produced by the body in the pathway for production of heme. In the present work, a fluorescence spectroscopy system was developed to measure the characteristic spectrum and quantify the two types of porphyrins commonly present in human facial skin. The system is comprised of a Xe lamp both for fluorescence excitation and broadband light source for diffuse reflectance measurements. A computer-controlled filter wheel enables acquisition of sequential spectra, first excited by blue light at 405 nm then followed by the broadband light source, at the same location. The diffuse reflectance spectrum was used to correct the fluorescence spectrum due to the presence of skin chromophores, such as blood and melanin. The resulting fluorescence spectra were employed for the quantification of porphyrin concentration in a population of healthy subjects. The results show great variability on the concentration of these porphyrins and further studies are being conducted to correlate them with skin conditions such as inflammation and acne vulgaris.

  8. Cation-cation interaction in neptunyl(V) compounds

    International Nuclear Information System (INIS)

    The original manuscript was prepared by Professor N.N. Krot of Institute of Physical Chemistry, Russian Academy of Sciences, in 1997. Saeki tried to translate that into Japanese and to add some new data since 1997. The contents include the whole picture of cation-cation interactions mainly in 5-valence neptunium compounds. Firstly, characteristic structures of neptunium are summarized of the cation-cation bonding in compounds. Secondly, it is mentioned how the cation-cation bonding affects physical and chemical properties of the compounds. Then, characterization-methods for the cation-cation bonding in the compounds are discussed. Finally, the cation-cation interactions in compounds of other actinide-ions are shortly reviewed. (author)

  9. Interfacial organization of achiral porphyrins via unidirectional compression: a general method for chiroptical porphyrin assemblies of selected chirality.

    Science.gov (United States)

    Zhang, Xiao; Wang, Yanping; Chen, Penglei; Rong, Yunlong; Liu, Minghua

    2016-05-18

    Porphyrins are considered to be important scaffolds bridging supramolecular chemistry and chiral chemistry, where chirality selection via physical effects such as directional stirring and spin-coating has aroused particular interest. Nevertheless, these protocols could only work on a limited number of achiral porphyrins. It still remains a formidable challenge to pave a general avenue for the construction of chiral assemblies using achiral porphyrins. By means of a unique Langmuir-Schaefer (LS) technique of a unidirectional compression configuration, we herein have demonstrated that a series of achiral porphyrins could be facilely organized to form chiral interfacial assemblies of controlled supramolecular chirality. It has been disclosed that such a fascinating chirality selection scenario is intimately related to the direction of the compression-generated vortex-like flow, while the compression speed, one of the most significant parameters of the Langmuir technique, contributes less to this issue. With regard to a surface-pressure-dependent chirality selection phenomenon, it is suggested that the directional vortex-like flow generated by lateral compression might play a role in promoting the preferential growth of chiral assemblies showing an enhanced yet controlled CD signal. Our protocol might be, to some extent, a general method for achieving chiral porphyrin assemblies of controlled chirality. PMID:27156996

  10. Interaction of porphyrins with CdTe quantum dots

    International Nuclear Information System (INIS)

    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.

  11. 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...... behaviour of 4 and 5. While 4 gave rise to photovoltaic devices giving a moderate photovoltaic response that was symbatic with the absorption spectrum, 5 showed a photovoltaic response that was antibatic with a part of the absorption spectrum of the zinc-porphyrin constituent. We ascribe this behaviour to...

  12. Photoinduced triplet-state electron transfer of platinum porphyrin: A one-step direct method for sensing iodide with an unprecedented detection limit

    KAUST Repository

    Masih, Dilshad

    2014-02-05

    Here, we report for the first time a one-step direct method for sensing halides in aqueous solution using phosphorescence quenching of platinum-cationic porphyrin. This method offers an easy, rapid, environmentally friendly, ultra-sensitive (with a previously unattained detection limit of 1 × 10-12 M) and economical method for the determination of iodide. To fully understand the reaction mechanism responsible for the phosphorescence quenching process, we have employed cutting-edge time-resolved laser spectroscopy with broadband capabilities. This journal is © The Royal Society of Chemistry 2015.

  13. Photoinduced triplet-state electron transfer of platinum porphyrin: a one-step direct method for sensing iodide with an unprecedented detection limit

    KAUST Repository

    Masih, Dilshad

    2015-02-05

    Here, we report for the first time a one-step direct method for sensing halides in aqueous solution using phosphorescence quenching of platinum-cationic porphyrin. This method offers an easy, rapid, environmentally friendly, ultra-sensitive (with a previously unattained detection limit of 1 × 10−12 M) and economical method for the determination of iodide. To fully understand the reaction mechanism responsible for the phosphorescence quenching process, we have employed cutting-edge time-resolved laser spectroscopy with broadband capabilities.

  14. 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. PMID:26266818

  15. Photoinduced conductivity of a porphyrin-gold composite nanowire

    Energy Technology Data Exchange (ETDEWEB)

    Kilina, Svletana [Los Alamos National Laboratory; Balatsky, Alexander [Los Alamos National Laboratory; Kilin, Dmitri S [UNIV OF FL; Prezhdo, Oleg [UNIV OF WASHINGTON; Tsemekhman, Kiril [NON LANL

    2009-01-01

    Negatively charged phosphine groups on the backbone of DNA are known to attract gold nanoclusters from a colloid, assembling the clusters at fixed intervals. Bridging these intervals with porphyrin-dye linkers forms an infinite conducting chain, a quantum wire whose carrier mobility can be enhanced by photoexcitation. The resulting nanoassembly can be used as a gate: a wire with a controllable conductivity. The electronic structure of the porphyrin-gold wire is studied here by density functional theory, and the conductivity of the system is determined as a function of the photoexcitation energy. Photoexcitations of the dye are found to enhance the wire conductivity by orders of magnitude.

  16. Selective uptake of porphyrins within experimental atheromatous plaques: Potential for laser photodynamic therapy

    International Nuclear Information System (INIS)

    The authors investigated the selective uptake of various porphyrins atheromatous plaques. Grass and microscopic examination of atherosclorotic rabbit aortas under ultraviolet light 48 hours after porphyrin administration disclosed porphyrin fluorescence exclusively on the plaques. As judged from the fluorescence emission, the order of affinity of the porphyrins for plaque is as follows: photofrin II (PF II) > hematoporphyrin derivative (HPD) > tetrasulfonatophenyl porphyrin (TPPS) ≥ hydroxyethylvinyldeuteroporphyrin (HVD), hematoporphyrin (HP). The potential application of intravascular irradiation of plaques labeled with porphyrins in the treatment of atheroma can be investigated using the animal model. Matching the irradiation light wave length to the porphyrin absorption peak allows specific effects to be directed to the plaque without damaging the normal vessel wall

  17. Production, quality control, biodistribution assessment and preliminary dose evaluation of [177Lu]-tetra phenyl porphyrin complex as a possible therapeutic agent

    Directory of Open Access Journals (Sweden)

    Samaneh Zolghadri

    2015-06-01

    Full Text Available Due to interesting therapeutic properties of 177Lu and tumor avidity of tetraphenyl porphyrins (TPPs, 177Lu-tetraphenyl porphyrin was developed as a possible therapeutic compound. 177Lu of 2.6-3 GBq/mg specific activity was obtained by irradiation of natural Lu2O3sample with thermal neutron flux of 4 × 1013 n.cm-2.s-1. Tetraphenyl porphyrin was synthetized and labeled with 177Lu. Radiochemical purity of the complex was studied using Instant thin layer chromatography (ITLC method. Stability of the complex was checked in final formulation and human serum for 48 h. The biodistribution of the labeled compound in vital organs of wild-type rats was studied up to 7 d. The absorbed dose of each human organ was calculated by medical internal radiation dose (MIRD method. A detailed comparative pharmacokinetic study was performed for 177Lu cation and [177Lu]-TPP. The complex was prepared with a radiochemical purity: >97±1% and specific activity: 970-1000 MBq/mmol. Biodistribution data and dosimetric results showed that all tissues receive approximately an insignificant absorbed dose due to rapid excretion of the complex through the urinary tract. [177Lu]-TPP can be an interesting tumor targeting agent due to low liver uptake and very low absorbed dose of approximately 0.036 to the total body of human.

  18. Layered Hydroxide–Porphyrin Hybrid Materials: Synthesis, Structure, and Properties

    Czech Academy of Sciences Publication Activity Database

    Demel, Jan; Lang, Kamil

    2012-01-01

    Roč. 2012, č. 32 (2012), s. 5154-5164. ISSN 1434-1948 R&D Projects: GA ČR GAP207/10/1447 Institutional support: RVO:61388980 Keywords : layered compounds * intercalations * porphyrin oids * phthalocyanines * singlet oxygen Subject RIV: CA - Inorganic Chemistry Impact factor: 3.120, year: 2012

  19. Layered double hydroxides as carriers of photoactive porphyrin molecules

    Czech Academy of Sciences Publication Activity Database

    Lang, Kamil; Káfuňková, Eva; Kovanda, F.; Taviot-Guého, Ch.

    Bratislava : Institute of Inorganic Chemistry, Slovak Academy of Sciences, 2008. s. 246. ISBN 978-80-224-1019-9. [Conference on Solid State Chemistry /8./. 06.06.2008-11.06.2008, Bratislava] Institutional research plan: CEZ:AV0Z40320502 Keywords : photoactive porphyrin Subject RIV: CA - Inorganic Chemistry

  20. Intercalation of porphyrins into Mg-Al hydrotalcite

    Czech Academy of Sciences Publication Activity Database

    Kovanda, F.; Káfuňková, Eva; Rojka, T.; Lang, Kamil

    2008-01-01

    Roč. 15, č. 1 (2008), s. 28-32. ISSN 1211-5894 R&D Projects: GA AV ČR KAN100500651; GA ČR(CZ) GA203/06/1244 Institutional research plan: CEZ:AV0Z40320502 Keywords : Mg-Al hydrotalcite * layered double hydroxide * porphyrin Subject RIV: CA - Inorganic Chemistry

  1. Biotoxicity Evaluation of Singlet Oxygen Generated by Immobilized Porphyrin

    Czech Academy of Sciences Publication Activity Database

    Rychtáriková, Renata; Kuncová, Gabriela; Krulikovská, T.; Sviráková, E.; Hetflejš, Jiří

    - : -, 2008, P19 - 1-P19 - 4. [XVI International Conference on Bioencapsulation. Dublin (IE), 04.09.2008-06.09.2008] R&D Projects: GA ČR(CZ) GA203/06/1244; GA MŠk OC 121 Institutional research plan: CEZ:AV0Z40720504 Keywords : porphyrin s * singlet oxygen * immobilization Subject RIV: CE - Biochemistry

  2. Monitoring of Porphyrin Protonation by the Magnetic Circular Dichroism

    Czech Academy of Sciences Publication Activity Database

    Štěpánek, Petr; Bouř, Petr

    Oxford : Diamond, 2011. s. 21-21. [CD 2011. The International Conference on Chiroptical Spectroscopy /13./. 24.07.2011-28.07.2011, Oxford] Grant ostatní: 7th European Community Framework Program(XE) 230955 Institutional research plan: CEZ:AV0Z40550506 Keywords : porphyrin * magnetic circular dichroism * DFT calculation Subject RIV: CF - Physical ; Theoretical Chemistry

  3. First observation of an iron porphyrin in heavy crude oil

    International Nuclear Information System (INIS)

    Studying one of the iron rich crudes from Orinoco river region using Moessbauer effect, an iron porphyrin was clearly identified for the first time in a heavy oil; its structure is DPEP type and the iron state is divalent (FeII) with low spin. (Auth.)

  4. Tunneling electron induced luminescence from porphyrin molecules on monolayer graphene

    International Nuclear Information System (INIS)

    Using epitaxially grown graphene on Ru(0001) as a decoupling layer, we investigate the evolution of tunneling electron induced luminescence from different number of layers of porphyrin molecules. Light emission spectra and photon maps, acquired via a combined optical setup with scanning tunneling microscopy (STM), indicate that the electronic decoupling effect of a monolayer (ML) graphene alone is still insufficient for generating molecule-specific emission from both the 1st- and 2nd-layer porphyrin molecules. Nevertheless, interestingly, the plasmonic emission is enhanced for the 1st-layer but suppressed for the 2nd-layer in comparison with the plasmonic emission on the monolayer graphene. Intrinsic intramolecular molecular fluorescence occurs at the 3rd-layer porphyrin. Such molecular thickness is about two MLs thinner than previous reports where molecules were adsorbed directly on metals. These observations suggest that the monolayer graphene does weaken the interaction between molecule and metal substrate and contribute to the reduction of nonradiative decay rates. - Highlights: • Showing molecularly resolved photon maps of graphene and porphyrins on it. • Revealing the influence of spacer thickness on molecular electroluminescence. • Graphene does weaken the interaction between molecules and metal substrate

  5. Tunneling electron induced luminescence from porphyrin molecules on monolayer graphene

    Energy Technology Data Exchange (ETDEWEB)

    Geng, Feng; Kuang, Yanmin; Yu, Yunjie; Liao, Yuan; Zhang, Yao; Zhang, Yang; Dong, Zhenchao, E-mail: zcdong@ustc.edu.cn

    2015-01-15

    Using epitaxially grown graphene on Ru(0001) as a decoupling layer, we investigate the evolution of tunneling electron induced luminescence from different number of layers of porphyrin molecules. Light emission spectra and photon maps, acquired via a combined optical setup with scanning tunneling microscopy (STM), indicate that the electronic decoupling effect of a monolayer (ML) graphene alone is still insufficient for generating molecule-specific emission from both the 1st- and 2nd-layer porphyrin molecules. Nevertheless, interestingly, the plasmonic emission is enhanced for the 1st-layer but suppressed for the 2nd-layer in comparison with the plasmonic emission on the monolayer graphene. Intrinsic intramolecular molecular fluorescence occurs at the 3rd-layer porphyrin. Such molecular thickness is about two MLs thinner than previous reports where molecules were adsorbed directly on metals. These observations suggest that the monolayer graphene does weaken the interaction between molecule and metal substrate and contribute to the reduction of nonradiative decay rates. - Highlights: • Showing molecularly resolved photon maps of graphene and porphyrins on it. • Revealing the influence of spacer thickness on molecular electroluminescence. • Graphene does weaken the interaction between molecules and metal substrate.

  6. Absorption Complex between Porphyrin and Phenothiazine in Reverse Micelles

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The interaction between amphiphilic porphyrin and phenothiazine in AOT/isooctane/ water reverse micelle was investigated by UV-Vis spectra. A new absorption complex between the two species is formed in such circumstances, which is ascribed to the enrichment of the components by the reverse micelle. The fluorescence quenching of CHTTP by PTH becomes more efficient after the formation of the absorption complex.

  7. 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.

  8. Preparation and characterization of free-standing pure porphyrin nanoparticles

    Indian Academy of Sciences (India)

    Arun Kumar Perepogu; Prakriti Ranjan Bangal

    2008-09-01

    Preparation and characterization of absolutely pure and stable nanoparticles of 5,10,15,20-meso-tetrakis phenyl porphyrin (TPP) and catalytically repute 5,10,15,20-meso-tetrakis pentaflurophenyl porphyrin (H2F20TPP) by improved ‘reprecipitation method’ is described. The innovation of this modified `reprecipitation method’ lies on the judicial selection of organic solvent and amount of porphyrin solution to be injected in the aqueous media. Exactly similar process produces relatively small nanoparticles for TPP than that of H2F20TPP while the stability of the H2F20TPP nanoparticles is bit higher than nanoparticles of TPP. Absorption and emission spectra reveal that the formation of nanoparticles for both the cases is induced by J- and H-type aggregation. DFT calculations predict the optimized geometries and frontier molecular orbital, which favours the strength of face-to-face interaction with neighbour molecules to be more facile for TPP than that of H2F20TPP helping the latter to form bigger and relatively more stable and free-standing nanoparticles. The use of no other compounds except dichloromethane, a highly volatile organic solvent and respective porphyrins give absolutely pure nanoparticles. This improved method will lead to produce organic nanoparticles of -conjugated systems easily and efficiently.

  9. Synthesis of metallic nanoshells on porphyrin-stabilized emulsions

    Science.gov (United States)

    Wang, Haorong; Song, Yujiang; Shelnutt, John A.; Medforth, Craig J.

    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.

  10. Photoproduction of singlet oxygen by porphyrins intercalated in layered materials

    Czech Academy of Sciences Publication Activity Database

    Lang, Kamil; Bourdelande, J.L.; Hernando, J.; Kovanda, F.; Kubát, Pavel; Mosinger, Jiří; Wagnerová, Dana Marie

    Bad Hofgastein : EPA , 2006, s. 27-27. [Central European Conference on Photochemistry. Bad Hohgastein (AT), 05.03.2006-09.03.2006] Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : porphyrin Subject RIV: CA - Inorganic Chemistry

  11. Cyclic porphyrin dimers as hosts for coordinating ligands

    Indian Academy of Sciences (India)

    G Vaijayanthimala; V Krishnan; S K Mandal

    2008-01-01

    Bicovalently linked tetraphenylporphyrins bearing dioxypentane groups at the opposite (transoid, H4A) and adjacent (cisoid, H4B) aryl groups have been synthesised. Protonation of the free-base porphyrins leads to fully protonated species H8A4+/H8A4+ accompanied by expansion of cavity size of the bisporphyrins. The electrochemical redox studies of these porphyrins and their Zinc(II) derivatives revealed that the first ring oxidation proceeds through a two-electron process while the second ring oxidation occurs at two distinct one-electron steps indicating unsymmetrical charge distribution in the oxidized intermediate. The axial ligation properties of the Zinc(Il) derivatives of H4A/H4B with DABCO and PMDA investigated by spectroscopic and single crystal X-ray diffraction studies showed predominant existence of 1 : I complex. The Zn2A.DABCO complex assumes an interesting eclipsed structure wherein DABCO is located inside the cavity between the two porphyrin planes with Zn-N distances at 2.08 and 2.22 Å. The Zn atoms are pulled into the cavity due to coordination towards nitrogen atoms of DABCO and deviate from the mean porphyrin plane by 0.35 Å. The electrochemical redox potentials of the axially ligated metal derivatives are found to be sensitive function of the relative coordinating ability of the ligands and the conformation of the hosts.

  12. Electronic transport through tape-porphyrin molecular bridges

    International Nuclear Information System (INIS)

    We investigated theoretically how molecular conjugation affects current-voltage (I-V) curves through three types of oligoporphyrin molecules, i.e., the tape-porphyrin, the butadiyne-linked porphyrin, and the edge-fused porphyrin molecules. Among these, the tape-porphyrin molecule is found to be the most conductive due to its extremely small HOMO-LUMO energy gap. Furthermore, the I-V curves through this type of molecule are found to depend considerably on atomic sites to which electrodes are connected. In particular, as long as the applied bias is weak, the current is found to flow strongest when both electrodes are connected to the atomic sites referred to as meso sites. This feature is caused by the fact that the HOMO relevant to resonant tunneling has a higher charge density on the meso sites. These findings indicate that designing not only molecules but also contact structures is highly significant for realizing a desirable function in single molecular devices

  13. 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 ostatní: 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: 2.639, year: 2014

  14. Porphyrin Induced Laser Deactivation of Trypsinogen-Trypsin Conversion

    Science.gov (United States)

    Perido, Joanna; Brancaleon, Lorenzo

    2015-03-01

    Pancreatitis is caused by the inflammation of the pancreas, where the digestive enzyme trypsin is activated from the precursor enzyme trypsinogen while still in the pancreas. The presence of trypsin in the pancreas causes auto-activation of trypsinogen, resulting in greater inflammation and auto-digestion of the pancreas. In severe cases, this cascade effect can lead to organ failure, diabetes, and pancreatic cancer. Our hypothesis is that if trypsinogen is prevented from auto-activating into trypsin, then this cascade can be stopped. We propose to do this by inducing conformational changes in trypsinogen when bound to a photoactive porphyrin dye. Porphyrins are comprised of four linked heterocyclic groups forming a flat ring, and bind well with proteins such as trypsinogen. In this study we used spectroscopic techniques to probe the binding of meso-tetrakis (4-sulfonatephenyl) porphyrin (TSPP) to trypsinogen in vitro, as a preliminary step to then prompt and characterize conformational changes of trypsinogen through irradiation. If conformational changes are detected the trypsinogen will be tested for trypsin inactivation. This investigation may provide promising initial results to the possible use of porphyrins as an inhibitor of the self-activation of trypsinogen into trypsin, and a potential inhibitor of pancreatitis. MARC*U-STAR.

  15. Structural investigation of nickel (II) octaethyl-meso-nitro-porphyrins

    International Nuclear Information System (INIS)

    Dual-channel resonance Raman spectra are presented for Ni(II) octaethyl-mononitro-porphyrin (NiOEMNP) and Ni(II) octaethyl-tetranitro-porphyrin (NiOETNP) in coordinating and non-coordinating solvents. Molecular mechanics calculations for NiOETNP predict a structure as distorted from planarity as that found for Ni(II) octaethyl-tetraphenylporphyrin (NiOETPP). Structurally-sensitive porphyrin vibrational modes ν4, ν3, ν2 and ν10 are observed at 1377 1513, 1589 and 1647 cm-1, respectively, for NiOEMNP and at 1368, 1488, 1570 and 1605 cm-1 for NiOETNP. Decreased frequencies for NiOENTP are consistent with the predicted highly non-planar conformation of the macrocycle that results from steric interactions of the ethyl substituents with the four meso-NO2 groups. The authors' results suggest that the ruffling of the porphyrin dominates the observed shifts in vibrational frequencies. Vibrational mode assignments are also made for the NO2 moieties with slightly different frequencies for the mono- and tetra-substitutioal species. unlike NiOETPP, where non-planarity prevents the binding of even strong-field ligands. NiOETNP is found to bind relatively weak ligands such as methanol. NiOETNPs high ligand affinity is probably a result of the strong electron-withdrawing character of the four NO2 groups

  16. The effects of urea, guanidinium chloride and sorbitol on porphyrin aggregation: Molecular dynamics simulation

    Indian Academy of Sciences (India)

    Maryam Ghadamgahi; Davood Ajloo

    2013-05-01

    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 have a large effect — positive or negative, depending on the concentration — on the aggregation of the porphyrin. The effect of urea, Gdn and sorbitol on porphyrin aggregation has been inferred from the effect of these solutes on the hydration layer of porphyrin. It appears that the Gdn is more suitable than urea for decreasing the hydration layer of porphyrin while several osmolites like sorbitol are known to increase hydration layer and thus might stabilize the porphyrin aggregation. Results of radial distribution function (RDF), distributed atoms or molecules around target species, indicated that the increase and exclusion of solvent around porphyrin by osmolytes and Gdn would affect significantly on porphyrin aggregation. There was a sizeable difference in potency between the Gdn and urea, with the urea being less potent to decrease hydration layer and porphyrin aggregation.

  17. Synthesis, Characterization and Weak Intramolecular Interactions of Porphyrins Bearing Nucleobases

    Institute of Scientific and Technical Information of China (English)

    阮文娟; 李瑛; 赵小菁; 王传忠; 朱志昂; 缪方明

    2003-01-01

    5,10, 15-Triphenyl-20-{2- [α- (adenine-9 ) acetylamino]} phenyl porphyrin ( 1 ), 5,10, 15-triphenyl-20-{2-[α-(cytosine-1)acetylamino]} phenyl porphyrin (2), 5, 10, 15-triphenyl-20-{4-[α-(cytosine-1)ethoxy]} phenyl porphyrin (3) and their zinc complexes Zn-1, Zn-2 and Zn-3 have been prepared and characterized by 1H NMR spectra, elemental analyses, electronic absorption spectra and mass spectra (FAB). Intramolecular π-π interactions and intramolecular metal-~ interaction for 1, 2, Zn-1,and Zn-2 have been investigated by several methods. 1H NMR studies demonstrate that the porphyrin π-system in 1 and 2 is parallel to the adenine and the cytosine aromatic ring, respectively. The electronic absorption spectral properties of free porphyrin derivatives and their zinc complexes have been compared with those of H2TPP and ZnTPP. The results show that the UV-vis spectra of 1 and 2 are the same as that of H2TPP,whereas the spectra of their zinc complexes show 7 nm red shifts of the Soret bands compared to that of ZnTPP. The emission spectra of Zn-1 and Zn-2 are independent of excitation wavelength. From combination of the evidence of absorption and emission spectra it is suggested the existence of intramolecular metal-π interaction in Zn-1 and Zn-2. The results of conformational analysis agreed quite nicely with that of experiments, thus it was further to validate the experimental conclusions.

  18. Sol-gel reaction of porphyrin-based superstructures in the organogel phase: creation of mechanically reinforced porphyrin hybrids.

    Science.gov (United States)

    Kishida, Takanori; Fujita, Norifumi; Sada, Kazuki; Shinkai, Seiji

    2005-05-25

    We have demonstrated that a one-dimensional molecular assembly created by an H-aggregated porphyrin.Cu(II) stack can be immobilized, without a morphological change, by sol-gel polycondensation of the peripheral triethoxysilyl groups. The resultant gel prepared according to this flowchart has gained a very high thermal stability as well as a unique mechanical strength. PMID:15898763

  19. The Role of Porphyrin-Free-Base in the Electronic Structures and Related Properties of N-Fused Carbazole-Zinc Porphyrin Dye Sensitizers

    Directory of Open Access Journals (Sweden)

    Xing-Yu Li

    2015-11-01

    Full Text Available Dye sensitizers can significantly affect power conversion efficiency of dye-sensitized solar cells (DSSCs. Porphyrin-based dyes are promising sensitizers due to their performances in DSSCs. Here, based upon a N-fused carbazole-zinc porphyrin-free-base porphyrin triad containing an ethynyl-linkage (coded as DTBC, the novel porphyrin dyes named DTBC-MP and DTBC-TP were designed by varying the porphyrin-free-base units in the π conjugation of DTBC in order to study the effect of porphyrin-free-base in the modification of electronic structures and related properties. The calculated results indicate that, the extension of the conjugate bridge with the porphyrin-free-base unit results in elevation of the highest occupied molecular orbital (HOMO energies, decrease of the lowest unoccupied molecular orbital (LUMO energies, reduction of the HOMO-LUMO gap, red-shift of the absorption bands, and enhancement of the absorbance. The free energy changes demonstrate that introducing more porphyrin-free-base units in the conjugate bridge induces a faster rate of electron injection. The transition properties and molecular orbital characters suggest that the different transition properties might lead to a different electron injection mechanism. In terms of electronic structure, absorption spectra, light harvesting capability, and free energy changes, the designed DTBC-TP is a promising candidate dye sensitizer for DSSCs.

  20. Photophysical properties of novel Porphyrin-Flavin Dyads

    International Nuclear Information System (INIS)

    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

  1. Photosynthetic reaction center mimicry of a "special pair" dimer linked to electron acceptors by a supramolecular approach: self-assembled cofacial zinc porphyrin dimer complexed with fullerene(s).

    Science.gov (United States)

    D'Souza, Francis; Chitta, Raghu; Gadde, Suresh; Rogers, Lisa M; Karr, Paul A; Zandler, Melvin E; Sandanayaka, Atula S D; Araki, Yasuyaki; Ito, Osamu

    2007-01-01

    Biomimetic bacterial photosynthetic reaction center complexes have been constructed using well-defined self-assembled supramolecular approaches. The "special pair" donor, a cofacial porphyrin dimer, was formed via potassium ion induced dimerization of meso-(benzo-[15]crown-5)porphyrinatozinc. The dimer was subsequently self-assembled with functionalized fullerenes via axial coordination and crown ether-alkyl ammonium cation complexation to form the donor-acceptor pairs, mimicking the noncovalently bound entities of the photosynthetic reaction center. The adopted self-assembly methodology yielded supramolecular complexes of higher stability, with defined geometry and orientation. Efficient forward electron transfer from the singlet excited zinc porphyrin dimer to the fullerene entity and relatively slow reverse electron transfer, important steps in the photosynthetic light energy conversion have been achieved in these novel biomimetic model systems. PMID:17066393

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

    OpenAIRE

    Lin Wu; Ronan McHale; Guoqiang Feng; Xiaosong Wang

    2011-01-01

    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-PDMA)4 and P-(PDMA-PS)4 (...

  3. Differential localization and potency of manganese porphyrin superoxide dismutase-mimicking compounds in Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    Alice Ma Li

    2014-01-01

    Full Text Available Cationic Mn(III porphyrin complexes based on MnTM-2-PyP are among the most promising superoxide dismutase (SOD mimicking compounds being considered as potential anti-inflammatory drugs. We studied four of these active compounds in the yeast Saccharomyces cerevisiae, MnTM-2-PyP, MnTE-2-PyP, MnTnHex-2-PyP, and MnTnBu-2-PyP, each of which differs only in the length of its alkyl substituents. Each was active in improving the aerobic growth of yeast lacking SOD (sod1∆ in complete medium, and the efficacy of each mimic was correlated with its characteristic catalytic activity. We also studied the partitioning of these compounds between mitochondria and cytosol and found that the more hydrophobic members of the series accumulated in the mitochondria. Moreover, the degree to which a mimic mitigated the sod1Δ auxotrophic phenotype for lysine relative to its auxotrophic phenotype for methionine depended upon its level of lipophilicity-dependent accumulation inside the mitochondria. We conclude that localization within the cell is an important factor in biological efficacy in addition to the degree of catalytic activity, and we discuss possible explanations for this effect.

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

    Directory of Open Access Journals (Sweden)

    Eugenia Fagadar-Cosma

    2010-09-01

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

  5. Stepwise transformation of the molecular building blocks in a porphyrin-encapsulating metal-organic material

    KAUST Repository

    Zhang, ZhenJie

    2013-04-24

    When immersed in solutions containing Cu(II) cations, the microporous metal-organic material P11 ([Cd4(BPT)4]·[Cd(C 44H36N8)(S)]·[S], BPT = biphenyl-3,4′,5-tricarboxylate) undergoes a transformation of its [Cd 2(COO)6]2- molecular building blocks (MBBs) into novel tetranuclear [Cu4X2(COO)6(S) 2] MBBs to form P11-Cu. The transformation occurs in single-crystal to single-crystal fashion, and its stepwise mechanism was studied by varying the Cd2+/Cu2+ ratio of the solution in which crystals of P11 were immersed. P11-16/1 (Cd in framework retained, Cd in encapsulated porphyrins exchanged) and other intermediate phases were thereby isolated and structurally characterized. P11-16/1 and P11-Cu retain the microporosity of P11, and the relatively larger MBBs in P11-Cu permit a 20% unit cell expansion and afford a higher surface area and a larger pore size. © 2013 American Chemical Society.

  6. Antibacterial effect of cationic porphyrazines and anionic phthalocyanine and their interaction with plasmid DNA

    Science.gov (United States)

    Hassani, Leila; Hakimian, Fatemeh; Safaei, Elham; Fazeli, Zahra

    2013-11-01

    Resistance to antibiotics is a public health issue and identification of new antibacterial agents is one of the most important goals of pharmacological research. Among the novel developed antibacterial agents, porphyrin complexes and their derivatives are ideal candidates for use in medical applications. Phthalocyanines differ from porphyrins by having nitrogen atoms link the individual pyrrol units. The aza analogues of the phthalocyanines (azaPcs) such as tetramethylmetalloporphyrazines are heterocyclic Pc analogues. In this investigation, interaction of an anionic phthalocyanine (Cu(PcTs)) and two cationic tetrapyridinoporphyrazines including [Cu(2,3-tmtppa)]4+ and [Cu(3,4-tmtppa)]4+ complexes with plasmid DNA was studied using spectroscopic and gel electrophoresis methods. In addition, antibacterial effect of the complexes against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria was investigated using dilution test method. The results indicated that both porphyrazines have significant antibacterial properties, but Cu(PcTs) has weak antibacterial effect. Compairing the binding of the phthalocyanine and the porphyrazines to DNA demonstrated that the interaction of cationic porphyrazines is stronger than the anionic phthalocyanine remarkably. The extent of hypochromicity and red shift of absorption spectra indicated preferential intercalation of the two porphyrazine into the base pairs of DNA helix. Gel electrophoresis result implied Cu(2,3-tmtppa) and Cu(3,4-tmtppa) are able to perform cleavage of the plasmid DNA. Consequently, DNA binding and cleavage might be one of the antibacterial mechanisms of the complexes.

  7. Synthesis and Characterization of One-dimensional and Two-Dimensional Porphyrin Polymers* (

    Institute of Scientific and Technical Information of China (English)

    LI; Xiang-qing

    2001-01-01

    Porphyrin polymers are of interest in relation to conductive materials[1, 2], catalysts for  photosynthetic charge separation[3], or the fundamental features in biological systems[4].There have been many versatile studies about them[5,6]. The one-dimensional “Shish Kebab”porphyrin polymers synthesized with a new method different from those reported and Schiff base porphyrin polymers with two-dimensional nano-structure have provided a new field of study. The present paper covers highly ordered porphyrin polymers.……

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

    International Nuclear Information System (INIS)

    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 B9C2 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

  9. Characterization of designed cobaltacarborane porphyrins using conductive probe atomic force microscopy

    Directory of Open Access Journals (Sweden)

    Venetia D. Lyles

    2016-03-01

    Full Text Available Porphyrins and metalloporphyrins have unique chemical and electronic properties and thus provide useful model structures for studies of nanoscale electronic properties. The rigid planar structures and -conjugated backbones of porphyrins convey robust electrical characteristics. For our investigations, cobaltacarborane porphyrins were synthesized using a ring-opening zwitterionic reaction to produce isomers with selected arrangements of carborane clusters on each macrocycle. Experiments were designed to investigate how the molecular structure influences the self-organization, surface assembly, and conductive properties of three molecular structures with 2, 4, or 8 cobaltacarborane substituents. Current versus voltage (I-V spectra for designed cobaltacarborane porphyrins deposited on conductive gold substrates were acquired using conductive probe atomic force microscopy (CP-AFM. Characterizations with CP-AFM provide capabilities for obtaining physical measurements and structural information with unprecedented sensitivity. We found that the morphology of cobaltacarborane porphyrin structures formed on surfaces depends on a complex interplay of factors such as the solvent used for dissolution, the nature of the substrate, and the design of the parent molecule. The conductive properties of cobaltacarborane porphyrins were observed to change according to the arrangement of cobaltacarborane substituents. Specifically, the number and placement of the cobaltacarborane ligands on the porphyrin macrocycle affect the interactions that drive porphyrin self-assembly and crystallization. Interestingly, coulombic staircase I-V profiles were detected for a porphyrin with two cobaltacarborane substituents.

  10. Cationic Antimicrobial Peptide Cytotoxicity

    OpenAIRE

    Laverty, Garry; Gilmore, Brendan

    2014-01-01

    Fluorescence microscopy serves as a valuable tool for assessing the structural integrity and viability of eukaryotic cells. Through the use of calcein AM and the DNA stain 4,6-diamidino-2 phenylindole (DAPI), cell viability and membrane integrity can be qualified. Our group has previously shown the ultra-short cationic antimicrobial peptide H-OOWW-NH2; the amphibian derived 27-mer peptide Maximin-4and the ultra-short lipopeptide C12-OOWW-NH2 to be effective against a range of bacterial biofil...

  11. Spatially resolved micro-photoluminescence imaging of porphyrin single crystals

    Science.gov (United States)

    Marin, Dawn M.; Castaneda, Jose; Kaushal, Meesha; Kaouk, Ghallia; Jones, Daniel S.; Walter, Michael G.

    2016-08-01

    We describe the collection of both time-resolved and steady-state micro-photoluminescence data from solution-grown single crystals of 5,15-bis(4-carbomethoxyphenyl)porphyrin (BCM2PP). Linking molecular orientation and structure with excited-state dynamics is crucial for engineering efficient organic solar cells, light-emitting diodes, and related molecular electronics. Photoluminescence features of single porphyrin crystals were imaged using a laser scanning confocal microscope equipped with time-correlated single photon counting (TCSPC). We show enhanced exciton lifetimes (τs1 = 2.6 ns) and stronger steady-state emission in crystalline BCM2PP samples relative to semicrystalline thin films (τs1 = 1.8 ns).

  12. Site-isolated porphyrin catalysts in imprinted polymers.

    Science.gov (United States)

    Burri, Estelle; Ohm, Margarita; Daguenet, Corinne; Severin, Kay

    2005-08-19

    A meso-tetraaryl ruthenium porphyrin complex having four polymerizable vinylbenzoxy groups (2) has been synthesized by reaction of pyrrole with 4-(vinylbenzoxy)benzaldehyde and subsequent metalation with [Ru3(CO)12]. The porphyrin complex was immobilized by copolymerization with ethylene glycol dimethacrylate. The resulting polymer P2 was found to catalyze the oxidation of alcohols and alkanes with 2,6-dichloropyridine N-oxide without activation by mineral acids. Under similar conditions, the homogeneous catalyst 2 was completely inefficient. By using diphenylaminomethane and 1-aminoadamantane as coordinatively bound templates during the polymerization procedure, the molecularly imprinted polymers P3 and P4 have been synthesized. Compared with the polymer P2, the imprinted catalysts displayed a significantly increased activity with rate enhancements of up to a factor of 16. PMID:15977282

  13. Layered double hydroxides with intercalated porphyrin as photofuncional materials

    Czech Academy of Sciences Publication Activity Database

    Lang, Kamil; Kubát, Pavel; Mosinger, Jiří; Bujdák, J.; Káfuňková, Eva; Kovanda, F.

    Bad Hofgastein : Graz University of Technology, 2008. s. 59. [Central European Conference on Photochemistry. 10.02.2008-14.02.2008, Bad Hofgastein] R&D Projects: GA ČR(CZ) GA203/06/1244; GA ČR GA203/07/1424 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : porphyrin Subject RIV: CA - Inorganic Chemistry

  14. Photoactive materials based on porphyrin / layered double hydroxide hybrid films

    Czech Academy of Sciences Publication Activity Database

    Bujdák, J.; Lang, Kamil; Iyi, N.

    Tours : UK Centre for Materials Education, 2009. B2.1.16. [International Conference on Multifunctional, Hybrid and Nanomaterials /1./. 15.03.2009-19.03.2009, Tours] R&D Projects: GA ČR(CZ) GA203/06/1244 Institutional research plan: CEZ:AV0Z40320502 Keywords : porphyrin * photochemistry * layered double hydroxide Subject RIV: CA - Inorganic Chemistry www.hybridmaterialsconference.com

  15. How intercalated porphyrins in layered double hydroxides produce singlet oxygen

    Czech Academy of Sciences Publication Activity Database

    Lang, Kamil; Káfuňková, Eva; Kovanda, F.; Taviot-Guého, Ch.

    Tours : UK Centre for Materials Education, 2009. B2.1.62. [International Conference on Multifunctional, Hybrid and Nanomaterials /1./. 15.03.2009-19.03.2009, Tours] R&D Projects: GA ČR(CZ) GA203/06/1244; GA AV ČR KAN100500651 Institutional research plan: CEZ:AV0Z40320502 Keywords : layered double hydroxides * porphyrin * singlet oxygen Subject RIV: CA - Inorganic Chemistry www.hybridmaterialsconference.com

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

    Science.gov (United States)

    Jin, Cheng S.

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

  17. Design and Investigation of Novel Porphyrin(oid) Conjugate Systems

    OpenAIRE

    Biedermann, Miriam

    2013-01-01

    Within the first part of this thesis novel water-soluble donor-acceptor arrays built up by porphyrins and pyrene or perylene derivatives were designed via a copper(I)-catalysed 1,3-dipolar azide-alkyne cycloaddition reaction. For this purpose, suitable precursors, which were available by well-established synthetic literature procedures, were combined with newly developed complementary “click” counterparts. Thus, also the substance library of ortho-benzylic functionalised tetraarylporphyrins w...

  18. Optical Biosensors with Porphyrins Immobilized into Polysilsesquioxane Matrices

    Czech Academy of Sciences Publication Activity Database

    Rychtáriková, Renata; Kuncová, Gabriela; Šabata, Stanislav; Hetflejš, Jiří; Šviráková, E.

    - : -, 2007, P3-06 /1/ -P3-06 /4/. [International Workshop on Bioencapsulation /15./. Vienna (AT), 06.09.2007-08.09.2007] R&D Projects: GA ČR(CZ) GA104/05/2637; GA ČR(CZ) GA203/06/1244; GA MŠk OC 121 Institutional research plan: CEZ:AV0Z40720504 Keywords : biosensor * porphyrin Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  19. Light harvesting with non covalent carbon nanotube / porphyrin compounds.

    OpenAIRE

    Roquelet, Cyrielle; Langlois, Benjamin; Vialla, Fabien; Garrot, Damien; Lauret, Jean-Sébastien; Voisin, Christophe

    2013-01-01

    We present recent developments in the synthesis and in the functional study of non covalently bound porphyrin/carbon nanotube compounds. The issue of the chemical stability of non covalent compounds is tackled by means of micelle assisted chemistry. The non covalent functionalization allows to preserve the electronic integrity of the nanotubes that display bright NIR luminescence. In the same time, the coupling between the subunits is very strong and leads to e cient energy transfer and PL qu...

  20. Supramolecular complex composed of a covalently linked zinc porphyrin dimer and fulleropyrrolidine bearing two axially coordinating pyridine entities.

    Science.gov (United States)

    D'Souza, Francis; Gadde, Suresh; Zandler, Melvin E; Itou, Mitsunari; Araki, Yasuyuki; Ito, Osamu

    2004-10-21

    A zinc porphyrin dimer-fullerene supramolecular complex with a large association constant is assembled; efficient intramolecular photoinduced electron transfer from the singlet excited state of zinc porphyrin to the fullerene is observed. PMID:15489978

  1. Plasmon enhanced photoconduction in porphyrin-gold nanoparticle assemblies

    Science.gov (United States)

    Conklin, David J.

    2011-07-01

    This thesis describes a series of experiments to both determine the origins of charge transport and enhanced photoconduction in metal nanoparticle arrays linked with zinc-porphyrin complexes, but to also determine the nucleation and growth mechanisms related to Ferroelectric Nanolithography (FNL) as a platform for hybrid devices. The development of test structures on glass substrates was undertaken to not only allow the study of the mechanisms controlling charge transport but the photoconduction of zinc-porphyrin linked gold nanoparticle (AuNP) arrays. In this study, the dominate charge transport mechanism was determined to be thermally assisted tunneling and the origins of enhanced photoconduction in these systems was attributed to three mechanisms: direct exciton formation in the molecules, hot electrons and a field effect (optical antenna) due to the excitation of surface plasmons. In the hope of developing a platform for hybrid devices, FNL was utilized to systematically vary the parameters that effect the deposition of metal nanoparticles through domain directed deposition on ferroelectric surfaces. The nucleation and growth mechanisms were determined through this work, where the integrated photon flux controlled the particle density and the interface between the particle and the ferroelectric surface determined the particles size. Finally, with the ability to control the deposition of AuNPs on a ferroelectric surface, hybrid devices of zinc-porphyrin linked AuNPs were realized with FNL.

  2. (99m)Tc-labeled porphyrin-lipid nanovesicles.

    Science.gov (United States)

    Lee, Jae-Ho; Shao, Shuai; Cheng, Kenneth T; Lovell, Jonathan F; Paik, Chang H

    2015-01-01

    Porphyrin-lipid nanovesicles (PLN) have been developed with intrinsic capabilities as activatable multimodal photonic contrast agents. Radiolabeling of PLN encapsulating drugs could eventually be able to provide quantitative in vivo information for diagnosing and treating diseases. In this study, we developed (99m)Tc-labeled porphyrin-lipid nanovesicles ((99m)Tc-PLN) as a cargo-encapsulated formulation without significant impact on liposome integrity and encapsulation stability. 50 mM calcein was encapsulated into PLN by probe sonication. The size of the PLN was about 150 nm. The PLN were then reacted with (99m)Tc using SnCl2 dissolved in 1 mM HCl as a reducing agent and incubated for 10 min at 22 °C. The radiolabeling efficiency and stability of (99m)Tc-PLN were evaluated by instant thin-layer chromatography and low-pressure liquid chromatography (LPLC). (99m)Tc labeling was successful with a >92% labeling efficiency. LPLC showed that the liposomal elution peaks of the porphyrin-lipid and the calcein overlapped with the radioactivity elution peak of (99m)Tc-labeled PLN. The (99m)Tc-labeling procedure did not change the size of PLN. Encapsulated calcein remained inert inside PLN. Thus, this work lays out a simple and effective radiolabeling method using SnCl2 in HCl in the preparation of (99m)Tc-PLN. PMID:24963601

  3. Highly Stable Mesoporous Zirconium Porphyrinic Frameworks with Distinct Flexibility.

    Science.gov (United States)

    Xu, Lei; Luo, Yan-Ping; Sun, Lin; Xu, Yan; Cai, Zhong-Sheng; Fang, Min; Yuan, Rong-Xin; Du, Hong-Bin

    2016-04-25

    The construction of highly stable metal-porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light-harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal-porphyrinic framework (denoted as NUPF-1) and its catalytic properties. NUPF-1 is constructed from a new porphyrin linker and a Zr6 O8 structural building unit, possessing an unprecedented doubly interpenetrating scu net. The structure exhibits not only remarkable chemical and thermal stabilities, but also a distinct structural flexibility, which is seldom seen in metal-organic framework (MOF) materials. By the merit of high chemical stability, NUPF-1 could be easily post-metallized with [Ru3 (CO)12 ], and the resulting {NUPF-1-RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp(3) )-H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved. PMID:26960623

  4. Synthesis of o- and m-carborane derivatives of 5,10,15,20-tetra-(p-anionphenyl)porphyrin

    International Nuclear Information System (INIS)

    The data on synthesis of o- and m-carborane-containing porphyrins, which derivatives through boron atom of polyhedral nucleus are presented. The reaction of the porphyrin amino group acylation may be used for production of the porphyrin carborane derivative with high boron content (up to 30 %) with the purpose of applying them in boron neutron-capture cancer therapy

  5. Air oxidation of the kerogen/asphaltene vanadyl porphyrins: an electron spin resonance study

    Directory of Open Access Journals (Sweden)

    MIRJANA S. PAVLOVIC

    2000-02-01

    Full Text Available The thermal behavior of vanadyl porphyrins was studied by electron spin resonance during heating of kerogens, isolated from the La Luna (Venezuela and Serpiano (Switzerland bituminous rocks, at 25°C for 1 to 20 days in the presence of air. During the thermal treatment of the kerogens, the vanadyl porphyrins resonance signals decrease monotonically and become quite small after 6 days of heating. Concomitantly, new vanadyl signals appear and, at longer heating times, dominate the spectrum. It is suggested that the secondary vanadyl species must have been formed from vanadyl porphyrins. Similar conversions of vanadyl porphyrins are observed under the same experimental conditions for asphaltenes extracted from the La Luna and Serpiano rocks, and floating asphalt from the Dead Sea (Israel. A comparison of the spin-Hamiltonian parameters for vanadyl porphyrins and the vanadyl compounds obtained during pyrolysis of the kerogens/asphaltenes suggests that the latter are of a non-porphyrin type. For comparison a study was conducted on Western Kentucky No. 9 coal enriched with vanadium (>>400 ppm from six mines. All the coal samples show only the presence of predominant by non-porphyrin vanadyl compounds, similar to those generated through laboratory heating of the kerogens/asphaltenes in air. In addition, some samples also contain a minor amount of vanadyl porphyrins.

  6. Palladium-Catalyzed Polyfluorophenylation of Porphyrins with Bis(polyfluorophenylzinc Reagents

    Directory of Open Access Journals (Sweden)

    Toshikatsu Takanami

    2013-10-01

    Full Text Available A facile and efficient method for the synthesis of pentafluorophenyl- and related polyfluorophenyl-substituted porphyrins has been achieved via palladium-catalyzed cross-coupling reactions of brominated porphyrins with bis(polyfluorophenylzinc reagents. The reaction is applicable to a variety of free-base bromoporphyrins, their metal complexes, and a number of bis(polyfluorophenylzinc reagents.

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

    International Nuclear Information System (INIS)

    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)

  8. 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

    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...

  9. Liquid chromatography of urinary porphyrins for the biological monitoring of occupational exposure to porphyrinogenic substances

    Energy Technology Data Exchange (ETDEWEB)

    Colombi, A.; Maroni, M.; Ferioli, A.; Valla, C.; Coletti, G.; Foa, V.

    1983-01-01

    Very sensitive and precise analytical methods for measuring total porphyrin excretion and the relative amounts of different porphyrins in urine are required in order to monitor the biological effects of porphyrinogenic substances in workers and the general population. Many analytical steps of a HPLC method for measuring porphyrins as methyl esters in urine have been perfected. Sensitivity is 0.1 microgram/1 for each type of porphyrin, and average recovery is 92% in the range of 50-450 micrograms/liter porphyrins. The coefficient of variation is 3.4% within a series and 12.5% between series. Chemical oxidation before analysis and appropriate storing of the samples are the key points in achieving high quality results. The urinary excretion of porphyrins in healthy male workers varies within the range 21 to 161 micrograms/liter (95% limits of a group of 78 subjects). Concomitant factors, like drug use or liver disorders, were found to alter urinary porphyrin excretion. The proposed method permits the detection of extremely small alterations in porphyrin excretion resulting from occupational exposure to industrial chemicals such as, for example, mild coproporphyrinuria or early stages of chemical porphyria induced by polyhalogenated arylhydrocarbons.

  10. Characterisation of nanohybrids of porphyrins with metallic and semiconducting carbon nanotubes by EPR and optical spectroscopy.

    Science.gov (United States)

    Cambré, Sofie; Wenseleers, Wim; Culin, Jelena; Van Doorslaer, Sabine; Fonseca, Antonio; Nagy, Janos B; Goovaerts, Etienne

    2008-09-15

    Single-walled carbon nanotubes (SWCNTs) are noncovalently functionalised with octaethylporphyrins (OEPs) and the resulting nanohybrids are isolated from the free OEPs. Electron paramagnetic resonance (EPR) spectroscopy of cobalt(II)OEP, adsorbed on the nanotube walls by pi-pi-stacking, demonstrates that the CNTs act as electron acceptors. EPR is shown to be very effective in resolving the different interactions for metallic and semiconducting tubes. Moreover, molecular oxygen is shown to bind selectively to nanohybrids with semiconducting tubes. Water solubilisation of the porphyrin/CNT nanohybrids using bile salts, after applying a thorough washing procedure, yields solutions in which at least 99% of the porphyrins are interacting with the CNTs. Due to this purification, we observe, for the first time, the isolated absorption spectrum of the interacting porphyrins, which is strongly red-shifted compared to the free porphyrin absorption. In addition a quasi-complete quenching of the porphyrin fluorescence is also observed. PMID:18712730

  11. Absorption and fluorescence properties of aryl substituted porphyrins in different media

    Science.gov (United States)

    Bozkurt, Serap Seyhan; Merdivan, Melek; Ayata, Sevda

    2010-02-01

    Absorption and fluorescence properties of aryl substituted porphyrins, 5,10,15,20-tetra-4-oxy(aceticacid)phenylporphyrin (TAPP), 5,10,15,20-tetra-(4-phenoxyphenyl) porphyrin (TPPP), 5,10,15,20-tetra-(3-bromo-4-hydroxyphenyl) porphyrin (TBHPP), and 5,10,15,20-tetra-p-chloromethylphenyl porphyrin (CMPP) were investigated. The UV/vis absorption, fluorescence and excited spectra as the fluorescence quantum yields and fluorescence lifetimes for the compounds were measured in organic solvents (chloroform (CHCl 3), tetrahydrofuran (THF)) and immobilized media (PVC film, sol-gel matrix). The fluorescence quantum yields of TAPP and TPPP were higher than the others. The fluorescence lifetimes of all studied porphyrin derivates were found to be fifty percent lower and their fluorescence intensities were increased fifty percent more in both of immobilized mediums, as compared to organic solvents.

  12. Photochromic system of an acid-sensing porphyrin; Sankan`osei porufuirin no hotokuromizumu

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, K.; Okumura, H.; Deguchi, M.; Iwata, S. [Seikei Univ., Musashino, Tokyo (Japan)

    1998-07-10

    The photochromism of porphyrin caused by addition and elimination of hydrogen chloride generated by the photodegradation of a solvent is investigated. The effects of solvents and porphyrin substituents on the photochromism are examined. The experiments show that 50% 2-chloroethanol/ethyl acetate is suitable as solvent because of quick generation of hydrogen chloride by photoirradiation and the facile abstraction of hydrogen chloride from porphyrin hydrochloride upon heating. Among examined porphyrins, 5,10,15,20-tetrakis(4-trifluoromethylphenyl)porphyrin (CF3TPP) is found to be fitted because of its sufficient light resistance. The photochromic system composed of CF3TPP and 50% 2-chloroethanol/ethyl acetate reveals to be stable to the repeated addition and abstraction of hydrogen chloride by irradiation and heating. 8 refs., 5 figs., 1 tab.

  13. Out-of-Plane Coordinated Porphyrin Nanotubes with Enhanced Singlet Oxygen Generation Efficiency.

    Science.gov (United States)

    Zhao, Qiang; Wang, Yao; Xu, Yanshuang; Yan, Yun; Huang, Jianbin

    2016-01-01

    A supramolecular porphyrin nanotube displaying J-aggregation feature was constructed by out-of-plane coordinated bismuth-porphyrin. Significantly, compared to traditional J-aggregated porphyrin suffering from fluorescence and singlet oxygen quenching, the nanotube exhibits excellent bio-imaging ability and enhanced production efficiency of singlet oxygen. The out-of-plane structure of bismuth to porphyrin makes the aggregation an appropriate material for theranostics. Furthermore, it is also a potential radio-therapeutic drug owing to the presence of radio-active bismuth. Thus, the self-assembly of out-of-plane coordinated porphyrin can be a facile approach toward effective therapy of tumors and other diseases. PMID:27527403

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  15. Ion exchange behaviour of polymeric zirconium cations

    International Nuclear Information System (INIS)

    Polymeric zirconium cations formed in weakly acid solutions (pH2) are taken up strongly into macroporous cation exchange resins, while uptake into normal cation exchange resins (pore diameter about 1 nm) is low. Macroporous cation exchange resins loaded with polymeric Zr cations are shown to function as ligand exchange sorbents. (Authors)

  16. 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 ostatní: 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

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

    Czech Academy of Sciences Publication Activity Database

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

    2013-01-01

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

  18. The effect on photohaemolysis of variation in the structure of the porphyrin photosensitizer.

    Science.gov (United States)

    de Paolis, A; Chandra, S; Charalambides, A A; Bonnett, R; Magnus, I A

    1985-01-01

    A comparison of the photosensitizing ability of a variety of porphyrins for photohaemolysis gives the following order of activity: protoporphyrin greater than deuteroporphyrin, mesoporphyrin, haematoporphyrin dimethyl ester much greater than haematoporphyrin diacetate, haematoporphyrin greater than haematoporphyrin monoacetate, coproporphyrin III, haematoporphyrin derivative, coproporphyrin III tetramethyl ester greater than uroporphyrin I, meso-tetra-(N-methyl-4-pyridinium)porphyrin tetratoluene-p-sulphonate, meso-tetra-(p-carboxyphenyl)porphyrin, protoporphyrin dimethyl ester, meso-tetra-(p-hydroxy-sulphonylphenyl)porphyrin tetrasodium salt, uroporphyrin III, deuteroporphyrin-3,8-disulphonic acid and protohaemin. The results for the metal-free porphyrins are rationalized in terms of solubility and partition properties, and a model is proposed for the incorporation of amphipathic porphyrins into the membrane lipid bilayer. Experiments with erythrocytes from patients with erythropoeitic protoporphyria and with normal erythrocytes to which porphyrin was added in a deuterium oxide medium do not lead to an increase in the rate of photohaemolysis. A possible explanation for this somewhat surprising observation is outlined. PMID:2985045

  19. Electronic Structure and Absorption Properties of Strongly Coupled Porphyrin-Perylene Arrays.

    Science.gov (United States)

    High, Judah S; Virgil, Kyle A; Jakubikova, Elena

    2015-09-24

    Porphyrin-perylene arrays are ideal candidates for light-harvesting systems capable of panchromatic absorption. In this work, we employ density functional theory (DFT) and time-dependent DFT to investigate the unique UV-vis absorption properties exhibited by a series of ethynyl-linked porphyrin-perylene arrays that were previously synthesized and characterized spectroscopically [Chem. Commun. 2014, 50, 14512-5]. We find that the ethynyl linker is responsible for strong electronic coupling of porphyrin and perylene subunits in these systems. Additionally, these arrays exhibit a low barrier to rotation around the ethynyl linker (<1.4 kcal/mol per one perylene substituent), which results in a wide range of molecular conformations characterized by different porphyrin-perylene dihedral angles being accessible at room temperature. The best match between the calculated and experimental UV-vis spectra is obtained by averaging the calculated UV-vis spectra over the range of conformations defined by the porphyrin-perylene dihedral angles. Finally, our calculations suggest that the transitions in the lower energy region (550-750 nm) can be assigned to the excitations originating from the porphyrin subunit; the mid-energy region transitions (450-550 nm) are assigned to the perylene-centered excitations, while the high-energy transitions (350-450 nm) involve contributions from both porphyrin and perylene subunits. PMID:26322743

  20. Masked imidazolyl-dipyrromethanes in the synthesis of imidazole-substituted porphyrins.

    Science.gov (United States)

    Bhaumik, Jayeeta; Yao, Zhen; Borbas, K Eszter; Taniguchi, Masahiko; Lindsey, Jonathan S

    2006-11-10

    Imidazole-substituted metalloporphyrins are valuable for studies of self-assembly and for applications where water solubility is required. Rational syntheses of porphyrins bearing one or two imidazol-2-yl or imidazol-4-yl groups at the meso positions have been developed. The syntheses employ dipyrromethanes, 1-acyldipyrromethanes, and 1,9-diacyldipyrromethanes bearing an imidazole group at the 5-position. The polar, reactive imidazole unit was successfully masked by use of (1) the 2-(trimethylsilyl)ethoxymethyl (SEM) group at the imidazole pyrrolic nitrogen, and (2) a dialkylboron motif bound to the pyrrole of the dipyrromethane and coordinated to the imidazole imino nitrogen. The nonpolar nature of such doubly masked imidazolyl-dipyrromethanes facilitated handling. Selected masked dipyrromethanes were characterized by 11B and 15N NMR spectroscopy. Five distinct methods were examined to obtain trans-A2B2-, trans-AB2C-, and trans-AB-porphyrins. Each porphyrin contained one or two SEM-protected imidazole units. The SEM group could be removed with TBAF or HCl. Two zinc(II) porphyrins and a palladium(II) porphyrin bearing a single imidazole moiety were prepared and subjected to alkylation (with ethyl iodide, 1,3-propane sultone, or 1,4-butane sultone) to give water-soluble imidazolium- porphyrins. This work establishes the foundation for the rational synthesis of a variety of porphyrins containing imidazole units. PMID:17081010

  1. Magnetic and electronic properties of porphyrin-based molecular nanowires

    Directory of Open Access Journals (Sweden)

    Jia-Jia Zheng

    2016-01-01

    Full Text Available Using spin-polarized density functional theory calculations, we performed theoretical investigations on the electronic and magnetic properties of transition metal embedded porphyrin-based nanowires (TM-PNWs, TM = Cr, Mn, Co, Ni, Cu, and Zn. Our results indicate that Ni-PNW and Zn-PNW are nonmagnetic while the rest species are magnetic, and the magnetic moments in TM-PNWs and their corresponding isolated monomer structures are found to be the same. In addition, the spin coupling in the magnetic nanowires can be ignored leading to their degenerate AFM and FM states. These results can be ascribed to the weak intermetallic interactions because of the relatively large distances between neighbor TM atoms. Among all TM-PNW structures considered here, only Mn-PNW shows a half-metallic property while the others are predicted to be semiconducting. The present work paves a new way of obtaining ferromagnetic porphyrin-based nanowires with TM atoms distributed separately and orderly, which are expected to be good candidates for catalysts, energy storage and molecular spintronics.

  2. Free Base Porphyrins as Ionophores for Heavy Metal Sensors

    Directory of Open Access Journals (Sweden)

    Liliana Olenic

    2008-08-01

    Full Text Available Two functionalized porphyrins: 5,10,15,20-tetrakis(3,4-dimethoxyphenyl porphyrin (A and 5,10,15,20-tetrakis(3-hydroxyphenylporphyrin (B obtained and characterized by us were used as ionophores (I for preparing PVC-based membrane sensors selective to Ag+, Pb2+ and Cu2+. The membranes were prepared using three different plasticizers: (bis(2-ethylhexylsebacate (DOS, dioctylphtalate (DOP, o-nitrophenyl octyl ether (NPOE and potassium tetrakis(4-chlorophenylborate (KTClPB as additive. The functional parameters (linear concentration range, slope and selectivity of the sensors with membrane composition: (I:PVC:KTClPB:Plasticizer in different ratios were investigated. The best results were obtained for the membranes in the ratio I:PVC:KTClPB:Plasticizer 10:165:5:330. The influence of pH on the sensors response was studied. The sensors were used for a period of four months and their utility has been tested on synthetic and real samples.

  3. Charge transfer energies of tetraphenyl-porphyrin-fullerene dyads

    Science.gov (United States)

    Zope, Rajendra; Olguin, Marco; Baruah, Tunna

    2011-03-01

    Porphyrin-fullerene dyads are extensively studied for their photoinduced charge transfer properties. They form a donor-acceptor pair where the fullerene is the acceptor. Accurate theoretical estimate of the charge transfer energies in such systems has proven to be a challenge. In this study we examine the charge transfer energetics for such dyads using our recently developed density functional based excited state method which can yield reliable estimates of charge transfer energetics. In this study the effect of varying both the donor and acceptor components are studied by changing the tetra-phenyl-porphyrin (TPP) to Zn-TPP. Similarly the acceptor component is changed from C60 to C70. The structures were optimized using DFT-D3 theory at the all-electron level. Among the donor-acceptor pairs studied, we find that the ZnTPP-C60 has the lowest charge transfer energy (1.69 eV) and the TPP-C70 (2.13 eV) has the highest charge transfer energy. Supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences of the US Department of Energy through grant DE-SC0002168.

  4. Electron transfer reactions involving porphyrins and chlorophyll a

    International Nuclear Information System (INIS)

    Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H2TPP), its tetracarboxy derivative (H2TCPP), the sodium and zinc compounds (Na2TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH3)2CO-. Reduction by (CH3)2COH 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 H2TCPP-., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H2TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 107-109 M-1 s-1 which depend on the pH and the quinone reduction potential. Reactions of Na2TPP-., ZnTPP-., and Chl a-. with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 109 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

  5. 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)

  6. Surface-confined Ullmann coupling of thiophene substituted porphyrins

    Science.gov (United States)

    Beggan, J. P.; Boyle, N. M.; Pryce, M. T.; Cafolla, A. A.

    2015-09-01

    The covalent coupling of (5,10,15,20-tetrabromothien-2-ylporphyrinato)zinc(II) (TBrThP) molecules on the Ag(111) surface has been investigated under ultra-high-vacuum conditions, using scanning tunnelling microscopy and x-ray photoelectron spectroscopy. The findings provide atomic-level insight into surface-confined Ullmann coupling of thiophene substituted porphyrins, analyzing the progression of organometallic intermediate to final coupled state. Adsorption of the TBrThP molecules on the Ag(111) surface at room temperature is found to result in the reductive dehalogenation of the bromothienyl substituents and the subsequent formation of single strand and crosslinked coordination networks. The coordinated substrate atoms bridge the proximal thienyl groups of the organometallic intermediate, while the cleaved bromine atoms are bound on the adjacent Ag(111) surface. The intermediate complex displays a thermal lability at ˜423 K that results in the dissociation of the proximal thienyl groups with the concomitant loss of the surface bound bromine. At the thermally induced dissociation of the intermediate complex the resultant thienylporphyrin derivatives covalently couple, leading to the formation of a polymeric network of thiophene linked and meso-meso fused porphyrins.

  7. Toxicity of polychlorinated biphenyl with special reference to porphyrin metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Sano, S.; Kawanishi, S.; Seki, Y.

    1985-02-01

    Oral administration of a commercial PCB mixture to chickens caused a hepatic-type porphyria characterized by hepatic accumulation and urinary excretion of uroporphyrin. To clarify the mechanism of the porphyrinogenic activity of these PCBs, the authors studied the structural requirement of synthetic PCB for porphyrinogenic activities by using the cultured chick embryo liver cells and examined the relationship between induction of delta-aminolevulinic acid (ALA) synthetase and inhibition of uroporphyrinogen decarboxylase. They established that the porphyrinogenic effect of PCBs exhibits a sharply defined structure-activity relationship in that only 3,4,3',4'-tetrachlorobiphenyl and 3,4,5,3',4',5'-hexachlorobiphenyl produced a marked accumulation of uroporphyrin. They also demonstrated that in ALA-supplemented cultures, these same compounds lead to accumulation of a large amount of uroporphyrin III, whereas with other PCBs, which were weak inducers of porphyrin synthesis, the accumulated porphyrin was mostly protoporphyrin. Kinetic studies of the sequential decarboxylation of uroporphyrinogen with purified uroporphyrinogen decarboxylase were performed. The 3,4,3',4'-tetrachlorobiphenyl and 3,4,5,3',4',5'-hexachlorobiphenyl strongly inhibit uroporphyrinogen decarboxylase directly at two steps. The results confirmed that porphyrinogenic PCBs primarily inhibit uroporphyrinogen decarboxylase, leading to a depletion of heme as a result of which synthesis of ALA synthetase increased.

  8. Magnetic and electronic properties of porphyrin-based molecular nanowires

    International Nuclear Information System (INIS)

    Using spin-polarized density functional theory calculations, we performed theoretical investigations on the electronic and magnetic properties of transition metal embedded porphyrin-based nanowires (TM-PNWs, TM = Cr, Mn, Co, Ni, Cu, and Zn). Our results indicate that Ni-PNW and Zn-PNW are nonmagnetic while the rest species are magnetic, and the magnetic moments in TM-PNWs and their corresponding isolated monomer structures are found to be the same. In addition, the spin coupling in the magnetic nanowires can be ignored leading to their degenerate AFM and FM states. These results can be ascribed to the weak intermetallic interactions because of the relatively large distances between neighbor TM atoms. Among all TM-PNW structures considered here, only Mn-PNW shows a half-metallic property while the others are predicted to be semiconducting. The present work paves a new way of obtaining ferromagnetic porphyrin-based nanowires with TM atoms distributed separately and orderly, which are expected to be good candidates for catalysts, energy storage and molecular spintronics

  9. Magnetic and electronic properties of porphyrin-based molecular nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jia-Jia; Li, Qiao-Zhi; Dang, Jing-Shuang; Zhao, Xiang, E-mail: xzhao@mail.xjtu.edu.cn [Institute for Chemical Physics & Department of Chemistry, MOE Key Laboratory for Non-equilibrium Condensed Matter and Quantum Engineering, School of Science, Xi’an Jiaotong University, Xi’an 710049 (China); Wang, Wei-Wei [Research Center for Computational Science, Institute for Molecular Science, Okazaki, Aichi 444-8585 (Japan)

    2016-01-15

    Using spin-polarized density functional theory calculations, we performed theoretical investigations on the electronic and magnetic properties of transition metal embedded porphyrin-based nanowires (TM-PNWs, TM = Cr, Mn, Co, Ni, Cu, and Zn). Our results indicate that Ni-PNW and Zn-PNW are nonmagnetic while the rest species are magnetic, and the magnetic moments in TM-PNWs and their corresponding isolated monomer structures are found to be the same. In addition, the spin coupling in the magnetic nanowires can be ignored leading to their degenerate AFM and FM states. These results can be ascribed to the weak intermetallic interactions because of the relatively large distances between neighbor TM atoms. Among all TM-PNW structures considered here, only Mn-PNW shows a half-metallic property while the others are predicted to be semiconducting. The present work paves a new way of obtaining ferromagnetic porphyrin-based nanowires with TM atoms distributed separately and orderly, which are expected to be good candidates for catalysts, energy storage and molecular spintronics.

  10. Cu(II) porphyrins modified TiO{sub 2} photocatalysts: Accumulated patterns of Cu(II) porphyrin molecules on the surface of TiO{sub 2} and influence on photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Su, Xiao-qin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069 (China); Shaanxi Key Laboratory of Photoelectric Functional Materials and Devices, School of Materials and Chemical Engineering, Xi’an Technological University, Xi’an, Shaanxi 710021 (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, Xi’an, Shaanxi 710069 (China); Zhang, Zeng-qi; Yu, Mi-mi; Yuan, Lin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069 (China)

    2015-03-25

    Highlights: • Two new crystal structures of copper porphyrins containing meso-tetra(ester and carboxyl) were obtained. • The two copper porphyrins were used to modify TiO{sub 2} for the first time. • The accumulated patterns of copper porphyrin molecules on the TiO{sub 2} surface is an important factor for the photocatalytic activity. • The peripheral groups of copper porphyrins influence their stacking patterns in solid state. - Abstract: The accumulated patterns of porphyrin molecules on the surface of TiO{sub 2} have an important effect on the photoactivity of porphyrin/TiO{sub 2} photocatalysts. Herein, two copper porphyrins containing flexible peripheral functional groups (meso-tetra(ester, carboxy)), Cu(II)5,10,15,20-tetrakis[4-(carboethoxymethyleneoxy)phenyl]porphyrin (CuPp(2a)) and Cu(II)5,10,15,20-tetrakis[4-(carboxymethyleneoxy)phenyl]porphyrin (CuPp(2b)), were synthesized and characterized spectroscopically. Their crystal structures were also determined by single crystal X-ray diffraction. The Cu(II) porphyrin-TiO{sub 2} composites were also prepared and characterized. The accumulated patterns of synthesized copper porphyrins on the surface of TiO{sub 2} were proposed for the first time. The photoactivity of the composites was investigated by carrying out the degradation of 4-nitrophenol (4-NP) in aqueous solution under UV–visible light. The results indicated that the CuPp(2b)-TiO{sub 2} showed the higher photocatalytic activity than that of CuPp(2a)-TiO{sub 2}. Above all, it can be concluded that the accumulated patterns of porphyrins on the surface of TiO{sub 2} is an important factor for the photocatalytic efficiency of porphyrin/TiO{sub 2}.

  11. Cu(II) porphyrins modified TiO2 photocatalysts: Accumulated patterns of Cu(II) porphyrin molecules on the surface of TiO2 and influence on photocatalytic activity

    International Nuclear Information System (INIS)

    Highlights: • Two new crystal structures of copper porphyrins containing meso-tetra(ester and carboxyl) were obtained. • The two copper porphyrins were used to modify TiO2 for the first time. • The accumulated patterns of copper porphyrin molecules on the TiO2 surface is an important factor for the photocatalytic activity. • The peripheral groups of copper porphyrins influence their stacking patterns in solid state. - Abstract: The accumulated patterns of porphyrin molecules on the surface of TiO2 have an important effect on the photoactivity of porphyrin/TiO2 photocatalysts. Herein, two copper porphyrins containing flexible peripheral functional groups (meso-tetra(ester, carboxy)), Cu(II)5,10,15,20-tetrakis[4-(carboethoxymethyleneoxy)phenyl]porphyrin (CuPp(2a)) and Cu(II)5,10,15,20-tetrakis[4-(carboxymethyleneoxy)phenyl]porphyrin (CuPp(2b)), were synthesized and characterized spectroscopically. Their crystal structures were also determined by single crystal X-ray diffraction. The Cu(II) porphyrin-TiO2 composites were also prepared and characterized. The accumulated patterns of synthesized copper porphyrins on the surface of TiO2 were proposed for the first time. The photoactivity of the composites was investigated by carrying out the degradation of 4-nitrophenol (4-NP) in aqueous solution under UV–visible light. The results indicated that the CuPp(2b)-TiO2 showed the higher photocatalytic activity than that of CuPp(2a)-TiO2. Above all, it can be concluded that the accumulated patterns of porphyrins on the surface of TiO2 is an important factor for the photocatalytic efficiency of porphyrin/TiO2

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

    International Nuclear Information System (INIS)

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

  13. The self-aggregation of chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The self-aggregation of chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes in water-alcohol system and water-alcohol-NaCl system has been studied by circular dichroism (CD),UV-Vis absorption spectra and fluorescence spectra methods.The experiment results indicate that chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes have two different kinds of aggregates in water-alcohol system and water-alcohol-NaCl system.And the porphyrins may form highly organized and orientated aggregates in water-alcohol-NaCl system.The aggregates in water-alcohol-NaCl system may have helical structures.

  14. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl-, NO3-, C2O42-) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu2+, Zn2+, UO22+, Fe3+, Nd3+, Eu3+, Th4+) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author)

  15. Bionano donor-acceptor hybrids of porphyrin, ssDNA, and semiconductive single-wall carbon nanotubes for electron transfer via porphyrin excitation.

    Science.gov (United States)

    D'Souza, Francis; Das, Sushanta K; Zandler, Melvin E; Sandanayaka, Atula S D; Ito, Osamu

    2011-12-14

    Photoinduced electron transfer in self-assemblies of porphyrins ion-paired with ssDNA wrapped around single-wall carbon nanotubes (SWCNTs) has been reported. To accomplish the three-component hybrids, two kinds of diameter-sorted semiconducting SWCNT(n,m)s of different diameter ((n,m) = (6,5) and (7,6)) and free-base or zinc porphyrin bearing peripheral positive charges ((TMPyP(+))M (tetrakis(4-N-methylpyridyl)porphyrin); M = Zn and H(2)) serving as light-absorbing photoactive materials are utilized. The donor-acceptor hybrids are held by ion-pairing between the negatively charged phosphate groups of ssDNA on the surface of the SWCNT and the positively charged at the ring periphery porphyrin macrocycle. The newly assembled bionano donor-acceptor hybrids have been characterized by transmission electron microscopy (TEM) and spectroscopic methods. Photoinduced electron transfer from the excited singlet porphyrin to the SWCNTs directly and/or via ssDNA as an electron mediator has been established by performing systematic studies involving the steady-state and time-resolved emission as well as the transient absorption studies. Higher charge-separation efficiency has been successfully demonstrated by the selection of the appropriate semiconductive SWCNTs with the right band gap, in addition to the aid of ssDNA as the electron mediator. PMID:22088093

  16. Synthesis, characterization and photophysical studies of -triazolomethyl-bridged porphyrin-benzo--pyrone dyads

    Indian Academy of Sciences (India)

    Dileep Kumar Singh; Mahendra Nath

    2016-04-01

    A new series of zinc(II) -triazolomethyl-bridged porphyrin-benzo--pyrone dyads have been synthesized in appreciable yields through a copper(I)-catalyzed “click” reaction of zinc(II) 2-azidomethyl-5,10,15,20-tetraphenylporphyrin with various benzo--pyronoalkynes. These novel zinc(II) porphyrin-benzo--pyrone dyads successfully underwent demetallation in the presence of concentrated hydrochloric acid in chloroform at 25°C to form the corresponding free-base porphyrin analogues in good yields. The newly synthesized products were characterized on the basis of spectral data and evaluated for their electronic absorption and fluorescence properties. Some of these molecules have shown a significant intramolecular energy transfer between the benzo--pyrone and porphyrin subunits.

  17. Competetive inhibition of porphyrin oxygen reduction catalysts in one- and two-phase liquid systems

    Czech Academy of Sciences Publication Activity Database

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

    2013-01-01

    Roč. 59, č. 3 (2013), s. 179-179. ISSN 0034-6691 R&D Projects: GA ČR GAP208/11/0697 Institutional support: RVO:61388955 Keywords : porphyrin oxygen * electrochemistry Subject RIV: CG - Electrochemistry

  18. Determination of Mass Spectrometric Sensitivity of Different Metalloporphyrin Esters Relative to Porphyrin Ester

    DEFF Research Database (Denmark)

    Larsen, Elfinn; Egsgaard, Helge; Møller, J.;

    1977-01-01

    Quantitative determination of metalloporphyrin contamination in preparations of biologically important porphyrins was achieved mass spectrometrically by application of the integrated ion current technique. For this purpose, the relative molecular ion sensitivities of the contaminating metal...... complexes were determined from the ratios of the integrated molecular ion currents of a series of calibration samples containing a porphyrin ester and one of its metal complexes in known molar ratio. Complexes formed with divalent ions of Cu, Zn, Fe, Co and Ni of copro- as well as uro......-prophyrin permethylester were all found to have the same molecular ion sensitivities as their metal-free porphyrin ester. The relative metalloporphyrin ester content in a sample of porphyrin ester was thus obtained directly as the integrated ion current ratios of the normalized molecular ions. The preparation of...

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

    Directory of Open Access Journals (Sweden)

    Camille De Souza

    2014-06-01

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

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

    KAUST Repository

    Börjesson, Karl

    2010-09-28

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

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

    Directory of Open Access Journals (Sweden)

    Paulo Cesar Bega

    2014-02-01

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

  2. 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.

  3. Hybrid organic – silica nanomaterials based on novel A{sub 3}B mixed substituted porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Fagadar-Cosma, Eugenia [Institute of Chemistry -Timisoara of Romanian Academy, M. Viteazul Ave, No. 24, 300223 Timisoara (Romania); Dudás, Zoltán, E-mail: dudas.zoltan@wigner.mta.hu [Institute of Chemistry -Timisoara of Romanian Academy, M. Viteazul Ave, No. 24, 300223 Timisoara (Romania); MTA Wigner Research Center for Physics, Konkoly Thege Miklós Street, No. 29-33, 1121 Budapest (Hungary); Birdeanu, Mihaela [Institute of Chemistry -Timisoara of Romanian Academy, M. Viteazul Ave, No. 24, 300223 Timisoara (Romania); National Institute for Research and Development in Electrochemistry and Condensed Matter, 1 Plautius Andronescu Street, 300224 Timisoara (Romania); Almásy, László [MTA Wigner Research Center for Physics, Konkoly Thege Miklós Street, No. 29-33, 1121 Budapest (Hungary)

    2014-11-14

    A new A{sub 3}B porphyrin structure, namely: 5-(4-phenoxyphenyl)-10,15,20-tris(4-pyridyl)-porphyrin was synthetized and characterized by FT-IR, UV–vis, Fluorescence, MS, {sup 1}H NMR, TLC and HPLC. Novel hybrid-silica porphyrin nanomaterials were obtained by immobilizing the porphyrin in silica supports synthesized from tetraethoxysilane, tetramethoxysilane or mixtures of tetraethoxysilane/methyltriethoxysilane. Since the behavior and performance of immobilized porphyrin molecules in the silica matrices strongly depend on the structure of the porous network, a comparative characterization of the silica support and the hybrid porphyrin-silica materials was carried out using specific physicochemical characterization methods: UV–vis, Fluorencence, FT-IR spectroscopy, thermal analysis, AFM, nitrogen adsorption and small-angle neutron scattering. The UV–vis spectra show that no protonation and aggregation of porphyrin takes place in the gels made from methyltriethoxysilane precursor. Most of the emission spectra preserve both the shape and the intensity of the corresponding free porphyrin. Due to the lack of aggregation, when using the methyltriethoxysilane precursor, the quenching of fluorescence is also diminished. No matter of the preparation method the specific surface areas increase in the following order: TEOS < TMOS < TEOS/MTES 3:1 < TEOS/MTES 2:1 < TEOS/MTES 1:1. Due to their optical properties, both the novel porphyrin and its derived hybrid materials, especially those synthesized in situ with mixtures of silica precursors TEOS/MTES will be sent for further medical trials in PDT, having characteristics of second generation photosensitizers. Due to large specific surface areas, the same materials will be used as sensitive materials in microsensors for air quality control, to detect the presence of CO, NO{sub x}, excess of CO{sub 2} and low level of O{sub 2}. - Highlights: • Synthesis of new A{sub 3}B type porphyrin exhibiting high fluorescence

  4. Hybrid organic – silica nanomaterials based on novel A3B mixed substituted porphyrin

    International Nuclear Information System (INIS)

    A new A3B porphyrin structure, namely: 5-(4-phenoxyphenyl)-10,15,20-tris(4-pyridyl)-porphyrin was synthetized and characterized by FT-IR, UV–vis, Fluorescence, MS, 1H NMR, TLC and HPLC. Novel hybrid-silica porphyrin nanomaterials were obtained by immobilizing the porphyrin in silica supports synthesized from tetraethoxysilane, tetramethoxysilane or mixtures of tetraethoxysilane/methyltriethoxysilane. Since the behavior and performance of immobilized porphyrin molecules in the silica matrices strongly depend on the structure of the porous network, a comparative characterization of the silica support and the hybrid porphyrin-silica materials was carried out using specific physicochemical characterization methods: UV–vis, Fluorencence, FT-IR spectroscopy, thermal analysis, AFM, nitrogen adsorption and small-angle neutron scattering. The UV–vis spectra show that no protonation and aggregation of porphyrin takes place in the gels made from methyltriethoxysilane precursor. Most of the emission spectra preserve both the shape and the intensity of the corresponding free porphyrin. Due to the lack of aggregation, when using the methyltriethoxysilane precursor, the quenching of fluorescence is also diminished. No matter of the preparation method the specific surface areas increase in the following order: TEOS < TMOS < TEOS/MTES 3:1 < TEOS/MTES 2:1 < TEOS/MTES 1:1. Due to their optical properties, both the novel porphyrin and its derived hybrid materials, especially those synthesized in situ with mixtures of silica precursors TEOS/MTES will be sent for further medical trials in PDT, having characteristics of second generation photosensitizers. Due to large specific surface areas, the same materials will be used as sensitive materials in microsensors for air quality control, to detect the presence of CO, NOx, excess of CO2 and low level of O2. - Highlights: • Synthesis of new A3B type porphyrin exhibiting high fluorescence quantum yield. • Synthesis of hybrid

  5. Spectroscopic properties of porphyrins and effect of lanthanide ions on their luminescence efficiency

    International Nuclear Information System (INIS)

    Spectroscopic properties of H2TPP porphyrin and Tb(III)TPP(acac) in solid and methanolic solutions have been compared. Emission from the S1 singlet state of Tb(III)TPP(acac) have been recorded at 296 and 77 K. Spectroscopic investigations of new types of porphyrins soluble in organic solvents (e.g. methanol), PP(AA)2, and porphyrins soluble in water, PP(AA)2(Arg)2 (where AA, alanine or serine; Arg, arginine), are presented. Interaction of PP(AA)2 with lanthanide ions (Yb(III), Eu(III)) has been studied. It has been found that the lanthanide (III) ions decrease efficiency of the porphyrin emission. For the alanine derivative, the stronger losses are caused by the Eu(III) ions as compared to the Yb(III) ions. On the other hand, the emission quenching by both lanthanide ions is similar in the case of the serine derivative. Influence of the Pr(III) and Eu(III) ions on the PP(AA)2(Arg)2 emission has also been investigated. An unexpected increase of the porphyrin emission intensity has been observed in solution for the lowest concentration of Pr(III) added, whereas the Eu(III) ions quench the emission in the full range of its concentration. The observed phenomena are analyzed, and the mechanisms of the excited-state dynamics in which the f-excited states take part in the porphyrin emission quenching are considered. It has been found that the lanthanide ions influence the absorption spectrum as well as the relative intensities of the respective bands in the emission spectra. The luminescence intensities of these porphyrins as a function of pH, the concentration and the type of the porphyrine substituent have been analyzed. Significant influence of the above factors on the emission properties of the porphyrins has been found and discussed. Efficiency of the emission has been determined for these M-porphyrin systems in comparison to the free porphyrins in methanol solutions. The observed effects can be explained by formation of polymeric chains and decrease of face

  6. Structural, NMR, and EPR studies of S = (1)/(2) and S = (3)/(2) Fe(III) bis(4-cyanopyridine) complexes of dodecasubstituted porphyrins.

    Science.gov (United States)

    Yatsunyk, Liliya A; Walker, F Ann

    2004-01-26

    LS species with g = 3.03 is also present. However, distinct from previous conclusions, large negative phenyl-H shift differences delta(m) - delta(o) and delta(m) - delta(p) in the (1)H NMR spectra indicate significant negative spin density at the meso-carbons, and the larger than expected positive average CH(2) shifts are also consistent with a significant population of the S = 2 Fe(II), S = (1)/(2) porphyrin pi-cation radical state, with antiferromagnetic coupling between the metal and porphyrin unpaired electrons. This is the first example of this type of porphyrin-to-metal electron transfer to produce a partial or complete porphyrinate radical state, with antiferromagnetic coupling between metal and macrocycle unpaired electrons in an iron porphyrinate. The kinetics of ring inversion were studied for the [FeOETPP(4-CNPy)(2)]ClO(4) complex using NOESY/EXSY techniques and for the [FeTC(6)TPP(4-CNPy)(2)]ClO(4) complex using DNMR techniques. For the former, the free energy of activation, deltaG, and rate of ring inversion in CD(2)Cl(2) extrapolated to 298 K are 63(2) kJ mol(-)(1) and 59 s(-)(1), respectively, while for the latter the rate of ring inversion at 298 K is at least 4.4 x 10(7) s(-)(1), which attests to the much greater flexibility of the TC(6)TPP ring. The NMR and EPR data are consistent with solution magnetic susceptibility measurements that show S = (3)/(2) in the temperature range from 320 to 180 K for [FeOETPP(4-CNPy)(2)](+), while both [FeOMTPP(4-CNPy)(2)](+) and [FeTC(6)TPP(4-CNPy)(2)](+) change their spin state from S = (3)/(2) at room temperature to mainly LS (S = (1)/(2)) upon cooling to 180 K. PMID:14731040

  7. Synthesis of a Polyimide Porous Porphyrin Polymer for Selective CO2 Capture

    OpenAIRE

    Neti, Venkata S. Pavan K.; Jun Wang; Shuguang Deng; Luis Echegoyen

    2015-01-01

    A new microporous porphyrin-based imide linked polymer, PyP, was synthesized in an m-cresol/isoquinoline mixture between a porphyrin and a naphthalene tetra-carboxylic dianhydride. The resultant amorphous polymer demonstrates a moderate surface area (SBET = 428 m2 g−1) and CO2 adsorption ability (3.5 wt%) and a CO2/CH4 selectivity of 5.6 at 273 K/1 bar.

  8. 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. PMID:17406705

  9. Synthesis of o- and m-carborane substituted porphyrins of natural type

    International Nuclear Information System (INIS)

    Synthesis of new mono- and dicarborane-containing porphyrins on the basis of protoporphyrin IX, its monobenzene esters, deuteroporphyrin IX, 9-hydroxymethyl-m- and 9-hydroxymethyl-o-carboranes was conducted. The yield of the products amounted to 24 - 76 %. All the compounds prepared were characterized using electronic, 1H NMR and IR spectroscopy and mass spectrometry. Relying on spectral data, the structure of porphyrin nucleus in the compounds was confirmed

  10. Dendrimers Containing Ferrocene and Porphyrin Moieties: Synthesis and Cubic Non-Linear Optical Behavior

    OpenAIRE

    Eric G. Morales-Espinoza; Sanchez-Montes, Karla E.; Elena Klimova; Tatiana Klimova; Lijanova, Irina V.; Maldonado, José L.; Gabriel Ramos-Ortíz; Simón Hernández-Ortega; Marcos Martínez-García

    2010-01-01

    Dendrons with ferrocenyl ended groups joined by styryl moieties were attached to a porphyrin core. All the dendrons used for dendrimer synthesis showed trans configuration. The chemical structure of the first generation dendron was confirmed by X-ray crystallographic studies. The structure of the synthesized dendrimers was confirmed by 1H- and 13C-NMR, electrospray mass spectrometry and elemental analysis. Cubic non-linear optical behavior of the ferrocene and porphyrin-containing dendrimers ...

  11. Parent Anions of Iron, Manganese, and Nickel Tetraphenyl Porphyrins: Photoelectron Spectroscopy and Computations.

    Science.gov (United States)

    Buytendyk, Allyson M; Graham, Jacob D; Gould, Julian; Bowen, Kit H

    2015-08-13

    The singly charged, parent anions of three transition metal, tetraphenyl porphyrins, M(TPP) [Fe(TPP), Mn(TPP), and Ni(TPP)], were studied by negative ion photoelectron spectroscopy. The observed (vertical) transitions from the ground state anions of these porphyrins to the various electronic states of their neutral counterparts were modeled by density functional theory computations. Our experimental and theoretical results were in good agreement. PMID:26186172

  12. 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.

  13. Mutual and self-diffusion of charged porphyrines in aqueous solutions

    International Nuclear Information System (INIS)

    Highlights: ► Self and mutual diffusion coefficients of charged porphyrines in aqueous dilute solutions. ► Complementary molecular mechanics studies. ► Effect of association in diffusion of charged porphyrines. - Abstract: We have investigated the diffusion properties for an ionic porphyrin in water. Specifically, for the {tetrasodium tetraphenylporphyrintetrasulfonate (Na4TPPS) + water} binary system, the self-diffusion coefficients of TPPS4− and Na+, and the mutual diffusion coefficients were experimentally determined as a function of Na4TPPS concentration from (0 to 4) · 10−3 mol · dm−3 at T = 298.15 K. Absorption spectra for this system were obtained over the same concentration range. Molecular mechanics were used to compute size and shape of the TPPS4− porphyrin. We have found that, at low solute concentrations (−3 mol · dm−3), the mutual diffusion coefficient sharply decreases as the concentration increases. This can be related to both the ionic nature of the porphyrin and complex associative processes in solution. Our experimental results are discussed on the basis of the Nernst equation, Onsager–Fuoss theory and porphyrin metal ion association. In addition, self-diffusion of TPPS4− was used, together with the Stokes–Einstein equation, to determine the equivalent hydrodynamic radius of TPPS4−. By approximating this porphyrin to a disk, we have estimated structural parameters of TPPS4−. These were found to be in good agreement with those obtained using molecular mechanics. Our work shows how the self-diffusion coefficient of an ionic porphyrin in water is substantially different from the corresponding mutual-diffusion coefficient in both magnitude and concentration dependence. This aspect should be taken into account when diffusion-based transport is modelled for in vitro and in vivo applications of pharmaceutical relevance.

  14. Signature of gate-tunable magnetism in graphene grafted with Pt-porphyrins

    OpenAIRE

    Li, Chuan; Komatsu, Katsuyoshi; Bertrand, S.; Clavé, G; Campidelli, S; Filoramo, A; Guéron, S.; Bouchiat, H.

    2013-01-01

    Inducing magnetism in graphene holds great promises, such as controlling the exchange interaction with a gate electrode, and generating exotic magnetic phases. Coating graphene with magnetic molecules or atoms has so far mostly led to decreased graphene mobility. In the present work, we show that Pt-porphyrin molecules adsorbed on graphene lead both to an enhanced mobility, and to gate-dependent magnetism. We report that porphyrins can act both as donor or acceptor molecules, depending on the...

  15. Glycoconjugates of porphyrins with carbohydrates: methods of synthesis and biological activity

    International Nuclear Information System (INIS)

    Data on the main approaches to preparation of mono- and oligodentate glycoconjugates based on porphyrin scaffolds are surveyed. The prospects for using these compounds as sensitizers for photodynamic therapy of cancer and for suppression of bacterial and viral pathogens are considered. Data on the synthesis of oligodentate blocking agents for carbohydrate-binding proteins (lectins) based on porphyrin scaffolds are discussed. The bibliography includes 161 references

  16. Quantum efficiency of energy transfer in noncovalent carbon nanotube/porphyrin compounds

    OpenAIRE

    Roquelet, Cyrielle; Garrot, Damien; Lauret, Jean-Sébastien; Voisin, C.; Alain-Rizzo, Valérie; Roussignol, Philippe; Delaire, Jacques,; Deleporte, Emmanuelle

    2010-01-01

    We report on the quantum yield of excitation energy transfer in non-covalently bound nan- otube/porphyrin compounds. Evidence for energy transfer is gained from photoluminescence exci- tation experiments. We perform a quantitative evaluation of the transfer quantum yield in the case of (6,5) nanotubes through three independent methods : quantitative PLE measurements, evalu- ation of the luminescence quenching of the donor (porphyrin) and ultrafast transient absorption measurements. The latter...

  17. Spin-coupling in ferric metalloporphyrin radical cation complexes: Mössbauer and susceptibility studies

    Science.gov (United States)

    Lang, George; Boso, Brian; Erler, Brian S.; Reed, Christopher A.

    1986-03-01

    The ferric metalloporphyrin π-radical cation complexes Fe(III) (OClO3)2 (TPP.) and [Fe(III) Cl (TPP.)] [SbCl6] were examined in microcrystalline form by Mössbauer spectroscopy and magnetic susceptometry over a range of temperatures and applied fields. All measurements on the six-coordinate Fe(OClO3)2 (TPP.) were consistent with isolated molecules having an S=5/2 iron site with zero field splitting (12 cm-1) S2z that is ferromagnetically coupled to the S=1/2 porphyrin radical by an energy term (-110 cm-1) Sṡs. Thus the ground state is overall spin-3. In the five-coordinate [FeCl (TPP.)] [SbCl6] the susceptibility is in reasonable agreement with the results of a calculation based on zero field splitting (12 cm-1) S2z for the S=5/2 iron and antiferromagnetic coupling (200 cm-1) Sṡs with the radical to give an overall spin-2 ground state. However, the Mössbauer measurements require a more complicated model having the same large intramolecular iron-radical coupling, a smaller zero field splitting (3 cm-1) S2z, and weak intermolecular antiferromagnetic coupling between heme pairs given by (32 cm-1) s1ṡs2 or, equivalently, (0.65 cm-1) S1ṡS2. A slightly improved correspondence with the measured susceptibility results. The intermolecular antiferromagnetic coupling probably results from crystallization of the [FeCl (TPP.)]+ cations in face-to-face dimers as observed in other closely related five-coordinate iron (III) porphyrins.

  18. Lipophilicity of porphyrins and their retention in IAM, C8-C18 and HILIC chromatographic systems.

    Science.gov (United States)

    Essaid, D; Chaminade, P; Maillard, Ph; Kasselouri, A

    2015-10-10

    Porphyrins are a class of photosensitizers used in photodynamic therapy (PDT). Understanding the interaction of porphyrins with membrane cells components is important in order to improve this therapy. Many analytical methods can be used for this aim. High performance liquid chromatography (HPLC) was used for the separation of porphyrins on RP and HILIC stationary phases as well as on a biomimetic membrane IAM phase. Twenty-six tetraphenyl porphyrins (TPP) were successfully separated on an IAM column, a C18 Gravity RP column, a C8 Gravity RP column, a PolarTec RP column and a HILIC column. Stationary phases were chosen as the most appropriate to cover the study of different types of interactions. Elution was performed with a 45 min linear gradient. Obtained gradient retention times were converted to gradient chromatography hydrophobicity index (CHI) and to an apparent retention factor (kapp). The partition coefficients (logP) of the 26 compounds were measured in a 2-octanol/PBS system and estimated in silico. Correlation between kapp values was studied. Moreover, a multivariate analysis was performed to explain columns relationships. Obtained results show that porphyrins are separated mainly according to hydrophobic interactions that are relative to their structure (sugar number and the disposition around the porphyrin macrocycle). PMID:26099259

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

    International Nuclear Information System (INIS)

    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

  20. Synthesis and characterization of porphyrin nanotubes/rods for solar radiation harvesting and solar cells

    International Nuclear Information System (INIS)

    Energy transfer and electron transfer events as they occur between well arranged light harvesting antenna molecules, the reaction center and other factors determine the function of natural photosynthesis. The overall small reorganization energy and the well-balanced electronic coupling between each component bear key characters for the unique efficiency of natural photosynthesis. Such aspects permit the design and assembly of artificial systems that efficiently process solar energy, replicating the natural processes. The rich and extensive transitions seen in porphyrin-based materials hold great expectation as light harvesting building blocks in the construction of molecular architectures, allowing an efficient use of the solar spectrum. Hence in this study porphyrin nanorods are synthesized and characterized for future application in the construction of the artificial light harvesting system. Understanding the sizes and growth mechanism of porphyrins nanorods by self-assembly and molecular recognition is essential for their successful implementation in nanodevices. Spectroscopic and microscopic studies were carried out to investigate the effect that time, concentration and solvents have on the fabrication of porphyrin nanorods by ionic self-assembly of two oppositely charged porphyrins. We investigate in details the heteroaggregate behavior formation of [H4TPPS4]2− and [SnTPyP]2+ mixture by means of the UV–vis spectroscopy and aggregates structure and morphology by transmission electron microscopy (TEM). This study demonstrates the potential for using different concentrations and solvents to influence the physical and optical properties of porphyrin based nanorods.

  1. 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.

  2. A facile one-pot synthesis of higher yield porphyrin functionalized Co3O4 nanoparticles

    International Nuclear Information System (INIS)

    Graphical abstract: Porphyrins functionalized Co3O4 nanoparticles were prepared firstly via a facile one-step method. The high yield of prophyrin functionalized Co3O4 nanoparticles is more than 90%. - Highlights: • Por-Co3O4 NPs were first prepared via a facile one-pot hydrothermal method. • The yield of porphyrin-Co3O4 nanoparticles is more than 90%. • FT-IR reveals the coordination interaction between porphyin molecules and Co3O4. • Ethanol and the appropriate temperature are necessary in this experiment. - Abstract: Porphyrin functionalized Co3O4 nanoparticles were first prepared via a facile one-pot hydrothermal method. The functionalized nanoparticles were characterized by X-ray diffraction and transmission electron microscopy. Fourier transform infrared spectra revealed the coordination interaction between porphyrin molecules and Co3O4. The high yield of prophyrin functionalized Co3O4 nanoparticles is more than 90%. The phase, morphology and size of as-prepared nanoparticles were dramatically affected by the ratio of solvents, temperature and porphyrins with different substituents, respectively. Experimental results revealed that ethanol and the appropriate temperature were necessary for the formation of single-phase Co3O4. Furthermore, a probable growth mechanism of the formation of porphyrin functionalized Co3O4 nanoparticles was proposed

  3. 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.

  4. 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.

  5. Cationic speciation in nonaqueous media

    International Nuclear Information System (INIS)

    Electronic spectra of solutions of d transition elements in the superacids HF, H2SO4, HSO3F, and CF3SO3H and in chloroaluminate melts indicate that in acidic monaqueous media the elements are present as solvated cations, whereas in basic media the speciation is anionic, the same situation as in aqueous solutions. Further, in very highly acidic media, cations in very low oxidation states are stable (e.g., Ti2+), but these disproportionate on addition of base to the system. In this paper spectra, where available, of U, Np, and Pu in oxidation states III and IV in aqueous media, in protonic superacids, and in chloroaluminates are presented to postulate cationic speciation of these early actinides in highly acidic media

  6. Respiratory Monitoring by Porphyrin Modified Quartz Crystal Microbalance Sensors

    Directory of Open Access Journals (Sweden)

    Seung-Woo Lee

    2011-01-01

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

  7. 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

  8. Application of clean laser transfer for porphyrin micropatterning

    International Nuclear Information System (INIS)

    Blister-based laser-induced forward transfer is proposed as a promising tool for clean, cold and liquid-free local transfer of various organic substances. The feature of the given technique is non-destructive local deformation of an absorbing metal film on a transparent support avoiding the metal sputtering. Application of the blister-based laser transfer of a Langmuir film to fabricate mesotetraphenylporphyrin micropatterns on a silica substrate has been demonstrated. The metal film thickness is found to be a key parameter, which determines the laser fluence range allowing the clean transfer, predominant mechanism of the blister formation and laser-induced heating of the transferred material. According to the numerical modelling confirmed by UV-vis absorption spectroscopy, the target with 1.5 μm thick titanium film provides negligible heating of the porphyrin transferred by 5 ns laser pulses.

  9. Manganese porphyrin sensor for the determination of bromate.

    Science.gov (United States)

    Sheen, Shanty; Jos, Theresa; Rajith, Leena; Kumar, Krishnapillai Girish

    2016-03-01

    The electro reductive behavior and determination of bromate on [5, 10, 15, 20-tetrakis (4-methoxyphenylporphyrinato] Manganese (III) chloride (TMOPPMn(III)Cl) modified Gold electrode(GE) was investigated by Square wave voltammetry (SWV). Bromate showed an irreversible reduction peak at -164 mV in 0.1 M pH 7 Na2SO4 solution. The cathodic peak of bromate showed a reduction in potential of 88 mV on modifying GE with a porphyrin film. The peak current varied linearly with concentration with a detection limit of 3.56 × 10(-9) M. The influence of pH, scan rate, supporting electrolyte and interferents on the reduction peak current of bromate were studied. The developed sensor was proposed for the determination of bromate in bread samples and compared with the standard method. PMID:27570281

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

    OpenAIRE

    Giuseppe Vasapollo; Selma Elaine Mazzetto; Lucia D’Accolti; Luigi Carbone; Giuseppe Colafemmina; Giuseppe Mele; Ermelinda Bloise

    2012-01-01

    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 cho...

  11. Spectroscopy of free-base N-confused tetraphenylporphyrin radical anion and radical cation.

    Science.gov (United States)

    Alemán, Elvin A; Manríquez Rocha, Juan; Wongwitwichote, Wongwit; Godínez Mora-Tovar, Luis Arturo; Modarelli, David A

    2011-06-23

    The radical anions and radical cations of the two tautomers (1e and 1i) of 5,10,15,20-tetraphenyl N-confused free-base porphyrin have been studied using a combination of cyclic voltammetry, steady state absorption spectroscopy, and computational chemistry. N-Confused porphyrins (NCPs), alternatively called 2-aza-21-carba-5,10,15,20-tetraphenylporphyrins or inverted porphyrins, are of great interest for their potential as building blocks in assemblies designed for artificial photosynthesis, and understanding the absorption spectra of the corresponding radical ions is paramount to future studies in multicomponent arrays where electron-transfer reactions are involved. NCP 1e was shown to oxidize at a potential of E(ox) 0.65 V vs Fc(+)|Fc in DMF and reduce at E(red) -1.42 V, while the corresponding values for 1i in toluene were E(ox) 0.60 V and E(red) -1.64 V. The geometries of these radical ions were computed at the B3LYP/6-31+G(d)//B3LYP/6-31G(d) level in the gas phase and in solution using the polarizable continuum model (PCM). From these structures and that of H(2)TPP and its corresponding radical ions, the computed redox potentials for 1e and 1i were calculated using the Born-Haber cycle. While the computed reduction potentials and electron affinities were in excellent agreement with the experimental reduction potentials, the calculated oxidation potentials displayed a somewhat less ideal relationship with experiment. The absorption spectra of the four radical ions were also measured experimentally, with radical cations 1e(•+) and 1i(•+) displaying significant changes in the Soret and Q-band regions as well as new low energy absorption bands in the near-IR region. The changes in the absorption spectra of radical anions 1e(•-) and 1i(•-) were not as dramatic, with the changes occurring only in the Soret and Q-band regions. These results were favorably modeled using time-dependent density functional calculations at the TD-B3LYP/6-31+G(d)//B3LYP/6-31G

  12. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.

  13. Liquid-solid extraction of metallic cations by cationic amphiphiles

    International Nuclear Information System (INIS)

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

  14. A Sensitive A3B Porphyrin Nanomaterial for CO2 Detection

    Directory of Open Access Journals (Sweden)

    Eugenia Fagadar-Cosma

    2014-12-01

    Full Text Available The present report deals with the tailoring, preparation and characterization of novel nanomaterials sensitive to CO2 for use in detection of this gas during space habitation missions. A new nanostructured material based on mixed substituted asymmetrical A3B porphyrin: 5-(4-pyridyl-10,15,20-tris(3,4-dimethoxyphenyl-porphyrin (PyTDMeOPP was synthesized and characterized by 1H-NMR, FT-IR, UV-vis, fluorescence, MS, HPLC and AFM. Introducing one pyridyl substituent in the 5-meso-position of porphyrin macrocycle confers some degree of hydrophilicity, which may cause self-assembly properties and a better response to increased acidity. The influence of pH and nature of the solvent upon H and J aggregates of the porphyrin are discussed. Porphyrin aggregation at the air–THF interface gave a triangular type morphology, randomly distributed but uniformly oriented. When deposition was made by multiple drop-casting operations, a network of triangles of uniform size was created and a porous structure was obtained, being reorganized finally in rings. When the deposition was made from CHCl3, ring structures ranging in internal diameter from 300 nm to 1 µm, but with the same width of the corona circular of approx. 200 nm were obtained. This porphyrin-based material, capable of generating ring aggregates in both THF and CHCl3, has been proven to be sensitive to CO2 detection. The dependence between the intensity of porphyrin UV-vis absorption and the concentration of CO2 has a good correlation of 98.4%.

  15. Interaction of tetraphenyl-porphyrin derivatives with DPPC-liposomes: an EPR study.

    Science.gov (United States)

    Voszka, István; Szabó, Zsófia; Csík, Gabriella; Maillard, Philip; Gróf, Pál

    2005-05-13

    The effect of the symmetry and polarity of the porphyrin molecules on their membrane localization and interaction with membrane lipids were investigated by electron paramagnetic resonance (EPR). For this purpose, two glycoconjugated tetraphenyl porphyrin derivatives were selected, respectively, symmetrically and asymmetrically substituted. Small unilamellar liposomes composed of dipalmitoylphosphatidylcholine (DPPC) and spin labeled stearic acids were prepared. The spin probe was located at the 5th or 7th or 12th or 16th position of the hydrocarbon chain in order to monitor various regions of the lipid bilayer. EPR spectra of porphyrin-free and porphyrin-bound liposomes were recorded at various temperatures below and above the phase transition temperature of DPPC. The effect on membrane fluidity proved to be stronger with the asymmetrical porphyrin derivative than with the symmetrical one. The rigidity increased when the spin label was near lipid head groups. The difference observed between control and porphyrin-treated samples when measured below the main lipid transition temperature disappeared at higher temperature. When the spin label was near the end of the hydrophobic tails, the symmetrical porphyrin derivative caused increase in fluidity, while the asymmetrical one slightly decreased it. To explain this phenomenon we propose that the asymmetrical derivative exerts a stronger ordering effect caused by its fluorophenyl group located at the level of the lipid heads, which is attenuated to the hydrophobic tails. The perturbing effect of the symmetric derivative could not lead to similar extent of ordering at the head groups and looses the hydrocarbon chains deeper in the membrane. PMID:15878112

  16. Signature of gate-tunable magnetism in graphene grafted with Pt-porphyrins

    Science.gov (United States)

    Li, Chuan; Komatsu, Katsuyoshi; Bertrand, S.; Clavé, G.; Campidelli, S.; Filoramo, A.; Guéron, S.; Bouchiat, H.

    2016-01-01

    Inducing magnetism in graphene holds great promises, such as controlling the exchange interaction with a gate electrode, and generating exotic magnetic phases. Coating graphene with magnetic molecules or atoms has so far mostly led to decreased graphene mobility. In the present work, we show that Pt-porphyrin molecules adsorbed on graphene lead both to an enhanced mobility, and to gate-dependent magnetism. We report that porphyrins can act both as donor or acceptor molecules, depending on the initial doping of the graphene sheet. The porphyrins transfer charge and ionize around the charged impurities on graphene, and, consequently, the graphene doping is decreased and its mobility is enhanced. In addition, ionized porphyrin molecules carry a magnetic moment. Using the sensitivity of mesoscopic transport to magnetism, in particular, the superconducting proximity effect and conductance fluctuations, we explore the magnetic order induced in graphene by the interacting magnetic moments of the ionized porphyrin molecules. Among the signatures of magnetism, we find two-terminal-magnetoresistance fluctuations with an odd component, a tell-tale sign of time-reversal symmetry breaking at zero field, which does not exist in uncoated graphene samples. When graphene is connected to superconducting electrodes, the induced magnetism leads to a gate-voltage-dependent suppression of the supercurrent, modified magnetic interference patterns, and gate-voltage-dependent magnetic hysteresis. The magnetic signatures are greatest for long superconductor/graphene/superconductor junctions, and for samples with the highest initial doping, compatible with a greater number of ionized, and thus magnetic porphyrin molecules. Our findings suggest that long-range (of the order of the coherence length, or micrometers) magnetism is induced through graphene by the ionized porphyrins' magnetic moment. This magnetic interaction is controled by the density of carriers in graphene, a tunability that

  17. Urinary porphyrins as biomarkers for arsenic exposure among susceptible populations in Guizhou province, China

    International Nuclear Information System (INIS)

    Coal is widely used in PR China. Unfortunately, coal from some areas in Guizhou Province contains elevated levels of arsenic. This has caused arsenicosis in individuals who use arsenic-contaminated coal for the purposes of heating, cooking and drying of food in poorly ventilated dwellings. The population at risk has been estimated to be approximately 200,000 people. Clinical symptoms of arsenicosis may include changes of skin pigmentation, hyperkeratosis of hand and feet, skin cancers, liver damage, persistent cough and chronic bronchitis. We analyzed the porphyrin excretion profile using a HPLC method in urine samples collected from 113 villagers who lived in Xing Ren district, a coal-borne arsenicosis endemic area and from 30 villagers from Xing Yi where arsenicosis is not prevalent. Urinary porphyrins were higher in the arsenic exposed group than those in the control group. The correlation between urinary arsenic and porphyrin concentrations demonstrated the effect of arsenic on heme biosynthesis resulting in increased porphyrin excretion. Both uroporphyrin and coproporphyrin III showed significant increases in the excretion profile of the younger age (<20 years) arsenic-exposed group, suggesting that porphyrins could be used as early warning biomarkers of chronic arsenic exposure in humans. Greater increases of urinary arsenic and porphyrins in women, children and older age groups who spend much of their time indoors suggest that they might be at a higher risk. Whether elevated porphyrins could predict adverse health effects associated with both cancer and non-cancer end-points in chronically arsenic-exposed populations need further investigation

  18. Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings

    Science.gov (United States)

    Zahran, Zaki N.; Mohamed, Eman A.; Naruta, Yoshinori

    2016-04-01

    Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe‑containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push‑pull mechanism. Bio‑inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe‑Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe‑Fe separation distance.

  19. Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings.

    Science.gov (United States)

    Zahran, Zaki N; Mohamed, Eman A; Naruta, Yoshinori

    2016-01-01

    Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe-containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push-pull mechanism. Bio-inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe-Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe-Fe separation distance. PMID:27087483

  20. Enhanced intersystem crossing due to long-range exchange interaction in copper(II) porphyrin-free base porphyrin dimers: HOMO and spacer dependence

    International Nuclear Information System (INIS)

    Highlights: • We found a parallel relationship between the two correlation lines of ln Δkisc vs. number of bonds. • Effects of HOMO of the terminal chromophore appear as the intercept of the correlation lines. • Difference of HOMO of the terminal porphyrin does not affect the interaction within the bridge part. • An expression involving both HOMO and spacer dependence for EISC rate was derived. - Abstract: Photodynamics induced by long-range exchange interaction was studied in two series of copper(II) porphyrin – free base porphyrin dimers linked via an aromatic spacer: one has a2u orbital as HOMO in the porphyrin π-system and the other has a1u orbital. Dependence on the HOMO as well as that on the spacer is presented for enhanced intersystem crossing (EISC) occurring in the free base half due to long-range coupling with the copper unpaired electron. Semilogarithmic plots of EISC rates vs. number of bonds show a linear correlation in each series of dimers. It was found that the two correlation lines show the same slope but different intercepts. This clearly indicates that electronic communication within the linkage does not depend on the terminal chromophore, while the terminal π-system affects the magnitude of EISC rates. Separately, a general expression for EISC rate, involving coupling between the terminal and linkage, was derived theoretically

  1. Porphyrins-cyclodextrin. 2. Dissociation, reduction, and proton relaxivity of an iron(III) porphyrin μ-oxo dimer in cyclodextrin solutions

    International Nuclear Information System (INIS)

    Spectrophotometric evidence for the dissociation of an Fe(III) porphyrin μ-oxo dimer induced by porphyrin-cyclodextrin complexation in aqueous solution is reported. Depending on the pH, the monomer may be in a diaquo monohydroxo or diaquo dihydroxo form with pK values of 6.4 or 8.5, respectively. In the absence of β-cyclodextrin (β-CD), the μ-oxo dimer exists as mono- or dihydroxo species with a pK of 11.7. γ- and pulse radiolysis techniques are used to study the Fe(III)/Fe(II) reduction. FeIIITSPP(H2O)2 (TSPP is tetrakis(4-sulfonatophenyl)porphyrin) is reduced by hydrated electrons and CH2OHsm-bullet radicals into FeIITSPP(H2O)2 whereas FeIIITSPP(OH-)2 and (H2O)FeTSPP-O-FeTSPP(OH-) are both reduced to the monohydroxo FeIITSPP(H2O)(OH-) monomer. The FeII-O-FeII dimer may be formed in strongly alkaline solution. Measurements of the proton (NMR) relaxivity values of this Fe(III) porphyrin in the absence and in the presence of β-CD indicate the possibility of using FeIIITSPP in conjunction with β-CD as a paramagnetic contrast agent for in vivo imaging of tumors and tissue

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

    Science.gov (United States)

    Zhong, Qiwen

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

  3. Polyelectrolyte Condensation Induced by Linear Cations

    OpenAIRE

    Guáqueta, Camilo; Luijten, Erik

    2007-01-01

    We examine the role of the condensing agent in the formation of polyelectrolyte bundles, via grand-canonical Monte Carlo simulations. Following recent experiments we use linear, rigid divalent cations of various lengths to induce condensation. Our results clarify and explain the experimental results for short cations. For longer cations we observe novel condensation behavior owing to alignment of the cations. We also study the role of the polyelectrolyte surface charge density, and find a non...

  4. Thiolate coordination to Fe(II)-porphyrin NO centers.

    Science.gov (United States)

    Praneeth, V K K; Haupt, Erhard; Lehnert, Nicolai

    2005-04-01

    The interaction of the Fe(II)-porphyrin NO model complex [Fe(TPP)(NO)] (1, TPP=tetraphenylporphyrin) with thiophenolate ligands and tetrahydrothiophene is explored both computationally and experimentally. Complex 1 is reacted with substituted thiophenolates and the obtained six-coordinate adducts of type [Fe(TPP)(SR)(NO)](-) are investigated in solution using electron paramagnetic resonance (EPR) spectroscopy. From the obtained g values and (14)N hyperfine pattern of the NO ligand it is concluded that the interaction of the thiophenolates with the Fe(II) center is weak in comparison to the corresponding 1-methylimidazole adduct. The strength of the Fe-S bond is increased when alkylthiolates are used as evidenced by comparison with the published EPR spectra of ferrous NO adducts in cytochromes P450 and P450nor, which have an axial cysteinate ligand. These results are further evaluated by density functional (DFT) calculations. The six-coordinate model complex [Fe(P)(SMe)(NO)](-) (1-SMe; P=porphine ligand used for the calculations) has an interesting electronic structure where NO acts as a medium strong sigma donor and pi acceptor ligand. Compared to the N-donor adducts with 1-methylimidazole (1-MeIm), etc., donation from the pi(h)( *) orbital of NO to Fe(II) is reduced due to the stronger trans effect of the alkylthiolate ligand. This is reflected by the predicted longer Fe-NO bond length and smaller Fe-NO force constant for 1-SMe compared to the 1-MeIm adduct. Therefore, the Fe(II)-porphyrin NO adducts with trans alkylthiolate coordination have to be described as Fe(II)-NO(radical) systems. The N-O stretching frequency of these complexes is predicted below 1600cm(-1) in agreement with the available experimental data. In addition, 1-SMe has a unique spin density distribution where Fe has a negative spin density of -0.26 from the calculations. The implications of this unusual electronic structure for the reactivity of the Fe(II)-NO alkylthiolate adducts as they occur

  5. Cationic electrodepositable coating composition comprising lignin

    Science.gov (United States)

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

    2013-07-30

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

  6. Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(V)-oxo species

    Science.gov (United States)

    Zhang, Rui; Vanover, Eric; Luo, Weilong; Newcomb, Martin

    2014-01-01

    Photo-disproportionation of a bis-porphyrin-diruthenium(IV) μ-oxo dimer gave a porphyrin-ruthenium(III) species and a putative poprhyrin-ruthenium(V)-oxo species that can be detected and studied in real time via laser flash photolysis methods. As determined by its spectral and kinetic behavior, the same oxo transient was also formed by photolysis of a porphyrin-ruthenium(III) N-oxide adduct. Second-order rate constants for reactions with several substrates at 22 °C were determined; representative values of rate constants were kox = 6.6 × 103 M−1 s−1 for diphenylmethanol, kox = 2.5 × 103 M−1 s−1 for styrene, and kox = 1.8 × 103 M−1 s−1 for cyclohexene. The putative porphyrin-ruthenium(V)-oxo transient reacted 5–6 orders of magnitude faster than the corresponding trans-dioxoruthenium(VI)-oxo porphyrins, and the rate constants obtained in this work were similar to those of corrole-iron(V)-oxo derivative. The high reactivity for the photochemically generated ruthenium-oxo species in comparison to other poprhyrin-metal-oxo intermediates suggests it is a true ruthenium(V)-oxo species. PMID:24770388

  7. Serum organochlorines and urinary porphyrin pattern in a population highly exposed to hexachlorobenzene

    Directory of Open Access Journals (Sweden)

    Ribas-Fitó Núria

    2002-07-01

    Full Text Available Abstract Background Porphyria cutanea tarda (PCT is caused by hexachlorobenzene (HCB in several species of laboratory mammals, but the human evidence is contradictory. In a study among adults of a population highly exposed to HCB (Flix, Catalonia, Spain, the prevalence of PCT was not increased. We aimed at analysing the association of individual urinary porphyrins with the serum concentrations of HCB and other organochlorine compounds in this highly exposed population. Methods A cross-sectional study on total porphyrins was carried out in 1994 on 604 inhabitants of the general population of Flix, older than 14 years. Of them, 241 subjects (comprising a random sample and the subgroup with the highest exposure were included for the present study. The porphyrin profile was determined by high-pressure liquid chromatography. Serum concentrations of HCB, as well as common organochlorine compounds, were determined by gas chromatography coupled to electron capture detection. Results Coproporphyrin I (CPI and coproporphyrin III (CPIII were the major porphyrins excreted, while uroporphyrins I and III were only detected in 2% and 36% of the subjects respectively, and heptaporphyrins I and III in 1% and 6%, respectively. CPI and CPIII decreased with increasing HCB concentrations (p Conclusion HCB exposure in this highly exposed population did not increase urinary concentrations of individual porphyrins.

  8. 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.

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

    International Nuclear Information System (INIS)

    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

  10. Redox and photochemical behaviour of a porphyrin monolayer on an indium-tin oxide electrode

    International Nuclear Information System (INIS)

    In order to investigate photoluminescence behaviour of an ordered molecular porphyrin monolayer and its quenching properties by oxygen gas, a porphyrin with long alkyl chains, 5,10,15,20-tetrakis[4-(11-carboxylundecane-1-oxy)phenyl]porphyrin (4), was synthesized and adsorbed onto an indium-tin oxide (ITO) substrate by a chemical dipping method. Cyclic voltammetry was used to analyze the ITO electrode coated with 4. The peak current of the first oxidation was proportional to the sweep rate, and the surface coverage was estimated to be 2.3-2.5 x 10-10 mol cm-2. The UV-vis spectrum of the monolayer showed a broadened Soret band, which shifted to longer wavelength. These features suggest that the porphyrin moieties of 4 are packed to form a J-type structure. The oxygen quenching ratio of the porphyrin 4 monolayer on the ITO electrode, I 0/I 100, was estimated to be 1.25, where I 0 and I 100 are, respectively, luminescence intensity values in 100% argon and 100% oxygen. On repeated step cycling between 100% argon and 100% oxygen atmospheres, the response times of luminescence quenching were 10 s (argon to oxygen) and 23 s (oxygen to argon). These findings suggest that a monolayer of sensing dye is applicable for oxygen sensing system without deterioration of size-accuracy of models

  11. Visible Light Sensitization of Titanium Dioxide with Self-Organized Porphyrins : Organic P-I-N Solar Cells

    NARCIS (Netherlands)

    Wienke, J.; Schaafsma, T.J.; Goossens, A.

    1999-01-01

    Free base 5,10,15,20-tetrakis(4-n-octylphenyl) porphyrin (H2TOPP) belongs to a class of self-organizing porphyrins. Since its LUMO lies above the conduction band of titanium dioxide (TiO2) and its visible light absorption is very strong, sensitization of TiO2 with H2TOPP thin films is possible. Afte

  12. Organometallic cation-exchanged phyllosilicates

    OpenAIRE

    Fleming, Shay

    1991-01-01

    Organotin (IV) complexes formed between 0 01 M dimethyltin dichloride solutions prepared at pH 2 6 and 4 0, and trimethyltin chloride prepared at pH 3 4, with Na- 119 montmori 1lonite clay have been characterised using Sn Mflssbauer spectroscopy, X-ray diffraction, thermogravimetric analysis and water sorption isotherms Following cation exchange, Mttssbauer spectroscopy identified two tin species in the dimethyltin (IV)-exchanged clay prepared at pH 2 6 A cis specie...

  13. Calorimetric study of cationic photopolymerization

    International Nuclear Information System (INIS)

    The photopolymerization of penta-erythritol tetra-glycidyl ether (initiator Degacure KI-85) was studied by a du Pont 910 type DSC. From our experimental results the following conclusions can be drawn: (1) During the cationic polymerization reaction the lifetime of the initiating centers are long compared to the lifetime of free radicals in case of radical polymerization. (2) The rate of deactivation of the initiating centers increases with increasing temperature. (author)

  14. 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.

  15. Electroluminescent property of tetrakis(phenyl)porphyrin carbonyl ruthenium (Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    GUO Jianhua; WU Ying; YE Kaiqi; SUN Yinghui; WANG Yue

    2004-01-01

    Luminescent tetrakis(phenyl)porphyrin car bonyl ruthenium ( II ) (RuTPPCO) complex was employed as a doped emitting material to fabricate red organic electroluminescent (EL) devices. The EL device structure was [ITO/copper phthalocyanine (Cu-Pc) (15.0 nm)/N,N′-di(αnaphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4, 4′-diamine (NPB) (60.0 nm)/tris(8-hydroxyquinolinato)aluminum (Alq3):RuTPPCO (50.0 nm)/LiF (1.0 nm)/Al (200.0 nm)]. The codeposited films of AIq3:RuTPPCO were utilized as the emitting layer to construct EL devices. Experimental results showed that energy transfer from Alq3 to RuTPPCO occurred in the codeposited films. The EL property of the codeposited AIq3:RuTPPCO films with different RuTPPCO concentrations was described. For the EL device with the RuTPPCO concentration of 15% by weight, deep red electroluminescence at 656 nm with the maximum EL efficiency of 0.32 cd/A was achieved.

  16. Modulation of porphyrin photoluminescence by nanoscale spacers on silicon substrates

    Science.gov (United States)

    Fang, Y. C.; Zhang, Y.; Gao, H. Y.; Chen, L. G.; Gao, B.; He, W. Z.; Meng, Q. S.; Zhang, C.; Dong, Z. C.

    2013-11-01

    We investigate photoluminescence (PL) properties of quasi-monolayered tetraphenyl porphyrin (TPP) molecules on silicon substrates modulated by three different nanoscale spacers: native oxide layer (NOL), hydrogen (H)-passivated layer, and Ag nanoparticle (AgNP) thin film, respectively. In comparison with the PL intensity from the TPP molecules on the NOL-covered silicon, the fluorescence intensity from the molecules on the AgNP-covered surface was greatly enhanced while that for the H-passivated surface was found dramatically suppressed. Time-resolved fluorescence spectra indicated shortened lifetimes for TPP molecules in both cases, but the decay kinetics is believed to be different. The suppressed emission for the H-passivated sample was attributed to the weaker decoupling effect of the monolayer of hydrogen atoms as compared to the NOL, leading to increased nonradiative decay rate; whereas the enhanced fluorescence with shortened lifetime for the AgNP-covered sample is attributed not only to the resonant excitation by local surface plasmons, but also to the increased radiative decay rate originating from the emission enhancement in plasmonic "hot-spots".

  17. Modulation of porphyrin photoluminescence by nanoscale spacers on silicon substrates

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Y.C. [Department of Vacuum Science and Engineering, Hefei University of Technology, Hefei, Anhui, 230009 (China); HFNL, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Zhang, Y.; Gao, H.Y.; Chen, L.G.; Gao, B.; He, W.Z.; Meng, Q.S.; Zhang, C. [HFNL, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Dong, Z.C., E-mail: zcdong@ustc.edu.cn [HFNL, University of Science and Technology of China, Hefei, Anhui, 230026 (China)

    2013-11-15

    We investigate photoluminescence (PL) properties of quasi-monolayered tetraphenyl porphyrin (TPP) molecules on silicon substrates modulated by three different nanoscale spacers: native oxide layer (NOL), hydrogen (H)-passivated layer, and Ag nanoparticle (AgNP) thin film, respectively. In comparison with the PL intensity from the TPP molecules on the NOL-covered silicon, the fluorescence intensity from the molecules on the AgNP-covered surface was greatly enhanced while that for the H-passivated surface was found dramatically suppressed. Time-resolved fluorescence spectra indicated shortened lifetimes for TPP molecules in both cases, but the decay kinetics is believed to be different. The suppressed emission for the H-passivated sample was attributed to the weaker decoupling effect of the monolayer of hydrogen atoms as compared to the NOL, leading to increased nonradiative decay rate; whereas the enhanced fluorescence with shortened lifetime for the AgNP-covered sample is attributed not only to the resonant excitation by local surface plasmons, but also to the increased radiative decay rate originating from the emission enhancement in plasmonic “hot-spots”.

  18. Porphyrin-based design of bioinspired multitarget quadruplex ligands.

    Science.gov (United States)

    Laguerre, Aurélien; Desbois, Nicolas; Stefan, Loic; Richard, Philippe; Gros, Claude P; Monchaud, David

    2014-09-01

    Secondary nucleic acid structures, such as DNA and RNA quadruplexes, are potential targets for cancer therapies. Ligands that interact with these targets could thus find application as anticancer agents. Synthetic G-quartets have recently found numerous applications, including use as bioinspired G-quadruplex ligands. Herein, the design, synthesis and preliminary biophysical evaluation of a new prototype multitarget G-quadruplex ligand, (PNA)PorphySQ, are reported, where peptidic nucleic acid guanine ((PNA)G) was incorporated in the porphyrin-templated synthetic G-quartet (PorphySQ). Using fluorescence resonance energy transfer (FRET)-melting experiments, PorphySQ was shown to possess enhanced quadruplex-interacting properties thanks to the presence of four positively charged (PNA)G residues that improve its electrostatic interactions with the binding site of both DNA and RNA quadruplexes (i.e., their negatively charged and accessible G-quartets), thereby making (PNA)PorphySQ an interesting prototype of a multitarget ligand. Both the chemical stability and water solubility of (PNA)PorphySQ are improved over the non-PNA derivative (PorphySQ), which are desirable properties for drug development, and while improvements remain to be made, this ligand is a promising lead for the further development of multitarget G-quadruplex ligands. PMID:24678052

  19. Preparation, nano purification, quality control and labeling optimization of [64Cu]-5,10,15,20-tetrakis (penta fluoro phenyl) porphyrin complex as a possible imaging agent

    International Nuclear Information System (INIS)

    Cu-64 was produced via the 68Zn (p,αn)64Cu nuclear reaction (∼200 mCi, >95 % chemical yield at 180 μA for 1.1 h irradiation, (radionuclidic purity >96 %, copper-67 as impurity) followed by purification with amino functionalized nano magnetic oxide, Fe3O4 aiming to remove trace amount of heavy metal ions from aqueous media due to achieve ultra pure [64Cu] CuCl2 for labeling step. [64Cu] labeled 5,10,15,20-tetrakis(penta fluoro phenyl) porphyrin ([64Cu]-TFPP) was prepared using freshly prepared [64Cu] CuCl2 (Cu-64; T1/2 = 12.7 h) and 5,10,15,20-tetrakis(penta fluoro phenyl)porphyrin (H2TFPP) for 60 min at 100 deg C under reflux condition (radiochemical purity: >97 % ITLC, >98 % HPLC, specific activity: 14-16 GBq/mmol). Stability of the complex was checked in final formulation and human serum for 24 h. The partition coefficient was calculated for the compound (log P = 0.73). The biodistribution of the labeled compound in vital organs of wild-type rats was studied using scarification studies and PET imaging up in 2 and 4 h after injection. A detailed comparative pharmacokinetic study performed for 64Cu cation and [64Cu]-TFPP. The complex is mostly washed out from the circulation through kidneys and liver and can be an interesting tumor imaging/targeting agent due to high specific uptake and rapid excretion through the urinary tract. (author)

  20. Fully Oriented Bilirubin Oxidase on Porphyrin-Functionalized Carbon Nanotube Electrodes for Electrocatalytic Oxygen Reduction.

    Science.gov (United States)

    Lalaoui, Noémie; Le Goff, Alan; Holzinger, Michael; Cosnier, Serge

    2015-11-16

    The efficient immobilization and orientation of bilirubin oxidase from Myrothecium verrucaria on multi-walled carbon nanotube electrodes by using π-stacked porphyrins as a direct electron-transfer promoter is reported. By comparing the use of different types of porphyrin, the rational effect of the porphyrin structure on both the immobilization and orientation of the enzyme is demonstrated. The best performances were obtained for protoporphyrin IX, which is the natural precursor of bilirubin. These electrodes exhibit full orientation of the enzyme, as confirmed by the observable non-catalytic redox system corresponding to the T1 copper center associated with pure Nernstian electrocatalytic behavior with high catalytic currents of almost 5 mA cm(-2) at neutral pH. PMID:26449635

  1. 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.

  2. Structural and electrochemical properties of -tetrabromo-mesotetrakis(4-alkyloxyphenyl)porphyrins and their metal complexes

    Indian Academy of Sciences (India)

    P Bhyrappa; C Arunkumar

    2010-03-01

    Crystal structure of 2,3,12,13-tetrabromo-5,10,15,20-tetrakis(4-butyloxy phenyl)porphinato copper(II) tetrahydrofuran solvate was examined and it features enhanced non-planar distortion of the porphyrin ring. The normal coordinate structural decomposition (NSD) analysis for the out-of-plane displacement of atoms of the macrocyclic ring in CuT(4-CnP)PBr4 ( = 4, 6) indicates mainly saddled distortion combined with small contribution from wave conformation. The electrochemical studies on MT (4-CnP)PBr4 (M = 2H, Cu(II), Zn(II)) revealed cathodic shift in redox potentials in contrast to the corresponding brominated porphyrins, MTPPBr4. This is perhaps due to non-planarity of the porphyrin ring and the positive inductive effect of the alkyloxy groups.

  3. Surface-Mediated in Situ Metalation of Porphyrins at the Solid-Vacuum Interface.

    Science.gov (United States)

    Marbach, Hubertus

    2015-09-15

    The investigation of porphyrin derivatives at the solid-vacuum interface has become a vivid research field with the prospect to tailor functional molecular architectures and as prototype examples to study the fundamental properties of porphyrin derivatives in regard to their vital role in many natural processes. The functional properties of the porphyrin derivatives are mainly determined by the central metal atom. Thus, the recent exploration of the surface-confined in situ metalation of porphyrins is an important step toward the realization of molecule-based functional devices. The corresponding metalation reaction of free base porphyrin derivatives can be conveniently realized in situ in ultrahigh vacuum by post- or predeposition of metal atoms or directly with substrate atoms in the so-called self-metalation. Moderate heating above room temperature (RT) might be necessary either to realize the transport of the metal to the porphyrin via diffusion or to overcome an activation barrier determined by the redox reaction itself. Surface science techniques like scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and temperature-programmed desorption (TPD) are powerful tools to scrutinize the reaction and give valuable insights into the metalation process. For example, the completed metalation can be reflected in an enhanced apparent height of the corresponding porphyrin in STM or can be evidenced by characteristic changes in the N 1s region in XPS. These signatures allow monitoring of the progress of the metalation, and it was found that the reaction generally proceeds with very high yield. Surface diffusion of the coadsorbed metal atoms mediates the reaction and is crucial for the high yields of the corresponding reactions with pre- and postadsorbed metals. It was also demonstrated that the completed metalation can indeed significantly alter the adsorption behavior and the electronic properties and thus the functionality of the porphyrin

  4. Molecular design of high performance fused porphyrin one-dimensional wire: A DFT study

    International Nuclear Information System (INIS)

    Hybrid density functional theory (DFT) calculations have been carried out for oligomer species of a fused porphyrin, denoted by P(n), where n represents the number of porphyrin rings in the oligomer, to elucidate the electronic structures at ground and excited states. A polymer of fused porphyrin (p-Por) was also investigated using one-dimensional periodic boundary conditions (PBC) for comparison. It was found that the lowest energy band is located below 0.6 eV in the case of oligomers larger than n = 8, which corresponds to a band gap of p-Por. Carrier transport pathways in p-Por were discussed on the basis of theoretical results.

  5. Effect of Central Metal on Nonlinear Optical Properties of Porphyrins and Their Graphene Composites

    Science.gov (United States)

    Leng, Jian-Cai; Zhao, Li-Yun; Zhang, Yu-Jin; Ma, Hong

    2016-09-01

    The nonlinear optical properties of a series of newly synthesized porphyrins with different central metals and their covalently linked graphene composites are theoretically studied by numerically solving the rate equations and field intensity equation. Calculated results show that all the studied compounds are promising candidates for optical limiters, and graphene-porphyrin composites are expected to be preferable optical limiters because of their excellent nonlinear absorption abilities. In addition, the central metal in the porphyrin is found to be crucial to the optical power limiting and two-photon absorption performances of the compounds. Our results reproduce the experimental measurements. Additionally, special emphasis is placed on the factors that can affect the nonlinear optical properties of the compounds, indicating that one can create favorable nonlinear optical properties of the compounds by changing either the parameters of the absorber, including the concentration and thickness, or the pulse duration.

  6. Synthesis and comparative toxicology of a series of polyhedral borane anion-substituted tetraphenyl porphyrins.

    Science.gov (United States)

    Koo, Myoung-Seo; Ozawa, Tomoko; Santos, Raquel A; Lamborn, Kathleen R; Bollen, Andrew W; Deen, Dennis F; Kahl, Stephen B

    2007-02-22

    Three structurally similar tetraphenylporphyrins bearing polyhedral borane anions have been synthesized and their toxicological profiles obtained in rats. These conjugates were found to have quite different acute toxicities as manifested at the maximum tolerated dose (MTD). When given at the MTD and observed over 28 days, the most acutely toxic porphyrin was found to be devoid of toxicity, as measured by blood chemistry panels. The remaining two less acutely toxic compounds both elicited significant changes, characterized by moderate to severe thrombocytopenia, failure to gain weight normally and changes in liver enzymes indicative of mild hepatotoxicity. All toxic effects were transient, with platelets rebounding to above normal levels at day 28. We conclude that thrombocytopenia is the dose limiting toxicity for boronated porphyrins in mammals and suggest that these effects may be due to the porphyrin, not the borane or carborane. PMID:17253677

  7. Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions.

    Science.gov (United States)

    Zhang, Zhan; Kim, Dong Sub; Lin, Chung-Yon; Zhang, Huacheng; Lammer, Aaron D; Lynch, Vincent M; Popov, Ilya; Miljanić, Ognjen Š; Anslyn, Eric V; Sessler, Jonathan L

    2015-06-24

    Porphyrins have been used frequently to construct supramolecular assemblies. In contrast, noncovalent ensembles derived from expanded porphyrins, larger congeners of naturally occurring tetrapyrrole macrocycles, are all but unknown. Here we report a series of expanded porphyrin-anion supramolecular assemblies. These systems display unique environmentally responsive behavior. Addition of polar organic solvents or common anions to the ensembles leads to either a visible color change, a change in the fluorescence emission features, or differences in solubility. The actual response, which could be followed easily by the naked eye, was found to depend on the specifics of the assembly, as well as the choice of analyte. Using the ensembles of this study, it proved possible to differentiate between common solvents, such as diethyl ether, THF, ethyl acetate, acetone, alcohol, acetonitrile, DMF, and DMSO, identify complex solvent systems, as well as distinguish between the fluoride, chloride, bromide, nitrate, and sulfate anions. PMID:25965790

  8. Nonlinear optical properties of porphyrin and chlorophyll dimers studied by degenerated four wave mixing

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L.X.Q.

    1992-12-31

    As one of the important elements in natural and artificial electron transfer and energy transfer processes, porphyrin and its derivatives have received much attention in photoelectronics and photoelectronic materials. As our first attempt to relate the {pi}-{pi} electronic couplings between porphyrin macrocycles to apparent third order nonlinear susceptibilities, we measured {chi}({sup 3}) for several porphyrin and chlorophyll a derivatives, including dimers with different configurations. Our preliminary results show that the dimers have enhanced {chi}({sup 3}) compared to those of the monomer. This enhancement is related to the relative orientations between the two macrocycles in the dimers. The parallel dimers with close face-to-face distances seem to have the highest enhancement in {chi}({sup 3}). Thus, we believe that {chi}({sup 3}) is strongly related to the {pi}-{pi} electronic coupling between the two conjugated ring systems.

  9. Nonlinear optical properties of porphyrin and chlorophyll dimers studied by degenerated four wave mixing

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L.X.Q.

    1992-01-01

    As one of the important elements in natural and artificial electron transfer and energy transfer processes, porphyrin and its derivatives have received much attention in photoelectronics and photoelectronic materials. As our first attempt to relate the [pi]-[pi] electronic couplings between porphyrin macrocycles to apparent third order nonlinear susceptibilities, we measured [chi]([sup 3]) for several porphyrin and chlorophyll a derivatives, including dimers with different configurations. Our preliminary results show that the dimers have enhanced [chi]([sup 3]) compared to those of the monomer. This enhancement is related to the relative orientations between the two macrocycles in the dimers. The parallel dimers with close face-to-face distances seem to have the highest enhancement in [chi]([sup 3]). Thus, we believe that [chi]([sup 3]) is strongly related to the [pi]-[pi] electronic coupling between the two conjugated ring systems.

  10. Radiosynthesis and biological evaluation of 166Ho labeled methoxylated porphyrins as possible therapeutic agents

    International Nuclear Information System (INIS)

    166Ho labeled 5,10,15,20-tetrakis(3,4-dimethoxyphenyl) porphyrin, and 5,10,15,20-tetrakis(3,4,5-trimethoxyphenyl) porphyrin ([166Ho]-TDMPP and [166Ho]-TTMPP respectively) were prepared with acceptable radiochemical purity and specific activities. Stability and partition coefficient of the complexes were determined in the final formulations and biodistribution studies in mouse demonstrated high accumulation of [166Ho]-TDMPP in the lung and liver and less excretion through the kidney. while [166Ho]-TTMPP was mostly excreted into intestines and kidneys while lungs were a minor accumulation site. In contrast to other reported radiolanthanide labeled porphyrins these two complexes showed less liver accumulation. Further investigation of their potential therapeutic properties is of interest. (author)

  11. Syntheses, Spectroscopic and AFM Characterization of Some Manganese Porphyrins and Their Hybrid Silica Nanomaterials

    Directory of Open Access Journals (Sweden)

    Gheorghe Fagadar-Cosma

    2009-03-01

    Full Text Available The present work is concerned with the manganese complexes of 5,10,15,20-tetraphenylporphyrin and of 5,10,15,20-tetra(3-hydroxyphenylporphyrin, which were prepared by metallation of the corresponding porphyrin ligands, and the study of their spectroscopic and photophysical behavior under strongly acidic and alkaline conditions. The second objective was to obtain and study some new hybrid materials, with special optoelectronic and surface properties, by impregnation of silica gels obtained by one step acid and by two steps acid-base catalysis with these Mn-porphyrins. The resulting nanomaterials exhibited interesting bathochromic and hyperchromic effects of their second band in the emission spectra in comparison with the Mn-porphyrins and also they have distinct orientation of the aggregates on surfaces, as shown by AFM images, making them useful for applications in medicine, formulation of sensors and for environmental-friendly catalysts for photodegradation of organic compounds.

  12. Synthetic Methodology for the Fabrication of Porous Porphyrin Materials with Metal-Organic-Polymer Aerogels.

    Science.gov (United States)

    Zhao, Xin; Yuan, Lin; Zhang, Zeng-Qi; Wang, Yong-Song; Yu, Qiong; Li, Jun

    2016-06-01

    A promising fabrication strategy used for designing porous porphyrin materials and a group of rigid carboxyl porphyrins based metal-organic-polymer aerogels (MOPAs) has been proposed recently. These newly synthesized MOPAs were exemplarily characterized by FT-IR, UV-vis-DRS, EDS, PXRD, TGA, SEM, TEM, and gas sorption measurements. A gelation study has shown that solvents, molar ratio, temperature, and peripheral carboxyl number in porphyrins all affect gel generation. The MOPA series exhibit eminent thermal stability, high removal efficiency in dye adsorption, versatile morphologies, and permanent tunable porosity; also the BET surface areas fall within the range 249-779 m(2) g(-1). All of the mentioned properties are significantly superior to some other porous materials, which enable these compounds to be potential candidates for dye uptake, gas storage, and separation. PMID:27159626

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

    OpenAIRE

    Ambrish Singh; Yuanhua Lin; Mumtaz A. Quraishi; Olasunkanmi, Lukman O.; Omolola E. Fayemi; Yesudass Sasikumar; Baskar Ramaganthan; Indra Bahadur; Ime B. Obot; Abolanle S. Adekunle; Mwadham M. Kabanda; Eno E. Ebenso

    2015-01-01

    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-tetrayl)tetrakis(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 ...

  14. Photophysics of the porphyrins and hybrid materials obtained on their basis: A prospective chiral biosensor

    Energy Technology Data Exchange (ETDEWEB)

    Pedziwiatr, M.; Wiglusz, R. [Faculty of Chemistry, University of Wroclaw, 50-383 Wroclaw (Poland); Graczyk, A. [Institute of Optoelectronics, Military Technical University, Warsaw (Poland); Legendziewicz, J. [Faculty of Chemistry, University of Wroclaw, 50-383 Wroclaw (Poland)], E-mail: jl@wchuwr.chem.uni.wroc.pl

    2008-02-28

    Porphyrins are known to play a significant role in several biological systems. The research conducted for many years proved the versatility of applications involving porphyrin, often including the different areas of life [M. Gouterman, in: D. Dolphin (Ed.), The Porphyrins, vol. III, Academic Press, 1978, p. 1]. They can be used as active elements of biosensors, molecular switching devices and in non-linear optical materials, and in photodynamic cancer therapy as well. High quality optical materials with extremely good thermal and chemical stabilities can be produced by using a technique of silica sol-gel derived matrices [M. Rui Pereira, J.A. Ferreira, G. Hungrford, J. Photochem. Photobiol. 172 (2005) 7-17; J. Sokolnicki, R. Wiglusz, S. Radzki, A. Graczyk, J. Legendziewicz, Opt. Mater. 26 (2004) 199-206; R. Reisfeld, New materials for nonlinear optics. Optical and electronic phenomena in sol-gel glasses and modern applications, in: R. Reisfeld, C.K. Jorgensen (Eds.), Struct. Bond. 85 (1996) 99-147; B.G. Gregg, M.A. Fox, A.J. Bard, J. Am. Chem. Soc. 111 (1989) 3024; M. Ochsner, J. Photochem. Photobiol. 39 (1997) 1]. Recently, we have reported the photophysical behavior of the selected porphyrins contained within solution and entrapped in silica sol-gel derived matrices [J. Sokolnicki, R. Wiglusz, S. Radzki, A. Graczyk, J. Legendziewicz, Opt. Mater. 26 (2004) 199-206; R. Wiglusz, J. Legendziewicz, A. Graczyk, S. Radzki, P. Gawryszewska, J. Sokolnicki, J. Alloys Compd. 380 (2004) 396-404]. The present paper is devoted to photophysical characteristics of new - also chiral - porphyrins, and incorporated in silica sol-gel matrices; perspective chiral biosensors. In this paper, the synthesis and spectroscopic studies of porphyrin derivatives, at room and low temperatures in solutions and hybrid organic-inorganic materials obtained in different conditions by the sol-gel route are performed. An effect of different factors on emission efficiency is discussed.

  15. Photophysics of the porphyrins and hybrid materials obtained on their basis: A prospective chiral biosensor

    International Nuclear Information System (INIS)

    Porphyrins are known to play a significant role in several biological systems. The research conducted for many years proved the versatility of applications involving porphyrin, often including the different areas of life [M. Gouterman, in: D. Dolphin (Ed.), The Porphyrins, vol. III, Academic Press, 1978, p. 1]. They can be used as active elements of biosensors, molecular switching devices and in non-linear optical materials, and in photodynamic cancer therapy as well. High quality optical materials with extremely good thermal and chemical stabilities can be produced by using a technique of silica sol-gel derived matrices [M. Rui Pereira, J.A. Ferreira, G. Hungrford, J. Photochem. Photobiol. 172 (2005) 7-17; J. Sokolnicki, R. Wiglusz, S. Radzki, A. Graczyk, J. Legendziewicz, Opt. Mater. 26 (2004) 199-206; R. Reisfeld, New materials for nonlinear optics. Optical and electronic phenomena in sol-gel glasses and modern applications, in: R. Reisfeld, C.K. Jorgensen (Eds.), Struct. Bond. 85 (1996) 99-147; B.G. Gregg, M.A. Fox, A.J. Bard, J. Am. Chem. Soc. 111 (1989) 3024; M. Ochsner, J. Photochem. Photobiol. 39 (1997) 1]. Recently, we have reported the photophysical behavior of the selected porphyrins contained within solution and entrapped in silica sol-gel derived matrices [J. Sokolnicki, R. Wiglusz, S. Radzki, A. Graczyk, J. Legendziewicz, Opt. Mater. 26 (2004) 199-206; R. Wiglusz, J. Legendziewicz, A. Graczyk, S. Radzki, P. Gawryszewska, J. Sokolnicki, J. Alloys Compd. 380 (2004) 396-404]. The present paper is devoted to photophysical characteristics of new - also chiral - porphyrins, and incorporated in silica sol-gel matrices; perspective chiral biosensors. In this paper, the synthesis and spectroscopic studies of porphyrin derivatives, at room and low temperatures in solutions and hybrid organic-inorganic materials obtained in different conditions by the sol-gel route are performed. An effect of different factors on emission efficiency is discussed

  16. 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.

  17. Synthesis of porphyrin-introduced silica gels by sol-gel process.

    Science.gov (United States)

    Tanaka, Hidekazu; Yamada, Toshiyuki; Sugiyama, Shinichiro; Shiratori, Hideo; Hino, Ryozi

    2005-06-15

    Using a hydroxyl group appended free base porphyrin derivative (HP), porphyrin-introduced silica gels were synthesized by a sol-gel process. The HP content in the materials linearly increased with increasing the HP concentration. Meanwhile, free base tetraphenylporphyrin (TPP) with no hydroxyl groups were almost not incorporated into the silica gels. These facts suggested that the interaction between hydroxyl groups of the HP molecules and silica network is considerably strong. The UV-vis characters of HP-introduced materials were almost the same as pure HP molecules. The Beer's plot indicated that the HP molecules in the materials are dispersed. PMID:15897099

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

    Directory of Open Access Journals (Sweden)

    Cláudia M. B. Neves

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

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

  20. Synthesis of Five-Porphyrin Nanorings by Using Ferrocene and Corannulene Templates.

    Science.gov (United States)

    Liu, Pengpeng; Hisamune, Yutaka; Peeks, Martin D; Odell, Barbara; Gong, Juliane Q; Herz, Laura M; Anderson, Harry L

    2016-07-11

    The smallest and most strained member of a family of π-conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene. Both templates are effective for directing the synthesis of the butadiyne-linked cyclic pentamer, despite the fact that the radii of their N5 donor sets are too small by 0.5 Å and 0.9 Å, respectively (from DFT calculations). The five-porphyrin nanoring exhibits a structured absorption spectrum and its fluorescence extends to 1200 nm, reflecting strong π conjugation and Herzberg-Teller vibronic coupling. PMID:27213825

  1. Probing Flexibility in Porphyrin-Based Molecular Wires Using Double Electron Electron Resonance

    OpenAIRE

    Lovett, Janet E.; Hoffmann, Markus; Cnossen, Arjen; Shutter, Alexander T. J.; Hogben, Hannah J.; Warren, John E; Pascu, Sofia I.; Kay, Christopher W. M.; Timmel, Christiane R.; Anderson, Harry L.

    2009-01-01

    A series of butadiyne-linked zinc porphyrin oligomers, with one, two, three, and four porphyrin units and lengths of up to 75 angstrom, have been spin-labeled at both ends with stable nitroxide TEMPO radicals. The pulsed EPR technique of double electron electron resonance (DEER) was used to probe the distribution of intramolecular end-to-end distances, under a range of conditions. DEER measurements were carried out at 50 K in two types of dilute solution glasses: deutero-toluene (with 10% deu...

  2. Determination of Mass Spectrometric Sensitivity of Different Metalloporphyrin Esters Relative to Porphyrin Ester

    DEFF Research Database (Denmark)

    Larsen, Elfinn; Egsgaard, Helge; Møller, J.; With, T. K.

    1977-01-01

    Quantitative determination of metalloporphyrin contamination in preparations of biologically important porphyrins was achieved mass spectrometrically by application of the integrated ion current technique. For this purpose, the relative molecular ion sensitivities of the contaminating metal compl...... complexes were determined from the ratios of the integrated molecular ion currents of a series of calibration samples containing a porphyrin ester and one of its metal complexes in known molar ratio. Complexes formed with divalent ions of Cu, Zn, Fe, Co and Ni of copro- as well as uro...

  3. Electron transport property of cobalt-centered porphyrin-armchair graphene nanoribbon (AGNR) junction

    International Nuclear Information System (INIS)

    We have investigated the electron transport properties of Cobalt-centered (Co-centered) porphyrin molecule using the density functional theory and non-equilibrium greens function method. Here we have reported transmission coefficient as well as current voltage characteristics of Co-centered porphyrine molecule connected between armchair graphene nanoribbons. It has been found that at low bias region i.e., 0 V to 0.3 V it does not contribute any current. Gradual increase of bias voltage results different order of magnitude of current in different bias region

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

    International Nuclear Information System (INIS)

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

  5. Magnetic configuration dependence of magnetoresistance in a Fe-porphyrin-like carbon nanotube spintronic device

    International Nuclear Information System (INIS)

    By using nonequilibrium Green's functions in combination with the density functional theory, we investigate the spin-dependent transport properties in a Fe-porphyrin-like carbon nanotube spintronic device. The results show that magnetoresistance ratio is strongly dependent on the magnetic configuration of the Fe-porphyrin-like carbon nanotube. Under the application of the external magnetic field, the magnetoresistance ratio of the device can be increased from about 19% to about 1020% by tuning the magnetic configuration in the device. Our results confirm that the magnetic configuration is a key factor for obtaining a high-performance spintronic device

  6. Cation coordination in oxychloride glasses

    Science.gov (United States)

    Johnson, J. A.; Holland, D.; Bland, J.; Johnson, C. E.; Thomas, M. F.

    2003-02-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb2O3]x - [ZnCl2]1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Mössbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb)2(OZn)] and [Zn(ClZn)2(OSb)2].

  7. Cation coordination in oxychloride glasses

    International Nuclear Information System (INIS)

    Glasses containing mixtures of cations and anions of nominal compositions [Sb2O3]x - [ZnCl2]1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb)2(OZn)] and [Zn(ClZn)2(OSb)2

  8. Cation coordination in oxychloride glasses

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J A [Energy Technology Division, Argonne National Laboratory, Argonne, IL (United States); Holland, D [Physics Department, Warwick University, Coventry (United Kingdom); Bland, J [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom); Johnson, C E [Physics Department, Northern Illinois University, DeKalb, IL (United States); Thomas, M F [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom)

    2003-02-19

    Glasses containing mixtures of cations and anions of nominal compositions [Sb{sub 2}O{sub 3}]{sub x} - [ZnCl{sub 2}]{sub 1-x} where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb){sub 2}(OZn)] and [Zn(ClZn){sub 2}(OSb){sub 2}].

  9. Use of laser induced photoacoustic spectroscopy (LIPAS) to determine equilibrium constants of cation-cation complexes

    International Nuclear Information System (INIS)

    Laser Induced PhotoAcoustic Spectroscopy (LIPAS) is a relatively new, photothermal technique to examine solutions. Studies in the past have shown it to be more sensitive than conventional absorption spectroscopy, while, yielding the same information thus allowing lower concentrations to be used. This study is using LIPAS to examine solutions to determine the equilibrium constants of cation-cation complexes. It has been found that actinyl(V) cations form cation-cation complexes with a variety of cations, including actinyl(VI) cations. The radioactive nature of the actinide elements requires special handling techniques and also require limits be placed on the amount of material that can be used. The sensitivity of some oxidation states of the actinides to oxygen also presents a problem. Preliminary results will be presented for actinyl(V)-actinyl(VI) cation-cation complexes that were studied using a remote LIPAS system incorporating fiber optics for transmission of laser signals

  10. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.

    2010-03-01

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

  11. STM-induced light emission from the surface of H2TBP porphyrin/PFP porphyrin/Cu(1 0 0)

    International Nuclear Information System (INIS)

    Molecular fluorescence from the surface of H2TBP porphyrin (H2TBPP) monolayer on the top of PFP porphyrin (PFPP) multilayers on Cu(1 0 0) substrate is studied by an ultrahigh-vacuum scanning tunneling microscope. H2TBPP molecular luminescence spectra are well defined and in perfect matching with conventional photoluminescence spectra excited from the corresponding bulk molecule. The electronic states of H2TBPP monolayer are effectively decoupled from the metal surface by controlling the thickness of PFPP multilayers in a nanoscale regime. The excitation mechanism is probably attributed to the hot electron injection. These results provide a new way for the development of nanoscale molecular light source and spectroscopy

  12. 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.

  13. Anti-inflammatory activity of cationic lipids

    OpenAIRE

    Filion, Mario C; Phillips, Nigel C

    1997-01-01

    The effect of liposome phospholipid composition has been assumed to be relatively unimportant because of the presumed inert nature of phospholipids.We have previously shown that cationic liposome formulations used for gene therapy inhibit, through their cationic component, the synthesis by activated macrophages of the pro-inflammatory mediators nitric oxide (NO) and tumour necrosis factor-α (TNF-α).In this study, we have evaluated the ability of different cationic lipids to reduce footpad inf...

  14. Sol-gel hosts doped with porphyrin derivatives. Part I. Spectroscopy, hole-burning and spectral diffusion

    Science.gov (United States)

    Kulikov, S. G.; Veret-Lemarinier, A. V.; Galaup, J. P.; Chaput, F.; Boilot, J. P.

    1997-03-01

    Pure inorganic sol-gel matrices as well as hybrid organic/inorganic xerogels have been doped with porphyrins derivatives and studied using line narrowing techniques. The role of residual hydroxyl groups is investigated. Free-base porphyrins are protonated in pure inorganic hosts, but the matrix acidity is reduced in hybrid matrices or when fluorinated porphyrins derivatives are used. The linear electron-phonon coupling can be controlled with the choice of the organic group in organic/inorganic matrices. Persistent spectral hole widths increase with temperature according a glass-like Tn dependence and evidence of spectral diffusion is shown in one of these systems.

  15. First example of a lipophilic porphyrin-cardanol hybrid embedded in a cardanol-based micellar nanodispersion.

    Science.gov (United States)

    Bloise, Ermelinda; Carbone, Luigi; Colafemmina, Giuseppe; D'Accolti, Lucia; Mazzetto, Selma Elaine; Vasapollo, Giuseppe; Mele, Giuseppe

    2012-01-01

    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. PMID:23079496

  16. Anti-inflammatory activity of cationic lipids.

    Science.gov (United States)

    Filion, M C; Phillips, N C

    1997-10-01

    1. The effect of liposome phospholipid composition has been assumed to be relatively unimportant because of the presumed inert nature of phospholipids. 2. We have previously shown that cationic liposome formulations used for gene therapy inhibit, through their cationic component, the synthesis by activated macrophages of the pro-inflammatory mediators nitric oxide (NO) and tumour necrosis factor-alpha (TNF-alpha). 3. In this study, we have evaluated the ability of different cationic lipids to reduce footpad inflammation induced by carrageenan and by sheep red blood cell challenge. 4. Parenteral (i.p. or s.c) or local injection of the positively charged lipids dimethyldioctadecylammomium bromide (DDAB), dioleyoltrimethylammonium propane (DOTAP), dimyristoyltrimethylammonium propane (DMTAP) or dimethylaminoethanecarbamoyl cholesterol (DC-Chol) significantly reduced the inflammation observed in both models in a dose-dependent manner (maximum inhibition: 70-95%). 5. Cationic lipids associated with dioleyol- or dipalmitoyl-phosphatidylethanolamine retained their anti-inflammatory activity while cationic lipids associated with dipalmitoylphosphatidylcholine (DPPC) or dimyristoylphosphatidylglycerol (DMPG) showed no anti-inflammatory activity, indicating that the release of cationic lipids into the macrophage cytoplasm is a necessary step for anti-inflammatory activity. The anti-inflammatory activity of cationic lipids was abrogated by the addition of dipalmitoylphosphatidylethanolamine-poly(ethylene)glycol-2000 (DPPE-PEG2000) which blocks the interaction of cationic lipids with macrophages. 6. Because of the significant role of protein kinase C (PKC) in the inflammatory process we have determined whether the cationic lipids used in this study inhibit PKC activity. The cationic lipids significantly inhibited the activity of PKC but not the activity of a non-related protein kinase, PKA. The synthesis of interleukin-6 (IL-6), which is not dependent on PKC activity for its

  17. A Tb–Zn tetra(4-sulfonatophenyl)porphyrin hybrid: Preparation, structure, photophysical and electrochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wen-Tong, E-mail: wtchen_2000@aliyun.com [Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji' an 343009, Jiangxi (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian (China); Hu, Rong-Hua; Wang, Yin-Feng; Zhang, Xian [Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji' an 343009, Jiangxi (China); Liu, Juan [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian (China)

    2014-05-01

    A terbium-zinc porphyrin, i.e. [TbZn(TPPS)H{sub 3}O]{sub n} (1) (TPPS=tetra(4-sulfonatophenyl)porphyrin), has been obtained from a solvothermal reaction and structurally analyzed by single-crystal X-ray diffraction. Compound 1 is characteristic of a condensed three-dimensional (3-D) porous open framework with two types of infinite one-dimensional (1-D) chain-like structure. Compound 1 exhibits a void space of 215 Å{sup 3}, which is 9.2% of the unit-cell volume. TG/DTA measurement reveals that the framework of compound 1 is thermally stable up to 336 °C. In order to reveal its photophysical and electrochemical properties, we investigated compound 1 in detail with UV–vis spectra, fluorescence, quantum yield, luminescence lifetime, and CV/DPV. - Graphical abstract: A terbium–zinc porphyrin [TbZn(TPPS)H{sub 3}O]{sub n} has been obtained from a solvothermal reaction. It features a condensed 3-D porous open framework. It shows good thermal stability. - Highlights: • This paper reports a novel terbium–zinc porphyrin. • It features a novel condensed three-dimensional porous open framework. • The title compound is thermally stable up to 336 °C. • It is studied by UV–vis, fluorescence, quantum yield, lifetime, and CV/DPV.

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

    Czech Academy of Sciences Publication Activity Database

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

    2012-01-01

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

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

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Samec, Zdeněk

    2012-01-01

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

  20. Mg-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments

    Czech Academy of Sciences Publication Activity Database

    Kovář, P.; Pospíšil, M.; Káfuňková, Eva; Lang, Kamil; Kovanda, F.

    2010-01-01

    Roč. 16, č. 2 (2010), s. 223-233. ISSN 1610-2940 R&D Projects: GA ČR(CZ) GA203/06/1244; GA AV ČR KAN100500651 Institutional research plan: CEZ:AV0Z40320502 Keywords : layered double hydroxide * porphyrin * molecular simulations Subject RIV: CA - Inorganic Chemistry Impact factor: 1.871, year: 2010

  1. Redox tuning of cytochrome b562 through facile metal porphyrin substitution

    DEFF Research Database (Denmark)

    Della Pia, Eduardo Antonio; Chi, Qijin; Elliott, Martin; Macdonald, J. Emyr; Ulstrup, Jens; Jones, D. Dafydd

    2012-01-01

    The biologically and nanotechnologically important heme protein cytochrome b562 was reconstructed with zinc and copper porphyrins, leading to significant changes in the spectral, redox and electron transfer properties. The Cu form shifts the redox potential by +300 mV and exhibits high electron...

  2. Controlled electropolymerisation of a carbazole-functionalised iron porphyrin electrocatalyst for CO2 reduction

    DEFF Research Database (Denmark)

    Hu, Xinming; Salmi, Zakaria; Lillethorup, Mie; Bjerglund Pedersen, Emil; Robert, Marc; Pedersen, Steen U.; Skrydstrup, Troels; Daasbjerg, Kim

    2016-01-01

    Using a one-step electropolymerisation procedure, CO2 absorbing microporous carbazole-functionalised films of iron porphyrins are prepared in a controlled manner. The electrocatalytic reduction of CO2 for these films is investigated to elucidate their efficiency and the origin of their ultimate...

  3. Porphyrin-cyclodextrin conjugates as a nanosystem for versatile drug delivery and multimodal cancer therapy

    Czech Academy of Sciences Publication Activity Database

    Králová, Jarmila; Kejík, Z.; Bříza, T.; Poučková, P.; Kral, A.; Martásek, P.; Král, V.

    2010-01-01

    Roč. 53, č. 1 (2010), s. 128-138. ISSN 0022-2623 Institutional research plan: CEZ:AV0Z50520514 Keywords : photodynamic therapy * cancer therapy * porphyrin conjugate Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 5.207, year: 2010

  4. Zn-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments

    Czech Academy of Sciences Publication Activity Database

    Kovář, P.; Pospíšil, M.; Futera, Z.; Lang, Kamil; Káfuňková, Eva; Taviot-Guého, Ch.; Bezdička, Petr

    Castellaneta Marina : AISA, 2009. s. 477. ISBN 978-88-7522-027-3. [International Clay Conference /14./. 14.06.2009-20.06.2009, Castellaneta Marina] R&D Projects: GA ČR(CZ) GA203/06/1244 Institutional research plan: CEZ:AV0Z40320502 Keywords : porphyrin s * layered double hydroxides * molecular modeling Subject RIV: CA - Inorganic Chemistry

  5. Transient Anisotropy in Degenerate Systems: Experimental Observation in a Cd-porphyrin

    Directory of Open Access Journals (Sweden)

    Unterreiner A.-N.

    2013-03-01

    Full Text Available An unusual high transient anisotropy up to 0.65 in cadmium meso-tetraphenyl porphyrin in tetrahydrofuran was recorded which dacays on a 100 ps timescale. Opposite to previous work, this behaviour was explained by an incoherent mixing of excited state absorption, ground state bleach and stimulated emission.

  6. Novel Receptors Based on the Porphyrin-Calix[4]Arene Conjugates

    Czech Academy of Sciences Publication Activity Database

    Dudic, M.; Lang, Kamil

    Leuven: Global Supramolecular Chemistry Network, 2000. s. 88 [International Conference on Supramolecular Science & Technology /2./. 10.09.2000-14.09.2000, Leuven] Institutional research plan: CEZ:AV0Z4032918 Keywords : porphyrin * receptors * calix[4]arene Subject RIV: CA - Inorganic Chemistry

  7. 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...

  8. Gallium and Functionalized-Porphyrins Combine to Form Potential Lysosome-Specific Multimodal Bioprobes.

    Science.gov (United States)

    Pan, Jie; Harriss, Bethany I; Chan, Chi-Fai; Jiang, Lijun; Tsoi, Tik-Hung; Long, Nicholas J; Wong, Wing-Tak; Wong, Wai-Kwok; Wong, Ka-Leung

    2016-07-18

    A water-soluble bimetallic normal ("cold") and radiochemical ("hot") gallium-porphyrin-ruthenium-bipyridine complex (GaporRu-1) has been synthesized by microwave methodology in short reaction times with good (>85%) yields. (68)GaporRu-1 is demonstrated to be a potential multimodal and functional bioprobe for positron emission tomography (PET), lysosome specific optical imaging, and photodynamic therapy. PMID:27355871

  9. Silica-porphyrin hybrid nanotubes for in vivo cell tracking by near-infrared fluorescence imaging.

    Science.gov (United States)

    Hayashi, Koichiro; Nakamura, Michihiro; Ishimura, Kazunori

    2012-04-21

    Near-infrared fluorescent silica-porphyrin hybrid nanotubes (HNTs) were successfully synthesized by π-π stacking, electrostatic interaction and a sol-gel reaction. The HNTs-labeled macrophages were detected in vivo, and the minimum detectable number of cells was 200. Furthermore, the biodistribution of HNTs-labeled macrophages was tracked by fluorescence imaging. PMID:22437325

  10. Expanded porphyrins as third order non-linear optical materials: Some structure-function correlations

    Indian Academy of Sciences (India)

    Sabapathi Gokulnath; Tavarekere K Chandrashekar

    2008-01-01

    In this paper, the non-linear optical properties of representative core-modified expanded porphyrins have been investigated with an emphasis on the structure-property relationship between the aromaticity and conformational behaviour. It has been shown that the measured two-photon absorption cross section (2) values depend on the structure of macrocycle, its aromaticity and the number of -electrons in conjugation.

  11. Effect of geometrical orientation on the charge transfer energetics of supramolecular (tetraphenyl)-porphyrin/fullerens dyads

    Science.gov (United States)

    Olguin, Marco; Zope, Rajendra; Baruah, Tunna

    2013-03-01

    We present our study of several low lying charge-transfer (CT) excitation energies for a widely used donor-acceptor system composed of a porphyrin-fullerene pair. The dyad systems consist of C60 and C70 acceptor systems coupled to tetraphenyl-porphyrin (TPP) and tetraphenyl-(zinc)porphyrin (ZnTPP) donor systems in a co-facial orientation. We find that replacing C60 by C70 in a given dyad may increase the lowest charge transfer excitation energy by about 0.27 eV, whereas varying the donor in these complexes had marginal effect on the lowest charge transfer excitation energy. Additionally, we examined the effect of geometrical orientation on the CT energy by calculating several CT excited state energies for an end-on orientation of the porphyrin-fullerene dyads. The CT excitation energies are larger for the end-on orientation in comparison to the co-facial orientation by 0.6 eV - 0.75 eV. The difference is attributed to a reduced exciton binding energy in going from the co-facial to the end-on orientation. Supported by Office of Basic Energy Sciences of the US Department of Energy.

  12. The effect of porphyrin and radiation on ferrochelatase and 5-aminolevulinic acid synthase in epidermal cells

    International Nuclear Information System (INIS)

    The effects of ultraviolet A (UVA) and blue light on ferrochelatase protein, and its mRNA level, in 5-aminolevulinic acid (ALA)-loaded A431 cells was evaluated. Western blot analysis of ferrochelatase protein showed a protein band of 43 kDA. There was a decrease in the protein concentration 24 h and 48 h after irradiation of these cells. In contrast, as judged by Northern blot analysis, there was no change in ferochelatase mRNA level. Measurement of ALA synthase activity showed an ALA dose-dependent but radiation-independent decrease of enzyme activity, suggesting an end-product feedback inhibition. Since reactive oxygen species generated by porphyrin-induced photochemical reaction may be involved in the decrease in ferrochelatase protein, the effect of scavengers of reactive oxygen species was evaluated by measuring porphyrin accumulation in irradiated, ALA-loaded A431 cells. Porphyrin accumulation was significantly decreased in the presence of singlet oxygen scavenger sodium azide (0.05 mM, 40.6% suppression) or hydroxyl radical scavenger mannitol (5.0 mM, 45% suppression). These data suggest that the photochemical reaction induced by porphyrin and irradiation resulted in a decrease in ferrochelatase protein content, but had no effect on ferrochelatase mRNA level nor on ALA synthase activity. The decrease in protein was partly mediated by the reactive oxygen species. (au)

  13. Thermal and electrical properties of porphyrin derivatives and their relevance for molecule interferometry

    NARCIS (Netherlands)

    Deachapunya, S.; Stefanov, A.; Berninger, M.; Ulbricht, H.; Reiger, E.; Doltsinis, N.L.; Arndt, M.

    2007-01-01

    The authors present new measurements of thermal and electrical properties for two porphyrin derivatives. They determine their sublimation enthalpy from the temperature dependence of the effusive beam intensity. The authors study H2TPP and Fe(TPP)Cl in matter-wave interferometry. Both molecules have

  14. A flexible porphyrin-annulene hybrid: a nonporphyrin conformation for meso-tetraaryldivacataporphyrin.

    Science.gov (United States)

    Pacholska-Dudziak, Ewa; Szterenberg, Ludmiła; Latos-Grażyński, Lechosław

    2011-03-14

    An annulene-porphyrin hybrid, the diaaza-deficient porphyrin 5,10,15,20-tetraaryl-21,23-divacataporphyrin, has been synthesized by an extrusion of tellurium atom(s) from 5,10,15,20-tetraaryl-21,23-ditelluraporphyrin under treatment with HCl. In addition, a monoaza-deficient 5,10,15,20-tetraaryl-21-tellura-23-vacataporphyrin was formed in the same reaction. The two new members of the vacataporphyrin family were characterized by X-ray crystallography, as well as UV/Vis and NMR spectroscopy. These aromatic molecules preserve the fundamental structural and spectroscopic features of the parent tetraarylporphyrin. The X-ray crystal structures of 21,23-divacataporphyrin and 21-tellura-23-vacataporphyrin show typical porphyrin patterns. The molecules are not strictly planar and show distortion of the annulene moieties. The N22⋅⋅⋅N24 distances (5.23 and 5.09 Å) are considerably longer than in regular porphyrins. For 21,23-divacataporphyrin, variable-temperature (1)H NMR spectroscopy data allowed the identification of divacataporphyrin stereoisomers differentiated by the geometry of the butadiene bridges. The forms remain in thermodynamic equilibrium. PMID:21341322

  15. A [3]rotaxane with two porphyrinic plates acting as an adaptable receptor.

    Science.gov (United States)

    Frey, Julien; Tock, Christian; Collin, Jean-Paul; Heitz, Valérie; Sauvage, Jean-Pierre

    2008-04-01

    Following a multistep procedure, the copper(I)-templated strategy allowed preparation of a multifunctional [3]rotaxane. The dumbbell consists of a central two-bidentate chelate unit and two terminal stoppers. The two rings threaded on the rotaxane axis consist each of a 1,10-phenanthroline-incorporating macrocycle, rigidly connected to an appended zinc-complexed porphyrin. The copper(I) template can be removed, affording a free rotaxane whose two rings can glide freely along the axis and spin around it. The dumbbell being very long (approximately 85 A in its extended conformation from one stopper to the other), the porphyrin-porphyrin distance can be varied over a wide range. The two porphyrinic plates constitute the key elements of a receptor able to complex various guests between the plates. The ability of the threaded rings to move freely makes the host perfectly adjustable, allowing capture of geometrically very different guests. The copper(I)-complexed rotaxane also acts as an efficient receptor, although its adaptability is obviously more limited than that of its free rotaxane counterpart. PMID:18338892

  16. Probing flexibility in porphyrin-based molecular wires using double electron electron resonance.

    Science.gov (United States)

    Lovett, Janet E; Hoffmann, Markus; Cnossen, Arjen; Shutter, Alexander T J; Hogben, Hannah J; Warren, John E; Pascu, Sofia I; Kay, Christopher W M; Timmel, Christiane R; Anderson, Harry L

    2009-09-30

    A series of butadiyne-linked zinc porphyrin oligomers, with one, two, three, and four porphyrin units and lengths of up to 75 A, have been spin-labeled at both ends with stable nitroxide TEMPO radicals. The pulsed EPR technique of double electron electron resonance (DEER) was used to probe the distribution of intramolecular end-to-end distances, under a range of conditions. DEER measurements were carried out at 50 K in two types of dilute solution glasses: deutero-toluene (with 10% deutero-pyridine) and deutero-o-terphenyl (with 5% 4-benzyl pyridine). The complexes of the porphyrin oligomers with monodentate ligands (pyridine or 4-benzyl pyridine) principally adopt linear conformations. Nonlinear conformations are less populated in the lower glass-transition temperature solvent. When the oligomers bind star-shaped multidentate ligands, they are forced to bend into nonlinear geometries, and the experimental end-to-end distances for these complexes match those from molecular mechanics calculations. Our results show that porphyrin-based molecular wires are shape-persistent, and yet that their shapes can deformed by binding to multivalent ligands. Self-assembled ladder-shaped 2:2 complexes were also investigated to illustrate the scope of DEER measurements for providing structural information on synthetic noncovalent nanostructures. PMID:19736940

  17. The very low ionization potentials of porphyrins and the possible role of Rydberg states in photosynthesis

    International Nuclear Information System (INIS)

    The very low ionization potentials of porphyrins lead to the prediction that in addition to bands due to (π,πsup(*)) transitions, bands due to Rydberg transitions should exist in their visible spectra. The suggestion is made that Rydberg excited states could be important in photosynthesis. (orig.)

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

    Directory of Open Access Journals (Sweden)

    Lin Wu

    2011-01-01

    Full Text Available Reversible addition fragmentation chain transfer (RAFT synthesis and self-assembly of free-base porphyrin cored star polymers are reported. The polymerization, in the presence of a free-base porphyrin cored chain transfer agent (CTA-FBP, produced porphyrin star polymers with controlled molecular weights and narrow polydispersities for a number of monomers including N, N-dimethylacrylamide (DMA and styrene (St. Well-defined amphiphilic star block copolymers, P-(PS-PDMA4 and P-(PDMA-PS4 (P: porphyrin, were also prepared and used for self-assembly studies. In methanol, a selective solvent for PDMA, spherical micelles were observed for both block copolymers as characterized by TEM. UV-vis studies suggested star-like micelles were formed from P-(PS-PDMA4, while P-(PDMA-PS4 aggregated into flower-like micelles. Spectrophotometric titrations indicated that the optical response of these two micelles to external ions was a function of micellar structures. These structure-related properties will be used for micelle studies and functional material development in the future.

  19. Vibrational spectroscopy of –/ – stretching vibrations of copper tetramesityl porphyrin: An algebraic approach

    Indian Academy of Sciences (India)

    Srinivasa Rao Karumuri; Joydeep Choudhury; Nirmal Kumar Sarkar; Ramendu Bhattacharjee

    2010-01-01

    Using Lie algebraic techniques and simpler expressions of the matrix elements of Majorana and Casimir operators given by us, we obtain an effective Hamiltonian operator which conveniently describes stretching vibrations of biomolecules. For a copper tetramesityl porphyrin molecule, the higher excited vibrational levels are calculated by applying the (2) algebraic approach.

  20. Biosynthesis of porphyrins and immune status of children and teenagers exposed to irradiation in low doses

    International Nuclear Information System (INIS)

    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

  1. 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.

  2. 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...

  3. Interfacial electron transfer between the photoexcited porphyrin molecule and TiO2 nanoparticles: effect of catecholate binding.

    Science.gov (United States)

    Ramakrishna, G; Verma, Sandeep; Jose, D Amilan; Kumar, D Krishna; Das, Amitava; Palit, Dipak K; Ghosh, Hirendra N

    2006-05-11

    Interfacial electron transfer (ET) dynamics of 5,10,15-trisphenyl-20-(3,4-dihydroxybenzene) porphyrin (TPP-cat) adsorbed on TiO2 nanoparticles has been studied by femtosecond transient absorption spectroscopy in the visible and near-IR region exciting at 400 and 800 nm. TPP-cat molecule forms a charge transfer (CT) complex with TiO2 nanoparticles through the catechol moiety with the formation of a five-membered ring. Optical absorption measurements have shown that the Q-band of TPP-cat interacts strongly with TiO2 due to chelation; however, the Soret band is affected very little. Optical absorption measurements indicate that the catechol moiety also interacts with TiO2 nanoparticles showing the characteristic band of pure catechol-TiO2 charge transfer (CT) in the visible region. Electron injection has been confirmed by monitoring the cation radical, instant bleach, and injected electron in the conduction band of TiO2 nanoparticles. Electron injection time has been measured to be < 100 fs and recombination kinetics has been best fitted with a multiexponential function, where the majority of the injected electrons come back to the parent cation radical with a time constant of approximately 800 fs for both excitation wavelengths. However, the reaction channel for the electron injection process has been found to be different for both wavelengths. Excitation at 800 nm, found to populate the CT state of the Q-band, and from the photoexcited CT state electron injection into the conduction band, takes place through diffusion. On the other hand, with excitation at 400 nm, a complicated reaction channel takes place. Excitation with 400 nm light excites both the CT band of Cat-TiO2 and also the Soret band of TPP-cat. We have discussed the reaction path in the TPP-cat/TiO2 system after exciting with both 400 and 800 nm laser light. We have also compared ET dynamics by exciting at both wavelengths. PMID:16671709

  4. Porphyrin dye into biopolymeric chitosan films for localized photodynamic therapy of cancer.

    Science.gov (United States)

    Ferreira, D P; Conceição, D S; Calhelha, R C; Sousa, T; Socoteanu, Radu; Ferreira, I C F R; Vieira Ferreira, L F

    2016-10-20

    Porphyrins and some of its derivatives are well known and widely used as photosensitizers (PSs) for Photodynamic Therapy of Cancer (PDT). The present study regards the characterization and evaluation of a synthesized asymmetric porphyrin dye in solution to be used as PS for PDT. This molecule was also incorporated into biopolymeric films composed by chitosan, polyethylene glycol (PEG) and gelatin in order to overtake some of the disadvantages inherent to the PS, but more important, to evaluate the potential of a system composed by the porphyrin/biopolymer to be applied as localized therapeutic agents. FTIR spectroscopy showed a strong interaction between the polymers involved in the preparation of the films under study: film 1: chitosan, film 2: chitosan/PEG and film 3: chitosan/gelatin. Photochemical studies were performed for the dye in solution and into the three different biopolymeric films. Ground state absorption showed the characteristic bands of these kinds of dyes in solution and also incorporated into the films. The films composed by porphyrin/chitosan and porphyrin into chitosan/gelatin, revealed the presence of non-emissive aggregates exhibiting a strong quenching effect in the fluorescence intensity, quantum yields and lifetimes. In this way, the system composed by the porphyrin incorporated into the chitosan/PEG film presents the best fluorescence quantum yield and lifetime. The transient absorption spectra were obtained for all the systems indicating the formation of an excited triplet state of the porphyrins following excitation, which takes special importance in the generation of phototoxic species namely singlet oxygen. Singlet oxygen quantum yields were also determined and the results obtained were very promising for the dye in solution but also for the dye into the different substrates. The release of the dye from the three different films onto a buffer solution was evaluated and we conclude that after a few days the dye was completely released

  5. Strain-Level Differences in Porphyrin Production and Regulation in Propionibacterium acnes Elucidate Disease Associations

    Science.gov (United States)

    Johnson, Tremylla; Kang, Dezhi; Barnard, Emma

    2016-01-01

    ABSTRACT Propionibacterium acnes is an important skin commensal, but it is also considered a pathogenic factor in several diseases including acne vulgaris, the most common skin disease. While previous studies have revealed P. acnes strain-level differences in health and disease associations, the underlying molecular mechanisms remain unknown. Recently, we demonstrated that vitamin B12 supplementation increases P. acnes production of porphyrins, a group of proinflammatory metabolites important in acne development (D. Kang, B. Shi, M. C. Erfe, N. Craft, and H. Li, Sci. Transl. Med. 7:293ra103, 2015, doi:10.1126/scitranslmed.aab2009). In this study, we compared the porphyrin production and regulation of multiple P. acnes strains. We revealed that acne-associated type IA-2 strains inherently produced significantly higher levels of porphyrins, which were further enhanced by vitamin B12 supplementation. On the other hand, health-associated type II strains produced low levels of porphyrins and did not respond to vitamin B12. Using a small-molecule substrate and inhibitor, we demonstrated that porphyrin biosynthesis was modulated at the metabolic level. We identified a repressor gene (deoR) of porphyrin biosynthesis that was carried in all health-associated type II strains, but not in acne-associated type IA-2 strains. The expression of deoR suggests additional regulation of porphyrin production at the transcriptional level in health-associated strains. Our findings provide one potential molecular mechanism for the different contributions of P. acnes strains to skin health and disease and support the role of vitamin B12 in acne pathogenesis. Our study emphasizes the importance of understanding the role of the commensal microbial community in health and disease at the strain level and suggests potential utility of health-associated P. acnes strains in acne treatment. IMPORTANCE Propionibacterium acnes is a dominant bacterium residing on skin, and it has been thought

  6. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick

    2010-01-01

    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  7. Synthesis of water-soluble silicon-porphyrin: protolytic behaviour of axially coordinated hydroxy groups.

    Science.gov (United States)

    Remello, Sebastian Nybin; Kuttassery, Fazalurahman; Hirano, Takehiro; Nabetani, Yu; Yamamoto, Daisuke; Onuki, Satomi; Tachibana, Hiroshi; Inoue, Haruo

    2015-12-14

    A new water-soluble silicon(IV)-tetra(4-carboxyphenyl)porphyrin (SiTCPP) with silicon(iv), the second most abundant element on Earth, in the center of porphyrin was synthesized. Fundamental properties including protolytic behaviour of axially coordinating hydroxy groups, and electrochemical behaviour were characterized. The properties were compared with those of silicon(IV)-tetra(2,4,6-trimethylphenyl)porphyrin (SiTMP) and silicon(IV)-tetra(4-trifluoromethylphenyl)porphyrin (SiTFMPP) and discussed in respect to the electron donating/withdrawing effect of the substituents. Two axially coordinating hydroxy groups of SiTCPP exhibit a four-step protolytic behaviour under the acidic conditions along with a single step protolysis of peripheral carboxyl groups. Though SiTCPP and SiTFMPP did not show any reactivity in the photochemical oxygenation of a substrate with K2PtCl6 as a sacrificial electron acceptor, the first oxidation wave in the electrochemical process of SiTCPP and SiTFMPP showed catalytic behaviour in aqueous acetonitrile solution at any pH condition, in contrast to SiTMP which has only a reversible oxidation wave under neutral and weakly acidic conditions. The criteria for the electrochemical oxidative activation of water and the photooxygenation of the substrate were obtained. The higher oxidation wave of Si-porphyrins than ∼0.86 volt vs. SHE is required for the electrochemical oxidation of water, while suitable protecting groups such as a methyl substituent is a requisite for the photochemical oxygenation with K2PtCl6 as a sacrificial electron acceptor. PMID:26526697

  8. Synthesis and characterization of novel D–A porphyrin-containing copolymers for polymer solar cells

    International Nuclear Information System (INIS)

    Highlights: ► A novel asymmetrical D–A zinc porphyrin derivative was first synthesized. ► Two copolymers containing D–A zinc porphyrin derivatives were synthesized. ► Polymer solar cells were fabricated and exhibited a maximal PCE of 1.26%. - Abstract: A novel asymmetrical D–A zinc porphyrin derivative with dimehtyl triphenylamine (donor unit) and methyl benzoate (acceptor unit) as para-arms was first synthesized. Then, two new copolymers (P1 and P2) containing D–A zinc porphyrin derivatives were synthesized by the Stille coupling method and applied in PSCs. Their structures, photophysical and electrochemical properties were characterized by 1H NMR, 13C NMR, gel permeation chromatography, thermogravimetric analysis, UV–vis absorption spectroscopy, photoluminescence spectroscopy, and cyclic voltammetry. The two copolymers exhibited good thermal stability and film-forming ability. The results showed that P1 containing D–A zinc porphyrin exhibits a strong absorption in the range of 400–500 nm. By the introduction of thiophene derivative with 4,7-di(4-hexylthiophen-2-yl)benzothiadiazole (T-DTBT) conjugated side-chain unit, P2 showed broader absorption in the region of 300–650 nm than P1. The photoluminescence spectra made clear that charge transfer between the whole main chain and side chain can be effective. Cyclic voltammograms revealed that the LUMO energy levels of P2 was reduced in comparison with P1 due to the introduction of electron-deficient T-DTBT conjugated side-chain unit, indicating that electron-injection and transporting properties have been improved. Polymer solar cells were fabricated based on the blend of the copolymers and methanofullerene[6,6]-phenyl C61-butyric acid methyl ester (PC61BM). The PSC based on P2:PC61BM (1:2, w/w) exhibited a power conversion efficiency of 1.26% under AM 1.5, 100 mW cm−2.

  9. 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.

  10. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

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

  11. Advancements in Anion Exchange Membrane Cations

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, Matthew R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Long, Hai [National Renewable Energy Lab. (NREL), Golden, CO (United States); Park, Andrew M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pivovar, Bryan S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  12. Theoretical Investigation on the Second-order Nonlinear Optical Properties of Chiral Amino Acid Zinc(Ⅱ) Porphyrins

    Institute of Scientific and Technical Information of China (English)

    LIU Hai-Yang; TIAN Jun-Chun; YING Xiao; XU Zhi-Guang; LIAO Shi-Jun; CHANG Chi-Kwong

    2005-01-01

    Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipolarizabilities, and they may be ascribed as the "mixture" of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic х (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.

  13. 5,10,15,20-Tetrakis(p-4-fluorobenzoyloxy)phenyl Porphyrin and Its Transition Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10,15,20-tetrakis(p-4-fluorobenzoyloxy) phenyl porphyrin(TFBOPPH2) and its transition metal complexes {TFBOPPM [M=Mn(Ⅲ), Fe(Ⅲ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ)]} were synthesized and characterized by means of UV-Vis, IR photoacoustic spectrometry, 1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrin molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balanceable anion in Fe(Ⅲ) and Mn(Ⅲ) complexes.

  14. Ultrafast Energy Transfer and Enhanced Two-Photon Absorption in a Novel Porphyrin Side-Chain Polymer

    Institute of Scientific and Technical Information of China (English)

    WANG Hui; HUANG Ya-Ping; DENG Li; ZHAO Fu-Li; LIN Wei-Zhu; WANG Jian; LIANG Zhao-Xi

    2004-01-01

    @@ Ultrafast relaxation processes and transient two-photon absorption are studied in a novel porphyrin side-chain polymer, 5-hydroxy-10, 15,20-triphenyl-porphyrin-poly(glycidyl methacrylate) (HTPP-PGMA), by using picosecond luminescence spectroscopy and femtosecond pump-probe techniques. HTPP-PGMA exhibits the ultrafast initial luminescence decay (~300ps), which is absent in the conventional porphyrin monomer such as TPP. Enhanced two-photon absorption was observed in HTPP-PGMA; the corresponding Im x(a) is about 2.8× 10-11 esu, which is almost one order of magnitude larger than that of the conventional porphyrin monomer (TPP) (~1.3 × 10-12 esu).The ultrafast energy transfer plays an important role in the excited-state relaxation dynamics observed in HTPPPGMA. The potential application of HTPP-PGMA in optical switching is discussed.

  15. Assembly of individual TiO2-C60/porphyrin hybrid nanoparticles for enhancement of photoconversion efficiency

    International Nuclear Information System (INIS)

    Rational organization of porphyrin and C60 on the electrode surface in photovoltaic structures is essential to yield high quantum efficiency. In the present work, individual TiO2 nanoparticles were modified by introducing C60 and porphyrin units on the surface, and then electrophoretically deposited on an ITO/SnO2 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 C60 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 C60 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.

  16. Octopus Manganese Porphyrin with Polyglycol Chains as a Catalyst for the β-Selective Epoxidation of Cholesterol Derivatives

    Institute of Scientific and Technical Information of China (English)

    Run Hua LI; Yuan Cong ZHAO; Jiang WU; Jing Song YOU; Xiao Qi YU

    2004-01-01

    Synthesis of a novel octopus porphyrin with polyglycol chains 1a was achieved.The catalytic activity of 1a's manganese complex for the epoxidation of cholesterol derivatives with PhIO give a satisfactory conversion and regioselectivity.

  17. Iodinated silica/porphyrin hybrid nanoparticles for X-ray computed tomography/fluorescence dual-modal imaging of tumors

    OpenAIRE

    Koichiro Hayashi; Sakamoto Wataru; Toshinobu Yogo

    2014-01-01

    Silica nanoparticles containing covalently linked iodine and a near-infrared (NIR) fluorescence dye, namely porphyrin, have been synthesized through a one-pot sol–gel reaction. These particles are called iodinated silica/porphyrin hybrid nanoparticles (ISP HNPs). The ISP HNPs have both high X-ray absorption coefficient and NIR fluorescence. The ISP HNPs modified with folic acid (FA) and polyethylene glycol (PEG), denoted as FA-PEG-ISP HNPs, enabled the successful visualization of tumors in mi...

  18. Observations and comments on the mechanism of epoxidation of alkenes by manganese(III) porphyrins with hypochlorite.

    OpenAIRE

    Lee, R W; Nakagaki, P C; Balasubramanian, P N; Bruice, T C

    1988-01-01

    The kinetics of olefin epoxidation in a methylene chloride/water biphase containing a phase-transfer agent with hypochlorite as oxygen transfer reagent and manganese(III) tetraphenylporphyrin catalysts has been reinvestigated. The results do not support the accumulation of an intermediate composed of an alkene and a hypervalent metaloxo porphyrin. Second-order rate constants for oxygen transfer from hypochlorite to the manganese porphyrin, comproprotionation of the hypervalent manganese-oxo p...

  19. 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

  20. A facile one-pot synthesis of higher yield porphyrin functionalized Co{sub 3}O{sub 4} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qingyun, E-mail: qyliu@sdust.edu.cn [School of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China); Zhu, Renren; Jiang, Yanling; Zhang, Leyou [School of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China); Yin, Hailiang [Academy of Science & Technology, China University of Petroleum, Dongying 257061 (China); Liu, Shunxiang; Jia, Qingyan; Chen, Pengpeng [School of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China)

    2015-08-15

    Graphical abstract: Porphyrins functionalized Co3O4 nanoparticles were prepared firstly via a facile one-step method. The high yield of prophyrin functionalized Co3O4 nanoparticles is more than 90%. - Highlights: • Por-Co{sub 3}O{sub 4} NPs were first prepared via a facile one-pot hydrothermal method. • The yield of porphyrin-Co{sub 3}O{sub 4} nanoparticles is more than 90%. • FT-IR reveals the coordination interaction between porphyin molecules and Co{sub 3}O{sub 4.} • Ethanol and the appropriate temperature are necessary in this experiment. - Abstract: Porphyrin functionalized Co{sub 3}O{sub 4} nanoparticles were first prepared via a facile one-pot hydrothermal method. The functionalized nanoparticles were characterized by X-ray diffraction and transmission electron microscopy. Fourier transform infrared spectra revealed the coordination interaction between porphyrin molecules and Co{sub 3}O{sub 4}. The high yield of prophyrin functionalized Co{sub 3}O{sub 4} nanoparticles is more than 90%. The phase, morphology and size of as-prepared nanoparticles were dramatically affected by the ratio of solvents, temperature and porphyrins with different substituents, respectively. Experimental results revealed that ethanol and the appropriate temperature were necessary for the formation of single-phase Co{sub 3}O{sub 4}. Furthermore, a probable growth mechanism of the formation of porphyrin functionalized Co{sub 3}O{sub 4} nanoparticles was proposed.

  1. Concerning the deactivation of cobalt(III)-based porphyrin and salen catalysts in epoxide/CO2 copolymerization.

    Science.gov (United States)

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

    2015-03-01

    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. PMID:25656829

  2. The fast method of Cu-porphyrin complex synthesis for potential use in positron emission tomography imaging

    Science.gov (United States)

    Kilian, Krzysztof; Pęgier, Maria; Pyrzyńska, Krystyna

    2016-04-01

    Porphyrin based photosensitizers are useful agents for photodynamic therapy and fluorescence imaging of cancer. Additionally, porphyrins are excellent metal chelators, forming stable metalo-complexes and 64Cu isotope can serve as a positron emitter (t1/2 = 12.7 h). The other advantage of 64Cu is its decay characteristics that facilitates the use of 64Cu-porphyrin complex as a therapeutic agent. Thus, 64Cu chelation with porphyrin photosensitizer may become a simple and versatile labeling strategy for clinical positron emission tomography. The present study reports a convenient method for the synthesis of Cu complex with tetrakis(4-carboxyphenyl)porphyrin (TCPP). The experimental conditions for labeling, such as the metal-to-ligand molar ratio, pH and time of reaction were optimized to achieve a high complexation efficiency in a short period of time as possible. In order to accelerate the metallation, the use of substitution reactions of cadmium or lead porphyrin and the presence of reducing agent, such as ascorbic acid, hydroxylamine and flavonoid - morin, were evaluated. The optimum conditions for the synthesis of the copper complex were borate buffer at pH 9 with the addition of 10-fold molar excess, with respect to Cu2 + ions and TCPP and ascorbic acid which resulted in reduction of the reaction time from 30 min to below 1 min.

  3. 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.

  4. 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

    2015-01-01

    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. PMID:26197316

  5. Cationic Bolaamphiphiles for Gene Delivery

    Science.gov (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad

    2014-05-01

    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  6. Porphyrin gels reinforced by sol-gel reaction via the organogel phase.

    Science.gov (United States)

    Kishida, Takanori; Fujita, Norifumi; Sada, Kazuki; Shinkai, Seiji

    2005-10-11

    Porphyrins bearing four urea-linked dodecyl groups (3a) or four urea-linked triethoxysilylpropyl groups (3TEOS) at their peripheral positions were synthesized. 3a tends to assemble into a sheetlike two-dimensional structure due to the predominant hydrogen-bonding interaction among the urea groups and acts as a moderate gelator of organic solvents. On the other hand, its Cu(II) compelx (3a.Cu) tends to assemble into a fibrous one-dimensional structure due to the predominant porphyrin-porphyrin pi-pi stacking interaction and acts as an excellent gelator of many organic solvents. 3TEOS and 3TEOS.Cu, which also act as gelators, afforded similar superstructures as those of 3a and 3a.Cu, respectively, and as evidenced by SEM and TEM observations and XRD measurements, the original superstructures could be precisely immobilized by in situ sol-gel polycondensation of the triethoxysilyl groups. The TEM images of 3a gels and 3TEOS gels after sol-gel polycondensation showed a fine striped structure, the periodical distance of which was either 2 or 4 nm. X-ray crystallographic analysis of a single crystal obtained from a reference porphyrin bearing four urea-linked butyl groups revealed that there are two different porphyrin-stacked columns in the crystal and both the 2 nm distance and the 4 nm distance can appear, depending on the observation tilting angle. The hybrid gel prepared from 3TEOS.Cu by sol-gel polycondensation showed unique physicochemical properties such as a high sol-gel phase-transition temperature (>160 degrees C), sufficient elasticity, high mechanical strength, etc. Thus, the present study has established new concepts for molecular design of porphyrin-based gelators on the basis of cooperative and/or competitive actions of hydrogen-bonding and pi-pi stacking interactions and for immobilization of their superstructures leading to development of new functional organic/inorganic hybrid materials. PMID:16207018

  7. Cationic ruthenium alkylidene catalysts bearing phosphine ligands

    OpenAIRE

    Endo, Koji; Grubbs, Robert H.

    2016-01-01

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bear-ing bulky phosphine ligands. Simple ligand exchange using silver(I) salts of non-coordinating or weakly coordinating anions pro-vided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported...

  8. Cation substitution in two coccolithophore species

    OpenAIRE

    Melteig, Hanna Elina

    2016-01-01

    Few things would be better than getting rid of CO2 while producing useful materials. Coccolithophores use CO2 in their photorespiration, in addition to using CO2 to produce coccoliths – small platelets made of calcite. Ca is a central cation in this process, and the goal of this project is to investigate to what extent other divalent cations can partially substitute for Ca and become part of the growing coccolith. The long term goal is to enable algae to harvest cations and produce mate...

  9. Communication: Charge-transfer rate constants in zinc-porphyrin-porphyrin-derived dyads: A Fermi golden rule first-principles-based study

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Arun K.; Dunietz, Barry D., E-mail: bdunietz@kent.edu [Department of Chemistry, Kent State University, Kent, Ohio 44242 (United States)

    2014-09-28

    We investigate photoinduced charge transfer (CT) processes within dyads consisting of porphyrin derivatives in which one ring ligates a Zn metal center and where the rings vary by their degree of conjugation. Using a first-principles approach, we show that molecular-scale means can tune CT rates through stabilization affected by the polar environment. Such means of CT tuning are important for achieving high efficiency optoelectronic applications using organic semiconducting materials. Our fully quantum mechanical scheme is necessary for reliably modeling the CT process across different regimes, in contrast to the pervading semi-classical Marcus picture that grossly underestimates transfer in the far-inverted regime.

  10. Aggregation-Enhanced Raman Scattering by a Water-Soluble Porphyrin

    Science.gov (United States)

    Akins, Daniel L.

    1995-01-01

    Much interest in our laboratory has focused on aggregation of organic compounds, particularly cyanine dyes and porphyrins. For this discussion we have applied absorption and Raman scattering spectroscopies to characterize aggregated TSPP (tetrakis-(p-sulfonatophynyl) porphyrin) in aqueous solution. Based on concentration, pH and ionic strength dependence of TSPP absorption, we deduce that aggregation evolves through the formation of TSPP diacid and that the diacid is the repeating unit in the aggregate. The Raman bands of TSPP in strongly acidic solution lead us further to conclude that vibrations of adjacent molecules are perturbed in a fashion that is consistent with the pyrrolic ring in the porphinato macrocycle being ruffled, and that two aggregate arrangements occur: specifically J- and H-type aggregates. Furthermore, aggregation enhancement is advanced as a viable mechanism to explain enhanced Raman Scattering for homogeneous aqueous phase TSPP, where the surface-enhancement mechanism is not applicable.

  11. 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.

  12. Tunneling electron induced molecular electroluminescence from individual porphyrin J-aggregates

    Science.gov (United States)

    Meng, Qiushi; Zhang, Chao; Zhang, Yang; Zhang, Yao; Liao, Yuan; Dong, Zhenchao

    2015-07-01

    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.

  13. Porphyrin synthesized from cashew nut shell liquid as part of a novel superparamagnetic fluorescence nanosystem

    Energy Technology Data Exchange (ETDEWEB)

    Clemente, C. S.; Ribeiro, V. G. P.; Sousa, J. E. A.; Maia, F. J. N.; Barreto, A. C. H. [Universidade Federal do Ceara, Laboratorio de Produtos e Tecnologia em Processos (LPT) (Brazil); Andrade, N. F. [Universidade Federal do Ceara, Departamento de Fisica (Brazil); Denardin, J. C. [Universidad de Santiago de Chile (USACH), Departamento de Fisica (Chile); Mele, G. [Universita del Salento, Dipartimento di Ingegneria dell' Innovazione (Italy); Carbone, L. [NNL, Istituto Nanoscienze UOS Lecce (Italy); Mazzetto, S. E. [Universidade Federal do Ceara, Laboratorio de Produtos e Tecnologia em Processos (LPT) (Brazil); Fechine, P. B. A., E-mail: fechine@ufc.br [Universidade Federal do Ceara (UFC), Grupo de Quimica de Materiais Avancados (GQMAT), Departamento de Quimica Analitica e Fisico-Quimica (Brazil)

    2013-06-15

    Magnetic Fe{sub 3}O{sub 4} nanoparticles with average size approximately 11 nm were first oleic acid coated to interact with the meso-porphyrin derivative from CNSL. This procedure produced a novel superparamagnetic fluorescent nanosystem (SFN) linked by van der Waals interactions. This system was characterized by transmission electron microscope, infrared spectroscopy, thermogravimetric analysis, magnetic measurements, UV-Vis absorption, and fluorescence emission measurements. These results showed that SFN has good thermal stability, excellent magnetization, and nanosized dimensions ({approx}13 nm). It exhibited emission peaks at 668 and 725 nm with a maximum emission at 467 nm of excitation wavelength. The type of interaction between porphyrin and magnetic nanoparticles allowed to obtain a material with interesting optical properties which might be used as an imaging agent for contrast in cells as well as heterogeneous photocatalysis.

  14. Synthesis and Characterization of New Conjugated Fluorenyl-Porphyrin Dendrimers for Optics.

    Science.gov (United States)

    Yao, Dandan; Zhang, Xu; Mongin, Olivier; Paul, Frédéric; Paul-Roth, Christine O

    2016-04-11

    A new family of conjugated meso-tetraphenylporphyrin-based dendrimers with four (TPP1, TPP2), eight (TPP3, TPP4, TPP5) and up to sixteen (TPP6) fluorenyl groups has been synthesized and fully characterized. These tetraphenylporphyrin-cored dendrimers present peripheral alkynyl π-conjugated dendrons with fluorenyl termini. The meso-aryl rings of these porphyrins are functionalized either in para- (TPP1, TPP2, and TPP3) or meta-positions (TPP4, TPP5, and TPP6). Their detailed luminescence properties are discussed in reference to two porphyrins lacking fluorenyl dendrons (TPP-H1,2,3 and TPP-H4,5,6 ). A strong dependence of their luminescence quantum yield and lifetime on their structures is stated, their nonlinear optical properties were also discussed. PMID:26933931

  15. -pyrrole substituted porphyrin-pyrene dyads using vinylene spacer: Synthesis, characterization and photophysical properties

    Indian Academy of Sciences (India)

    P Silviya Reeta; Ravi Kumar Kanaparthi; L Giribabu

    2013-03-01

    We have designed and synthesized donor-acceptor conjugates having donor pyrene at the pyrrole- position of either free-base porphyrin or Zn(II) porphyrin using vinylene spacer. Both the dyads have been completely characterized by elemental analysis,MALDI-MS, UV-Vis., and fluorescence (steady state and timeresolved) spectroscopies as well as cyclic voltammetry. The absorption maxima of both dyads are red-shifted by 8-12 nm. The ground state properties showed that there exist minimum - interaction between the aromatic subunits of these D-A systems. Quenched emission was observed in both the dyads when excited at 290 nm. The quenched emission explained in terms of intramolecular excitation energy transfer competes with the photo-induced electron transfer reaction in these D-A system.

  16. Manipulation of the electronic structure by reversible dehydrogenation of tetra(p-hydroxyphenyl)porphyrin molecules

    CERN Document Server

    Smykalla, Lars; Mende, Carola; Rüffer, Tobias; Lang, Heinrich; Hietschold, Michael

    2014-01-01

    The controlled and reversible interconversion between the free-base and the doubly dehydrogenated form of a 5,10,15,20-tetra(p-hydroxyphenyl)porphyrin molecule in an ordered array is demonstrated. This is achieved through voltage pulses by hydrogen transfer between the center of the porphyrin and the tip of a scanning tunneling microscope (STM). The local dehydrogenation leads to significant shifts in the energetic positions of the molecular orbitals. Density functional theory (DFT) calculations corroborate our conclusions and allow to gain more insight into the different energy level alignment before and after dehydrogenation. Due to the different conductance at a given voltage a clear distinction of both molecular species is possible, which also enables the application as a single-molecular switch.

  17. Adsorption property of manganese(III)-tetrakis(sulfoaryl)porphyrin derivatives to atheroma

    International Nuclear Information System (INIS)

    In order to obtain a new magnetic resonance imaging (MRI) agent which adsorbs selectively to atheroma, eight kinds of manganese(III)-tetrakis(sulfoaryl)porphyrin derivatives were synthesized. Among these, manganese(III) α, β, γ, δ-tetrakis(4-sulfobiphenylyl)porphyrin (Mn-TSBP) which have four sulfobiphenylyl groups, has the following merits : (i) High solubility in water (solubility : 5 x 10-3 mol · dm-3 at 25degC and pH = 7.0,), (ii) stable (it did not dissociate the manganese at pH range from 1.5 to 13.5), and (iii) it adsorbed well to deoxycolic acid as an atheroma model. The Mn-TSBP, injected to male New Zedland white rabits with experimental atheroma, was selectively adsorbed to atheroma more than 2 ∼ 6 fold of that normal aortic wall. (author)

  18. Urinary porphyrins in children exposed transplacentally to polyhalogenated aromatics in Taiwan

    Energy Technology Data Exchange (ETDEWEB)

    Gladen, B.C.; Rogan, W.J.; Ragan, N.B.; Spierto, F.W.

    In 1979, there was a large (>2000 cases) outbreak of poisoning due to contaminated rice oil in central Taiwan. The causal agent was a mixture of thermally degraded polychlorinated biphenyls (PCBs), polychlorinated quaterphenyls, and polychlorinated dibenzofurans, which had become mixed with the oil during processing. Patients remained symptomatic for several years afterward, and the chemicals persisted in their tissue. Women who became pregnant had children with high perinatal mortality and a dysmorphic syndrome. We examined urines from 75 children born to exposed mothers after the oil was confiscated, 74 controls, and 12 sibs of the exposed children. Four of the transplancentally exposed children, 2 controls, and 1 sib had a type B hepatic porphyria (i.e., uroporphyrin > coproporphyrin); total porphyrin excretion was elevated in the exposed children as a group (95 vs. 81 ..mu..g/L); and 8 of the 75 exposed children and 2 controls had total urinary porphyrin concentrations of >200 ..mu..g/L.

  19. Soret band porphyrin structure index via 3rd derivative UV/VIS spectroscopy

    International Nuclear Information System (INIS)

    This paper reports on Soret band wavelength which provides a porphyrin structure index which is useful to classify natural metalloporphyrin extracts. The approach involves rapid measurement by photodiode array spectrophotometry. The average value for a porphyrin mixture. λSoret ± 0.1 nm, is obtained by third derivative computation. A blue shift in λSoret implies an increasing etio to exocycle ratio. High ratios have been associated with catagenesis (Dydik, 1975, Baker, et al., 1978, 1983), and with predispositional generation (Baker and Louda (1984). As a reference, we measured the Soret band response to simulated maturation of a Woodford Shale (350 Ma) sample after hydrous pyrolysis (Lewan, 1981), as described in greater detail elsewhere at this meeting

  20. Tunneling electron induced molecular electroluminescence from individual porphyrin J-aggregates

    International Nuclear Information System (INIS)

    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

  1. Iron normal mode dynamics in a porphyrin-imidazole model for deoxyheme proteins

    International Nuclear Information System (INIS)

    Iron vibrational modes of a deoxyheme protein model (2-methylimidazole)(tetraphenylporphinato)iron(II), [Fe(TPP)(2-MeImH)], have been studied by refining normal mode calculations to nuclear resonance vibrational spectroscopy (NRVS) data. The NRVS measurements give quantitative frequencies and iron amplitudes of all modes with significant Fe vibrational motion. Modes with in-plane displacement of iron are distinguished from those involving out-of-plane motion by measurements on oriented single-crystal samples. Normal modes having large overlaps with in-plane ν42, ν50, and ν53 modes of the porphyrin core are identified, as well as several modes with large iron-imidazole stretch components. An out-of-plane mode at 78 cm-1 shows significant doming of the porphyrin core, but the largest Fe doming motion arises from the coupling of phenyls and imidazole at 25 cm-1

  2. Kinetic Investigation of Olefin Oxidation by Al(III)-Porphyrin Complexes

    International Nuclear Information System (INIS)

    Kinetic studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (ρ- X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and ( ρ-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin

  3. Radiolabeled porphyrin versus gallium-67 citrate for the detection of human melanoma in athymic mice

    International Nuclear Information System (INIS)

    We performed the biodistribution and imaging studies of 111In and 67Ga labeled tetra(4-N-methylpyridyl) porphine, (T4NMPYP), and compared it to that of 67Ga citrate in athymic mice bearing a human melanoma xenograft. The biodistribution results of both 111In and 67Ga labeled T4NMPYP (3, 6, 24, and 48 hours) were similar but differed from that of 67Ga citrate (48 hours). The optimum tumor uptake of both radiolabeled porphyrins was at 6 hours postinjection and was lower than the tumor uptake of 67Ga citrate at 48 hours postinjection. Kidney was the only organ showing higher uptake of radiolabeled porphyrin compared to that of 67Ga citrate. The imaging studies performed with 111In T4NMPYP and 67Ga citrate correspond to the biodistribution results. Osteomyelitis present in one mouse showed good localization of 111In T4NMPYP. 15 refs., 3 figs., 5 tabs

  4. Optical switching of electric charge transfer pathways in porphyrin: a light-controlled nanoscale current router.

    Science.gov (United States)

    Thanopulos, Ioannis; Paspalakis, Emmanuel; Yannopapas, Vassilios

    2008-11-01

    We introduce a novel molecular junction based on a thiol-functionalized porphyrin derivative with two almost energetically degenerate equilibrium configurations. We show that each equilibrium structure defines a pathway of maximal electric charge transfer through the molecular junction and that these two conduction pathways are spatially orthogonal. We further demonstrate computationally how to switch between the two equilibrium structures of the compound by coherent light. The optical switching mechanism is presented in the relevant configuration subspace of the compound, and the corresponding potential and electric dipole surfaces are obtained by ab initio methods. The laser-induced isomerization takes place in two steps in tandem, while each step is induced by a two-photon process. The effect of metallic electrodes on the electromagnetic irradiation driving the optical switching is also investigated. Our study demonstrates the potential for using thiol-functionalized porphyrin derivatives for the development of a light-controlled nanoscale current router. PMID:21832723

  5. Optical switching of electric charge transfer pathways in porphyrin: a light-controlled nanoscale current router

    International Nuclear Information System (INIS)

    We introduce a novel molecular junction based on a thiol-functionalized porphyrin derivative with two almost energetically degenerate equilibrium configurations. We show that each equilibrium structure defines a pathway of maximal electric charge transfer through the molecular junction and that these two conduction pathways are spatially orthogonal. We further demonstrate computationally how to switch between the two equilibrium structures of the compound by coherent light. The optical switching mechanism is presented in the relevant configuration subspace of the compound, and the corresponding potential and electric dipole surfaces are obtained by ab initio methods. The laser-induced isomerization takes place in two steps in tandem, while each step is induced by a two-photon process. The effect of metallic electrodes on the electromagnetic irradiation driving the optical switching is also investigated. Our study demonstrates the potential for using thiol-functionalized porphyrin derivatives for the development of a light-controlled nanoscale current router.

  6. Porphyrin-layered double hydroxide/polymer composites as novel ecological photoactive surfaces

    Czech Academy of Sciences Publication Activity Database

    Káfuňková, Eva; Lang, Kamil; Kubát, Pavel; Klementová, Mariana; Mosinger, Jiří; Šlouf, Miroslav; Troutier-Thuilliez, A. L.; Leroux, F.; Verney, V.; Taviot-Guého, Ch.

    2010-01-01

    Roč. 20, č. 42 (2010), s. 9423-9432. ISSN 0959-9428 R&D Projects: GA ČR GAP207/10/1447 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503; CEZ:AV0Z40500505 Keywords : porphyrin s * nanoparticles * hydroxide/polymer composites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.101, year: 2010

  7. Preparation of Porphyrin Based HPLC Columns for the Separation of Fullerenes

    Czech Academy of Sciences Publication Activity Database

    Slavíček, J.; Šabata, Stanislav; Lang, Kamil; Lhoták, P.

    Praha : Česká společnost chemická, 2012, s1351. ISSN 0009-2770. [EuCheMS Chemistry Congress /4./. Praha (CZ), 26.08.2012-30.08.2012] R&D Projects: GA ČR GA203/09/0691 Institutional support: RVO:67985858 ; RVO:61388980 Keywords : fullerens * porphyrin * separation Subject RIV: CC - Organic Chemistry http://www.euchems-prague2012.cz/basic-information.htm

  8. Facile one-pot synthesis of porphyrin based porous polymer networks (PPNs) as biomimetic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zou, LF; Feng, DW; Liu, TF; Chen, YP; Fordham, S; Yuan, S; Tian, J; Zhou, HC

    2015-01-01

    Stable porphyrin based porous polymer networks, PPN-23 and PPN-24, have been synthesized through a facile one-pot approach by the aromatic substitution reactions of pyrrole and aldehydes. PPN-24(Fe) shows high catalytic efficiency as a biomimetic catalyst in the oxidation reaction of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) in the presence of H2O2.

  9. Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

    KAUST Repository

    Fathalla, Maher

    2015-05-18

    A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

  10. Interaction of porphyrin and sapphyrin macrocycles with nucleobases and nucleosides. Spectroscopic, quantum chemical and chromatographic investigation

    Czech Academy of Sciences Publication Activity Database

    Záruba, K.; Tománková, Z.; Sýkora, D.; Charvátová, J.; Kavenová, I.; Bouř, Petr; Matějka, P.; Fähnrich, J.; Volka, K.; Král, V.

    2001-01-01

    Roč. 437, - (2001), s. 39-53. ISSN 0003-2670 R&D Projects: GA ČR GA203/01/0031; GA MŠk VS97135; GA ČR GV301/98/K042 Grant ostatní: HHMI(US) 75195-541101 Institutional research plan: CEZ:AV0Z4055905 Keywords : HPLC * porphyrin Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.073, year: 2001

  11. DNA sequence preferences for an intercalating porphyrin compound revealed by footprinting.

    OpenAIRE

    Ford, K; Fox, K R; Neidle, S; Waring, M J

    1987-01-01

    The DNA sequence preferences of the compound meso-tetra-(4-N-methyl(pyridyl) porphyrin and its nickel complex have been investigated by means of footprinting experiments on several DNA fragments, using DNAase I and micrococcal nuclease as footprinting agents. A complex pattern of both AT and GC-protected sites was found. Ligand-induced long-range conformational changes were inferred in several instances to be related to the observed large-scale blockages of enzymatic cutting.

  12. Diameter-selective non-covalent functionalization of carbon nanotubes with porphyrin monomers

    Science.gov (United States)

    Vialla, F.; Delport, G.; Chassagneux, Y.; Roussignol, Ph.; Lauret, J. S.; Voisin, C.

    2016-01-01

    We report on the spontaneous non-covalent functionalization of carbon nanotubes with hydrophobic porphyrin molecules in micellar aqueous solution. By monitoring the species concentrations with optical spectroscopies, we can follow the kinetics of the reaction and study its thermodynamical equilibrium as a function of the reagent concentrations. We show that the reaction is well accounted for by a cooperative Hill equation, reaching a molecular coverage close to a compact monolayer for a porphyrin concentration larger than a diameter-specific threshold concentration. The equilibrium constant is measured for 16 nanotube chiral species. The Gibbs energy of the reaction (of the order of -40 kJ mol-1) and its evolution with the nanotube diameter is consistent with theoretical calculations of the binding energy. This thermodynamical study shows a strong preferential binding of TPP molecules to larger diameter nanotubes. This original curvature selectivity can be used to induce diameter selective species enrichment.We report on the spontaneous non-covalent functionalization of carbon nanotubes with hydrophobic porphyrin molecules in micellar aqueous solution. By monitoring the species concentrations with optical spectroscopies, we can follow the kinetics of the reaction and study its thermodynamical equilibrium as a function of the reagent concentrations. We show that the reaction is well accounted for by a cooperative Hill equation, reaching a molecular coverage close to a compact monolayer for a porphyrin concentration larger than a diameter-specific threshold concentration. The equilibrium constant is measured for 16 nanotube chiral species. The Gibbs energy of the reaction (of the order of -40 kJ mol-1) and its evolution with the nanotube diameter is consistent with theoretical calculations of the binding energy. This thermodynamical study shows a strong preferential binding of TPP molecules to larger diameter nanotubes. This original curvature selectivity can be used

  13. Theoretical Study on Metal Porphyrin Chain for Use as a Nanoscale Device

    Science.gov (United States)

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

    2003-03-01

    Recently, the molecular electronics has attracted strong attention as a ``post-silicone technology'' to realize a future nanoscale electronics device. A quarter century ago Aviram and Ratner (1) have first demonstrated how an organic molecule could function as a molecular rectifying diode. Further this has been supported by many experimental results. Aromatic molecules have ¥pi-conjugation systems through which electrons can flow easily. By substituting different functional groups on an aromatic system it is possible to increase or decrease the ¥pi-electron density and thereby creating acceptor (p-type) and donor (n-type) molecular subunits. Therefore, a rectifier could be built by combining these two molecular subunits between two electrodes in which electrons can flow from cathode to the acceptor or from donor to the anode (2-3). Porphyrin possesses good electron-donating properties due to its large easily ionized ¥pi-electron system, and a long molecular wire of fully conjugated porphyrin. In this study, we propose rectifier diode can be created by combining two metal porphyrin molecules with different metal atom. To estimate the electron transport through this molecule, we have analyzed the spatial extent of the frontier orbitals (HOMO and LUMO), providing a strategy by which the rectifying properties of the porphyrin polymer can be understood. This study was performed through Special Coordination Funds for Promoting Science and Technology of the Ministry of Education, Culture, Sports, Science and Technology of the Japanese Government. (1) A. Aviram and M. A. Ratner, Chem. Phys. Lett. Vol. 29 (1974) 277. (2) C. Majumder, H. Mizuseki, and Y. Kawazoe, J. Phys. Chem. A, Vol. 105 (2001) 9454. (3) H. Mizuseki, K. Niimura, C. Majumder, and Y. Kawazoe, Comput. Mater. Sci., in press.

  14. Light and drug dosimetry considerations in porphyrin precursor–based photodynamic therapy

    OpenAIRE

    2007-01-01

    This thesis concerns light and drug dosimetry for photodynamic cancer treatment – a treatment modality where a photosensitizer uses the energy of light to damage biological matter. Porphyrin precursors were used as prodrugs which are synthesized into photosensitizers inside cells. Human subjects were studied as a part of developing a treatment for non-melanotic skin cancer. A 3-hour application of a topical cream photosensitized the tumor tissue with good selectivity versus normal skin, wh...

  15. Studies on the synthesis of new porphyrins from cardanol and glycerol

    OpenAIRE

    Daiane Santana Souza; Rosangela da Silva Lopes; Dênis P. de Lima; Kleber Thiago de Oliveira; Adilson Beatriz

    2012-01-01

    Porphyrins are very attractive compounds due to their wide application in many areas of new materials as chemical technology, ecology, medicine and, electronics. In the last years, they are also been a focus of attention owing to their implications to many photocatalytic reactions. Cardanol (isolated form cashew nut shell liquid) and glycerol (side product of biodiesel industry) are raw materials of low aggregated value; however, they hold chemical structures with functionalities that can lea...

  16. Perylene anhydride fused porphyrins as near-infrared sensitizers for dye-sensitized solar cells

    KAUST Repository

    Jiao, Chongjun

    2011-07-15

    Two perylene anhydride fused porphyrins 1 and 2 have been synthesized and employed successfully in dye-sensitized solar cells (DSCs). Both compounds showed broad incident monochromatic photon-to-current conversion efficiency spectra covering the entire visible spectral region and even extending into the near-infrared (NIR) region up to 1000 nm, which is impressive for ruthenium-free dyes in DSCs. © 2011 American Chemical Society.

  17. Sulfonated graphenes catalyzed synthesis of expanded porphyrins and their supramolecular interactions with pristine graphene

    Indian Academy of Sciences (India)

    Sweta Mishra; Smriti Arora; Ritika Nagpal; Shive Murat Singh Chauhan

    2014-11-01

    A newer synthesis of sulfonic acid functionalized graphenes have been developed, which have been characterized, examined as heterogeneous solid acid carbocatalyst in the synthesis of selected expanded porphyrins in different reaction conditions. This environment-friendly catalyst avoids the use of toxic catalysts and enhances the yields of porphyrinoids. The non-covalent interaction of porphyrinoids has also been studied with exfoliated graphene solution in organic solvents by UV-Visible and fluorescence spectroscopy.

  18. Synthetic molecular systems based on porphyrins as models for the study of energy transfer in photosynthesis

    International Nuclear Information System (INIS)

    The published data on the synthesis and photochemical properties of porphyrin-based molecular ensembles which represent models of natural photosynthetic light-harvesting complexes are generalised and systematised. The dependence of the transfer of excitation energy on the distance between donor and acceptor components, their mutual arrangement, electronic and environmental factors are discussed. Two mechanisms of energy transfer reactions, viz., 'through space' and 'through bond', are considered. The bibliography includes 96 references.

  19. Glycol porphyrin derivatives as potent photodynamic inducers of apoptosis in tumor cells

    Czech Academy of Sciences Publication Activity Database

    Králová, Jarmila; Bříza, T.; Moserová, Irena; Dolenský, B.; Vašek, P.; Poučková, P.; Kejík, Z.; Kaplánek, R.; Martásek, P.; Dvořák, Michal; Král, V.

    2008-01-01

    Roč. 51, č. 19 (2008), s. 5964-5973. ISSN 0022-2623 R&D Projects: GA MŠk(CZ) LC06077; GA ČR(CZ) GA203/06/1038; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z50520514 Keywords : glycol porphyrin derivative * apoptosis * photodynamic therapy Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 4.898, year: 2008

  20. Stacking and separation of urinary porphyrins in capillary electrophoresis: optimization of concentration efficiency and resolution.

    Science.gov (United States)

    Li, Jinhua; Cai, Zongwei

    2008-10-19

    We demonstrated that anionic porphyrins could be stacked and separated in micellar electrokinetic chromatography (MEKC) and microemulsion electrokinetic chromatography (MEEKC) by applying acetonitrile and high salt content in human urine sample matrix. The introduction of sample containing acetonitrile and sodium chloride into the CE capillary at more than 10% of the total capillary volume resulted in the improvement of peak resolution and the enhancement of detection sensitivity. The achieved acetonitrile stacking enrichment factors of six porphyrins ranged from 12 to 32 in MEKC and from 28 to 33 in MEEKC, respectively. The stacking technique was successfully applied for analyzing porphyrins present in urine samples that were deproteinized with acetonitrile. For the analysis of coproporphyrin isomers, addition of the sodium cholate (SC) into micelle and microemulsion solutions provided adequate resolution. Calibration curves obtained for the determination of coproporphyrin isomers were found linear between 30 and 400 nmol L(-1), and the limit of detection (LOD) was 20 nmol L(-1) in MEEKC. Intra- and interday precisions (n=11) in the microemulsion separation system for the isomers at spiked concentrations of 40-400 nmol L(-1) in urine were in the range of 0.1-0.4% and 0.7-7.6% for migration time and peak area, respectively. Coproporphyrin III, coproporphyrin I and uroporphyrin were detected at levels of 80.7 nmol L(-1), 32.3 nmol L(-1) and 19.8 nmol L(-1), respectively, in the urine samples collected from healthy individuals. Different porphyrin profiles, however, were observed in urine samples from porphyria cutanea tarda (PCT) patients. PMID:18804642

  1. Hydrogen Bond Acceptors and Additional Cationic Charges in Methylene Blue Derivatives: Photophysics and Antimicrobial Efficiency

    Directory of Open Access Journals (Sweden)

    Ariane Felgenträger

    2013-01-01

    ca. 600–680 nm,  L mol−1 cm−1, their low toxicity, and their attachment/penetration abilities. Except simple substituents like alkyl or hydroxyalkyl residues, nearly no modifications of the phenothiaziniums have been pursued at the auxochromic sites. By this, the properties of methylene blue derivatives and their fields of application are limited; it remains unclear if their potential antimicrobial efficacy may be enhanced, also to compete with porphyrins. We prepared a set of six mainly novel methylene blue derivatives with the ability of additional hydrogen bonding and/or additional cationic charges to study the substituents’ effect on their activity/toxicity profiles and photophysical properties. Direct detection of singlet oxygen was performed at 1270 nm and the singlet oxygen quantum yields were determined. In suspensions with both, Gram-positive and Gram-negative bacteria, some derivatives were highly active upon illumination to inactivate S. aureus and E. coli up to 7 log10 steps (99.99999% without inherent toxicities in the nonirradiated state.

  2. Cationization of heparin for film applications

    Czech Academy of Sciences Publication Activity Database

    Šimkovic, I.; Mendichi, R.; Kelnar, Ivan; Filip, J.; Hricovíni, M.

    2015-01-01

    Roč. 115, 22 January (2015), s. 551-558. ISSN 0144-8617 Institutional support: RVO:61389013 Keywords : heparin * cationization * NMR Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.074, year: 2014

  3. Cation locations and dislocations in zeolites

    Science.gov (United States)

    Smith, Luis James

    The focus of this dissertation is the extra-framework cation sites in a particular structural family of zeolites, chabazite. Cation sites play a particularly important role in the application of these sieves for ion exchange, gas separation, catalysis, and, when the cation is a proton, acid catalysis. Structural characterization is commonly performed through the use of powder diffraction and Rietveld analysis of powder diffraction data. Use of high-resolution nuclear magnetic resonance, in the study of the local order of the various constituent nuclei of zeolites, complements well the long-range order information produced by diffraction. Recent developments in solid state NMR techniques allow for increased study of disorder in zeolites particularly when such phenomena test the detection limits of diffraction. These two powerful characterization techniques, powder diffraction and NMR, offer many insights into the complex interaction of cations with the zeolite framework. The acids site locations in SSZ-13, a high silica chabazite, and SAPO-34, a silicoaluminophosphate with the chabazite structure, were determined. The structure of SAPO-34 upon selective hydration was also determined. The insensitivity of X-rays to hydrogen was avoided through deuteration of the acid zeolites and neutron powder diffraction methods. Protons at inequivalent positions were found to have different acid strengths in both SSZ-13 and SAPO-34. Other light elements are incorporated into zeolites in the form of extra-framework cations, among these are lithium, sodium, and calcium. Not amenable by X-ray powder diffraction methods, the positions of such light cations in fully ion-exchanged versions of synthetic chabazite were determined through neutron powder diffraction methods. The study of more complex binary cation systems were conducted. Powder diffraction and solid state NMR methods (MAS, MQMAS) were used to examine cation site preferences and dislocations in these mixed-akali chabazites

  4. Thermodynamics and Kinetics of Guest-Induced Switching between “Basket Handle” Porphyrin Isomers

    Directory of Open Access Journals (Sweden)

    Alexander B. C. Deutman

    2014-04-01

    Full Text Available The synthesis and switching properties of two “basket handle” porphyrin isomers is described. The cis-oriented meso-phenyl groups of these porphyrins are linked at their ortho-positons via benzocrown-ether-based spacers, which as a result of slow atropisomerization are located either on the same side of the porphyrin plane (cis, or on opposite sides (trans. In solution, the cis-linked isomer slowly isomerizes in the direction of the thermodynamically more stable trans-isomer. In the presence of viologen (N,N'-dialkyl-4,4'-bipyridinium derivatives, which have different affinities for the two isomers, the isomerization equilibrium could be significantly influenced. In addition, the presence of these guests was found to enhance the rate of the switching process, which was suggested to be caused by favorable interactions between the positively charged guest and the crown ethers of the receptor, stabilizing the transition state energies of the isomerization reaction between the two isomers.

  5. 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

    2016-01-01

    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. PMID:27077840

  6. Functionalization of SnO₂ crystals with a covalently-assembled porphyrin monolayer.

    Science.gov (United States)

    Cristaldi, Domenico A; Gulino, Antonino

    2013-06-01

    The functionalization of micro- and nano-sized metal-oxide powders offers many advantages because of their large surface areas and, therefore, the large number of functional molecules that can be grafted onto the grain surfaces. Porphyrin molecules on large band-gap semiconducting metal oxides represent key materials for many different optical and electronic applications. Herein, we have proposed a general two-step procedure for the functionalization of metal-oxide crystals with dye-sensitizers. In particular, we functionalized SnO₂ nanoparticles with a monolayer of the bifunctional trichloro[4-(chloromethyl)phenyl]silane. Then, a monolayer of 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphyne was covalently bound to the silanized SnO₂ grains. IR, UV/Vis, and luminescence measurements were used for optical characterization. The measured footprint of the grafted porphyrin molecules indicated total surface coverage of the grains. The surface electronic characterization was performed by using X-ray photoelectron spectroscopy. Emission measurements revealed two strong bands at 664.1 and 721.0 nm that were attributed to the porphyrin monolayer assembled on the surface of the SnO₂ crystals. PMID:23610085

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

    International Nuclear Information System (INIS)

    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 ≤C34 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 >C33 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

  8. Evaluation of the oxidative activity of some free base porphyrins by a chemiluminescence method

    Directory of Open Access Journals (Sweden)

    MARIANA VOICESCU

    2010-03-01

    Full Text Available Due to their spectral characteristics, phototoxicity and high affinity for tumour tissues, porphyrins and their derivatives are widely used in modern medicine as contrast agents for cancer diagnostics and as sensitizers in photodynamic therapy, where they kill tumours via enhancement of tumour oxidative stress. The aim of this work was to simulate in vitro the effects caused by oxidation of two free base porphyrins, 5,10,15,20-tetraphenylporphyrin (TPP and 5,10,15,20‑tetra(4‑methoxyphenylporphyrin (TMOPP. The kinetic study was monitored using spectral techniques and chemiluminescence. The effect of both porphyrins on an oxidation process was evidenced using the chemilumi-nescent system, luminal–hydrogen peroxide, in a phosphate buffer at pH 7. It was found that at low concentration, TPP exerts the anti-oxidative effect in the employed chemiluminescent system, while at higher concentrations; its effect is pro-oxidative. TMOPP exerts a pro-oxidant effect, which was more pronounced than TPP. The results are discussed with respect to oxidative stress.

  9. Synthesis and photobactericidal properties of a neutral porphyrin grafted onto lignocellulosic fibers.

    Science.gov (United States)

    Nzambe Ta Keki, Jean Kerim; Ouk, Tan-Sothéa; Zerrouki, Rachida; Faugeras, Pierre-Antoine; Sol, Vincent; Brouillette, François

    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 (9.5J/cm(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. PMID:26952398

  10. Light-activated nanotube-porphyrin conjugates as effective antiviral agents

    Science.gov (United States)

    Banerjee, Indrani; Douaisi, Marc P.; Mondal, Dhananjoy; Kane, Ravi S.

    2012-03-01

    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.

  11. Electron, Hole, Singlet, and Triplet Energy Transfer in Photoexcited Porphyrin-Naphthalenediimide Dyads.

    Science.gov (United States)

    Yushchenko, Oleksandr; Hangarge, Rahul V; Mosquera-Vazquez, Sandra; Boshale, Sheshanath V; Vauthey, Eric

    2015-06-18

    The excited-state dynamics of two molecular dyads, consisting of zinc (1) and free-base (2) porphyrin connected via a peptide linker to a core-substituted naphthalenediimide (NDI) have been investigated using optical spectroscopy. These dyads exhibit rich photophysics because of the large number of electronic excited states below 3 eV. In the case of 1 in apolar solvents, excitation energy transfer from the vibrationally hot singlet excited porphyrin to the NDI takes place with a 500 fs time constant. Electronic energy ends up in the NDI-localized triplet state, which decays to the ground state on a microsecond timescale. In polar solvents, ground-state recovery is faster by 5 orders of magnitude because of the occurrence of charge separation followed by recombination. On the other hand, excitation energy transfer in 2 takes place in the opposite direction, namely from the NDI to the porphyrin, which then undergoes intersystem crossing to the triplet state, followed by triplet energy transfer back to the NDI. Therefore, four distinct local electronic excited states are consecutively populated after excitation of the NDI unit of 2, with the energy shuttling between the two ends of the dyad. PMID:25418961

  12. Cycloaliphatic epoxide resins for cationic UV - cure

    International Nuclear Information System (INIS)

    This paper introduces the cyclo - aliphatic epoxide resins used for the various applications of radiation curing and their comparison with acrylate chemistry. Radiation curable coatings and inks are pre - dominantly based on acrylate chemistry but over the last few years, cationic chemistry has emerged successfully with the unique properties inherent with cyclo - aliphatic epoxide ring structures. Wide variety of cationic resins and diluents, the formulation techniques to achieve the desired properties greatly contributes to the advancement of UV - curing technology

  13. Test procedure for cation exchange chromatography

    International Nuclear Information System (INIS)

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

  14. Silica-based cationic bilayers as immunoadjuvants

    OpenAIRE

    Carmona-Ribeiro Ana M; da Costa Maria; Faquim-Mauro Eliana; Santana Mariana RA; Lincopan Nilton

    2009-01-01

    Abstract Background Silica particles cationized by dioctadecyldimethylammonium bromide (DODAB) bilayer were previously described. This work shows the efficiency of these particulates for antigen adsorption and presentation to the immune system and proves the concept that silica-based cationic bilayers exhibit better performance than alum regarding colloid stability and cellular immune responses for vaccine design. Results Firstly, the silica/DODAB assembly was characterized at 1 mM NaCl, pH 6...

  15. Cations and activated sludge floc structure

    OpenAIRE

    Park, Chul

    2002-01-01

    This research was designed to investigate the effect of cations on activated sludge characteristics and also to determine their influence on digestion performance. For this purpose, cations in solution and in floc were evaluated along with various activated sludge characteristics and the collected waste activated sludge underwent both anaerobic and aerobic digestion. It was found that large amounts of biopolymer (protein + polysaccharide) remained in the effluent of WWTP that received high in...

  16. Structural Studies on Porphyrin-PNA Conjugates in Parallel PNA:PNA Duplexes: Effect of Stacking Interactions on Helicity.

    Science.gov (United States)

    Accetta, Alessandro; Petrovic, Ana G; Marchelli, Rosangela; Berova, Nina; Corradini, Roberto

    2015-12-01

    Parallel PNA:PNA duplexes were synthesized and conjugated with meso-tris(pyridyl)phenylporphyrin carboxylic acid at the N-terminus. The introduction of one porphyrin unit was shown to affect slightly the stability of the PNA:PNA parallel duplex, whereas the presence of two porphyrin units at the same end resulted in a dramatic increase of the melting temperature, accompanied by hysteresis between melting and cooling curves. The circular dichroism (CD) profile of the Soret band and fluorescence quenching strongly support the occurrence of a face-to-face interaction between the two porphyrin units. Introduction of a L-lysine residue at the C-terminal of one strand of the parallel duplex induced a left-handed helical structure in the PNA:PNA duplex if the latter contains only one or no porphyrin moiety. The left-handed helicity was revealed by nucleobase CD profile at 240-280 nm and by the induced-CD observed in the presence of the DiSC2 (5) cyanine dye at ~500-550 nm. Surprisingly, the presence of two porphyrin units led to the disappearance of the nucleobase CD signal and the absence of CD exciton coupling within the Soret band region. In addition, a dramatic decrease of induced CD of DiSC2 (5) was observed. These results are in agreement with a model where the porphyrin-porphyrin interactions cause partial loss of chirality of the PNA:PNA parallel duplex, forcing it to adopt a ladder-like conformation. PMID:26412743

  17. 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).

  18. 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.

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

    Science.gov (United States)

    Singh, Ambrish; Lin, Yuanhua; Quraishi, Mumtaz A; Olasunkanmi, Lukman O; Fayemi, Omolola E; Sasikumar, Yesudass; Ramaganthan, Baskar; Bahadur, Indra; Obot, Ime B; Adekunle, Abolanle S; Kabanda, Mwadham M; Ebenso, Eno E

    2015-01-01

    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-tetrayl)tetrakis(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. PMID:26295223

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

    Science.gov (United States)

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

    2016-05-01

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

  1. Experimental study on the fragmentation of Adenine and Porphyrin molecules induced by low energy multicharged ion impact

    International Nuclear Information System (INIS)

    Since the dissociation of small molecules might play key roles in the understanding of radiation induced damages of living tissues at the primary steps and at the molecular levels, fragmentation dynamics of small biomolecules have drawn much attention. The knowledge of the internal energy is of fundamental importance for understanding its fragmentation dynamics following external excitation. For a long time however, it was difficult to measure this parameter in coincidence with the fragmentation patterns until the development of CIDEC (Collision Induced Dissociation under Energy Control) method in 2007. In this work, the CIDEC method was extended to study the fragmentation of gas-phase biomolecules adenine (Ade: H5C5N5) and porphyrin chloride FeTPPCl (C44H28N4FeCl). The population distribution for each dissociation channel as a function of the excitation energy of the parent molecular ions at a well-determined initial charge state has been experimentally determined, which could shed some light on the fragmentation dynamics of these molecules. In collisions between Cl+ and Ade at 3 keV, the fragmentation pattern of Ade2+ is dominated by the loss of H2CN+ and the successive emission of HCN. The energy distribution of the parent dication confirms the successive emission dynamics. A specific decay channel is observed, i.e. the emission of a charged H2CN+ followed by the emission of HC2N2. The measured mean excitation energies of this channel and other competitive channels are compared. In Kr8+ - FeTPPCl collisions at 80 keV, parent ions FeTPPCL1+,2+,3+ are observed, along with the corresponding decay patterns. It is found that, in the first step the dominant low-energy-cost decay channel is the emission of Cl0 independent of the initial charge state of FeTPPClr+. For the resulted dication FeTPP2+, the dominant fragmentation channel is the neutral evaporation; for the tri-cation however, the dominant fragmentation channel is the asymmetrical fission by emission of a

  2. A novel 177Lu-labeled porphyrin for possible use in targeted tumor therapy

    International Nuclear Information System (INIS)

    Introduction: Porphyrin and its derivatives exhibit inherent affinity for localization in tumors. Hence, porphyrin derivatives radiolabeled with suitable therapeutic radionuclides could be envisaged as potential agents for targeted tumor therapy. In this direction, a water-soluble porphyrin derivative, viz., 5,10,15,20-tetrakis[4-carboxymethyleneoxyphenyl]porphyrin was synthesized in-house and radiolabeled with 177Lu with an aim to prepare an agent for targeted tumor therapy. 177Lu is an attractive radionuclide for the development of targeted radiotherapeutic agents owing to its suitable decay characteristics [T1/2=6.73 d, Eβ(max)=0.49 MeV, Eγ=208 keV (11%)], comparatively longer half-life and ease of production with high specific activity. Methods: 177Lu was produced by irradiation of enriched Lu2O3 (64.3% 176Lu) at a thermal neutron flux of 1x1014 n/cm2.s for 14 d. The porphyrin was coupled to a suitable chelator, namely, p-aminobenzyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid for complexation with 177Lu. The radiolabeling was achieved by incubating 50 μg of the conjugate with 177LuCl3 (200 ng Lu) in acetate buffer (pH ∼5) at 50oC for 1 h. The radiolabeled conjugate was characterized by high-performance liquid chromatography and its biological efficacy was studied in Swiss mice bearing fibrosarcoma tumors. Results: 177Lu was obtained with a specific activity of ∼550 TBq/g and radionuclidic purity of 99.98%. The 177Lu-labeled porphyrin conjugate was obtained with 99% radiochemical purity and it exhibited good in vitro stability. Biodistribution studies revealed good tumor uptake (2.01% IA/g) within 3 h post injection (p.i.) with >94% injected activity exhibiting renal clearance. No significant accumulation of activity was observed in any of the vital organs/tissue. The tumor/blood and tumor/muscle ratios were 2.89 and 16.80, respectively, at 3 h p.i. and further increased till 2 days p.i. up to which the studies continued. Serial

  3. Characterization of Porphyrin-Co(III)-'Nitrene Radical' Species Relevant in Catalytic Nitrene Transfer Reactions.

    Science.gov (United States)

    Goswami, Monalisa; Lyaskovskyy, Volodymyr; Domingos, Sérgio R; Buma, Wybren Jan; Woutersen, Sander; Troeppner, Oliver; Ivanović-Burmazović, Ivana; Lu, Hongjian; Cui, Xin; Zhang, X Peter; Reijerse, Edward J; DeBeer, Serena; van Schooneveld, Matti M; Pfaff, Florian Felix; Ray, Kallol; de Bruin, Bas

    2015-04-29

    To fully characterize the Co(III)-'nitrene radical' species that are proposed as intermediates in nitrene transfer reactions mediated by cobalt(II) porphyrins, different combinations of cobalt(II) complexes of porphyrins and nitrene transfer reagents were combined, and the generated species were studied using EPR, UV-vis, IR, VCD, UHR-ESI-MS, and XANES/XAFS measurements. Reactions of cobalt(II) porphyrins 1(P1) (P1 = meso-tetraphenylporphyrin (TPP)) and 1(P2) (P2 = 3,5-Di(t)Bu-ChenPhyrin) with organic azides 2(Ns) (NsN3), 2(Ts) (TsN3), and 2(Troc) (TrocN3) led to the formation of mono-nitrene species 3(P1)(Ns), 3(P2)(Ts), and 3(P2)(Troc), respectively, which are best described as [Co(III)(por)(NR″(•-))] nitrene radicals (imidyl radicals) resulting from single electron transfer from the cobalt(II) porphyrin to the 'nitrene' moiety (Ns: R″ = -SO2-p-C6H5NO2; Ts: R″ = -SO2C6H6; Troc: R″ = -C(O)OCH2CCl3). Remarkably, the reaction of 1(P1) with N-nosyl iminoiodane (PhI═NNs) 4(Ns) led to the formation of a bis-nitrene species 5(P1)(Ns). This species is best described as a triple-radical complex [(por(•-))Co(III)(NR″(•-))2] containing three ligand-centered unpaired electrons: two nitrene radicals (NR″(•-)) and one oxidized porphyrin radical (por(•-)). Thus, the formation of the second nitrene radical involves another intramolecular one-electron transfer to the "nitrene" moiety, but now from the porphyrin ring instead of the metal center. Interestingly, this bis-nitrene species is observed only on reacting 4(Ns) with 1(P1). Reaction of the more bulky 1(P2) with 4(Ns) results again in formation of mainly mono-nitrene species 3(P2)(Ns) according to EPR and ESI-MS spectroscopic studies. The mono- and bis-nitrene species were initially expected to be five- and six-coordinate species, respectively, but XANES data revealed that both mono- and bis-nitrene species are six-coordinate O(h) species. The nature of the sixth ligand bound to cobalt(III) in the

  4. Accelerators for forming cationic technetium complexes useful as radiodiagnostic images

    International Nuclear Information System (INIS)

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

  5. Investigating the possible use of a tetra (hydroxyphenyl) porphyrin as a fluorescence probe for the supramolecular detection of phospholipids

    International Nuclear Information System (INIS)

    The present work explores the interest of using the 5,10,15,20-tetrakis(3-hydroxyphenyl)-21H,23H-porphine (m-THPP), a commercially available porphyrin, as a polarity probe for the detection of phospholipids. Feasibility of the process was first tested by direct fluorimetry and it was established that emission enhancement in the presence of lipids was maximum for a methanol content of 15% (v/v), a neutral pH (6-8) and a probe concentration of 2x10-7 M in the working solution. Detection with m-THPP in these conditions presents higher response factor but shorter linear range than diphenylhexatriene (DPH), the reference dye for the supramolecular detection of lipids. Insights on the mechanism of m-THPP-lipid association demonstrated that, at high lipid concentrations, porphyrin is associated to lipid assemblies in monomer form and located in the interior of bilayer; in low lipid content, porphyrin aggregates coexist with the monomer. Finally it was assessed that the method can be successfully coupled with micro-bore liquid chromatography. - Highlights: → Use of a tetraphenyl porphyrin as a probe for the detection of phospholipids (PL). → Evidence of the experimental conditions optimising fluorescence emission. → Mechanism of incorporation and localisation of porphyrin in the PL assemblies. → Comparison with the most common probe for lipid detection (DPH). → Application to micro-chromatography.

  6. Preparation and enhanced visible light-driven catalytic activity of ZnO microrods sensitized by porphyrin heteroaggregate

    International Nuclear Information System (INIS)

    An inorganic-organic composite (ZnO/TAPPI-CoTPPS) composed of ZnO microrods and nano-heteroaggregates containing tetrakis(4-trimethylaminophenyl) porphyrin (TAPPI) and tetrakis(4-sulfonatophenyl) porphyrin cobalt(II) (CoTPPS), has been achieved by a simple mixing method. From the solid diffuse reflectance UV-vis spectrum of ZnO/TAPPI-CoTPPS, it can be observed that the Soret band of the porphyrin heteroaggregate of ZnO/TAPPI-CoTPPS is blue-shifted in comparison with that of the pure TAPPI-CoTPPS heteroaggregate while the Q bands are red-shifted, which demonstrates that there exists some interaction between the porphyrin heteroaggregate and ZnO. In addition, the photodegradation of rhodamine B (RhB) in water catalyzed by ZnO/TAPPI-CoTPPS was investigated at room temperature. Under visible light irradiation (λ ≥ 420 nm), the photocatalytic activity of the ZnO/TAPPI-CoTPPS composite was higher than those of the porphyrin monomers modified ZnO composite and pure ZnO.

  7. 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

    2016-01-01

    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. PMID:27011265

  8. 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.

  9. Topology-guided design and syntheses of highly stable mesoporous porphyrinic zirconium metal-organic frameworks with high surface area

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Tian -Fu [Texas A & M Univ., College Station, TX (United States); Feng, Dawei [Texas A & M Univ., College Station, TX (United States); Chen, Ying -Pin [Texas A & M Univ., College Station, TX (United States); Zou, Lanfang [Texas A & M Univ., College Station, TX (United States); Bosch, Mathieu [Texas A & M Univ., College Station, TX (United States); Yuan, Shuai [Texas A & M Univ., College Station, TX (United States); Wei, Zhangwen [Texas A & M Univ., College Station, TX (United States); Fordham, Stephen [Texas A & M Univ., College Station, TX (United States); Wang, Kecheng [Texas A & M Univ., College Station, TX (United States); Zhou, Hong -Cai [Texas A & M Univ., College Station, TX (United States)

    2015-01-14

    Through a topology-guided strategy, a series of Zr₆-containing isoreticular porphyrinic metal–organic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the structures range from 2.5 to 3.8 nm, and PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr₈ cluster with a smaller Zr₆ cluster in a topologically identical framework. The high connectivity of the Zr₆ cluster yields frameworks with enhanced stability despite high porosity and ultralarge linker. As a representative example, PCN-230, constructed with the most extended porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for construction of stable mesoporous MOFs.

  10. Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal-Organic Frameworks with High Surface Area

    Energy Technology Data Exchange (ETDEWEB)

    Liu, TF; Feng, DW; Chen, YP; Zou, LF; Bosch, M; Yuan, S; Wei, ZW; Fordham, S; Wang, KC; Zhou, HC

    2015-01-14

    Through a topology-guided strategy, a series of Zr-6-containing isoreticular porphyrinic metalorganic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the structures range from 2.5 to 3.8 nm, and PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr-8 cluster with a smaller Zr-6 cluster in a topologically identical framework. The high connectivity of the Zr-6 cluster yields frameworks with enhanced stability despite high porosity and ultralarge linker. As a representative example, PCN-230, constructed with the most extended porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for construction of stable mesoporous MOFs.

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

    International Nuclear Information System (INIS)

    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, 1H NMR and FAB-MS. The photophysics, photochemical and photobleaching properties of chlorine 4 have been evaluated. Its quantum yield of photobleaching (φPb, mol Einstein-1) was 0.047±0.014. In order to demonstrate the production of 1O2 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)

  12. Molecular and mesoscale mechanism for hierarchical self-assembly of dipeptide and porphyrin light-harvesting system.

    Science.gov (United States)

    Liu, Kai; Kang, Yu; Ma, Guanghui; Möhwald, Helmuth; Yan, Xuehai

    2016-06-22

    A multi-scale theoretical investigation of dipeptide-porphyrin co-assembly systems has been carried out to establish such understanding, where two different types of the dipeptides, dilysine (KK(3+)) and diphenylalanine (FF(+)) are compared on tuning the porphyrin organization. Density functional theory results reveal that the electrostatic attraction between different functional groups has significantly strengthened the hydrogen bonds between them, which are considered as the driving force of the self-assembly at the molecular level. All-atom molecular dynamics (MD) simulation further indicates that the formation of the core-shell nanorods is driven and stabilized by the hydrophobic interaction between dipeptides and negatively charged porphyrin (H2TPPS(2-)), where the packed porphyrins stay inside as the core of the nanorods and the hydrophilic groups (amino- and carboxyl-groups) as the shell. With stronger hydrophobicity, FF(+) is more likely to insert into the porphyrin aggregates and build crosslinks than KK(3+). Moreover, dissipative particle dynamics (DPD) simulation suggests equilibrium morphologies with different dipeptides, where KK(3+)-H2TPPS(2-) assembled in fiber bundles, whereas FF(+)-H2TPPS(2-) assembled as microspheres, corresponding to the different packing behavior in MD simulations. The consistency of these results at different scales is discussed. The method used in this work could be extended for studying similar issues in hierarchical self-assembly of building blocks such biomaterials. PMID:27270974

  13. Combination and cleavage of HBV DNA fragments by triple helix-forming oligonucleotides modified with manganese porphyrin in vitro

    Institute of Scientific and Technical Information of China (English)

    光丽霞; 袁发焕; 奚敏; 赵聪敏; 刘立; 温恩懿; 艾友萍

    2003-01-01

    Objective To observe the ability of triple helix-forming oligonucleotides (TFOs) modified with manganese porphyrin to combine with and cleave HBV DNA fractions. Methods TFO were modified with manganese porphyrin and acridines, and then reacted with the 32P labeled HBV DNA fragments at 37℃ in vitro (pH 7.4). Electrophoretic mobility shift assays and Dnase Ⅰ footprinting tests were used to show the affinity and specificity of TFO to bind to target sequences. The ability of TFO to cleave HBV DNA fragments was tested by cleavage experiments. Results TFO modified with manganese porphyrin and acridine could bind to the target sequence in a sequence-dependent manner, with a Kd value of 3.5×10-7 mol/L and a relative affinity of 0.008. In the presence of potassium monopersulfate (KHSO5), TFO modified with manganese porphyrin and acridine could cleave the target sequence where the triplex DNA was formed. Conclusion In the presence of KHSO5, TFO modified with manganese porphyrin and acridine could bind and cleave the target HBV-DNA in a sequence-dependent manner.

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

    International Nuclear Information System (INIS)

    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 TiO2 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 TiO2 electrode surface in supramolecular solar cells

  15. 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

    2016-01-01

    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. PMID:27011265

  16. Importance of the Reorganization Energy Barrier in Computational Design of Porphyrin-Based Solar Cells with Cobalt-Based Redox Mediators

    DEFF Research Database (Denmark)

    Ørnsø, Kristian Baruël; Jónsson, Elvar Örn; Jacobsen, Karsten Wedel;

    2015-01-01

    calculated using ab initio molecular dynamics with explicit solvent. These results are then combined with a Marcus-based extrapolation scheme to obtain the reorganization energies of more than 5000 porphyrin-based dyes. We propose a scheme for scoring the performance of the porphyrin dyes, which is able to...

  17. Electrospun Poly(acrylonitrile-co-acrylic acid) Nanofibrous Membranes for Catalase Immobilization:Effect of Porphyrin Filling on the Enzyme Activity

    Institute of Scientific and Technical Information of China (English)

    KE Bei-bei; WAN Ling-shu; HUANG Xiao-jun; XU Zhi-kang

    2011-01-01

    Porphyrin-filled nanofibrous membranes were facilely prepared by electrospinning of the mixtures of poly(acryionitrile-co-acrylic acid)(PANCAA) and porphyrins. 5,10,15,20-Tetraphenyiporphyrin(TPP) and its metalloderivatives(ZnTPP and CuTPP) were studied as filling mediators for the immobilization of redox enzyme. Results indicate that the introduction of TPP, ZnTPP and CuTPP improves the retention activity of the immobilized catalase.Among these three porphyrins, the ZnTPP-filled PANCAA nanofibrous membrane exhibits an activity retention of 93%, which is an exciting improvement. This improvement is attributed to both the strong catalase-porphyrin affinity and the possible facilitated electron transfer induced by the porphyrin as evidenced by quartz crystal microbalance (QCM) and fluorescence spectroscopy studies.

  18. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.

    1991-10-01

    The objective of this project is to make use of products obtained from renewable plant sources as monomers for the direct production of polymers which can be used for a wide range of plastic applications. In this report is described progress in the synthesis and polymerization of cationically polymerizable monomers and oligomers derived from botanical oils, terpenes, natural rubber, and lignin. Nine different botanical oils were obtained from various sources, characterized and then epoxidized. Their photopolymerization was carried out using cationic photoinitiators and the mechanical properties of the resulting polymers characterized. Preliminary biodegradation studies are being conducted on the photopolymerized films from several of these oils. Limonene was cationically polymerized to give dimers and the dimers epoxidized to yield highly reactive monomers suitable for coatings, inks and adhesives. The direct phase transfer epoxidation of squalene and natural rubber was carried out. The modified rubbers undergo facile photocrosslinking in the presence of onium salts to give crosslinked elastomers. 12 refs., 3 figs., 10 tabs.

  19. Fluorescent tetraruthenated porphyrins embedded in monolithic SiO2 gels by the sol-gel process.

    Science.gov (United States)

    Santos, Shirleny F; Santos, Marcelo L; Almeida, Luis E; Costa, Nivan B; Gimenez, Iara F; Araki, Koiti; Mayer, Ildemar; Engelmann, Fabio Monaro; Toma, Henrique Eisi; Barreto, Ledjane S

    2007-01-15

    In this work silica gels have been prepared by a sol-gel method using tetraethylorthosilicate as gel precursor. The tetraruthenated porphyrins H2(3-TRPyP), Co(3-TRPyP), and H2(4-TRPyP) were incorporated into the systems during gel formation without problems commonly found in the process, such as aggregation. Spectroscopic studies of the resulting silica gels revealed the presence of absorption bands in the range 200-400 nm associated with the transitions of the groups ruthenium-bipyridine, along with the Soret band at the same wavelengths observed in solution. The porphyrins were found to preserve fluorescence emission properties in the range 650-700 nm even after the aging period. Study of the thermal behavior and decomposition kinetics evidenced that the porphyrin H2(4-TRPyP) is the least stable of the group and that all compounds decompose according to first-order kinetics. PMID:17074358

  20. Interaction between certain porphyrins and CdS colloids: A steady state and time resolved fluorescence quenching study

    Science.gov (United States)

    Jhonsi, M. Asha; Kathiravan, A.; Renganathan, R.

    2008-12-01

    The interaction between porphyrins namely, meso-tetrakis (4-methoxyphenyl)porphyrin (TMeOPP), protoporphyrin IX (PPIX) and Zinc(II) meso-tetraphenylporphyrin (ZnTPP) with colloidal CdS has been studied by using steady state and time resolved fluorescence quenching measurements. The porphyrins adsorbed on the surface of colloidal CdS due to electrostatic interaction. This adsorption leads to changes in the absorption spectra related to the complex formation. The apparent association constant ( Kapp) was in the order of 4.34-5.58 × 10 5 M -1 from the effect of colloidal CdS on the absorption spectra and 0.64-1.6 × 10 5 M -1 from fluorescence quenching data. Quenching is attributable mainly to static mechanism through ground state complex formation as confirmed by lifetime measurements.