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Sample records for pheny1 porphyrin glassy

  1. Porphyrins

    NASA Astrophysics Data System (ADS)

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

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

  2. Porphyrins

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

    1996-01-01

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided. The novel compositions and others made according to the process of the invention are useful as hydrocarbon conversion catalysts; for example, for the oxidation of alkanes and the decomposition of hydroperoxides.

  3. Porphyrins

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.

    1996-11-05

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided. The novel compositions and others made according to the process of the invention are useful as hydrocarbon conversion catalysts; for example, for the oxidation of alkanes and the decomposition of hydroperoxides.

  4. Determination of serotonin on a glassy carbon electrode modified by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin and single walled carbon nanotubes.

    PubMed

    Kim, Seul Ki; Ahmed, Mohammad Shamsuddin; Jeong, Haesang; You, Jung-Min; Jeon, Seungwon

    2011-03-01

    A chemically modified electrode [poly(TAPP)-SWNT/GCE] was prepared by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin (TAPP)-single walled carbon nanotubes (SWNT) on the surface of a glassy carbon electrode (GCE). This modified electrode was employed as an electrochemical biosensor for the determination of serotonin concentration and exhibited a typical enhance effect on the current response of serotonin and lower oxidation overpotential. The biosensor was very effective to determined 5-HT in a mixture. The linear response was in the range 2.0 x 10(-7) to 1.0 x 10(-5) M, with a correlation coefficient of 0.999 [i(p)(microA) = 3.406 C (microM)+0.132] on the anodic current, with a detection limit of 1 x 10(-9) M. Due to the relatively low currents and different potentials in the electrochemical responses to ascorbic acid and dopamine, the modified electrode is a useful and effective sensing device for the selective and sensitive serotonin determination in the presence of ascorbic acid and dopamine.

  5. Synthesis of porphyrin nanostructures

    DOEpatents

    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.

  6. Soluble porphyrin polymers

    SciTech Connect

    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.

  7. Functionalized expanded porphyrins

    DOEpatents

    Sessler, Jonathan L; Pantos, Patricia J

    2013-11-12

    Disclosed are functionalized expanded porphyrins that can be used as spectrometric sensors for high-valent actinide cations. The disclosed functionalized expanded porphyrins have the advantage over unfunctionalized systems in that they can be immobilized via covalent attachment to a solid support comprising an inorganic or organic polymer or other common substrates. Substrates comprising the disclosed functionalized expanded porphyrins are also disclosed. Further, disclosed are methods of making the disclosed compounds (immobilized and free), methods of using them as sensors to detect high valent actinides, devices that comprise the disclosed compounds, and kits.

  8. Electrically conducting porphyrin and porphyrin-fullerene electropolymers

    DOEpatents

    Gust, Jr., John Devens; Liddell, Paul Anthony; Gervaldo, Miguel Andres; Bridgewater, James Ward; Brennan, Bradley James; Moore, Thomas Andrew; Moore, Ana Lorenzelli

    2014-03-11

    Compounds with aryl ring(s) at porphyrin meso position(s) bearing an amino group in position 4 relative to the porphyrin macrocycle, and at least one unsubstituted 5 (hydrogen-bearing) meso position with the 10-, 15-, and/or 20-relationship to the aryl ring bearing the amino group, and metal complexes thereof, feature broad spectral absorption throughout the visible region. These compounds are electropolymerized to form electrically conducting porphyrin and porphyrin-fullerene polymers that are useful in photovoltaic applications. The structure of one such electrically conducting porphyrin polymer is shown below. ##STR00001##

  9. Triphenylsilane-fused Porphyrins.

    PubMed

    Kato, Kenichi; Kim, Jun Oh; Yorimitsu, Hideki; Kim, Dongho; Osuka, Atsuhiro

    2016-06-01

    A reaction sequence of 2-(diphenylsilyl)phenylation by Negishi coupling and intramolecular sila-Friedel-Crafts reaction has been explored for the synthesis of mono-triphenylsilane-fused porphyrins 5 M and 6 M (M= Ni, Zn) and bis-triphenylsilane-fused porphyrins 7 M and 8 Ni. A triply linked triphenylsilane-fused Ni(II) porphyrin, 13 Ni, was synthesized in a stepwise manner involving the above reaction sequence and a final Pd-catalyzed C-H activating arylative cyclization. The silicon atom in 13 Ni takes a distorted planarized structure with an almost perpendicular Si-phenyl group, causing an electronic effect due to effective σ*-π* interaction. PMID:27124659

  10. Preparation and electrochemical performance of manganese porphyrin /titanate intercalated nanocomposite

    NASA Astrophysics Data System (ADS)

    Sun, Y.; Deng, J. P.; Tu, Z. Y.; Ma, J. J.

    2016-07-01

    A new nanocomposite of manganese porphyrin/titanate (MnPP-Ti4O9) was prepared successfully by delamination/reassembling (DR) method, with layered titanate as the host material, manganese porphyrin (MnPP) as the guest material. The microstucture of MnPP-Ti4O9 was characterized by XRD, UV-Vis, SEM and TEM. MnPP molecules were closely tilted against the host nanosheets at an inclined angle of 42.7°, by simple geometric calculation. The electrochemical performance of the nanocomposite was measured using cyclic voltammetry (CV). It was found that MnPP-Ti4O9 modified glassy carbon electrode (MTGCE) showed desired electrochemical performance and good catalytic activity for oxygen reduction.

  11. Porphyrin analysis and coal rank. A porphyrin index of coalification

    SciTech Connect

    Bonnett, R.; Hughes, P.S. )

    1989-03-01

    The stable aromatic nature of the porphyrin nucleus might be expected to make biomarkers containing it excellent bases for the study of the maturation of sedimentary deposits. Thus the porphyrin macroring can be thought of as an inert carrier of information contained in eight or nine peripheral substituents the increased cracking of which would reveal increased maturation. For non-migrating fossil fuels such as lignite and coal, a relationship between the distribution of porphyrin molecular mass and coal rank would result. This idea is examined for a series of well characterized bituminous coals from the British Carboniferous. Extraction of porphyrins and metalloporphyrins is carried out with methanolic sulfuric acid, and the gallium porphyrin concentrates are analyzed both by HPLC and by mass spectrometry. A Porphyrin Index of Coalification (PIC Number) is derived and related to other maturity indices. Within the range of examples chosen it appears to provide a useful scientifically-based indicator of coal maturity.

  12. Molecular Simulations of Porphyrins and Heme Proteins

    SciTech Connect

    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.

  13. Porphyrins at interfaces

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  14. Glassy correlations in nematic elastomers

    NASA Astrophysics Data System (ADS)

    Lu, Bing; Goldbart, Paul; Mao, Xiaoming

    2009-03-01

    We address the physical properties of an isotropic melt or solution of nematogenic polymers that is then cross-linked beyond the vulcanization point. To do this, we construct a replica Landau theory involving a coupled pair of order- parameter fields: one describing vulcanization, the other describing local nematic order. Thermal nematic fluctuations, present at the time of cross-linking, are trapped by cross- linking into the vulcanized network. The resulting glassy nematic fluctuations are analyzed in the Gaussian approximation in two regimes. When the localization length is shorter than the thermal nematic correlation length, the nematic correlations are well captured as glassy correlations. In the opposite regime, fluctuations in the positions of the localized polymers partially wash out the glassy nematic correlations.

  15. Molecular Catalysis of O2 Reduction by Iron Porphyrins in Water: Heterogeneous versus Homogeneous Pathways.

    PubMed

    Costentin, Cyrille; Dridi, Hachem; Savéant, Jean-Michel

    2015-10-28

    Despite decades of active attention, important problems remain pending in the catalysis of dioxygen reduction by iron porphyrins in water in terms of selectivity and mechanisms. This is what happens, for example, for the distinction between heterogeneous and homogeneous catalysis for soluble porphyrins, for the estimation of H2O2/H2O product selectivity, and for the determination of the reaction mechanism in the two situations. With water-soluble iron tetrakis(N-methyl-4-pyridyl)porphyrin as an example, procedures are described that allow one to operate this distinction and determine the H2O2/H2O product ratio in each case separately. It is noteworthy that, despite the weak adsorption of the iron(II) porphyrin on the glassy carbon electrode, the contribution of the adsorbed complex to catalysis rivals that of its solution counterpart. Depending on the electrode potential, two successive catalytic pathways have been identified and characterized in terms of current-potential responses and H2O2/H2O selectivity. These observations are interpreted in the framework of the commonly accepted mechanism for catalytic reduction of dioxygen by iron porphyrins, after checking its compatibility with a change of oxygen concentration and pH. The difference in intrinsic catalytic reactivity between the catalyst in the adsorbed state and in solution is also discussed. The role of heterogeneous catalysis with iron tetrakis(N-methyl-4-pyridyl)porphyrin has been overlooked in previous studies because of its water solubility. The main objective of the present contribution is therefore to call attention, by means of this emblematic example, to such possibilities to reach a correct identification of the catalyst, its performances, and reaction mechanism. This is a question of general interest, so that reduction of dioxygen remains a topic of high importance in the context of contemporary energy challenges.

  16. Glassy composition for hermetic seals

    DOEpatents

    Wilder, Jr., James A.

    1980-01-01

    The invention relates to a glassy composition adaptable for sealing to aluminum-based alloys to form a hermetically-sealed insulator body. The composition may either be employed as a glass or, after devitrifying heat treatment, as a glass-ceramic.

  17. Self-Organized Porphyrinic Materials

    PubMed Central

    Drain, Charles Michael; Varotto, Alessandro; Radivojevic, Ivana

    2009-01-01

    The self-assembly and self-organization of porphyrins and related macrocycles enables the bottom-up fabrication of photonic materials for fundamental studies of the photophysics of these materials and for diverse applications. This rapidly developing field encompasses a broad range of disciplines including molecular design and synthesis, materials formation and characterization, and the design and evaluation of devices. Since the self-assembly of porphyrins by electrostatic interactions in the late 1980s to the present, there has been an ever increasing degree of sophistication in the design of porphyrins that self-assemble into discrete arrays or self-organize into polymeric systems. These strategies exploit ionic interactions, hydrogen bonding, coordination chemistry, and dispersion forces to form supramolecular systems with varying degrees of hierarchical order. This review concentrates on the methods to form supramolecular porphyrinic systems by intermolecular interactions other than coordination chemistry, the characterization and properties of these photonic materials, and the prospects for using these in devices. The review is heuristically organized by the predominant intermolecular interactions used and emphasizes how the organization affects properties and potential performance in devices. PMID:19253946

  18. Supramolecular Allosteric Cofacial Porphyrin Complexes

    SciTech Connect

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

    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 macrocyclic cavity.

  19. The Antimicrobial Activity of Porphyrin Attached Polymers

    NASA Astrophysics Data System (ADS)

    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.

  20. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

    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.

  1. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

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

    2013-09-10

    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.

  2. Porphyrin Microparticles for Biological and Biomedical Applications

    NASA Astrophysics Data System (ADS)

    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.

  3. Glassy features of crystal plasticity

    NASA Astrophysics Data System (ADS)

    Lehtinen, Arttu; Costantini, Giulio; Alava, Mikko J.; Zapperi, Stefano; Laurson, Lasse

    2016-08-01

    Crystal plasticity occurs by deformation bursts due to the avalanchelike motion of dislocations. Here we perform extensive numerical simulations of a three-dimensional dislocation dynamics model under quasistatic stress-controlled loading. Our results show that avalanches are power-law distributed and display peculiar stress and sample size dependence: The average avalanche size grows exponentially with the applied stress, and the amount of slip increases with the system size. These results suggest that intermittent deformation processes in crystalline materials exhibit an extended critical-like phase in analogy to glassy systems instead of originating from a nonequilibrium phase transition critical point.

  4. Quantitative measurement of porphyrins in biological tissues and evaluation of tissue porphyrins during toxicant exposures.

    PubMed

    Woods, J S; Miller, H D

    1993-10-01

    Porphyrins are formed in most eukaryotic tissues as intermediates in the biosynthesis of heme. Assessment of changes in tissue porphyrin levels occurring in response to the actions of various drugs or toxicants is potentially useful in the evaluation of chemical exposures and effects. The present paper describes a rapid and sensitive method for the extraction and quantitation of porphyrins in biological tissues which overcomes difficulties encountered in previously described methods, particularly the loss of porphyrins during extraction and interference of porphyrin quantitation by coeluting fluorescent tissue constituents. In this procedure 8- through 2-carboxyl porphyrins are quantitatively extracted from tissue homogenates using HCl and methanol and are subsequently separated from potentially interfering contaminants by sequential methanol/phosphate elution on a C-18 preparatory column. Porphyrins are then separated and measured by reversed-phase high-performance liquid chromatography and spectrofluorometric techniques. Recovery of tissue porphyrins using this method is close to 100% with an intraassay variability of less than 10%. We have employed this procedure to measure liver and kidney porphyrin concentrations in male Fischer rats and to define the distinctive changes in tissue porphyrin patterns associated with treatment with the hepatic and renal porphyrinogenic chemicals, allylisopropylacetamide, and methyl mercury hydroxide, respectively. This method is applicable to the measurement of tissue porphyrin changes resulting from drug or toxicant exposures in clinical, experimental or environmental assessments.

  5. Structural order in glassy water.

    PubMed

    Giovambattista, Nicolas; Debenedetti, Pablo G; Sciortino, Francesco; Stanley, H Eugene

    2005-06-01

    We investigate structural order in glassy water by performing classical molecular dynamics simulations using the extended simple point charge (SPC/E) model of water. We perform isochoric cooling simulations across the glass transition temperature at different cooling rates and densities. We quantify structural order by orientational and translational order metrics. Upon cooling the liquid into the glassy state, both the orientational order parameter Q and translational order parameter tau increase. At T=0 K, the glasses fall on a line in the Q-tau plane or order map. The position of this line depends only on density and coincides with the location in the order map of the inherent structures (IS) sampled upon cooling. We evaluate the energy of the IS, eIS(T), and find that both order parameters for the IS are proportional to eIS. We also study the structural order during the transformation of low-density amorphous ice (LDA) to high-density amorphous ice (HDA) upon isothermal compression and are able to identify distinct regions in the order map corresponding to these glasses. Comparison of the order parameters for LDA and HDA with those obtained upon isochoric cooling indicates major structural differences between glasses obtained by cooling and glasses obtained by compression. These structural differences are only weakly reflected in the pair correlation function. We also characterize the evolution of structural order upon isobaric annealing, leading at high pressure to very-high density amorphous ice (VHDA). PMID:16089741

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

    NASA Astrophysics Data System (ADS)

    Kotteswaran, S.; Pandian, M. Senthil; Ramasamy, P.

    2016-05-01

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

  7. Nonplanarity and the protonation behavior of porphyrins

    SciTech Connect

    SOMMA,MARIA S.; MEDFORTH,CRAIG J.; TH,KEVIN M.; SHELNUTT,JOHN A.

    2000-03-21

    {sup 1}H NMR studies of the protonation of highly nonplanar porphyrins with strong acids reveal the presence of the previously elusive monocation, and show that its stability can be related to the amount of saddle distortion induced by protonation; the amount of saddle distortion for a porphyrin dication is also found to correlate well with the rate of intermolecular proton transfer.

  8. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, Jr., Paul E.; Langdale, Wayne A.

    1997-01-01

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  9. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, P.E. Jr.; Langdale, W.A.

    1997-08-19

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  10. Ending Aging in Super Glassy Polymer Membranes

    SciTech Connect

    Lau, CH; Nguyen, PT; Hill, MR; Thornton, AW; Konstas, K; Doherty, CM; Mulder, RJ; Bourgeois, L; Liu, ACY; Sprouster, DJ; Sullivan, JP; Bastow, TJ; Hill, AJ; Gin, DL; Noble, RD

    2014-04-16

    Aging in super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP), poly(4-methyl-2-pentyne) (PMP), and polymers with intrinsic microporosity (PIM-1) reduces gas permeabilities and limits their application as gas-separation membranes. While super glassy polymers are initially very porous, and ultra-permeable, they quickly pack into a denser phase becoming less porous and permeable. This age-old problem has been solved by adding an ultraporous additive that maintains the low density, porous, initial stage of super glassy polymers through absorbing a portion of the polymer chains within its pores thereby holding the chains in their open position. This result is the first time that aging in super glassy polymers is inhibited whilst maintaining enhanced CO2 permeability for one year and improving CO2/N-2 selectivity. This approach could allow super glassy polymers to be revisited for commercial application in gas separations.

  11. Porphyrins as Second Order Nonlinear Optical Materials

    NASA Astrophysics Data System (ADS)

    Chou, Homer

    Because of the unusually high thermal and chemical stability of porphyrins as well as their very large pi-conjugated systems, three classes of high beta-value push-pull porphyrins were synthesized and subsequently successfully engineered into Langmuir-Blodgett (LB) films for a systematic evaluation of porphyrins as chi^{(2)} materials. Class I explored the effects of the number of donor-acceptor groups on the porphyrin periphery (i.e., H_2(an_3P), H_2 (cis-a_2n_2P), H_2(a_3nP), H _2(a_4P) where a = 4-(N-octadecylamido)phenyl or 4-(N-octadecyl-amino)phenyl; n = 4-nitrophenyl; P = 5,10,15,20 substituted tetraarylporphyrinate (2-).). Class II examined the effect of varying the strength of cis-substituted donor-acceptor pairs on the porphyrin periphery (i.e., H_2(cis-a_2n _2P), H_2(cis-c _2p_2P), and H_2 (cis-h_2py_2P) where c = 4-(2-cholesteryloxy)-ethoxyphenyl; h = 4-hydroxyphenyl or 4-methoxyphenyl; and py = 4-pyridyl or 4-(N-octadecyl) pyridiniumyl). Class III looked at the respone of a heterosubstituted bis- push-pull cerium sandwich porphyrin complex, (Ce ^{IV}(TPyP)(TMeP)) ^{4+}I_4 (where Py = 4-(N-octadecyl)pyridiniumyl and Me = 4-methoxyphenyl). Characterization of the porphyrin LB films reveals rather surprising behavior. The isotherm data show that the mean molecular area of the porphyrins increase smoothly from 80-200A as the number of aliphatic chains increase around the porphyrin periphery from one to four. In addition, based on UV-visible linear dichroism, all of the porphyrin films possess C _{infty v} symmetry and adopt a tilt angle, theta, of about 33^circ with respect to the fused quartz substrate. The proposed fixed orientation model suggests that the interporphyrin pi -pi interactions dominate the porphyrin orientation while the number of aliphatic chains around the porphyrin periphery determines the porphyrin's packing density in the LB film. After these monolayers were transferred to fused quartz substrates, the chi^{(2)} response of these

  12. Syntheses and Functionalizations of Porphyrin Macrocycles

    PubMed Central

    Vicente, Maria da G.H.; Smith, Kevin M.

    2014-01-01

    Porphyrin macrocycles have been the subject of intense study in the last century because they are widely distributed in nature, usually as metal complexes of either iron or magnesium. As such, they serve as the prosthetic groups in a wide variety of primary metabolites, such as hemoglobins, myoglobins, cytochromes, catalases, peroxidases, chlorophylls, and bacteriochlorophylls; these compounds have multiple applications in materials science, biology and medicine. This article describes current methodology for preparation of simple, symmetrical model porphyrins, as well as more complex protocols for preparation of unsymmetrically substituted porphyrin macrocycles similar to those found in nature. The basic chemical reactivity of porphyrins and metalloporphyrin is also described, including electrophilic and nucleophilic reactions, oxidations, reductions, and metal-mediated cross-coupling reactions. Using the synthetic approaches and reactivity profiles presented, eventually almost any substituted porphyrin system can be prepared for applications in a variety of areas, including in catalysis, electron transport, model biological systems and therapeutics. PMID:25484638

  13. Cooperative strings and glassy interfaces.

    PubMed

    Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari; Raphaël, Elie; Forrest, James A

    2015-07-01

    We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam-Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel-Fulcher-Tammann relation is derived. Moreover, the random and string-like characters of the cooperative rearrangement allow us to predict a temperature-dependent expression for the cooperative length ξ of bulk relaxation. Finally, we explore the influence of sample boundaries when the system size becomes comparable to ξ. The theory is in agreement with measurements of the glass-transition temperature of thin polymer films, and allows quantification of the temperature-dependent thickness hm of the interfacial mobile layer. PMID:26100908

  14. Cooperative strings and glassy interfaces.

    PubMed

    Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari; Raphaël, Elie; Forrest, James A

    2015-07-01

    We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam-Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel-Fulcher-Tammann relation is derived. Moreover, the random and string-like characters of the cooperative rearrangement allow us to predict a temperature-dependent expression for the cooperative length ξ of bulk relaxation. Finally, we explore the influence of sample boundaries when the system size becomes comparable to ξ. The theory is in agreement with measurements of the glass-transition temperature of thin polymer films, and allows quantification of the temperature-dependent thickness hm of the interfacial mobile layer.

  15. Porphyrin-Based Photocatalytic Lithography

    SciTech Connect

    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

    PubMed Central

    Bearinger, Jane P.; Stone, Gary; Dugan, Lawrence C.; El Dasher, Bassem; Stockton, Cheryl; Conway, James W.; Kuenzler, Tobias; Hubbell, Jeffrey A.

    2009-01-01

    Nanoarray fabrication is a multidisciplinary endeavor encompassing materials science, chemical engineering, and biology. We formed nanoarrays via a new technique, porphyrin-based photocatalytic nanolithography. The nanoarrays, with controlled features as small as 200 nm, exhibited regularly ordered patterns and may be appropriate for (a) rapid and parallel proteomics screening of immobilized biomolecules, (b) protein-protein interactions, and/or (c) biophysical and molecular biology studies involving spatially dictated ligand placement. We demonstrated protein immobilization utilizing nanoarrays fabricated via photocatalytic nanolithography on silicon substrates where the immobilized proteins are surrounded by a non-fouling polymer background. PMID:19406753

  17. Porphyrin-based Photocatalytic Nanolithography

    SciTech Connect

    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.

  18. Smaragdyrins: emeralds of expanded porphyrin family.

    PubMed

    Pareek, Yogita; Ravikanth, M; Chandrashekar, T K

    2012-10-16

    Porphyrins are tetrapyrrolic 18 π electron conjugated macrocycles with wide applications that range from materials to medicine. Expanded porphyrins, synthetic analogues of porphyrins that contain more than 18 π electrons in the conjugated pathway, have an increased number of pyrroles or other heterocyles or multiple meso-carbon bridges. The expanded porphyrins have attracted tremendous attention because of unique features such as anion binding or transport that are not present in porphyrins. Expanded porphyrins exhibit wide applications that include their use in the coordination of large metal ions, as contrasting agents in magnetic resonance imaging (MRI), as sensitizers for photodynamic therapy (PDT) and as materials for nonlinear optical (NLO) studies. Pentaphyrin 1, sapphyrin 2, and smaragdyrin 3 are expanded porphyrins that include five pyrroles or heterocyclic rings. They differ from each other in the number of bridging carbons and direct bonds that connect the five heterocyclic rings. Sapphyrins were the first stable expanded porphyrins reported in the literature and remain one of the most extensively studied macrocycles. The strategies used to synthesize sapphyrins are well established, and these macrocycles are versatile anion binding agents. They possess rich porphyrin-like coordination chemistry and have been used in diverse applications. This Account reviews developments in smaragdyrin chemistry. Although smaragdyrins were discovered at the same time as sapphyrins, the chemistry of smaragdyrins remained underdeveloped because of synthetic difficulties and their comparative instability. Earlier efforts resulted in the isolation of stable β-substituted smaragdyrins and meso-aryl isosmaragdyrins. Recently, researchers have synthesized stable meso-aryl smaragdyrins by [3 + 2] oxidative coupling reactions. These results have stimulated renewed research interest in the exploration of these compounds for anion and cation binding, energy transfer

  19. Smaragdyrins: emeralds of expanded porphyrin family.

    PubMed

    Pareek, Yogita; Ravikanth, M; Chandrashekar, T K

    2012-10-16

    Porphyrins are tetrapyrrolic 18 π electron conjugated macrocycles with wide applications that range from materials to medicine. Expanded porphyrins, synthetic analogues of porphyrins that contain more than 18 π electrons in the conjugated pathway, have an increased number of pyrroles or other heterocyles or multiple meso-carbon bridges. The expanded porphyrins have attracted tremendous attention because of unique features such as anion binding or transport that are not present in porphyrins. Expanded porphyrins exhibit wide applications that include their use in the coordination of large metal ions, as contrasting agents in magnetic resonance imaging (MRI), as sensitizers for photodynamic therapy (PDT) and as materials for nonlinear optical (NLO) studies. Pentaphyrin 1, sapphyrin 2, and smaragdyrin 3 are expanded porphyrins that include five pyrroles or heterocyclic rings. They differ from each other in the number of bridging carbons and direct bonds that connect the five heterocyclic rings. Sapphyrins were the first stable expanded porphyrins reported in the literature and remain one of the most extensively studied macrocycles. The strategies used to synthesize sapphyrins are well established, and these macrocycles are versatile anion binding agents. They possess rich porphyrin-like coordination chemistry and have been used in diverse applications. This Account reviews developments in smaragdyrin chemistry. Although smaragdyrins were discovered at the same time as sapphyrins, the chemistry of smaragdyrins remained underdeveloped because of synthetic difficulties and their comparative instability. Earlier efforts resulted in the isolation of stable β-substituted smaragdyrins and meso-aryl isosmaragdyrins. Recently, researchers have synthesized stable meso-aryl smaragdyrins by [3 + 2] oxidative coupling reactions. These results have stimulated renewed research interest in the exploration of these compounds for anion and cation binding, energy transfer

  20. Nickel porphyrins for memory optical applications

    DOEpatents

    Shelnutt, John A.; Jia, Songling; Medforth, Craig; Holten, Dewey; Nelson, Nora Y.; Smith, Kevin M.

    2000-01-01

    The present invention relates to a nickel-porphyrin derivative in a matrix, the nickel-porphyrin derivative comprising at least two conformational isomers, a lower-energy-state conformer and a higher-energy-state conformer, such that when the higher-energy-state conformer is generated from the lower-energy-state conformer following absorption of a photon of suitable energy, the time to return to the lower-energy-state conformer is greater than 40 nanoseconds at approximately room temperature. The nickel-porphyrin derivative is useful in optical memory applications.

  1. Porphyrinic Molecular Devices: Towards Nanoscaled Processes

    PubMed Central

    Latter, Melissa J.; Langford, Steven J.

    2010-01-01

    The structural, coordinative, photochemical and electrochemical properties of the porphyrin macrocycle that make them the functional element of choice in ubiquitous biological systems, e.g., chlorophyll, cytochrome P450 and hemoglobin, also contribute to making porphyrins and metalloporphyrins desirable in a “bottom-up” approach to the construction of nanosized devices. This paper highlights some recent advances in the construction of supramolecular assemblies based on the porphyrin macrocycle that display optically readable functions as a result of photonic or chemical stimuli. PMID:20480048

  2. Molecular mobility in glassy dispersions.

    PubMed

    Mehta, Mehak; McKenna, Gregory B; Suryanarayanan, Raj

    2016-05-28

    Dielectric spectroscopy was used to characterize the structural relaxation in pharmaceutical dispersions containing nifedipine (NIF) and either poly(vinyl) pyrrolidone (PVP) or hydroxypropyl methylcellulose acetate succinate (HPMCAS). The shape of the dielectric response (permittivity versus log time) curve was observed to be independent of temperature. Thus, for the pure NIF as well as the dispersions, the validity of the time-temperature superposition principle was established. Furthermore, though the shape of the full dielectric response varied with polymer concentration, the regime related to the α- or structural relaxation was found to superimpose for the dispersions, though not with the response of the NIF itself. Hence, there is a limited time-temperature-concentration superposition for these systems as well. Therefore, in this polymer concentration range, calculation of long relaxation times in these glass-forming systems becomes possible. We found that strong drug-polymer hydrogen bonding interactions improved the physical stability (i.e., delayed crystallization) by reducing the molecular mobility. The strength of hydrogen bonding, structural relaxation time, and crystallization followed the order: NIF-PV P>NIF-HPMCAS>NIF. With an increase in polymer concentration, the relaxation times were longer indicating a decrease in molecular mobility. The temperature dependence of relaxation time, in other words fragility, was independent of polymer concentration. This is the first application of the superposition principle to characterize structural relaxation in glassy pharmaceutical dispersions.

  3. Molecular mobility in glassy dispersions

    NASA Astrophysics Data System (ADS)

    Mehta, Mehak; McKenna, Gregory B.; Suryanarayanan, Raj

    2016-05-01

    Dielectric spectroscopy was used to characterize the structural relaxation in pharmaceutical dispersions containing nifedipine (NIF) and either poly(vinyl) pyrrolidone (PVP) or hydroxypropyl methylcellulose acetate succinate (HPMCAS). The shape of the dielectric response (permittivity versus log time) curve was observed to be independent of temperature. Thus, for the pure NIF as well as the dispersions, the validity of the time-temperature superposition principle was established. Furthermore, though the shape of the full dielectric response varied with polymer concentration, the regime related to the α- or structural relaxation was found to superimpose for the dispersions, though not with the response of the NIF itself. Hence, there is a limited time-temperature-concentration superposition for these systems as well. Therefore, in this polymer concentration range, calculation of long relaxation times in these glass-forming systems becomes possible. We found that strong drug-polymer hydrogen bonding interactions improved the physical stability (i.e., delayed crystallization) by reducing the molecular mobility. The strength of hydrogen bonding, structural relaxation time, and crystallization followed the order: NIF-PV P>NIF-HPMCAS>NIF. With an increase in polymer concentration, the relaxation times were longer indicating a decrease in molecular mobility. The temperature dependence of relaxation time, in other words fragility, was independent of polymer concentration. This is the first application of the superposition principle to characterize structural relaxation in glassy pharmaceutical dispersions.

  4. Porphyrin-loaded nanoparticles for cancer theranostics

    NASA Astrophysics Data System (ADS)

    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.

  5. Porphyrin content of the cysticercus of Taenia solium.

    PubMed

    Larralde, C; Zedillo, G M; Lagunoff, D; Ludowyke, R; Montoya, R M; Goodsaid, F; Dreyfus, G; Sciutto, E; Govezensky, T; Diaz, M L

    1986-08-01

    The strong red fluorescence of the cysticercus of Taenia solium depends on the presence of several porphyrins in the vesicular fluid of the parasite: probably protoporphyrin IX, coproporphyin I or III, and 2 decarboxylated porphyrins intermediate between uroporphyrin and coproporphyrin. Cyst porphyrins associated to form conglomerates of high molecular weight that dissociated in acid solutions and were not antigenic themselves nor associated with antigenic molecules. An appreciable fraction of the porphyrins was capable of undergoing oxidation and reduction, indicating that some of the porphyrins were complexed with metal ions. The metabolic basis for the accumulation of porphyrins is unknown. Preliminary results suggest that conditions deleterious to the cysticercus cause release of porphyrins so that the appearance of porphyrins in the cerebrospinal fluid of neurocysticercotic patients may prove useful in monitoring therapeutic attacks on the parasite.

  6. Electrocatalytic Transformation of Carbon Dioxide into Low Carbon Compounds on Conducting Polymers Derived from Multimetallic Porphyrins.

    PubMed

    Dreyse, Paulina; Honores, Jessica; Quezada, Diego; Isaacs, Mauricio

    2015-11-01

    The electrochemical reduction of carbon dioxide is studied herein by using conducting polymers based on metallotetraruthenated porphyrins (MTRPs). The polymers on glassy carbon electrodes were obtained by electropolymerization processes of the monomeric MTRP. The linear sweep voltammetry technique resulted in polymeric films that showed electrocatalytic activity toward carbon dioxide reduction with an onset potential of -0.70 V. The reduction products obtained were hydrogen, formic acid, formaldehyde, and methanol, with a tendency for a high production of methanol with a maximum value of turnover frequency equal to 15.07 when using a zinc(II) polymeric surface. Studies of the morphology (AFM) and electrochemical impedance spectroscopy results provide an adequate background to explain that the electrochemical reduction is governed by the roughness of the polymer, for which the possible mechanism involves a series of one-electron reduction reactions.

  7. A light-harvesting array of synthetic porphyrins

    NASA Astrophysics Data System (ADS)

    Davila, Jorge; Harriman, Anthony; Milgrom, Lionel R.

    1987-05-01

    An array of five porphyrin molecules has been synthesized and used as a simple model of the light-harvesting complex found in natural photosynthesis. Efficient Förster energy transfer occurs from antenna zinc porphyrins to a central free-base porphyrin molecule. This central porphyrin retains long-lived singlet and triplet excited states that can be quenched by diffusional processes, Both electron and energy transfer quenching reactions can be observed.

  8. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, James E.; Ellis, Jr., Paul E.; Wagner, Richard W.

    1996-01-01

    Transition metal complexes of Gable porphyrins having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  9. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, J.E.; Ellis, P.E. Jr.; Wagner, R.W.

    1996-01-02

    Transition metal complexes of Gable porphyrins are disclosed having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  10. Bilirubin, copper-porphyrins, and the bronze-baby syndrome.

    PubMed

    McDonagh, Antony F

    2011-01-01

    Controlled in vitro spectroscopic measurements reveal that bilirubin does not photosensitize the degradation of copper-porphyrins, as has been proposed for the mechanism of the bronze-baby syndrome, an uncommon side-effect of phototherapy. Calculations also show that copper-porphyrins are unlikely to cause the "bronzing." In conclusion, the copper-porphyrin hypothesis is photochemically implausible.

  11. On the Marginal Stability of Glassy Systems

    NASA Astrophysics Data System (ADS)

    Yan, Le; Baity-Jesi, Marco; Müller, Markus; Wyart, Matthieu

    2015-03-01

    In various glassy systems that are out of equilibrium, like spin glasses and granular packings, the dynamics appears to be critical: avalanches involving almost the whole system could happen. A recent conceptual breakthrough argues that such glassy systems sample the ensemble of marginal stable states, which inevitably results into critical dynamics. However, it is unclear how the marginal stability is dynamically guaranteed. We investigate this marginal stability assumption by studying specifically the critical athermal dynamics of the Sherrington-Kirkpatrick model. We discuss how a pseudo-gap in the density distribution of local fields characterizing the marginal stability arises dynamically.

  12. Active cage model of glassy dynamics.

    PubMed

    Fodor, Étienne; Hayakawa, Hisao; Visco, Paolo; van Wijland, Frédéric

    2016-07-01

    We build up a phenomenological picture in terms of the effective dynamics of a tracer confined in a cage experiencing random hops to capture some characteristics of glassy systems. This minimal description exhibits scale invariance properties for the small-displacement distribution that echo experimental observations. We predict the existence of exponential tails as a crossover between two Gaussian regimes. Moreover, we demonstrate that the onset of glassy behavior is controlled only by two dimensionless numbers: the number of hops occurring during the relaxation of the particle within a local cage and the ratio of the hopping length to the cage size. PMID:27575182

  13. Active cage model of glassy dynamics

    NASA Astrophysics Data System (ADS)

    Fodor, Étienne; Hayakawa, Hisao; Visco, Paolo; van Wijland, Frédéric

    2016-07-01

    We build up a phenomenological picture in terms of the effective dynamics of a tracer confined in a cage experiencing random hops to capture some characteristics of glassy systems. This minimal description exhibits scale invariance properties for the small-displacement distribution that echo experimental observations. We predict the existence of exponential tails as a crossover between two Gaussian regimes. Moreover, we demonstrate that the onset of glassy behavior is controlled only by two dimensionless numbers: the number of hops occurring during the relaxation of the particle within a local cage and the ratio of the hopping length to the cage size.

  14. Blood porphyrin luminescence and tumor growth correlation

    NASA Astrophysics Data System (ADS)

    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.

  15. Optically Active Porphyrin and Phthalocyanine Systems.

    PubMed

    Lu, Hua; Kobayashi, Nagao

    2016-05-25

    This review highlights and summarizes various optically active porphyrin and phthalocyanine molecules prepared using a wide range of structural modification methods to improve the design of novel structures and their applications. The induced chirality of some illustrative achiral bis-porphyrins with a chiral guest molecule is introduced because these systems are ideal for the identification and separation of chiral biologically active substrates. In addition, the relationship between CD signal and the absolute configuration of the molecule is analyzed through an analysis of the results of molecular modeling calculations. Possible future research directions are also discussed. PMID:27186902

  16. Deformation and Fracture Behavior of Metallic Glassy Alloys and Glassy-Crystal Composites

    NASA Astrophysics Data System (ADS)

    Louzguine-Luzgin, D. V.; Vinogradov, A.; Li, S.; Kawashima, A.; Xie, G.; Yavari, A. R.; Inoue, A.

    2011-06-01

    The present work demonstrates the deformation behavior of Zr-Cu-Ni-Al bulk glassy alloys and Zr-Ni-Cu-Al-Pd glassy foils as well as Ni-Cu-Ti-Zr bulk crystal-glassy composites. Fracture of Zr60Cu16Ni14Al10 and Zr64.13Ni10.12Cu15.75Al10 bulk glassy alloys is featured by nearly equal fraction areas of cleavage-like and vein-type relief. The observed pattern of alternating cleavage-like and vein-type patterns illustrates a result of dynamically self-organizing shear propagation at the final catastrophic stage. The deformation behavior of Zr64.13Ni10.12Cu15.75Al10 alloy has also been tested at LN2 temperature. The strength of the sample decreases with temperature, and no clear serrated flow typical for bulk glassy samples tested at room temperature is observed in the case of the samples tested at LN2 temperature. We also studied the deformation behavior of Zr-Ni-Cu-Al-Pd glassy foils thinned to electron transparency in situ in tension in a transmission electron microscope. We also present a Ni-Cu-Ti-Zr crystal-glassy composite material having a superior strength paired with a considerable ductility exceeding 10 pct. The metastable cP2 crystalline phase promotes a strain-induced martensitic transformation leading to pseudoelastic behavior as well as enhanced plasticity at room temperature. Underlying mechanisms of plastic deformation are discussed in terms of the interplay between the dislocation slip in the crystalline phase and the shear deformation in the glassy matrix.

  17. Surface morphology and optical properties of porphyrin/Au and Au/porphyrin/Au systems

    PubMed Central

    2013-01-01

    Porphyrin/Au and Au/porphyrin/Au systems were prepared by vacuum evaporation and vacuum sputtering onto glass substrate. The surface morphology of as-prepared systems and those subjected to annealing at 160°C was studied by optical microscopy, atomic force microscopy, and scanning electron microscopy techniques. Absorption and luminescence spectra of as-prepared and annealed samples were measured. Annealing leads to disintegration of the initially continuous gold layer and formation of gold nanoclusters. An amplification of Soret band magnitude was observed on the Au/meso-tetraphenyl porphyrin (TPP) system in comparison with mere TPP. Additional enhancement of luminescence was observed after the sample annealing. In the case of sandwich Au/porphyrin/Au structure, suppression of one of the two porphyrins’ luminescence maxima and sufficient enhancement of the second one were observed. PMID:24373347

  18. Supramolecular fullerene-porphyrin chemistry. Fullerene complexation by metalated "jaws porphyrin" hosts.

    PubMed

    Sun, Dayong; Tham, Fook S; Reed, Christopher A; Chaker, Leila; Boyd, Peter D W

    2002-06-12

    Porphyrins and fullerenes are spontaneously attracted to each other. This new supramolecular recognition element is explored in discrete, soluble, coordinatively linked porphyrin and metalloporphyrin dimers. Jawlike clefts in these bis-porphyrins are effective hosts for fullerene guests. X-ray structures of the Cu complex with C60 and free-base complexes with C70 and a pyrrolidine-derivatized C60 have been obtained. The electron-rich 6:6 ring-juncture bonds of C60 show unusually close approach to the porphyrin or metalloporphyrin plane. Binding constants in toluene solution increase in the order Fe(II) < Pd(II) < Zn(II) < Mn(II) < Co(II) < Cu(II) < 2H and span the range 490-5200 M-1. Unexpectedly, the free-base porphyrin binds C60 more strongly than the metalated porphyrins. This is ascribed to electrostatic forces, enhancing the largely van der Waals forces of the pi-pi interaction. The ordering with metals is ascribed to a subtle interplay of solvation and weak interaction forces. Conflicting opinions on the relative importance of van der Waals forces, charge transfer, electrostatic attraction, and coordinate bonding are addressed. The supramolecular design principles arising from these studies have potential applications in the preparation of photophysical devices, molecular magnets, molecular conductors, and porous metal-organic frameworks. PMID:12047181

  19. Detection of hydrogen peroxide produced during the oxygen reduction reaction at self-assembled thiol-porphyrin monolayers on gold using SECM and nanoelectrodes.

    PubMed

    Mezour, Mohamed A; Cornut, Renaud; Hussien, Emad Mohamed; Morin, Mario; Mauzeroll, Janine

    2010-08-01

    Porphyrin molecules were immobilized on polycrystalline gold and glassy carbon by coordinating cobalt(II) 5,10,15,20-tetraphenyl-21H,23H-porphine to a 4-aminothiophenol self-assembled monolayer. The resulting electrocatalytic activity of the metalloporphyrin-modified substrates with regard to the oxygen reduction reaction was characterized by means of cyclic voltammetry and scanning electrochemical microscopy (SECM) using nanoelectrodes of well-defined geometry. From substrate generation tip collection (SG-TC) mode SECM measurements performed under steady-state conditions and at different applied substrate potentials, it is possible to extract kinetic information relevant to electrocatalyst substrates such as metalloporphyrin-modified gold and glassy-carbon electrodes. Such an approach allows for the isolation of the unique contribution of the electrocatalyst to the oxygen reduction reaction and peroxide formation.

  20. A p-quinodimethane-bridged porphyrin dimer.

    PubMed

    Zeng, Wangdong; Ishida, Masatoshi; Lee, Sangsu; Sung, Young Mo; Zeng, Zebing; Ni, Yong; Chi, Chunyan; Kim, Dongho; Wu, Jishan

    2013-12-01

    A p-quinodimethane (p-QDM)-bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross-conjugated keto-linked porphyrin dimers 8a and 8b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel-Crafts alkylation of the diol-linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one-photon absorption (OPA, λ(max)=955 nm, ε=45400 M(-1) cm(-1)) and a large two-photon absorption (TPA) cross-section (σ((2))(max)=2080 GM at 1800 nm) in the near-infrared (NIR) region due to its extended π-conjugation and quinoidal character. It also exhibits a short singlet excited-state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground-state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto-linked dimer 8b. This research has revealed that incorporation of a p-QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore.

  1. Metallic nanoshells on porphyrin-stabilized emulsions

    DOEpatents

    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.

  2. Porphyrins for boron neutron capture therapy

    DOEpatents

    Miura, Michiko; Gabel, Detlef

    1990-01-01

    Novel compounds for treatment of brain tumors in Boron Neutron Capture Therapy are disclosed. A method for preparing the compounds as well as pharmaceutical compositions containing said compounds are also disclosed. The compounds are water soluble, non-toxic and non-labile boronated porphyrins which show significant uptake and retention in tumors.

  3. Mass spectrometric studies on porphyrins and geoporphyrins

    SciTech Connect

    Quirke, J.; Martin, E.; Yost, R.A.

    1995-12-31

    Porphyrins are among the more important compound classes, playing significant roles in such diverse areas as medicine, material sciences, catalysis and the petroleum industry. The most valuable property of the porphyrin macrocycle is its ability to chelate with any metallic element. In organic geochemistry, geologically-occurring porphyrins, geoporphyrins, are of both academic and commercial consequence. Geoporphyrins occur as complicated mixtures of nickel(II) and vanadyl(II) [VO(II)] complexes in a wide range of sedimentary environments. They are believed to be formed by transformation of the functional groups of biologically-occurring cyclic tetrapyrroles, especially chlorophyll a into alkyl or hydrogen substituents coupled with the oxidation of the chlorin (dihydroporphyin) to the porphyrinic system. This proposal, the Treibs` hypothesis, is the cornerstone of molecular organic geochemistry. The precise composition of geoporphyrin mixtures varies from crude oil to crude oil. For this reason, analysis of geoporphyrin mixtures is a valuable tool for the correlation of crude oils with other oils and/or source rocks. Less happily, the geoporphyrins, especially the vanadyl complexes, poison catalysts in cracking of crude oil and industrial processes. Mass spectrometry is perhaps the most valuable too for analysis of geoporphyrin mixtures. Such analyses present the mass spectrometrist with several challenging problems. Geoporphyrin mixtures are composed of overlapping pseudohomologous series least nine skeletal types. Carbon number ranges of C{sub 28}-C{sub 50} are not uncommon. The upper limit of the carbon number range is still unclear.

  4. Plastic flow modeling in glassy polymers

    SciTech Connect

    Clements, Brad

    2010-12-13

    Glassy amorphous and semi-crystalline polymers exhibit strong rate, temperature, and pressure dependent polymeric yield. As a rule of thumb, in uniaxial compression experiments the yield stress increases with the loading rate and applied pressure, and decreases as the temperature increases. Moreover, by varying the loading state itself complex yield behavior can be observed. One example that illustrates this complexity is that most polymers in their glassy regimes (i.e., when the temperature is below their characteristic glass transition temperature) exhibit very pronounced yield in their uniaxial stress stress-strain response but very nebulous yield in their uniaxial strain response. In uniaxial compression, a prototypical glassy-polymer stress-strain curve has a stress plateau, often followed by softening, and upon further straining, a hardening response. Uniaxial compression experiments of this type are typically done from rates of 10{sup -5} s{sup -1} up to about 1 s{sup -1}. At still higher rates, say at several thousands per second as determined from Split Hopkinson Pressure Bar experiments, the yield can again be measured and is consistent with the above rule of thumb. One might expect that that these two sets of experiments should allow for a successful extrapolation to yet higher rates. A standard means to probe high rates (on the order of 105-107 S-I) is to use a uniaxial strain plate impact experiment. It is well known that in plate impact experiments on metals that the yield stress is manifested in a well-defined Hugoniot Elastic Limit (HEL). In contrast however, when plate impact experiments are done on glassy polymers, the HEL is arguably not observed, let alone observed at the stress estimated by extrapolating from the lower strain rate experiments. One might argue that polymer yield is still active but somehow masked by the experiment. After reviewing relevant experiments, we attempt to address this issue. We begin by first presenting our recently

  5. Photoluminescence of silver in glassy matrices

    SciTech Connect

    Garcia, M.A.; Garcia-Heras, M.; Cano, E.; Bastidas, J.M.; Villegas, M.A.; Montero, E.; Llopis, J.; Sada, C.; Marchi, G. de; Battaglin, G.; Mazzoldi, P.

    2004-10-01

    This work studies the behavior of Ag{sup +} ions incorporated in different silica-based glassy matrices. To this end, Ag-doped silica coatings, prepared via sol-gel and deposited on pure silica and soda-lime glasses, are investigated by means of structural and optical spectroscopy techniques. Silver tends to segregate towards the interface during the annealing process, but in the case of soda-lime glassy substrates the exchange process favors its diffusion into the substrate. The environment of Ag{sup +} ions during the annealing process determines their final oxidation state. In the pure silica matrix, Ag{sup +} ions are found to be unstable and tend to reduce to Ag{sup 0}, with the subsequent formation of metallic nanoparticles. However, the presence of network formers and modifiers gives rise to the appearance of nonbridging oxygen, which allows the stabilization of Ag{sup +} ions in the matrix.

  6. Wafer-level microstructuring of glassy carbon

    NASA Astrophysics Data System (ADS)

    Hans, Loïc. E.; Prater, Karin; Kilchoer, Cédric; Scharf, Toralf; Herzig, Hans Peter; Hermerschmidt, Andreas

    2014-03-01

    Glassy carbon is used nowadays for a variety of applications because of its mechanical strength, thermal stability and non-sticking adhesion properties. One application is glass molding that allows to realize high resolution diffractive optical elements on large areas and at affordable price appropriate for mass production. We study glassy carbon microstructuring for future precision compression molding of low and high glass-transition temperature. For applications in optics the uniformity, surface roughness, edge definition and lateral resolution are very important parameters for a stamp and the final product. We study different methods of microstructuring of glassy carbon by etching and milling. Reactive ion etching with different protection layers such as photoresists, aluminium and titanium hard masks have been performed and will be compare with Ion beam etching. We comment on the quality of the structure definition and give process details as well as drawbacks for the different methods. In our fabrications we were able to realize optically flat diffractive structures with slope angles of 80° at typical feature sizes of 5 micron and 700 nm depth qualified for high precision glass molding.

  7. A porphyrin-PEG polymer with rapid renal clearance.

    PubMed

    Huang, Haoyuan; Hernandez, Reinier; Geng, Jumin; Sun, Haotian; Song, Wentao; Chen, Feng; Graves, Stephen A; Nickles, Robert J; Cheng, Chong; Cai, Weibo; Lovell, Jonathan F

    2016-01-01

    Tetracarboxylic porphyrins and polyethylene glycol (PEG) diamines were crosslinked in conditions that gave rise to a water-soluble porphyrin polyamide. Using PEG linkers 2 kDa or larger prevented fluorescence self-quenching. This networked porphyrin mesh was retained during dialysis with membranes with a 100 kDa pore size, yet passed through the membrane when centrifugal filtration was applied. Following intravenous administration, the porphyrin mesh, but not the free porphyrin, was rapidly cleared via renal excretion. The process could be monitored by fluorescence analysis of collected urine, with minimal background due to the large Stokes shift of the porphyrin (230 nm separating excitation and emission peaks). In a rhabdomyolysis mouse model of renal failure, porphyrin mesh urinary clearance was significantly impaired. This led to slower accumulation in the bladder, which could be visualized non-invasively via fluorescence imaging. Without further modification, the porphyrin mesh was chelated with (64)Cu for dynamic whole body positron emission tomography imaging of renal clearance. Together, these data show that small porphyrin-PEG polymers can serve as effective multimodal markers of renal function. PMID:26517562

  8. Water-splitting using photocatalytic porphyrin-nanotube composite devices

    DOEpatents

    Shelnutt, John A.; Miller, James E.; Wang, Zhongchun; Medforth, Craig J.

    2008-03-04

    A method for generating hydrogen by photocatalytic decomposition of water using porphyrin nanotube composites. In some embodiments, both hydrogen and oxygen are generated by photocatalytic decomposition of water.

  9. A porphyrin-PEG polymer with rapid renal clearance.

    PubMed

    Huang, Haoyuan; Hernandez, Reinier; Geng, Jumin; Sun, Haotian; Song, Wentao; Chen, Feng; Graves, Stephen A; Nickles, Robert J; Cheng, Chong; Cai, Weibo; Lovell, Jonathan F

    2016-01-01

    Tetracarboxylic porphyrins and polyethylene glycol (PEG) diamines were crosslinked in conditions that gave rise to a water-soluble porphyrin polyamide. Using PEG linkers 2 kDa or larger prevented fluorescence self-quenching. This networked porphyrin mesh was retained during dialysis with membranes with a 100 kDa pore size, yet passed through the membrane when centrifugal filtration was applied. Following intravenous administration, the porphyrin mesh, but not the free porphyrin, was rapidly cleared via renal excretion. The process could be monitored by fluorescence analysis of collected urine, with minimal background due to the large Stokes shift of the porphyrin (230 nm separating excitation and emission peaks). In a rhabdomyolysis mouse model of renal failure, porphyrin mesh urinary clearance was significantly impaired. This led to slower accumulation in the bladder, which could be visualized non-invasively via fluorescence imaging. Without further modification, the porphyrin mesh was chelated with (64)Cu for dynamic whole body positron emission tomography imaging of renal clearance. Together, these data show that small porphyrin-PEG polymers can serve as effective multimodal markers of renal function.

  10. Porphyrin and heme metabolism and the porphyrias.

    PubMed

    Bonkovsky, Herbert L; Guo, Jun-Tao; Hou, Weihong; Li, Ting; Narang, Tarun; Thapar, Manish

    2013-01-01

    Porphyrins and metalloporphyrins are the key pigments of life on earth as we know it, because they include chlorophyll (a magnesium-containing metalloporphyrin) and heme (iron protoporphyrin). In eukaryotes, porphyrins and heme are synthesized by a multistep pathway that involves eight enzymes. The first and rate-controlling step is the formation of delta-aminolevulinic acid (ALA) from glycine plus succinyl CoA, catalyzed by ALA synthase. Intermediate steps occur in the cytoplasm, with formation of the monopyrrole porphobilinogen and the tetrapyrroles hydroxymethylbilane and a series of porphyrinogens, which are serially decarboxylated. Heme is utilized chiefly for the formation of hemoglobin in erythrocytes, myoglobin in muscle cells, cytochromes P-450 and mitochondrial cytochromes, and other hemoproteins in hepatocytes. The rate-controlling step of heme breakdown is catalyzed by heme oxygenase (HMOX), of which there are two isoforms, called HMOX1 and HMOX2. HMOX breaks down heme to form biliverdin, carbon monoxide, and iron. The porphyrias are a group of disorders, mainly inherited, in which there are defects in normal porphyrin and heme synthesis. The cardinal clinical features are cutaneous (due to the skin-damaging effects of excess deposited porphyrins) or neurovisceral attacks of pain, sometimes with weakness, delirium, seizures, and the like (probably due mainly to neurotoxic effects of ALA). The treatment of choice for the acute hepatic porphyrias is intravenous heme therapy, which repletes a critical regulatory heme pool in hepatocytes and leads to downregulation of hepatic ALA synthase, which is a biochemical hallmark of all forms of acute porphyria in relapse.

  11. Past and future: porphyria and porphyrins.

    PubMed

    Norman, Robert A

    2005-01-01

    Porphyria is a compelling disease--disrupted enzyme pathways, heightened sensitivities, and a fascinating history tied in with tales of Dracula. This review discusses the history, pathophysiology, classification, and treatment of porphyria. It further discusses the way in which research on the etiologies of the various porphyrias has led to the development of porphyrin-based photodynamic therapy, which shows great promise in targeted therapy for a variety of serious pathologies.

  12. Lighting porphyrins and phthalocyanines for molecular photovoltaics.

    PubMed

    Martínez-Díaz, M Victoria; de la Torre, Gema; Torres, Tomás

    2010-10-14

    The field of organic photovoltaics (OPV) represents one of the most promising technological areas. Porphyrins and phthalocyanines are perfectly suited for their integration in light energy conversion systems. These colored macrocycles exhibit very attractive physical properties, particularly very high extinction coefficients in the visible and near IR regions, where the maximum of the solar photon flux occurs, that is necessary for efficient photon harvesting, besides a rich redox chemistry, as well as photoinduced electron transfer and semiconducting capabilities.

  13. Glassy aerosols heterogeneously nucleate cirrus ice particles

    NASA Astrophysics Data System (ADS)

    Wilson, Theodore W.; Murray, Benjamin J.; Dobbie, Steven; Cui, Zhiqiang; Al-Jumur, Sardar M. R. K.; Möhler, Ottmar; Schnaiter, Martin; Wagner, Robert; Benz, Stefan; Niemand, Monika; Saathoff, Harald; Ebert, Volker; Wagner, Steven; Kärcher, Bernd

    2010-05-01

    Ice clouds in the tropical tropopause layer (TTL, ~12-18 km, ~180-200 K) play a key role in dehydrating air entering the stratosphere. However, in-situ measurements show that air within these clouds is unexpectedly supersaturated(1); normally the growth of ice crystals rapidly quenches any supersaturation. A number of explanations for high in-cloud humidity have been put forward, but recent research suggests high humidity may be related to the low numbers of ice crystals found within these clouds(1). Low ice number densities can be produced through selective nucleation by a small subset of aerosol particles. This is inconsistent with homogeneous nucleation of ice in liquid aerosols. However, droplets rich in organic material, ubiquitous in the TTL, are known to become glassy (amorphous, non-crystalline solid) under TTL conditions(2,3). Here we show, using a large cloud simulation chamber, that glassy solution droplets nucleate ice heterogeneously at low supersaturations. Using a one-dimensional cirrus model we also show that nucleation by glassy aerosol in the TTL may explain low TTL ice number densities and high in-cloud humidity. Recent measurements of the composition of TTL cirrus residues are consistent with our findings(4). (1) Krämer, M. et al. Ice supersaturations and cirrus cloud crystal numbers. Atm. Chem. Phys. 9, 3505-3522 (2009). (2) Murray, B. J. Inhibition of ice crystallisation in highly viscous aqueous organic acid droplets. Atm. Chem. Phys. 8, 5423-5433 (2008). (3) Zobrist, B., Marcolli, C., Pedernera, D. A. & Koop, T. Do atmospheric aerosols form glasses? Atm. Chem. Phys. 8, 5221-5244 (2008). (4) Froyd, K. D., Murphy, D. M., Lawson, P., Baumgardner, D. & Herman, R. L. Aerosols that form subvisible cirrus at the tropical tropopause. Atmos. Chem. Phys. 10, 209-218 (2010).

  14. Water sorption and diffusion in glassy polymers

    NASA Astrophysics Data System (ADS)

    Davis, Eric Mikel

    Water sorption and diffusion in glassy polymers is important in many fields, including drug delivery, desalination, energy storage and delivery, and packaging. Accurately measuring and understanding the underlying transport mechanisms of water in these glassy polymers is often complex due to both the nonequilibrium state of the polymer and the self-associating nature of water (e.g., hydrogen bonding). In this work, water sorption and diffusion in a number of glassy polymers were measured using gravimetric and spectroscopic techniques, including quartz spring microbalance, quartz crystal microbalance, and in situ time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Non-Fickian diffusion was observed in all polymers studied, indicated by an initial stage of water uptake, followed by a second stage of continuous, gradual uptake of water at later experimental times. These phenomena were attributed to diffusion driven by a concentration gradient, as well as diffusion driven by slow polymer relaxation resulting in additional water ingress over time. In order to gain additional insight into these phenomena, which are a product of nonequilibrium state of the polymers, diffusion-relaxation models were developed and employed to determine the time scales for both diffusion and polymer relaxation, where the ratio of these values (Deborah number) confirmed the observed non-Fickian water diffusion. In addition, the solubility of water in these polymers was predicted using two nonequilibrium thermodynamic models: the nonequilibrium lattice fluid (NELF) model and the nonequilibrium statistical associating fluid theory (NE-SAFT), where excellent agreement between the NE-SAFT predictions and experimental data was obtained over the entire water vapor activity range explored. Furthermore, the states of water were analyzed using the Zimm-Lundberg clustering theory, as well as in situ FTIR-ATR spectroscopy, where the latter technique provides a

  15. Porphyrin-based sensor nanoarchitectonics in diverse physical detection modes.

    PubMed

    Ishihara, Shinsuke; Labuta, Jan; Van Rossom, Wim; Ishikawa, Daisuke; Minami, Kosuke; Hill, Jonathan P; Ariga, Katsuhiko

    2014-06-01

    Porphyrins and related families of molecules are important organic modules as has been reflected in the award of the Nobel Prizes in Chemistry in 1915, 1930, 1961, 1962, 1965, and 1988 for work on porphyrin-related biological functionalities. The porphyrin core can be synthetically modified by introduction of various functional groups and other elements, allowing creation of numerous types of porphyrin derivatives. This feature makes porphyrins extremely useful molecules especially in combination with their other interesting photonic, electronic and magnetic properties, which in turn is reflected in their diverse signal input-output functionalities based on interactions with other molecules and external stimuli. Therefore, porphyrins and related macrocycles play a preeminent role in sensing applications involving chromophores. In this review, we discuss recent developments in porphyrin-based sensing applications in conjunction with the new advanced concept of nanoarchitectonics, which creates functional nanostructures based on a profound understanding of mutual interactions between the individual nanostructures and their arbitrary arrangements. Following a brief explanation of the basics of porphyrin chemistry and physics, recent examples in the corresponding fields are discussed according to a classification based on physical modes of detection including optical detection (absorption/photoluminescence spectroscopy and energy and electron transfer processes), other spectral modes (circular dichroism, plasmon and nuclear magnetic resonance), electronic and electrochemical modes, and other sensing modes.

  16. Effects of polyhalogenated aromatic compounds on porphyrin metabolism.

    PubMed Central

    Hill, R H

    1985-01-01

    Heme production is a vital metabolic process that occurs in the bone marrow and liver. Porphyrins are unused by-products of this biosynthetic process and normally occur in urine and other body fluids in low concentrations. Various disorders can disrupt the heme biosynthetic process, causing greater quantities of porphyrins in urine. The porphyrias are a group of diseases characterized by excessive porphyrins and other precursors in urine. Porphyrias may be either hereditary or acquired through exposure to certain drugs or chemicals. Porphyria cutanea tarda (PCT) is the disease associated with exposure to polyhalogenated aromatic compounds. The urinary porphyrin pattern is of great value in diagnosing PCT and defining the etiology of the disease. As this liver disease from chemical damage develops, the urinary pattern progressively changes. With the development of a rapid and sensitive high-performance liquid chromatography analysis, urinary porphyrin patterns can be easily monitored. All free porphyrin acids can be quantitatively analyzed in less than 15 min. In our studies of groups exposed to porphyrinogenic chemicals, we have not observed clear differences in the urinary porphyrin patterns of cases when compared with carefully selected controls. In animal studies, however, PCT was clearly associated with polybrominated biphenyl exposure. Future evaluation of the utility of urinary porphyrin patterns as a diagnostic tool will require a cohort that has received a recent, well-documented exposure and a comparable control population. Assay of erythrocyte uroporphyrinogen decarboxylase activity will also be needed to define the form of the PCT. PMID:4029097

  17. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1993-05-18

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

  18. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1995-01-17

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

  19. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1995-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  20. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1993-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  1. Zinc porphyrin-fullerene derivative noncovalently functionalized graphene hybrid as interfacial material for electrocatalytic application.

    PubMed

    Fan, Suhua; Yang, Jiao; Wei, Ting; Zhang, Jie; Zhang, Ni; Chai, Mengqing; Jin, Xiaoyan; Wu, Hai

    2016-11-01

    In this paper, a p-methoxy zinc porphyrin-fullerene derivative (ZnPp-C60) noncovalently functionalized electrochemically reduced graphene oxide (ERGO) hybrid (ERGO@ZnPp-C60) was facilely obtained by π-π stacking interaction between zinc porphyrin ring and ERGO. The hybrid was characterized by scanning electron microscope (SEM), electrochemistry, UV-vis spectra, and density functional theory (DFT), which demonstrated that the presence of ERGO caused more redox reversibility and higher electrocatalytic activity of ZnPp-C60. By using their synergistic effects of the remarkable mechanical, electrical, catalytic, and structural properties, ERGO@ZnPp-C60 incorporated in tetraoctylammonium bromide (TOAB) film was modified on the glassy carbon electrode (GCE) to construct a novel non-enzymatic electrochemical sensor. The sensor exhibited enhancing response sensitivity for the electrocatalyic reduction of hydrogen peroxide with a high sensitivity of 451.3μAmM(-1) and a limit of detection (LOD) as low as 0.27μM. The sensitivity is 2-fold larger than that of TOAB/ZnPp-C60/GCE in the absence of ERGO. Although a high detecting sensitivity of 162.5μAmM(-1) for electrocatalytic oxidation of nitrite could be also obtained on the presented sensor, the sensitivity is lower than that of TOAB/ZnPp-C60/GCE (233.9μAmM(-1)) due to the change in the structure of ZnPp-C60 and the electronic interactions between GO and ZnPp-C60. Even though, the smart hybrid (ERGO@ZnPp-C60) possesses obvious advantage for the fabrication of non-enzymatic electrochemical sensor and paves a new avenue for constructing C60 derivative and graphene based materials. PMID:27591667

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed Central

    Johnson, Brandy J.; Anderson, Nicole E.; Charles, Paul T.; Malanoski, Anthony P.; Melde, Brian J.; Nasir, Mansoor; 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 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. PMID:22346609

  4. How Glassy States Affect Brown Carbon Production?

    NASA Astrophysics Data System (ADS)

    Liu, P.; Li, Y.; Wang, Y.; Bateman, A. P.; Zhang, Y.; Gong, Z.; Gilles, M. K.; Martin, S. T.

    2015-12-01

    Secondary organic material (SOM) can become light-absorbing (i.e. brown carbon) via multiphase reactions with nitrogen-containing species such as ammonia and amines. The physical states of SOM, however, potentially slow the diffusion of reactant molecules in organic matrix under conditions that semisolids or solids prevail, thus inhibiting the browning reaction pathways. In this study, the physical states and the in-particle diffusivity were investigated by measuring the evaporation kinetics of both water and organics from aromatic-derived SOMs using a quartz-crystal-microbalance (QCM). The results indicate that the SOMs derived from aromatic precursors toluene and m-xylene became solid (glassy) and the in particle diffusion was significantly impeded for sufficiently low relative humidity ( < 20% RH) at 293 K. Optical properties and the AMS spectra were measured for toluene-derived SOM after ammonia exposure at varied RHs. The results suggest that the production of light-absorbing nitrogen-containing compounds from multiphase reactions with ammonia was kinetically limited in the glassy organic matrix, which otherwise produce brown carbon. The results of this study have significant implications for production and optical properties of brown carbon in urban atmospheres that ultimately influence the climate and tropospheric photochemistry.

  5. Porphyrin-magnetite nanoconjugates for biological imaging

    PubMed Central

    2011-01-01

    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. PMID:21477294

  6. Water Dispersible and Biocompatible Porphyrin-Based Nanospheres for Biophotonics Applications: A Novel Surfactant and Polyelectrolyte-Based Fabrication Strategy for Modifying Hydrophobic Porphyrins.

    PubMed

    Sheng, Ning; Zong, Shenfei; Cao, Wei; Jiang, Jianzhuang; Wang, Zhuyuan; Cui, Yiping

    2015-09-01

    The hydrophobility of most porphyrin and porphyrin derivatives has limited their applications in medicine and biology. Herein, we developed a novel and general strategy for the design of porphyrin nanospheres with good biocompatibility and water dispersibility for biological applications using hydrophobic porphyrins. In order to display the generality of the method, we used two hydrophobic porphyrin isomers as starting material which have different structures confirmed by an X-ray technique. The porphyrin nanospheres were fabricated through two main steps. First, the uniform porphyrin nanospheres stabilized by surfactant were prepared by an interfacially driven microemulsion method, and then the layer-by-layer method was used for the synthesis of polyelectrolyte-coated porphyrin nanospheres to reduce the toxicity of the surfactant as well as improve the biocompatibility of the nanospheres. The newly fabricated porphyrin nanospheres were characterized by TEM techniques, the electronic absorption spectra, photoluminescence emission spectra, dynamic light scattering, and cytotoxicity examination. The resulting nanospheres demonstrated good biocompatibility, excellent water dispersibility and low toxicity. In order to show their application in biophotonics, these porphyrin nanospheres were successfully applied in targeted living cancer cell imaging. The results showed an effective method had been explored to prepare water dispersible and highly stable porphyrin nanomaterial for biophotonics applications using hydrophobic porphyrin. The approach we reported shows obvious flexibility because the surfactants and polyelectrolytes can be optionally selected in accordance with the characteristics of the hydrophobic material. This strategy will expand the applications of hydrophobic porphyrins owning excellent properties in medicine and biology.

  7. Water Dispersible and Biocompatible Porphyrin-Based Nanospheres for Biophotonics Applications: A Novel Surfactant and Polyelectrolyte-Based Fabrication Strategy for Modifying Hydrophobic Porphyrins.

    PubMed

    Sheng, Ning; Zong, Shenfei; Cao, Wei; Jiang, Jianzhuang; Wang, Zhuyuan; Cui, Yiping

    2015-09-01

    The hydrophobility of most porphyrin and porphyrin derivatives has limited their applications in medicine and biology. Herein, we developed a novel and general strategy for the design of porphyrin nanospheres with good biocompatibility and water dispersibility for biological applications using hydrophobic porphyrins. In order to display the generality of the method, we used two hydrophobic porphyrin isomers as starting material which have different structures confirmed by an X-ray technique. The porphyrin nanospheres were fabricated through two main steps. First, the uniform porphyrin nanospheres stabilized by surfactant were prepared by an interfacially driven microemulsion method, and then the layer-by-layer method was used for the synthesis of polyelectrolyte-coated porphyrin nanospheres to reduce the toxicity of the surfactant as well as improve the biocompatibility of the nanospheres. The newly fabricated porphyrin nanospheres were characterized by TEM techniques, the electronic absorption spectra, photoluminescence emission spectra, dynamic light scattering, and cytotoxicity examination. The resulting nanospheres demonstrated good biocompatibility, excellent water dispersibility and low toxicity. In order to show their application in biophotonics, these porphyrin nanospheres were successfully applied in targeted living cancer cell imaging. The results showed an effective method had been explored to prepare water dispersible and highly stable porphyrin nanomaterial for biophotonics applications using hydrophobic porphyrin. The approach we reported shows obvious flexibility because the surfactants and polyelectrolytes can be optionally selected in accordance with the characteristics of the hydrophobic material. This strategy will expand the applications of hydrophobic porphyrins owning excellent properties in medicine and biology. PMID:26292182

  8. Deformation and failure of glassy materials

    NASA Astrophysics Data System (ADS)

    Rottler, Joerg Gerhard

    Elastoplastic deformation of disordered solids and the formation of polymer crazes in amorphous polymer glasses are studied using large-scale molecular dynamics simulations. It is shown that the pressure-modified von Mises criterion accurately describes the maximum shear yield stress under general loading conditions. The pressure coefficient is insensitive to most model parameters, but is related to the bead geometry in analogy to friction coefficients. The yield stress decreases linearly with rising temperature and the strain rate dependence can be described by a power-law, or in a limited range, by a logarithm. The rate dependence does not vary with temperature, which is inconsistent with simple rate-state models of thermal activation such as the Eyring model. An analysis of the dynamics of the local stress distribution as well as modern phenomenological theories of rheology of glassy materials are discussed in light of these findings. We then present a comprehensive investigation of the deformation of glassy polymeric systems into a dense load-bearing network of fibrils and voids called a craze at large strains. This expansion takes place in the form of a drawing process, where the strain rate is strongly localized in a narrow interface region between dense polymer and craze. The expansion is controlled by some polymer chain segments between entanglements that are stretched taut during crazing. We also find that the distribution of tension in the craze develops an exponential force tail in close analogy to compressed jammed systems such as granular media. This highly anisotropic stress distribution and the localization of large forces on relatively few chains indicate that earlier models of the crazing process that treat the polymer as a viscous fluid with hydrodynamic interactions are incorrect. Simulations and simple scaling arguments are presented that describe craze breakdown through disentanglement or chain scission. Glassy polymers exhibit an unusually

  9. The two-step mechanochemical synthesis of porphyrins.

    PubMed

    Shy, Hannah; Mackin, Paula; Orvieto, Andrea S; Gharbharan, Deepa; Peterson, Geneva R; Bampos, Nick; Hamilton, Tamara D

    2014-01-01

    Porphyrin synthesis under solvent-free conditions represents the "greening" of a traditional synthesis that normally requires large amounts of organic solvent, and has hindered the industrial-scale synthesis of this useful class of molecules. We have found that the four-fold acid-catalysed condensation of aldehyde and pyrrole to yield a tetra-substituted porphyrin is possible through mechanochemical techniques, without a solvent present. This represents one of the still-rare examples of carbon-carbon bond formation by mechanochemistry. Specifically, upon grinding equimolar amounts of pyrrole and benzaldehyde in the presence of an acid catalyst, cyclization takes place to give reduced porphyrin precursors (reversible), which upon oxidation form tetraphenylporphyrin (TPP). The approach has been found to be suitable for the synthesis of a variety of meso-tetrasubstituted porphyrins. Oxidation can occur either by using an oxidizing agent in solution, to give yields comparable to those published for traditional methods of porphyrin synthesis, or through mechanochemical means resulting in a two-step mechanochemical synthesis to give slightly lower yields that are still being optimized. We are also working on "green" methods of porphyrin isolation, including entrainment sublimation, which would hopefully further reduce the need for large amounts of organic solvent. These results hold promise for the development of mechanochemical synthetic protocols for porphyrins and related classes of compounds.

  10. Active fluidization in dense glassy systems.

    PubMed

    Mandal, Rituparno; Bhuyan, Pranab Jyoti; Rao, Madan; Dasgupta, Chandan

    2016-07-20

    Dense soft glasses show strong collective caging behavior at sufficiently low temperatures. Using molecular dynamics simulations of a model glass former, we show that the incorporation of activity or self-propulsion, f0, can induce cage breaking and fluidization, resulting in the disappearance of the glassy phase beyond a critical f0. The diffusion coefficient crosses over from being strongly to weakly temperature dependent as f0 is increased. In addition, we demonstrate that activity induces a crossover from a fragile to a strong glass and a tendency of active particles to cluster. Our results are of direct relevance to the collective dynamics of dense active colloidal glasses and to recent experiments on tagged particle diffusion in living cells. PMID:27380935

  11. NRA of hydrogen in glassy polymeric carbon

    NASA Astrophysics Data System (ADS)

    Zimmerman, R. L.; Ila, D.; Jenkins, G. M.; Hirvonen, J. K.; Maleki, H.

    1997-02-01

    Glassy Polymeric Carbon (GPC) is prepared from a precursor resin by careful heat treatment. Heat Treatment Temperatures (HTT) above 1500 °C are believed to expel all hydrogen and oxygen from the grafene structure of GPC. However, we have shown that significant amounts of oxygen remain sequestered in the pores of GPC even at HTT's above 1500 °C. In the present study we report the detection of similar amounts of hydrogen for various heat treatment temperatures up to 2500 °C. A Nuclear Reaction Analysis (NRA) method with the 1H(15N,αγ)12C reaction and a specifically designed coincidence array is used to detect the 4.43 MeV gamma ray whose yield is proportional to the hydrogen content in the GPC. The H:C atomic ratio decreases with increasing HTT and we show that it exceeds 1:100 even for a HTT of 2500 °C.

  12. Glassy Behavior in a Micellar Polyelectrolyte System

    NASA Astrophysics Data System (ADS)

    Bhatia, Surita; Crichton, Mark; Mourchid, Ahmed

    2003-03-01

    We present SANS and rheology for micellar solutions of polystyrene-poly(acrylic acid) block copolymers that can be regarded as attractive colloids. These systems form gels at high effective micellar volume fractions that are suggestive of disordered colloidal glasses. At the gel point, the solution rheology follows the scaling predicted by classical percolation theory. We argue that this scaling could be due either to formation of a percolated network or a pre-transitional glassy phase. The addition of cationic and anionic surfactants (DTAB and SDS) can be used to modify the intermicellar interactions and solution rheology. Addition of an anionic surfactant acts to screen attractive interactions and causes a monotonic decrease in the elastic modulus. However, the addition of a cationic surfactant appears to initially induce a stronger intermicellar attraction, leading to gels with a higher elastic modulus. At higher surfactant concentrations, the cationic surfactant begins to screen intermicellar association, leading to a decrease in elasticity.

  13. Plastic and glassy crystal states of caffeine.

    PubMed

    Descamps, Marc; Correia, Natalia T; Derollez, Patrick; Danede, Florence; Capet, Frédéric

    2005-08-25

    The present paper focuses on the high temperature form I of caffeine and on its low temperature metastable form. Structural, dynamic, and kinetic information has been obtained by X-ray, dielectric, and calorimetric investigations. This study shows the following features: (1) The high temperature phase (I) of caffeine is in a state of dynamically orientationally disordered crystalline state (so-called "plastic, or rotator, phase"). (2) This high-symmetry hexagonal phase can be maintained at low temperature in a metastable situation. (3) Under deep undercooling of form I a glass transition occurs in the disordered crystalline state near room temperature. It is associated with the orientational freezing in of the molecular motions. Otherwise stated, the metastable state I enters into a nonergodic unstable state, so-called "glassy crystal" state. These findings rationalize the difficulties seen with caffeine in pharmaceutical science.

  14. Biaxial stress relaxation in glassy polymers - Polymethylmethacrylate.

    NASA Technical Reports Server (NTRS)

    Sternstein, S. S.; Ho, T. C.

    1972-01-01

    Biaxial stress relaxation studies were performed on glassy polymethylmethacrylate in combined torsion-tension strain fields using a specially designed apparatus with exceptionally high stiffness and low cross talk between the torsional and tensile load measuring transducers. It was found that at low strain levels uniaxial tension relaxation is slower than pure torsion relaxation; tensile-component relaxation rates are unaffected by the level of torsional strain; torsional-component relaxation rates decrease as tensile strain is increased; uniaxial tension relaxation rates approach the pure torsion rates at higher strains (about 2%). A phenomenological treatment is presented which shows that relaxation rates can be coupled to the strain fields in which they are observed and yet be consistent with the concepts of linear viscoelasticity and the Boltzmann superposition integral.

  15. Glassy Dynamics, Cell Mechanics and Endothelial Permeability

    PubMed Central

    Hardin, Corey; Rajendran, Kavitha; Manomohan, Greeshma; Tambe, Dhananjay T.; Butler, James P.; Fredberg, Jeffrey J.; Martinelli, Roberta; Carman, Christopher V.; Krishnan, Ramaswamy

    2013-01-01

    A key feature of all inflammatory processes is disruption of the vascular endothelial barrier. Such disruption is initiated in part through active contraction of the cytoskeleton of the endothelial cell (EC). Because contractile forces are propagated from cell to cell across a great many cell-cell junctions, this contractile process is strongly cooperative and highly nonlocal. We show here that the characteristic length scale of propagation is modulated by agonists and antagonists that impact permeability of the endothelial barrier. In the presence of agonists including thrombin, histamine, and H202, force correlation length increases, whereas in the presence of antagonists including sphingosine-1-phosphate, hepatocyte growth factor, and the rho kinase inhibitor, Y27632, force correlation length decreases. Intercellular force chains and force clusters are also evident, both of which are reminiscent of soft glassy materials approaching a glass transition. PMID:23638866

  16. Shock-wave studies of anomalous compressibility of glassy carbon

    NASA Astrophysics Data System (ADS)

    Molodets, A. M.; Golyshev, A. A.; Savinykh, A. S.; Kim, V. V.

    2016-02-01

    The physico-mechanical properties of amorphous glassy carbon are investigated under shock compression up to 10 GPa. Experiments are carried out on the continuous recording of the mass velocity of compression pulses propagating in glassy carbon samples with initial densities of 1.502(5) g/cm3 and 1.55(2) g/cm3. It is shown that, in both cases, a compression wave in glassy carbon contains a leading precursor with amplitude of 0.135(5) GPa. It is established that, in the range of pressures up to 2 GPa, a shock discontinuity in glassy carbon is transformed into a broadened compression wave, and shock waves are formed in the release wave, which generally means the anomalous compressibility of the material in both the compression and release waves. It is shown that, at pressure higher than 3 GPa, anomalous behavior turns into normal behavior, accompanied by the formation of a shock compression wave. In the investigated area of pressure, possible structural changes in glassy carbon under shock compression have a reversible character. A physico-mechanical model of glassy carbon is proposed that involves the equation of state and a constitutive relation for Poisson's ratio and allows the numerical simulation of physico-mechanical and thermophysical properties of glassy carbon of different densities in the region of its anomalous compressibility.

  17. High temperature annealing studies of strontium ion implanted glassy carbon

    NASA Astrophysics Data System (ADS)

    Odutemowo, O. S.; Malherbe, J. B.; Prinsloo, L.; Langa, D. F.; Wendler, E.

    2016-03-01

    Glassy carbon samples were implanted with 200 keV strontium ions to a fluence of 2 × 1016 ions/cm2 at room temperature. Analysis with Raman spectroscopy showed that ion bombardment amorphises the glassy carbon structure. Partial recovery of the glassy carbon structure was achieved after the implanted sample was vacuum annealed at 900 °C for 1 h. Annealing the strontium ion bombarded sample at 2000 °C for 5 h resulted in recovery of the glassy carbon substrate with the intensity of the D peak becoming lower than that of the pristine glassy carbon. Rutherford backscattering spectroscopy (RBS) showed that the implanted strontium diffused towards the surface of the glassy carbon after annealing the sample at 900 °C. This diffusion was also accompanied by loss of the implanted strontium. Comparison between the as-implanted and 900 °C depth profiles showed that less than 30% of the strontium was retained in the glassy carbon after heat treatment at 900 °C. The RBS profile after annealing at 2000 °C indicated that no strontium ions were retained after heat treatment at this temperature.

  18. Biosynthetic porphyrins and the origin of photosynthesis

    NASA Technical Reports Server (NTRS)

    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.

  19. Oxidative aromatic coupling of meso-arylamino-porphyrins.

    PubMed

    Nowak-Król, Agnieszka; Gryko, Daniel T

    2013-11-15

    Strategic placement of the bis-arylamino group at the meso-position of porphyrins allowed fusion of these two moieties via aromatic dehydrogenation. By placing two di(naphthalene-2-yl)amine or bis(3,5-dimethoxyphenyl)amine groups at positions 5 and 15 of the porphyrin, the oxidative aromatic coupling was directed toward closing one six-membered ring. The extension of the porphyrin chromophore leads to significant change in linear optical properties, such as a bathochromic shift of absorption and broadening of the Q-band. PMID:24168727

  20. Porphyrin Interactions with Wild Type and Mutant Mouse Ferrochelatase

    SciTech Connect

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

    1999-05-19

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

  1. Anodic electrosynthesis of some peroxy compounds on glassy carbon electrodes

    SciTech Connect

    Khomutov, N.E.; Zakhodyakina, N.A.; Svirida, L.V.; Nesvat, N.V.

    1987-11-10

    The authors present the results of a study of the anodic electrosynthesis of hydrogen peroxide and its derivatives on glassy carbon in solutions of sodium carbonate and sodium carbonate with sodium borate. We studied the kinetics of anodic processes on glassy carbon with the aid of polarization measurements and a method for determining the concentrations of active oxygen in the anolyte and the current efficiency. The current efficiencies with respect to active oxygen obtained on glassy carbon in the mixed solution of sodium borate and sodium carbonate are close to the current efficiencies which are observed on platinum anodes in the industrial electrosynthesis of perborates.

  2. Challenging Density Functional Theory Calculations with Hemes and Porphyrins

    PubMed Central

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

    2016-01-01

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

  3. Challenging Density Functional Theory Calculations with Hemes and Porphyrins.

    PubMed

    de Visser, Sam P; Stillman, Martin J

    2016-01-01

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

  4. Porphyrin Electropolymers For Application In Hyphenated Chemical Sensors

    NASA Astrophysics Data System (ADS)

    Lvova, L.; Mastroianni, M.; Martinelli, E.; Di Natale, C.; D'Amico, A.; Filippini, D.; Lundström, I.; Paolesse, R.

    2009-05-01

    A series of pyrrole-substituted porphyrin monomers have been rationally prepared to tune the properties of the resulting polymeric film. Free-base porphyrins and their metallic complexes have been deposited onto Indium-Tin-Oxide (ITO) glass electrodes by electropolymerization technique. Electropolymers were characterized by UV-visible spectroscopy and Atomic Force Microscopy (AFM). Cyclic voltammetry has been utilised to study the electropolymerisation mechanism and to evaluate the polymer surface coverge parameters. The obtained porphyrin electropolymers have been exploited as sensing materials for hyphenated potentiometric and optical measurements with CSPT-potentiometric analytical system. Different food matrices, such as mineral waters, wines and vegetable oils, have been analysed by means of the resulting porphyrin based CSPT-potentiometric system.

  5. Studies on porphyrin photoproducts in solution, cells, and tumor tissue

    NASA Astrophysics Data System (ADS)

    Koenig, Karsten; Schneckenburger, Herbert; Rueck, Angelika C.; Koenig, Roland

    1994-07-01

    Light excitation of photosensitizing porphyrins leads to cytotoxic reactions. In addition, photobleaching and photoproduct formation occur indicating photosensitizer destruction. Photoproducts from hematoporphyrin (HP) fluoresce in aqueous solution at 642 nm, whereas photoproducts from protoporphyrin (PP) in hydrophobic environment emit around 670 nm and exhibit pronounced absorption at 665 nm. Photoproduct formation depends on singlet oxygen. The photoproducts exhibit faster fluorescence decay kinetics compared with nonirradiated porphyrins, as shown by time-grated spectroscopy and fluorescence decay measurements. Photoproduct fluorescence was observed during light exposure of cells and of tumor-bearing, nude mice, following administration of Hematoporphyrin Derivative (HpD), tetramethyl-HP, and PP. Photoconversion was also detected with naturally-occurring porphyrins (PP-producing bacteria) and ALA-simulated biosynthesis of PP in tumor tissue and in skin lesions of patients (psoriasis, mycosis fungoides). The efficiency of PDT with porphyrin photoproducts was found to be low in spite of the strong electronic transitions in the red spectral region.

  6. Challenging Density Functional Theory Calculations with Hemes and Porphyrins.

    PubMed

    de Visser, Sam P; Stillman, Martin J

    2016-01-01

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

  7. A structural approach to relaxation in glassy liquids

    NASA Astrophysics Data System (ADS)

    Schoenholz, S. S.; Cubuk, E. D.; Sussman, D. M.; Kaxiras, E.; Liu, A. J.

    2016-05-01

    In contrast with crystallization, there is no noticeable structural change at the glass transition. Characteristic features of glassy dynamics that appear below an onset temperature, T0 (refs ,,), are qualitatively captured by mean field theory, which assumes uniform local structure. Studies of more realistic systems have found only weak correlations between structure and dynamics. This raises the question: is structure important to glassy dynamics in three dimensions? We answer this question affirmatively, using machine learning to identify a new field, `softness' which characterizes local structure and is strongly correlated with dynamics. We find that the onset of glassy dynamics at T0 corresponds to the onset of correlations between softness (that is, structure) and dynamics. Moreover, we construct a simple model of relaxation that agrees well with our simulation results, showing that a theory of the evolution of softness in time would constitute a theory of glassy dynamics.

  8. Ductile mode electrochemical oxidation assisted micromachining for glassy carbon

    NASA Astrophysics Data System (ADS)

    Nam, Eunseok; Lee, Chan-Young; Jun, Martin B. G.; Min, Byung-Kwon

    2015-04-01

    Recently, a new mechanical machining process using electrochemical oxidation was reported. Electrochemical oxidation assisted micromachining was applied to the machining of glassy carbon. The material removal process of the electrochemical oxidation assisted micromachining consists of repeated cycles of oxidation followed by removal of the oxide layer. In this paper, we experimentally investigate and compare the critical chip thickness for ductile mode cutting in mechanical machining and electrochemical oxidation assisted micromachining of glassy carbon. The theoretical critical chip thickness is calculated for mechanical machining of glassy carbon and experimentally verified. The effect of electrochemical oxidation on the critical chip thickness for ductile mode micromachining is also studied for glassy carbon. It is found that the critical chip thickness is increased for the electrochemical oxidation assisted micromachining.

  9. Discrete cyclic porphyrin arrays as artificial light-harvesting antenna.

    PubMed

    Aratani, Naoki; Kim, Dongho; Osuka, Atsuhiro

    2009-12-21

    The importance of photosynthesis has driven researchers to seek ways to mimic its fundamental features in simplified systems. The absorption of a photon by light-harvesting (antenna) complexes made up of a large number of protein-embedded pigments initiates photosynthesis. Subsequently the many pigments within the antenna system shuttle that photon via an efficient excitation energy transfer (EET) until it encounters a reaction center. Since the 1995 discovery of the circularly arranged chromophoric assemblies in the crystal structure of light-harvesting antenna complex LH2 of purple bacteria Rps. Acidophila, many designs of light-harvesting antenna systems have focused on cyclic porphyrin wheels that allow for efficient EET. In this Account, we review recent research in our laboratories in the synthesis of covalently and noncovalently linked discrete cyclic porphyrin arrays as models of the photosynthetic light-harvesting antenna complexes. On the basis of the silver(I)-promoted oxidative coupling strategy, we have prepared a series of extremely long yet discrete meso-meso-linked porphyrin arrays and covalently linked large porphyrin rings. We examined the photophysical properties of these molecules using steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related to the EET processes within the porphyrin rings. Within these structures, the exciton-exciton annihilation time and the polarization anisotropy rise time are well-described in terms of the Forster-type incoherent energy hopping model. In noncoordinating solvents such as CHCl(3), meso-pyridine-appended zinc(II) porphyrins and their meso-meso-linked dimers spontaneously assemble to form tetrameric porphyrin squares and porphyrin boxes, respectively. In the latter case, we have demonstrated

  10. Optical properties of porphyrin molecules immobilized in nano-porous silicon.

    PubMed

    Parkhutik, V; Chirvony, V; Matveyeva, E

    2007-02-01

    The paper aims at studying optical properties of porous silicon powders and thin films which were impregnated with different porphyrin molecules. It has been shown that introducing porphyrins into porous silicon matrix results in quenching of luminescence from porous silicon, while luminescence of porphyrins survives, though its structure changes. At the same time, porphyrins in porous silicon matrix which was preliminarily oxidized does not alter luminescence from porphyrins. Generation of singlet oxygen by illuminated porphyrin/porous silicon composite is confirmed by additional oxidation of porous silicon and by the observation of characteristic 1270 nm luminescence band. PMID:16893681

  11. Adhesion in hydrogels and model glassy polymers

    NASA Astrophysics Data System (ADS)

    Guvendiren, Murat

    Two main topics are addressed in this dissertation: (1) adhesion in hydrogels; (2) interfacial interactions between model glassy polymers. A self-assembly technique for the formation of hydrogels from acrylic triblock copolymer solutions was developed, based on vapor phase solvent exchange. Structure formation in the gels was characterized by small angle X-ray scattering, and swelling was measured in controlled pH buffer solutions. Strong gels are formed with polymer weight fractions between 0.01 and 0.15, and with shear moduli between 0.6 kPa and 3.5 kPa. Adhesive functionality, based on 3,4-dihydroxy-L-phenylalanine (DOPA) was also incorporated into the triblock copolymers. The effect of DOPA concentration on gel formation and swelling was investigated in detail. The adhesive properties of DOPA-functionalized hydrogels on TiO2 were investigated with an axisymmetric adhesion method. It was shown that the presence of DOPA enhances the adhesive properties of the hydrogels, but that the effect is minimized at pH values below 10, where the DOPA groups are hydrophobic. Thin film membranes were produced in order to study the specific interactions between DOPA and TiO2 and DOPA and tissue, using a membrane inflation method. The presence of DOPA in the membranes enhances the adhesion on TiO 2 and tissue, although adhesion to tissue requires that the DOPA groups be oxidized while in contact with the tissue of interest. Porous hydrogel scaffolds for tissue engineering applications were formed by adding salt crystals to the triblock copolymer solution prior to solvent exchange. Salt was then leached out by immersing the gel into water. Structures of the porous hydrogels were characterized by confocal laser scanning microscopy. These hydrogels were shown to be suitable for tissue regeneration and drug delivery applications. Diffusion-mediated adhesion between two component miscible polymer systems having very different glassy temperatures was also investigated. Axisymmetric

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

    PubMed

    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.

  13. Synthesis and characterization of novel glassy liquid crystals

    NASA Astrophysics Data System (ADS)

    Chen, Huang-Ming Philip

    As an emerging class of photonic and electronic materials, glassy liquid crystals are capable of preserving in the solid state molecular order characteristic of liquid crystals. Because of superior chemical purity and favorable rheological properties, glassy liquid crystals can be readily processed into large-area monodomain films. This thesis aimed at deterministic synthesis of glassy chiral nematics, photochromic glassy nematics, and glassy discotics. The most significant contributions are recapitulated as follows: (1) Through deterministic synthesis of multifunctional materials via enzymatic and chemical approaches, enantiomeric glassy chiral nematics were prepared efficiently and shown to possess a glass transition temperature over 60°C and a cholesteric fluid temperature range wider than 100°C. Device concepts were also demonstrated for high-performance circular polarizers, notch filters and reflectors in the ultraviolet, across the visible, and to the infrared region. (2) The first photochromic glassy nematic liquid crystal was successfully designed, synthesized and characterized to possess a glass transition temperature over 100°C and a clearing point over 200°C. A large-area solid film was prepared through melt processing to demonstrate high-speed switching of anisotropic refractive indices and optical birefringence as a novel approach to rewritable optical memory and photonic switching in solid films. (3) Glassy discotic liquid crystals were synthesized and characterized by x-ray diffraction, polarizing optical microscopy, differential scanning calorimetry, and dynamic mechanical analysis to reveal sub-freezing glass transition temperatures. However, the absence of recrystallization at room temperature over a period of over four years was a manifestation of morphological stability of the discotics.

  14. No inherent glassiness in a Penrose tiling quasicrystal

    SciTech Connect

    Strandburg, K.J.; Dressel, P.R.

    1988-11-01

    Consideration of the structure of the Penrose pattern has led to speculation that a system with a Penrose tiling ground state might be subject to inherent glassy behavior. Monte Carol simulations show, using a simple model of the energetics, that there is no inherent glassiness in the Penrose tiling. Thermodynamic quantities measured are completely reversible, displaying no observable hysterisis, and the system may be easily cooled from a highly disordered configuration into its lowest energy state. 11 refs., 7 figs.

  15. Self assembly of coiled-coil peptide-porphyrin complexes.

    PubMed

    Kokona, Bashkim; Kim, Andrew M; Roden, R Claire; Daniels, Joshua P; Pepe-Mooney, Brian J; Kovaric, Brian C; de Paula, Julio C; Johnson, Karl A; Fairman, Robert

    2009-06-01

    We are interested in the controlled assembly of photoelectronic materials using peptides as scaffolds and porphyrins as the conducting material. We describe the integration of a peptide-based polymer strategy with the ability of designed basic peptides to bind anionic porphyrins in order to create regulated photoelectronically active biomaterials. We have described our peptide system in earlier work, which demonstrates the ability of a peptide to form filamentous materials made up of self-assembling coiled-coil structures. We have modified this peptide system to include lysine residues appropriately positioned to specifically bind meso-tetrakis(4-sulfonatophenyl)porphine (TPPS(4)), a porphyrin that contains four negatively charged sulfonate groups at neutral pH. We measure the binding of TPPS(4) to our peptide using UV--visible and fluorescence spectroscopies to follow the porphyrin signature. We determine the concomitant acquisition of helical secondary structure in the peptide upon TPPS(4) binding using circular dichroism spectropolarimetry. This binding fosters polymerization of the peptide, as shown by absorbance extinction effects in the peptide CD spectra. The morphologies of the peptide/porphyrin complexes, as imaged by atomic force microscopy, are consistent with the coiled-coil polymers that we had characterized earlier, except that the heights are slightly higher, consistent with porphyrin binding. Evidence for exciton coupling in the copolymers is shown by red-shifting in the UV--visible data, however, the coupling is weak based on a lack of fluorescence quenching in fluorescence experiments.

  16. Preparation and characterization of porphyrin nanoparticles.

    PubMed

    Gong, Xianchang; Milic, Tatjana; Xu, Chang; Batteas, James D; Drain, Charles Michael

    2002-12-01

    The synthesis, characterization, and stability of porphyrin nanoparticles of 20-200 nm diameter presented herein is general for meso arylporphyrins. The elegance of the method lies in its simplicity. This work shows that the agent used to prevent agglomeration can be covalently attached to the dye forming the particle or be part of the solvent system. It also demonstrates that these and other types of dyes with a range of photonic properties do not need to be prepared by inclusion in external matrices or by designed self-assembly a priori. The matrix may severely limit the functionality of the particles in the former case, and at present this size of particle is difficult to achieve via the latter.

  17. The distribution and thermal conversion performance of porphyrin and non-porphyrin nickel in Gudao and Shengli residues

    SciTech Connect

    Guohe Que; Chenguang Liu; Baoquan Mu

    1995-12-31

    The residues of Shengli and Gudao crude oils have been separated into some fractions using alumina chromatography and supercritical fluid extraction. The petroporphyrin nickel compounds of the residues and its fractions were concentrated by silica column chromatography eluted with cyclohexane, cyclohexane-dichloromethane and dichloromethane-acetone. The results show that a large part of nickel porphyrins are present in the resin-asphaltene fractions of the residues. The distribution of the porphyrin nickel reveals a bimodal distribution pattern with a maximum at the light resin. The data show that it is difficult to remove petroporphyrin nickel by solvent deasphalting. Data also indicate that the thermal reaction of residue is of benefit to removal of porphyrin and non-porphyrin nickel by solvent deasphalting technique.

  18. Porphyrin dimers as photosensitizers in photodynamic therapy

    SciTech Connect

    Pandey, R.K.; Smith, K.M.; Dougherty, T.J. )

    1990-07-01

    Porphyrin dimers 9 with either linkages and possible isomers bis(1-(6,7-bis(2-(methoxycarbonyl)ethyl)-1,3,5,8-tetramethyl-2- vinylporphin-4-yl)ethyl) ether (10) bis(1-(6,7-bis(2-(methoxycarbonyl)ethyl)-1,3,5,8-tetramethyl-4- vinylporphin-2-yl)ethyl) ether (11), and 1-(6,7-bis(2-(methoxycarbonyl)ethyl)-1,3,5,8-tetramethyl-2-vinylporph in- 4-yl)ethyl 1-(6,7-bis(2-(methoxycarbonyl)ethyl)-1,3,5,8-tetramethyl-4-vinylporph in- 2-yl)ethyl ether (12) were synthesized from the corresponding (1-hydroxyethyl)vinyldeuteroporphyrin IX dimethyl esters (Hvd). The pure Hvd isomers 2-(1-hydroxyethyl)-4-vinyldeuteroporphyrin IX dimethyl ester (7) and 4-(1-hydroxyethyl)-2-vinyldeuteroporphyrin IX dimethyl ester (8) were obtained from 2-acetyl-4-(1-hydroxyethyl) deuteroporphyrin IX dimethyl ester (3) and 4-acetyl-2-(1-hydroxyethyl)deuteroporphyrin IX dimethyl ester (4). Porphyrins 3 and 4 were prepared either by partial reduction of 2,4-diacetyldeuteroporphyrin IX dimethyl ester (2) or by oxidation of hematoporphyrin IX dimethyl ester (1) by using tetra-n-propylammonium perruthenate (Prn4N)(RuO4) with N-methylmorpholine N-oxide as an oxidizing agent. The in vivo photosensitizing ability and therapeutic ratios of dimers 9-12 were compared with that of Photofrin II in the SMT-F tumor growing subcutaneously in DBA/2 Ha mice. These dimers were found to have better tumoricidal activity than Photofrin II with reduced skin phototoxicity.

  19. Structural Properties of Defects in Glassy Liquids.

    PubMed

    Cubuk, Ekin D; Schoenholz, Samuel S; Kaxiras, Efthimios; Liu, Andrea J

    2016-07-01

    At zero temperature a disordered solid corresponds to a local minimum in the energy landscape. As the temperature is raised or the system is driven with a mechanical load, the system explores different minima via dynamical events in which particles rearrange their relative positions. We have shown recently that the dynamics of particle rearrangements are strongly correlated with a structural quantity associated with each particle, "softness", which we can identify using supervised machine learning. Particles of a given softness have a well-defined energy scale that governs local rearrangements; because of this property, softness greatly simplifies our understanding of glassy dynamics. Here we investigate the correlation of softness with other commonly used structural quantities, such as coordination number and local potential energy. We show that although softness strongly correlates with these properties, its predictive power for rearrangement dynamics is much higher. We introduce a useful metric for quantifying the quality of structural quantities as predictors of dynamics. We hope that, in the future, authors introducing new structural measures of dynamics will compare their proposals quantitatively to softness using this metric. We also show how softness correlations give insight into rearrangements. Finally, we explore the physical meaning of softness using unsupervised dimensionality reduction and reduced curve-fitting models, and show that softness can be recast in a form that is amenable to analytical treatment.

  20. Lithium ion diffusion through glassy carbon plate

    SciTech Connect

    Inaba, M.; Nohmi, S.; Funabiki, A.; Abe, T.; Ogumi, Z.

    1998-07-01

    The electrochemical permeation method was applied to the determination of the diffusion coefficient of Li{sup +} ion (D{sub Li{sup +}}) in a glassy carbon (GC) plate. The cell was composed of two compartments, which were separated by the GC plate. Li{sup +} ions were inserted electrochemically from one face, and extracted from the other. The flux of the permeated Li{sup +} ions was monitored as an oxidation current at the latter face. The diffusion coefficient was determined by fitting the transient current curve with a theoretical one derived from Fick's law. When the potential was stepped between two potentials in the range of 0 to 0.5 V, transient curves were well fitted with the theoretical one, which gave D{sub Li{sup +}} values on the order of 10{sup {minus}8} cm{sup {minus}2} s{sup {minus}1}. In contrast, when the potential was stepped between two potentials across 0.5 V, significant deviation was observed. The deviation indicated the presence of trap sites as well as diffusion sites for Li{sup +} ions, the former of which is the origin of the irreversible capacity of GC.

  1. Development and characterization of porphyrin chromophores for solar energy conversion

    NASA Astrophysics Data System (ADS)

    Splan, Kathryn Elizabeth

    Increased public awareness of the Earth's depleting oil reserves and the adverse effect of greenhouse gasses are driving the development of alternative energy resources, including solar power. While the supply of energy from the Sun to the Earth is enormous, exploitation of this formidable natural resource remains a scientific challenge. Considerable efforts in fundamental research are still necessary for solar power to become a reality. The interesting optical and electronic properties and synthetic versatility of porphyrin chromophores constitute a valuable tool for further understanding the processes involved in efficient light-harvesting and current generation. This thesis describes the design and characterization of several porphyrin-based systems for solar energy conversion studies. Chapter 2 reports on the synthesis, photophysical characterization, and energy transfer (EnT) applications of a series of porphyrin dimers based on Re(l) pyridyl ligation that, despite incorporation of rhenium into the assembly, remain significantly fluorescent. In the context of solar energy conversion, the dimers allow for the systematic study of factors that modulate interpigment EnT. Chapter 3 presents a scheme for porphyrin-based multilayer sensitization of dye-sensitized solar cells (DSSCs). Porous, chromophoric, thin films based on tetrameric porphyrin squares were fabricated via layer-by-layer zirconium phosphonate chemistry, and their photoelectrochemical responses were evaluated. The studies reveal an additional, cathodic-current generating mechanism, which represents a parasitic process in the context of DSSCs. In Chapters 4 and 5, second generation porphyrin compounds are developed in efforts of optimizing the multilayer response. Porphyrin thin films are presented in which both excited state lifetime and mobility are enhanced. The photoelectrochemical response of the films in the context of DSSCs is evaluated. In chapter 6 a strategy is described in which the narrow

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

    SciTech Connect

    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.

  3. Shear banding in soft glassy materials

    NASA Astrophysics Data System (ADS)

    Fielding, S. M.

    2014-10-01

    Many soft materials, including microgels, dense colloidal emulsions, star polymers, dense packings of multilamellar vesicles, and textured morphologies of liquid crystals, share the basic ‘glassy’ features of structural disorder and metastability. These in turn give rise to several notable features in the low frequency shear rheology (deformation and flow properties) of these materials: in particular, the existence of a yield stress below which the material behaves like a solid, and above which it flows like a liquid. In the last decade, intense experimental activity has also revealed that these materials often display a phenomenon known as shear banding, in which the flow profile across the shear cell exhibits macroscopic bands of different viscosity. Two distinct classes of yield stress fluid have been identified: those in which the shear bands apparently persist permanently (for as long as the flow remains applied), and those in which banding arises only transiently during a process in which a steady flowing state is established out of an initial rest state (for example, in a shear startup or step stress experiment). Despite being technically transient, such bands may in practice persist for a very long time and so be mistaken for the true steady state response of the material in experimental practice. After surveying the motivating experimental data, we describe recent progress in addressing it theoretically, using the soft glassy rheology model and a simple fluidity model. We also briefly place these theoretical approaches in the context of others in the literature, including elasto-plastic models, shear transformation zone theories, and molecular dynamics simulations. We discuss finally some challenges that remain open to theory and experiment alike.

  4. Communication: Substrate induced dehydrogenation: Transformation of octa-ethyl-porphyrin into tetra-benzo-porphyrin

    NASA Astrophysics Data System (ADS)

    van Vörden, D.; Lange, M.; Schmuck, M.; Schaffert, J.; Cottin, M. C.; Bobisch, C. A.; Möller, R.

    2013-06-01

    Individual molecules of octa-ethyl-porhphyrin-iron(III)-chloride adsorbed on a Cu(111) surface are studied by scanning tunneling microscopy. Upon moderate heating the molecules are found to transform into Fe-tetra-benzo-porphyrin at a surprisingly low temperature of 380 K. If the annealing is interrupted, the different steps of the transformation can be imaged. By evaluating the ratio of transformed molecules as function of annealing temperature, an approximate activation energy of 1.2 eV ± 0.1 eV could be determined.

  5. Porphyrin and bodipy molecular rotors as microviscometers

    NASA Astrophysics Data System (ADS)

    Kimball, Joseph Daniel, III

    Viscosity, a fluid's internal resistance to flow and resist molecular diffusion, is a fundamental property of fluid media. Determining the bulk viscosity of a fluid has been easy to relatively simple to accomplish for many years, yet in the recent decade there has been a focus on techniques to measure a fluid's microviscosity. Microviscosity differs from bulk viscosity such that microviscosity is the friction experienced by a single particle interacting with its micron-sized local environment. Macroscopic methods to evaluate the viscosity are well established, but methods to determine viscosity on the microscale level remains unclear. This work determines the viability of three molecular rotors designed as probes for microviscosity in organic media, ionic liquids, and in the cellular microenvironment. Understanding microviscosity is important because it one of the main properties of any fluid and thus has an effect on any diffusion related processes. A variety of mass and signal transport phenomena as well as intermolecular interactions are often governed by viscosity. Molecular rotors are a subclass of intramolecular charge transfer fluorophores which form a lower energy twisted state. This results in a charge separated species which is highly sensitive to its surrounding microenviroment's viscosity as high viscosity limits its ability to form this twisted state. Once excited, there are deactivation routes which the excited fluorophore can undergo: radiative and non-radiative. Both were studied in this work. In the case of a radiative decay, as seen in porphyrin dimer, the energy is released in the form of a photon and is seen as a shifted band in the emission structure. The conformation of the porphyrin dimer was found to be influenced differently by ionic liquids as compared to molecular solvents, indicating the microheterogenous nature of ionic liquids play a role in the conformation. For non-radiative decays, BODIPY dyads and triads were investigated. The

  6. Fluorescence spectroscopy for endogenous porphyrins in human facial skin

    NASA Astrophysics Data System (ADS)

    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.

  7. Thermal Barrier Coatings Resistant to Glassy Deposits

    NASA Astrophysics Data System (ADS)

    Drexler, Julie Marie

    Engineering of alloys has for years allowed aircraft turbine engines to become more efficient and operate at higher temperatures. As advancements in these alloy systems have become more difficult, ceramic thermal barrier coatings (TBCs), often yttria (7 wt %) stabilized zirconia (7YSZ), have been utilized for thermal protection. TBCs have allowed for higher engine operating temperatures and better fuel efficiency but have also created new engineering problems. Specifically, silica based particles such as sand and volcanic ash that enter the engine during operation form glassy deposits on the TBCs. These deposits can cause the current industrial 7YSZ thermal barrier coatings to fail since the glass formed penetrates and chemically interacts with the TBC. When this occurs, coating failure may occur due to a loss of strain tolerance, which can lead to fracture, and phase changes of the TBC material. There have been several approaches used to stop calcium-magnesium aluminio-silcate (CMAS) glasses (molten sand) from destroying the entire TBC, but overall there is still limited knowledge. In this thesis, 7YSZ and new TBC materials will be examined for thermochemical and thermomechanical performance in the presence of molten CMAS and volcanic ash. Two air plasma sprayed TBCs will be shown to be resistant to volcanic ash and CMAS. The first type of coating is a modified 7YSZ coating with 20 mol% Al2O3 and 5 mol% TiO2 in solid solution (YSZ+20Al+5Ti). The second TBC is made of gadolinium zirconate. These novel TBCs impede CMAS and ash penetration by interacting with the molten CMAS or ash and drastically changing the chemistry. The chemically modified CMAS or ash will crystallize into an apatite or anorthite phase, blocking the CMAS or ash from further destroying the coating. A presented mechanism study will show these coatings are effective due to the large amount of solute (Gd, Al) in the zirconia structure, which is the key to creating the crystalline apatite or

  8. Optical speckles of blood proteins embedded in porous glassy substrate

    NASA Astrophysics Data System (ADS)

    Holden, T.; Dehipawala, S.; Kokkinos, D.; Berisha, A.; Cheung, E.; Nguyen, A.; Golebiewska, U.; Schneider, P.; Tremberger, G., Jr.; Lieberman, D.; Cheung, T.

    2012-03-01

    Blood protein molecules could be embedded in porous glassy substrate with 10-nm pores. The embedding principle is based on blood cell dehydration with the destruction of the cell membrane, and reconstitution and centrifuge could yield a suitable solution for doping into a porous glassy medium. The doped glassy substrate speckle pattern under laser illumination could be used to characterize the protein size distribution. Calibration with known protein embedded samples would result in an optical procedure for the characterization of a blood sample. Samples embedded with larger kilo-Dalton protein molecule show more variation in the speckle patterns, consistent with protein folding interaction inside a pore cavity. A regression model has been used to correlate the protein molecule sizes with speckle sizes. The use of diffusion mean free path information to study protein folding in the embedding process is briefly discussed.

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

    PubMed

    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.

  10. Photodynamics in stable complexes composed of a zinc porphyrin tripod and pyridyl porphyrins assembled by multiple coordination bonds.

    PubMed

    Takai, Atsuro; Gros, Claude P; Barbe, Jean-Michel; Fukuzumi, Shunichi

    2010-10-14

    A tripod zinc porphyrin (TPZn(3)) forms a stable 1:1 complex with gold(III) tetra(4-pyridyl)porphyrin (AuTPyP(+)) and free-base tris(4-pyridyl)porphyrin (2H-Py(3)P) in nonpolar solvents. The strong binding of TPZn(3) with AuTPyP(+) or 2H-Py(3)P results from the encapsulation of AuTPyP(+) or 2H-Py(3)P inside the cavity of TPZn(3) through multiple coordination bonds, as indicated by UV-vis-NIR, ESI-MS, (1)H NMR, electrochemistry and computational studies. The binding constants of monomer zinc porphyrin (MPZn) with AuTPyP(+) and 2H-Py(3)P drastically decrease as compared with TPZn(3). Detailed photophysical studies have been carried out on these composites using laser flash photolysis as well as emission spectroscopy. The efficient quenching of the singlet excited state of TPZn(3) occurs via a photoinduced electron-transfer pathway in the TPZn(3)-AuTPyP(+) complex. In contrast, energy transfer occurs in the TPZn(3)-2H-Py(3)P complex due to the smaller driving force of the photoinduced electron-transfer pathway. Neither electron transfer nor energy transfer occurs from MPZn to AuTPyP(+) under the same experimental conditions due to the small association constant of the monomer zinc porphyrin. PMID:20714588

  11. Role of complement in porphyrin-induced photosensitivity

    SciTech Connect

    Lim, H.W.; Gigli, I.

    1981-01-01

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

  12. Doubly Cavitand-Capped Porphyrin Capsule by Hydrogen Bonds.

    PubMed

    Kishimoto, Kazuki; Nakamura, Munechika; Kobayashi, Kenji

    2016-02-18

    The components of a 1:2 mixture of meso-tetrakis(4-dodecyl-3,5-dihydroxyphenyl)porphyrin (1) and a bowl-shaped tetrakis(4-pyridylethynyl)cavitand (2) in CDCl3 or C6 D6 self-assemble quantitatively into the doubly cavitand-capped porphyrin capsule 2⋅1⋅2 through eight ArOH⋅⋅⋅Npy hydrogen bonds. Capsule 2⋅1⋅2 possesses two cavities divided by the porphyrin ring and encapsulates two molecules of 1-acetoxy-3,5-dimethoxybenzene (G) as a guest to form G/G@(2⋅1⋅2). Remarkable solvent effect was observed, in which the apparent association constant of 2⋅1⋅2 with G in C6 D6 was much greater than that in CDCl3. PMID:26728330

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

  14. The Erevan howardite: Petrology of glassy clasts and mineral chemistry

    NASA Technical Reports Server (NTRS)

    Nazarov, M. A.; Ariskin, A. A.

    1993-01-01

    The Erevan howardite is a polymict regolith breccia containing xenoliths of carbonaceous chondrites. In this work, we studied glassy clasts, which could be considered as primary quenched melts, and mineral chemistry of the breccia. The study reveals that the Erevan howardite consists of common rocks of the HED suite. However, unique glassy clasts, which are present in some eucritic melts, were identified. The mineral chemistry and the simulation of crystallization of the melts suggest that the compositions of the melts reflect those of some primary lithologies of EPB.

  15. Trilobolide-porphyrin conjugates: on synthesis and biological effects evaluation.

    PubMed

    Tomanová, Pavla; Rimpelová, Silvie; Jurášek, Michal; Buděšínský, Miloš; Vejvodová, Lucie; Ruml, Tomáš; Kmoníčková, Eva; Drašar, Pavel B

    2015-05-01

    Trilobolide (Tb), a potent natural counterpart of thapsigargin, is a sesquiterpene lactone of guaianolide type isolated from horse caraway (Laser trilobum, L. Borkh). Tb exerts remarkable pharmacological properties based on irreversible inhibition of sarco/endoplasmic reticulum calcium ATPase (SERCA), thus being of increasing interest for cancer cure. Additionally, another pharmacological activity of Tb, as well as of thapsigargin, was reported in several studies, Tb as being an effective inductor of nitric oxide and cytokine production. These extraordinary biological properties move these molecules in further pre-clinical evaluation. Because of ubiquitous character of SERCA expression, development of specifically targeted bioactive molecules is inevitable. Since it is well known that porphyrins are preferentially taken up by cancer cells, we have designed and synthesized novel Tb-porphyrin conjugates. Copper-catalyzed azide-alkyne cycloaddition was used to link Tb with porphyrin at once. Two model conjugates of Tb and porphyrin were synthesized and properly characterized. Employing naturally occurring fluorescence properties of porphyrins, we investigated the intracellular localization of the conjugates employing fluorescence microscopy in living cells. Intriguingly, the prepared conjugates localized both in mitochondria and lysosomes of HeLa and LNCaP cells. Furthermore, the cytotoxicity of Tb-porphyrin conjugates was assessed in a number of human cancer cell lines and rat peritoneal cells. Likewise in cancer cell lines, viability of rat peritoneal cells was not affected by the tested conjugates. Interestingly, we observed dose-dependent nitric oxide (iNOS) production induced by the tested conjugates. The effect was related to the type of a linker used and the overall size of the molecule. Another potent immunobiological effects are under evaluation. In summary, the results presented here indicate notable immunobiological potential of the prepared Tb conjugates

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

    PubMed

    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.

  17. Synthesis and characterization of "face-to-face" porphyrins.

    PubMed Central

    Collman, J P; Elliott, C M; Halbert, T R; Tovrog, B S

    1977-01-01

    The syntheses of four binary porphyrins, two of which are constrained to a "face-to-face" conformation, and their Co2+ and Cu2+ derivatives are described. Electron spin resonance indicates that the intermetallic separation in the binuclear "face-to-face" porphyrins is about 6.5-6.8 A. Electronic spectra and proton magnetic resonance spectra support the postulated "face-to-face" conformations. A hypothesis that related compounds may serve as multielectron redox catalysts for O2 and N2 is presented. PMID:189304

  18. Reductive precipitation of metals photosensitized by tin and antimony porphyrins

    DOEpatents

    Shelnutt, John A.; Gong, Weiliang; Abdelouas, Abdesselam; Lutze, Werner

    2003-09-30

    A method for reducing metals using a tin or antimony porphyrin by forming an aqueous solution of a tin or antimony porphyrin, an electron donor, such as ethylenediaminetetraaceticacid, triethylamine, triethanolamine, and sodium nitrite, and at least one metal compound selected from a uranium-containing compound, a mercury-containing compound, a copper-containing compound, a lead-containing compound, a gold-containing compound, a silver-containing compound, and a platinum-containing compound through irradiating the aqueous solution with light.

  19. Photoinduced conductivity of a porphyrin-gold composite nanowire

    SciTech Connect

    Kilina, Svletana; Balatsky, Alexander; Kilin, Dmitri S; Prezhdo, Oleg; Tsemekhman, Kiril

    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.

  20. Rotational libration of a double-decker porphyrin visualized.

    PubMed

    Otsuki, Joe; Komatsu, Yuji; Kobayashi, Daiya; Asakawa, Masumi; Miyake, Koji

    2010-05-26

    Scanning tunneling microscopy has revealed the reorientation of one of the macrocyclic rings of the double-decker porphyrin complex [Ce(TPP-Fc)(C(22)OPP)] [TPP-Fc = 5-(4-(4-ferrocenylphenylethynyl)phenyl)-10,15,20-triphenylporphyrin; C(22)OPP = 5,10,15,20-tetrakis(4-docosyloxyphenyl)porphyrin] by 90 degrees between scans when the other ring is fixed on a surface. This libration was evidenced by monitoring the location of the appended ferrocene unit, which functioned as a molecular beacon signaling its position.

  1. Micropatterning of porphyrin nanotubes thin film using focused laser writing.

    PubMed

    Gupta, Jyotsana; Lim, Xiaodai; Sow, Chorng-Haur; Vijayan, C

    2011-05-01

    We report an effective process to create micropatterns on a thin film of porphyrin nanotubes PNTs on Si substrate using focused laser beam. The optical properties of the newly synthesized porphyrin nanotubes are investigated and micropatterning is demonstrated using laser fabrication, an increasingly important tool in various fields of research. We made use of this laser cutting method to create interesting and useful two-dimensional patterned structures. The shapes and sizes of the structures created can be controlled by varying the power of the laser, angle of incident of the focused laser beam, the relative speed with which the laser beam traverse through the film and the magnification of objective lens used.

  2. Catalytic and Biocatalytic Iron Porphyrin Carbene Formation: Effects of Binding Mode, Carbene Substituent, Porphyrin Substituent, and Protein Axial Ligand

    PubMed Central

    2016-01-01

    Iron porphyrin carbenes (IPCs) are important intermediates in various chemical reactions catalyzed by iron porphyrins and engineered heme proteins, as well as in the metabolism of various xenobiotics by cytochrome P450. However, there are no prior theoretical reports to help understand their formation mechanisms and identify key information governing the binding mode, formation feasibility, and stability/reactivity. A systematic quantum chemical study was performed to investigate the effects of carbene substituent, porphyrin substituent, and axial ligand on IPC formation pathways. Results not only are consistent with available experimental data but also provide a number of unprecedented insights into electronic, steric, and H-bonding effects of various structural factors on IPC formation mechanisms. These results shall facilitate research on IPC and related systems for sustainable chemical catalysis and biocatalysis. PMID:26067900

  3. Noncovalent binding between fullerenes and protonated porphyrins in the gas phase.

    PubMed

    Jung, Sunghan; Seo, Jongcheol; Shin, Seung Koo

    2010-11-01

    Noncovalent interactions between protonated porphyrin and fullerenes (C₆₀ and C₇₀) were studied with five different meso-substituted porphyrins in the gas phase. The protonated porphyrin-fullerene complexes were generated by electrospray ionization of the porphyrin-fullerene mixture in 3:1 dichloromethane/methanol containing formic acid. All singly protonated porphyrins formed the 1:1 complexes, whereas porphyrins doubly protonated on the porphine center yielded no complexes. The complex ion was mass-selected and then characterized by collision-induced dissociation with Xe. Collisional activation exclusively led to a loss of neutral fullerene, indicating noncovalent binding of fullerene to protonated porphyrin. In addition, the dissociation yield was measured as a function of collision energy, and the energy inducing 50% dissociation was determined as a measure of binding energy. Experimental results show that C₇₀ binds to the protonated porphyrins more strongly than C₆₀, and electron-donating substituents at the meso positions increase the fullerene binding energy, whereas electron-withdrawing substituents decrease it. To gain insight into π-π interactions between protonated porphyrin and fullerene, we calculated the proton affinity and HOMO and LUMO energies of porphyrin using Hartree-Fock and configuration interaction singles theory and obtained the binding energy of the protonated porphyrin-fullerene complex using density functional theory. Theory suggests that the protonated porphyrin-fullerene complex is stabilized by π-π interactions where the protonated porphyrin accepts π-electrons from fullerene, and porphyrins carrying bulky substituents prefer the end-on binding of C₇₀ due to the steric hindrance, whereas those carrying less-bulky substituents favor the side-on binding of C₇₀.

  4. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    PubMed Central

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

    2016-01-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  5. The nonequilibrium glassy dynamics of self-propelled particles.

    PubMed

    Flenner, Elijah; Szamel, Grzegorz; Berthier, Ludovic

    2016-09-14

    We study the glassy dynamics taking place in dense assemblies of athermal active particles that are driven solely by a nonequilibrium self-propulsion mechanism. Active forces are modeled as an Ornstein-Uhlenbeck stochastic process, characterized by a persistence time and an effective temperature, and particles interact via a Lennard-Jones potential that yields well-studied glassy behavior in the Brownian limit, which is obtained as the persistence time vanishes. By increasing the persistence time, the system departs more strongly from thermal equilibrium and we provide a comprehensive numerical analysis of the structure and dynamics of the resulting active fluid. Finite persistence times profoundly affect the static structure of the fluid and give rise to nonequilibrium velocity correlations that are absent in thermal systems. Despite these nonequilibrium features, for any value of the persistence time we observe a nonequilibrium glass transition as the effective temperature is decreased. Surprisingly, increasing departure from thermal equilibrium is found to promote (rather than suppress) the glassy dynamics. Overall, our results suggest that with increasing persistence time, microscopic properties of the active fluid change quantitatively, but the general features of the nonequilibrium glassy dynamics observed with decreasing the effective temperature remain qualitatively similar to those of thermal glass-formers. PMID:27499055

  6. Introduction to the Glassy State in the Undergraduate Curriculum

    ERIC Educational Resources Information Center

    Johari, Gyan P.

    1974-01-01

    Presents fundamentals of the glassy state which can serve as an introductory, phenomenological, and nonmathematical exposure to undergraduates in at most two lectures. Suggests the use of the material following students' acquisition of an elementary knowledge of thermodynamics, liquids, and the crystalline state. (CC)

  7. Pressure-induced transformations in computer simulations of glassy water.

    PubMed

    Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

    2013-11-14

    Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water. PMID:24320281

  8. A method for determining the nitrogen isotopic composition of porphyrins.

    PubMed

    Higgins, Meytal B; Robinson, Rebecca S; Casciotti, Karen L; McIlvin, Matthew R; Pearson, Ann

    2009-01-01

    We describe a new method for analysis of the nitrogen isotopic composition of sedimentary porphyrins. This method involves separation and purification of geoporphyrins from sediment samples using liquid chromatography and HPLC, oxidation of the nitrogen within porphyrin-enriched fractions using a two-step process, and isotopic analysis of the resulting nitrate using the denitrifier method. By analysis of these degradation products of chlorophylls, we are able to measure an isotopic signature that reflects the nitrogen utilized by primary producers. The high sensitivity of the denitrifier method allows measurement of small samples that contain low concentrations of porphyrins. Extraction of only 50 nmol of nitrogen (nmol N) allows the following five analyses to be made (each on approximately 10 nmol N): nitrogen concentration, an assessment of potential contamination by nonporphyrin N, and three replicate isotopic measurements. The measured values of delta15N have an average analytical precision of +/-0.5 per thousand (1sigma) and an average contribution from Rayleigh fractionation of 0.7 per thousand from incomplete oxidation of porphyrin N to nitrate. The overall method will enable high-resolution records of delta15N values to be obtained for geological and ecological applications.

  9. Bis(porphyrin)-anthraquinone triads: synthesis, spectroscopy, and photochemistry.

    PubMed

    Giribabu, L; Reeta, P Silviya; Kanaparthi, Ravi Kumar; Srikanth, Malladi; Soujanya, Y

    2013-04-11

    Molecular triads based on bis(porphyrin)-anthraquinone having azomethine bridge at the pyrrole-β position have been designed and synthesized. Both free-base AQ-(H2)2 and zinc AQ-(Zn)2 triads are characterized by elemental analysis, MALDI-MS, (1)H NMR, UV-visible, and fluorescence spectroscopy (steady-state and time-resolved) as well as electrochemical method. The absorption spectra of both Soret and Q-bands of the triads are red-shifted by 12-20 nm with respect to their monomer units. The study supported by theoretical calculations manifests that there exists a negligible electronic communication in the ground state between the donor porphyrin and acceptor anthraquinone of these triads. However, interestingly, both the triads exhibit significant fluorescence emission quenching (51-92%) of the porphyrin emission compared to their monomeric units. The emission quenching is attributed to the excited-state intramolecular photoinduced electron transfer from porphyrins to anthraquinone. The electron-transfer rates (kET) of these triads are found in the range 1.0 × 10(8) to 7.7 × 10(9) s(-1) and are found to be solvent dependent.

  10. Potentiometric detection and removal of copper using porphyrins

    PubMed Central

    2013-01-01

    Background Copper is an essential trace element with a great importance in industry, environment and biological systems. The great advantage of ion-selective sensors in comparison with other proposed techniques is that they are measuring the free metal ion activity which is responsible for their toxicity. Porphyrins are known to be among the best ionophores in formulation of ion-selective sensors. Results A symmetrically substituted meso-porphyrin, namely: 5,10,15,20-tetrakis(4-allyloxyphenyl)porphyrin (TAPP) was used in the construction of a new copper selective-sensor and was also tested for the removal of copper from waste waters. The potentiometric response characteristics (slope and selectivity) of copper-selective electrodes based on TAPP in o-nitrophenyloctylether (o-NPOE), dioctyl phtalate (DOP) and dioctyl sebacate (DOS) plasticized with poly(vinyl chloride) membranes are compared. Conclusions The best results were obtained for the membrane plasticized with DOP. The sensor has linear response in the range 1x10-7 – 1x10-1 M with 28.4 ± 0.4 mV/decade near-Nernstian slope towards copper ions and presents good selectivity. Due to its chelating nature, the same porphyrin was also tested for the retention of copper from synthetic copper samples, showing a maximum adsorption capacity of 280 mg/g. PMID:23829792

  11. Porphyrin-Based Supramolecular Nanoarchitectures for Solar Energy Conversion.

    PubMed

    Hasobe, Taku

    2013-06-01

    Photofunctional molecular architectures with well-defined shapes and sizes are of great interest because of various applications such as photovoltaics, photocatalysis, and electronics. Porphyrins are promising building blocks for organized nanoscale superstructures, which perform many of the essential light-harvesting and photoinduced electron/energy transfer reaction. In this Perspective, we present the recent advances in supramolecular architectures of porphyrins for solar energy conversion. First, we state preparation and light energy conversion properties of porphyrin (donor: D) and fullerene (acceptor: A)-based composite spherical nanoassemblies. The interfacial control of D/A molecules based on our supramolecular strategy successfully demonstrates the drastic enhancement of light energy conversion properties as compared to the corresponding nonorganized systems. Then, bar-shaped structures composed of two different D and A molecules with separated inside and outside layers are discussed. This unusual rod formation shows a possibility for a novel zeolite-like photoreaction cavity with efficient visible light absorption. Finally, photophysical and phoelectrochemical properties of supramolecular composites between porphyrins and carbon naotubes/graphenes are briefly described. PMID:26283108

  12. Porphyrin involvement in redshift fluorescence in dentin decay

    NASA Astrophysics Data System (ADS)

    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.

  13. Modulation of Group I Ribozyme Activity by Cationic Porphyrins

    PubMed Central

    Matsumura, Shigeyoshi; Ito, Tatsunobu; Tanaka, Takahiro; Furuta, Hiroyuki; Ikawa, Yoshiya

    2015-01-01

    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. PMID:25811638

  14. Porphyrin Induced Laser Deactivation of Trypsinogen-Trypsin Conversion

    NASA Astrophysics Data System (ADS)

    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. Synthesis of metallic nanoshells on porphyrin-stabilized emulsions

    DOEpatents

    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.

  16. Hexamodal imaging with porphyrin-phospholipid-coated upconversion nanoparticles.

    PubMed

    Rieffel, James; Chen, Feng; Kim, Jeesu; Chen, Guanying; Shao, Wei; Shao, Shuai; Chitgupi, Upendra; Hernandez, Reinier; Graves, Stephen A; Nickles, Robert J; Prasad, Paras N; Kim, Chulhong; Cai, Weibo; Lovell, Jonathan F

    2015-03-11

    Hexamodal imaging using simple nanoparticles is demonstrated. Porphyrin-phospholipids are used to coat upconversion nanoparticles in order to generate a new biocompatible material. The nanoparticles are characterized in vitro and in vivo for imaging via fluorescence, upconversion, positron emission tomography, computed tomography, Cerenkov luminescence, and photoacoustic tomography.

  17. Highly fluorescent peptide nanoribbon impregnated with Sn-porphyrin as a potent DNA sensor.

    PubMed

    Parayil, Sreenivasan Koliyat; Lee, Jooran; Yoon, Minjoong

    2013-05-01

    Highly fluorescent and thermo-stable peptide nanoribbons (PNRs) were fabricated by solvothermal self-assembly of a single peptide (D,D-diphenyl alanine peptides) with Sn-porphyrin (trans-dihydroxo[5,10,15,20-tetrakis(p-tolyl)porphyrinato] Sn(IV) (SnTTP(OH)2)). The structural characterization of the as-prepared nanoribbons was performed by transmitting electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM), FT-IR and Raman spectroscopy, indicating that the lipophilic Sn-porphyrins are impregnated into the porous surface formed in the process of nanoribbon formation through intermolecular hydrogen bonding of the peptide main chains. Consequently the Sn-porphyrin-impregnated peptide nanoribbons (Sn-porphyrin-PNRs) exhibited typical UV-visible absorption spectrum of the monomer porphyrin with a red shifted Q-band, and their fluorescence quantum yield was observed to be enhanced compared to that of free Sn-porphyrin. Interestingly the fluorescence intensity and lifetimes of Sn-porphyrin-PNRs were selectively affected upon interaction with nucleotide base sequences of DNA while those of free Sn-porphyrins were not affected by binding with any of the DNA studied, indicating that DNA-induced changes in the fluorescence properties of Sn-porphyrin-PNRs are due to interaction between DNA and the PNR scaffold. These results imply that Sn-porphyrin-PNR will be useful as a potent fluorescent protein analogue and as a biocompatible DNA sensor.

  18. Electronic Structure and Dynamics of Nitrosyl Porphyrins

    PubMed Central

    Scheidt, W. Robert; Barabanschikov, Alexander; Pavlik, Jeffrey W.; Silvernail, Nathan J.; Sage, J. Timothy

    2010-01-01

    Nitric oxide (NO) is a signalling molecule employed to regulate essential physiological processes. Thus, there is great interest in understanding the interaction of NO with heme, which is found at the active site of many proteins that recognize NO, as well those involved in its creation and elimination. We summarize what we have learned from investigations of the structure, vibrational properties, and conformational dynamics of NO complexes with ferrous porphyrins, as well as computational investigations in support of these experimental studies. Multi-temperature crystallographic data reveals variations in the orientational disorder of the nitrosyl ligand. In some cases, equilibria among NO orientations can be analyzed using the vant Hoff relationship and the free energy and the enthalpy of the solid-state transitions evaluated experimentally. DFT calculations predict that intrinsic barriers to torsional rotations are smaller than thermal energies at physiological temperatures, and the coincidence of observed NO orientations with minima in molecular mechanics potentials indicates that nonbonded interactions with other chemical groups control the conformational freedom of the bound NO. In favorable cases, reduced disorder at low temperatures exposes subtle structural features including off-axis tilting of the Fe–NO bond and anisotropy of the equatorial Fe–N bonds. We also present the results of nuclear resonance vibrational spectroscopy (NRVS) measurements on oriented single crystals of [Fe(TPP)(NO)] and [Fe(TPP)(1-MeIm)(NO)]. These describe the anisotropic vibrational motion of Fe in five-and six-coordinate heme-NO complexes, and reveal vibrations of all Fe-ligand bonds as well as low frequency molecular distortions associated with the doming of the heme upon ligand binding. Quantitative comparison with predicted frequencies, amplitudes and directions facilitates identification of vibrational modes, but also suggests that commonly used DFT functionals are not

  19. Comparison of maturity based on steroid and vanadyl porphyrin parameters: A new vanadyl porphyrin maturity parameter for higher maturities

    NASA Astrophysics Data System (ADS)

    Sundararaman, Padmanabhan; Moldowan, J. Michael

    1993-03-01

    Correlations are demonstrated between steroid maturity parameters and the porphyrin maturity parameter (PMP) which is based on the ratio of specific vanadyl porphyrins C 28E /(C 28E + C 32D) measured by HPLC. Measurements from a global selection of > 100 rock extracts and oils show that PMP parallels changes in the C 29-sterane 20S/(20S + 20R) and tri/(tri + mono) aromatic steroid ratios, and that all three parameters appear to attain their maximum values at similar maturity levels. The triaromatic steroid side chain cracking parameter, TA I/(I + II), reaches approximately 20% of its maximum value when PMP has reached 100%. These results suggest that PMP is effective in the early to peak portion of the oil window. A new parameter, PMP-2, based on changes in the relative concentrations of two peaks in the HPLC fingerprint (vanadyl "etio" porphyrins), appears effective in assessing the maturity of source rocks beyond peak oil generation. In combination with PMP this parameter extends the effective range of vanadyl porphyrins parameters to higher maturities as demonstrated by a suite of oils from the Oriente Basin, Ecuador, South America.

  20. Exogenous delta-animolevulinic acid induces the porphyrin biosynthesis in human skin organ cultures with different porphyrin patterns in normal and malignant human tissue

    NASA Astrophysics Data System (ADS)

    Fritsch, Clemens; Batz, Janine; Bolsen, Klaus; Schulte, Klaus; Ruzicka, Thomas; Goerz, Guenter

    1995-03-01

    The carboxylation state of porphyrin metabolites causes their hydrophilic or lipophilic properties and subsequently their distribution in tissues, cells, and subcellular compartments. The profile of porphyrin metabolites either in normal skin or in malignant skin tumors after administration of (delta) -aminolevulinic acid has been studied in detail, yet. Explant cultures of normal skin and neoplastic tissues, e.g., keratoakanthoma and basal cell carcinoma, were incubated with 1 mM ALA for 36 h. Total porphyrin concentration and percentage of porphyrin metabolites were determined quantitatively in tissues and corresponding supernatants. Seventy - ninety percent of total porphyrins could be detected in the supernatants of all samples. The highly carboxylated porphyrins were the prevailing metabolites in the supernatants as well as in the tissues. The basal cell carcinoma produced significantly more protoporphyrin and the keratoakanthoma significantly more coproporphyrin as compared to normal skin. The results show that explant cultures offer an easy approach to examine the enzymatic capacity in porphyrin biosynthesis of various tissues. Benign and malignant human tissues produce different porphyrin metabolites, which may be useful for selective and more effective photodynamic diagnosis or therapy.

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

    PubMed Central

    Li, Xing-Yu; Zhang, Cai-Rong; Wu, You-Zhi; Zhang, Hai-Min; Wang, Wei; Yuan, Li-Hua; Yang, Hua; Liu, Zi-Jiang; Chen, Hong-Shan

    2015-01-01

    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. PMID:26610469

  2. Loss of halogens from crystallized and glassy silicic volcanic rocks

    USGS Publications Warehouse

    Noble, D.C.; Smith, V.C.; Peck, L.C.

    1967-01-01

    One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

  3. Glassy correlations and thermal fluctuations in nematic elastomers

    NASA Astrophysics Data System (ADS)

    Lu, Bing; Xing, Xiangjun; Ye, Fangfu; Goldbart, Paul

    2010-03-01

    By means of the vulcanization theory framework we address the properties of nematic elastomers prepared in the isotropic liquid state and subsequently randomly cross-linked beyond the gelation point. We base our analysis on a model replica Landau free energy, in which the vulcanization order parameter is coupled to the order parameter describing the local degree of nematic ordering, retaining fluctuation terms to the Gaussian level. We explore how the cross-linking renormalizes the thermal correlations of the local nematic order, and also results in frozen-in, glassy nematic correlations. We examine these thermal and glassy correlations for two different preparation histories of the system: in the first, the cross-linking is done at temperatures close to the isotropic-nematic transition; in the other, the cross-linking is done at higher temperatures, but the system is subsequently cooled to near this transition temperature.

  4. Understanding soft glassy materials using an energy landscape approach

    NASA Astrophysics Data System (ADS)

    Hwang, Hyun Joo; Riggleman, Robert A.; Crocker, John C.

    2016-09-01

    Many seemingly different soft materials--such as soap foams, mayonnaise, toothpaste and living cells--display strikingly similar viscoelastic behaviour. A fundamental physical understanding of such soft glassy rheology and how it can manifest in such diverse materials, however, remains unknown. Here, by using a model soap foam consisting of compressible spherical bubbles, whose sizes slowly evolve and whose collective motion is simply dictated by energy minimization, we study the foam's dynamics as it corresponds to downhill motion on an energy landscape function spanning a high-dimensional configuration space. We find that these downhill paths, when viewed in this configuration space, are, surprisingly, fractal. The complex behaviour of our model, including power-law rheology and non-diffusive bubble motion and avalanches, stems directly from the fractal dimension and energy function of these paths. Our results suggest that ubiquitous soft glassy rheology may be a consequence of emergent fractal geometry in the energy landscapes of many complex fluids.

  5. 2H NMR studies of supercooled and glassy aspirin

    NASA Astrophysics Data System (ADS)

    Nath, R.; Nowaczyk, A.; Geil, B.; Bohmer, R.

    2007-11-01

    Acetyl salicylic acid, deuterated at the methyl group, was investigated using 2H-NMR in its supercooled and glassy states. Just above the glass transition temperature the molecular reorientations were studied using stimulated-echo spectroscopy and demonstrated a large degree of similarity with other glass formers. Deep in the glassy phase the NMR spectra look similar to those reported for the crystal [A. Detken, P. Focke, H. Zimmermann, U. Haeberlen, Z. Olejniczak, Z. T. Lalowicz, Z. Naturforsch. A 50 (1995) 95] and below 20 K they are indicative for rotational tunneling with a relatively large tunneling frequency. Measurements of the spin-lattice relaxation times for temperatures below 150 K reveal a broad distribution of correlation times in the glass. The dominant energy barrier characterizing the slow-down of the methyl group is significantly smaller than the well defined barrier in the crystal.

  6. Understanding soft glassy materials using an energy landscape approach.

    PubMed

    Hwang, Hyun Joo; Riggleman, Robert A; Crocker, John C

    2016-09-01

    Many seemingly different soft materials-such as soap foams, mayonnaise, toothpaste and living cells-display strikingly similar viscoelastic behaviour. A fundamental physical understanding of such soft glassy rheology and how it can manifest in such diverse materials, however, remains unknown. Here, by using a model soap foam consisting of compressible spherical bubbles, whose sizes slowly evolve and whose collective motion is simply dictated by energy minimization, we study the foam's dynamics as it corresponds to downhill motion on an energy landscape function spanning a high-dimensional configuration space. We find that these downhill paths, when viewed in this configuration space, are, surprisingly, fractal. The complex behaviour of our model, including power-law rheology and non-diffusive bubble motion and avalanches, stems directly from the fractal dimension and energy function of these paths. Our results suggest that ubiquitous soft glassy rheology may be a consequence of emergent fractal geometry in the energy landscapes of many complex fluids. PMID:27322823

  7. Glassy states in fermionic systems with strong disorder and interactions

    NASA Astrophysics Data System (ADS)

    Schwab, David J.; Chakravarty, Sudip

    2009-03-01

    We study the competition between interactions and disorder in two dimensions. Whereas a noninteracting system is always Anderson localized by disorder in two dimensions, a pure system can develop a Mott gap for sufficiently strong interactions. Within a simple model, with short-ranged repulsive interactions, we show that, even in the limit of strong interaction, the Mott gap is completely washed out by disorder for an infinite system for dimensions D≤2 , leading to a glassy state. Moreover, the Mott insulator cannot maintain a broken symmetry in the presence of disorder. We then show that the probability of a nonzero gap as a function of system size falls onto a universal curve, reflecting the glassy dynamics. An analytic calculation is also presented in one dimension that provides further insight into the nature of slow dynamics.

  8. Microscale determination of the spectral characteristics and carbon-isotopic compositions of porphyrins

    NASA Technical Reports Server (NTRS)

    Popp, B. N.; Hayes, J. M.; Boreham, C. J.

    1993-01-01

    Molar extinction coefficients for band III of Ni porphyrins are calculated from results of spectrophotometric and manometric analyses of individual etioporphyrins, DPEP, cyclic, and diDPEP porphyrins known to initially be pure from mass spectrometry, 1H NMR, and analytical HPLC studies. A method for determining carbon-isotopic compositions and purity of micromolar quantities of individual porphyrins using combined spectrophotometric and manometric techniques is presented.

  9. Localization and Glassy Dynamics in the Immune System

    NASA Astrophysics Data System (ADS)

    Sun, Jun; Earl, David J.; Deem, Michael W.

    We discuss use of the generalized NK model to examine evolutionary dynamics within the immune system. We describe how randomness and diversity play key roles in the immune response and how their effects are captured by this hierarchical spin glass model. We discuss analytical aspects of the model as well as practical applications to design of the annual influenza vaccine. We discuss the subtle role that the glassy evolutionary dynamics plays in suppressing autoimmune disease.

  10. Three-dimensionally arranged windmill and grid porphyrin arrays by AgI-promoted meso-meso block oligomerization

    PubMed

    Nakano; Yamazaki; Nishimura; Yamazaki; Osuka

    2000-09-01

    The syntheses of soluble windmill and grid porphyrin arrays through the AgI-promoted coupling reaction of 1,4-phenylene-bridged linear porphyrin arrays, which are comprised of a central ZnII beta-free porphyrin and flanking peripheral NiII beta-octaalkylporphyrins, are described. The coupling reaction is advantageous in light of its high regioselectivity occurring only at the meso-position of the ZnII beta-free porphyrin as well as its easy extension to large porphyrin arrays. The windmill porphyrin arrays in turn serve as an effective substrate for further coupling reactions, to give three-dimensionally arranged grid porphyrin arrays. Further the grid porphyrin 12-mer (a tetramer of the linear porphyrin trimer) was also coupled to afford grid porphyrins (24-mer, 36-mer, and 48-mer). These porphyrin arrays were isolated in a discrete form by repetitive GPC/HPLC (GPC= gel-permiation chromatography). Competitive experiments with three linear porphyrin trimers bearing different peripheral metalloporphyrins (ZnII, NiII, and Cull), and the trapping experiment of the radical cation at the peripheral porphyrin with AgNO2, suggested that an initial one-electron oxidation of the easily oxidizable peripheral ZnII beta-octaalkylporphyrin with an AgI ion and a subsequent endothermic hole transfer assist the generation of the radical cation at the central ZnII beta-free porphyrin. In all ZnII-metallated windmill porphyrin arrays, the energy level of the S1 state of the meso-meso-linked diporphyrin core is lower than that of the peripheral porphyrins, thereby allowing an energy flow from the peripheral porphyrins to the central diporphyrin core; this has been confirmed by measurements of fluorescence lifetimes and picosecond time-resolved fluorescence spectra. The excitation energy transfer in the arrays encourages their potential use as an light-harvesting antenna.

  11. Yield Stress Enhancement in Glassy-Polyethylene Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Polyethylene (PE) has the highest annual production volume of all synthetic polymers worldwide, and is valuable across many applications due to its low cost, toughness, processability, and chemical resistance. However, PE is not well suited to certain applications due to its modest yield stress and Young's modulus (approximately 30 MPa and 1 GPa, respectively for linear, high-density PE). Irreversible deformation of PE results from dislocation of crystal stems and eventual crystal fragmentation under applied stress. The liquid-like amorphous fraction provides no useful mechanical support to the crystal fold surface in a PE homopolymer, so the only method to enhance the force required for crystal slip, and hence the yield stress, is crystal thickening via thermal treatment. An alternative route towards modifying the mechanical properties of PE involves copolymerization of a minority high-glass transition temperature block into a majority-PE block copolymer. In this work, we investigate a system of glassy/linear-PE block copolymers prepared via ring-opening metathesis polymerization of cyclopentene and substituted norbornene monomers followed by hydrogenation. We demonstrate that a large change in mechanical properties can be achieved with the addition of a short glassy block (e.g. a doubling of the yield stress and Young's modulus versus PE homopolymer with the addition of 25 percent glassy block). Furthermore, owing to the low interaction energy between PE and the substituted polynorbornene blocks employed, these high-yield PE block copolymers can exhibit single-phase melts for ease of processability.

  12. Non-Equilibrium Water-Glassy Polymer Dynamics

    NASA Astrophysics Data System (ADS)

    Davis, Eric; Minelli, Matteo; Baschetti, Marco; Sarti, Giulio; Elabd, Yossef

    2012-02-01

    For many applications (e.g., medical implants, packaging), an accurate assessment and fundamental understanding of the dynamics of water-glassy polymer interactions is of great interest. In this study, sorption and diffusion of pure water in several glassy polymers films, such as poly(styrene) (PS), poly(methyl methacrylate) (PMMA), poly(lactide) (PLA), were measured over a wide range of vapor activities and temperatures using several experimental techniques, including quartz spring microbalance (QSM), quartz crystal microbalance (QCM), and time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Non-Fickian behavior (diffusion-relaxation phenomena) was observed by all three techniques, while FTIR-ATR spectroscopy also provides information about the distribution of the states of water and water transport mechanisms on a molecular-level. Specifically, the states of water are significantly different in PS compared to PMMA and PLA. Additionally, a purely predictive non-equilibrium lattice fluid (NELF) model was applied to predict the sorption isotherms of water in these glassy polymers.

  13. Exploration for facultative endosymbionts of glassy-wingedsharpshooter (Hemiptera: Cicadellidae)

    SciTech Connect

    Montllor-Curley, C.; Brodie, E.L.; Lechner, M.G.; Purcell, A.H.

    2006-07-01

    Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae),glassy-winged sharpshooter, was collected in California and severalstates in the southeastern United States in 2002 and 2003 and analyzedfor endosymbiotic bacteria. Hemolymph, eggs, and bacteriomes wereexamined for the presence of bacteria by polymerase chain reaction. Asubset of hemolymph and egg samples had their 16S rRNA gene ampliconscloned and sequenced or analyzed by restriction digest patterns ofsamples compared with known bacterial DNA. Baumannia cicadellinicola, oneof the primary symbionts of glassy-winged sharpshooter, was found in themajority of hemolymph samples, although it has been considered until nowto reside primarily inside the specialized host bacteriocytes. Wolbachiasp., a common secondary symbiont in many insect taxa investigated todate, was the second most frequently detected bacterium in hemolymphsamples. In addition, we detected bacteria that were most closely related(by 16S rRNA gene sequence) to Pseudomonas, Stenotrophomonas, andAcinetobacter in hemolymph samples of one and/or two glassy-wingedsharpshooters, but their origin is uncertain.

  14. Thermodynamics of Water Sorption in High Performance Glassy Thermoplastic Polymers

    NASA Astrophysics Data System (ADS)

    Mensitieri, Giuseppe; Scherillo, Giuseppe; Petretta, Mauro; Galizia, Michele; La Manna, Pietro; Musto, Pellegrino

    2014-05-01

    Sorption thermodynamics of water in two glassy polymers, polyetherimide (PEI) and polyetheretherketone (PEEK), is investigated by coupling gravimetry and on line FTIR spectroscopy in order to gather information on the total amount of sorbed water as well as on the different species of water molecules absorbed within the polymers, addressing the issue of cross- and self-interactions occurring in the polymer/water systems. Water sorption isotherms have been determined at temperatures ranging fro 30 to 70°C while FTIR spectroscopy has been performed only at 30°C. The experimental analysis provided information on the groups present on the polymer backbones involved in hydrogen bonding interactions with absorbed water molecules. Moreover, it also supplied qualitative indications about the different’populations’ of water molecules present within the PEEK and a quantitative assessment of these ‘populations’ in the case of PEI.The results of the experimental analysis have been interpreted using an equation of state theory based on a compressible lattice fluid model for the Gibbs energy of the polymer-water mixture, developed by extending to the case of out of equilibrium glassy polymers a previous model intended for equilibrium rubbery polymers. The model accounts for the non equilibrium nature of glassy poymers as well as for mean field and for hydrogen bonding interactions, providing a satisfactory quantitative interpretation of the experimental data.

  15. Quantifying glassy and crystalline basalt partitioning in the oceanic crust

    NASA Astrophysics Data System (ADS)

    Moore, Rachael; Ménez, Bénédicte

    2016-04-01

    The upper layers of the oceanic crust are predominately basaltic rock, some of which hosts microbial life. Current studies of microbial life within the ocean crust mainly focus on the sedimentary rock fraction, or those organisms found within glassy basalts while the potential habitability of crystalline basalts are poorly explored. Recently, there has been recognition that microbial life develops within fractures and grain boundaries of crystalline basalts, therefore estimations of total biomass within the oceanic crust may be largely under evaluated. A deeper understanding of the bulk composition and fractionation of rocks within the oceanic crust is required before more accurate estimations of biomass can be made. To augment our understanding of glassy and crystalline basalts within the oceanic crust we created two end-member models describing basalt fractionation: a pillow basalt with massive, or sheet, flows crust and a pillow basalt with sheeted dike crust. Using known measurements of massive flow thickness, dike thickness, chilled margin thickness, pillow lava size, and pillow lava glass thickness, we have calculated the percentage of glassy versus crystalline basalts within the oceanic crust for each model. These models aid our understanding of textural fractionation within the oceanic crust, and can be applied with bioenergetics models to better constrain deep biomass estimates.

  16. Fast algorithms for glassy materials: methods and explorations

    NASA Astrophysics Data System (ADS)

    Middleton, A. Alan

    2014-03-01

    Glassy materials with frozen disorder, including random magnets such as spin glasses and interfaces in disordered materials, exhibit striking non-equilibrium behavior such as the ability to store a history of external parameters (memory). Precisely due to their glassy nature, direct simulation of models of these materials is very slow. In some fortunate cases, however, algorithms exist that exactly compute thermodynamic quantities. Such cases include spin glasses in two dimensions and interfaces and random field magnets in arbitrary dimensions at zero temperature. Using algorithms built using ideas developed by computer scientists and mathematicians, one can even directly sample equilibrium configurations in very large systems, as if one picked the configurations out of a ``hat'' of all configurations weighted by their Boltzmann factors. This talk will provide some of the background for these methods and discuss the connections between physics and computer science, as used by a number of groups. Recent applications of these methods to investigating phase transitions in glassy materials and to answering qualitative questions about the free energy landscape and memory effects will be discussed. This work was supported in part by NSF grant DMR-1006731. Creighton Thomas and David Huse also contributed to much of the work to be presented.

  17. Three-dimensional jamming and flows of soft glassy materials.

    PubMed

    Ovarlez, G; Barral, Q; Coussot, P

    2010-02-01

    Various disordered dense systems, such as foams, gels, emulsions and colloidal suspensions, undergo a jamming transition from a liquid state (they flow) to a solid state below a yield stress. Their structure, which has been thoroughly studied with powerful means of three-dimensional characterization, shows some analogy with that of glasses, which led to them being named soft glassy materials. However, despite its importance for geophysical and industrial applications, their rheological behaviour, and its microscopic origin, is still poorly known, in particular because of its nonlinear nature. Here we show from two original experiments that a simple three-dimensional continuum description of the behaviour of soft glassy materials can be built. We first show that when a flow is imposed in some direction there is no yield resistance to a secondary flow: these systems are always unjammed simultaneously in all directions of space. The three-dimensional jamming criterion seems to be the plasticity criterion encountered in most solids. We also find that they behave as simple liquids in the direction orthogonal to that of the main flow; their viscosity is inversely proportional to the main flow shear rate, as a signature of shear-induced structural relaxation, in close similarity to the structural relaxations driven by temperature and density in other glassy systems. PMID:20062046

  18. Magnetoresistance, electrical conductivity, and Hall effect of glassy carbon

    SciTech Connect

    Baker, D.F.

    1983-02-01

    These properties of glassy carbon heat treated for three hours between 1200 and 2700/sup 0/C were measured from 3 to 300/sup 0/K in magnetic fields up to 5 tesla. The magnetoresistance was generally negative and saturated with reciprocal temperature, but still increased as a function of magnetic field. The maximum negative magnetoresistance measured was 2.2% for 2700/sup 0/C material. Several models based on the negative magnetoresistance being proportional to the square of the magnetic moment were attempted; the best fit was obtained for the simplest model combining Curie and Pauli paramagnetism for heat treatments above 1600/sup 0/C. Positive magnetoresistance was found only in less than 1600/sup 0/C treated glassy carbon. The electrical conductivity, of the order of 200 (ohm-cm)/sup -1/ at room temperature, can be empirically written as sigma = A + Bexp(-CT/sup -1/4) - DT/sup -1/2. The Hall coefficient was independent of magnetic field, insensitive to temperature, but was a strong function of heat treatment temperature, crossing over from negative to positive at about 1700/sup 0/C and ranging from -0.048 to 0.126 cm/sup 3//coul. The idea of one-dimensional filaments in glassy carbon suggested by the electrical conductivity is compatible with the present consensus view of the microstructure.

  19. π-Extended "Earring" Porphyrins with Multiple Cavities and Near-Infrared Absorption.

    PubMed

    Rao, Yutao; Kim, Taeyeon; Park, Kyu Hyung; Peng, Fulei; Liu, Lei; Liu, Yunmei; Wen, Bin; Liu, Shubin; Kirk, Steven Robert; Wu, Licheng; Chen, Bo; Ma, Ming; Zhou, Mingbo; Yin, Bangshao; Zhang, Yuexing; Kim, Dongho; Song, Jianxin

    2016-05-23

    β,β-tripyrrin-bridged earring porphyrins were synthesized through Suzuki-Miyaura cross coupling reactions. These porphyrinoids have multiple cavities and can accommodate two or three metal ions per molecule. The structures of the porphyrins have been elucidated by x-ray diffraction analysis, and feature curved π planes. The electronic spectra of the porphyrins exhibit near-infrared (NIR) absorptions and metal insertion leads to red-shifted and intensified absorption features. Electrochemical analysis and transient absorption measurements indicated that the porphyrins exhibit effective electronic communication between their central and peripheral moieties. PMID:27038255

  20. Synthesis of supramolecular fullerene-porphyrin-Cu(phen)(2)-ferrocene architectures. A heteroleptic approach towards tetrads.

    PubMed

    Schmittel, Michael; Kishore, Ravuri S K; Bats, Jan W

    2007-01-01

    Four supramolecular fullerene-porphyrin-Cu(phen)(2)-ferrocene architectures were accessed by a twofold coordination strategy. At first, the phenanthroline-linked zinc porphyrins , conceived as supramolecular synthons, were combined with a ferrocene module, 3,8-(diferrocenylethynyl)phenanthroline, by a Cu(i)-mediated heteroleptic bisphenanthroline complexation (HETPHEN) protocol to furnish the porphyrin-Cu(phen)(2)-ferrocene aggregates . Subsequently, the fullerene module was incorporated by axial pyridyl coordination to the zinc porphyrin, affording . Their suitability as tetrads was interrogated using electrochemical and photophysical data.

  1. Template-directed synthesis of flexible porphyrin nanocage and nanorings via one-step olefin metathesis.

    PubMed

    Zhu, Bin; Chen, Huanxin; Lin, Wei; Ye, Yang; Wu, Jing; Li, Shijun

    2014-10-29

    We describe the fabrication of a suite of flexible porphyrin cages and nanorings from a simple tetraalkene-derived zinc porphyrin monomer via a highly efficient template-directed strategy. The zinc porphyrin monomers were preorganized together by coordination with N atoms of multidentate ligands. Subsequent one-step olefin metathesis furnished a bisporphyrin cage, a triporphyrin nanoring, and a hexaporphyrin nanoring. In the case of the hexaporphyrin nanoring, 24 terminal olefins from six porphyrin monomers reacted with each other to form 12 new double bonds, delivering the final product. The triporphyrin and hexaporphyrin nanorings were further employed as hosts to encapsulate C60 and C70. PMID:25303609

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

    SciTech Connect

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

    1988-01-01

    Several chemical methods are available for the solubilization of boronated porphyrins. We have previously reported the tumor localization of nido carboranyl porphyrins in which the icosahedral carborane cages have been opened to give B/sub 9/C/sub 2/ anions. One of these species has shown tumor boron levels of nearly 50 ..mu..g 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.

  3. Template-directed synthesis of flexible porphyrin nanocage and nanorings via one-step olefin metathesis.

    PubMed

    Zhu, Bin; Chen, Huanxin; Lin, Wei; Ye, Yang; Wu, Jing; Li, Shijun

    2014-10-29

    We describe the fabrication of a suite of flexible porphyrin cages and nanorings from a simple tetraalkene-derived zinc porphyrin monomer via a highly efficient template-directed strategy. The zinc porphyrin monomers were preorganized together by coordination with N atoms of multidentate ligands. Subsequent one-step olefin metathesis furnished a bisporphyrin cage, a triporphyrin nanoring, and a hexaporphyrin nanoring. In the case of the hexaporphyrin nanoring, 24 terminal olefins from six porphyrin monomers reacted with each other to form 12 new double bonds, delivering the final product. The triporphyrin and hexaporphyrin nanorings were further employed as hosts to encapsulate C60 and C70.

  4. The bronze baby syndrome: evidence of increased tissue concentration of copper porphyrins.

    PubMed

    Rubaltelli, F F; Da Riol, R; D'Amore, E S; Jori, G

    1996-03-01

    A case regarding a newborn infant with severe Rh haemolytic disease, who presented with the bronze baby syndrome and eventually died, is reported. The postmortem examination showed marked extramedullary haematopoiesis in the liver and spleen, heavy hepatic haemosiderosis and mild intralobular cholestasis. The porphyrin content, which was assayed in different tissues, was very high in the liver, suggesting that the increased erythropoiesis seen in Rh haemolytic disease leads to an increased synthesis of porphyrins as by-products of haem synthesis. Phototherapy causes photodestruction, sensitized by bilirubin, of porphyrins (mainly copper porphyrins), yielding brown photoproducts.

  5. Binding of porphyrins by the tumor-specific lectin, jacalin [Jack fruit (Artocarpus integrifolia) agglutinin].

    PubMed

    Komath, S S; Bhanu, K; Maiya, B G; Swamy, M J

    2000-08-01

    Jacalin (Artocarpus integrifolia agglutinin) specifically recognizes the tumor-associated T-antigenic disaccharide structure, Gal beta13GalNAc. Porphyrins and their derivatives are currently used as photosensitizers in photodynamic therapy to treat malignant tumors. In this study, the interaction of several free base porphyrins and their metal derivatives with jacalin is investigated by absorption and fluorescence spectroscopy. Each lectin subunit was found to bind one porphyrin molecule and the association constants were estimated to be in the range of 2.4 x 10(3) M(-1) to 1.3 x 10(5) M(-1) at room temperature for the interaction of different porphyrins with jacalin. These values are in the same range as those obtained for the interaction of monosaccharides to jacalin. Both free lectin and lectin saturated with the specific saccharide were found to bind different porphyrins with comparable binding strength indicating that porphyrin binding takes place at a site different from the sugar binding site. Further, both anionic and cationic porphyrins were found to interact with the lectin with comparable affinity, clearly indicating that the charge on the porphyrin does not play any role in the binding process and that most likely the interaction is mediated by hydrophobic forces. These results suggest that jacalin and other lectins may potentially be useful for targeted delivery of porphyrins to tumor tissues in photodynamic therapy.

  6. Porphyrin fluorescence dominates UV photoemission of folded cytochrome c.

    PubMed

    Löwenich, Dennis; Kleinermanns, Karl

    2007-01-01

    In this article we reinvestigate the bimodal fluorescence of cytochrome c (Cyt c) by using excitation-wavelength-dependent fluorescence spectroscopy. We show that its major contributions at pH 3-7 do not arise from tryptophan (Trp-59) fluorescence as hitherto assumed. Instead, different chromophores of Cyt c contribute at different pH values. At pH 3-7, the porphyrin system contributes about 80% and tryptophan about 20% to the total fluorescence upon excitation of Cyt c at 280 nm. At pH 2, the fluorescence originates nearly completely from the tryptophan residue. Porphyrin fluorescence is still present at pH 2 but its contribution is too small for quantitative deconvolution. Our results show that the UV fluorescence of Cyt c has to be deconvoluted before it can be used to perform time-resolved measurements of the folding of this small protein.

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

    NASA Astrophysics Data System (ADS)

    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).

  8. Controlled templating of porphyrins by a molecular command layer.

    PubMed

    den Boer, Duncan; Habets, Thomas; Coenen, Michiel J J; van der Maas, Minko; Peters, Theo P J; Crossley, Maxwell J; Khoury, Tony; Rowan, Alan E; Nolte, Roeland J M; Speller, Sylvia; Elemans, Johannes A A W

    2011-03-15

    The copper porphyrin (5,10,15,20-tetraundecylporphyrinato)copper(II) can be templated in a well-defined arrangement using p-(hexadecyloxycarbonyl)phenylacetylene as a command layer on graphite. The bicomponent system was characterized at the submolecular level at a solid/liquid interface by scanning tunneling microscopy (STM). It is proposed that the layer of copper porphyrins is templated on top of the command layer in a hierarchical fashion, via a combination of intermolecular π-π stacking and van der Waals interactions. A very subtle effect, i.e., a superstructure in the alkyl chain region of the phenylacetylene monolayers, was identified as a decisive factor for the templating process.

  9. Enhanced solar energy collection in porphyrin based photoconversion schemes

    NASA Astrophysics Data System (ADS)

    Gust, D.; Moore, T. A.

    1983-02-01

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

  10. Investigation of glassy state molecular motions in thermoset polymers

    NASA Astrophysics Data System (ADS)

    Tu, Jianwei

    This dissertation presents the investigation of the glassy state molecular motions in isomeric thermoset epoxies by means of solid-state deuterium (2H) NMR spectroscopy technique. The network structure of crosslinked epoxies was altered through monomer isomerism; specifically, diglycidyl ether of bisphenol A (DGEBA) was cured with isomeric amine curatives, i.e., the meta-substituted diaminodiphenylsulfone (33DDS) and para-substituted diaminodiphenylsulfone (44DDS). The use of structural isomerism provided a path way for altering macroscopic material properties while maintaining identical chemical composition within the crosslinked networks. The effects of structural isomerism on the glassy state molecular motions were studied using solid-state 2H NMR spectroscopy, which offers unrivaled power to monitor site-specific molecular motions. Three distinctive molecular groups on each isomeric network, i.e., the phenylene rings in the bisphenol A structure (BPA), the phenylene rings in the diaminodiphenylsulfone structure (DDS), and the hydroxypropoyl ether group (HPE) have been selectively deuterated for a comprehensive study of the structure-dynamics- property relationships in thermoset epoxies. Quadrupolar echo experiments and line shape simulations were employed as the main research approach to gain both qualitative and quantitative motional information of the epoxy networks in the glassy state. Quantitative information on the geometry and rate of the molecular motions allows the elucidation of the relationship between molecular motions and macro physical properties and the role of these motions in the mechanical relaxation. Specifically, it is revealed that both the BPA and HPE moieties in the isomeric networks have almost identical behaviors in the deep glassy state, which indicates that the molecular motions in the glassy state are localized, and the correlation length of the motions does not exceed the length of the DGEBA repeat unit. BPA ring motions contribute

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

    NASA Astrophysics Data System (ADS)

    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.

  12. A single crystalline porphyrinic titanium metal–organic framework

    SciTech Connect

    Yuan, Shuai; Liu, Tian -Fu; Feng, Dawei; Tian, Jian; Wang, Kecheng; Qin, Junsheng; Zhang, Qiang; Chen, Ying -Pin; Bosch, Mathieu; Zou, Lanfang; Teat, Simon J.; Dalgarno, Scott J.; Zhou, Hong -Cai

    2015-04-28

    We successfully assembled the photocatalytic titanium-oxo cluster and photosensitizing porphyrinic linker into a metal–organic framework (MOF), namely PCN-22. A preformed titanium-oxo carboxylate cluster is adopted as the starting material to judiciously control the MOF growth process to afford single crystals. This synthetic method is useful to obtain highly crystalline titanium MOFs, which has been a daunting challenge in this field. Moreover, PCN-22 demonstrated permanent porosity and photocatalytic activities toward alcohol oxidation.

  13. Potential use of radiolabelled porphyrins for tumor scanning

    SciTech Connect

    Thaller, R.A.; Lyster, D.M.; Dolphin, D.

    1983-01-01

    Fe-TMPI, Fe-TCP and protohemins showed high initial uptake using tissue culture techniques with mouse tumor cells (P815). However, the tumor uptake in the in vivo model was poor. Of the radionuclides investigated, iron labelled to TMPI demonstrated the best uptake by tumor in vitro. As has been previously demonstrated, the unnatural meso-arylporphyrin derivatives showed better uptake than did naturally occurring porphyrins and their derivatives.

  14. Quantitative vibrational dynamics of iron in nitrosyl porphyrins.

    PubMed

    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.

  15. Cobalt(III) porphyrin catalyzed aza-Diels-Alder reaction.

    PubMed

    Wakabayashi, Ryota; Kurahashi, Takuya; Matsubara, Seijiro

    2012-09-21

    An efficient protocol for the aza-Diels-Alder reaction of electron-deficient 1,3-dienes with unactivated imines in the presence of a cationic cobalt(III) porphyrin complex was developed. The transformation proceeded smoothly to afford the desired piperidine scaffold within 2 h at ambient temperature. Highly chemoselective cycloaddition of imines with dienes in the presence of a variety of carbonyl compounds was also demonstrated.

  16. Active-Site-Accessible, Porphyrinic Metal;#8722;Organic Framework Materials

    SciTech Connect

    Farha, Omar K.; Shultz, Abraham M.; Sarjeant, Amy A.; Nguyen, SonBinh T.; Hupp, Joseph T.

    2012-02-06

    On account of their structural similarity to cofactors found in many metallo-enzymes, metalloporphyrins are obvious potential building blocks for catalytically active, metal-organic framework (MOF) materials. While numerous porphyrin-based MOFs have already been described, versions featuring highly accessible active sites and permanent microporosity are remarkably scarce. Indeed, of the more than 70 previously reported porphyrinic MOFs, only one has been shown to be both permanently microporous and contain internally accessible active sites for chemical catalysis. Attempts to generalize the design approach used in this single successful case have failed. Reported here, however, is the synthesis of an extended family of MOFs that directly incorporate a variety of metalloporphyrins (specifically Al{sup 3+}, Zn{sup 2+}, Pd{sup 2+}, Mn{sup 3+}, and Fe{sup 3+} complexes). These robust porphyrinic materials (RPMs) feature large channels and readily accessible active sites. As an illustrative example, one of the manganese-containing RPMs is shown to be catalytically competent for the oxidation of alkenes and alkanes.

  17. Plasmon enhanced photoconduction in porphyrin-gold nanoparticle assemblies

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  19. Galactodendritic porphyrinic conjugates as new biomimetic catalysts for oxidation reactions.

    PubMed

    Castro, Kelly A D F; Silva, Sandrina; Pereira, Patrícia M R; Simões, Mário M Q; Neves, Maria da Graça P M S; Cavaleiro, José A S; Wypych, Fernando; Tomé, João P C; Nakagaki, Shirley

    2015-05-01

    This work employed [5,10,15,20-tetrakis(pentafluorophenyl)porphyrin] ([H2(TPPF20)], H2P1) as the platform to prepare a tetrasubstituted galactodendritic conjugate porphyrin (H2P3). After metalation with excess copper(II) acetate, H2P3 afforded a new solid porphyrin material, Cu4CuP3S. This work also assessed the ability of the copper(II) complex (CuP3) of H2P3 to coordinate with zinc(II) acetate, to yield the new material Zn4CuP3S. UV-visible, Fourier transform infrared, and electron paramagnetic resonance spectroscopies aided full characterization of the synthesized solids. (Z)-Cyclooctene epoxidation under heterogeneous conditions helped to evaluate the catalytic activity of Cu4CuP3S and Zn4CuP3S. The efficiency of Cu4CuP3S in the oxidation of another organic substrate, catechol, was also investigated. According to the results obtained in the heterogeneous process, Cu4CuP3S mimicked the activity of cytochrome P-450 and catecholase. In addition, Cu4CuP3S was reusable after recovery and reactivation. The data obtained herein were compared with the results achieved for the copper complex (CuP1) of [H2(TPPF20)] and for CuP3 under homogeneous conditions.

  20. Siamese-Twin Porphyrin Origami: Oxidative Fusing and Folding.

    PubMed

    Vogel, Anastasia; Dechert, Sebastian; John, Michael; Brückner, Christian; Meyer, Franc

    2016-02-12

    Oxidation of a nonaromatic Siamese-twin porphyrin, a pyrazole-containing expanded porphyrin with two porphyrinlike binding pockets, with a stoichiometric amount of the two-electron, two-proton oxidizing agent 2,3-dichloro-5,6-dicyano-1,4-benzochinone led to the formation of a single N(pz) -C(o-Ph) linkage between the pyrazole unit with a neighboring meso-phenyl group, forming a pyrazolo- [1,5-a]indole moiety. Repeated treatment with a second equivalent of the oxidant yielded a doubly N-fused species, involving the second pyrazole moiety. The conversion products were characterized by variable-temperature and multinuclear 1D and 2D NMR spectroscopy. The fusions strongly alter the conformation of the macrocycles, as shown by X-ray diffraction analyses of all three compounds, eventually leading to a folded structure. UV/Vis and NMR-spectroscopic investigations indicated the presence of highly delocalized but nonmacrocycle-aromatic π systems. This behavior of the Siamese-twin porphyrin in response to oxidation is in contrast to the behavior of related all-pyrrole-based expanded macrocycles that switch, by redox processes and protonation, between Hückel and Möbius aromatic states. PMID:26670580

  1. Crystallization of the glassy grain boundary phase in silicon nitride ceramics

    NASA Technical Reports Server (NTRS)

    Drummond, Charles H., III

    1991-01-01

    The role was studied of the intergranular glassy phase in silicon nitride as-processed with yttria as a sintering aid. The microstructure, crystallization, and viscosity of the glassy phase were areas studied. Crystallization of the intergranular glassy phase to more refractory crystalline phases should improve the high temperature mechanical properties of the silicon nitride. The addition of a nucleating agent will increase the rate of crystallization. The measurement of the viscosity of the glassy phase will permit the estimation of the high temperature deformation of the silicon nitride.

  2. Iron Porphyrins with Different Imidazole Ligands. A Theoretical Comparative Study

    PubMed Central

    Liao, Meng-Sheng; Huang, Ming-Ju; Watts, John D.

    2010-01-01

    A theoretical comparative study of a series of five- and six-coordinate iron porphyrins, FeP(L) and FeP(L)(O2), has been carried out using DFT methods, where P = porphine and L = imidazole (Im), 1-methylimidazole (1-MeIm), 2-methylimidazole (2-MeIm), 1,2-dimethylimidazole (1,2-Me2Im), 4-ethylimidazole (4-EtIm), or histidine (His). Two ligated “picket fence” iron porphyrins, FeTpivPP(2-MeIm) and FeTpivPP(2-MeIm)(O2), were also included in the study for comparison. A number of density functionals were employed in the computations in order to obtain reliable results. The performance of functionals and basis set effects were investigated in detail on FeP, FeP(Im), and FeP(Im)(O2), for which certain experimental information is available and there are some previous calculations in the literature for comparison. Many subtle distinctions in the effects of the different imidazole ligands on the structures and energetics of the deoxy- and oxy iron porphyrins are revealed. While FeP(2-MeIm) is identified to be high spin (S = 2), the ground state of FeP(1-MeIm) may be an admixture of a high-spin (S = 2) and an intermediate-spin (S = 1) state. The ground state of FeP(L)(O2) may be different with different L. A weaker Fe-L bond more likely leads to an open-shell singlet ground state for the oxy complex. The 2-methyl group in 2-MeIm, which increases steric contact between the ligand and the porphyrinato skeleton, weakens the Fe-O2 bond, and thus iron porphyrins with 2-MeIm mimic T-state (low affinity) hemoglobin. The calculated FeP(2-MeIm)–O2 bonding energy is comparable to the FeTpivPP(2-MeIm)–O2 one, in agreement with the fact that the “picket-fence” iron porphyrin binds O2 with affinity similar to that of myoglobin, but different from the result obtained by the CPMD scheme. Im and 4-EtIm closely resemble His, the biologically axial base, and so future computations on hemoprotein models can be simplified safely by using Im. PMID:20712371

  3. Selective four electron reduction of O2 by an iron porphyrin electrocatalyst under fast and slow electron fluxes.

    PubMed

    Samanta, Subhra; Sengupta, Kushal; Mittra, Kaustuv; Bandyopadhyay, Sabyasachi; Dey, Abhishek

    2012-08-01

    An iron porphyrin catalyst with four electron donor groups is reported. The porphyrin ligand bears a distal hydrogen bonding pocket which inverts the normal axial ligand binding selectivity exhibited by porphyrins bearing sterically crowded distal structures. This catalyst specifically reduces O(2) by four electrons under both fast and slow electron fluxes at pH 7.

  4. Anionic porphyrin as a new powerful cell death inducer of Tobacco Bright Yellow-2 cells.

    PubMed

    Riou, C; Calliste, C A; Da Silva, A; Guillaumot, D; Rezazgui, O; Sol, V; Leroy-Lhez, S

    2014-04-01

    For the first time, the behaviour of tobacco cell suspensions submitted to four porphyrins was described. The potential killer effect of these photosensitizers on tobacco cells was evaluated. Biological results were correlated with photophysical properties and the reactive oxygen species production capacity of tested compounds. Surprisingly, the anionic free-base porphyrin showed the strongest phototoxic effect.

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

    SciTech Connect

    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.

  6. The first porphyrin-subphthalocyaninatoboron(iii)-fused hybrid with unique conformation and intramolecular charge transfer behavior.

    PubMed

    Zhang, Yuehong; Oh, Juwon; Wang, Kang; Shin, Dongju; Zhan, Xiaopeng; Zheng, Yingting; Kim, Dongho; Jiang, Jianzhuang

    2016-08-18

    Porphyrin and subphthalocyaninatoboron(iii) chromophores have been fused through a quinoxaline moiety, resulting in the first porphyrin-subphthalocyaninatoboron(iii)-fused hybrid with intramolecular charge transfer from tetrapyrrole/tripyrrole chromophores to the quinoxaline moiety. The unique plane-bowl molecular structure of this hybrid was revealed based on single crystal X-ray diffraction analysis for the first time. PMID:27492136

  7. Porphyrin derivatives as potent and selective blockers of neuronal Kv1 channels.

    PubMed

    Daly, D; Al-Sabi, A; Kinsella, G K; Nolan, K; Dolly, J O

    2015-01-21

    Selective inhibitors of voltage-activated K(+) channels are needed for the treatment of multiple sclerosis. In this work it was discovered that porphyrins bearing 2-4 carbon alkyl ammonium side chains predominantly blocked the Kv1.1 current whilst Kv1.2 was susceptible to a porphyrin bearing polyamine side chains.

  8. Some Recent Developments in Structure and Glassy Behavior of Proteins

    NASA Astrophysics Data System (ADS)

    Hu, Chin-Kun

    2012-02-01

    We have used ARVO developed by us to find that the ratio of volume and surface area of proteins in Protein Data Bank distributed in a very narrow region [1]. Such result is useful for the determination of protein 3D structures. It has been widely known that a spin glass model can be used to understand the slow relaxation behavior of a glass at low temperatures [2]. We have used molecular dynamics and simple models of polymer chains to study relaxation and aggregation of proteins under various conditions and found that polymer chains with neighboring monomers connected by rigid bonds can relax very slowly and show glassy behavior [3]. We have also found that native collagen fibrils show glassy behavior at room temperatures [4]. The results of [3] and [4] about the glassy behavior of polymers or proteins are useful for understanding the mechanism for a biological system to maintain in a non-equilibrium state, including the ancient seed [5], which can maintain in a non-equilibrium state for a very long time. (1) M.-C. Wu, M. S. Li, W.-J. Ma, M. Kouza, and C.-K. Hu, EPL, in press (2011); (2) C. Dasgupta, S.-K. Ma, and C.-K. Hu. Phys. Rev. B 20, 3837-3849 (1979); (3) W.-J. Ma and C.-K. Hu, J. Phys. Soc. Japan 79, 024005, 024006, 054001, and 104002 (2010), C.-K. Hu and W.-J. Ma, Prog. Theor. Phys. Supp. 184, 369 (2010); S. G. Gevorkian, A. E. Allahverdyan, D. S. Gevorgyan and C.-K. Hu, EPL 95, 23001 (2011); S. Sallon, et al. Science 320, 1464 (2008).

  9. Evidence for a glassy state in strongly driven carbon.

    PubMed

    Brown, C R D; Gericke, D O; Cammarata, M; Cho, B I; Döppner, T; Engelhorn, K; Förster, E; Fortmann, C; Fritz, D; Galtier, E; Glenzer, S H; Harmand, M; Heimann, P; Kugland, N L; Lamb, D Q; Lee, H J; Lee, R W; Lemke, H; Makita, M; Moinard, A; Murphy, C D; Nagler, B; Neumayer, P; Plagemann, K-U; Redmer, R; Riley, D; Rosmej, F B; Sperling, P; Toleikis, S; Vinko, S M; Vorberger, J; White, S; White, T G; Wünsch, K; Zastrau, U; Zhu, D; Tschentscher, T; Gregori, G

    2014-01-01

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen close to their original positions in the fluid.

  10. Microscale rheology of a soft glassy material close to yielding.

    PubMed

    Jop, Pierre; Mansard, Vincent; Chaudhuri, Pinaki; Bocquet, Lydéric; Colin, Annie

    2012-04-01

    Using confocal microscopy, we study the flow of a model soft glassy material: a concentrated emulsion. We demonstrate the micro-macro link between in situ measured movements of droplets during the flow and the macroscopic rheological response of a concentrated emulsion, in the form of scaling relationships connecting the rheological "fluidity" with local standard deviation of the strain-rate tensor. Furthermore, we measure correlations between these local fluctuations, thereby extracting a correlation length which increases while approaching the yielding transition, in accordance with recent theoretical predictions.

  11. Positronics of radiation-induced effects in chalcogenide glassy semiconductors

    SciTech Connect

    Shpotyuk, O.; Kozyukhin, S. A.; Shpotyuk, M.; Ingram, A.; Szatanik, R.

    2015-03-15

    Using As{sub 2}S{sub 3} and AsS{sub 2} glasses as an example, the principal possibility of using positron annihilation spectroscopy methods for studying the evolution of the free volume of hollow nanoobjects in chalcogenide glassy semiconductors exposed to radiation is shown. The results obtained by measurements of the positron annihilation lifetime and Doppler broadening of the annihilation line in reverse chronological order are in full agreement with the optical spectroscopy data in the region of the fundamental absorption edge, being adequately described within coordination defect-formation and physical-aging models.

  12. Anomalous glassy relaxation near the isotropic-nematic phase transition

    NASA Astrophysics Data System (ADS)

    Jose, Prasanth P.; Chakrabarti, Dwaipayan; Bagchi, Biman

    2005-03-01

    Dynamical heterogeneity in a system of Gay-Berne ellipsoids near its isotropic-nematic (I-N) transition, and also in an equimolar mixture of Lennard-Jones spheres and Gay-Berne ellipsoids in deeply supercooled regime, is probed by the time evolution of non-Gaussian parameters (NGP). The appearance of a dominant second peak in the rotational NGP near the I-N transition signals the growth of pseudonematic domains. Surprisingly, such a second peak is instead observed in the translational NGP for the glassy binary mixture. Localization of orientational motion near the I-N transition is found to be responsible for the observed anomalous orientational relaxation.

  13. Evidence for a glassy state in strongly driven carbon

    SciTech Connect

    Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; Cho, B. I.; Gwangju Inst. of Science and Technology, Gwangju; Inst. for Basic Science, Gwangju ; Döppner, T.; Engelhorn, K.; Förster, E.; Fortmann, C.; Fritz, D.; Galtier, E.; Glenzer, S. H.; Harmand, M.; Heimann, P.; Kugland, N. L.; Lamb, D. Q.; Lee, H. J.; Lee, R. W.; Lemke, H.; Makita, M.; Moinard, A.; Murphy, C. D.; Nagler, B.; Neumayer, P.; Plagemann, K. -U.; Redmer, R.; Riley, D.; Rosmej, F. B.; Sperling, P.; Toleikis, S.; Vinko, S. M.; Vorberger, J.; White, S.; White, T. G.; Wünsch, K.; Zastrau, U.; Zhu, D.; Tschentscher, T.; Gregori, G.

    2014-06-09

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen close to their original positions in the fluid.

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

    SciTech Connect

    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. Kinetic study of delta-Ala induced porphyrins in mice using photoacoustic and fluorescence spectroscopies.

    PubMed

    Stolik, Suren; Tomás, Sergio A; Ramón-Gallegos, Eva; Sánchez, Feliciano

    2002-11-01

    The production of delta-aminolevulinic acid (ALA)-induced porphyrins in mice skin and blood was studied by photoacoustic and fluorescence spectroscopies. Mice were intraperitoneally administered with 30 mg/kg of ALA. The abdominal skin was subsequently excised at specific times within an 8-h interval and its absorption spectrum obtained by photoacoustics. The highest porphyrins concentration in skin, determined from the optical absorption of the Soret band at 410 nm, was found to occur nearly 2 h after ALA administration, but a first peak was also observed at approximately 15 min. Our hypothesis that the first peak represents the porphyrins content in blood vessels within the skin, whereas the second peak corresponds to porphyrins production in skin tissue, was confirmed by analysing the evolution of protoporphyrin IX content in plasma extracted intracardiacally. By finally applying phase resolved photoacoustic spectroscopy, we were able to evaluate the mean depth at which porphyrins are generated.

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

    PubMed

    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

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

    PubMed Central

    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

  18. Regioselective borylation of porphyrins by C-H bond activation under iridium catalysis to afford useful building blocks for porphyrin assemblies.

    PubMed

    Hata, Hiroshi; Yamaguchi, Shigeru; Mori, Goro; Nakazono, Satomi; Katoh, Taisuke; Takatsu, Keishi; Hiroto, Satoru; Shinokubo, Hiroshi; Osuka, Atsuhiro

    2007-07-01

    Highly regioselective and efficient borylation of a variety of porphyrins has been achieved by reaction with bis(pinacolato)diboron through C-H bond activation under iridium catalysis on the basis of the synthetic protocol developed by Miyaura, Hartwig, and Smith. A boryl group can be selectively introduced at sterically uncongested positions in the peripheral aryl groups of porphyrin substrates whose peripheral beta-positions are sterically hindered. Curiously, beta substituents adjacent to the aryl group to be borylated have unexpectedly large effects on the regioselectivity, because the iridium catalyst can discriminate between subtle steric differences. Chemoselective borylation was also achieved for several functionalized porphyrins. This borylation protocol can be applied to various monomeric and oligomeric functional porphyrins, hence offering an efficient route to elaborate multiporphyrin-based molecular constructs.

  19. Deformation in Thin Glassy Polymer Films from Surface towards Interior

    NASA Astrophysics Data System (ADS)

    Chowdhury, Mithun; de Silva, Johann P.; Cross, Graham L. W.

    Polymer thin glassy films occupy an important place in last two decades of condensed matter research, concerning its surprising surface mobility and spatially dependent structural relaxation. However, ranges of cleverly designed indirect measurements on confined polymer glassy films already probed its mechanical properties; it is still a challenging task to directly probe such small confined volume through conventional mechanical testing. We have designed confined layer compression testing with a precisely designed and aligned flat probe during nanoindentation, which was further accompanied with atomic force microscopy. Due to natural confinement from the surrounding material, we show that a state of `uniaxial strain' is created beneath the probe under small axial strains. By this methodology we are able to directly probe uniaxial flows under both anelastic and plastic conditions while doing controlled creep studies at different positions in the film starting from surface towards interior. Depending on the extent of deformation, we found ranges of effects, such as densification, anelastic yield, and plastic yield. Enhanced creep rate upon deformation supports the idea of `deformation induced mobility'. Work performed at Trinity College Dublin.

  20. Electrical studies on silver based fast ion conducting glassy materials

    SciTech Connect

    Rao, B. Appa Kumar, E. Ramesh Kumari, K. Rajani Bhikshamaiah, G.

    2014-04-24

    Among all the available fast ion conductors, silver based glasses exhibit high conductivity. Further, glasses containing silver iodide enhances fast ion conducting behavior at room temperature. Glasses of various compositions of silver based fast ion conductors in the AgI−Ag{sub 2}O−[(1−x)B{sub 2}O{sub 3}−xTeO{sub 2}] (x=0 to1 mol% in steps of 0.2) glassy system have been prepared by melt quenching method. The glassy nature of the compounds has been confirmed by X-ray diffraction. The electrical conductivity (AC) measurements have been carried out in the frequency range of 1 KHz–3MHz by Impedance Analyzer in the temperature range 303–423K. The DC conductivity measurements were also carried out in the temperature range 300–523K. From both AC and DC conductivity studies, it is found that the conductivity increases and activation energy decreases with increasing the concentration of TeO{sub 2} as well as with temperature. The conductivity of the present glass system is found to be of the order of 10{sup −2} S/cm at room temperature. The ionic transport number of these glasses is found to be 0.999 indicating that these glasses can be used as electrolyte in batteries.

  1. Dynamics of caged ions in glassy ionic conductors.

    PubMed

    Habasaki, J; Ngai, K L; Hiwatari, Y

    2004-05-01

    At sufficiently high frequency and low temperature, the dielectric responses of glassy, crystalline, and molten ionic conductors all invariably exhibit nearly constant loss. This ubiquitous characteristic occurs in the short-time regime when the ions are still caged, indicating that it could be a determining factor of the mobility of the ions in conduction at longer times. An improved understanding of its origin should benefit the research of ion conducting materials for portable energy source as well as the resolution of the fundamental problem of the dynamics of ions. We perform molecular dynamics simulations of glassy lithium metasilicate (Li2SiO3) and find that the length scales of the caged Li+ ions motions are distributed according to a Levy distribution that has a long tail. These results suggest that the nearly constant loss originates from "dynamic anharmonicity" experienced by the moving but caged Li+ ions and provided by the surrounding matrix atoms executing correlated movements. The results pave the way for rigorous treatments of caged ion dynamics by nonlinear Hamiltonian dynamics.

  2. Urinary porphyrin profiles as a biomarker of mercury exposure: Studies on dentists with occupational exposure to mercury vapor

    SciTech Connect

    Woods, J.S. Battelle Seattle Research Center, WA ); Martin, M.D. ); Naleway, C.A. ); Echeverria, D. )

    1993-01-01

    Porphyrins are formed as intermediates in the biosynthesis of heme. In humans and other mammals, porphyrins with eight, seven, six, five, and four carboxyl groups are excreted in the urine in a well-established pattern. Mercury selectively alters porphyrin metabolism in kidney proximal tubule cells, leading to an altered urinary porphyrin excretion pattern. Previous studies in rats have shown that changes in the urinary porphyrin profile during exposure to mercury as methylmercury hydroxide are uniquely characterized by highly elevated (20- to 30-fold) levels of four- and five-carboxyl porphyrins and by the excretion of an atypical porphyrin ([open quotes]precoproporphyrin[close quotes]), which elutes on high performance liquid chromatography (HPLC) approximately midway between penta- and coproporphyrins. Changes in the urinary porphyrin profile are highly correlated with the dose and duration of mercury exposure and persist for up to 20 wk following cessation of mercury treatment. In the present studies, the utility of urinary porphyrin profile changes as a biomarker of mercury exposure in human subjects was evaluated. Urinary porphyrin concentrations were measured in dentists participating in the Health Screening Programs conducted during the 1991 and 1992 annual meetings of the American Dental Association dentists with no detectable urinary mercury, mean concentrations of urinary porphyrins were within the established normal ranges for male human subjects. 23 refs., 3 figs., 5 tabs.

  3. Effects of glassy-winged sharpshooter feeding, size, and lipid content on egg maturation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (Homalodisca vitripennis) is synovigenic and must feed during the adult stage to produce eggs. While glassy-winged sharpshooter egg production is related to adult feeding, rates of egg production are variable. In this study, effects of lipid allocation to eggs and fema...

  4. Use of glassy carbon as a working electrode in controlled potential coulometry.

    PubMed

    Plock, C E; Vasquez, J

    1969-11-01

    Glassy carbon has been used as the working electrode in controlled potential coulometry. The results of coulometric investigations of chromium, copper, iron, uranium and neptunium are compared with results obtained with platinum or mercury working electrodes. The accuracy of results with the glassy carbon electrode compares favourably with the results obtainable with the other electrodes, but the precision is poorer.

  5. Use of glassy carbon as a working electrode in controlled potential coulometry.

    PubMed

    Plock, C E; Vasquez, J

    1969-11-01

    Glassy carbon has been used as the working electrode in controlled potential coulometry. The results of coulometric investigations of chromium, copper, iron, uranium and neptunium are compared with results obtained with platinum or mercury working electrodes. The accuracy of results with the glassy carbon electrode compares favourably with the results obtainable with the other electrodes, but the precision is poorer. PMID:18960665

  6. Silicon-tin oxynitride glassy composition and use as anode for lithium-ion battery

    DOEpatents

    Neudecker, Bernd J.; Bates, John B.

    2001-01-01

    Disclosed are silicon-tin oxynitride glassy compositions which are especially useful in the construction of anode material for thin-film electrochemical devices including rechargeable lithium-ion batteries, electrochromic mirrors, electrochromic windows, and actuators. Additional applications of silicon-tin oxynitride glassy compositions include optical fibers and optical waveguides.

  7. Evaluation of grapevine as a host for the glassy-winged sharpshooter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Grapevine was evaluated as a feeding and oviposition host for the glassy-winged sharpshooter. Two sets of experiments were conducted. The first set compared performance and preference of glassy-winged sharpshooter females for grapevine (cv. Chardonnay) versus cowpea (Vigna unguiculata cultivar black...

  8. Effect of glassy modes on electron spin-lattice relaxation in solid ethanol

    NASA Astrophysics Data System (ADS)

    Merunka, Dalibor; Kveder, Marina; Jokić, Milan; Rakvin, Boris

    2013-03-01

    Electron spin-lattice relaxation (SLR) of TEMPO radical was measured in the crystalline and glassy states of deuterated ethanol in the temperature range 5-80 K using X-band electron paramagnetic resonance (EPR). The measured SLR rates are higher in the glassy than in crystalline state and the excess SLR rate in glassy state is much lower than in ethanol. This result suggests that extra modes in glassy state, i.e. glassy modes, produce the excess SLR rate via the electron-nuclear dipolar (END) interaction between the electron spin of radical and the matrix protons or deuterons. Using the soft-potential model and assuming the END interaction between the electron spin and the matrix protons, the contributions to SLR rate of various mechanisms of glassy modes were theoretically analyzed. The evaluations of SLR rates in glassy ethanol indicate two main mechanisms of glassy modes: thermally activated relaxation of double-well systems and phonon-induced relaxation of quasi-harmonic local modes. The SLR rates induced by these mechanisms correlate well with the experimental data.

  9. Effects of meso-substituents and core-modification on photophysical and electrochemical properties of porphyrin-ferrocene conjugates

    NASA Astrophysics Data System (ADS)

    Rai, Smita; Gayatri, G.; Narahari Sastry, G.; Ravikanth, M.

    2008-12-01

    The effects of meso-substituents and porphyrin core-modification on electronic communication between ferrocene and porphyrin in covalently linked porphyrin-ferrocene conjugates are described. The electrochemical and photophysical studies indicated that the electronic communication between porphyrin and ferrocene is strong when meso-substituents are five membered aryl groups than six membered aryl groups. This may be traced to the near orthogonal arrangement of porphyrin ring with six membered meso-aryl groups leading to weaker interaction between the porphyrin and ferrocenyl groups in conjugates, while the five membered furyl and thienyl groups are closer to the porphyrin plane than being orthogonal. Molecular orbital studies are performed at semiempirical PM3 and BLYP levels to rationalize the results.

  10. Porphyrins and their synthesis from dipyrromethanes and aldehydes

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.

    1998-06-02

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided.

  11. Porphyrins and their synthesis from dipyrromethanes and aldehydes

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

    1998-01-01

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided.

  12. Aggregates of a cationic porphyrin as supramolecular probes for biopolymers.

    PubMed

    Occhiuto, Ilaria Giuseppina; Samperi, Mario; Trapani, Mariachiara; De Luca, Giovanna; Romeo, Andrea; Pasternack, Robert F; Scolaro, Luigi Monsù

    2015-12-01

    The copper(II) derivative of the dicationic trans-bis(N-methylpyridinium-4-yl)diphenylporphyrin (t-CuPagg) forms large fractal aggregates in aqueous solution under moderate ionic strength conditions. A kinetic investigation of the aggregation process allows for a choice of experimental conditions to quickly obtain stable assemblies in solution. These positively charged aggregates are able to interact efficiently with negatively charged chiral species, (including bacterial spores) leading to induced circular dichroism signals in the Soret region of the porphyrin, now acting as a sensitive chiroptical probe. PMID:26490712

  13. Aggregates of a cationic porphyrin as supramolecular probes for biopolymers.

    PubMed

    Occhiuto, Ilaria Giuseppina; Samperi, Mario; Trapani, Mariachiara; De Luca, Giovanna; Romeo, Andrea; Pasternack, Robert F; Scolaro, Luigi Monsù

    2015-12-01

    The copper(II) derivative of the dicationic trans-bis(N-methylpyridinium-4-yl)diphenylporphyrin (t-CuPagg) forms large fractal aggregates in aqueous solution under moderate ionic strength conditions. A kinetic investigation of the aggregation process allows for a choice of experimental conditions to quickly obtain stable assemblies in solution. These positively charged aggregates are able to interact efficiently with negatively charged chiral species, (including bacterial spores) leading to induced circular dichroism signals in the Soret region of the porphyrin, now acting as a sensitive chiroptical probe.

  14. Inverted meso-aryl porphyrins with heteroatoms; characterization of thia, selena, and oxa N-confused porphyrins.

    PubMed

    Pushpan, S K; Srinivasan, A; Anand, V R; Chandrashekar, T K; Subramanian, A; Roy, R; Sugiura, K; Sakata, Y

    2001-01-12

    Synthesis and characterization of inverted porphyrins containing S, Se, and O are reported. A simple 3 + 1 MacDonald-type condensation using modified tripyrrane containing the N-confused ring and diols afforded various N-confused porphyrins 6a-f in 19-30% yield. The single-crystal X-ray structure of 6b shows a ruffled conformation with tilt angles of 21.11 degrees and 31.23 degrees for the N-confused ring and the adjacent pyrrole ring III, respectively, revealing its severe nonplanarity. Significant changes in C alpha-C beta, C beta-C beta, and C alpha-X bond lengths are observed in 6b relative to free thiophene and pyrrole, suggesting the altered delocalization pathway in the modified N-confused porphyrins. The two molecules in the unit cell show a cyclophane-type noncovalent dimer with a face to face orientation of two N-confused pyrrole rings as a result of the presence of weak N-H...N and C-H...N intermolecular hydrogen bonds involving pyrrole-NH, the N atom of the N-confused ring, and the C atom of the pyrrole ring. A detailed 1H and 13C NMR study by 1D and 2D methods allowed assignments of all the peaks in the free base and protonated forms. NMR studies reveal the presence of three different tautomeric forms in solution for 6c in CDCl3 at low temperature. UV-visible studies reveal absorption band shifts upon heteroatom substitution, and the magnitudes of these shifts are dependent on the nature of the heteroatom. In all cases both monoprotonated and diprotonated species have been identified, and on addition of acid, the first proton goes to the outer N2 atom of the N-confused ring.

  15. Tissue distribution and kinetics of endogenous porphyrins synthesized after topical application of ALA in different vehicles

    PubMed Central

    Casas, A; Fukuda, H; Batlle, A M del C

    1999-01-01

    The use of 5-aminolaevulinic acid (ALA) is gaining increasing attention for photosensitization in photodynamic therapy of superficially localized tumours. The aim of this work was to determine the kinetics of porphyrin generation in tissues after topical application of ALA delivered in different vehicles on the skin overlying the tumour and normal skin of mice. Maximal accumulation was found in tumour 3 h after ALA application in both cream and lotion preparations. Normal and overlying tumour skin tissues showed different kinetic patterns, reflecting histological changes when the latter is invaded by tumour cells. Liver, kidney, spleen and blood porphyrins also raised from basal levels, showing that ALA and/or ALA-induced porphyrins reach all tissues after topical application. During the first 24 h of ALA topical application, precursors and porphyrins are excreted by both urine and faeces. ALA lotion applied on the skin overlying the tumour induced higher accumulation of tumoural porphyrins than cream, and lotion applied on normal skin appeared to be the most efficient upon inducing total body porphyrins. This work has demonstrated the great influence of the formulation of ALA vehicle on penetration through the skin. Knowledge of the kinetics of porphyrin generation after different conditions of ALA application is needed for the optimization of diagnosis and phototherapy in human tumours. © 1999 Cancer Research Campaign PMID:10487606

  16. Urinary porphyrins as biomarkers for arsenic exposure among susceptible populations in Guizhou Province, China

    SciTech Connect

    Ng, J.C.; Wang, J.P.; Zheng, B.S.; Zhai, C.; Maddalena, R.; Liu, F.; Moore, M.R.

    2005-08-07

    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. 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 ({lt} 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.

  17. Tissue distribution and kinetics of endogenous porphyrins synthesized after topical application of ALA in different vehicles.

    PubMed

    Casas, A; Fukuda, H; Batlle, A M

    1999-09-01

    The use of 5-aminolaevulinic acid (ALA) is gaining increasing attention for photosensitization in photodynamic therapy of superficially localized tumours. The aim of this work was to determine the kinetics of porphyrin generation in tissues after topical application of ALA delivered in different vehicles on the skin overlying the tumour and normal skin of mice. Maximal accumulation was found in tumour 3 h after ALA application in both cream and lotion preparations. Normal and overlying tumour skin tissues showed different kinetic patterns, reflecting histological changes when the latter is invaded by tumour cells. Liver, kidney, spleen and blood porphyrins also raised from basal levels, showing that ALA and/or ALA-induced porphyrins reach all tissues after topical application. During the first 24 h of ALA topical application, precursors and porphyrins are excreted by both urine and faeces. ALA lotion applied on the skin overlying the tumour induced higher accumulation of tumoural porphyrins than cream, and lotion applied on normal skin appeared to be the most efficient upon inducing total body porphyrins. This work has demonstrated the great influence of the formulation of ALA vehicle on penetration through the skin. Knowledge of the kinetics of porphyrin generation after different conditions of ALA application is needed for the optimization of diagnosis and phototherapy in human tumours.

  18. Supramolecular ssDNA templated porphyrin and metalloporphyrin nanoassemblies with tunable helicity.

    PubMed

    Sargsyan, Gevorg; Leonard, Brian M; Kubelka, Jan; Balaz, Milan

    2014-02-10

    Free-base and nickel porphyrin-diaminopurine conjugates were formed by hydrogen-bond directed assembly on single-stranded oligothymidine templates of different lengths into helical multiporphyrin nanoassemblies with highly modular structural and chiroptical properties. Large red-shifts of the Soret band in the UV/Vis spectroscopy confirmed strong electronic coupling among assembled porphyrin-diaminopurine units. Slow annealing rates yielded preferentially right-handed nanostructures, whereas fast annealing yielded left-handed nanostructures. Time-dependent DFT simulations of UV/Vis and CD spectra for model porphyrin clusters templated on the canonical B-DNA and its enantiomeric form, were employed to confirm the origin of observed chiroptical properties and to assign the helicity of porphyrin nanoassemblies. Molar CD and CD anisotropy g factors of dialyzed templated porphyrin nanoassemblies showed very high chiroptical anisotropy. The DNA-templated porphyrin nanoassemblies displayed high thermal and pH stability. The structure and handedness of all assemblies was preserved at temperatures up to +85 °C and pH between 3 and 12. High-resolution transition electron microscopy confirmed formation of DNA-templated nickel(II) porphyrin nanoassemblies and their self-assembly into helical fibrils with micrometer lengths.

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

    PubMed Central

    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

  20. Determination of porphyrins in oral bacteria by liquid chromatography electrospray ionization tandem mass spectrometry.

    PubMed

    Fyrestam, Jonas; Bjurshammar, Nadja; Paulsson, Elin; Johannsen, Annsofi; Östman, Conny

    2015-09-01

    Biofilms in the oral cavity can be visualized by fluorescence and a common assumption is that the endogenously produced porphyrins in certain bacteria give rise to this fluorescence. Porphyrin content in oral bacteria has been sparingly investigated, and non-selective detection techniques such as utilizing the Soret fluorescence band of porphyrins are often used. In the present study, a quantitative and selective method for the determination of porphyrins in oral bacteria has been developed and validated using high performance liquid chromatography-tandem mass spectrometry. Lysis of bacteria using Tris-EDTA buffer together with ultrasonication showed high microbial killing efficiency ≥99.98%, and sample clean-up using C18-solid phase extraction resulted in low matrix effects ≤14% for all analytes. Using this method, the porphyrin content was determined in the two oral pathogens Aggregatibacter actinomycetemcomitans and Porphyromonas gingivalis, as well as for baker's yeast, Saccharomyces cerevisiae. Uroporphyrin, 7-carboxylporphyrin, 6-carboxylporphyrin, coproporphyrin, and protoporphyrin IX were identified in the investigated microorganisms, and it was shown that the porphyrin profile differs between the two bacteria, as well as for S. cerevisiae. To our knowledge, this is the first time the porphyrin profile has been determined for the bacterium A. actinomycetemcomitans. PMID:26168965

  1. Determination of porphyrins in oral bacteria by liquid chromatography electrospray ionization tandem mass spectrometry.

    PubMed

    Fyrestam, Jonas; Bjurshammar, Nadja; Paulsson, Elin; Johannsen, Annsofi; Östman, Conny

    2015-09-01

    Biofilms in the oral cavity can be visualized by fluorescence and a common assumption is that the endogenously produced porphyrins in certain bacteria give rise to this fluorescence. Porphyrin content in oral bacteria has been sparingly investigated, and non-selective detection techniques such as utilizing the Soret fluorescence band of porphyrins are often used. In the present study, a quantitative and selective method for the determination of porphyrins in oral bacteria has been developed and validated using high performance liquid chromatography-tandem mass spectrometry. Lysis of bacteria using Tris-EDTA buffer together with ultrasonication showed high microbial killing efficiency ≥99.98%, and sample clean-up using C18-solid phase extraction resulted in low matrix effects ≤14% for all analytes. Using this method, the porphyrin content was determined in the two oral pathogens Aggregatibacter actinomycetemcomitans and Porphyromonas gingivalis, as well as for baker's yeast, Saccharomyces cerevisiae. Uroporphyrin, 7-carboxylporphyrin, 6-carboxylporphyrin, coproporphyrin, and protoporphyrin IX were identified in the investigated microorganisms, and it was shown that the porphyrin profile differs between the two bacteria, as well as for S. cerevisiae. To our knowledge, this is the first time the porphyrin profile has been determined for the bacterium A. actinomycetemcomitans.

  2. Modification of protein structure and function using photoactivated porphyrin ligands

    NASA Astrophysics Data System (ADS)

    Moreno, Gabriel

    2015-03-01

    The tremendous advances in genomic research have sparked an interest in investigating the possibility to ``manipulate'' the structure of proteins that modify existing functionality. This study makes use of small molecules (e.g., porphyrins) to photosensitize proteins and modify the higher order structure of the polypeptide with the goal of engineering novel functions, or affecting/eliminating native functions. The irradiation of non-covalently bound ligands prompts charge transfer events that have the potential to locally modify the structure of the host protein. The characterization of photoinduced conformational changes in the protein/porphyrin complex is carried out using a combination of electronic spectroscopy and kinetics (e.g., fluorescence spectroscopy, fluorescence decay, circular dichroism). This study is focused primarily on human serum albumin (HSA) as a model. The structure of HSA is well established, the binding sites for an array of ligands are well characterized (including one for protoporphyrins), and HSA provides a series of functions (including some allosteric activity) that can be tested.

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

    SciTech Connect

    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.

  4. Anticancer Gold(III) Porphyrins Target Mitochondrial Chaperone Hsp60.

    PubMed

    Hu, Di; Liu, Yungen; Lai, Yau-Tsz; Tong, Ka-Chung; Fung, Yi-Man; Lok, Chun-Nam; Che, Chi-Ming

    2016-01-22

    Identification of the molecular target(s) of anticancer metal complexes is a formidable challenge since most of them are unstable toward ligand exchange reaction(s) or biological reduction under physiological conditions. Gold(III) meso-tetraphenylporphyrin (gold-1 a) is notable for its high stability in biological milieux and potent in vitro and in vivo anticancer activities. Herein, extensive chemical biology approaches employing photo-affinity labeling, click chemistry, chemical proteomics, cellular thermal shift, saturation-transfer difference NMR, protein fluorescence quenching, and protein chaperone assays were used to provide compelling evidence that heat-shock protein 60 (Hsp60), a mitochondrial chaperone and potential anticancer target, is a direct target of gold-1 a in vitro and in cells. Structure-activity studies with a panel of non-porphyrin gold(III) complexes and other metalloporphyrins revealed that Hsp60 inhibition is specifically dependent on both the gold(III) ion and the porphyrin ligand.

  5. Tin-porphyrin-assisted formation of coordination frameworks

    NASA Astrophysics Data System (ADS)

    Titi, Hatem M.

    2016-09-01

    Novel 3D networks synthesized by two different methods are reported in this article. Structure 1 {[CdL2]·(solvent)}n consists of CdII-single metallic nodes held together by coordinated isonicotinate ligands (L) to form a 3D chiral framework (P41212). The resulting structure exhibits threefold-interpenetrated dia coordination networks. After a few weeks the crystals were re-measured to form 1a {[Cd(L)2(H2O)]·DMF}n with two interpenetrated dia nets which is thermodynamically more stable. On the other hand, the addition of the tin(IV)-porphyrin to the same reaction mixture led to the formation of 3D pseudo-isostructures, based on oxo-centered CdII and MnII/III cluster nodes, 2 {[Cd3(OH)L4(H2O)3](ClO4)}n and 3 {[Mn3(O)L4(DMF)3](ClO4)}n. These structures represent topologically bcg nets. Possible synthetic mechanism was proposed to emphasize the role of the tin(IV)-porphyrin that led to the construction of oxo-centered trinuclear clusters in 2 and 3.

  6. Assembly artificial proteins and conjugated porphyrins for biomolecular materials

    NASA Astrophysics Data System (ADS)

    Xu, Ting; Strzalka, Joe; Ye, Shixin; Wu, Sophia; Wang, Jiayu; Russell, Thomas P.; Therien, Michael; Blasie, J. Kent

    2006-03-01

    It is non-trivia to incorporate both the electron donor and acceptor in a controlled manner into amphiphilic 4-helix bundle peptides. Extended pi-electronÊsystems have been designed and tailored, with appropriate donors, acceptors and constituents, exhibit selected light-induced electron transport and/or proton translocation over large distances. We studied the binding between a series of conjugated porphyrins and the designed amphiphilic 4-helix bundles peptides at selected locations. Incorporation of the conjugated porphyrins into the 4-helix bundle did not interfere the protein secondary structure or the 4-helix bundle formation. The amphiphilic protein/cofactor complexes have good thermal stability.The artificial protein Langmuir monolayers, both the apo- and holo-form, can be oriented vectorially at the air/water interface upon compression. GID show a glass-like inter-bundle positional ordering in the monolayer plane. We will discuss the efforts on re-designing the artificial proteins to incorporate them into these nanoporous templates made from diblock copolymers .

  7. Porphyrin Based neuton capture agents for cancer therapy

    DOEpatents

    Vicente, Maria Da; Shetty, Shankar Jayaram; Jaquinod, Laurent; Smith, Kevin M.

    2006-06-27

    The invention describes the synthesis of a panel of novel carbon-carbon linked carboranyl-containing 5,10,15,20-tetraphenylporphyrins bearing 25–44% boron by weight. In certain embodiments, a phenyl porphyrin compound has a carboranyl group attached to the phenyl group by a carbon-carbon linkage, wherein the phenyl group corresponds to the following formula embedded image
    where R7 through R11 are hydrogen, a carboranyl group, or are selected from the group consisting of hydroxyl, NMe3+, PMePh2+, PO(OH)2, SO3H, COOH, and NH2. In this embodiment, the carboranyl group is attached to the phenyl group by a carbon-carbon linkage, either one or two of R7 through R11 are other than hydrogen; and the phenyl porphyrin compound contains at least one phenyl group having at least one of said carboranyl groups.

  8. Estimation of porphyrin concentration in the kerogen fraction of shales using high-resolution reflectance spectroscopy

    NASA Technical Reports Server (NTRS)

    Holden, Peter N.; Gaffey, Michael J.; Sundararaman, P.

    1991-01-01

    An interpretive model for estimating porphyrin concentration in bitumen and kerogen from spectral reaflectance data in the visible and near-ultraviolet region of the spectrum is derived and calibrated. Preliminary results obtained using the model are consistent with concentrations determined from the bitumen extract and suggest that 40 to 60 percent of the total porphyrin concentration remains in the kerogen after extraction of bitumen from thermally immature samples. The reflectance technique will contribute to porphyrin and kerogen studies and can be applied at its present level of development to several areas of geologic and paleo-oceanographic research.

  9. Self-assembling discotic liquid crystal porphyrin into more controllable ordered nanostructure mediated by fluorophobic effect

    SciTech Connect

    Zhou, Xiaoli; Kang, Shin-Woong; Kumar, Satyendra; Li, Quan

    2009-09-02

    The novel nanoscale discotic liquid crystal porphyrin with partial chain perfluorination, which has the same basic structure as the best photoreceptor in nature (chlorophyll), shows an exceptionally enhanced tendency to self-assemble into ordered nanostructure. Defect-free homeotropically aligned fluorinated porphyrin thin films were, for the first time, fabricated and characterised. The ability to self-assemble large {pi}-conjugated discotic molecules into highly ordered nanostructure via partial chain perfluorination provides new insight for the bottom-up nanofabrication of molecular devices. The controllable ordered porphyrin nanostructure with directed molecular arrangement holds great promise for use in high-performance electronic devices.

  10. The aerobic oxidation of alcohols with a ruthenium porphyrin catalyst in organic and fluorinated solvents.

    PubMed

    Korotchenko, Vasily N; Severin, Kay; Gagné, Michel R

    2008-06-01

    Carbonylruthenium tetrakis(pentafluorophenyl)porphyrin Ru(TPFPP)(CO) was utilized for the aerobic oxidation of alcohols. The in situ activation of the catalyst with mCPBA provided a species capable of catalyzing the oxidation of alcohols with molecular oxygen. The choice of solvent and additive was crucial to obtaining high activity and selectivity. Secondary aromatic alcohols were oxidized in the presence of the ruthenium porphyrin and tetrabutyl ammonium hydroxide in the solvent bromotrichloromethane, enabling high yields to be achieved (up to 99%). Alternatively, alcohols could be oxidized in perfluoro(methyldecalin) with the ruthenium porphyrin at higher temperatures (140 degrees C) and elevated oxygen pressures (50 psi).

  11. Normal-Coordinate Structural Decomposition and the Vibronic Spectra of Porphyrins

    SciTech Connect

    SHELNUTT,JOHN A.

    1999-11-09

    The connection is made between the normal-coordinate structural decomposition (NSD) and the vibronic molecular states and spectra of porphyrins. NSD is a procedure that provides a description of the distortion of a porphyrin from a D{sub 4h} symmetric reference structure in terms of equivalent displacements along the normal coordinates. Expressions for the optical absorption spectra with vibrational structure are developed with these NSD-determined deformations as parameters, and the expressions are applied to the UV-visible absorption spectra porphyrins.

  12. Surface treatment of Glassy Polymeric Carbon artifacts for medical applications

    SciTech Connect

    Rodrigues, M. G.; Zimmerman, R. L.; Rezende, M. C.

    1999-06-10

    Glassy Polymeric Carbon (GPC) has been used for mechanical cardiac valves. GCP valves are chemically biocompatible and durable, but less thromboresistant than biological valves. Enhanced thromboresistance of mechanical cardiac components with porous surface has been demonstrated. The endothelialized tissue blood-contacting surface adheres to the porous prosthetic component and decreases the formation of thrombus. Our experience has shown that the porosity of GPC can be increased and controlled by MeV ion bombardment. We report here that the surface roughness of heat-treated GPC bombarded with C, O, Si and Au is also enhanced. The surface roughness of the ion-bombarded samples is on a smaller scale than those roughened by sand blasting (measurements made with Perthomete S and P). The roughness decreases slightly after heat treatment, in linear proportion to the shrinkage of the test piece. Possible beneficial effects of the imbedded ions on tissue adherence and thromboresistance must be determined by in vivo animal experiments.

  13. Anomalous glassy relaxation near the isotropic-nematic phase transition.

    PubMed

    Jose, Prasanth P; Chakrabarti, Dwaipayan; Bagchi, Biman

    2005-03-01

    Dynamical heterogeneity in a system of Gay-Berne ellipsoids near its isotropic-nematic (I-N) transition, and also in an equimolar mixture of Lennard-Jones spheres and Gay-Berne ellipsoids in deeply supercooled regime, is probed by the time evolution of non-Gaussian parameters (NGP). The appearance of a dominant second peak in the rotational NGP near the I-N transition signals the growth of pseudonematic domains. Surprisingly, such a second peak is instead observed in the translational NGP for the glassy binary mixture. Localization of orientational motion near the I-N transition is found to be responsible for the observed anomalous orientational relaxation. PMID:15903399

  14. Manufacturing of glassy thin shell for adaptive optics: results achieved

    NASA Astrophysics Data System (ADS)

    Poutriquet, F.; Rinchet, A.; Carel, J.-L.; Leplan, H.; Ruch, E.; Geyl, R.; Marque, G.

    2012-07-01

    Glassy thin shells are key components for the development of adaptive optics and are part of future & innovative projects such as ELT. However, manufacturing thin shells is a real challenge. Even though optical requirements for the front face - or optical face - are relaxed compared to conventional passive mirrors, requirements concerning thickness uniformity are difficult to achieve. In addition, process has to be completely re-defined as thin mirror generates new manufacturing issues. In particular, scratches and digs requirement is more difficult as this could weaken the shell, handling is also an important issue due to the fragility of the mirror. Sagem, through REOSC program, has recently manufactured different types of thin shells in the frame of European projects: E-ELT M4 prototypes and VLT Deformable Secondary Mirror (VLT DSM).

  15. Determination of Fracture Patterns in Glass and Glassy Polymers.

    PubMed

    Baca, Allison C; Thornton, John I; Tulleners, Frederic A

    2016-01-01

    The study of fractures of glass, glassy-type materials, and plastic has long been of interest to the forensic community. The focus of this interest has been the use of glass and polymer fractures to associate items of evidence under the assumption that each fracture is different. Generally, it is well-accepted that deviations exist; however, the emphasis has been on classifying and predicting fracture rather than determining that each fracture is different. This study documented the controlled fracture patterns of 60 glass panes, 60 glass bottles, and 60 plastic tail light lens covers using both dynamic impact and static pressure methods under closely controlled conditions. Each pattern was intercompared, and based on the limited specimens tested in this study, the results illustrate that the fracture patterns are different. Further repetitive studies, under controlled conditions, will be needed to provide more statistical significance to the theory that each fracture forms a nonreproducible fracture pattern. PMID:26524485

  16. Evidence for a glassy state in strongly driven carbon

    DOE PAGESBeta

    Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; Cho, B. I.; Döppner, T.; Engelhorn, K.; Förster, E.; Fortmann, C.; Fritz, D.; Galtier, E.; et al

    2014-06-09

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen closemore » to their original positions in the fluid.« less

  17. Evidence for a glassy state in strongly driven carbon

    PubMed Central

    Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; Cho, B. I.; Döppner, T.; Engelhorn, K.; Förster, E.; Fortmann, C.; Fritz, D.; Galtier, E.; Glenzer, S. H.; Harmand, M.; Heimann, P.; Kugland, N. L.; Lamb, D. Q.; Lee, H. J.; Lee, R. W.; Lemke, H.; Makita, M.; Moinard, A.; Murphy, C. D.; Nagler, B.; Neumayer, P.; Plagemann, K.-U.; Redmer, R.; Riley, D.; Rosmej, F. B.; Sperling, P.; Toleikis, S.; Vinko, S. M.; Vorberger, J.; White, S.; White, T. G.; Wünsch, K.; Zastrau, U.; Zhu, D.; Tschentscher, T.; Gregori, G.

    2014-01-01

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen close to their original positions in the fluid. PMID:24909903

  18. Electroanalytical study of nifedipine using activated glassy carbon electrode.

    PubMed

    Sentürk, Z; Ozkan, S A; Ozkan, Y

    1998-01-01

    The electrochemical properties of nifedipine have been investigated in aqueous solution by linear sweep and cyclic voltammetry. The method is based both on the reduction and on the oxidation of the drug at a glassy carbon electrode activated by applying a new pre-treatment. The voltammograms of nifedipine on pH, concentration and scan rate have been carefully examined. Both the electroreduction and electrooxidation of nifedipine allow its determination at pH 1.5 in the concentration range of 2 x 10(-5)-6 x 10(-4) M and 8 x 10(-5)-1 x 10(-3) M, respectively. The method has been applied to commercial samples (tablets and capsules).

  19. Development of an Automatic Fabrication System for Cast Glassy Alloys

    NASA Astrophysics Data System (ADS)

    Yokoyama, Yoshihiko

    2015-04-01

    The developed automatic fabrication system comprised three component functions: weighing, alloying, and casting. The measurement error of automatic weighing specimen was about less 1 pct for Zr-based master alloys (approximately 30 g). Especially, sufficient stirrer effect of arc-melting ingot for homogeneity can be achieved by the development of sinusoidal arcing and applying magnetic field. In order to achieve superior homogeneity of the glass structure with no secondary phase ( i.e., an intermetallic compound with a high melting temperature), a prealloying process should be advisable. In this study, high reliability of the density and mechanical properties of automatic processed cast glassy alloys (CGAs) was successfully obtained. The developed automatic fabrication process has a potential to accelerate the industrial application of CGAs in the near future.

  20. Point-to-set lengths, local structure, and glassiness

    NASA Astrophysics Data System (ADS)

    Yaida, Sho; Berthier, Ludovic; Charbonneau, Patrick; Tarjus, Gilles

    2016-09-01

    The growing sluggishness of glass-forming liquids is thought to be accompanied by growing structural order. The nature of such order, however, remains hotly debated. A decade ago, point-to-set (PTS) correlation lengths were proposed as measures of amorphous order in glass formers, but recent results raise doubts as to their generality. Here, we extend the definition of PTS correlations to agnostically capture any type of growing order in liquids, be it local or amorphous. This advance enables the formulation of a clear distinction between slowing down due to conventional critical ordering and that due to glassiness, and provides a unified framework to assess the relative importance of specific local order and generic amorphous order in glass formation.

  1. Evidence for a glassy state in strongly driven carbon.

    PubMed

    Brown, C R D; Gericke, D O; Cammarata, M; Cho, B I; Döppner, T; Engelhorn, K; Förster, E; Fortmann, C; Fritz, D; Galtier, E; Glenzer, S H; Harmand, M; Heimann, P; Kugland, N L; Lamb, D Q; Lee, H J; Lee, R W; Lemke, H; Makita, M; Moinard, A; Murphy, C D; Nagler, B; Neumayer, P; Plagemann, K-U; Redmer, R; Riley, D; Rosmej, F B; Sperling, P; Toleikis, S; Vinko, S M; Vorberger, J; White, S; White, T G; Wünsch, K; Zastrau, U; Zhu, D; Tschentscher, T; Gregori, G

    2014-01-01

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen close to their original positions in the fluid. PMID:24909903

  2. Poly(4-vinylpyridine)-coated glassy carbon flow detectors

    SciTech Connect

    Wang, J.; Golden, T.; Tuzhi, P.

    1987-03-01

    The performance of a thin-layer flow detector with a glassy carbon electrode coated with a film of protonated poly(4-vinylpyridine) is described. Substantial improvement in the selectivity of amperometric detection for liquid chromatography and flow injection systems is observed as a result of excluding cationic species from the surface. The detector response was evaluated with respect to flow rate, solute concentration, coating scheme, film-to-film reproducibility, and other variables. Despite the increase in diffusional resistance, low detection limits of ca. 0.04 and 0.10 ng of ascorbic acid and uric acid, respectively, are maintained. Protection from organic surfactants can be coupled to the charge exclusion effect by using a bilayer coating, with a cellulose acetate film atop the poly(4-vinylpyridine) layer. Applicability to urine sample is demonstrated.

  3. Electroanalysis of trimethoprim on metalloporphyrin incorporated glassy carbon electrode.

    PubMed

    Rajith, Leena; Kumar, Krishnapillai Girish

    2010-09-01

    Trimethoprim (TMP) is a bacteriostatic antibiotic mainly used in the prophylaxis and treatment of urinary tract infections. It belongs to the class of chemotherapeutic agents known as dihydrofolate reductase inhibitors. Its use is associated with idiosyncratic reactions, including liver toxicity and agranulocytosis. In order to determine TMP electrochemically, a metalloporphyrin modified glassy carbon electrode was prepared by coating [5,10,15,20- tetrakis(4-methoxyphenyl) porphyrinato]Mn (III)chloride (TMOPPMn(III)Cl) solution on the surface of the electrode. The electrochemical behaviour of TMP in Phosphate buffer solution (PBS) on TMOPPMn(III)Cl modified glassy carbon electrode (TMOPPMn(III)Cl/GCE) was explored using differential pulse voltammetry (DPV). The voltammograms showed enhanced oxidation response at the TMOPPMn (III)Cl/GCE with respect to the bare GCE for TMP, attributable to the electrocatalytic activity of TMOPPMn(III)Cl. Electrochemical parameters of the oxidation of TMP on the modified electrode were analyzed. The electro-oxidation of TMP was found to be irreversible, pH dependent and adsorption controlled on the modified electrode. It is found that the oxidation peak current is proportional to the concentration of TMP over the range 6 × 10⁻⁸ - 1 × 10⁻⁶ M with a very low detection limit of 3 × 10⁻⁹ M at 2 min open circuit accumulation. The repeatability expressed as relative standard deviation (RSD) for n = 9 was 3.2% and the operational stability was found to be 20 days. Another striking feature is that equimolar concentration of sulfamethoxazole did not interfere in the determination of TMP. Applicability to assay the drug in urine and tablet samples has also been studied.

  4. Porphyrins-cyclodextrin—III. Breaking of cofacial dimers and multi-electron-reduction of free-base porphyrin within and outside of cyclodextrin cavities

    NASA Astrophysics Data System (ADS)

    Mosseri, S.; Mialocq, J. C.; Perly, B.

    γ-Radiolysis, pulse radiolysis, proton nuclear magnetic resonance, absorption and fluorescence spectroscopies were used for the study and the characterization of the inclusion complex of the free base porphyrin H 2TSPP in aqueous solution of β-cyclodextrin (β-CD). In reducing media and independently of the presence or the absence of β-CD the porphyrin ring is reduced to give the radical anion P -., the dianion P 2-, the tetraanion P 4- and finally the colorless hexaanion P 6-. The absorption spectra of the various reduction states and the degree of their reversibility to P 0 upon admission of oxygen in the solution are reported. The effect of β-CD on the electron transfer from the CH 2OH . radical to the porphyrin ring was examined. Our NMR data show that up to pH=10.5 the complexation of the porphyrin with β-CD is intracavity but the reactivity of the porphyrin monomers towards reducing species is only slightly affected. At pH=13 dimer breaking is observed in the presence of β-CD due to the anti-shielding of the sulfonatophenyl groups.

  5. 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

    SciTech Connect

    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.

  6. Polymorphism in glassy silicon: Inherited from liquid-liquid phase transition in supercooled liquid

    NASA Astrophysics Data System (ADS)

    Zhang, Shiliang; Wang, Li-Min; Zhang, Xinyu; Qi, Li; Zhang, Suhong; Ma, Mingzhen; Liu, Riping

    2015-02-01

    Combining molecular dynamics (MD) simulation and Voronoi polyhedral analyses, we discussed the microstructure evolution in liquid and glassy silicon during cooling by focusing on the fraction of various clusters. Liquid-liquid phase transition (LLPT) is detected in supercooled liquid silicon However, freezing the high-density liquid (HDL) to the glassy state is not achieved as the quenching rate goes up to 1014 K/s. The polyamorphism in glassy silicon is found to be mainly associated with low-density liquid (LDL).

  7. Cyclic 2,12-porphyrinylene nanorings as a porphyrin analogue of cycloparaphenylenes.

    PubMed

    Jiang, Hua-Wei; Tanaka, Takayuki; Mori, Hirotaka; Park, Kyu Hyung; Kim, Dongho; Osuka, Atsuhiro

    2015-02-18

    β-to-β Directly linked cyclic Ni(II) porphyrin trimer, tetramer, and pentamer ([3]CP, [4]CP, and [5]CP) have been synthesized by reaction of a 2,12-diborylated Ni(II) porphyrin with Pt(cod)Cl2 followed by reductive elimination. The structures of these cyclic porphyrin arrays have been revealed by X-ray diffraction analysis. The strain energies of these cyclic oligomers are calculated to be 77, 57, and 47 kcal/mol for [3]CP, [4]CP, and [5]CP, respectively. Intramolecular excitation energy hopping was observed between the (3)(d,d) states of the Ni(II) porphyrins with rates of 3.0, 4.4, and 4.6 ps for [3]CP, [4]CP, and [5]CP, respectively, reflecting the close proximity of the Ni(II) centers. PMID:25633052

  8. Porphyrin Metabolisms in Human Skin Commensal Propionibacterium acnes Bacteria: Potential Application to Monitor Human Radiation Risk

    PubMed Central

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

    2013-01-01

    Propionibacterium acnes (P. acnes), a Gram-positive anaerobic bacterium, is a commensal organism in human skin. Like human cells, the bacteria produce porphyrins, which exhibit fluorescence properties and make bacteria visible with a Wood’s lamp. In this review, we compare the porphyrin biosynthesis in humans and P. acnes. Also, since P. acnes living on the surface of skin receive the same radiation exposure as humans, we envision that the changes in porphyrin profiles (the absorption spectra and/or metabolism) of P. acnes by radiation may mirror the response of human cells to radiation. The porphyrin profiles of P. acnes may be a more accurate reflection of radiation risk to the patient than other biodosimeters/biomarkers such as gene up-/down-regulation, which may be non-specific due to patient related factors such as autoimmune diseases. Lastly, we discuss the challenges and possible solutions for using the P. acnes response to predict the radiation risk. PMID:23231351

  9. Synthesis, Spectroscopic, and Biological Studies on New Zirconium(IV) Porphyrins with Axial Ligand

    PubMed Central

    Bajju, Gauri D.; Devi, Gita; Katoch, Sapna; Bhagat, Madhulika; Deepmala; Ashu; Kundan, Sujata; Anand, Sunil Kumar

    2013-01-01

    A series of parasubstituted tetraphenylporphyrin zirconium(IV) salicylate complexes (SA/5-SSAZr(IV)RTPP, R = p-H, p-CH3, p-NO2, p-Cl, SA = salicylate, and 5-SSA = 5-sulfosalicylate) have been synthesized, and the spectral properties of free base porphyrins, their corresponding metallated, and axially ligated zirconium(IV) porphyrin compounds were compared with each other. A detailed analysis of ultraviolet-visible (UV-vis), proton nulcear magnetic resonance (1H NMR) spectroscopy, infrared (IR) spectroscopy, and elemental analysis suggested the transformation from free base porphyrins to zirconium(IV) porphyrins. The ability of the metal in this complex for extra coordination of solvent molecules was confirmed by ESI-MS spectra. Besides the fluorescence, cyclic voltammetry, and thermogravimetric studies, the complexes were also screened for antimicrobial and anticancer activities. Among all the complexes, 5-SSAZr(p-NO2TPP) shows high antibacterial activity. PMID:24106455

  10. (Metallo)porphyrins as potent phototoxic anti-cancer agents after irradiation with red light.

    PubMed

    Antoni, Philipp M; Naik, Anu; Albert, Ina; Rubbiani, Riccardo; Gupta, Susmita; Ruiz-Sanchez, Pilar; Munikorn, Pornkanok; Mateos, José M; Luginbuehl, Vera; Thamyongkit, Patchanita; Ziegler, Urs; Gasser, Gilles; Jeschke, Gunnar; Spingler, Bernhard

    2015-01-12

    Novel photoactive (metallo)porphyrins were synthesised and characterised. When irradiated with light at a wavelength greater than 600 nm, these porphyrins act as photosensitisers and show high cytotoxicity towards two different human cancer cell lines with IC50 values down to 0.4 μM. A paramagnetic copper(II) porphyrin is the first photosensitiser to display excellent phototoxicity, explained by the electron paramagnetic resonance (EPR) spin trapping of hydroxy radicals and experimentally confirmed by the discovery of elevated levels of reactive oxygen species (ROS) inside A2780 cells after irradiation with red light. This finding indicates that paramagnetic compounds should be considered for photodynamic therapy (PDT). Furthermore, an additive effect of cisplatin and a zinc porphyrin, both at subtherapeutic concentrations of 0.22 μM, was observed.

  11. Electron-transport properties of ethyne-bridged diphenyl zinc-porphyrin molecules

    NASA Astrophysics Data System (ADS)

    Duy Nguyen, Huy; Ono, Tomoya

    2015-05-01

    We investigate the electron-transport properties of ethyne-bridged diphenyl zinc-porphyrin molecules suspended between gold (111) electrodes by first-principles calculations within the framework of density functional theory. It is found that the conductance of a molecular junction in which phenyl and porphyrin rings are perpendicular is reduced by three orders of magnitude compared with that of a junction in which the phenyl and porphyrin rings are coplanar. In the coplanar configuration, electrons are transmitted through π states, which extend over the whole molecule. In the perpendicular configuration, the conductance is suppressed because of the reduction of electron hopping between π states of the phenyl ring and σ states of the porphyrin ring.

  12. Bis(cyano)iron(III) Porphyrinates: What is the Ground State?

    PubMed Central

    Li, Jianfeng; Noll, Bruce C.; Schulz, Charles E.; Scheidt, W. Robert

    2015-01-01

    The synthesis of six new bis(cyano) iron(III) porphyrinate derivatives is reported. The anionic porphyrin complexes utilized tetraphenylporphyrin, tetramesitylporphyrin, and tetratolylporphyrin as the porphyrin ligand. The potassium salts of Kryptofix-222 and 18-C-6 were used as the cations. These complexes have been characterized by X-ray structure analysis, solid-state Mössbauer spectroscopy, and EPR spectroscopy, both in frozen CH2Cl2 solution and the microcrystalline state. These data show that these anionic complexes can exist in either the (dxz,dyz)4(dxy)1 or (dxy)2(dxz,dyz)3 electronic configuration and some can clearly readily interconvert. This is a reflection that these two states can be very close in energy. In addition to the effects of varying the porphyrin ligand, subtle effects of the cyanide ligand environment in the solid-state and in solution are sufficient to shift the balance between the two electronic states. PMID:26098173

  13. Design and synthesis of new conjugated porphyrin copolymers for optical-electronic applications

    SciTech Connect

    Jiang, B.; Yang, S.W.; Lam, P.T.; Jones, W.E. Jr.

    1998-07-01

    New linear conjugated porphyrin polymers were synthesized by a palladium-catalyzed cross-coupling reaction of [5,15-bis(ethynyl)-10,20-bis (mesityl)porphyrin]zinc and diiodobenzene derivatives. Enhanced solubility of the conjugated porphyrin polymers was achieved by attachment of long alkyl ether or dialkyl amide groups to the aryl moiety, resulting in unambiguous characterization by {sup 1}H NMR, IR, GPC, UV-Vis and fluorescence spectroscopies. The introduction of alkyl ether (electron donor) or dialkyl amide (electron acceptor) results in significant modulation of the electronic properties of the conjugated porphyrin polymers due to strong electronic coupling. The spectroscopic and electronic characterization of these materials provides for comparison to earlier preparations of ethynyl bridged conjugated copolymers in which electronic coupling was substantially weaker.

  14. Porphyrin-quinone compounds as synthetic models of the reaction centre in photosynthesis

    NASA Astrophysics Data System (ADS)

    Borovkov, V. V.; Evstigneeva, Rima P.; Strekova, L. N.; Filippovich, E. I.

    1989-06-01

    Data on the synthesis, steric structure, and photochemical properties of porphyrin-quinone compounds as synthetic models of the reaction centre in photosynthesis are examined and described systematically. The bibliography includes 113 references.

  15. Syntheses, spectroscopic and AFM characterization of some manganese porphyrins and their hybrid silica nanomaterials.

    PubMed

    Fagadar-Cosma, Eugenia; Mirica, Marius Constantin; Balcu, Ionel; Bucovicean, Carmen; Cretu, Carmen; Armeanu, Ileana; Fagadar-Cosma, Gheorghe

    2009-01-01

    The present work is concerned with the manganese complexes of 5,10,15,20-tetraphenylporphyrin and of 5,10,15,20-tetra(3-hydroxyphenyl)porphyrin, 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.

  16. Chiroptical properties of an alternatingly functionalized cellotriose bearing two porphyrin groups

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Alternatingly functionalized cellulose molecules have potential applications in optoelectronics and molecular receptors. For example, cellulose-based solar cells have been proposed. As a prototype for such molecules, the trisaccharide fragment of cellulose was modified by attachment of porphyrin gro...

  17. Graphene-supported ferric porphyrin as a peroxidase mimic for electrochemical DNA biosensing.

    PubMed

    Wang, Quanbo; Lei, Jianping; Deng, Shengyuan; Zhang, Lei; Ju, Huangxian

    2013-01-30

    A novel peroxidase mimic was designed by loading ferric porphyrin and streptavidin onto graphene, which was used to recognize a biotinylated molecular beacon for specific electrochemical detection of DNA down to attomolar levels.

  18. A Two-dimensional Porphyrin-based Porous Network Featuring Communicating Cavities

    NASA Astrophysics Data System (ADS)

    Kiebele, A.; Spillmann, H.; Stoehr, M.; Wintjes, N.; Jung, T.; Bonifazi, D.; Cheng, F.; Diederich, F.

    2006-03-01

    Metallo-porphyrins and their derivatives have been shown to be exceedingly useful building blocks for the construction of 3D supramolecular functional networks due to their excellent thermal and chemical stability and synthetic versatility. Nonetheless, no 2D analogon has been reported so far, although these could be interesting for various potential applications such as molecular sieves or chemical sensors. Herein we report on an unprecedented 2D porphyrin network featuring pores capable of hosting fullerenes following a bottom-up approach at a single crystal silver surface. Surface- and porphyrin-driven long-range interactions between the C60 guest molecules and porphyrin layer resulted in the formation of exceptionally large supramolecular hybrid chains and islands as evidenced by Scanning Tunneling Microscopy.

  19. Micelle-Encapsulated Quantum Dot-Porphyrin Assemblies as in Vivo Two-Photon Oxygen Sensors

    PubMed Central

    Lemon, Christopher M.; Karnas, Elizabeth; Han, Xiaoxing; Bruns, Oliver T.; Kempa, Thomas J.; Fukumura, Dai; Bawendi, Moungi G.; Jain, Rakesh K.; Duda, Dan G.; Nocera, Daniel G.

    2016-01-01

    Micelles have been employed to encapsulate the supramolecular assembly of quantum dots with palladium(II) porphyrins for the quantification of O2 levels in aqueous media and in vivo. Förster resonance energy transfer from the quantum dot (QD) to the palladium porphyrin provides a means for signal transduction under both one- and two-photon excitation. The palladium porphyrins are sensitive to O2 concentrations in the range of 0–160 Torr. The micelle-encapsulated QD-porphyrin assemblies have been employed for in vivo multiphoton imaging and lifetime-based oxygen measurements in mice with chronic dorsal skinfold chambers or cranial windows. Our results establish the utility of the QD-micelle approach for in vivo biological sensing applications. PMID:26149349

  20. Porphyrin electrode films prepared by electrooxidation of metalloprotoporphyrins

    SciTech Connect

    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.

  1. Investigation of Porphyrin and Lipid Supramolecular Assemblies for Cancer Imaging and Therapy

    NASA Astrophysics Data System (ADS)

    Ng, Kenneth Ka-Seng

    Aerobic life on earth is made possible through the functions of the porphyrin. These colorful and ubiquitous chromophores are efficient at concentrating and converting sunlight into chemical energetic potential which sustain biological life. Humans have had a longstanding fascination with these molecules, especially for their applications in photodynamic therapy. The photophysical properties of porphyrins are highly influenced by their surrounding environment. Intermolecular interactions between these pigments can lead to excited state quenching, energy transfer and large changes to their absorption and fluorescence spectra. This thesis is focused on utilizing molecular self-assembly strategies to develop nanoscale porphyrin and phospholipid structures. The rationale being that intermolecular interactions between porphyrins in these nanostructures can induce changes which can be exploited in novel biomedical imaging and therapeutic applications. Four lipid-based structural platforms are studied including: nanoemulsions, bilayer discs and nanovesicles. In Chapter 1, I provide a background on the photophysics of porphyrins and the effect of intermolecular porphyrin interactions on photophysical properties. I also discuss phospholipids and their self-assembly process. Lastly I review current biomedical photonics techniques and discuss how these strategies can be used in conjugation with porphyrin and lipid supramolecular assemblies. In Chapter 2, I investigate the influence that loading a novel bacteriochlorin photosensitizer into a protein-stabilized lipid emulsion has on its spectral properties. I discovered that while the dye can be incorporated into the lipid emulsion, no changes were observed in its spectral properties. In Chapter 3, an amphipathic alpha-helical protein is used to stabilize and organize porphyrin-lipid molecules into bilayer discs. Close packing between porphyrin molecules causes quenching, which can be reversed by structural degradation of the

  2. Interactions of water soluble porphyrins with Z-poly(dG-dC).

    PubMed

    Pasternack, R F; Sidney, D; Hunt, P A; Snowden, E A; Gibbs, E J

    1986-05-12

    The water soluble porphyrin tetrakis(4-N-methylpyridyl)porphine (H2TMpyP) and its copper(II) derivative (CuTMpyP) convert Z-poly(dG-dC) to the B-form. For H2TMpyP, the fraction Z character (fr-Z) is given by fr-Z = 1.0 - 21 rO and for CuTMpyP, fr-Z = .94 - 12 rO where rO identical to [Porphyrin]O/[DNA]O. Neither the manganese(III) derivative of of this porphyrin (MnTMpyP) nor tetrakis(2-N-methylpyridyl)porphine (H2TMpyP-2) is nearly as effective at causing the conversion. The former two porphyrins have been shown to intercalate into B-poly(dG-dC) whereas the latter two porphyrins do not. The kinetics of the Z----B conversion are independent of porphyrin or poly(dG-dC) concentration for 1/rO greater than 6. At smaller values of 1/rO, the conversion rate is greatly increased for H2TMpyP and CuTMpyP. The interaction of these porphyrins with Z-poly(dG-dC) follows simple first order kinetics in this latter concentration range. It is proposed that for small values of 1/rO the sequence of events begins with a porphyrin-unassisted distortion of the Z-duplex (with a rate constant of 0.6 s-1) followed by a rapid uptake of porphyrin in what may be an intercalative mode. The porphyrin thus located in Z-regions brings about rapid conversion to the B-form. Binding of H2TMpyP or CuTMpyP to B-regions of a predominantly Z-strand leads to conversion of Z to B. However, this conversion process is considerably slower than when the porphyrins bind directly to Z-regions.

  3. Fused porphyrin-single-walled carbon nanotube hybrids: efficient formation and photophysical characterization.

    PubMed

    Zhong, Qiwen; Diev, Vyacheslav V; Roberts, Sean T; Antunez, Priscilla D; Brutchey, Richard L; Bradforth, Stephen E; Thompson, Mark E

    2013-04-23

    A systematic study of the interaction between π-extended porphyrins and single-walled carbon nanotubes (SWNTs) is reported here. Zinc porphyrins with 1-pyrenyl groups in the 5,15-meso positions, 1, as well as compounds where one or both of the pyrene groups have been fused at the meso and β positions of the porphyrin core, 2 and 3, respectively, have been examined. The strongest binding to SWNTs is observed for porphyrin 3, leading to debundling of the nanotubes and formation of stable suspensions of 3-SWNT hybrids in a range of common organic solvents. Absorption spectra of 3-SWNT suspensions are broad and continuous (λ=400-1400 nm), and the Q-band of 3 displays a significant bathochromic shift of 33 nm. The surface coverage of the SWNTs in the nanohybrids was estimated by spectroscopic and analytical methods and found to reach 64% for (7,6) nanotubes. The size and shape of π-conjugated porphyrins were found to be important factors in determining the strength of the π-π interactions, as the linear anti-3 isomer displays more than 90% binding selectivity compared to the bent syn-3 isomer. Steady-state photoluminescence measurements show quenching of porphyrin emission from the nanohybrids. Femtosecond transient absorption spectroscopy reveals that this quenching results from ultrafast electron transfer from the photoexcited porphyrin to the SWNT (1/kCT=260 fs) followed by rapid charge recombination on a picosecond time scale. Overall, our data demonstrate that direct π-π interaction between fused porphyrins and SWNTs leads to electronically coupled stable nanohybrids.

  4. Hybrid orbital deformation (HOD) effect and spectral red-shift property of nonplanar porphyrin.

    PubMed

    Zhou, Zaichun; Cao, Chenzhong; Liu, Qiuhua; Jiang, Rongqing

    2010-04-16

    A series of 5,15-meso,meso-strapped nonplanar porphyrins with different degrees of ruffling distortion, as a model system, have been synthesized and characterized. The spectral red-shift of the nonplanar porphyrins was experimentally demonstrated to mainly originate from the hybrid orbital deformation (HOD) effect due to the distortion in the tetrapyrrole macrocycle, which confirmed previous explanations to the red-shift phenomenon.

  5. Triplet State Delocalization in a Conjugated Porphyrin Dimer Probed by Transient Electron Paramagnetic Resonance Techniques

    PubMed Central

    2015-01-01

    The delocalization of the photoexcited triplet state in a linear butadiyne-linked porphyrin dimer is investigated by time-resolved and pulse electron paramagnetic resonance (EPR) with laser excitation. The transient EPR spectra of the photoexcited triplet states of the porphyrin monomer and dimer are characterized by significantly different spin polarizations and an increase of the zero-field splitting parameter D from monomer to dimer. The proton and nitrogen hyperfine couplings, determined using electron nuclear double resonance (ENDOR) and X- and Q-band HYSCORE, are reduced to about half in the porphyrin dimer. These data unequivocally prove the delocalization of the triplet state over both porphyrin units, in contrast to the conclusions from previous studies on the triplet states of closely related porphyrin dimers. The results presented here demonstrate that the most accurate estimate of the extent of triplet state delocalization can be obtained from the hyperfine couplings, while interpretation of the zero-field splitting parameter D can lead to underestimation of the delocalization length, unless combined with quantum chemical calculations. Furthermore, orientation-selective ENDOR and HYSCORE results, in combination with the results of density functional theory (DFT) calculations, allowed determination of the orientations of the zero-field splitting tensors with respect to the molecular frame in both porphyrin monomer and dimer. The results provide evidence for a reorientation of the zero-field splitting tensor and a change in the sign of the zero-field splitting D value. The direction of maximum dipolar coupling shifts from the out-of-plane direction in the porphyrin monomer to the vector connecting the two porphyrin units in the dimer. This reorientation, leading to an alignment of the principal optical transition moment and the axis of maximum dipolar coupling, is also confirmed by magnetophotoselection experiments. PMID:25914154

  6. Evidence of Porphyrin-Like Structures in Natural Melanin Pigments Using Electrochemical Fingerprinting.

    PubMed

    Kim, Young Jo; Khetan, Abhishek; Wu, Wei; Chun, Sang-Eun; Viswanathan, Venkatasubramanian; Whitacre, Jay F; Bettinger, Christopher J

    2016-04-01

    Eumelanins are extended heterogeneous biopolymers composed of molecular subunits with ambiguous macromolecular topology. Here, an electrochemical fingerprinting technique is described, which suggests that natural eumelanin pigments contain indole-based tetramers that are arranged into porphyrin-like domains. Spectroscopy and density functional theory calculations suggest that sodium ions undergo occupancy-dependent stepwise insertion into the core of porphyrin-like tetramers in natural eumelanins at discrete potentials.

  7. Porphyrins-Functionalized Single-Walled Carbon Nanotubes Chemiresistive Sensor Arrays for VOCs

    PubMed Central

    Shirsat, Mahendra D.; Sarkar, Tapan; Kakoullis, James; Myung, Nosang V.; Konnanath, Bharatan; Spanias, Andreas; Mulchandani, Ashok

    2012-01-01

    Single-walled carbon nanotubes (SWNTs) have been used extensively for sensor fabrication due to its high surface to volume ratio, nanosized structure and interesting electronic property. Lack of selectivity is a major limitation for SWNTs-based sensors. However, surface modification of SWNTs with a suitable molecular recognition system can enhance the sensitivity. On the other hand, porphyrins have been widely investigated as functional materials for chemical sensor fabrication due to their several unique and interesting physico-chemical properties. Structural differences between free-base and metal substituted porphyrins make them suitable for improving selectivity of sensors. However, their poor conductivity is an impediment in fabrication of prophyrin-based chemiresistor sensors. The present attempt is to resolve these issues by combining freebase- and metallo-porphyrins with SWNTs to fabricate SWNTs-porphyrin hybrid chemiresistor sensor arrays for monitoring volatile organic carbons (VOCs) in air. Differences in sensing performance were noticed for porphyrin with different functional group and with different central metal atom. The mechanistic study for acetone sensing was done using field-effect transistor (FET) measurements and revealed that the sensing mechanism of ruthenium octaethyl porphyrin hybrid device was governed by electrostatic gating effect, whereas iron tetraphenyl porphyrin hybrid device was governed by electrostatic gating and Schottky barrier modulation in combination. Further, the recorded electronic responses for all hybrid sensors were analyzed using a pattern-recognition analysis tool. The pattern-recognition analysis confirmed a definite pattern in response for different hybrid material and could efficiently differentiate analytes from one another. This discriminating capability of the hybrid nanosensor devices open up the possibilities for further development of highly dense nanosensor array with suitable porphyrin for E-nose application

  8. Interaction of a tricationic meso-substituted porphyrin with guanine-containing polyribonucleotides of various structures

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    The interaction of a tricationic water-soluble meso-(N-methylpyridinium)-substituted porphyrin, TMPyP3+, derived from classic TMPyP4, with double-stranded poly(G)  ṡ  poly(C) and four-stranded poly(G) polyribonucleotides has been studied in aqueous buffered solutions, pH 6.9, of low and near-physiological ionic strengths in a wide range of molar phosphate-to-dye ratios (P/D). To clarify the binding modes of TMPyP3+ to biopolymers various spectroscopic techniques, including absorption and polarized fluorescence spectroscopy, Raman spectroscopy, and resonance light scattering, were used. As a result, two competitive binding modes were revealed. In solution of low ionic strength outside binding of the porphyrin to the polynucleotide backbone with self-stacking prevailed at low P/D ratios (P/D  <  3.5). It manifested itself by the substantial quenching of porphyrin fluorescence. Also the formation of large-scale porphyrin aggregates was observed near the stoichiometric binding ratio. The spectral changes observed at P/D  >  30 including emission enhancement were supposed to be caused by the embedding of partially stacked porphyrin J-dimers into the polymer groove. TMPyP3+ binding to poly(G) induced a fluorescence increase 2.5 times as large as that observed for poly(G)  ṡ  poly(C). In solution of near-physiological ionic strength the efficiency of external porphyrin binding was reduced substantially due to the competitive binding of Na+ ions with the polymer backbone. The spectroscopic characteristics of porphyrin bound to polynucleotides at different conditions were compared with those for free porphyrin.

  9. Iron porphyrin polymer films: Materials for the modification of electrode surfaces and the detection of nitric oxide

    SciTech Connect

    McGuire, M.; Drew, S.M.

    1996-10-01

    We are currently investigating a new method for the detection and quantification of nitric oxide (NO) based on a carbon electrode chemically modified with an iron porphyrin polymer film. Commercially available vinyl-substituted iron porphyrin monomers can be polymerized directly onto electrode surfaces through a published electrochemical polymerization process. We are also developing a synthesis for a new vinyl-substituted monomer, iron 5,10,15-triphenyl-20-vinyl porphyrin chloride, in hopes of improving polymer film stability. The electrochemistry of NO is also being investigated at electrodes chemically modified with an iron porphyrin polymer film. We are studying the catalytic oxidation of iron porphyrin bound NO to nitrate by molecular oxygen. The reaction with molecular oxygen is preceded by a one electron reduction of the iron porphyrin-NO complex. If currents proportional to nitric oxide concentration can be measured, a new NO electrochemical sensor will be designed.

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

    NASA Astrophysics Data System (ADS)

    Asano, Motoko S.; Okamura, Kazuma; Jin-mon, Akihoro; Takahashi, Sadaharu; Kaizu, Youkoh

    2013-06-01

    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.

  11. Equilibrium and kinetic studies of the interactions of a porphyrin with low-density lipoproteins.

    PubMed Central

    Bonneau, Stéphanie; Vever-Bizet, Christine; Morlière, Patrice; Mazière, Jean-Claude; Brault, Daniel

    2002-01-01

    Low-density lipoproteins (LDL) play a key role in the delivery of photosensitizers to tumor cells in photodynamic therapy. The interaction of deuteroporphyrin, an amphiphilic porphyrin, with LDL is examined at equilibrium and the kinetics of association/dissociation are determined by stopped-flow. Changes in apoprotein and porphyrin fluorescence suggest two classes of bound porphyrins. The first class, characterized by tryptophan fluorescence quenching, involves four well-defined sites. The affinity constant per site is 8.75 x 10(7) M(-1) (cumulative affinity 3.5 x 10(8) M(-1)). The second class corresponds to the incorporation of up to 50 molecules into the outer lipidic layer of LDL with an affinity constant of 2 x 10(8) M(-1). Stopped-flow experiments involving direct LDL porphyrin mixing or porphyrin transfer from preloaded LDL to albumin provide kinetic characterization of the two classes. The rate constants for dissociation of the first and second classes are 5.8 and 15 s(-1); the association rate constants are 5 x 10(8) M(-1) s(-1) per site and 3 x 10(9) M(-1) s(-1), respectively. Both fluorescence and kinetic analysis indicate that the first class involves regions at the boundary between lipids and the apoprotein. The kinetics of porphyrin-LDL interactions indicates that changes in the distribution of photosensitizers among various carriers could be very sensitive to the specific tumor microenvironment. PMID:12496113

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

    NASA Astrophysics Data System (ADS)

    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.

  13. ATP-dependent mitochondrial porphyrin importer ABCB6 protects against phenylhydrazine toxicity.

    PubMed

    Ulrich, Dagny L; Lynch, John; Wang, Yao; Fukuda, Yu; Nachagari, Deepa; Du, Guoqing; Sun, Daxi; Fan, Yiping; Tsurkan, Lyudmila; Potter, Philip M; Rehg, Jerold E; Schuetz, John D

    2012-04-13

    Abcb6 is a mammalian mitochondrial ATP-binding cassette (ABC) transporter that regulates de novo porphyrin synthesis. In previous studies, haploinsufficient (Abcb6(+/-)) embryonic stem cells showed impaired porphyrin synthesis. Unexpectedly, Abcb6(-/-) mice derived from these stem cells appeared phenotypically normal. We hypothesized that other ATP-dependent and/or -independent mechanisms conserve porphyrins. Here, we demonstrate that Abcb6(-/-) mice lack mitochondrial ATP-driven import of coproporphyrin III. Gene expression analysis revealed that loss of Abcb6 results in up-regulation of compensatory porphyrin and iron pathways, associated with elevated protoporphyrin IX (PPIX). Phenylhydrazine-induced stress caused higher mortality in Abcb6(-/-) mice, possibly because of sustained elevation of PPIX and an inability to convert PPIX to heme despite elevated ferrochelatase levels. Therefore, Abcb6 is the sole ATP-dependent porphyrin importer, and loss of Abcb6 produces up-regulation of heme and iron pathways necessary for normal development. However, under extreme demand for porphyrins (e.g. phenylhydrazine stress), these adaptations appear inadequate, which suggests that under these conditions Abcb6 is important for optimal survival.

  14. ATP-dependent Mitochondrial Porphyrin Importer ABCB6 Protects against Phenylhydrazine Toxicity*

    PubMed Central

    Ulrich, Dagny L.; Lynch, John; Wang, Yao; Fukuda, Yu; Nachagari, Deepa; Du, Guoqing; Sun, Daxi; Fan, Yiping; Tsurkan, Lyudmila; Potter, Philip M.; Rehg, Jerold E.; Schuetz, John D.

    2012-01-01

    Abcb6 is a mammalian mitochondrial ATP-binding cassette (ABC) transporter that regulates de novo porphyrin synthesis. In previous studies, haploinsufficient (Abcb6+/−) embryonic stem cells showed impaired porphyrin synthesis. Unexpectedly, Abcb6−/− mice derived from these stem cells appeared phenotypically normal. We hypothesized that other ATP-dependent and/or -independent mechanisms conserve porphyrins. Here, we demonstrate that Abcb6−/− mice lack mitochondrial ATP-driven import of coproporphyrin III. Gene expression analysis revealed that loss of Abcb6 results in up-regulation of compensatory porphyrin and iron pathways, associated with elevated protoporphyrin IX (PPIX). Phenylhydrazine-induced stress caused higher mortality in Abcb6−/− mice, possibly because of sustained elevation of PPIX and an inability to convert PPIX to heme despite elevated ferrochelatase levels. Therefore, Abcb6 is the sole ATP-dependent porphyrin importer, and loss of Abcb6 produces up-regulation of heme and iron pathways necessary for normal development. However, under extreme demand for porphyrins (e.g. phenylhydrazine stress), these adaptations appear inadequate, which suggests that under these conditions Abcb6 is important for optimal survival. PMID:22294697

  15. Designing supramolecular porphyrin arrays that self-organize into nanoscale optical and magnetic materials

    PubMed Central

    Drain, Charles Michael; Batteas, James D.; Flynn, George W.; Milic, Tatjana; Chi, Ning; Yablon, Dalia G.; Sommers, Heather

    2002-01-01

    Tessellation of nine free-base porphyrins into a 3 × 3 array is accomplished by the self-assembly of 21 molecular entities of four different kinds, one central, four corner, and four side porphyrins with 12 trans Pd(II) complexes, by specifically designed and targeted intermolecular interactions. Strikingly, the self-assembly of 30 components into a metalloporphyrin nonamer results from the addition of nine equivalents of a first-row transition metal to the above milieu. In this case each porphyrin in the nonameric array coordinates the same metal such as Mn(II), Ni(II), Co(II), or Zn(II). This feat is accomplished by taking advantage of the highly selective porphyrin complexation kinetics and thermodynamics for different metals. In a second, hierarchical self-assembly process, nonspecific intermolecular interactions can be exploited to form nanoscaled three-dimensional aggregates of the supramolecular porphyrin arrays. In solution, the size of the nanoscaled aggregate can be directed by fine-tuning the properties of the component macrocycles, by choice of metalloporphyrin, and the kinetics of the secondary self-assembly process. As precursors to device formation, nanoscale structures of the porphyrin arrays and aggregates of controlled size may be deposited on surfaces. Atomic force microscopy and scanning tunneling microscopy of these materials show that the choice of surface (gold, mica, glass, etc.) may be used to modulate the aggregate size and thus its photophysical properties. Once on the surface the materials are extremely robust. PMID:11880598

  16. Physicochemical properties of potential porphyrin photosensitizers for photodynamic therapy

    NASA Astrophysics Data System (ADS)

    Kempa, Marta; Kozub, Patrycja; Kimball, Joseph; Rojkiewicz, Marcin; Kuś, Piotr; Gryczyński, Zugmunt; Ratuszna, Alicja

    2015-07-01

    This research evaluated the suitability of synthetic photosensitizers for their use as potential photosensitizers in photodynamic therapy using steady state and time-resolved spectroscopic techniques. Four tetraphenylporphyrin derivatives were studied in ethanol and dimethyl sulfoxide. The spectroscopic properties namely electronic absorption and emission spectra, ability to generate singlet oxygen, lifetimes of the triplet state, as well as their fluorescence quantum yield were determined. Also time-correlated single photon counting method was used to precisely determine fluorescence lifetimes for all four compounds. Tested compounds exhibit high generation of singlet oxygen, low generation of fluorescence and they are chemical stable during irradiation. The studies show that the tested porphyrins satisfy the conditions of a potential drug in terms of physicochemical properties.

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

    PubMed

    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

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

    PubMed

    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

  19. Manganese porphyrin sensor for the determination of bromate.

    PubMed

    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

  20. Tomato metabolism and porphyrin-catalyzed oxidation of pyriproxyfen.

    PubMed

    Fukushima, Masao; Fujisawa, Takuo; Katagi, Toshiyuki

    2005-06-29

    Investigation of the metabolism of [(14)C]pyriproxyfen [4-phenoxyphenyl (R,S)-2-(2-pyridyloxy)propyl ether] in tomato fruits (Lycopersicon esculentum Mill. cv. Ponterosa) was conducted by topical application of acetonitrile solution or emulsifiable concentration formulation three times at 35, 21, and 7 days before harvest. Most of the radioactivity remained on the fruit surface or in the plant tissues as intact pyriproxyfen with minor metabolites formed via hydroxylation at the 4'-position of the phenoxy ring or cleavage of ether linkages. The biomimic chemical oxidation model using iron porphyrin as a catalyst and hydrogen peroxide was found to well reproduce the primary metabolites detected in the metabolism study. The electrophilic reaction indices obtained by AM1 molecular orbital calculations supposing involvement of cytochrome P-450 were successfully applied to evaluate the potentially higher reactive sites in pyriproxyfen.

  1. Phenothiazine-bridged cyclic porphyrin dimers as high-affinity hosts for fullerenes and linear array of C60 in self-assembled porphyrin nanotube.

    PubMed

    Sakaguchi, Ken-ichi; Kamimura, Takuya; Uno, Hidemitsu; Mori, Shigeki; Ozako, Shuwa; Nobukuni, Hirofumi; Ishida, Masatoshi; Tani, Fumito

    2014-04-01

    Free-bases and a nickel(II) complex of phenothiazine-bridged cyclic porphyrin dimers bearing self-assembling 4-pyridyl groups (M2-Ptz-CPDPy(OCn); M = H2 or Ni, OCn = OC6 or OC3) at opposite meso-positions have been prepared as host molecules for fullerenes. The free-base dimer (H4-Ptz-CPDPy(OC6)) includes fullerenes with remarkably high association constants such as 3.9 ± 0.7 × 10(6) M(-1) for C60 and 7.4 ± 0.8 × 10(7) M(-1) for C70 in toluene. This C60 affinity is the highest value ever among reported receptors composed of free-base porphyrins. The nickel dimer (Ni2-Ptz-CPDPy(OC6)) also shows high affinities for C60 (1.3 ± 0.2 × 10(6) M(-1)) and C70 (over 10(7) M(-1)). In the crystal structure of the inclusion complex of C60 within H4-Ptz-CPDpy(OC3), the C60 molecule is located just above the centers of the porphyrins. The two porphyrin planes are almost parallel to each other and the center-to-center distance (12.454 Å) is close to the optimal separation (∼12.5 Å) for C60 inclusion. The cyclic porphyrin dimer forms a nanotube through its self-assembly induced by C-H···N hydrogen bonds between porphyrin β-CH groups and pyridyl nitrogens as well as π-π interactions of the pyridyl groups. The C60 molecules are linearly arranged in the inner channel of this nanotube.

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

    PubMed

    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.

  3. Quantitative Vibrational Dynamics of Iron in Carbonyl Porphyrins

    PubMed Central

    Leu, Bogdan M.; Silvernail, Nathan J.; Zgierski, Marek Z.; Wyllie, Graeme R. A.; Ellison, Mary K.; Scheidt, W. Robert; Zhao, Jiyong; Sturhahn, Wolfgang; Alp, E. Ercan; Sage, J. Timothy

    2007-01-01

    We use nuclear resonance vibrational spectroscopy and computational predictions based on density functional theory (DFT) to explore the vibrational dynamics of 57Fe in porphyrins that mimic the active sites of histidine-ligated heme proteins complexed with carbon monoxide. Nuclear resonance vibrational spectroscopy yields the complete vibrational spectrum of a Mössbauer isotope, and provides a valuable probe that is not only selective for protein active sites but quantifies the mean-squared amplitude and direction of the motion of the probe nucleus, in addition to vibrational frequencies. Quantitative comparison of the experimental results with DFT calculations provides a detailed, rigorous test of the vibrational predictions, which in turn provide a reliable description of the observed vibrational features. In addition to the well-studied stretching vibration of the Fe-CO bond, vibrations involving the Fe-imidazole bond, and the Fe-Npyr bonds to the pyrrole nitrogens of the porphyrin contribute prominently to the observed experimental signal. All of these frequencies show structural sensitivity to the corresponding bond lengths, but previous studies have failed to identify the latter vibrations, presumably because the coupling to the electronic excitation is too small in resonance Raman measurements. We also observe the FeCO bending vibrations, which are not Raman active for these unhindered model compounds. The observed Fe amplitude is strongly inconsistent with three-body oscillator descriptions of the FeCO fragment, but agrees quantitatively with DFT predictions. Over the past decade, quantum chemical calculations have suggested revised estimates of the importance of steric distortion of the bound CO in preventing poisoning of heme proteins by carbon monoxide. Quantitative agreement with the predicted frequency, amplitude, and direction of Fe motion for the FeCO bending vibrations provides direct experimental support for the quantum chemical description of the

  4. N-confused porphyrin tautomers: lessons from density functional theory.

    PubMed

    Marchand, Gabriel; Roy, Hélène; Mendive-Tapia, David; Jacquemin, Denis

    2015-02-21

    Using first-principle calculations, we characterize the properties of N-confused porphyrins (NCP), with a focus on the differences between the 2H and 3H tautomers. We find that NCP-3H is almost as strongly aromatic as porphyrin, and about twice as aromatic, i.e., remarkably more stable, than NCP-2H, due to the less efficient π-conjugation in the latter form. The deprotonation of the NH-group at the external side of the inverted ring of NCP-2H, adds a lone pair to the π-system, which restores a strong aromaticity, while methylation has no significant effect. Investigating the impact of solvation using a continuum model, we find quite stable solvation energies with a relative dielectric constant, εr, in the 5-40 range, for both tautomers. NCP-3H presents a slightly lower energy than its NCP-2H counterpart in all solvents. However, the energy differences between the two species are of the order of the error margin of the method, hence too small to discuss the experimentally observed stabilization of NCP-3H in dichloromethane (DCM, a poorly polar solvent) and NCP-2H in N,N-dimethylformamide (DMF, a strongly polar solvent) or to extract the population ratios between the two forms in the different solvents. Therefore, the vibronic absorption spectra are also investigated in an effort to rationalize the complex absorption profiles of these NCP derivatives. We find very distinct spectra for the 2H and 3H forms in DMF and DCM, respectively, each fairly reproducing the experiment. We also find that, in the same solvent, the two species exhibit very different signatures, which allows us to conclude that the 2H and 3H tautomers are largely dominant in DMF and DCM, respectively. Interestingly, the vibrational motions that strongly participate in the shoulder of the Soret band and the multiple maxima of the Q-bands largely differ in the two tautomers.

  5. Plasmon-assisted photocurrent generation from silver nanoparticle monolayers combined with porphyrins via their different chain-length alkylcarboxylates.

    PubMed

    Kakuta, Takayoshi; Kon, Hiroki; Kajikawa, Azusa; Kanaizuka, Katsuhiko; Yagyu, Shigeta; Miyake, Ryosuke; Ishizakil, Manabu; Uruma, Keirei; Togashi, Takanari; Sakamoto, Masatomi; Kurihara, Masato

    2014-06-01

    Three-typed porphyrin derivatives with a different chain-length alkylcarboxylic acid as their peripheral anchor group have been prepared. Anodic photocurrents were observed in a simple system where the porphyrin derivatives were directly anchored on an indium tin oxide (ITO) electrode. Cathodic photocurrents and their plasmon-assisted enhancement appeared from an Ag nanoparticle (Ag NP) composite monolayer combined with the porphyrin derivatives on the ITO electrode. In the photocurrent generation mechanism, Ag NPs played both the roles as photon- and energy-transfer to the porphyrin derivatives. The plasmon-assisted enhancement was affected by the chain-lengths of the peripheral anchor groups. PMID:24738356

  6. Surface micro-structuring of glassy carbon for precision glass molding of diffractive optical elements

    NASA Astrophysics Data System (ADS)

    Prater, Karin; Dukwen, Julia; Scharf, Toralf; Herzig, Hans Peter; Hermerschmidt, Andreas

    2014-09-01

    Glassy carbon is used nowadays for a variety of applications because of its mechanical strength, thermal stability and non-sticking adhesion properties. This makes it also a suitable candidate as mold material for precision compression molding of low and high glass-transition temperature materials. To fabricate molds for diffractive optics a highresolution structuring technique is needed. We introduce a process that allows the micro-structuring of glassy carbon by reactive ion etching. Key parameters such as uniformity, surface roughness, edge definition and lateral resolution are discussed. They are the most relevant parameters for a stamp in optical applications. The use of titanium as a hard mask makes it possible to achieve a reasonable selectivity of 4:1, which has so far been one of the main problems in microstructuring of glassy carbon. We investigate the titanium surface structure with its 5-10 nm thick layer of TiO2 grains and its influence on the shape of the hard mask. In our fabrication procedure we were able to realize optically flat diffractive structures with slope angles of more than 80° at typical feature sizes of 5 μm and at 700 nm depth. The fabricated glassy carbon molds were applied to thermal imprinting onto different glasses. Glassy carbon molds with 1 mm thickness were tested with binary optical structures. Our experiments show the suitability of glassy carbon as molds for cost efficient mass production with a high quality.

  7. Long-range electronic communication in free-base meso-poly(ferrocenyl)-containing porphyrins.

    PubMed

    Nemykin, Victor N; Rohde, Gregory T; Barrett, Christopher D; Hadt, Ryan G; Sabin, Jared R; Reina, Giacomo; Galloni, Pierluca; Floris, Barbara

    2010-08-16

    H(2)FcPh(3)P [FcPh(3)P = 5-ferrocenyl-10,15,20-triphenyl porphyrin(2-)], cis-H(2)Fc(2)Ph(2)P [cis-Fc(2)Ph(2)P = 5,10-bisferrocenyl-15,20-diphenyl porphyrin(2-)], trans-H(2)Fc(2)Ph(2)P [trans-Fc(2)Ph(2)P = 5,15-bisferrocenyl-10,20-diphenyl porphyrin(2-)], and H(2)Fc(3)PhP [Fc(3)PhP = 5,10,15-trisferrocenyl-20-phenyl porphyrin(2-)] along with H(2)TPP [TPP = 5,10,15,20-tetraphenylporphyrin] and H(2)TFcP [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2-)] were isolated from the direct cross-condensation reaction between pyrrole, benzaldehyde, and ferrocene carboxaldehyde or from the reaction between ferrocenyl-2,2'-dipyrromethane and benzaldehyde, suggesting a scrambling reaction mechanism for the last approach. All compounds were characterized by UV-vis, MCD, and NMR spectroscopy; APCI MS and MS/MS methods; as well as high-resolution ESI MS spectrometry. The conformational flexibility of ferrocene substituents in all compounds was confirmed using variable-temperature NMR and computational methods. DFT calculations were employed to understand the degree of nonplanarity of the porphyrin core as well as the electronic structure of ferrocene-containing porphyrins. In all cases, a set of occupied, predominantly ferrocene-based molecular orbitals was found between the highest occupied and the lowest unoccupied, predominantly porphyrin-based molecular pi orbitals. The redox properties of all ferrocene-containing porphyrins were investigated in a CH(2)Cl(2)/TFAB [TFAB = tetrabutylammonium tetrakis(perfluorophenyl)borate] system using cyclic voltammetry, differential pulse voltammetry, and square wave voltammetry methods. In all cases, oxidations of individual ferrocene substituent(s) along with porphyrin core oxidation(s) and reductions have been observed. Mixed-valence [cis-H(2)Fc(2)Ph(2)P](+), [trans-H(2)Fc(2)Ph(2)P](+), [H(2)Fc(3)PhP](+), and [H(2)Fc(3)PhP](2+) complexes were formed in situ under spectroelectrochemical and chemical oxidation conditions and were characterized

  8. Terbium induced glassy magnetism in La,Ca-based cobaltites

    SciTech Connect

    Maryško, M. Hejtmánek, J.; Jirák, Z.; Kaman, O.; Knížek, K.

    2014-05-07

    The La{sub 0.8–x}Tb{sub x}Ca{sub 0.2}CoO{sub 3} cobaltites of orthoperovskite Pbnm structure were investigated by the X-ray and neutron diffraction, specific heat, and magnetization measurements. The terbium doping has two important effects, it increases the size disorder on perovskite A-sites and influences the magnetic properties due to large Ising-type moments (∼8.9 Bohr magnetons per Tb). The compounds show a bulk magnetic moment below T{sub C} = 82 K, 53 K, and 30 K for x = 0.1, 0.2, and 0.3, respectively. The neutron diffraction evidences a long-range ferromagnetic arrangement of cobalt moments, combined below ∼20 K with ordering of terbium moments in a canted arrangement. A homogeneous magnetic phase is proved for the x = 0.1 sample, while x = 0.2 and 0.3 are in an intrinsically non-homogeneous magnetic state with long-range ordering only comprising 55% and 30% of the sample volumes. The ac susceptibility experiments prove a glassy character of the terbium doped samples and provide arguments for the short-range ordering above T{sub C} and wide distribution of relaxation times.

  9. Mechanics of particulate composites with glassy polymer binders in compression

    PubMed Central

    Jordan, J. L.; Spowart, J. E.; Kendall, M. J.; Woodworth, B.; Siviour, C. R.

    2014-01-01

    Whether used as structural components in design or matrix materials for composites, the mechanical properties of polymers are increasingly important. The compressive response of extruded polymethyl methacrylate (PMMA) rod with aligned polymer chains and Al–Ni–PMMA particulate composites are investigated across a range of strain rates and temperatures. The particulate composites were prepared using an injection-moulding technique resulting in highly anisotropic microstructures. The mechanics of these materials are discussed in the light of theories of deformation for glassy polymers. The experimental data from this study are compared with PMMA results from the literature as well as epoxy-based composites with identical particulates. The PMMA exhibited the expected strain rate and temperature dependence and brittle failure was observed at the highest strain rates and lowest temperatures. The Al–Ni–PMMA composites were found to have similar stress–strain response to the PMMA with reduced strain softening after yield. Increasing volume fraction of particulates in the composite resulted in decreased strength. PMID:24711495

  10. Glassy state and cryopreservation of mint shoot tips.

    PubMed

    Teixeira, Aline S; González-Benito, M Elena; Molina-García, Antonio D

    2013-01-01

    Vitrification refers to the physical process by which a liquid supercools to very low temperatures and finally solidifies into a metastable glass, without undergoing crystallization at a practical cooling rate. Thus, vitrification is an effective freeze-avoidance mechanism and living tissue cryopreservation is, in most cases, relying on it. As a glass is exceedingly viscous and stops all chemical reactions that require molecular diffusion, its formation leads to metabolic inactivity and stability over time. To investigate glassy state in cryopreserved plant material, mint shoot tips were submitted to the different stages of a frequently used cryopreservation protocol (droplet-vitrification) and evaluated for water content reduction and sucrose content, as determined by ion chromatography, frozen water fraction and glass transitions occurrence by differential scanning calorimetry, and investigated by low-temperature scanning electron microscopy, as a way to ascertain if their cellular content was vitrified. Results show how tissues at intermediate treatment steps develop ice crystals during liquid nitrogen cooling, while specimens whose treatment was completed become vitrified, with no evidence of ice formation. The agreement between calorimetric and microscopic observations was perfect. Besides finding a higher sucrose concentration in tissues at the more advanced protocol steps, this level was also higher in plants precultured at 25/-1°C than in plants cultivated at 25°C.

  11. Dielectric studies of molecular motions in glassy and liquid nicotine

    NASA Astrophysics Data System (ADS)

    Kaminski, K.; Paluch, M.; Ziolo, J.; Ngai, K. L.

    2006-06-01

    The dielectric permittivity and loss spectra of glassy and liquid states of nicotine have been measured over the frequency range 10-2-109 Hz. The relaxation spectra are similar to common small molecular glass-forming substances, showing the structural α-relaxation and its precursor, the Johari-Goldstein β-relaxation. The α-relaxation is well described by the Fourier transform of the Kohlrausch-Williams-Watts stretched exponential function with an approximately constant stretch exponent that is equal to 0.70 as the glass transition temperature is approached. The dielectric α-relaxation time measured over 11 orders of magnitude cannot be described by a single Vogel-Fulcher-Tamman-Hesse equation. The most probable Johari-Goldstein β-relaxation time determined from the dielectric spectra is in good agreement with the primitive relaxation time of the coupling model calculated from parameters of the structural α-relaxation. The shape of the dielectric spectra of nicotine is compared with that of other glass-formers having about the same stretch exponent, and they are shown to be nearly isomorphic. The results indicate that the molecular dynamics of nicotine conform to the general pattern found in other glass-formers, and the presence of the universal Johari-Goldstein secondary relaxation, which plays a role in the crystallization of amorphous pharmaceuticals.

  12. Glassy cell carcinoma of the cervix: a literature review.

    PubMed

    Zolciak-Siwinska, A; Jonska-Gmyrek, J

    2014-08-01

    Glassy cell carcinoma (GCC) is a histologically aggressive subtype of cervical cancer with rapid growth and early metastases. The prognosis for patients with GCC is poor. This article reviews the literature pertinent to the epidemiology, cytology, pathology, immunohistochemistry, treatment and prognosis of GCC. MEDLINE (PubMed) was searched for all articles or abstracts on patients diagnosed with GCC published (in English) since the original definition by Glucksmann and Cherry, Cancer 1956;9:971. Accurate diagnosis of GCC enables implementation of the correct treatment strategy. Early-stage GCC should be treated with hysterectomy and pelvic lymph node dissection, with adjuvant radiochemotherapy if at least one intermediate or high risk factor for cervical cancer is present. Advanced GCC should be treated with neoadjuvant radiochemotherapy or chemotherapy with the aim of making the disease operable. There is a need for retrospective evaluation of GCC treatment from several centres to explore knowledge about this rare entity. Future studies should explore the role of targeted therapies and the most efficient chemotherapy regimen for the management of GCC.

  13. Mathematical modeling of glassy-winged sharpshooter population.

    PubMed

    Yoon, Jeong-Mi; Hrynkiv, Volodymyr; Morano, Lisa; Nguyen, Anh Tuan; Wilder, Sara; Mitchell, Forrest

    2014-06-01

    Pierce's disease (PD) is a fatal disease of grapevines which results from an infection by the plant pathogen Xyllela fastidiosa. This bacterium grows in the xylem (water-conducting) vessels of the plant blocking movement of water. PD can kill vines in one year and poses a serious threat to both the California and the expanding Texas wine industries. Bacteria are vectored from one vine to the next by a number of xylem feeding insect species. Of these, the Glassy-winged Sharpshooter (GWSS) is considered to be the primary xylem feeding insect in Texas vineyards. An extensive database of the xylem-feeding population frequencies was collected by USDA-APHIS for Texas vineyards over multiple years. This project focused on a subset of data, GWSS frequencies within 25 vineyards in Edwards Plateau located in central Texas. The proposed model investigates the natural population dynamics and the decline in GWSS, likely the result of pest management campaigns on the insects within the region. The model is a delay Gompertz differential equation with harvesting and immigration terms, and we use the data to estimate the model parameters.

  14. Mathematical modeling of glassy-winged sharpshooter population.

    PubMed

    Yoon, Jeong-Mi; Hrynkiv, Volodymyr; Morano, Lisa; Nguyen, Anh Tuan; Wilder, Sara; Mitchell, Forrest

    2014-06-01

    Pierce's disease (PD) is a fatal disease of grapevines which results from an infection by the plant pathogen Xyllela fastidiosa. This bacterium grows in the xylem (water-conducting) vessels of the plant blocking movement of water. PD can kill vines in one year and poses a serious threat to both the California and the expanding Texas wine industries. Bacteria are vectored from one vine to the next by a number of xylem feeding insect species. Of these, the Glassy-winged Sharpshooter (GWSS) is considered to be the primary xylem feeding insect in Texas vineyards. An extensive database of the xylem-feeding population frequencies was collected by USDA-APHIS for Texas vineyards over multiple years. This project focused on a subset of data, GWSS frequencies within 25 vineyards in Edwards Plateau located in central Texas. The proposed model investigates the natural population dynamics and the decline in GWSS, likely the result of pest management campaigns on the insects within the region. The model is a delay Gompertz differential equation with harvesting and immigration terms, and we use the data to estimate the model parameters. PMID:24506556

  15. Structural origin of low temperature glassy relaxation in magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Laha, Suvra; Regmi, Rajesh; Lawes, Gavin

    2013-03-01

    Magnetic nanoparticles often exhibit glass-like relaxation features at low temperatures. Here we discuss the effects of doping boron, cobalt, gadolinium and lanthanum on the low temperature magnetic properties of Fe3O4 nanoparticles. We investigated the structure of the nanoparticles using both X-ray diffraction and Raman studies, and find evidence for secondary phase formation in certain samples. We acquired Transmission Electron Microscopic images to give direct information on the morphology and microstructure of these doped nanoparticles. We measured the ac out-of-phase susceptibility (χ//) vs temperature (T) to parameterize the low temperature glassy magnetic relaxation. All samples show low temperature magnetic relaxation, but the amplitude of the signal increases dramatically for certain dopants. We attribute these low temperature frequency-dependent magnetic relaxation features to structural defects, which are enhanced in some of the doped Fe3O4 nanoparticles. These studies also confirm that the low temperature relaxation in nanoparticles arises from single particle effects and are not associated with interparticle interactions.

  16. Surface temperatures and glassy state investigations in tribology, part 1

    NASA Technical Reports Server (NTRS)

    Winer, W. O.; Sanborn, D. M.

    1978-01-01

    The research in this report is divided into two categories: (1) lubricant rheological behavior, and (2) thermal behavior of a simulated elastohydrodynamic contact. The studies of the lubricant rheological behavior consists of high pressure, low shear rate viscosity measurements, viscoelastic transition measurements, by volume dilatometry, dielectric transitions at atmospheric pressure and light scattering transitions. Lubricant shear stress-strain behavior in the amorphous glassy state was measured on several fluids. It appears clear from these investigations that many lubricants undergo viscoplastic transitions in typical EHD contacts and that the lubricant has a limiting maximum shear stress it can support which in turn will determine the traction in the contact except in cases of very low slide-roll ratio. Surface temperature measurements were made for a naphthenic mineral oil and a polyphenyl ether. The maximum surface temperature in these experiments was approximately symmetrical about the zero slide-roll ration except for absolute values of slide-roll ratio greater than about 0.9. Additional surface temperature measurements were made in contacts with rough surfaces where the composite surface roughness was approximately equal to the EHD film thickness. A regression analysis was done to obtain a predictive equation for surface temperatures as a function of pressure, sliding speed, and surface roughness. A correction factor for surface roughness effects to the typical flash temperature analysis was found.

  17. J-aggregate formation of a water-soluble porphyrin in acidic aqueous media

    NASA Astrophysics Data System (ADS)

    Ohno, Osamu; Kaizu, Youkoh; Kobayashi, Hiroshi

    1993-09-01

    J aggregate of a water-soluble porphyrin, 5,10,15,20-tetra(4-sulfophenyl)porphyrin (H2TPPS44-), formed in acidified aqueous solutions, exhibits sharp and intense absorption bands at 491 and 707 nm. These characteristic transitions, J bands, are of linear oscillators polarized in the long axis of rodlike aggregate. The molecules in the aggregate stack so as to lift the degeneracy of the porphyrin planar oscillator excited states. Measurements of flow-induced linear dichroism, circular dichroism, magnetic circular dichroism, as well as polarized fluorescence excitation spectra provide evidence not only of linear oscillator character of the intense J band at 491 nm, but also of presence of another diffuse absorption band around at 420 nm polarized in the short axis of the aggregate, which is the counterpart of the 491 nm band of porphyrin Soret origin. Extrinsic circular dichroism is induced upon addition of L-tartaric acid or by mechanical swirling flow in the period of aggregate growth. Resonance Raman spectrum of the aggregate is rather similar to that of the monomeric diacid except the polarization. The observed shifts of Raman peaks to lower frequency are ascribed to a deformation of porphyrin moiety and/or hydrophobic interaction between component molecules in the aggregate. The sharp and intense J bands polarized in the long axis of aggregate cannot be well described without taking into account the participation of interporphyrin charge resonance excited states, whereas the broadbands polarized in the short axis are exclusively ascribed to exciton resonance excited states. The porphyrin J band is characterized as sustaining an exchange narrowing by fast migration of excitation over the whole system of chromophores in a linear array of the porphyrin planar oscillators in slipped face-to-face stacking.

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

    PubMed

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

    2010-01-01

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

  19. Noncovalent functionalization of carbon nanotubes with porphyrins: meso-tetraphenylporphine and its transition metal complexes.

    PubMed

    Basiuk, Elena V; Basiuk, Vladimir A; Santiago, Patricia; Puente-Lee, Iván

    2007-01-01

    Noncovalent functionalization of carbon nanotubes with meso-tetraphenylporphine (H2TPP) and its metal(II) complexes NiTPP and CoTPP was studied by means of different experimental techniques and theoretical calculations. As follows from the experimental adsorption curves, free H2TPP ligand exhibits the strongest adsorption of three porphyrins tested, followed by CoTPP and NiTPP. At the highest porphyrin concentrations studied, the adsorption at multi-walled carbon nanotubes was about 2% (by weight) for H2TPP, 1% for CoTPP, and 0.5% for NiTPP. Transmission electron microscopy observations revealed carbon nanotubes with a variable degree of surface coverage with porphyrin molecules. According to scanning electron microscopy, the nanotubes glue together rather than debundle; apparently, a large porphyrin excess resulting in polymolecular adsorption is essential for exfoliation/debundling of the nanotube ropes. The nanotube/porphyrins hybrids were studied by infrared and Raman spectroscopy, as well as by scanning tunneling microscopy. Electronic structure calculations were performed at the B3LYP/LANL2MB theoretical level with the unsubstituted porphine (H2P) and its Co(II) complex, on one hand, and open-end armchair (5,5) (ANT) and zigzag (8,0) (ZNT) SWNT models, on the other hand. The interaction of H2P with ANT was found to be by 3.9 kcal mol(-1) stronger than that of CoP. At the same time, CoP+ZNT complex is more stable by 42.7 kcal mol(-1) as compared to H2P+ZNT According to these calculated results, the free porphyrins interact less selectively with zigzag and armchair (i.e., semiconducting and metallic) nanotubes, whereas the difference becomes very large for the metal porphyrins. HOMO-LUMO structure, electrostatic potential and spin density distribution for the paramagnetic cobalt(II) complexes were analyzed. PMID:17450922

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

    PubMed

    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

  1. Catalytic electron-transfer oxygenation of substrates with water as an oxygen source using manganese porphyrins.

    PubMed

    Fukuzumi, Shunichi; Mizuno, Takuya; Ojiri, Tetsuya

    2012-12-01

    Manganese(V)-oxo-porphyrins are produced by the electron-transfer oxidation of manganese-porphyrins with tris(2,2'-bipyridine)ruthenium(III) ([Ru(bpy)(3)](3+); 2 equiv) in acetonitrile (CH(3)CN) containing water. The rate constants of the electron-transfer oxidation of manganese-porphyrins have been determined and evaluated in light of the Marcus theory of electron transfer. Addition of [Ru(bpy)(3)](3+) to a solution of olefins (styrene and cyclohexene) in CH(3)CN containing water in the presence of a catalytic amount of manganese-porphyrins afforded epoxides, diols, and aldehydes efficiently. Epoxides were converted to the corresponding diols by hydrolysis, and were further oxidized to the corresponding aldehydes. The turnover numbers vary significantly depending on the type of manganese-porphyrin used owing to the difference in their oxidation potentials and the steric bulkiness of the ligand. Ethylbenzene was also oxidized to 1-phenylethanol using manganese-porphyrins as electron-transfer catalysts. The oxygen source in the substrate oxygenation was confirmed to be water by using (18)O-labeled water. The rate constant of the reaction of the manganese(V)-oxo species with cyclohexene was determined directly under single-turnover conditions by monitoring the increase in absorbance attributable to the manganese(III) species produced in the reaction with cyclohexene. It has been shown that the rate-determining step in the catalytic electron-transfer oxygenation of cyclohexene is electron transfer from [Ru(bpy)(3)](3+) to the manganese-porphyrins.

  2. Comprehensive physiology and toxicology of ecdysogens--The metabolically activated porphyrin-ecdysteroid complexes in insects.

    PubMed

    Sláma, Karel; Zhylitskaya, Halina

    2016-01-01

    The polyhydroxylated derivatives of 6-keto,7-dehydrocholesterol (ecdysone, ecdysteroids, Ecd) are natural compounds widely distributed in plants. They exhibit strong anabolic, vitamin D-like, pharmacological effects in vertebrate animals and in the human body. In the larval stages of insects, injections of pure Ecd cause serious pathophysiological, "hyperecdysonic" syndromes associated with neuromuscular paralysis, premature cuticular apolysis and complete inhibition of ecdysis. Ecds do not penetrate insect cuticle. For this reason, all previous attempts to induce ecdysone responses by topical applications of Ecd failed. In this work, we tried to induce the topical effects of Ecd by preparation of more lipophilic complexes, with 2 or 4 molecules of 20-hydroxyecdysone (E20) attached to a relatively large nucleus of the porphyrin. The resulting porphyrin-E20 complexes (ecdysogens) have been subjected to standardised assays for ecdysone activity in the ligatured larvae ("dauerlarvae") of the greater waxmoth (Galleria mellonella). Similarly like the free E20 alone, porphyrin-E20 complexes had no effect when applied on the body surface or administered in the larval diet. When injected, however, they exhibited delayed effects, but the adverse ("hyperecdysonic") pathophysiological syndromes were reduced or abolished. It is concluded, therefore, that the replacement of pathophysiological, precocious or "hyperecdysonic" moults by the larval-pupal transformation, was due to successive metabolic liberation of the biologically active, free E20 from the porphyrin-E20 complex. The biological status of Ecd does not agree with their definition as the prothoracic gland (PG) hormone of insects, nor with the assumptions about a growth hormone of plants. A possibility that the most important status of Ecd may depend on the pharmacological properties of a sterolic D6 vitamin has been discussed. PMID:26802554

  3. Development of the glassy state of benzophenone and effect of heating rate from the glassy state on solidification

    SciTech Connect

    Thoma, P.E.; Boehm, J.J.

    1997-12-31

    Benzophenone supercools to a glass when cooled to {minus}100 C. In fact, it is difficult to freeze benzophenone on cooling. In this investigation, the effect of cooling rate and the minimum cooling rate to obtain benzophenone as a glass is determined. From the glassy state, the influence of heating rate on the solidification temperature of benzophenone is determined. When heated at 3 C/min., solidification starts at about {minus}29 C. Upon additional heating, melting usually starts at about +24 C, which is 23 C lower than the solid equilibrium structure melting temperature of 47 C. Occasionally the solid that forms at about {minus}29 C undergoes a solid state phase transformation at about +22 C, when heated at 3 C/min. If this solid state phase transformation occurs, then the solid benzophenone starts to melt at 47 C. When solid benzophenone with the equilibrium structure is cooled to {minus}100 C, no solid state phase transformation occurs. It appears that the structure that solidified at {minus}29 C is metastable.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Immobilization of DNA at Glassy Ccarbon Electrodes: A Critical Study of Adsorbed Layer

    PubMed Central

    Pedano, M. L.; Rivas, G. A.

    2005-01-01

    In this work we present a critical study of the nucleic acid layer immobilized at glassy carbon electrodes. Different studies were performed in order to assess the nature of the interaction between DNA and the electrode surface. The adsorption and electrooxidation of DNA demonstrated to be highly dependent on the surface and nature of the glassy carbon electrode. The DNA layer immobilized at a freshly polished glassy carbon electrode was very stable even after applying highly negative potentials. The electron transfer of potassium ferricyanide, catechol and dopamine at glassy carbon surfaces modified with thin (obtained by adsorption under controlled potential conditions) and thick (obtained by casting the glassy carbon surface with highly concentrated DNA solutions) DNA layers was slower than that at the bare glassy carbon electrode, although this effect was dependent on the thickness of the layer and was not charge selective. Raman experiments showed an important decrease of the vibrational modes assigned to the nucleobases residues, suggesting a strong interaction of these residues with the electrode surface. The hybridization of oligo(dG)21 and oligo(dC)21 was evaluated from the guanine oxidation signal and the reduction of the redox indicator Co(phen)33+. In both cases the chronopotentiometric response indicated that the compromise of the bases in the interaction of DNA with the electrode surface is too strong, preventing further hybridization. In summary, glassy carbon is a useful electrode material to detect DNA in a direct and very sensitive way, but not to be used for the preparation of biorecognition layers by direct adsorption of the probe sequence on the electrode surface for detecting the hybridization event.

  9. How important are glassy SOA ice nuclei for the formation of cirrus clouds?

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Penner, J. E.; Lin, G.; Liu, X.; Wang, M.

    2014-12-01

    Extremely low ice numbers (i.e. 5 - 100 / L) have been observed in the tropical troposphere layer (TTL) in a variety of field campaigns. Various mechanisms have been proposed to explain these low numbers, including the effect of glassy secondary organic aerosol acting as heterogeneous ice nuclei (IN). In this study, we explored these effects using the CAM5.3 model. SOA fields were provided by an offline version of the University of Michigan-IMPACT model, which has a detailed process-based mechanism that describes aerosol microphysics and SOA formation through both gas phase and multiphase reactions. The transition criterion of SOA to glassy heterogeneous IN follows the parameterization developed by Wang et al. 2012. With this parameterization, glassy SOA IN form mainly when the temperature (T) is lower than 210K. In the default CAM5.3 set-up in which only the fraction of Aitken mode sulfate aerosols with diameter larger than 100nm participate in the ice nucleation (Liu and Penner 2005 parameterization), glassy SOA IN are shown to decrease the ice number (Ni) by suppressing some of the homogeneous freezing at low temperatures thereby leading to an improved representation of the relationship between Ni and T compared to the observations summarized by Kramer et al. 2009. However, when we allow the total number of the Aitken mode sulfate particles to participate in homogeneous freezing, glassy SOA IN have only a small impact on the relationship between Ni and T. If the subgrid updraft velocity is decreased to 0.1 m/s (compared to 0.2 m/s in the default set-up), there is a large decrease of Ni, since homogeneous freezing is more easily suppressed by glassy SOA IN at these updrafts. We also present the effects of glassy SOA IN using an alternative ice nucleation scheme (Barahona and Nenes, 2009).

  10. How fast is water uptake on glassy and amorphous aerosol?

    NASA Astrophysics Data System (ADS)

    Bones, D. L.; Lienhard, D. M.; Krieger, U.; Reid, J. P.

    2011-12-01

    Atmospheric aerosol particles are typically complex mixtures of organic and inorganic species with correspondingly complex behaviour in their response to changes in humidity. Indeed, it has been recently recognised that many aerosols exist as highly viscous solutions or as amorphous glasses, rather than a crystalline state, over a wide range of relative humidities (Virtanen, et al. 2010). In this work, we investigate the formation of glassy or highly viscous phases in aqueous sugar aerosols such as sucrose and levoglucosan and aerosols of mixtures of sugars and inorganic compounds, reporting the timescale for the mass transfer of water between the particle and the gas phase with variation in water activity. Optical tweezers are used to trap single aerosol particles and examine the time-dependent response in their size to stepwise changes in RH, which result in the evaporation or condensation of water. The evolving particle size and homogeneity in composition are estimated from the wavelengths of specific resonance modes of the cavity enhanced Raman scattering spectra, deducing size changes with an accuracy of better than 1 nm. The experimental data is compared with a kinetic model of diffusional limited size change (Zobrist, et al. 2011), in which the diffusion of water within the particle bulk limits the rate of water transport between the gas and condensed phases. We report measurements in which ternary mixtures, with varying mole ratios of sucrose and sodium chloride, have allowed us to examine the water transport and response time in particle size over a wide range of bulk viscosities. Changes in size are dramatically hindered at low RH, with time scales approaching 10000s, for both increasing and decreasing RH regimes (Tong, et al. 2011). We also observe a marked relative shift in resonance modes, suggesting initial formation of a layer of water on the surface of the glassy particle and subsequent establishment of a steep concentration gradient within the

  11. Charge transport and glassy dynamics in ionic liquids.

    PubMed

    Sangoro, Joshua R; Kremer, Friedrich

    2012-04-17

    Ionic liquids (ILs) exhibit unique features such as low melting points, low vapor pressures, wide liquidus temperature ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. As a result, they show promise for use in variety of applications: as reaction media, in batteries and supercapacitors, in solar and fuel cells, for electrochemical deposition of metals and semiconductors, for protein extraction and crystallization, and many others. Because of the ease with which they can be supercooled, ionic liquids offer new opportunities to investigate long-standing questions regarding the nature of the dynamic glass transition and its possible link to charge transport. Despite the significant steps achieved from experimental and theoretical studies, no generally accepted quantitative theory of dynamic glass transition to date has been capable of reproducing all the experimentally observed features. In this Account, we discuss recent studies of the interplay between charge transport and glassy dynamics in ionic liquids as investigated by a combination of several experimental techniques including broadband dielectric spectroscopy, pulsed field gradient nuclear magnetic resonance, dynamic mechanical spectroscopy, and differential scanning calorimetry. Based on Einstein-Smoluchowski relations, we use dielectric spectra of ionic liquids to determine diffusion coefficients in quantitative agreement with independent pulsed field gradient nuclear magnetic resonance measurements, but spanning a broader range of more than 10 orders of magnitude. This approach provides a novel opportunity to determine the electrical mobility and effective number density of charge carriers as well as their types of thermal activation from the measured dc conductivity separately. We also unravel the origin of the remarkable universality of charge transport in different classes of glass-forming ionic liquids.

  12. Charge Transport and Glassy Dynamics in Ionic Liquids

    SciTech Connect

    Sangoro, Joshua R; Kremer, Friedrich

    2012-01-01

    Ionic liquids (ILs) exhibit unique features such as low melting points, low vapor pressures, wide liquidus temperature ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. As a result, they show promise for use in variety of applications: as reaction media, in batteries and supercapacitors, in solar and fuel cells, for electrochemical deposition of metals and semiconductors, for protein extraction and crystallization, and many others. Because of the ease with which they can be supercooled, ionic liquids offer new opportunities to investigate long-standing questions regarding the nature of the dynamic glass transition and its possible link to charge transport. Despite the significant steps achieved from experimental and theoretical studies, no generally accepted quantitative theory of dynamic glass transition to date has been capable of reproducing all the experimentally observed features. In this Account, we discuss recent studies of the interplay between charge transport and glassy dynamics in ionic liquids as investigated by a combination of several experimental techniques including broadband dielectric spectroscopy, pulsed field gradient nuclear magnetic resonance, dynamic mechanical spectroscopy, and differential scanning calorimetry. Based on EinsteinSmoluchowski relations, we use dielectric spectra of ionic liquids to determine diffusion coefficients in quantitative agreement with independent pulsed field gradient nuclear magnetic resonance measurements, but spanning a broader range of more than 10 orders of magnitude. This approach provides a novel opportunity to determine the electrical mobility and effective number density of charge carriers as well as their types of thermal activation from the measured dc conductivity separately. We also unravel the origin of the remarkable universality of charge transport in different classes of glass-forming ionic liquids.

  13. Modeling mechanophore activation within a crosslinked glassy matrix

    NASA Astrophysics Data System (ADS)

    Silberstein, Meredith N.; Min, Kyoungmin; Cremar, Lee D.; Degen, Cassandra M.; Martinez, Todd J.; Aluru, Narayana R.; White, Scott R.; Sottos, Nancy R.

    2013-07-01

    Mechanically induced reactivity is a promising means for designing self-reporting materials. Mechanically sensitive chemical groups called mechanophores are covalently linked into polymers in order to trigger specific chemical reactions upon mechanical loading. These mechanophores can be linked either within the backbone or as crosslinks between backbone segments. Mechanophore response is sensitive to both the matrix properties and placement within the matrix, providing two avenues for material design. A model framework is developed to describe reactivity of mechanophores located as crosslinks in a glassy polymer matrix. Simulations are conducted at the molecular and macromolecular scales in order to develop macroscale constitutive relations. The model is developed specifically for the case of spiropyran (SP) in lightly crosslinked polymethylmethacrylate (PMMA). This optically trackable mechanophore (fluorescent when activated) allows the model to be assessed in terms of observed experimental behavior. The force modified potential energy surface (FMPES) framework is used in conjunction with ab initio steered molecular dynamics (MD) simulations of SP to determine the mechanophore kinetics. MD simulations of the crosslinked PMMA structure under shear deformation are used to determine the relationship between macroscale stress and local force on the crosslinks. A continuum model implemented in a finite element framework synthesizes these mechanochemical relations with the mechanical behavior. The continuum model with parameters taken directly from the FMPES and MD analyses under predicts stress-driven activation relative to experimental data. The continuum model, with the physically motivated modification of force fluctuations, provides an accurate prediction for monotonic loading across three decades of strain rate and creep loading, suggesting that the fundamental physics are captured.

  14. Bulk glassy and nonequilibrium crystalline alloys by stabilization of supercooled liquid: fabrication, functional properties and applications (Part 2)

    NASA Astrophysics Data System (ADS)

    Inoue, A.

    The novel stabilization phenomenon of supercooled liquid in special multi-component metallic alloys that follow the three component rules has enabled us to fabricate a number of bulk glassy and nonequilibrium crystalline alloys exhibiting useful characteristics. Following the previous review (Part 1; Proc. Jpn. Acad. Ser. B 81, 156-171), this paper (Part 2) reviews our recent results on the physical, chemical, mechanical and magnetic properties of the resulting bulk nonequilibrium materials including glassy single phase alloys, nanocrystal-, nanoquasicrystal- and dendritic crystal-dispersed glassy alloys and nanocrystalline alloys. Finally, the application potential of bulk glassy alloys is addressed, taking account of their novel engineering properties and production processes.

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

    PubMed

    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.

  16. A Perspective on the Trends and Challenges Facing Porphyrin-Based Anti-Microbial Materials.

    PubMed

    Jiang, Lu; Gan, Ching Ruey Raymond; Gao, Jian; Loh, Xian Jun

    2016-07-01

    The emergence of multidrug resistant bacterium threatens to unravel global healthcare systems, built up over centuries of medical research and development. Current antibiotics have little resistance against this onslaught as bacterium strains can quickly evolve effective defense mechanisms. Fortunately, alternative therapies exist and, at the forefront of research lays the photodynamic inhibition approach mediated by porphyrin based photosensitizers. This review will focus on the development of various porphyrins compounds and their incorporation as small molecules, into polymers, fibers and thin films as practical therapeutic agents, utilizing photodynamic therapy to inhibit a wide spectrum of bacterium. The use of photodynamic therapy of these porphyrin molecules are discussed and evaluated according to their electronic and bulk material effect on different bacterium strains. This review also provides an insight into the general direction and challenges facing porphyrins and derivatives as full-fledged therapeutic agents and what needs to be further done in order to be bestowed their rightful and equal status in modern medicine, similar to the very first antibiotic; penicillin itself. It is hoped that, with this perspective, new paradigms and strategies in the application of porphyrins and derivatives will progressively flourish and lead to advances against disease. PMID:27276371

  17. Solid-Supported Porphyrins Useful for the Synthesis of Conjugates with Oligomeric Biomolecules.

    PubMed

    Jadhav, Satish; Yim, Cheng-Bin; Rajander, Johan; Grönroos, Tove J; Solin, Olof; Virta, Pasi

    2016-04-20

    meso-Tris(pyridin-4-yl)(4-carboxyphenyl)porphyrin and 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a (Photochlor, HPPH) were amide-coupled to 1R,2S,3R,4R-2,3-dihydroxy-4-(hydromethyl)-1-aminocyclopentane and immobilized via an ester linkage to long chain alkyl amine-derivatized controlled pore glass (LCAA-CPG). The applicability of these supports (5 and 6) for the synthesis of porphyrin conjugates with oligomeric biomolecules was demonstrated using an automated phosphoramidite coupling chemistry. Cleavage from the support with concentrated ammonia gave the products, viz., porphyrin conjugates of oligonucleotides (7-9) and dendritic glycoclusters (10-13) and a cyclooctyne derivative (14) in 23-58% yield. In addition, the synthesized cyclooctyne derivative of meso-tris(pyridin-4-yl)(4-carboxyphenyl)porphyrin (14) was conjugated with an azidopropyl-modified hyaluronic acid (19). The hyaluronic acid-porphyrin conjugate (15) was radiolabeled with (64)Cu and its (15[(64)Cu]) receptor binding affinity to CD44-expressing tumor cells was evaluated. PMID:26898631

  18. Surface plasmon excitation of porphyrin self-assembly monolayers on an Au surface

    NASA Astrophysics Data System (ADS)

    Ishida, Akito; Majima, Tetsuro

    1999-09-01

    Surface plasmon (SP) enhanced fluorescence spectroscopy has been employed to elucidate the molecular orientation, molecular exchange process, and photoelectrochemical properties of photofunctional self-assembly monolayers (SAMs) for the first time. A 48 nm Au film on a BK-7 right-angle prism was treated with a porphyrin disulfide ((-S(CH2)10CONH-Por)2, Por = p-(tris(p-tolyl)porphyrinyl)phenyl) (1) giving a porphyrin SAM (2). SP excitation of 2 using p-polarized 425 nm light at an incident angle of 55° gave a strongly p-polarized fluorescence of the porphyrin. This indicates selective excitation of the porphyrins having transition moments effectively overlap with the SP field vectors and the suppressed molecular motions in 2. The Q bands in the fluorescence excitation spectrum were considerably enhanced attributable to the field enhancement of SP. The molecular exchange process of a decanethiol SAM with 1 has been elucidated based on changes in the fluorescence properties. The photoelectrochemical measurement using 632.8 nm light gave a much more intense photocurrent (18.6 µA cm-2) than that provided by conventional direct photoexcitation (2.7 µA cm-2). Moreover, the photocurrent was observed using near-IR light while the energy is considerably lower than the lowest singlet excited state of the porphyrin.

  19. O2 reduction reaction by biologically relevant anionic ligand bound iron porphyrin complexes.

    PubMed

    Samanta, Subhra; Das, Pradip Kumar; Chatterjee, Sudipta; Sengupta, Kushal; Mondal, Biswajit; Dey, Abhishek

    2013-11-18

    Iron porphyrin complex with a covalently attached thiolate ligand and another with a covalently attached phenolate ligand has been synthesized. The thiolate bound complex shows spectroscopic features characteristic of P450, including the hallmark absorption spectrum of the CO adduct. Electrocatalytic O2 reduction by this complex, which bears a terminal alkyne group, is investigated by both physiabsorbing on graphite surfaces (fast electron transfer rates) and covalent attachment to azide terminated self-assembled monolayer (physiologically relevant electron transfer rates) using the terminal alkyne group. Analysis of the steady state electrochemical kinetics reveals that this catalyst can selectively reduce O2 to H2O with a second-order k(cat.) ~10(7) M(-1 )s(-1) at pH 7. The analogous phenolate bound iron porphyrin complex reduces O2 with a second-order rate constant of 10(5) M(-1) s(-1) under the same conditions. The anionic ligand bound iron porphyrin complexes catalyze oxygen reduction reactions faster than any known synthetic heme porphyrin analogues. The kinetic parameters of O2 reduction of the synthetic thiolate bound complex, which is devoid of any second sphere effects present in protein active sites, provide fundamental insight into the role of the protein environment in tuning the reactivity of thiolate bound iron porphyrin containing metalloenzymes. PMID:24171513

  20. Host-guest complexation of [60]fullerenes and porphyrins enabled by "click chemistry".

    PubMed

    Ho, Khanh-Hy Le; Hijazi, Ismail; Rivier, Lucie; Gautier, Christelle; Jousselme, Bruno; de Miguel, Gustavo; Romero-Nieto, Carlos; Guldi, Dirk M; Heinrich, Benoit; Donnio, Bertrand; Campidelli, Stéphane

    2013-08-19

    Herein the synthesis, characterization, and organization of a first-generation dendritic fulleropyrrolidine bearing two pending porphyrins are reported. Both the dendron and the fullerene derivatives were synthesized by Cu(I) -catalyzed alkyne-azide cycloaddition (CuAAC). The electron-donor-acceptor conjugate possesses a shape that allows the formation of supramolecular complexes by encapsulation of C60 within the jaws of the two porphyrins of another molecule. The interactions between the two photoactive units (i.e., C60 and Zn-porphyrin) were confirmed by cyclic voltammetry as well as by steady-state and time-resolved spectroscopy. For example, a shift of about 85 mV was found for the first reduction of C60 in the electron-donor-acceptor conjugate compared with the parent molecules, which indicates that C60 is included in the jaws of the porphyrin. The fulleropyrrolidine compound exhibits a rich polymorphism, which was corroborated by AFM and SEM. In particular, it was found to form supramolecular fibrils when deposited on substrates. The morphology of the fibrils suggests that they are formed by several rows of fullerene-porphyrin complexes.

  1. Constructing bis(porphyrinato) rare earth double-decker complexes involving N-confused porphyrin.

    PubMed

    Zhang, Yuehong; Cao, Wei; Wang, Kang; Jiang, Jianzhuang

    2014-06-28

    Reaction of metal-free N-confused 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (H2NTClPP) with metal-free 5,10,15,20-tetrakis[(4-tert-butyl)phenyl]porphyrin (H2TBPP) in the presence of M(III)(acac)3·nH2O (acac = acetylacetonate) in refluxing 1,2,4-trichlorobenzene (TCB) led to the isolation of heteroleptic bis(porphyrinato) rare earth compounds M(III)(HNTClPP)(TBPP) (M = La, Pr) (1, 2) in 6.7-10% yield. These represent the first examples of sandwich-type porphyrin rare earth double-decker complexes that involve N-confused porphyrin ligand. Different from their homoleptic bis(porphyrinato) rare earth double-decker counterparts HM(III)(TBPP)2 (M = La, Pr) (3, 4), the acidic proton in the heteroleptic analogues was revealed to localize at the inverted pyrrole nitrogen atom of the N-confused porphyrin ligand on the basis of NMR spectroscopic studies. Nevertheless, their heteroleptic bis(porphyrinato) sandwich molecular nature was confirmed on the basis of single crystal X-ray diffraction analysis over the praseodymium double-decker complex. PMID:24809442

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

    PubMed

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

    2014-08-25

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

  3. Expanding the light absorption of poly(3-hexylthiophene) by end-functionalization with π-extended porphyrins.

    PubMed

    Chevrier, Michèle; Richeter, Sébastien; Coulembier, Olivier; Surin, Mathieu; Mehdi, Ahmad; Lazzaroni, Roberto; Evans, Rachel C; Dubois, Philippe; Clément, Sébastien

    2016-01-01

    Poly(3-hexylthiophene)s end-functionalized with π-extended porphyrins have been synthesized in a one-pot procedure. The polymers show a broad absorption profile extending to 700 nm and a fibrillar microstructure, which can be tuned through judicious selection of the porphyrin molar ratio. PMID:26506849

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

    NASA Astrophysics Data System (ADS)

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

    1992-02-01

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

  5. Influence of H2TOEtPyP4 porphyrin on the stability and conductivity of bilayer lipid membranes.

    PubMed

    Torosyan, Anahit; Arakelyan, Valeri

    2015-12-01

    Many water-soluble cationic porphyrins are known to be prospective chemotherapeutics and photosensitizers for cancer treatment and diagnosis. The physicochemical properties of porphyrins, in particular their interactions with membranes, are important determining factors of their biological activity. The influence of cationic meso-tetra-[4-N-(2'-hydroxyethyl) pyridyl] porphyrin (H2TOEtPyP) on the stability and conductivity of bilayer lipid membranes (BLMs) was studied. H2TOEtPyP4 porphyrin was shown to decrease the stability of BLMs made of a mixture of DOPS and DPPE (1:1) in an electric field because of a reduction of line tension of spontaneously formed pore edges in the BLM. The presence of cationic porphyrin was found to reduce BLM surface tension. This effect was enhanced with increasing porphyrin concentration. H2TOEtPyP4 increased the probability of spontaneous pore formation. Further investigating the cyclic current-voltage characteristics of BLMs allowed determining the electrical capacity and conductivity of BLMs in the presence of H2TOEtPyP4 porphyrin. It was shown that in the presence of cationic porphyrin the electrical capacity as well as conductivity of the BLM increases.

  6. Influence of H2TOEtPyP4 porphyrin on the stability and conductivity of bilayer lipid membranes.

    PubMed

    Torosyan, Anahit; Arakelyan, Valeri

    2015-12-01

    Many water-soluble cationic porphyrins are known to be prospective chemotherapeutics and photosensitizers for cancer treatment and diagnosis. The physicochemical properties of porphyrins, in particular their interactions with membranes, are important determining factors of their biological activity. The influence of cationic meso-tetra-[4-N-(2'-hydroxyethyl) pyridyl] porphyrin (H2TOEtPyP) on the stability and conductivity of bilayer lipid membranes (BLMs) was studied. H2TOEtPyP4 porphyrin was shown to decrease the stability of BLMs made of a mixture of DOPS and DPPE (1:1) in an electric field because of a reduction of line tension of spontaneously formed pore edges in the BLM. The presence of cationic porphyrin was found to reduce BLM surface tension. This effect was enhanced with increasing porphyrin concentration. H2TOEtPyP4 increased the probability of spontaneous pore formation. Further investigating the cyclic current-voltage characteristics of BLMs allowed determining the electrical capacity and conductivity of BLMs in the presence of H2TOEtPyP4 porphyrin. It was shown that in the presence of cationic porphyrin the electrical capacity as well as conductivity of the BLM increases. PMID:26307365

  7. Universality of the glassy transitions in the two-dimensional ±J Ising model.

    PubMed

    Parisen Toldin, Francesco; Pelissetto, Andrea; Vicari, Ettore

    2010-08-01

    We investigate the zero-temperature glassy transitions in the square-lattice ±J Ising model, with bond distribution P(J{xy})=pδ(J{xy}-J)+(1-p)δ(J{xy}+J) ; p=1 and p=1/2 correspond to the pure Ising model and to the Ising spin glass with symmetric bimodal distribution, respectively. We present finite-temperature Monte Carlo simulations at p=4/5 , which is close to the low-temperature paramagnetic-ferromagnetic transition line located at p≈0.89 , and at p=1/2 . Their comparison provides a strong evidence that the glassy critical behavior that occurs for 1-p{0}glassy and magnetic modes are not coupled at the multicritical zero-temperature point where the paramagnetic-ferromagnetic transition line and the T=0 glassy transition line meet. On the theoretical side we discuss the validity of finite-size scaling in glassy systems with a zero-temperature transition and a discrete Hamiltonian spectrum. Because of a freezing phenomenon which occurs in a finite volume at sufficiently low temperatures, the standard finite-size scaling limit in terms of TL(1/ν) does not exist; the renormalization-group invariant quantity ξ/L should be used instead as basic variable.

  8. Porphyrin adsorbed on the (101[combining macron]0) surface of the wurtzite structure of ZnO--conformation induced effects on the electron transfer characteristics.

    PubMed

    Niskanen, Mika; Kuisma, Mikael; Cramariuc, Oana; Golovanov, Viacheslav; Hukka, Terttu I; Tkachenko, Nikolai; Rantala, Tapio T

    2013-10-28

    Electron transfer at the adsorbate-surface interface is crucial in many applications but the steps taking place prior to and during the electron transfer are not always thoroughly understood. In this work a model system of 4-(porphyrin-5-yl)benzoic acid adsorbed as a corresponding benzoate on the ZnO wurtzite (101[combining macron]0) surface is studied using density functional theory (DFT) and time-dependent DFT. Emphasis is on the initial photoexcitation of porphyrin and on the strength of coupling between the porphyrin LUMO or LUMO + 1 and the ZnO conduction band that plays a role in the electron transfer. Firstly, ZnO wurtzite bulk is optimized to minimum energy geometry and the properties of the isolated ZnO (101[combining macron]0) surface model and the porphyrin model are discussed to gain insight into the combined system. Secondly, various orientations of the model porphyrin on the ZnO surface are studied: the porphyrin model standing perpendicularly to the surface and gradually brought close to the surface by tilting the linker in a few steps. The porphyrin model approaches the surface either sideways with hydrogen atoms of the porphyrin ring coming down first or twisted in a ca. 45° angle, giving rise to π-interactions of the porphyrin ring with ZnO. Because porphyrins are closely packed and near the surface, emerging van der Waals (vdW) interactions are examined using Grimme's D2 method. While the orientation affects the initial excitation of porphyrin only slightly, the coupling between the LUMO and LUMO + 1 of porphyrin and the conduction band of ZnO increases considerably if porphyrin is close to the surface, especially if the π-electrons are interacting with the surface. Based on the results of coupling studies, not only the distance between porphyrin and the ZnO surface but also the orientation of porphyrin can greatly affect the electron transfer. PMID:24022239

  9. Formation of Au and tetrapyridyl porphyrin complexes in superfluid helium.

    PubMed

    Feng, Cheng; Latimer, Elspeth; Spence, Daniel; Al Hindawi, Aula M A A; Bullen, Shem; Boatwright, Adrian; Ellis, Andrew M; Yang, Shengfu

    2015-07-14

    Binary clusters containing a large organic molecule and metal atoms have been formed by the co-addition of 5,10,15,20-tetra(4-pyridyl)porphyrin (H2TPyP) molecules and gold atoms to superfluid helium nanodroplets, and the resulting complexes were then investigated by electron impact mass spectrometry. In addition to the parent ion H2TPyP yields fragments mainly from pyrrole, pyridine and methylpyridine ions because of the stability of their ring structures. When Au is co-added to the droplets the mass spectra are dominated by H2TPyP fragment ions with one or more Au atoms attached. We also show that by switching the order in which Au and H2TPyP are added to the helium droplets, different types of H2TPyP-Au complexes are clearly evident from the mass spectra. This study suggests a new route for the control over the growth of metal-organic compounds inside superfluid helium nanodroplets.

  10. Tuning the thermoelectric properties of metallo-porphyrins.

    PubMed

    Al-Galiby, Qusiy H; Sadeghi, Hatef; Algharagholy, Laith A; Grace, Iain; Lambert, Colin

    2016-01-28

    We investigated the thermoelectric properties of metalloporphyrins connected by thiol anchor groups to gold electrodes. By varying the transition metal-centre over the family Mn, Co, Ni, Cu, Fe, and Zn we are able to tune the molecular energy levels relative to the Fermi energy of the electrodes. The resulting single-molecule room-temperature thermopowers range from almost zero for Co and Cu centres, to +80 μV K(-1) and +230 μV K(-1) for Ni and Zn respectively. In contrast, the thermopowers with Mn(II) or Fe(II) metal centres are negative and lie in the range -280 to -260 μV K(-1). Complexing these with a counter anion to form Fe(III) and Mn(III) changes both the sign and magnitude of their thermopowers to +218 and +95 respectively. The room-temperature power factors of Mn(II), Mn(III), Fe(III), Zn and Fe(II) porphyrins are predicted to be 5.9 × 10(-5) W m(-1) K(-2), 5.4 × 10(-4) W m(-1) K(-2), 9.5 × 10(-4) W m(-1) K(-2), 1.6 × 10(-4) W m(-1) K(-2) and 2.3 × 10(-4) W m(-1) K(-2) respectively, which makes these attractive materials for molecular-scale thermoelectric devices.

  11. Nanometer to Millimeter Scale Peptide-Porphyrin Materials

    SciTech Connect

    D Zaytsev; F Xie; M Mukherjee; A Bludin; B Demeler; R Breece; D Tierney; M Ogawa

    2011-12-31

    AQ-Pal14 is a 30-residue polypeptide that was designed to form an {alpha}-helical coiled coil that contains a metal-binding 4-pyridylalanine residue on its solvent-exposed surface. However, characterization of this peptide shows that it exists as a three-stranded coiled coil, not a two-stranded one as predicted from its design. Reaction with cobalt(III) protoporphyrin IX (Co-PPIX) produces a six-coordinate Co-PPIX(AQ-Pal14){sub 2} species that creates two coiled-coil oligomerization domains coordinated to opposite faces of the porphyrin ring. It is found that this species undergoes a buffer-dependent self-assembly process: nanometer-scale globular materials were formed when these components were reacted in unbuffered H{sub 2}O, while millimeter-scale, rod-like materials were prepared when the reaction was performed in phosphate buffer (20 mM, pH 7). It is suggested that assembly of the globular material is dictated by the conformational properties of the coiled-coil forming AQ-Pal14 peptide, whereas that of the rod-like material involves interactions between Co-PPIX and phosphate ion.

  12. Conservation of the conformation of the porphyrin macrocycle in hemoproteins.

    PubMed

    Jentzen, W; Ma, J G; Shelnutt, J A

    1998-02-01

    The out-of-plane distortions of porphyrins in hemoproteins are characterized by displacements along the lowest-frequency out-of-plane normal coordinates of the D4h-symmetric macrocycle. X-ray crystal structures are analyzed using a computational procedure developed for determining these orthogonal displacements. The x-ray crystal structures of the heme groups are described within experimental error, using the set composed of only the lowest frequency normal coordinate of each out-of-plane symmetry type. That is, the distortion is accurately simulated by a linear combination of these orthonormal deformations, which include saddling (B2u), ruffling (B1u), doming (A2u), waving (Eg), and propellering (A1u). For example, orthonormal structural decomposition of the hemes in deoxymyoglobins reveals a predominantly dom heme deformation combined with a smaller wav(y) deformation. Generally, the heme conformation is remarkably similar for proteins from different species. For cytochromes c, the conformation is conserved as long as the amino acids between the cysteine linkages to the heme are homologous. Differences occur if this short segment varies in the number or type of residues, suggesting that this small segment causes the nonplanar distortion. Some noncovalently linked hemes like those in the peroxidases also have highly conserved characteristic distortions. Conservation occurs even for some proteins with a large natural variation in the amino acid sequence.

  13. Real-time fluorescence microscopy monitoring of porphyrin biodistribution

    NASA Astrophysics Data System (ADS)

    Kimel, Sol; Gottfried, Varda; Kunzi-Rapp, Karin; Akguen, Nermin; Schneckenburger, Herbert

    1996-01-01

    In vivo uptake of the natural porphyrins, uroporphyrin III (UP), coproporphyrin III (CP) and protoporphyrin IX (PP), was monitored by fluorescence microscopy. Experiments were performed using the chick chorioallantoic membrane (CAM) model, which allowed video documentation of fluorescence both in real time and after integration over a chosen time interval (usually 2 s). Sensitizers at a concentration of 50 (mu) M (100 (mu) L) were injected into a medium-sized vein (diameter approximately 40 micrometer) using an ultra-fine 10 micrometer diameter needle. Fluorescence images were quantitated by subtracting the fluorescence intensity of surrounding CAM tissue (Fmatrix) from the intravascular fluorescence intensity (Fintravascular), after transformation of the video frames into digital form. The differential fluorescence intensity, Fintravascular - Fmatrix, is a measure of the biodistribution. Real time measurements clearly showed that CP and UP fluorescence is associated with moving erythrocytes and not with endothelial cells of the vessel wall. Fluorescence intensity was monitored, up to 60 minutes after injection, by averaging the fluorescence over time intervals of 2 s and recording the integrated images. The fluorescence intensity reached its maximum in about 20 - 30 min after injection, presumably after monomerization inside erythrocyte membranes. The results are interpreted in terms of physical-chemical characteristics (e.g. hydrophilicity) and correlated with the photodynamically induced hemostasis in CAM blood vessels.

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

    NASA Astrophysics Data System (ADS)

    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".

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

    SciTech Connect

    Hays, J.A.

    1993-11-05

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

  16. Hydrogels containing porphyrin-loaded nanoparticles for topical photodynamic applications.

    PubMed

    González-Delgado, José A; Castro, Pedro M; Machado, Alexandra; Araújo, Francisca; Rodrigues, Francisca; Korsak, Bárbara; Ferreira, Marta; Tomé, João P C; Sarmento, Bruno

    2016-08-20

    5,10,15,20-tetrakis(1-methylpyridinium-4-yl)-porphyrin tetra-iodide (TMPyP), a potent water-soluble photosensitizer (PS) used in antimicrobial applications, was encapsulated into poly(lactic-co-glycolic acid) (PLGA) nanoparticles (TMPyP-PLGA) for topical delivery purposes. Nanoparticles resulted in a mean particle size around 130nm, narrow polydispersity index (PdI), spherical morphology and association efficiency up to 93%. Free TMPyP and TMPyP-PLGA nanoparticles were incorporated into Carbopol(®) hydrogels, resulting in controlled TMPyP release of about 60% and 20% after 4.5h, respectively. Critical properties such as appearance, clarity, viscosity and pH were maintained over time, as hydrogels were stable during 6 months at 4°C, 25°C/60% RH and 40°C/75% RH. For photodynamic applications, the photoproduction of singlet oxygen from these hydrogels was quite efficient being both formulations very photostable after 20min. No TMPyP permeation through pig ear skin was observed after 24h, and histological assays did not show relevant damages in surrounding tissues. All these excellent characteristics make them promising platforms for photodynamic applications through topical clinical use. PMID:27321129

  17. Porous Azo-Bridged Porphyrin-Phthalocyanine Network with High Iodine Capture Capability.

    PubMed

    Li, Hui; Ding, Xuesong; Han, Bao-Hang

    2016-08-01

    We report a highly efficient iodine adsorbent achieved by rational design of a porous azo-bridged porphyrin-phthalocyanine network (AzoPPN), which was synthesized by a catalyst-free coupling reaction between free-base 5,10,15,20-tetrakis(4-nitrophenyl)-porphyrin and nickel tetraaminophthlocyanine. AzoPPN has a permanent porous structure and plenty of porphyrin and phthalocyanine units in the skeleton as effective sorption sites. It displays excellent adsorption of iodine vapor up to 290 wt. % and also shows remarkable capability as adsorbent for iodine in solution. This strategy of combining physisorption with chemisorption in one adsorbent will pave the way for the development of new materials for iodine capture. PMID:27412919

  18. Nonlinear optical behavior of porphyrin functionalized nanodiamonds: an efficient material for optical power limiting.

    PubMed

    Muller, Olivier; Pichot, Vincent; Merlat, Lionel; Schmidlin, Loic; Spitzer, Denis

    2016-05-10

    The nonlinear optical mechanisms and the optical limiting behavior of porphyrin functionalized detonation nanodiamonds are investigated and compared to the conventional detonation nanodiamonds (DNDs). The optical limiting behavior is characterized by means of nonlinear transmittance, Z-scan, and scattered intensity measurements when submitted to a nanosecond pulsed Nd:YAG laser operating at the second harmonic wavelength. We found that the largest nonlinear attenuation was observed on the 4,4',4'',4'''-(porphyrin-5, 10, 15, 20-tetrayl) tetrakis benzoic acid (PCOOH) suspension. Using Z-scan experiments, it is shown that nonlinear refraction predominates in the unfunctionalized DND suspension, while nonlinear absorption is the most relevant mechanism in the porphyrin functionalized DNDs. Furthermore, a stronger backscattered intensity signal is highlighted for the unfunctionalized DNDs through nonlinear scattering measurements. PMID:27168296

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Dendritic DNA-porphyrin as mimetic enzyme for amplified fluorescent detection of DNA.

    PubMed

    Xu, Nan; Lei, Jianping; Wang, Quanbo; Yang, Qianhui; Ju, Huangxian

    2016-04-01

    In this work, a novel dendritic DNA-porphyrin superstructure was designed as mimetic enzyme for the amplified fluorescent detection of DNA. The dendritic DNA superstructure was in situ assembled with three auxiliary DNAs via hybridization chain reaction. With groove interaction between iron porphyrin (FeTMPyP) and double-stranded DNA, the dendritic DNA superstructure is capable to gather abundant FeTMPyP molecules to form dendritic DNA-FeTMPyP mimetic enzyme. Using tyramine as a substrate, the dendritic DNA-FeTMPyP demonstrated excellent peroxidase-like catalytic oxidation of tyramine into fluorescent dityramine in the presence of H2O2. Based on an amplified fluorescence signal, a signal on strategy is proposed for DNA detection with high sensitivity, good specificity and practicability. The assembly of porphyrin with dendritic DNA not only provided the new avenue to construct mimetic enzyme but also established label-free sensing platform for a wide range of analytes.

  1. Interactions among lead, cadmium, and arsenic in relation to porphyrin excretion patterns.

    PubMed Central

    Fowler, B A; Mahaffey, K R

    1978-01-01

    This paper reviews the effects of lead (Pb), cadmium (Cd), and arsenic (As) on the mitrochondrion with emphasis on alteration of mitochondrial heme biosynthetic pathway. The information was used to examine results of a Pb x Cd x As interaction study which employed urinary porphyrin excretion patterns as one assessment criterion. Data from the study showed that dietary Pb produced increased urinary excretion of aminolevulinic acid (ALA) and coproporphyrin. Dietary exposure to organic or inorganic As caused increased excretion of uroporphyrin and to a lesser extent coproporphyrin, while dietary Cd caused no significant changes in urinary levels of any of the porphyrins measured. The combination of Pb plus As produced an additive effect on coproporphyrin excretion but not that of either ALA or uroporphyrin. These data are discussed in relation to utilization of urinary porphyrins for assessing toxicity and elemental interactions. PMID:720307

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

    SciTech Connect

    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.

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

    SciTech Connect

    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.

  4. Differences in faecal profiles of porphyrins among river otters exposed to the Exxon Valdez oil spill.

    PubMed

    Blajeski, A; Duffy, L K; Bowyer, R T

    1996-01-01

    Abstract River otters (Lutra canadensis) living in marine environments of Prince William Sound, Alaska, exposed to crude oil from the Exxon Valdez spill in March 1989, showed significantly elevated levels of faecal porphyrin over those of otters from non-oiled areas (oiled mean = 48.2, andnon-oiled mean = 34.5 nmol g(-1) dry faeces). Profiles of uro-, hepta-, hexa-, penta-, copro-, andprotoporphyrin profiles were qualitatively characterized by high-performance liquid chromatography. These findings suggest that river otters may serve as a suitable indicator species in which porphyrin profiles can be used to monitor the effects of marine andfreshwater crude oil exposure. Also, this is the first model showing the effects of an oil spill on porphyrins on a free-ranging mammal using a non-lethal methodology. These effects were detectable 1 year after the spill andfollowing a major effort to clean oil from the shorelines of Prince William Sound. PMID:23888993

  5. Controls on porphyrin concentrations of Pennsylvanian organic-rich shales, Western U.S.A.

    USGS Publications Warehouse

    Clayton, J.L.; Michael, G.E.

    1990-01-01

    Organic-rich black shales of Middle Pennsylvanian (Desmoinesian) age occur over much of the central U.S. and as far west as the northern Denver and southeastern Powder River basins. Total organic carbon contents (Corg) are commonly greater than 10 wt %. Porphyrin concentrations (vanadyl + nickel) are as high as 40000 ppm relative to extractable bitumen. In bulk, the organic matter contained in the shales is mostly type II and III (Rock-Eval hydrogen indexes 200-400 mg of hydrocarbons/g of Corg). The finding of high porphyrin concentrations in type III organic matter is unusual but can be explained by a depositional model wherein high preservation of primary organic production (water column photosynthesis) is combined with substantial input of allochthonous organic matter. The allochthonous organic matter (low porphyrin concentration) may come from erosion during advance of the sea across the area or from fluvial transport from shore.

  6. Differences in faecal profiles of porphyrins among river otters exposed to the Exxon Valdez oil spill.

    PubMed

    Blajeski, A; Duffy, L K; Bowyer, R T

    1996-01-01

    Abstract River otters (Lutra canadensis) living in marine environments of Prince William Sound, Alaska, exposed to crude oil from the Exxon Valdez spill in March 1989, showed significantly elevated levels of faecal porphyrin over those of otters from non-oiled areas (oiled mean = 48.2, andnon-oiled mean = 34.5 nmol g(-1) dry faeces). Profiles of uro-, hepta-, hexa-, penta-, copro-, andprotoporphyrin profiles were qualitatively characterized by high-performance liquid chromatography. These findings suggest that river otters may serve as a suitable indicator species in which porphyrin profiles can be used to monitor the effects of marine andfreshwater crude oil exposure. Also, this is the first model showing the effects of an oil spill on porphyrins on a free-ranging mammal using a non-lethal methodology. These effects were detectable 1 year after the spill andfollowing a major effort to clean oil from the shorelines of Prince William Sound.

  7. Thermodynamics and kinetics of guest-induced switching between "basket handle" porphyrin isomers.

    PubMed

    Deutman, Alexander B C; Woltinge, Tim; Smits, Jan M M; De Gelder, René; Elemans, Johannes A A W; Nolte, Roeland J M; Rowan, Alan E

    2014-01-01

    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. PMID:24762966

  8. Investigation of the Aggregation Properties of a Chiral Porphyrin Bearing Citronellal Meso Substituent Groups.

    PubMed

    Castriciano, Maria Angela; Zagami, Roberto; Trapani, Mariachiara; Romeo, Andrea; Patanè, Salvatore; Monsù Scolaro, Luigi

    2015-12-01

    A new porphyrin bearing four R or S hydrogenated citronellal units directly bound to the meso positions of the porphyrin ring was synthesized and fully characterized through MALDI-TOF, NMR, UV/Vis absorption, and fluorescence emission spectroscopies. Both enantiomers exhibit a monomeric nature in a series of organic solvents. Acting on the polarity of the solvent, i.e., increasing the amount of water in mixture with acetone, aggregation occurs, as revealed by UV/Vis absorption, fluorescence emission, and resonance light scattering. The occurrence of both H- and J-type aggregates was suggested by fluorescence lifetime measurements. In contrast to the monomeric species, these aggregates exhibit CD spectra reflecting the chirality of the building blocks. AFM microscopy shows that micrometer ribbon-like structures form by the casting solution of these porphyrins in acetone/water onto a glass surface.

  9. Thermodynamics and kinetics of guest-induced switching between "basket handle" porphyrin isomers.

    PubMed

    Deutman, Alexander B C; Woltinge, Tim; Smits, Jan M M; De Gelder, René; Elemans, Johannes A A W; Nolte, Roeland J M; Rowan, Alan E

    2014-01-01

    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.

  10. Temporal disconnectivity of the energy landscape in glassy systems

    NASA Astrophysics Data System (ADS)

    Lempesis, Nikolaos; Boulougouris, Georgios C.; Theodorou, Doros N.

    2013-03-01

    An alternative graphical representation of the potential energy landscape (PEL) has been developed and applied to a binary Lennard-Jones glassy system, providing insight into the unique topology of the system's potential energy hypersurface. With the help of this representation one is able to monitor the different explored basins of the PEL, as well as how - and mainly when - subsets of basins communicate with each other via transitions in such a way that details of the prior temporal history have been erased, i.e., local equilibration between the basins in each subset has been achieved. In this way, apart from detailed information about the structure of the PEL, the system's temporal evolution on the PEL is described. In order to gather all necessary information about the identities of two or more basins that are connected with each other, we consider two different approaches. The first one is based on consideration of the time needed for two basins to mutually equilibrate their populations according to the transition rate between them, in the absence of any effect induced by the rest of the landscape. The second approach is based on an analytical solution of the master equation that explicitly takes into account the entire explored landscape. It is shown that both approaches lead to the same result concerning the topology of the PEL and dynamical evolution on it. Moreover, a "temporal disconnectivity graph" is introduced to represent a lumped system stemming from the initial one. The lumped system is obtained via a specially designed algorithm [N. Lempesis, D. G. Tsalikis, G. C. Boulougouris, and D. N. Theodorou, J. Chem. Phys. 135, 204507 (2011), 10.1063/1.3663207]. The temporal disconnectivity graph provides useful information about both the lumped and the initial systems, including the definition of "metabasins" as collections of basins that communicate with each other via transitions that are fast relative to the observation time. Finally, the two examined

  11. Evidence for the Powdered, Glassy Nature of the Mercurian Surface

    NASA Astrophysics Data System (ADS)

    Cooper, B. L.; Potter, A. E., Jr.; Killen, R. M.; Morgan, T. H.

    1998-09-01

    We have developed a technique to obtain thermal IR spectra of Mercury in the 8-13 micron region in daylight [1]. We observed a smooth spectral curve for Mercury, with the exception of minor features near 9.6 microns and 12.7 microns. There was no evidence of a Christiansen feature down to the 8-micron limit of our spectra. This is in general agreement with Mercury spectra reported by [2], who found Christiansen peaks just at, or slightly below, 8 microns. Features near 9.6 microns are due to incomplete compensation of the ozone absorption band. There appears to be a shallow dip in the spectrum around 12.7 microns. This may represent a transparency peak in emission. Features in the Mercury spectrum have been reported at this wavelength [2], but as a shallow elevation instead of a dip. Most acidic silicates have a feature at around 12.2 microns, whereas mafic minerals (such as hypersthene and olivine) show this feature at longer wavelengths--12.7 to 13.2 microns [3]. The 12.7 micron feature could be evidence for mafic material on the Mercurian surface. However, the lack of a Christiansen feature at 8.5 - 9.0 microns (typical of hypersthene or olivine) makes this doubtful. The smoothness of the spectra suggests that the spectral contrast of the reststrahlen bands from the Mercury surface is below the signal-to-noise level of our data. The spectral contrast of reststrahlen features is greatly reduced in powdered minerals under vacuum, requiring S/N ratios of the order of 1000 to be detected [4]. Glass formation further reduces spectral contrast by disordering the crystal lattice. Consequently, our results imply that the surface of Mercury is covered by a fine powder, which is probably also glassy as a result of intense meteoroid bombardment [5]. References [1] Cooper et al. (1998) EOS, 79, no. 24, W59 [abstract] [2] Sprague and Roush (1998) Icarus, 133, 174. [3] Salisbury et al. (1988) USGS Open-File Report 88-686, Reston, Virginia. [4] Salisbury et al. (1997) Icarus

  12. Effect of entanglements on mechanical properties of glassy polymers

    NASA Astrophysics Data System (ADS)

    Hoy, Robert Scott

    Glass forming polymers are of great industrial importance and scientific interest because of their unique mechanical properties, which arise from the connectivity and random-walk-like structure of the constituent chains. In this thesis I study the relation of entanglements to the mechanical properties of model polymer glasses and brushes using molecular dynamics simulations. We perform extensive studies of glassy strain hardening, which stabilizes polymers against strain localization and fracture. Fundamental inconsistencies in existing entropic models of strain hardening imply that our understanding of its microscopic origins is far from complete. The dependence of stress on strain and entanglement density is consistent with experiment and entropic models. However, many of the assumptions of these models are totally inconsistent with our simulation results. The dependence on temperature, rate and interaction strength can be understood as reflecting changes in the plastic flow stress rather than a network entropy. A substantial energetic contribution to the stress rises rapidly as segments between entanglements are pulled taut. The thermal component of stress is less sensitive to entanglements, mostly irreversible, and directly related to the rate of local plastic arrangements. The deformation of the entanglement network is not affine to the macroscopic stretch. Entangled and unentangled chains show the same strain hardening when plotted against the microscopic chain orientation rather than the macroscopic strain. The entropic back stress responsible for shape recovery arises from chain orientation rather than entanglement. We also present some other results unrelated to strain hardening. We analyze the entanglement of polymer brushes embedded in long-chain melts and in implicit good and theta solvents. The melt-embedded brushes are more self-entangled than those in the solvents. The degree of self-entanglement of the brushes in the solvents follows a simple

  13. β-Cyclodextrin as a Metal-anionic Porphyrin Complexation Accelerator in Aqueous Media.

    PubMed

    Ohtomo, Takao; Yokoyama, Aya; Konno, Mitsuyuki; Ohno, Osamu; Igarashi, Shukuro; Takagai, Yoshitaka

    2016-01-01

    The rate of the complexation reaction between anionic porphyrins and 11 metal ions was found to be accelerated by the presence of β-cyclodextrin (β-CD) in aqueous media at room temperature without the need for additional heating or sonication. The porphyrin complexation reaction with metal ions under aqueous conditions can be difficult due to the strong hydration energy between the metal ions and water. In this study, the specific role of β-CD as an accelerator was determined and found to enhance the typically slow reaction of the porphyrin with metal ions. A significant acceleration effect was exhibited when the model anionic porphyrin, 5,10,15,20-tetraphenyl-21H,23H-porphine-tetrasulfonic acid, and Pb(II) ions were combined in the presence of β-CD. Other than for Hg ion, the addition of β-CD decreased the metalation reaction time from 30 to 2 min. The order in the degree of acceleration was Pb > Zn, Cd > Cu > Fe, Pd > Sn > Ag, Co, Mn. Using Pb(II) as the model ion, it was determined that the complexation rate constant was enhanced by a factor of 2.4, while the dissociation rate constant was diminished by a factor of 135 in the presence of added β-CD relative to that in its absence. Overall, the complex was much more stable (formation equilibrium constant 324-fold greater in the β-CD medium. The formation of a ternary complex (cf. bicapped complex; (β-CD)2-porphyrin-metal ion) was demonstrated through the use of nuclear magnetic-resonance spectroscopy and mass spectrometry. This acceleration effect is expected to be applicable systems in which porphyrin ligands are employed for determining of metal ions in chemical analysis and separation science. PMID:27302582

  14. Role of porphyrin sequestration in the biogenesis of iron-laden astrocytic inclusions in primary culture.

    PubMed

    Schipper, H M; Small, L; Wang, X; Brawer, J R

    2002-01-01

    Astrocytes in subcortical regions of the mammalian brain progressively accumulate iron-rich, autofluorecent cytoplasmic inclusions as a function of aging. Cysteamine (CSH) accelerates the appearance of this senescent glial phenotype in situ and in primary rat astroglial cultures. Porphyrins have been implicated as the source of orange-red autofluorescence in these glial inclusions. Yet, CSH has been shown to suppress porphyrin-heme biosynthesis in cultured astroglia. To determine whether porphyrin biosynthesis or sequestration participates in the biogenesis of these glial inclusions, the porphyrin precursor, (3)H-delta-aminolevulinic acid ((3)H-ALA) was administered to CSH-exposed and control rat astroglial cultures followed by light and electron microscopic autoradiography. Control cultures exhibited faint orange-red autofluorescence, intense (3)H-ALA labeling, numerous normal mitochondria and few cytoplasmic inclusions. In these cells, (3)H-ALA labeling largely occurred over normal mitochondria. The CSH-treated astroglia exhibited diminished (3)H-ALA labeling and contained numerous orange-red autofluorescent inclusions. The latter manifested internal compartments delimited by double membranes characteristic of damaged mitochondria. The complement of normal mitochondria in the CSH-exposed cells was markedly reduced. In the CSH-treated cells, (3)H-ALA labeling predominated over the large multi-compartmental inclusions. CSH attenuates de novo porphyrin-heme biosynthesis in astroglia but may induce punctate orange-red autofluorescence in the cytoplasm of these cells by promoting large numbers of damaged, porphyrin-containing mitochondria to form tight aggregates within the nascent gliosomes.

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

    PubMed

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

    2015-09-01

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

  16. Photophysical properties of porphyrins with sterically distorted and partially screened macrocycles

    NASA Astrophysics Data System (ADS)

    Ivashin, N. V.; Shchupak, E. E.; Panarin, A. Yu.; Sagun, E. I.

    2015-06-01

    We have experimentally studied the spectral-luminescent and photophysical properties, as well as interaction processes with molecular oxygen, of eclipsed β-alkyl-substituted porphyrins para-methoxyphenyl rings of which in opposite meso-positions of the macrocycle are linked with each other in the ortho-position with the (-OCH2)-Ph-(CH2O-) bridge. Using methods of the density functional theory, we have calculated the structures of these porphyrins in the ground and lowest triplet states, electronic transitions and vibrational states, and matrix elements of the direct spin-orbit interaction. It has been found that the lifetime of the T 1 state of the investigated compounds is noticeably shortened due to the enhancement of the internal conversion. This enhancement is caused by the conformational dynamics, which promotes increasing Franck-Condon factors and the spin-orbit interaction between the T 1 and S 0 states. Nevertheless, this does not lead to a considerable decrease in the singlet-oxygen formation quantum yield. We have calculated the structures of a porphin dimer and possible dimeric forms of examined porphyrins. It has been shown that distortion of the porphyrin macrocycle according to type of ruffling weakly affects the binding energy of the porphyrin macrocycles in the dimer, this effect being unable to prevent aggregation. At the same time, the screening of the macrocycle by the phenyl ring lowers the probability of formation of oligomeric structures, which, in view of the determined photophysical properties of investigated compounds, may be used in photochemical applications that require elevated concentrations of porphyrins.

  17. β-Cyclodextrin as a Metal-anionic Porphyrin Complexation Accelerator in Aqueous Media.

    PubMed

    Ohtomo, Takao; Yokoyama, Aya; Konno, Mitsuyuki; Ohno, Osamu; Igarashi, Shukuro; Takagai, Yoshitaka

    2016-01-01

    The rate of the complexation reaction between anionic porphyrins and 11 metal ions was found to be accelerated by the presence of β-cyclodextrin (β-CD) in aqueous media at room temperature without the need for additional heating or sonication. The porphyrin complexation reaction with metal ions under aqueous conditions can be difficult due to the strong hydration energy between the metal ions and water. In this study, the specific role of β-CD as an accelerator was determined and found to enhance the typically slow reaction of the porphyrin with metal ions. A significant acceleration effect was exhibited when the model anionic porphyrin, 5,10,15,20-tetraphenyl-21H,23H-porphine-tetrasulfonic acid, and Pb(II) ions were combined in the presence of β-CD. Other than for Hg ion, the addition of β-CD decreased the metalation reaction time from 30 to 2 min. The order in the degree of acceleration was Pb > Zn, Cd > Cu > Fe, Pd > Sn > Ag, Co, Mn. Using Pb(II) as the model ion, it was determined that the complexation rate constant was enhanced by a factor of 2.4, while the dissociation rate constant was diminished by a factor of 135 in the presence of added β-CD relative to that in its absence. Overall, the complex was much more stable (formation equilibrium constant 324-fold greater in the β-CD medium. The formation of a ternary complex (cf. bicapped complex; (β-CD)2-porphyrin-metal ion) was demonstrated through the use of nuclear magnetic-resonance spectroscopy and mass spectrometry. This acceleration effect is expected to be applicable systems in which porphyrin ligands are employed for determining of metal ions in chemical analysis and separation science.

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

    PubMed

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

    2015-09-01

    Nitrite reduction to nitric oxide by heme proteins was reported as a protective mechanism to hypoxic injury in mammalian physiology. In this study, the pathways of nitrite reduction to nitric oxide mediated by iron(II) porphyrin (P) complexes, which were generally recognized as models for heme proteins, were investigated by using density functional theory (DFT). In view of two type isomers of combination of nitrite and Fe(II)(P), N-nitro- and O-nitrito-Fe(II)-porphyrin complexes, and two binding sites of proton to the different O atoms of nitrite moiety, four main pathways for the conversion of nitrite into nitric oxide mediated by iron(II) porphyrins were proposed. The results indicate that the pathway of N-bound Fe(II)(P)(NO2) isomer into Fe(III)(P)(NO) and water is similar to that of O-bound isomer into nitric oxide and Fe(III)(P)(OH) in both thermodynamical and dynamical aspects. Based on the initial computational studies of five-coordinate nitrite complexes, the conversion of nitrite into NO mediated by Fe(II)(P)(L) complexes with 14 kinds of proximal ligands was also investigated. Generally, the same conclusion that the pathways of N-bound isomers are similar to those of O-bound isomer was obtained for iron(II) porphyrin with ligands. Different effects of ligands on the reduction reactions were also found. It is notable that the negative proximal ligands can improve reactive abilities of N-nitro-iron(II) porphyrins in the conversion of nitrite into nitric oxide compared to neutral ligands. The findings will be helpful to expand our understanding of the mechanism of nitrite reduction to nitric oxide by iron(II) porphyrins. PMID:26112152

  19. Novel amphiphilic cationic porphyrin and its Ag(II) complex as potential anticancer agents.

    PubMed

    Tovmasyan, Artak; Babayan, Nelli; Poghosyan, David; Margaryan, Kristine; Harutyunyan, Boris; Grigoryan, Rusanna; Sarkisyan, Natalia; Spasojevic, Ivan; Mamyan, Suren; Sahakyan, Lida; Aroutiounian, Rouben; Ghazaryan, Robert; Gasparyan, Gennadi

    2014-11-01

    In the present study we have synthesized a novel amphiphilic porphyrin and its Ag(II) complex through modification of water-soluble porphyrinic structure in order to increase its lipophilicity and in turn pharmacological potency. New cationic non-symmetrical meso-substituted porphyrins were characterized by UV-visible, electrospray ionization mass spectrometry (ESI-MS), (1)H NMR techniques, lipophilicity (thin-layer chromatographic retention factor, Rf), and elemental analysis. The key toxicological profile (i.e. cytotoxicity and cell line- (cancer type-) specificity; genotoxicity; cell cycle effects) of amphiphilic Ag porphyrin was studied in human normal and cancer cell lines of various tissue origins and compared with its water-soluble analog. Structural modification of the molecule from water-soluble to amphiphilic resulted in a certain increase in the cytotoxicity and a decrease in cell line-specificity. Importantly, Ag(II) porphyrin showed less toxicity to normal cells and greater toxicity to their cancerous counterparts as compared to cisplatin. The amphiphilic complex was also not genotoxic and demonstrated a slight cytostatic effect via the cell cycle delay due to the prolongation of S-phase. As expected, the performed structural modification affected also the photocytotoxic activity of metal-free amphiphilic porphyrin. The ligand tested on cancer cell line revealed a dramatic (more than 70-fold) amplification of its phototoxic activity as compared to its water-soluble tetracationic metal-free analog. The compound combines low dark cytotoxicity with 5 fold stronger phototoxicity relative to Chlorin e6 and could be considered as a potential photosensitizer for further development in photodynamic therapy.

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

    NASA Astrophysics Data System (ADS)

    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.

  1. Enhancing solar photocatalytic detoxification by adsorption of porphyrins onto TiO sub 2

    SciTech Connect

    Majumder, S.A.; Ondrias, M.R. . Dept. of Chemistry); Prairie, M.R.; Shelnutt, J.A. )

    1991-01-01

    Titanium dioxide (TiO{sub 2}) is a known photocatalyst for solar detoxification of water containing organic contaminants including PCB's and dioxins. Unfortunately, the UV light used by the photocatalyst only comprises about 4% of the strong spectrum. Metalloporphyrins strongly absorb in the visible and near infrared region. Using visible light, we have investigated Ni(II) uroporphyrin (NiUroP), Sn(IV)Cl{sub 2} uroporphyrin (SnUroP) and Sn(IV)Cl{sub 2} tetrakis(p-carboxyphenyl) porphyrin (SnTCPP) as possible enhancers of destruction of a model organic compound, salicylic acid (SA), by means of photosensitization of colloidal TiO{sub 2} particles. All three porphyrins are found to adsorb reversibly onto the colloidal TiO{sub 2} upon variation of pH. Adsorption of porphyrins results in the increased colloidal stability of fine TiO{sub 2} particles in the pH range 5--8. While NiUroP on TiO{sub 2} does not show any enhancement of photodestruction, the adsorption of SnUroP increases the destruction rate compared to that of the bare TiO{sub 2} surface. The effect of ambient oxygen on the observed photolability of the Sn porphyrins and enhancement of photodestruction of SA was also investigated. SnTCPP does not photodecompose upon illumination either in the presence or absence of TiO{sub 2}, but neither does it bind to the photocatalyst at pH 6. At pH 4.5 it adsorbs onto TiO{sub 2} but it also photodecompose at this pH. We are attempting to stabilize the adsorbed porphyrins by adding suitable peripheral substituents onto the porphyrin macrocycle. 27 refs., 6 figs.

  2. Microscopic origin of the non-Gaussian behavior of dynamic structure factors of glassy matter

    NASA Astrophysics Data System (ADS)

    Cabrillo, C.; González, M. A.; Cuello, G. J.; Bermejo, F. J.; Saboungi, M. L.; Price, D. L.

    2004-04-01

    We consider the Lamb-Mössbauer factors corresponding to the structure factors of a material (ethyl alcohol) showing two glassy phases, one of those being an orientationally disordered crystal. The deviations from the idealized Gaussian behavior expected for an isotropic-harmonic vibrator within the amorphous phase and disordered crystal are found to be remarkably close. Such proximity enables us to take advantage of the crystal symmetry to gain access to specific details of the effective interparticle potential. Once this is done the treatment is extended to include the fully amorphous material. The results depict atomic motions within the glassy matrices as significantly anisotropic and highly anharmonic and thus provide a way to understand the microscopic origin of phenomena considered as fingerprints of glassy dynamics.

  3. Direct Imaging of Dynamic Glassy Behavior in a Strained Manganite Film.

    PubMed

    Kundhikanjana, Worasom; Sheng, Zhigao; Yang, Yongliang; Lai, Keji; Ma, Eric Yue; Cui, Yong-Tao; Kelly, Michael A; Nakamura, Masao; Kawasaki, Masashi; Tokura, Yoshinori; Tang, Qiaochu; Zhang, Kun; Li, Xinxin; Shen, Zhi-Xun

    2015-12-31

    Complex many-body interaction in perovskite manganites gives rise to a strong competition between ferromagnetic metallic and charge-ordered phases with nanoscale electronic inhomogeneity and glassy behaviors. Investigating this glassy state requires high-resolution imaging techniques with sufficient sensitivity and stability. Here, we present the results of a near-field microwave microscope imaging on the strain-driven glassy state in a manganite film. The high contrast between the two electrically distinct phases allows direct visualization of the phase separation. The low-temperature microscopic configurations differ upon cooling with different thermal histories. At sufficiently high temperatures, we observe switching between the two phases in either direction. The dynamic switching, however, stops below the glass transition temperature. Compared with the magnetization data, the phase separation was microscopically frozen, while spin relaxation was found in a short period of time. PMID:26765006

  4. Novel ferroelectric liquid crystals consisting glassy liquid crystal as chiral dopants

    NASA Astrophysics Data System (ADS)

    Chen, Huang-Ming Philip; Tsai, Yun-Yen; Lin, Chi-Wen; Shieh, Han-Ping David

    2006-08-01

    A series of ferroelectric liquid crystals consisting new glassy liquid crystals (GLCs) as chiral dopants were prepared and evaluated for their potentials in fast switching ability less than 1 ms. The properties of pure ferroelectric glassy liquid crystals (FGLCs) and mixtures were reported in this paper. In particular, the novel FGLC possessing wide chiral smectic C mesophase over 100 °C is able to suppress smectic A phase of host. The mixture containing 2.0 % GLC-1 performs greater alignment ability and higher contrast ratio than R2301 (Clariant, Japan) in a 2 μm pre-made cell (EHC, Japan). These results indicate that novel FLC mixtures consisting glassy liquid crystals present a promising liquid crystal materials for fast switching field sequential color displays.

  5. InP synthesis by the synthesis, solute diffusion (SSD) method using glassy-carbon crucibles

    SciTech Connect

    Miskys, C.R.; Oliveira, C.E.M. de; Carvalho, M.M.G. de

    1996-12-31

    An Indium Phosphide (InP) Synthesis system by the Synthesis, Solute Diffusion (SSD) method has been built. It provides high purity InP charges with low carrier densities (3 {times} 10{sup 14} to 2 {times} 10{sup 15} cm{sup {minus}3}) to be used as starting material for InP single-crystal Liquid Encapsulated Czochralski (LEC) growth. Glassy-carbon is a refractory material with low vapor pressure that can be moulded in various forms and sizes. Indeed the glassy-carbon crucible is reusable after the synthesis because InP does not stick to its walls. Preliminary electrical characteristics measurements showed residual carrier concentration below 3 {times} 10{sup 15} cm{sup {minus}3}. These results are comparable with those achieved utilizing quartz crucibles. The features denoted makes glassy-carbon an interesting alternative in comparison with quartz and PBN crucibles.

  6. Broadband terahertz time-domain spectroscopy : crystalline and glassy drug materials

    NASA Astrophysics Data System (ADS)

    Kojima, Seiji; Shibata, Tomohiko; Igawa, Hikaru; Mori, Tatsuya

    2014-03-01

    Low-energy IR active modes of glassy and crystalline drug materials were studied by the broadband Terahertz Time Domain Spectroscopy (THz-TDS) in the frequency range from 0.5 to 6.5 THz using a Cherenkov type THz generator. In order to determine the real and imaginary parts of complex dielectric constant, all samples were measured by the transmission using a pure pellet without mixing polyethylene. For glassy indomethacine, the broadband THz spectrum of real part of dielectric constant shows step-wise decrease with the increase of frequency, while the imaginary part shows a broad peak at about 3 THz reflecting quenched glassy disordered structure. The observed spectra of crystalline racemic ketoprofen show the noncoincidence of peak frequencies between low-frequency Raman scattering and THz absorbance spectra. It can be attributed to the fact that the mutual exclusion principle between Raman and IR activities holds below 6 THz.

  7. Glassiness and exotic entropy scaling induced by quantum fluctuations in a disorder-free frustrated magnet

    PubMed Central

    Klich, I.; Lee, S.-H.; Iida, K.

    2014-01-01

    When spins are arranged in a lattice of triangular motif, the phenomenon of frustration leads to numerous energetically equivalent ground states, and results in exotic states such as spin liquid and spin ice. Here we report an alternative situation: a system, classically a liquid, freezes in the clean limit into a glassy state induced by quantum fluctuations. We call such glassy state a spin jam. The case in point is a frustrated magnet, where spins are arranged in a triangular network of bipyramids. Quantum corrections break the classical degeneracy into a set of aperiodic spin configurations forming local minima in a rugged energy landscape. This is established by mapping the problem into tiling with hexagonal tiles. The number of tessellations scales with the boundary length rather than its volume, showing the absence of local zero-energy modes. Low-temperature thermodynamics is discussed to compare it with other glassy materials. PMID:24686398

  8. A magnetic glassy phase in Fe(1+y)Se(x)Te(1-x) single crystals.

    PubMed

    Lamura, G; Shiroka, T; Bonfà, P; Sanna, S; Bernardini, F; De Renzi, R; Viennois, R; Giannini, E; Piriou, A; Emery, N; Cimberle, M R; Putti, M

    2013-04-17

    The evolution of magnetic order in Fe1+ySexTe1-x crystals as a function of Se content was investigated by means of ac/dc magnetometry and muon-spin spectroscopy. Experimental results and self-consistent density functional theory calculations both indicate that muons are implanted in vacant iron-excess sites, where they probe a local field mainly of dipolar origin, resulting from an antiferromagnetic (AFM) bicollinear arrangement of iron spins. This long-range AFM phase becomes progressively disordered with increasing Se content. At the same time all the tested samples manifest a marked glassy character that vanishes for high Se contents. The presence of local electronic/compositional inhomogeneities most likely favours the growth of clusters whose magnetic moment 'freezes' at low temperature. This glassy magnetic phase justifies both the coherent muon precession seen at short times in the asymmetry data, as well as the glassy behaviour evidenced by both dc and ac magnetometry.

  9. Direct Imaging of Dynamic Glassy Behavior in a Strained Manganite Film

    NASA Astrophysics Data System (ADS)

    Kundhikanjana, Worasom; Sheng, Zhigao; Yang, Yongliang; Lai, Keji; Ma, Eric Yue; Cui, Yong-Tao; Kelly, Michael A.; Nakamura, Masao; Kawasaki, Masashi; Tokura, Yoshinori; Tang, Qiaochu; Zhang, Kun; Li, Xinxin; Shen, Zhi-Xun

    2015-12-01

    Complex many-body interaction in perovskite manganites gives rise to a strong competition between ferromagnetic metallic and charge-ordered phases with nanoscale electronic inhomogeneity and glassy behaviors. Investigating this glassy state requires high-resolution imaging techniques with sufficient sensitivity and stability. Here, we present the results of a near-field microwave microscope imaging on the strain-driven glassy state in a manganite film. The high contrast between the two electrically distinct phases allows direct visualization of the phase separation. The low-temperature microscopic configurations differ upon cooling with different thermal histories. At sufficiently high temperatures, we observe switching between the two phases in either direction. The dynamic switching, however, stops below the glass transition temperature. Compared with the magnetization data, the phase separation was microscopically frozen, while spin relaxation was found in a short period of time.

  10. An expanded porphyrin approach toward transactinium chelation and the development of porphyrin-coated optical fibers as potential actinide sensors

    SciTech Connect

    Klunder, G.; Silva, R.

    1994-12-01

    Characterization of the contamination at DOE waste sites and facilities is necessary during environmental restoration. Characterization of toxic waste in containers and storage tanks is needed for effective waste management. Therefore, analytical and monitoring systems are needed for real-time analysis and feedback. The development of in-situ methods to measure chemical properties by specialized instrumentation capable of real-time analysis, without sacrificing sensitivity, has been identified as an area of needed development. Absorption spectroscopy is widely used and considered to be one of the most reliable techniques available for the qualitative and quantitative determination of sample composition. With the advancements in fiber optic technology, using light for remote in-situ sensing of groundwater contaminants has become practical. Significant progress has been made in the area of fiber-optic chemical sensors as can be seen by the number of recent review articles. The objective of this work is to develop a remote sensor for real-time measurement of actinides and concentrations in environmental or process waters based on absorption spectroscopy using internal reflection spectroscopy. Porphyrin coated silica wafers were prepared and the sensitivity and selectivity to actinides was determined.

  11. Functional cationic nanomagnet-porphyrin hybrids for the photoinactivation of microorganisms.

    PubMed

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

    2010-12-28

    Cationic nanomagnet-porphyrin hybrids were synthesized and their photodynamic therapy capabilities were investigated against the Gram (-) Escherichia coli bacteria, the Gram (+) Enterococcus faecalis bacteria and T4-like phage. The synthesis, structural characterization, photophysical properties, and antimicrobial activity of these new materials are discussed. The results show that these new multicharged nanomagnet-porphyrin hybrids are very stable in water and highly effective in the photoinactivation of bacteria and phages. Their remarkable antimicrobial activity, associated with their easy recovery, just by applying a magnetic field, makes these materials novel photosensitizers for water or wastewater disinfection.

  12. Simultaneous occurrence of three different valence tautomers in meso-vinylruthenium-modified zinc porphyrin radical cations.

    PubMed

    Chen, Jing; Wuttke, Evelyn; Polit, Walther; Exner, Thomas; Winter, Rainer F

    2013-03-01

    The mixed-valent radical cation of a styrylruthenium-modified meso-tetraarylzinc porphyrin forms a mixture of three different valence tautomers (VTs) in CH2Cl2 or 1,2-C2H4Cl2 solutions. One of these VTs has the charge and spin delocalized over the porphyrin and the styrylruthenium moieties, while the other two display charge and spin localization on just one of the different redox sites. The relative amounts of the three different VTs were determined by EPR and IR spectroscopies at variable temperatures, while delocalization in the ground state was confirmed by DFT calculations.

  13. Unique Diagnostic and Therapeutic Roles of Porphyrins and Phthalocyanines in Photodynamic Therapy, Imaging and Theranostics

    PubMed Central

    Josefsen, Leanne B.; Boyle, Ross W.

    2012-01-01

    Porphyrinic molecules have a unique theranostic role in disease therapy; they have been used to image, detect and treat different forms of diseased tissue including age-related macular degeneration and a number of different cancer types. Current focus is on the clinical imaging of tumour tissue; targeted delivery of photosensitisers and the potential of photosensitisers in multimodal biomedical theranostic nanoplatforms. The roles of porphyrinic molecules in imaging and pdt, along with research into improving their selective uptake in diseased tissue and their utility in theranostic applications are highlighted in this Review. PMID:23082103

  14. The evaluation of NIR-absorbing porphyrin derivatives as contrast agents in photoacoustic imaging

    PubMed Central

    Abuteen, Akram; Zanganeh, Saeid; Akhigbe, Joshua; Samankumara, Lalith P.; Aguirre, Andres; Biswal, Nrusingh; Braune, Marcel; Vollertsen, Anke; Röder, Beate; Brückner, Christian; Zhu, Quing

    2016-01-01

    Six free base tetrapyrrolic chromophores, three quinoline-annulated porphyrins and three morpholinobacteriochlorins, that absorb light in the near-IR range and possess, in comparison to regular porphyrins, unusually low fluorescence emission and 1O2 quantum yields were tested with respect to their efficacy as novel molecular photo-acoustic imaging contrast agents in a tissue phantom, providing an up to ~2.5-fold contrast enhancement over that of the benchmark contrast agent ICG. The testing protocol compares the photoacoustic signal output strength upon absorption of approximately the same light energy. Some relationships between photophysical parameters of the dyes and the resulting photoacoustic signal strength could be derived. PMID:24071709

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

    PubMed

    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.

  16. Discrete multiporphyrin pseudorotaxane assemblies from di- and tetravalent porphyrin building blocks

    PubMed Central

    Lohse, Mirko; von Krbek, Larissa K S; Radunz, Sebastian; Moorthy, Suresh

    2015-01-01

    Summary Two pairs of divalent and tetravalent porphyrin building blocks carrying the complementary supramolecular crown ether/secondary ammonium ion binding motif have been synthesized and their derived pseudorotaxanes have been studied by a combination of NMR spectroscopy in solution and ESI mass spectrometry in the gas phase. By simple mixing of the components the formation of discrete dimeric and trimeric (metallo)porphyrin complexes predominates, in accordance to binding stoichiometry, while the amount of alternative structures can be neglected. Our results illustrate the power of multivalency to program the multicomponent self-assembly of specific entities into discrete functional nanostructures. PMID:26124877

  17. Water Formation for the Metalation of Porphyrin Molecules on Oxidized Cu(111).

    PubMed

    Verdini, Alberto; Shinde, Prashant; Montanari, Gian Luca; Suran-Brunelli, Simone Tommaso; Caputo, Marco; Di Santo, Giovanni; Pignedoli, Carlo A; Floreano, Luca; Passerone, Daniele; Goldoni, Andrea

    2016-10-01

    Herein the formation of water molecules in the intermediate step of the redox reaction of porphyrins self-metalation on O/Cu(111) is demonstrated. Photoemission measurements show that the temperature on which porphyrins pick-up a substrate metal atom on O/Cu(111) is reduced by about 185±15 K with respect to the pure Cu(111). DFT calculations clearly indicate that the formation of a water molecule is less expensive than the formation of H2 on the O/Cu(111) substrate and, in some cases, it can be also exothermic. PMID:27555424

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

    SciTech Connect

    Mondal, Rajkumar; Sarkar, Utpal

    2015-06-24

    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.

  19. Identification of a Large Pool of Microorganisms with an Array of Porphyrin Based Gas Sensors.

    PubMed

    Zetola, Nicola M; Modongo, Chawangwa; Mathlagela, Keikantse; Sepako, Enoch; Matsiri, Ogopotse; Tamuhla, Tsaone; Mbongwe, Bontle; Martinelli, Eugenio; Sirugo, Giorgio; Paolesse, Roberto; Di Natale, Corrado

    2016-04-01

    The association between volatile compounds (VCs) and microorganisms, as demonstrated by several studies, may offer the ground for a rapid identification of pathogens. To this regard, chemical sensors are a key enabling technology for the exploitation of this opportunity. In this study, we investigated the performance of an array of porphyrin-coated quartz microbalance gas sensors in the identification of a panel of 12 bacteria and fungi. The porphyrins were metal complexes and the free base of a functionalized tetraphenylporphyrin. Our results show that the sensor array distinguishes the VC patterns produced by microorganisms in vitro. Besides being individually identified, bacteria are also sorted into Gram-positive and Gram-negative.

  20. Probing Ring Currents in Mg-Porphyrins by Pump–Probe Spectroscopy

    PubMed Central

    Rodriguez, Justo J.

    2013-01-01

    Theoretical studies of Manz et al. have shown that upon excitation of a Mg-porphyrin molecule with a circularly polarized laser pulse, a ring current can be generated that is much stronger than what can be induced by means of an external magnetic field with present technology. We show that the circular dichroism signal of a Mg-porphyrin molecule that has been excited to a state with an inner ring current is proportional to the magnitude of the probability of this ring current and can be used for the detection of this current. In analogy to magnetic circular dichroism, it probes the symmetry of degenerate excited states. PMID:22881200

  1. Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems.

    PubMed

    Okujima, Tetsuo; Mack, John; Nakamura, Jun; Kubheka, Gugu; Nyokong, Tebello; Zhu, Hua; Komobuchi, Naoki; Ono, Noboru; Yamada, Hiroko; Uno, Hidemitsu; Kobayashi, Nagao

    2016-10-01

    A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels-Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals. PMID:27558988

  2. Oxoferryl porphyrin cation radicals in model systems: Evidence for variable metal-radical spin coupling

    NASA Astrophysics Data System (ADS)

    Bill, E.; Bominaar, E. L.; Ding, X.-Q.; Trautwein, A. X.; Winkler, H.; Mandon, D.; Weiss, R.; Gold, A.; Jayaraj, K.; Toney, G. E.

    1990-07-01

    Magnetic properties of frozen solutions of highly oxidized iron porphyrin complexes were investigated by EPR and Mössbauer spectroscopy. The Mössbauer spectra, recorded at low temperatures in various magnetic fields, were analyzed on the basis of spin Hamiltonian simulations. Spin coupling between ferryl iron (FeIV) and porphyrin cation radical was taken into account explicitly. Hyperfine and spin-coupling parameters are given for several complexes, together with zero-field parameters. One of the complexes exhibits weak spin coupling, it is the first model system exhibiting properties comparable to those of the oxoferryl cation radical enzyme Horse Radish Peroxidase I.

  3. Tuning the Electronic Structure and Properties of Perylene-Porphyrin-Perylene Panchromatic Absorbers.

    PubMed

    Amanpour, Javad; Hu, Gongfang; Alexy, Eric J; Mandal, Amit Kumar; Kang, Hyun Suk; Yuen, Jonathan M; Diers, James R; Bocian, David F; Lindsey, Jonathan S; Holten, Dewey

    2016-09-29

    Light-harvesting architectures that afford strong absorption across the near-ultraviolet to near-infrared region, namely, panchromatic absorptivity, are potentially valuable for capturing the broad spectral distribution of sunlight. One previously reported triad consisting of two perylene monoimides strongly coupled to a free base porphyrin via ethyne linkers (FbT) shows panchromatic absorption together with a porphyrin-like S1 excited state albeit at lower energy than that of a typical monomeric porphyrin. Here, two new porphyrin-bis(perylene) triads have been prepared wherein the porphyrin bears two pentafluorophenyl substituents. The porphyrin is in the free base (FbT-F) or zinc chelate (ZnT-F) forms. The zinc chelate (ZnT) of the original triad bearing nonfluorinated aryl rings also was prepared. The triads were characterized using static and time-resolved optical spectroscopy. The results were analyzed with the aid of molecular-orbital characteristics obtained using density functional theory calculations. Of the four triads, FbT is the most panchromatic in affording the most even distribution of absorption spectral intensity as well as exhibiting the largest wavelength span (380-750 nm). The triads exhibit fluorescence yields (0.35 for FbT-F in toluene) that are substantially greater than for the porphyrin benchmarks (0.049 for FbP-F). The singlet excited-state lifetimes (τS) for the triads in toluene decrease in the order FbT-F (2.7 ns) > FbT (2.0 ns) > ZnT (1.2 ns) ∼ ZnT-F (1.1 ns). The τS values in benzonitrile are FbT (1.3 ns) > FbT-F (1.2 ns) > ZnT-F (0.6 ns) > ZnT (0.2 ns). Thus, the free base triads exhibit relatively long (1.2-2.7 ns) excited-state lifetimes in both polar and nonpolar media. The combined photophysical characteristics indicate that FbT and FbT-F are the best choices for panchromatic light-harvesting systems. Collectively, the findings afford insights into the effects of electronic structure on the panchromatic behavior of ethynyl

  4. Self-Induced Glassiness and Pattern Formation in Spin Systems Subject to Long-Range Interactions

    NASA Astrophysics Data System (ADS)

    Principi, Alessandro; Katsnelson, Mikhail I.

    2016-09-01

    We study the glass formation in two- and three-dimensional Ising and Heisenberg spin systems subject to competing interactions and uniaxial anisotropy with a mean-field approach. In three dimensions, for sufficiently strong anisotropy the systems always modulate in a striped phase. Below a critical strength of the anisotropy, a glassy phase exists in a finite range of temperature, and it becomes more stable as the system becomes more isotropic. In two dimensions the criticality is always avoided and the glassy phase always exists.

  5. Electrochemical assembling of methionine-gold nanoparticles and catalysis on the surface of glassy carbon electrode

    NASA Astrophysics Data System (ADS)

    Song, Y. Z.; Wang, J. H.; Zhang, X. M.; Cao, W.; Ge, A.; Zhou, L.

    2014-12-01

    In this paper cyclic voltammetry was used for the synthesis of linear array spherical gold nanoparticles on the surface of glassy carbon electrode using methionine as a stable reagent. The methionine-gold nanoparticles on the surface of glassy electrode were obtained. The methionine-gold nanoparticles were characterized by cyclic voltammetry, scanning electron microscopy, energy dispersive spectrometry and powder X-ray diffraction. Electrochemical behavior of methionine at methionine-gold nanoparticle modified electrode was investigated. It was demonstrated that the methionine-gold nanoparticles can catalyze electrochemical transformations of methionine.

  6. A Thermodynamic Theory of Solid Viscoelasticity. Part 3: Nonlinear Glassy Viscoelasticity, Stability Constraints, Specifications

    NASA Technical Reports Server (NTRS)

    Freed, Alan; Leonov, Arkady I.

    2002-01-01

    This paper, the last in the series, continues developing the nonlinear constitutive relations for non-isothermal, compressible, solid viscoelasticity. We initially discuss a single integral approach, more suitable for the glassy state of rubber-like materials, with basic functionals involved in the thermodynamic description for this type of viscoelasticity. Then we switch our attention to analyzing stability constraints, imposed on the general formulation of the nonlinear theory of solid viscoelasticity. Finally, we discuss specific (known from the literature or new) expressions for material functions that are involved in the constitutive formulations of both the rubber-like and glassy-like, complementary parts of the theory.

  7. Elastic properties of aspirin in its crystalline and glassy phases studied by micro-Brillouin scattering

    NASA Astrophysics Data System (ADS)

    Ko, Jae-Hyeon; Lee, Kwang-Sei; Ike, Yuji; Kojima, Seiji

    2008-11-01

    The acoustic waves propagating along the direction perpendicular to the (1 0 0) cleavage plane of aspirin crystal were investigated using micro-Brillouin spectroscopy from which C11, C55 and C66 were obtained. The temperature dependence of the longitudinal acoustic waves could be explained by normal anharmonic lattice models, while the transverse acoustic waves showed an abnormal increase in the hypersonic attenuation at low temperatures indicating their coupling to local remnant dynamics. The sound velocity as well as the attenuation of the longitudinal acoustic waves of glassy aspirin showed a substantial change at ˜235 K confirming a transition from glassy to supercooled liquid state in vitreous aspirin.

  8. Metallated porphyrin based porous organic polymers as efficient electrocatalysts

    NASA Astrophysics Data System (ADS)

    Lu, Guolong; Zhu, Youlong; Xu, Kongliang; Jin, Yinghua; Ren, Zhiyong Jason; Liu, Zhenning; Zhang, Wei

    2015-10-01

    Developing efficient, stable and low-cost catalysts for Oxygen Reduction Reaction (ORR) is of great significance to many emerging technologies including fuel cells and metal-air batteries. Herein, we report the development of a cobalt(ii) porphyrin based porous organic polymer (CoPOP) and its pyrolyzed derivatives as highly active ORR catalysts. The as-synthesized CoPOP exhibits high porosity and excellent catalytic performance stability, retaining ~100% constant ORR current over 50 000 s in both alkaline and acidic media. Pyrolysis of CoPOP at various temperatures (600 °C, 800 °C, and 1000 °C) yields the materials consisting of graphitic carbon layers and cobalt nanoparticles, which show greatly enhanced catalytic activity compared to the as-synthesized CoPOP. Among them, CoPOP-800/C pyrolyzed at 800 °C shows the highest specific surface area and ORR activity, displaying the most positive half-wave potential (0.825 V vs. RHE) and the largest limited diffusion current density (5.35 mA cm-2) in an alkaline medium, which are comparable to those of commercial Pt/C (20 wt%) (half-wave potential 0.829 V vs. RHE, limited diffusion current density 5.10 mA cm-2). RDE and RRDE experiments indicate that CoPOP-800/C directly reduces molecular oxygen to water through a 4-e- pathway in both alkaline and acidic media. More importantly, CoPOP-800/C exhibits excellent durability and methanol-tolerance under acidic and alkaline conditions, which surpass the Pt/C (20 wt%) system.Developing efficient, stable and low-cost catalysts for Oxygen Reduction Reaction (ORR) is of great significance to many emerging technologies including fuel cells and metal-air batteries. Herein, we report the development of a cobalt(ii) porphyrin based porous organic polymer (CoPOP) and its pyrolyzed derivatives as highly active ORR catalysts. The as-synthesized CoPOP exhibits high porosity and excellent catalytic performance stability, retaining ~100% constant ORR current over 50 000 s in both

  9. Effect of photocurrent enhancement in porphyrin-graphene covalent hybrids.

    PubMed

    Tang, Jianguo; Niu, Lin; Liu, Jixian; Wang, Yao; Huang, Zhen; Xie, Shiqiang; Huang, Linjun; Xu, Qingsong; Wang, Yuan; Belfiore, Laurence A

    2014-01-01

    Graphene oxide (GO) sheets were covalently functionalized with 5-p-aminophenyl-10,15,20-triphenylporphyrin (NH2TPP) by an amidation reaction between the amino group in NH2TPP and carboxyl groups in GO. The Fourier transform infrared spectroscopy, nuclear magnetic resonance, scanning and transmission electron microscopies reveal that NH2TPP covalent bonds form on the double surface of graphene oxide sheets, generating a unique nano-framework, i.e., NH2TPP-graphene-NH2TPP. Its UV-visible spectroscopy reveals that the absorption spectrum is not a linear superposition of the spectra of NH2TPP and graphene oxide, because a 59nm red shift of the strong graphene oxide absorption is observed from 238 to 297nm, with significant spectral broadening between 300 and 700nm. Fluorescence emission spectroscopy indicates efficient quenching of NH2TPP photoluminescence in this hybrid material, suggesting that photo-induced electron transfer occurs at the interface between NH2TPP and GO. A reversible on/off photo-current density of 47mA/cm(2) is observed when NH2TPP-graphene-NH2TPP hybrid sandwiches are subjected to pulsed white-light illumination. Covalently-bound porphyrins decrease the optical HOMO/LUMO band gap of graphene oxide by ≈1eV, according to UV-visible spectroscopy. Cyclic voltammetry predicts a small HOMO/LUMO band gap of 0.84eV for NH2TPP-graphene-NH2TPP hybrid sandwiches, which is consistent with efficient electron transfer and fluorescence quenching.

  10. Metallated porphyrin based porous organic polymers as efficient electrocatalysts.

    PubMed

    Lu, Guolong; Zhu, Youlong; Xu, Kongliang; Jin, Yinghua; Ren, Zhiyong Jason; Liu, Zhenning; Zhang, Wei

    2015-11-21

    Developing efficient, stable and low-cost catalysts for Oxygen Reduction Reaction (ORR) is of great significance to many emerging technologies including fuel cells and metal-air batteries. Herein, we report the development of a cobalt(II) porphyrin based porous organic polymer (CoPOP) and its pyrolyzed derivatives as highly active ORR catalysts. The as-synthesized CoPOP exhibits high porosity and excellent catalytic performance stability, retaining ∼100% constant ORR current over 50,000 s in both alkaline and acidic media. Pyrolysis of CoPOP at various temperatures (600 °C, 800 °C, and 1000 °C) yields the materials consisting of graphitic carbon layers and cobalt nanoparticles, which show greatly enhanced catalytic activity compared to the as-synthesized CoPOP. Among them, CoPOP-800/C pyrolyzed at 800 °C shows the highest specific surface area and ORR activity, displaying the most positive half-wave potential (0.825 V vs. RHE) and the largest limited diffusion current density (5.35 mA cm(-2)) in an alkaline medium, which are comparable to those of commercial Pt/C (20 wt%) (half-wave potential 0.829 V vs. RHE, limited diffusion current density 5.10 mA cm(-2)). RDE and RRDE experiments indicate that CoPOP-800/C directly reduces molecular oxygen to water through a 4-e(-) pathway in both alkaline and acidic media. More importantly, CoPOP-800/C exhibits excellent durability and methanol-tolerance under acidic and alkaline conditions, which surpass the Pt/C (20 wt%) system. PMID:26486413

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

    PubMed

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

    2016-06-01

    Photodynamic therapy (PDT) is a noninvasive treatment for solid malignant and flat tumors. Light activated sensitizers catalyze photochemical reactions that produce reactive oxygen species which can cause cancer cell death. In this work we investigated the photophysical properties of the photosensitizer ruthenium(II) porphyrin (RuP), along with its PDT efficiency onto rat bladder cancer cells (AY27). Optical spectroscopy verified that RuP is capable to activate singlet oxygen via blue and red absorption bands and inter system crossing (ISC) to the triplet state. In vitro experiments on AY27 indicated increased photo-toxicity of RuP (20μM, 18h incubation) after cell illumination (at 435nm), as a function of blue light exposure. Cell survival fraction was significantly reduced to 14% after illumination of 20μM RuP with 15.6J/cm(2), whereas the "dark toxicity" of 20μM RuP was 17%. Structural and morphological changes of cells were observed, due to RuP accumulation, as well as light-dependent cell death was recorded by confocal microscopy. Flow cytometry verified that PDT-RuP (50μM) triggered significant photo-induced cellular destruction with a photoxicity of (93%±0.9%). Interestingly, the present investigation of RuP-PDT showed that the dominating mode of cell death is necrosis. RuP "dark toxicity" compared to the conventional chemotherapeutic drug cisplatin was higher, both evaluated by the MTT assay (24h). In conclusion, the present investigation shows that RuP with or without photoactivation induces cell death of bladder cancer cells. PMID:26845686

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

    PubMed

    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

  13. Effect of interaction with micelles on the excited-state optical properties of zinc porphyrins and J-aggregates formation

    NASA Astrophysics Data System (ADS)

    Gonçalves, P. J.; Corrêa, D. S.; Franzen, P. L.; De Boni, L.; Almeida, L. M.; Mendonça, C. R.; Borissevitch, I. E.; Zílio, S. C.

    2013-08-01

    This work reports on the photophysical properties of zinc porphyrins meso-tetrakis methylpyridiniumyl (Zn2+TMPyP) and meso-tetrakis sulfonatophenyl (Zn2+TPPS) in homogeneous aqueous solutions and in the presence of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) micelles. The excited-state dynamic was investigated with the Z-scan technique, UV-Vis absorption, and fluorescence spectroscopy. Photophysical parameters were obtained by analyzing the experimental data with a conventional five-energy-level diagram. The interaction of the charged side porphyrin groups with oppositely charged surfactants can reduce the electrostatic repulsion between porphyrin molecules leading to aggregation, which affected the porphyrin characteristics such as absorption cross-sections, lifetimes and quantum yields. The interaction between anionic ZnTPPS with cationic CTAB micelles induced the formation of porphyrin J-aggregates, while this effect was not observed in the interaction of ZnTMPyP with SDS micelles. This difference is, probably, due to the difference in electrostatic repulsion between the porphyrin molecules. The insights obtained by these results are important for the understanding of the photophysical behavior of porphyrins, regarding potential applications in pharmacokinetics as encapsulation of photosensitizer for drug delivery systems and in its interaction with cellular membrane.

  14. Fabrication of Glassy and Crystalline Ferroelectric Oxide by Containerless Processing

    NASA Astrophysics Data System (ADS)

    Yoda, Shinichi

    1. Instruction Much effort has been devoted to forming bulk glass from the melt of ferroelectric crystalline materials without adding any network-forming oxides such as SiO2 due to the potential for producing transparent glass ceramics with high dielectric constant and enhanced piezoelectric, pyroelectric and electro-optic effects. However, they require a higher cooling rate than glass formed by conventional techniques. Therefore, only amorphous thin-films have been formed, using rapid quenching with a cooling rate >105 K/s. The containerless processing is an attractive synthesis technique as it can prevent melt contamination, minimize heterogeneous nucleation, and allow melt to achieve deep undercooling for forming metastable phase and glassy material. Recently a new ferroelectric materiel, monoclinic BaTi2 O5 , with Currie temperature as 747 K was reported. In this study, we fabricated a bulk BaTi2 O5 glass from melt using containerless processing to study the phase relations and ferroelectric properties of BaTi2 O5 . To our knowledge, this was the first time that a bulk glass of ferroelectric material was fabricated from melt without adding any network-forming oxide. 2. Experiments BaTi2 O5 sphere glass with 2mm diameter was fabricated using containerless processing in an Aerodynamic Levitation Furnace (ALF). The containerless processing allowed the melt to achieve deep undercooling for glass forming. High purity commercial BaTiO3 and TiO2 powders were mixed with a mole ratio of 1:1 and compressed into rods and then sintered at 1427 K for 10 h. Bulk samples with a mass of about 20 mg were cut from the rod, levitated with the ALF, and then melted by a CO2 laser beam. After quenching with a cooling rate of about 1000 K/s, 2 mm diameter sphere glass could be obtained. To analyze the glass structure, a high-energy x-ray diffraction experiment was performed using an incident photon energy of 113.5 keV at the high-energy x-ray diffraction beamline BL04B2 of SPring-8

  15. Transient EPR Reveals Triplet State Delocalization in a Series of Cyclic and Linear π-Conjugated Porphyrin Oligomers.

    PubMed

    Tait, Claudia E; Neuhaus, Patrik; Peeks, Martin D; Anderson, Harry L; Timmel, Christiane R

    2015-07-01

    The photoexcited triplet states of a series of linear and cyclic butadiyne-linked porphyrin oligomers were investigated by transient Electron Paramagnetic Resonance (EPR) and Electron Nuclear DOuble Resonance (ENDOR). The spatial delocalization of the triplet state wave function in systems with different numbers of porphyrin units and different geometries was analyzed in terms of zero-field splitting parameters and proton hyperfine couplings. Even though no significant change in the zero-field splitting parameters (D and E) is observed for linear oligomers with two to six porphyrin units, the spin polarization of the transient EPR spectra is particularly sensitive to the number of porphyrin units, implying a change of the mechanism of intersystem crossing. Analysis of the proton hyperfine couplings in linear oligomers with more than two porphyrin units, in combination with density functional theory calculations, indicates that the spin density is localized mainly on two to three porphyrin units rather than being distributed evenly over the whole π-system. The sensitivity of the zero-field splitting parameters to changes in geometry was investigated by comparing free linear oligomers with oligomers bound to a hexapyridyl template. Significant changes in the zero-field splitting parameter D were observed, while the proton hyperfine couplings show no change in the extent of triplet state delocalization. The triplet state of the cyclic porphyrin hexamer has a much decreased zero-field splitting parameter D and much smaller proton hyperfine couplings with respect to the monomeric unit, indicating complete delocalization over six porphyrin units in this symmetric system. This surprising result provides the first evidence for extensive triplet state delocalization in an artificial supramolecular assembly of porphyrins. PMID:26035477

  16. A fullerene C60-based ligand in a stationary phase for affine chromatography of membrane porphyrin-binding proteins

    NASA Astrophysics Data System (ADS)

    Amirshakhi, N.; Alyautdin, R. N.; Orlov, A. P.; Poloznikov, A. A.; Kuznetsov, D. A.

    2008-11-01

    A new affine chromatography technique is suggested for the purification of porphyrin-binding proteins (PBP) from mammal cell membranes. The procedure uses new fullerene-porphyrin ligands immobilized on agarose and bound to the polysaccharide matrix via the epoxycyclohexyl residue. A selective PBP stationary phase was used in a single-column chromatography run for the complete purification of a monomeric protein (17.6 kDa) from mitochondrial membranes of rat myocardium. This protein was characterized by high affinity for porphyrin-related structures. To separate it from other nonspecifically sorbed membrane proteins, synchronous linear pH and ionic strength gradients were used.

  17. Towards alternatives to anodic water oxidation: basket-handle thiolate Fe(III) porphyrins for electrocatalytic hydrocarbon oxidation.

    PubMed

    Li, Peiyi; Alenezi, Khalaf; Ibrahim, Saad K; Wright, Joseph A; Hughes, David L; Pickett, Christopher J

    2012-12-01

    Selective electrocatalytic oxidation of hydrocarbons to alcohols, epoxides or other (higher value) oxygenates should in principal present a useful complementary anodic half-cell reaction to cathodic generation of fuels from water or CO(2) viz. an alternative to oxygen evolution. A series of new basket-handle thiolate Fe(III) porphyrins have been synthesised and shown to mediate anodic oxidation of hydrocarbons, specifically adamantane hydroxylation and cyclooctene epoxidation. We compare yields obtained by electrochemical and chemical oxidation of the thiolate porphyrins and benchmark their behaviour against that of Fe(III) tetraphenyl porphyrin chloride and its tetrapentafluorophenyl analogue. PMID:22945754

  18. Study on the supramolecular system of meso-tetrakis (4-sulfonatophenyl) porphyrin and cyclodextrins by spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-ping; Pan, Jing-hao; Shuang, Shao-min

    2001-12-01

    The ability of β-cyclodextrin (β-CD), sulfurbutylether-β-CD (SBE-β-CD) and hydroxypropyl-β-CD (HP-β-CD) to break the aggregate of the meso-Tetrakis (4-sulfonatophenyl) porphyrin (TPPS 4) and to form 2:1 inclusion complexes has been studied by adsorption and fluorescence spectroscopy. The formation constants are calculated, respectively by fluoremetry, from which the inclusion capacity of different CDs is compared and the inclusion mechanism of charged-β-CD (SBE-β-CD) is quite different from that of parent β-CD. At lower pH, the complexation between HP-β-CD and H 2TPPS 42+ (the form of the diprotonated TPPS 4) hampers the continuous protonation of the pyrrole nitrogen of TPPS 4 and the hydrophobic cavity may prefer to bind an apolar neutral porphyrin molecule. 1HNMR data support the inclusion conformation of the porphyrin-cyclodextrin supramolecular system, indicating the interaction of meso-phenyl groups of TPPS 4 with the cavity of CDs. For this host-guest inclusion model, cyclodextrin, being regarded as the protein component, which acts as a carrier enveloping the active site of heme prosthetic group within its hydrophobic environment, provides a protective sheath for porphyrin, creating artificial analogues of heme-containing proteins. However, the TPPS 4, encapsulated within this saccharide-coated barrier, its physico-chemical, photophysical and photochemical properties changed strongly.

  19. Porphyrin Nanodroplets: Sub-micrometer Ultrasound and Photoacoustic Contrast Imaging Agents.

    PubMed

    Paproski, Robert J; Forbrich, Alexander; Huynh, Elizabeth; Chen, Juan; Lewis, John D; Zheng, Gang; Zemp, Roger J

    2016-01-20

    A novel class of all-organic nanoscale porphyrin nanodroplet agents is presented which is suitable for multimodality ultrasound and photoacoustic molecular imaging. Previous multimodality photoacoustic-ultrasound agents are either not organic, or not yet demonstrated to exhibit enhanced accumulation in leaky tumor vasculature, perhaps because of large diameters. In the current study, porphyrin nanodroplets are created with a mean diameter of 185 nm which is small enough to exhibit the enhanced permeability and retention effect. Porphyrin within the nanodroplet shell has strong optical absorption at 705 nm with an estimated molar extinction coefficient >5 × 10(9) m(-1) cm(-1) , allowing both ultrasound and photoacoustic contrast in the same nanoparticle using all organic materials. The potential of nanodroplets is that they may be phase-changed into microbubbles using high pressure ultrasound, providing ultrasound contrast with single-bubble sensitivity. Multispectral photoacoustic imaging allows visualization of nanodroplets when injected intratumorally in an HT1080 tumor in the chorioallantoic membrane of a chicken embryo. Intravital microscopy imaging of Hep3-GFP and HT1080-GFP tumors in chicken embryos determines that nanodroplets accumulated throughout or at the periphery of tumors, suggesting that porphyrin nanodroplets may be useful for enhancing the visualization of tumors with ultrasound and/or photoacoustic imaging.

  20. Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation.

    PubMed

    Yamada, Yasuyuki; Kato, Tatsuhisa; Tanaka, Kentaro

    2016-08-22

    A stacked assembly composed of a porphyrin and two phthalocyanines was prepared through fourfold rotaxane formation. Two phthalocyanine molecules, bearing four 24-crown-8 units, were assembled onto a porphyrin template incorporating four sidechains with two dialkylammonium ions each through pseudorotaxane formation between crown ether units and ammonium ions. The Staudinger phosphite reaction, as the stoppering reaction, resulted in the formation of the stacked heterotrimer composed of a porphyrin and two phthalocyanines connected through a fourfold rotaxane structure. UV/Vis spectroscopic and electrochemical studies of the heterotrimer indicated that there is a significant electronic interaction between the two phthalocyanine units due to the close stacking. The electrochemical oxidation process of the stacked heterotrimer was studied by cyclic voltammetry and spectroelectrochemistry. Electron paramagnetic resonance (EPR) spectroscopy of a dinuclear Cu(II) complex, in which two Cu(II) phthalocyanines were assembled on a metal-free porphyrin template, revealed that two Cu(II) phthalocyanines were located within the stacking distance, which resulted in an antiferromagnetic interaction between the two S=1/2 spins in the ground state of the Cu(2+) ions in the heterotrimer. PMID:27417388

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

    SciTech Connect

    Chen, Wen-Tong; Hu, Rong-Hua; Wang, Yin-Feng; Zhang, Xian; Liu, Juan

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Spherical porphyrin sensor array based on encoded colloidal crystal beads for VOC vapor detection.

    PubMed

    Xu, Hua; Cao, Kai-Di; Ding, Hai-Bo; Zhong, Qi-Feng; Gu, Hong-Cheng; Xie, Zhuo-Ying; Zhao, Yuan-Jin; Gu, Zhong-Ze

    2012-12-01

    A spherical porphyrin sensor array using colloidal crystal beads (CCBs) as the encoding microcarriers has been developed for VOC vapor detection. Six different porphyrins were coated onto the CCBs with distinctive encoded reflection peaks via physical adsorption and the sensor array was fabricated by placing the prepared porphyrin-modified CCBs together. The change in fluorescence color of the porphyrin-modified CCBs array serves as the detection signal for discriminating between different VOC vapors and the reflection peak of the CCBs serves as the encoding signal to distinguish between different sensors. It was demonstrated that the VOC vapors detection using the prepared sensor array showed excellent discrimination: not only could the compounds from the different chemical classes be easily differentiated (e.g., alcohol vs acids vs ketones) but similar compounds from the same chemical family (e.g., methanol vs ethanol) and the same compound with different concentration ((e.g., Sat. ethanol vs 60 ppm ethanol vs 10 ppm ethanol) could also be distinguished. The detection reproducibility and the humidity effect were also investigated. The present spherical sensor array, with its simple preparation, rapid response, high sensitivity, reproducibility, and humidity insensitivity, and especially with stable and high-throughput encoding, is promising for real applications in artificial olfactory systems. PMID:23163575

  4. Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation.

    PubMed

    Yamada, Yasuyuki; Kato, Tatsuhisa; Tanaka, Kentaro

    2016-08-22

    A stacked assembly composed of a porphyrin and two phthalocyanines was prepared through fourfold rotaxane formation. Two phthalocyanine molecules, bearing four 24-crown-8 units, were assembled onto a porphyrin template incorporating four sidechains with two dialkylammonium ions each through pseudorotaxane formation between crown ether units and ammonium ions. The Staudinger phosphite reaction, as the stoppering reaction, resulted in the formation of the stacked heterotrimer composed of a porphyrin and two phthalocyanines connected through a fourfold rotaxane structure. UV/Vis spectroscopic and electrochemical studies of the heterotrimer indicated that there is a significant electronic interaction between the two phthalocyanine units due to the close stacking. The electrochemical oxidation process of the stacked heterotrimer was studied by cyclic voltammetry and spectroelectrochemistry. Electron paramagnetic resonance (EPR) spectroscopy of a dinuclear Cu(II) complex, in which two Cu(II) phthalocyanines were assembled on a metal-free porphyrin template, revealed that two Cu(II) phthalocyanines were located within the stacking distance, which resulted in an antiferromagnetic interaction between the two S=1/2 spins in the ground state of the Cu(2+) ions in the heterotrimer.

  5. Organic solid state switches incorporating porphyrin compounds and method for producing organic solid state optical switches

    DOEpatents

    Wasielewski, Michael R.; Gaines, George L.; Niemczyk, Mark P.; Johnson, Douglas G.; Gosztola, David J.; O'Neil, Michael P.

    1996-01-01

    A light-intensity dependent molecular switch comprised of a compound which shuttles an electron or a plurality of electrons from a plurality of electron donors to an electron acceptor upon being stimulated with light of predetermined wavelengths, said donors selected from porphyrins and other compounds, and a method for making said compound.

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

    PubMed

    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

  7. The severity of hereditary porphyria is modulated by the porphyrin exporter and Lan antigen ABCB6

    PubMed Central

    Fukuda, Yu; Cheong, Pak Leng; Lynch, John; Brighton, Cheryl; Frase, Sharon; Kargas, Vasileios; Rampersaud, Evadnie; Wang, Yao; Sankaran, Vijay G.; Yu, Bing; Ney, Paul A.; Weiss, Mitchell J.; Vogel, Peter; Bond, Peter J.; Ford, Robert C.; Trent, Ronald J.; Schuetz, John D.

    2016-01-01

    Hereditary porphyrias are caused by mutations in genes that encode haem biosynthetic enzymes with resultant buildup of cytotoxic metabolic porphyrin intermediates. A long-standing open question is why the same causal porphyria mutations exhibit widely variable penetrance and expressivity in different individuals. Here we show that severely affected porphyria patients harbour variant alleles in the ABCB6 gene, also known as Lan, which encodes an ATP-binding cassette (ABC) transporter. Plasma membrane ABCB6 exports a variety of disease-related porphyrins. Functional studies show that most of these ABCB6 variants are expressed poorly and/or have impaired function. Accordingly, homozygous disruption of the Abcb6 gene in mice exacerbates porphyria phenotypes in the Fechm1Pas mouse model, as evidenced by increased porphyrin accumulation, and marked liver injury. Collectively, these studies support ABCB6 role as a genetic modifier of porphyria and suggest that porphyrin-inducing drugs may produce excessive toxicities in individuals with the rare Lan(−) blood type. PMID:27507172

  8. Simultaneous synthesis/assembly of anisotropic cake-shaped porphyrin particles toward colloidal microcrystals.

    PubMed

    Wang, Ting; Kuang, Minxuan; Jin, Feng; Cai, Jinhua; Shi, Lei; Zheng, Yongmei; Wang, Jingxia; Jiang, Lei

    2016-03-01

    The one-step synthesis/assembly of a cake-shaped porphyrin colloidal microcrystal with tailored height-diameter was demonstrated based on interfacial assembly and the water-droplet template. The as-fabricated anisotropic colloidal crystals showed special optic properties and enhanced optic-limiting behavior.

  9. Femtosecond transient grating studies of electron transfer in porphyrin and chlorophyll donor-acceptor molecules

    SciTech Connect

    Wiederrecht, G.P.; Svec, W.A.; Wasielewski, M.R.

    1994-04-01

    Transient grating studies of electron transfer in artificial photosynthetic systems are described. These systems include simple donor-acceptor molecules where the donor, a chlorophyll or porphyrin, is rigidly attached to an easily reduced species such as napthoquinone or benzoquinone. We have previously synthesized acceptor molecules which have well defined absorption bands upon reduction and are well removed from the excited and cationic states of porphyrins and chlorophylls. They also possess large molar extinction coefficients that dominate the spectra and have well defined polarization characteristics. These traits are ideal for polarization sensitive transient grating experiments which enable accurate determination of the angle of the transition dipole between the initial excitation and the acceptor probe, dynamic solvation effects on the charge separated species, and any time dependent rotation of the chromophores relative to each other. An example of the type of molecule utilized for these experiments is a free base porphyrin (HP) donor and a pyromellitic diimide (PI) acceptor directly bonded to the porphyrin ring.

  10. Synthesis, characterization and in vitro photodynamic antimicrobial activity of basic amino acid-porphyrin conjugates.

    PubMed

    Meng, Shuai; Xu, Zengping; Hong, Ge; Zhao, Lihui; Zhao, Zhanjuan; Guo, Jianghong; Ji, Haiying; Liu, Tianjun

    2015-03-01

    Photodynamic antimicrobial chemotherapy (PACT), as a novel and effective modality for the treatment of infection with the advantage of circumventing multidrug resistance, receives great attention in recent years. The photosensitizer is the crucial element in PACT, and cationic porphyrins have been demonstrated to usually be more efficient than neutral and negatively charged analogues towards bacteria in PACT. In this work, three native basic amino acids, l-lysine, l-histidine and l-arginine, were conjugated with amino porphyrins as cationic auxiliary groups, and 13 target compounds were synthesized. This paper reports their syntheses, structural characterizations, oil-water partition coefficients, singlet oxygen generation yields, photo-stability, as well as their photo inactivation efficacies against methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli and Pseudomonas aeruginosa in vitro. The preliminary structure-activity relationship was discussed. Compound 4i, with porphyrin bearing four lysine moieties, displays the highest photo inactivation efficacy against the tested bacterial strains at 3.91 μM with a low light dose (6 J/cm(2)), and it is stable in serum and lower cytotoxicity to A929 cells. These basic amino acid-porphyrin conjugates are potential photosensitizers for PACT.

  11. H.p.l.c. analysis of di- and tri-carboxylic porphyrins in porphyric patients.

    PubMed Central

    Jackson, A H; Rao, K R; Smith, S G; Lash, T D

    1985-01-01

    New h.p.l.c. methods have been developed for the quantitative determination of di- and tri-carboxylic porphyrin methyl esters, and applied to the analysis of faecal extracts from patients with four different types of porphyria. PMID:3994688

  12. Synthesis of some new porphyrins and their metalloderivatives as potential sensitizers in photo-dynamic therapy

    PubMed Central

    Rostami, Mahboubeh; Rafiee, Leila; Hassanzadeh, Farshid; Dadrass, Ali Reza; Khodarahmi, Ghadam Ali

    2015-01-01

    Porphyrins are a ubiquitous large class of naturally occurring macrocyclic compounds with many significant biological representatives comprising heme and chlorophyll. Some novel adaptable methods for the synthesis of free-based porphyrins as promising sensitizers for the use in photo-dynamic therapy by the virtue of their known tumor affinity, low dark cytotoxicity, and easy synthesis in good to high yields have already been discussed. In the present study, two new porphyrins including TAPFA, as a novel folic acid targeted porphyrin sensitizer, and TAP-Schiff base, as a novel sensitizer with better light absorption, were prepared for the first time and their structures were confirmed by 1H NMR, 13C NMR, FT-IR and UV-Vis spectroscopy as well as CHNS analysis. The compounds were metalized with Zn(II) and Fe(II) metal ions to study how the metal ions can improve the light absorption wavelength and their water solubility. The structures of metalized compounds were also confirmed by FT-IR and UV-Vis spectroscopy. PMID:26779270

  13. Binding of cationic porphyrin to isolated and encapsidated viral DNA analyzed by comprehensive spectroscopic methods.

    PubMed

    Zupán, Kristóf; Herényi, Levente; Tóth, Katalin; Majer, Zsuzsa; Csík, Gabriella

    2004-07-20

    The complexation of tetrakis(4-N-methylpyridyl)porphyrin (TMPyP) with free and encapsidated DNA of T7 bacteriophage was investigated. To identify binding modes and relative concentrations of bound TMPyP forms, the porphyrin absorption spectra at various base pair/porphyrin ratios were analyzed. Spectral decomposition, fluorescent lifetime, and circular dichroism measurements proved the presence of two main binding types of TMPyP, e.g., external binding and intercalation both in free and in encapsidated DNA. Optical melting studies revealed that TMPyP increases the strand separation temperature of both free and native phage DNA and does not change the phase transition temperature of phage capsid proteins. From these findings we concluded that TMPyP binding does not influence the protein structure and/or the protein-DNA interaction. A combined analysis of absorption spectra and fluorescence decay curves made possible the determination of concentrations of free, externally bound, and intercalated porphyrin. As a perspective, our results facilitate a qualitative analysis of the TMPyP binding process at various experimental conditions. PMID:15248772

  14. Characterization, direct electrochemistry, and amperometric biosensing of graphene by noncovalent functionalization with picket-fence porphyrin.

    PubMed

    Tu, Wenwen; Lei, Jianping; Zhang, Siyuan; Ju, Huangxian

    2010-09-17

    Reduced graphene oxide (RGO) was prepared and functionalized with picket-fence porphyrin, 5,10,15,20-tetrakis [αααα-2-trismethylammoniomethylphenyl] porphyrin iron(III) pentachloride (FeTMAPP), through π-π interactions. The resulting nanocomposite was characterized by atomic force microscopy (AFM); transmission electron microscopy (TEM); contact angle measurements; and fluorescence, Raman, and UV/Vis absorption spectroscopy. On account of the introduction of positively charged FeTMAPP, the functionalized RGO showed good dispersion in aqueous solution. The RGO could greatly accelerate the electron transfer of FeTMAPP to produce a well-defined redox couple of Fe(III)/Fe(II) at -0.291 and -0.314 V. Due to the synergic effect between RGO and the porphyrin, the nanocomposite showed excellent electrocatalytic activity toward the reduction of chlorite, thus leading to highly sensitive amperometric biosensing at low applied potential. The biosensor for chlorite showed a linear range from 5.0×10(-8) to 1.2×10(-4) mol L(-1) with a detection limit of 2.4×10(-8) mol L(-1) at a signal-to-noise ratio of 3. The picket-fence porphyrin could serve as an efficient species to functionalize graphene for electronic and optical applications.

  15. The Silver Complexes of Porphyrins, Corroles, and Carbaporphyrins: Silver in the Oxidation States II and III

    ERIC Educational Resources Information Center

    Bruckner, Christian

    2004-01-01

    Studies in relation to the silver complexes of porphyrins, corroles and carbaporphyrins are presented especially with relation to silver in the oxidation states II and III. It is seen that the Ag(sub III) complex was electrochemically readily and reversibly reduced to the corresponding Ag(sub II) complex, thus indicating that the complex could be…

  16. The position effect of electron-deficient quinoxaline moiety in porphyrin based sensitizers

    NASA Astrophysics Data System (ADS)

    Fan, Suhua; Lv, Kai; Sun, Hong; Zhou, Gang; Wang, Zhong-Sheng

    2015-04-01

    An electron-deficient group, 2,3-diphenylquinoxaline (DPQ), is incorporated as an auxiliary acceptor into the different positions of the porphyrin (Por) based donor-π bridge-acceptor (D-π-A) dye (FNE57) to construct D-A‧-Por-π-A (FNE58) and D-Por-A‧-π-A (FNE59) configurations. The incorporation of DPQ unit between the donor and porphyrin unit has negligible influence on the absorption property, whereas the DPQ unit located between the porphyrin unit and acceptor significantly increases the absorbance for the Soret band and the valley between the Soret and Q bands. Theoretical calculation reveals that incorporating the DPQ unit adjacent to the acceptor is more advantageous to delocalize the lowest unoccupied molecular orbital and enhance the electronic asymmetry, which facilitates the intramolecular charge transfer. The effect of DPQ unit and its linkage position on the performance of related quasi-solid-state dye-sensitized solar cells (DSSCs) is systematically investigated. The quasi-solid-state DSSC with sensitizer FNE59 displays a power conversion efficiency of 6.02%, which is 23% and 51% higher than those for FNE57 and FNE58 based DSSCs. Our studies facilitate the understanding of the crucial importance of molecular engineering and pave a new path to design novel porphyrin based sensitizers for highly efficient DSSCs.

  17. Synthesis, G-quadruplexes DNA binding, and photocytotoxicity of novel cationic expanded porphyrins.

    PubMed

    Jin, Shu-fang; Zhao, Ping; Xu, Lian-cai; Zheng, Min; Lu, Jia-zheng; Zhao, Peng-liang; Su, Qiu-lan; Chen, Hui-xian; Tang, Ding-tong; Chen, Jiong; Lin, Jia-qi

    2015-06-01

    Intensive reports allowed the conclusion that molecules with extended aromatic surfaces always do good jobs in the DNA interactions. Inspired by the previous successful researches, herein, we designed a series of cationic porphyrins with expanded planar substituents, and evaluated their binding behaviors to G-quadruplex DNA using the combination of surface-enhanced raman, circular dichroism, absorption spectroscopy and fluorescence resonance energy transfer melting assays. Asymmetrical tetracationic porphyrin with one phenyl-4-N-methyl-4-pyridyl group and three N-methyl-4-pyridyl groups exhibit the best G4-DNA binding affinities among all the designed compounds, suggesting that the bulk of the substituents should be matched to the width of the grooves they putatively lie in. Theoretical calculations applying the density functional theory have been carried out and explain the binding properties of these porphyrins reasonably. Meanwhile, these porphyrins were proved to be potential photochemotherapeutic agents since they have photocytotoxic activities against both myeloma cell (Ag8.653) and gliomas cell (U251) lines.

  18. Formation and helicity control of ssDNA templated porphyrin nanoassemblies.

    PubMed

    Sargsyan, Gevorg; Schatz, Alexandra A; Kubelka, Jan; Balaz, Milan

    2013-02-01

    We report the formation of left- (M-helix) and right-handed (P-helix) nanoassemblies of a porphyrin-diaminopurine conjugate (Por-DAP) templated by a single stranded oligodeoxythymidine (dT40) via directional hydrogen bonding. The supramolecular helicity can be controlled by the ionic strength, Por-DAP : dT40 ratio, and annealing rate.

  19. Self-assembly of peptide-porphyrin complexes leads to pH-dependent excitonic coupling.

    PubMed

    Kuciauskas, Darius; Caputo, Gregory A

    2009-10-29

    Using absorbance, fluorescence, resonance light scattering, and circular dichroism spectroscopy, we studied the self-assembly of the anionic meso-tetra(4-sulfonatophenyl)porphine (TPPS(4)(2-/4-)) and a cationic 22-residue polypeptide. We found that three TPPS(4)(2-/4-) molecules bind to the peptide, which contains nine lysine residues in the primary sequence. In acidic solutions, when the peptide is in the random-coil conformation, TPPS(4)(2-) bound to the peptide forms excitonically coupled J-aggregates. In pH 7.6 solutions, when the peptide secondary structure is partially alpha-helical, the porphyrin-to-peptide binding constants are approximately the same as in acidic solutions (approximately 3 x 10(6) M(-1)), but excitonic interactions between the porphyrins are insignificant. The binding of TPPS(4)(2-/4-) to lysine-containing peptides is cooperative and can be described by the Hill model. Our results show that porphyrin binding can be used to change the secondary structure of peptide-based biomaterials. In addition, binding to peptides could be used to optimize porphyrin intermolecular electronic interactions (exciton coupling), which is relevant for the design of light-harvesting antennas for artificial photosynthesis.

  20. Structural effects on photoinduced electron transfer in carotenoid-porphyrin-quinone triads

    SciTech Connect

    Kuciauskas, D.; Liddell, P.A.; Hung, S.C.; Lin, S.; Stone, S.; Seely, G.R.; Moore, A.L.; Moore, T.A.; Gust, D.

    1997-01-16

    meso-Polyarylporphyrins are often used as components of molecules that mimic photosynthetic reaction centers by carrying out photoinduced electron-transfer reactions. Studies of these systems have raised questions concerning the role of alkyl substituents at the `{beta}-pyrrolic` positions on the porphyrin periphery in limiting {pi}-{pi} overlap between the macrocycle and the aryl rings. The degree of overlap affects electronic coupling and, therefore, the rates of electron-transfer reactions. There is also evidence that when the linkages joining porphyrins to electron-acceptor or -donor moieties contain amide bonds, the sense of the amide linkage may strongly affect electron-transfer rate constants. In this study, three carotenoid-porphyrin-quinone molecular triads and various model compounds have been prepared, and electron-transfer has been studied using time-resolved emission and absorption techniques. The results show that steric hindrance due to methyl groups at the {beta}-pyrrolic positions reduces electron-transfer rate constants by a factor of approximately 1/5. In addition, amide-containing donor-acceptor linkages having the nitrogen atom attached to the porphyrin meso-aryl ring demonstrate electron-transfer rate constants approximately 30 times larger than those for similar linkages with the amide reversed, after correction for thermodynamic effects. 52 refs., 7 figs., 2 tabs.

  1. Improved photodynamic activity of porphyrin loaded into nanoparticles: an in vivo evaluation using chick embryos.

    PubMed

    Vargas, Angelica; Pegaz, Bernadette; Debefve, Elodie; Konan-Kouakou, Yvette; Lange, Norbert; Ballini, Jean-Pierre; van den Bergh, Hubert; Gurny, Robert; Delie, Florence

    2004-11-22

    Hydrophobic porphyrins are potentially interesting molecules for the photodynamic therapy (PDT) of solid cancers or ocular vascularization diseases. Their pharmaceutical development is, however, hampered by their lipophilicity, which renders formulation difficult especially when intravenous administration is needed. Encapsulation of a lipophilic derivative of porphyrin, the meso-tetra(p-hydroxyphenyl)porphyrin (p-THPP), into polymeric biodegradable poly(D,L-lactide-co-glycolide) (PLGA) nanoparticles proved to enhance its photodynamic activity against mammary tumour cells when compared to free drug. In order to further investigate these carriers, the efficacy of the encapsulated drug was assessed on the chick embryo chorioallantoic membrane (CAM) model. First, we identified a suitable solvent for the drug in terms of p-THPP solubility and tolerability by chick embryos. This solution was used as a reference. Then, the fluorescence pharmacokinetics and the photodynamic effects of the porphyrin on CAM vessels were evaluated after intravenous administration of either a p-THPP solution (free drug) or the drug loaded into nanoparticles. The results showed that: (i) the drug remained longer in the vascular compartment when incorporated into nanoparticles and (ii) vascular effects of p-THPP after light irradiation were enhanced with nanoparticle carriers. These results are discussed taking into account the extravasation of intravascular circulating photosensitizers and its influence on PDT performance. PMID:15501010

  2. Photodynamic efficiency of diethylene glycol-linked glycoconjugated porphyrins in human retinoblastoma cells.

    PubMed

    Laville, Isabelle; Pigaglio, Sophie; Blais, Jean-Claude; Doz, François; Loock, Bernard; Maillard, Philippe; Grierson, David S; Blais, Jocelyne

    2006-04-20

    Photodynamic therapy (PDT) is emerging as a new strategy for the conservative treatment of hereditary retinoblastoma. The glycoconjugated porphyrins TPP(p-Deg-O-alpha-GalOH)(3), TPP(p-Deg-O-beta-GalOH)(3), TPP(p-Deg-O-alpha-ManOH)(3), and their S-analogues were synthesized to obtain efficient photosensitizers with some retinoblastoma cell affinity. In these systems, a sugar motif and porphyrin core were linked by a diethylene glycol spacer (Deg). Cellular uptake, localization, and photoactivity have been examined in human retinoblastoma cells (Y79). After preincubation with corresponding glycosylated albumin, the uptake of TPP(p-Deg-O-beta-GalOH)(3) and TPP(p-Deg-O-alpha-ManOH)(3) was 40-45% inhibited, indicating a possible cell-sugar-receptor saturation. High photoactivity was observed for the two alpha-galacto/manno porphyrins 8 and 10 (LD(50) = 0.05 and 0.35 muM, respectively) at 514 nm and low fluence (1 J/cm(2)). Analysis by MALDI-TOF mass spectrometry only indicated a small metabolic cleavage of the O-glycoconjugates and a good stability of the S-glycoside porphyrins. On the basis of these in vitro data, TPP(p-Deg-O-alpha-GalOH)(3) and TPP(p-Deg-O-alpha-ManOH)(3) were selected for in vivo studies. PMID:16610799

  3. High-throughput synthesis and characterization of nanocrystalline porphyrinic zirconium metal-organic frameworks.

    PubMed

    Kelty, M L; Morris, W; Gallagher, A T; Anderson, J S; Brown, K A; Mirkin, C A; Harris, T D

    2016-06-14

    We describe and employ a high-throughput screening method to accelerate the synthesis and identification of pure-phase, nanocrystalline metal-organic frameworks (MOFs). We demonstrate the efficacy of this method through its application to a series of porphyrinic zirconium MOFs, resulting in the isolation of MOF-525, MOF-545, and PCN-223 on the nanoscale. PMID:27247981

  4. Extending supramolecular fullerene-porphyrin chemistry to pillared metal-organic frameworks

    PubMed Central

    Sun, Dayong; Tham, Fook S.; Reed, Christopher A.; Boyd, Peter D. W.

    2002-01-01

    Porphyrins and fullerenes are spontaneously attracted to each other. This supramolecular recognition element can be exploited to produce ordered arrays of interleaved porphyrins and fullerenes. C60⋅H2TpyP⋅Pb(NO3)2⋅1.5TCE (H2TpyP = tetra-4-pyridylporphyrin; TCE = 1,1,2,2-tetrachloroethane) crystallizes in the tetragonal P4/n space group and the structure has been solved to high resolution. The Pb2+ ions connect the pyridylporphyrins in infinite sheets with an interlayer spacing of 12.1 Å. The fullerenes are intercalated between these layers, acting as pillars. The 6:6 ring juncture bonds of C60 are centered over the porphyrins, bringing the layers into strict tetragonal register. This arranagement identifies the fullerene–porphyrin interaction as a structure-defining element. The same motif is seen in a related ribbon structure having C70 intercalated into HgI2-linked H2TpyTP. The supramolecular design principles involved in assembling these chromophores may have applications in materials science. PMID:11943855

  5. High-throughput synthesis and characterization of nanocrystalline porphyrinic zirconium metal-organic frameworks.

    PubMed

    Kelty, M L; Morris, W; Gallagher, A T; Anderson, J S; Brown, K A; Mirkin, C A; Harris, T D

    2016-06-14

    We describe and employ a high-throughput screening method to accelerate the synthesis and identification of pure-phase, nanocrystalline metal-organic frameworks (MOFs). We demonstrate the efficacy of this method through its application to a series of porphyrinic zirconium MOFs, resulting in the isolation of MOF-525, MOF-545, and PCN-223 on the nanoscale.

  6. Electrochemical oxidation of sugars at moderate potentials catalyzed by Rh porphyrins.

    PubMed

    Yamazaki, Shin-Ichi; Fujiwara, Naoko; Takeda, Sahori; Yasuda, Kazuaki

    2010-05-28

    In this communication, we demonstrate that certain kinds of Rh porphyrins on carbon black can electrochemically oxidize aldose at low potentials. The onset potential was much lower than those with the other complex-based catalysts. A product analysis suggested that this reaction involves 2-electron oxidation of the aldehyde group.

  7. ALA-based fluorescent diagnosis of malignant oral lesions in the presence of bacterial porphyrin formation

    NASA Astrophysics Data System (ADS)

    Schleier, P.; Berndt, A.; Zinner, K.; Zenk, W.; Dietel, W.; Pfister, W.

    2006-02-01

    The aminolevulinic acid (5-ALA) -based fluorescence diagnosis has been found to be promising for an early detection and demarcation of superficial oral squamous cell carcinomas (OSCC). This method has previously demonstrated high sensitivity, however this clinical trial showed a specificity of approximately 62 %. This specificity was mainly restricted by tumor detection in the oral cavity in the presence of bacteria. After topical ALA application in the mouth of patients with previously diagnosed OSSC, red fluorescent areas were observed which did not correlate to confirm histological findings. Swabs and plaque samples were taken from 44 patients and cultivated microbiologically. Fluorescence was investigated (OMA-system) from 32 different bacteria strains found naturally in the oral cavity. After ALA incubation, 30 of 32 strains were found to synthesize fluorescent porphyrins, mainly Protoporphyrin IX. Also multiple fluorescent spectra were obtained having peak wavelengths of 636 nm and around 618 nm - 620 nm indicating synthesis of different porphyrins, such as the lipophylic Protoporphyrin IX (PpIX) and hydrophylic porphyrins (water soluble porphyrins, wsp). Of the 32 fluorescent bacterial strains, 18 produced wsp, often in combination with PpIX, and 5 produced solely wsp. These results clarify that ALA-based fluorescence diagnosis without consideration or suppression of bacteria fluorescence may lead to false-positive findings. It is necessary to suppress bacteria fluorescence with suitable antiseptics before starting the procedure. In this study, when specific antiseptic pre-treatment was performed bacterial associated fluorescence was significantly reduced.

  8. The severity of hereditary porphyria is modulated by the porphyrin exporter and Lan antigen ABCB6.

    PubMed

    Fukuda, Yu; Cheong, Pak Leng; Lynch, John; Brighton, Cheryl; Frase, Sharon; Kargas, Vasileios; Rampersaud, Evadnie; Wang, Yao; Sankaran, Vijay G; Yu, Bing; Ney, Paul A; Weiss, Mitchell J; Vogel, Peter; Bond, Peter J; Ford, Robert C; Trent, Ronald J; Schuetz, John D

    2016-08-10

    Hereditary porphyrias are caused by mutations in genes that encode haem biosynthetic enzymes with resultant buildup of cytotoxic metabolic porphyrin intermediates. A long-standing open question is why the same causal porphyria mutations exhibit widely variable penetrance and expressivity in different individuals. Here we show that severely affected porphyria patients harbour variant alleles in the ABCB6 gene, also known as Lan, which encodes an ATP-binding cassette (ABC) transporter. Plasma membrane ABCB6 exports a variety of disease-related porphyrins. Functional studies show that most of these ABCB6 variants are expressed poorly and/or have impaired function. Accordingly, homozygous disruption of the Abcb6 gene in mice exacerbates porphyria phenotypes in the Fech(m1Pas) mouse model, as evidenced by increased porphyrin accumulation, and marked liver injury. Collectively, these studies support ABCB6 role as a genetic modifier of porphyria and suggest that porphyrin-inducing drugs may produce excessive toxicities in individuals with the rare Lan(-) blood type.

  9. Glassy-winged sharpshooter can use a mechanical mechanism to inoculate Xylella fastidiosa into grapevines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Xylem-feeding leafhoppers such as the glassy-winged sharpshooter, Homalodisca vitripennis (Cicadellidae: Cicadellinae), are thought to inoculate the bacterium Xylella fastidiosa (Xf) from colonies bound to cuticle of the sharpshooter’s functional foregut (precibarium and cibarium). The mechanism of ...

  10. Glassy-winged sharpshooter oviposition effects on foliar grapevine and red-tipped photinia terpenoid levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), is an important vector of Xylella fastidiosa, the bacterium that causes Pierce's disease of grapevine and is a threat to grape production throughout the United States. Female GWSS deposit egg masses be...

  11. Substrate-borne vibrational signals in intraspecific communication of glassy-winged sharpshooters (GWSS)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Exploitation of vibrational signals for suppressing glassy-winged sharpshooter (GWSS) populations could prove to be a useful tool. However, existing knowledge on GWSS vibrational communication is insufficient to implement a management program for this pest in California. Therefore, the objective of ...

  12. Effects of feeding on glassy-winged sharpshooter lipid content and egg production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glassy-winged sharpshooter females emerge without mature eggs, and females must feed to produce mature eggs. As a result, allocation of incoming resources must be balanced between egg production and maintenance of other critical biological functions. Central to this process is allocation of lipids s...

  13. Glassy-winged sharpshooter oviposition effects on photinia volatile chemistry with implications on egg parasitoid effectiveness

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An effective way to limit incidence of Pierce’s disease of grapevine is to reduce populations of glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), which transmit the causal bacterium, Xylella fastidiosa. One strategy is to utilize egg parasitoids such as ...

  14. Columbia River Basalt Chemistry, Degassing, and Eruption Dynamics: Insights From Quenched Glassy Lapilli and Tuffs

    NASA Astrophysics Data System (ADS)

    Davis, K.; Wolff, J.; Rowe, M. C.; Neill, O. K.

    2015-12-01

    Primary eruptive vent areas for several lavas in the Imnaha and Grande Ronde Formations of the Columbia River Basalt exhibit phreatomagmatic character, due to the interaction of rising flood basalt magma with groundwater and/or surface water. Vent constructional forms range from extensive (>1 km) maar complexes with abundant basement lithics to small (<<1 km), lithic-poor low-angle cones. Phreatomagmatic tephra is lithified and variably palagonitized, but glassy basaltic lapilli can be recovered from many locations. Many lapilli have experienced variable degrees of Na leaching but preserve magmatic abundances of most other elements; nonetheless in many cases pristine, unmodified glass is amenable to analysis. In addition, phenocrysts in lapilli have fully glassy melt inclusions. Glassy lapilli have highly variable S contents between ~100 and ~1300 ppm. This is consistent with quenching before degassing was complete, a common feature of phreatomagmatic eruptions. Melt inclusions have ≤2900 ppm S, ≤3400 ppm CO2 and ≤2.6 wt% H2O, allowing estimates of atmospheric input from the main phase of Columbia River volcanism. In addition, the lithophile trace element contents, and petrogenetically significant ratios such as Ba/Nb, of glassy lapilli exhibit differ from those in the equivalent 'stony' lava flows by up to a factor of 2. This suggests that processes in the flow and crystallization of lava serve to modify trace element abundances, and may place limits on the petrogenetic significance of trace element data from crystalline lava samples.

  15. Brittle metallic glass deforms plastically at room temperature in glassy multilayers

    NASA Astrophysics Data System (ADS)

    Sharma, Parmanand; Yubuta, Kunio; Kimura, Hisamichi; Inoue, Akihisa

    2009-07-01

    Bulk metallic glasses are emerging as a new class of materials that can have applications ranging from structural materials to materials for future nanotechnology. However, catastrophic mechanical failure is a serious issue hindering the use of these materials in engineering applications. Here we introduce an approach to understanding and solving the problem of brittleness of metallic glasses. We have shown that even a very brittle metallic glass (La based) can be forced to deform plastically at room temperature if it is made in the form of multilayers involving other metallic glasses, i.e., a two-phase glass. The mechanically soft glassy layer (La based) having a lower critical shear stress acts as a nucleation or an initiation site for shear bands and the mechanically hard glassy layer (Zr based) acts as an obstacle to the propagation of shear bands. This process results in the multiplication of shear bands. Since the shear bands are associated with a local rise in temperature, a large number of shear bands can raise the overall temperature of the soft layer and eventually can drive it to the supercooled liquid state, where deformation of metallic glass is very large and homogeneous. The results reported here not only clarify the mechanism of large plastic deformation in two-phase glassy alloys but also suggest the possibility of a different kind of two-phase bulk glassy alloys exhibiting large plastic deformation at room temperature.

  16. THE ROLE OF GLASSY-WINGED SHARPSHOOTER SALIVARY ENZYMES IN INFECTION AND MOVEMENT OF X. FASTIDIOSA

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The purpose of this project is to determine whether a vector’s enzymatic saliva aids the establishment of the few ‘pioneer’ Xylella fastidiosa (Xf) cells that are inoculated into a plant; thus the bacteria would co-localize with the saliva. Previous work showed that watery saliva of glassy-winged ...

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

    PubMed

    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

  18. Ice cloud processing of ultra-viscous/glassy aerosol particles leads to enhanced ice nucleation ability

    NASA Astrophysics Data System (ADS)

    Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Skrotzki, J.; Leisner, T.; Wilson, T. W.; Malkin, T. L.; Murray, B. J.

    2012-04-01

    The ice nucleation potential of airborne glassy aqueous aerosol particles has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 247 and 216 K. Four different solutes were used as proxies for oxygenated organic matter found in the atmosphere: raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA), levoglucosan, and a multi-component mixture of raffinose with five dicarboxylic acids and ammonium sulphate. Similar to previous experiments with citric acid aerosols, all particles were found to nucleate ice heterogeneously before reaching the homogeneous freezing threshold provided that the freezing cycles were started well below the respective glass transition temperatures of the compounds; this is discussed in detail in a separate article. In this contribution, we identify a further mechanism by which glassy aerosols can promote ice nucleation below the homogeneous freezing limit. If the glassy aerosol particles are probed in freezing cycles started only a few degrees below their respective glass transition temperatures, they enter the liquid regime of the state diagram upon increasing relative humidity (moisture-induced glass-to-liquid transition) before being able to act as heterogeneous ice nuclei. Ice formation then only occurs by homogeneous freezing at elevated supersaturation levels. When ice forms the remaining solution freeze concentrates and re-vitrifies. If these ice cloud processed glassy aerosol particles are then probed in a second freezing cycle at the same temperature, they catalyse ice formation at a supersaturation threshold between 5 and 30% with respect to ice. By analogy with the enhanced ice nucleation ability of insoluble ice nuclei like mineral dusts after they nucleate ice once, we refer to this phenomenon as pre-activation. We propose a number of possible explanations for why glassy aerosols that have re-vitrified in contact with the

  19. Ice cloud processing of ultra-viscous/glassy aerosol particles leads to enhanced ice nucleation ability

    NASA Astrophysics Data System (ADS)

    Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Skrotzki, J.; Leisner, T.; Wilson, T. W.; Malkin, T. L.; Murray, B. J.

    2012-09-01

    The ice nucleation potential of airborne glassy aqueous aerosol particles has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 247 and 216 K. Four different solutes were used as proxies for oxygenated organic matter found in the atmosphere: raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA), levoglucosan, and a multi-component mixture of raffinose with five dicarboxylic acids and ammonium sulphate. Similar to previous experiments with citric acid aerosols, all particles were found to nucleate ice heterogeneously before reaching the homogeneous freezing threshold provided that the freezing cycles were started well below the respective glass transition temperatures of the compounds; this is discussed in detail in a separate article. In this contribution, we identify a further mechanism by which glassy aerosols can promote ice nucleation below the homogeneous freezing limit. If the glassy aerosol particles are probed in freezing cycles started only a few degrees below their respective glass transition temperatures, they enter the liquid regime of the state diagram upon increasing relative humidity (moisture-induced glass-to-liquid transition) before being able to act as heterogeneous ice nuclei. Ice formation then only occurs by homogeneous freezing at elevated supersaturation levels. When ice forms the remaining solution freeze concentrates and re-vitrifies. If these ice cloud processed glassy aerosol particles are then probed in a second freezing cycle at the same temperature, they catalyse ice formation at a supersaturation threshold between 5 and 30% with respect to ice. By analogy with the enhanced ice nucleation ability of insoluble ice nuclei like mineral dusts after they nucleate ice once, we refer to this phenomenon as pre-activation. We propose a number of possible explanations for why glassy aerosol particles that have re-vitrified in contact

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

    PubMed Central

    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

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

    PubMed

    Johnson, Tremylla; Kang, Dezhi; Barnard, Emma; Li, Huiying

    2016-01-01

    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 to play a

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

    PubMed

    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.

  3. Stabilization of the charge-separated States of covalently linked zinc porphyrin-triphenylamine-[60]fullerene.

    PubMed

    El-Khouly, Mohamed E; Han, Ki-Jong; Kay, Kwang-Yol; Fukuzumi, Shunichi

    2010-06-01

    Spectroscopic, redox, computational, and electron transfer reactions of the covalently linked zinc porphyrin-triphenylamine-fulleropyrrolidine system are investigated in solvents of varying polarity. An appreciable interaction between triphenylamine and the porphyrin pi system is revealed by steady-state absorption and emission, redox, and computational studies. Free-energy calculations suggest that the light-induced processes via the singlet-excited porphyrin are exothermic in benzonitrile, dichlorobenzene, toluene, and benzene. The occurrence of fast and efficient charge-separation processes ( approximately 10(12) s(-1)) via the singlet-excited porphyrin is confirmed by femtosecond transient absorption measurements in solvents with dielectric constants ranging from 25.2 (benzonitrile) to 2.2 (benzene). The rates of the charge separation processes are much less solvent-dependent, which suggests that the charge-separation processes occur at the top region of the Marcus parabola. The lifetimes of the singlet radical-ion pair (70-3000 ps at room temperature) decrease substantially in more polar solvents, which suggests that the charge-recombination process is occurring in the Marcus inverted region. Interestingly, by utilizing the nanosecond transient absorption spectral technique we can obtain clear evidence about the existence of triplet radical-ion pairs with relatively long lifetimes of 0.71 mus (in benzonitrile) and 2.2 mus (in o-dichlorobenzene), but not in toluene and benzene due to energetic considerations. From the point of view of mechanistic information, the synthesized zinc porphyrin-triphenylamine-fulleropyrrolidine system has the advantage that both the lifetimes of the singlet and triplet radical-ion pair can be determined. PMID:20191657

  4. Determination of threshold dose with delta-aminolevulinic acid-induced porphyrins for effective photodynamic therapy

    NASA Astrophysics Data System (ADS)

    Fritsch, Clemens; Abels, Christoph; Bolsen, Klaus; Ruzicka, Thomas; Goetz, Alwin E.; Goerz, Guenter

    1995-03-01

    In this study the metabolism in tumors and various tissues of intravenously administered (delta) -aminolevulinic acid was investigated. Amelanotic melanoma (A-Mel-3) were implanted in the dorsal skin of Syrian golden hamsters. Distribution and metabolism of i.v. injected (delta) -aminolevulinic acid in blood was studied by determination of (delta) - aminolevulinic acid and protoporphyrin concentration in red blood cells. In addition extraction of various tissues, e.g. tumor, liver, kidney, and normal skin was performed, to verify fluorescence kinetic studies by determination of total porphyrin concentration by photometry and of distribution of the porphyrin metabolites by HPLC. In untreated animals the total porphyrin concentration in all tissues examined were comparably low. In red blood cells the maximal concentration of (delta) -aminolevulinic acid as well as protoporphyrin was detected 45 min after i.v. injection of (delta) -aminolevulinic acid. Porphyrins accumulated in melanoma reaching a maximum tumor:skin tissue ratio of 6.9:1 at 45 min after i.v. injection of (delta) -aminolevulinic acid. A second high tumor:skin tissue ratio of 5.7:1 could be measured at 24 h after injection, but at this point in time the protoporphyrin content in normal skin was higher than 45 min after injection. The kidney may not be strongly affected by i.v. administration of (delta) -aminolevulinic acid, whereas the liver reveals an accumulation of porphyrins, e.g. protoporphyrin. Concluding from these results in this experimental tumor model, i.v. administration of (delta) -aminolevulinic acid seems to be a promising modality to perform photodynamic therapy more effectively and more selectively by irradiation 45 - 180 min after injection of (delta) -aminolevulinic acid.

  5. Environmental conditions during the Frasnian-Fammenian mass extinction inferred from chlorophyll-derived porphyrin biomarkers.

    NASA Astrophysics Data System (ADS)

    Uveges, B. T.; Junium, C. K.; Cohen, P. A.; Boyer, D.

    2014-12-01

    The widespread mass extinction that occurred across the Frasnian- Fammenian (F-F) boundary was one of the largest losses of biodiversity in Earth's history. The F-F extinction interval is expressed in western New York State by two organic rich black shale intervals known as the Upper and Lower Kellwasser events. These shale intervals are well preserved, thermally immature, and are well constrained in age by conodont biostratigraphy, and thus provide an exceptional opportunity to study the organic material originating from the F-F boundary. In order to test hypotheses about the cause(s) and consequences of the FF biotic crisis, a broader knowledge of the organic carbon sources is needed, and a characterization of the marine primary producer communities will assist in this endeavor. One such avenue is through the study of chlorophyll-derived biomarkers (porphyrins). The organic extracts of powdered shale samples from the Kellwasser horizons were analyzed using HPLC/LC-MSn and diode array UV-Vis spectroscopy. Preliminary data from the Kellwasser intervals reveal only one porphyrin, with a mass (M+H) of 600. The UV-Vis absorbance spectrum (Soret = 405nm, α = 533nm, β = 570nm) of the metallated compound is consistent with that of a vanadyl porphyrin with a free-base (M+H) of 535. Collision-induced mass spectra displays mass losses of 43 and 57 daltons, which are consistent with an extended alkyl chain at the C-8 position. Extended alkyl chains at C-8 are exclusively associated with porphyrins derived from bacteriochlorophyll c, d or e. The presence of bacterioporphyrins is congruous with the episodic presence of anoxic and sulfidic conditions in the photic zone. What is surprising is that a bacteriochlorophyll- derived porphyrin is the most abundant in these sequences, and their study may help to elucidate the conditions surrounding the F-F mass extinction, and further constrain the fluctuations in marine oxygen content in the Upper Devonian Appalachian Basin.

  6. Computation Sheds Insight into Iron Porphyrin Carbenes' Electronic Structure, Formation, and N-H Insertion Reactivity.

    PubMed

    Sharon, Dina A; Mallick, Dibyendu; Wang, Binju; Shaik, Sason

    2016-08-01

    Iron porphyrin carbenes constitute a new frontier of species with considerable synthetic potential. Exquisitely engineered myoglobin and cytochrome P450 enzymes can generate these complexes and facilitate the transformations they mediate. The current work harnesses density functional theoretical methods to provide insight into the electronic structure, formation, and N-H insertion reactivity of an iron porphyrin carbene, [Fe(Por)(SCH3)(CHCO2Et)](-), a model of a complex believed to exist in an experimentally studied artificial metalloenzyme. The ground state electronic structure of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupled electrons residing on the iron center and carbene ligand. As we shall reveal, the bonding properties of [Fe(Por)(SCH3)(CHCO2Et)](-) are remarkably analogous to those of ferric heme superoxide complexes. The carbene forms by dinitrogen loss from ethyl diazoacetate. This reaction occurs preferentially through an open-shell singlet transition state: iron donates electron density to weaken the C-N bond undergoing cleavage. Once formed, the iron porphyrin carbene accomplishes N-H insertion via nucleophilic attack. The resulting ylide then rearranges, using an internal carbonyl base, to form an enol that leads to the product. The findings rationalize experimentally observed reactivity trends reported in artificial metalloenzymes employing iron porphyrin carbenes. Furthermore, these results suggest a possible expansion of enzymatic substrate scope, to include aliphatic amines. Thus, this work, among the first several computational explorations of these species, contributes insights and predictions to the surging interest in iron porphyrin carbenes and their synthetic potential. PMID:27347808

  7. Computation Sheds Insight into Iron Porphyrin Carbenes' Electronic Structure, Formation, and N-H Insertion Reactivity.

    PubMed

    Sharon, Dina A; Mallick, Dibyendu; Wang, Binju; Shaik, Sason

    2016-08-01

    Iron porphyrin carbenes constitute a new frontier of species with considerable synthetic potential. Exquisitely engineered myoglobin and cytochrome P450 enzymes can generate these complexes and facilitate the transformations they mediate. The current work harnesses density functional theoretical methods to provide insight into the electronic structure, formation, and N-H insertion reactivity of an iron porphyrin carbene, [Fe(Por)(SCH3)(CHCO2Et)](-), a model of a complex believed to exist in an experimentally studied artificial metalloenzyme. The ground state electronic structure of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupled electrons residing on the iron center and carbene ligand. As we shall reveal, the bonding properties of [Fe(Por)(SCH3)(CHCO2Et)](-) are remarkably analogous to those of ferric heme superoxide complexes. The carbene forms by dinitrogen loss from ethyl diazoacetate. This reaction occurs preferentially through an open-shell singlet transition state: iron donates electron density to weaken the C-N bond undergoing cleavage. Once formed, the iron porphyrin carbene accomplishes N-H insertion via nucleophilic attack. The resulting ylide then rearranges, using an internal carbonyl base, to form an enol that leads to the product. The findings rationalize experimentally observed reactivity trends reported in artificial metalloenzymes employing iron porphyrin carbenes. Furthermore, these results suggest a possible expansion of enzymatic substrate scope, to include aliphatic amines. Thus, this work, among the first several computational explorations of these species, contributes insights and predictions to the surging interest in iron porphyrin carbenes and their synthetic potential.

  8. Vibrational characterization of multiply metal-metal bonded osmium, molybdenum, and rhenium porphyrin dimers

    SciTech Connect

    Tait, C.D.; Sattelberger, A.P.; Woodruff, W.H. ); Garner, J.M.; Collman, J.P. )

    1989-12-06

    The resonance Raman (RR) scattering and infrared (IR) absorption spectra of ((M(OEP)){sub 2}){sup n+} complexes (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrin dianion; M = Os (n = 0-2), Re (n = 0-2), and Mo (n=0)) are reported. Resonance Raman studies reveal the Os-Os stretch to increase in frequency upon oxidation (233 cm{sup {minus}1} (n = 0), 254 cm{sup {minus}1} (n = 1), and 266 cm{sup {minus}1} (n = 2)), consistent with the removal of electrons from {pi}* metal-metal antibonding orbitals. The Mo-Mo stretch was also observed spectroscopically, producing a RR peak at 341 cm{sup {minus}1}, while the Re-Re stretch in ((Re(OEP)){sub 2}){sup 1+} was observed at 290 cm{sup {minus}1}. The corresponding metal-metal bond distances estimated from these stretching frequencies are 2.39, 2.31, and 2.27 {angstrom} for the osmium oxidation series, 2.23 {angstrom} for the molybdenum dimer, and 2.20 {angstrom} for the rhenium dimer. The porphyrin-centered vibrational modes (both RR and IR active) for the three osmium complexes are essentially independent of oxidation state, consistent with oxidation of metal-metal antibonding electrons. Little {pi} back-bonding between the metal and porphyrin macrocycle is suggested from porphyrin RR indicator modes, which are sensitive to {pi} electron density. Moreover, the porphyrin core size (center to nitrogen distance) is estimated from core size marker vibrations to be ca. 2.04 {angstrom} for all of the complexes studied. Finally, no vibrational evidence for ground-state intradimer coupling between the {pi} orbitals of the porphyrin rings is found.

  9. An efficient synthesis of porphyrins with different meso substituents that avoids scrambling in aqueous media.

    PubMed

    Nowak-Król, Agnieszka; Plamont, Rémi; Canard, Gabriel; Edzang, Judicaelle Andeme; Gryko, Daniel T; Balaban, Teodor Silviu

    2015-01-19

    We have developed new conditions that afford regioisomerically pure trans-A2B2-, A3B-, and trans-AB2C-porphyrins bearing aryl and arylethynyl substituents. The porphyrins were prepared by the acid-catalyzed condensation of dipyrromethanes with aldehydes followed by oxidation with p-chloranil or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Optimal conditions for the condensation were identified after examining various reaction parameters such as solvent composition, acid concentration, and reaction time. The conditions identified (for aromatic aldehydes: EtOH/H2O 4:1, [DPM] = 4 mM, [aldehyde] = 4 mM, [HCl] = 38 mM, 16 h; for arylethynyl aldehydes: THF/H2O 2:1, [DPM] = 13 mM, [aldehyde] = 13 mM, [HCl] = 150 mM, 3 h) resulted in the formation of porphyrins in yields of 9-38% without detectable scrambling. This synthesis is compatible with diverse functionalities such as ester or nitrile. In total, 20 new trans-A2B2-, A3B-, and trans-AB2C-porphyrins were prepared. The scope and limitations of the two sets of reaction conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in higher yields than by any other methodology and by using environmentally benign and nonhazardous chemicals. PMID:25417808

  10. Assessment of the photosensitization properties of cationic porphyrins in interaction with DNA nucleotide pairs.

    PubMed

    Cárdenas-Jirón, Gloria I; Cortez, Luis

    2013-07-01

    We present a theoretical assessment of the photosensitization properties of meso-mono(N-methylpyridyl) triphenylporphyrin (1, MmPyP(+)), which interacts with DNA nucleotide pairs [adenine (A)-thymine (T); guanine (G)-cytosine (C)] via an external binding mode. The photosensitization properties of the arrangements 1A, 1T, 1G and 1C were investigated. A set of density functionals (B3LYP, PBE0, CAM-B3LYP, M06-2X, B97D) with the 6-31G(d) basis set was used to calculate the electronic absorption spectra in solution (water) following TD-DFT methodology. In all the arrangements, with the exception of 1C, the functional PBE0 produced the lowest deviation of the Soret band (0.1-0.2 eV). Using this functional, we show that the porphyrin-nucleotide interaction is stabilized, as reflected by a larger HOMO-LUMO gap than free porphyrin. A more important effect of the interaction corresponds to the red-shift of the Soret band of MmPyP(+), which is in agreement with experimental results. This behavior could be explained by the higher symmetry found in arrangements with a lower dipole moment, and by the more symmetrical distribution of electronic density along the molecular orbitals, which provokes electronic transitions of lower energy. The structural model allowed us to show that MmPyP(+) improves the characteristics as a photosensitizer when it interacts with nucleotide pairs due to the longer wavelength required for the Soret band. Results obtained for porphyrins with larger monocationic substituents (2, MmAP+; 3, MONPP+) do not lead to the same behavior. Although the structural model is insufficient to describe porphyrin photosensitization, it suggests that improvements in this property are produced by the inclusion of a cationic charge in the pyridyl ring and a smaller size of the substituent leading to a better communication in the porphyrin-nucleotide pair.

  11. Glassy slags for minimum additive waste stabilization. Interim progress report, May 1993--February 1994

    SciTech Connect

    Feng, X.; Wronkiewicz, D.J.; Bates, J.K.; Brown, N.R.; Buck, E.C.; Dietz, N.L.; Gong, M.; Emery, J.W.

    1994-05-01

    Glassy slag waste forms are being developed to complement glass waste forms in implementing Minimum Additive Waste Stabilization (MAWS) for supporting DOE`s environmental restoration efforts. The glassy slag waste form is composed of various crystalline and metal oxide phases embedded in a silicate glass phase. The MAWS approach was adopted by blending multiple waste streams to achieve up to 100% waste loadings. The crystalline phases, such as spinels, are very durable and contain hazardous and radioactive elements in their lattice structures. These crystalline phases may account for up to 80% of the total volume of slags having over 80% metal loading. The structural bond strength model was used to quantify the correlation between glassy slag composition and chemical durability so that optimized slag compositions were obtained with limited crucible melting and testing. Slag compositions developed through crucible melts were also successfully generated in a pilot-scale Retech plasma centrifugal furnace at Ukiah, California. Utilization of glassy slag waste forms allows the MAWS approach to be applied to a much wider range of waste streams than glass waste forms. The initial work at ANL has indicated that glassy slags are good final waste forms because of (1) their high chemical durability; (2) their ability to incorporate large amounts of metal oxides; (3) their ability to incorporate waste streams having low contents of flux components; (4) their less stringent requirements on processing parameters, compared to glass waste forms; and (5) their low requirements for purchased additives, which means greater waste volume reduction and treatment cost savings.

  12. A 'two-point' bound zinc porphyrin-zinc phthalocyanine-fullerene supramolecular triad for sequential energy and electron transfer.

    PubMed

    KC, Chandra B; Ohkubo, Kei; Karr, Paul A; Fukuzumi, Shunichi; D'Souza, Francis

    2013-09-01

    A novel supramolecular triad composed of a zinc porphyrin-zinc phthalocyanine dyad and fullerenes has been assembled using a 'two-point' axial binding approach, and occurrence of efficient photoinduced energy transfer followed by electron transfer is demonstrated.

  13. Fluorinated porphyrin tweezer: a powerful reporter of absolute configuration for erythro and threo diols, amino alcohols, and diamines.

    PubMed

    Li, Xiaoyong; Tanasova, Marina; Vasileiou, Chrysoula; Borhan, Babak

    2008-02-13

    A general and sensitive nonempirical protocol to determine the absolute configurations of erythro and threo diols, amino alcohols, and diamines is reported. Binding of diols to the porphyrin tweezer system is greatly enhanced by increasing the Lewis acidity of the metalloporphyrin. Supramolecular complexes formed between the porphyrin tweezer host and chiral substrates exhibited exciton-coupled bisignate CD spectra with predictable signs based on the substituents on the chiral center. The working model suggests that the observed helicity of the porphyrin tweezer is dictated via steric differentiation experienced by the porphyrin ring bound to each chiral center. A variety of erythro and threo substrates were investigated to verify this chiroptical method. Their absolute configurations were unequivocally determined, and thus a general mnemonic is provided for the assignment of chirality.

  14. Synthesis of molecular complexes based on porphyrins for the investigation of the energy transfer and primary charge separation in photosynthesis

    NASA Astrophysics Data System (ADS)

    Gribkova, S. E.; Evstigneeva, Rima P.; Luzgina, Valentina N.

    1993-10-01

    Data on the synthesis, steric structures, and photochemical properties of molecular diad systems based on porphyrins as synthetic models of the reaction centre in photosynthesis are considered and treated systematically. The bibliography includes 102 references.

  15. Triply stacked heterogeneous array of porphyrins and phthalocyanine through stepwise formation of a fourfold rotaxane and an ionic complex.

    PubMed

    Yamada, Yasuyuki; Mihara, Nozomi; Shibano, Shinya; Sugimoto, Kunihisa; Tanaka, Kentaro

    2013-08-01

    We report the preparation and crystal structure of a triply stacked metal complex array in which a Cu-phthalocyanine is sandwiched between different Cu-porphyrins. The discrete heterogeneous assembly was prepared through formation of a fourfold rotaxane from a tetradactyl porphyrin with alkylammonium moieties and a phthalocyanine bearing four crown ethers and the subsequent formation of an ionic complex between the fourfold rotaxane and a tetraanionic porphyrin. The tetraanionic porphyrin, Cu-TPPS(4-), is selectively bound to the fourfold rotaxane through cooperative π-π and ionic interactions. The crystal structure revealed the columnar stacked array of the three planar building components in a precise order and spatial arrangement that promote intermolecular electronic communication. PMID:23889684

  16. Synthesis, spectroscopic, and photophysical characterization and photosensitizing activity toward prokaryotic and eukaryotic cells of porphyrin-magainin and -buforin conjugates.

    PubMed

    Dosselli, Ryan; Ruiz-González, Rubén; Moret, Francesca; Agnolon, Valentina; Compagnin, Chiara; Mognato, Maddalena; Sella, Valentina; Agut, Montserrat; Nonell, Santi; Gobbo, Marina; Reddi, Elena

    2014-02-27

    Cationic antimicrobial peptides (CAMPs) and photodynamic therapy (PDT) are attractive tools to combat infectious diseases and to stem further development of antibiotic resistance. In an attempt to increase the efficiency of bacteria inactivation, we conjugated a PDT photosensitizer, cationic or neutral porphyrin, to a CAMP, buforin or magainin. The neutral and hydrophobic porphyrin, which is not photoactive per se against Gram-negative bacteria, efficiently photoinactivated Escherichia coli after conjugation to either buforin or magainin. Conjugation to magainin resulted in the considerable strengthening of the cationic and hydrophilic porphyrin's interaction with the bacterial cells, as shown by the higher bacteria photoinactivation activity retained after washing the bacterial suspension. The porphyrin-peptide conjugates also exhibited strong interaction capability as well as photoactivity toward eukaryotic cells, namely, human fibroblasts. These findings suggest that these CAMPs have the potential to carry drugs and other types of cargo inside mammalian cells similar to cell-penetrating peptides.

  17. Synthesis of a multibranched porphyrin-oligonucleotide scaffold for the construction of DNA-based nano-architectures.

    PubMed

    Clavé, Guillaume; Chatelain, Grégory; Filoramo, Arianna; Gasparutto, Didier; Saint-Pierre, Christine; Le Cam, Eric; Piétrement, Olivier; Guérineau, Vincent; Campidelli, Stéphane

    2014-05-01

    The interest in the functionalization of oligonucleotides with organic molecules has grown considerably over the last decade. In this work, we report on the synthesis and characterization of porphyrin-oligonucleotide hybrids containing one to four DNA strands (P1-P4). The hybrid P4, which inserts one porphyrin and four DNA fragments, was combined with gold nanoparticles and imaged by transmission electron microscopy.

  18. Effects of protonation of pyridine moieties on the 2D assembly of porphyrin layers on Au(111) at electrochemical interfaces.

    PubMed

    Yoshimoto, Soichiro

    2012-05-14

    Unique molecular assemblies of a porphyrin derivative are prepared on Au(111) by controlling the protonation/unprotonation of the pyridine groups. The porphyrin derivative, driven by the protonation of the pyridine groups, can provide characteristic assemblies with specific molecular conformations on an Au(111) surface at the electrochemical interface. In situ scanning tunneling microscopy images revealed clear differences in the adlayer structures for the unprotonated and the protonated forms of the molecules that depended upon the electrochemical potential.

  19. Ytterbium(III) porpholactones: β-lactonization of porphyrin ligands enhances sensitization efficiency of lanthanide near-infrared luminescence.

    PubMed

    Ke, Xian-Sheng; Yang, Bo-Yan; Cheng, Xin; Chan, Sharon Lai-Fung; Zhang, Jun-Long

    2014-04-01

    The near-infrared (NIR) luminescence efficiency of lanthanide complexes is largely dependent on the electronic and photophysical properties of antenna ligands. Although porphyrin ligands are efficient sensitizers of lanthanide NIR luminescence, non-pyrrolic porphyrin analogues, which have unusual symmetry and electronic states, have been much less studied. In this work, we used porpholactones, a class of β-pyrrolic-modified porphyrins, as ligands and investigated the photophysical properties of lanthanide porpholactones Yb-1 a-5 a. Compared with Yb porphyrin complexes, the porpholactone complexes displayed remarkable enhancement of NIR emission (50-120 %). Estimating the triplet-state levels of porphyrin and porpholactone in Gd complexes revealed that β-lactonization of porphyrinic ligands lowers the ligand T1 state and results in a narrow energy gap between this state and the lowest excited state of Yb(3+) . Transient absorption spectra showed that Yb(III) porpholactone has a longer transient decay lifetime at the Soret band than the porphyrin analogue (30.8 versus 17.0 μs). Thus, the narrower energy gap and longer lifetime arising from β-lactonization are assumed to enhance NIR emission of Yb porpholactones. To demonstrate the potential applications of Yb porpholactone, a water-soluble Yb bioprobe was constructed by conjugating glucose to Yb-1 a. Interestingly, the NIR emission of this Yb porpholactone could be specifically switched on in the presence of glucose oxidase and then switched off by addition of glucose. This is the first demonstration that non-pyrrolic porphyrin ligands enhance the sensitization efficiency of lanthanide luminescence and also display switchable NIR emission in the region of biological analytes (800-1400 nm).

  20. Controlled intracellular generation of reactive oxygen species in human mesenchymal stem cells using porphyrin conjugated nanoparticles

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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

  2. Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa.

    PubMed

    Pham, Nhi-Thi; Kim, Jin-Gil; Jung, Sunyo

    2015-07-21

    We compared antioxidant responses and regulation of porphyrin metabolism in rice plants treated with oxyfluorfen (OF) or methyl viologen (MV). Plants treated with MV exhibited not only greater increases in conductivity and malondialdehyde but also a greater decline in Fv/Fm, compared to plants treated with OF. MV-treated plants had greater increases in activities of superoxide dismutase (SOD) and catalase (CAT) as well as transcript levels of SODA and CATA than OF-treated plants after 28 h of the treatments, whereas increases in ascorbate peroxidase (APX) activity and transcript levels of APXA and APXB were greater in OF-treated plants. Both OF- and MV-treated plants resulted in not only down-regulation of most genes involved in porphyrin biosynthesis but also disappearance of Mg-porphyrins during the late stage of photooxidative stress. By contrast, up-regulation of heme oxygenase 2 (HO2) is possibly part of an efficient antioxidant response to compensate photooxidative damage in both treatments. Our data show that down-regulated biosynthesis and degradation dynamics of porphyrin intermediates have important roles in photoprotection of plants from perturbed porphyrin biosynthesis and photosynthetic electron transport. This study suggests that porphyrin scavenging as well as strong antioxidative activities are required for mitigating reactive oxygen species (ROS) production under photooxidative stress caused by OF and MV.

  3. Application of Near-IR Absorption Porphyrin Dyes Derived from Click Chemistry as Third-Order Nonlinear Optical Materials.

    PubMed

    Mi, Yongsheng; Liang, Pengxia; Yang, Zhou; Wang, Dong; Cao, Hui; He, Wanli; Yang, Huai; Yu, Lian

    2016-02-01

    Recently, third-order nonlinear properties of porphyrins and porphyrin polymers and coordination compounds have been extensively studied in relation to their use in photomedicine and molecular photonics. A new functionalized porphyrin dye containing electron-rich alkynes was synthesized and further modified by formal [2+2] click reactions with click reagents tetracyanoethylene (TCNE) and 7, 7, 8, 8-tetracyanoquinodimethane (TCNQ). The photophysical properties of these porphyrin dyes, as well as the click reaction, were studied by UV/Vis spectroscopy. In particular, third-order nonlinear optical properties of the dyes, which showed typical d-π-A structures, were characterized by Z-scan techniques. In addition, the self-assembly properties were investigated through the phase-exchange method, and highly organized morphologies were observed by scanning electron microscopy (SEM). The effects of the click post-functionalization on the properties of the porphyrins were studied, and these functionalized porphyrin dyes represent an interesting set of candidates for optoelectronic device components.

  4. Oxygen Availability for Porphyrin Biosynthesis Enzymes Determines the Production of Protoporphyrin IX (PpIX) during Hypoxia.

    PubMed

    Otsuka, Shimpei; Matsumoto, Kentaro; Nakajima, Motowo; Tanaka, Tohru; Ogura, Shun-Ichiro

    2015-01-01

    5-Aminolevulinic acid (ALA), a precursor of porphyrin, is specifically converted to the fluorescent substance protoporphyrin IX (PpIX) in tumors to be used as a prodrug for photodynamic therapy and diagnosis. Hypoxia, a common feature of solid tumors, decreases the efficacy of ALA-based photodynamic therapy and diagnosis. This decrease results from the excretion of porphyrin precursor coproporphyrinogen III (CPgenIII), an intermediate in the biosynthesis of PpIX. However, the mechanism of CPgenIII excretion during hypoxia remains unclear. In this study, we revealed the importance of mitochondrial respiration for the production of PpIX during hypoxia. Porphyrin concentrations were estimated in human gastric cancer cell lines by HPLC. Expression levels of porphyrin biosynthesis genes were measured by qRT-PCR and immunoblotting. Blockage of porphyrin biosynthesis was an oxygen-dependent phenomenon resulting from decreased PpIX production in mitochondria under hypoxic conditions. PpIX production was increased by the inhibition of mitochondrial respiration complexes, which indicates that the enzymes of porphyrin biosynthesis compete with respiration complexes for molecular oxygen. Our results indicate that targeting the respiration complexes is a rationale for enhancing the effect of ALA-mediated treatment and diagnosis. PMID:26717566

  5. The fast method of Cu-porphyrin complex synthesis for potential use in positron emission tomography imaging.

    PubMed

    Kilian, Krzysztof; Pęgier, Maria; Pyrzyńska, Krystyna

    2016-04-15

    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 (64)Cu isotope can serve as a positron emitter (t1/2=12.7h). The other advantage of (64)Cu is its decay characteristics that facilitates the use of (64)Cu-porphyrin complex as a therapeutic agent. Thus, (64)Cu 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 pH9 with the addition of 10-fold molar excess, with respect to Cu(2+) ions and TCPP and ascorbic acid which resulted in reduction of the reaction time from 30 min to below 1 min.

  6. Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa

    PubMed Central

    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

  7. Porphyrin Binding to Gun4 Protein, Facilitated by a Flexible Loop, Controls Metabolite Flow through the Chlorophyll Biosynthetic Pathway.

    PubMed

    Kopečná, Jana; Cabeza de Vaca, Israel; Adams, Nathan B P; Davison, Paul A; Brindley, Amanda A; Hunter, C Neil; Guallar, Victor; Sobotka, Roman

    2015-11-20

    In oxygenic phototrophs, chlorophylls, hemes, and bilins are synthesized by a common branched pathway. Given the phototoxic nature of tetrapyrroles, this pathway must be tightly regulated, and an important regulatory role is attributed to magnesium chelatase enzyme at the branching between the heme and chlorophyll pathway. Gun4 is a porphyrin-binding protein known to stimulate in vitro the magnesium chelatase activity, but how the Gun4-porphyrin complex acts in the cell was unknown. To address this issue, we first performed simulations to determine the porphyrin-docking mechanism to the cyanobacterial Gun4 structure. After correcting crystallographic loop contacts, we determined the binding site for magnesium protoporphyrin IX. Molecular modeling revealed that the orientation of α6/α7 loop is critical for the binding, and the magnesium ion held within the porphyrin is coordinated by Asn-211 residue. We also identified the basis for stronger binding in the Gun4-1 variant and for weaker binding in the W192A mutant. The W192A-Gun4 was further characterized in magnesium chelatase assay showing that tight porphyrin binding in Gun4 facilitates its interaction with the magnesium chelatase ChlH subunit. Finally, we introduced the W192A mutation into cells and show that the Gun4-porphyrin complex is important for the accumulation of ChlH and for channeling metabolites into the chlorophyll biosynthetic pathway.

  8. Application of Near‐IR Absorption Porphyrin Dyes Derived from Click Chemistry as Third‐Order Nonlinear Optical Materials

    PubMed Central

    Mi, Yongsheng; Liang, Pengxia; Cao, Hui; He, Wanli

    2015-01-01

    Abstract Recently, third‐order nonlinear properties of porphyrins and porphyrin polymers and coordination compounds have been extensively studied in relation to their use in photomedicine and molecular photonics. A new functionalized porphyrin dye containing electron‐rich alkynes was synthesized and further modified by formal [2+2] click reactions with click reagents tetracyanoethylene (TCNE) and 7, 7, 8, 8‐tetracyanoquinodimethane (TCNQ). The photophysical properties of these porphyrin dyes, as well as the click reaction, were studied by UV/Vis spectroscopy. In particular, third‐order nonlinear optical properties of the dyes, which showed typical d‐π‐A structures, were characterized by Z‐scan techniques. In addition, the self‐assembly properties were investigated through the phase‐exchange method, and highly organized morphologies were observed by scanning electron microscopy (SEM). The effects of the click post‐functionalization on the properties of the porphyrins were studied, and these functionalized porphyrin dyes represent an interesting set of candidates for optoelectronic device components. PMID:27308215

  9. The fast method of Cu-porphyrin complex synthesis for potential use in positron emission tomography imaging

    NASA Astrophysics Data System (ADS)

    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.

  10. Oxygen Availability for Porphyrin Biosynthesis Enzymes Determines the Production of Protoporphyrin IX (PpIX) during Hypoxia

    PubMed Central

    Otsuka, Shimpei; Matsumoto, Kentaro; Nakajima, Motowo; Tanaka, Tohru; Ogura, Shun-ichiro

    2015-01-01

    5-Aminolevulinic acid (ALA), a precursor of porphyrin, is specifically converted to the fluorescent substance protoporphyrin IX (PpIX) in tumors to be used as a prodrug for photodynamic therapy and diagnosis. Hypoxia, a common feature of solid tumors, decreases the efficacy of ALA-based photodynamic therapy and diagnosis. This decrease results from the excretion of porphyrin precursor coproporphyrinogen III (CPgenIII), an intermediate in the biosynthesis of PpIX. However, the mechanism of CPgenIII excretion during hypoxia remains unclear. In this study, we revealed the importance of mitochondrial respiration for the production of PpIX during hypoxia. Porphyrin concentrations were estimated in human gastric cancer cell lines by HPLC. Expression levels of porphyrin biosynthesis genes were measured by qRT-PCR and immunoblotting. Blockage of porphyrin biosynthesis was an oxygen-dependent phenomenon resulting from decreased PpIX production in mitochondria under hypoxic conditions. PpIX production was increased by the inhibition of mitochondrial respiration complexes, which indicates that the enzymes of porphyrin biosynthesis compete with respiration complexes for molecular oxygen. Our results indicate that targeting the respiration complexes is a rationale for enhancing the effect of ALA-mediated treatment and diagnosis. PMID:26717566

  11. Effects of molecular architecture on fluid ingress behavior of glassy polymer networks

    NASA Astrophysics Data System (ADS)

    Jaskson, Matthew Blaine

    This manuscript demonstrates the synthesis of glassy polymer network isomers to control morphological variations and study solvent ingress behavior independent of chemical affinity. Well-controlled network architectures with varying free volume average hole-sizes have been shown to substantially influence solvent ingress within glassy polymer networks. Bisphenol-A diglycidyl ether (DGEBA), bisphenol-F diglycidyl ether (DGEBF), Triglycidyl p-aminophenol (pAP, MY0510), Triglycidyl maminophenol (mAP, MY0610), and tetraglydicyl-4,4'-diamino-diphenyl methane (TGDDM, MY721) were cured with 3,3'- and 4,4'-diaminodiphenyl sulfone (DDS) at a stoichiometric ratio of 1:1 oxirane to amine active hydrogen to generate a series of network architectures with an average free volume hole-size (Vh) ranging between 54-82 A3. Polymer networks were exposed to water and a broad range of organic solvents ranging in van der Waals (vdW) volumes from 18-88 A3 for up to 10,000h time. A clear relationship between glassy polymer network Vh and fluid penetration has been established. As penetrant vdW volume approached Vh, uptake kinetics significantly decreased, and as penetrant vdW volume exceeded Vh, a blocking mechanism dominated ingress and prevented penetrant transport. These results suggest that reducing the free volume hole-size is a reasonable approach to control solvent properties for glassy polymer networks. New techniques to monitor and predict the diffusion behavior of liquids through glassy networks are also presented. Digital Image Correlation (DIC) was employed to accurately measure the strain developed during case II diffusion. This technique also presented a new theory for a relationship between sample topology and irreversible macroscopic brittle failure induced by solvent absorption. A new modeling technique has been developed which can accurately predict the chemical and physical interactions a solvent may have with a glassy network. This new model can be used as a

  12. The observation of spectral variation indicative of porphyrin biomarkers in reflectance spectra of source rock - The application of remote sensing technology to petroleum geochemistry

    NASA Technical Reports Server (NTRS)

    Holden, Peter Newhall; Gaffey, Michael J.

    1990-01-01

    The spectral signature of porphyrin compounds, considered to be biomarkers of depositional environment and thermal maturity, have been identified in reflectance spectra of oil shales. The key bands identified, in order of intensity, are the Soret (0.40 microns), alpha (0.57 microns), and beta (0.53 microns) bands. The observed bands represent the composite spectral signature of all porphyrin compounds present in the sample and, therefore, change position and intensity in accordance with changes in porphyrin chemistry.

  13. Light-harvesting supramolecular porphyrin macrocycle accommodating a fullerene-tripodal ligand.

    PubMed

    Kuramochi, Yusuke; Satake, Akiharu; Itou, Mitsunari; Ogawa, Kazuya; Araki, Yasuyuki; Ito, Osamu; Kobuke, Yoshiaki

    2008-01-01

    Trisporphyrinatozinc(II) (1-Zn) with imidazolyl groups at both ends of the porphyrin self-assembles exclusively into a light-harvesting cyclic trimer (N-(1-Zn)(3)) through complementary coordination of imidazolyl to zinc(II). Because only the two terminal porphyrins in 1-Zn are employed in ring formation, macrocycle N-(1-Zn)(3) leaves three uncoordinated porphyrinatozinc(II) groups as a scaffold that can accommodate ligands into the central pore. A pyridyl tripodal ligand with an appended fullerene connected through an amide linkage (C(60)-Tripod) was synthesized by coupling tripodal ligand 3 with pyrrolidine-modified fullerene, and this ligand was incorporated into N-(1-Zn)(3). The binding constant for C(60)-Tripod in benzonitrile reached the order of 10(8) M(-1). This value is ten times larger than those of pyridyl tetrapodal ligand 2 and tripodal ligand 3. This behavior suggests that the fullerene moiety contributes to enhance the binding of C(60)-Tripod in N-(1-Zn)(3). The fluorescence of N-(1-Zn)(3) was almost completely quenched (approximately 97 %) by complexation with C(60)-Tripod, without any indication of the formation of charge-separated species or a triplet excited state of either porphyrin or fullerene in the transient absorption spectra. These observations are explained by the idea that the fullerene moiety of C(60)-Tripod is in direct contact with the porphyrin planes of N-(1-Zn)(3) through fullerene-porphyrin pi-pi interactions. Thus, C(60)-Tripod is accommodated in N-(1-Zn)(3) with a pi-pi interaction and two pyridyl coordinations. The cooperative interaction achieves a sufficiently high affinity for quantitative and specific introduction of one equivalent of tripodal guest into the antenna ring, even under dilute conditions ( approximately 10(-7) M) in polar solvents such as benzonitrile. Additionally, complete fluorescence quenching of N-(1-Zn)(3) when accommodating C(60)-Tripod demonstrates that all of the excitation energy collected by the nine

  14. Anticancer activity of cationic porphyrins in melanoma tumour-bearing mice and mechanistic in vitro studies

    PubMed Central

    2014-01-01

    Background Porphyrin TMPyP4 (P4) and its C14H28-alkyl derivative (C14) are G-quadruplex binders and singlet oxygen (1O2) generators. In contrast, TMPyP2 (P2) produces 1O2 but it is not a G-quadruplex binder. As their photosensitizing activity is currently undefined, we report in this study their efficacy against a melanoma skin tumour and describe an in vitro mechanistic study which gives insights into their anticancer activity. Methods Uptake and antiproliferative activity of photoactivated P2, P4 and C14 have been investigated in murine melanoma B78-H1 cells by FACS, clonogenic and migration assays. Apoptosis was investigated by PARP-1 cleavage and annexin-propidium iodide assays. Biodistribution and in vivo anticancer activity were tested in melanoma tumour-bearing mice. Porphyrin binding and photocleavage of G-rich mRNA regions were investigated by electrophoresis and RT-PCR. Porphyrin effect on ERK pathway was explored by Western blots. Results Thanks to its higher lipophylicity C14 was taken up by murine melanoma B78-H1 cells up to 30-fold more efficiently than P4. When photoactivated (7.2 J/cm2) in B78-H1 melanoma cells, P4 and C14, but not control P2, caused a strong inhibition of metabolic activity, clonogenic growth and cell migration. Biodistribution studies on melanoma tumour-bearing mice showed that P4 and C14 localize in the tumour. Upon irradiation (660 nm, 193 J/cm2), P4 and C14 retarded tumour growth and increased the median survival time of the treated mice by ~50% (P <0.01 by ANOVA), whereas porphyrin P2 did not. The light-dependent mechanism mediated by P4 and C14 is likely due to the binding to and photocleavage of G-rich quadruplex-forming sequences within the 5′-untranslated regions of the mitogenic ras genes. This causes a decrease of RAS protein and inhibition of downstream ERK pathway, which stimulates proliferation. Annexin V/propidium iodide and PARP-1 cleavage assays showed that the porphyrins arrested tumour growth by apoptosis

  15. Host plant effects on development and reproduction of the glassy-winged sharpshooter, Homalodisca vitripennis (Homoptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Development, survivorship, longevity, reproduction and life table parameters of the glassy-winged sharpshooter, Homalodisca vitripennis (Germar), were examined in the laboratory using three host plants, sunflower (Helianthus annuus L.), Chrysanthemum morifolium L. and euonymus (Euonymus japonica Thu...

  16. Communication: Charge-transfer rate constants in zinc-porphyrin-porphyrin-derived dyads: A Fermi golden rule first-principles-based study

    SciTech Connect

    Manna, Arun K.; Dunietz, Barry D.

    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.

  17. Elastic Properties of 4-6 nm-thick Glassy Carbon Thin Films

    NASA Astrophysics Data System (ADS)

    Manoharan, M. P.; Lee, H.; Rajagopalan, R.; Foley, H. C.; Haque, M. A.

    2010-01-01

    Glassy carbon is a disordered, nanoporous form of carbon with superior thermal and chemical stability in extreme environments. Freestanding glassy carbon specimens with 4-6 nm thickness and 0.5 nm average pore size were synthesized and fabricated from polyfurfuryl alcohol precursors. Elastic properties of the specimens were measured in situ inside a scanning electron microscope using a custom-built micro-electro-mechanical system. The Young’s modulus, fracture stress and strain values were measured to be about 62 GPa, 870 MPa and 1.3%, respectively; showing strong size effects compared to a modulus value of 30 GPa at the bulk scale. This size effect is explained on the basis of the increased significance of surface elastic properties at the nanometer length-scale.

  18. Age-dependent modes of extensional necking instability in soft glassy materials.

    PubMed

    Hoyle, David M; Fielding, Suzanne M

    2015-04-17

    We study the instability to necking of an initially cylindrical filament of soft glassy material subject to extensional stretching. By numerical simulation of the soft glassy rheology model and a simplified fluidity model, and by analytical predictions within a highly generic toy description, we show that the mode of instability is set by the age of the sample relative to the inverse of the applied extensional strain rate. Young samples neck gradually via a liquidlike mode, the onset of which is determined by both the elastic loading and plastic relaxation terms in the stress constitutive equation. Older samples fail at smaller draw ratios via a more rapid mode, the onset of which is determined only by the solidlike elastic loading terms (though plastic effects arise later, once appreciable necking develops). We show this solidlike mode to be the counterpart, for elastoplastic materials, of the Considère mode of necking in strain-rate-independent solids. PMID:25933343

  19. Relaxation of enthalpy fluctuations during sub-T(g) annealing of glassy selenium.

    PubMed

    Gulbiten, Ozgur; Mauro, John C; Lucas, Pierre

    2013-06-28

    The relaxation behavior of glass is influenced by the presence of dynamical heterogeneities, which lead to an intrinsically non-monotonic decay of fluctuations in density and enthalpy during isothermal annealing. This is apparently a universal feature of fragile glass forming systems associated with localized spatial variations in relaxation time. Here we present direct experimental observation of the nonmonotonic evolution of enthalpy fluctuations in glassy selenium annealed near room temperature. The nonmonotonic change in the distribution of enthalpy fluctuations measured by heat capacity spectroscopy offers direct evidence for the presence of dynamical heterogeneity in this glass. An enthalpy landscape model of selenium is then used to simulate annealing under identical conditions. The simulation results closely follow the evolution of enthalpy fluctuations observed experimentally. The close match between model and experiment demonstrate that enthalpy and density fluctuations are sources of dynamical heterogeneities in glassy materials.

  20. Mechanical properties of thin glassy polymer films filled with spherical polymer-grafted nanoparticles.

    PubMed

    Maillard, Damien; Kumar, Sanat K; Fragneaud, Benjamin; Kysar, Jeffrey W; Rungta, Atri; Benicewicz, Brian C; Deng, Hua; Brinson, L Cate; Douglas, Jack F

    2012-08-01

    It is commonly accepted that the addition of spherical nanoparticles (NPs) cannot simultaneously improve the elastic modulus, the yield stress, and the ductility of an amorphous glassy polymer matrix. In contrast to this conventional wisdom, we show that ductility can be substantially increased, while maintaining gains in the elastic modulus and yield stress, in glassy nanocomposite films composed of spherical silica NPs grafted with polystyrene (PS) chains in a PS matrix. The key to these improvements are (i) uniform NP spatial dispersion and (ii) strong interfacial binding between NPs and the matrix, by making the grafted chains sufficiently long relative to the matrix. Strikingly, the optimal conditions for the mechanical reinforcement of the same nanocomposite material in the melt state is completely different, requiring the presence of spatially extended NP clusters. Evidently, NP spatial dispersions that optimize material properties are crucially sensitive to the state (melt versus glass) of the polymeric material.