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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, 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.

  3. 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.

  4. Peripherally Silylated Porphyrins.

    PubMed

    Kato, Kenichi; Fujimoto, Keisuke; Yorimitsu, Hideki; Osuka, Atsuhiro

    2015-09-21

    Silylation of peripherally lithiated porphyrins with silyl electrophiles has realized the first synthesis of a series of directly silyl-substituted porphyrins. The meso-silyl group underwent facile protodesilylation, whereas the β-silyl group was entirely compatible with standard work-up and purification on silica gel. The meso-silyl group caused larger substituent effects to the porphyrin compared with the β-silyl group. Silylation of β-lithiated porphyrins with 1,2-dichlorodisilane furnished β-to-β disilane-bridged porphyrin dimers. A doubly β-to-β disilane-bridged Ni(II)-porphyrin dimer was also synthesized from a β,β-dilithiated Ni(II)-porphyrin and characterized by X-ray crystallographic analysis to take a steplike structure favorable for interporphyrinic interaction. Denickelation of β-silylporphyrins was achieved upon treatment with a 4-tolylmagnesium bromide to yield the corresponding freebase porphyrins. PMID:26356498

  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. 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.

  7. Soluble porphyrin polymers

    DOEpatents

    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.

  8. Porphyrin urine test (image)

    MedlinePlus

    ... important function of porphyrins is as components of heme, which is made from iron plus protoporphyrin. Hemoglobin ... made up of four globin proteins plus 4 heme groups. Oxygen binds to the iron in the ...

  9. Porphyrins as molecular nanomaterials

    NASA Astrophysics Data System (ADS)

    Faraon, Victor; Ion, Rodica-Mariana; Pop, Simona-Florentina; Van-Staden, Raluca; Van-Staden, Jacobus-Frederick

    2010-11-01

    Some pophyrins as molecular materials are discussed in this paper. Aggregates of these molecules have been known for some time to possess interesting properties. Their optical properties as isolated species in condensed phases have also recently become interesting, and their ability to form new hybrid materials, by mixing them with themselves or other molecules with different electron affinities and ionization potentials, now appears to be extremely attractive. Few porphyrin structures, 5,10,15,20-tetra-p-phenyl-porphyrin (TPP), 5,10,15,20-tetra-p-methoxy-phenyl-porphyrin (TMOPP), 5,10,15,20-tetra-p-tolyl-porphyrin (TTP), 5,10,15,20-tetra-p-sulphonato-phenyl-porphyrin (TSPP), have been synthesized in this paper. Some analytical investigations as UV-Vis spectrophotometry (UV-Vis), Fourier transformed infrared spectroscopy (FTIR), atomic force microscopy (AFM) have been discussed as purity and stability criteria. Also, some considerations about their aggregation ability are discussed, and not in the last time, their capacity to generate porphyrin nanotubes.

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

    PubMed Central

    De Souza, Camille; Zrig, Samia; Wang, Dengjun; Pham, Minh-Chau; Piro, Benoit

    2014-01-01

    Metalated porphyrins have been described to bind nucleic acids. Additionally, cobalt porphyrins present catalytic properties towards oxygen reduction. In this work, a carboxylic acid-functionalized cobalt porphyrin was physisorbed on reduced graphene oxide, then immobilized on glassy carbon electrodes. The carboxylic groups were used to covalently graft amino-terminated oligonucleotide probes which are complementary to a short microRNA target. It was shown that the catalytic oxygen electroreduction on cobalt porphyrin increases upon hybridization of miRNA strand (“signal-on” response). Current changes are amplified compared to non-catalytic amperometric system. Apart from oxygen, no added reagent is necessary. A limit of detection in the sub-nanomolar range was reached. This approach has never been described in the literature. PMID:24915180

  11. 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##

  12. 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

  13. The glassy wormlike chain

    NASA Astrophysics Data System (ADS)

    Kroy, Klaus; Glaser, Jens

    2007-11-01

    We introduce a new model for the dynamics of a wormlike chain (WLC) in an environment that gives rise to a rough free energy landscape, which we name the glassy WLC. It is obtained from the common WLC by an exponential stretching of the relaxation spectrum of its long-wavelength eigenmodes, controlled by a single parameter \\boldsymbol{\\cal E} . Predictions for pertinent observables such as the dynamic structure factor and the microrheological susceptibility exhibit the characteristics of soft glassy rheology and compare favourably with experimental data for reconstituted cytoskeletal networks and live cells. We speculate about the possible microscopic origin of the stretching, implications for the nonlinear rheology, and the potential physiological significance of our results.

  14. 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.

  15. Porphyrin-sensitized solar cells.

    PubMed

    Li, Lu-Lin; Diau, Eric Wei-Guang

    2013-01-01

    Nature has chosen chlorophylls in plants as antennae to harvest light for the conversion of solar energy in complicated photosynthetic processes. Inspired by natural photosynthesis, scientists utilized artificial chlorophylls - the porphyrins - as efficient centres to harvest light for solar cells sensitized with a porphyrin (PSSC). After the first example appeared in 1993 of a porphyrin of type copper chlorophyll as a photosensitizer for PSSC that achieved a power conversion efficiency of 2.6%, no significant advance of PSSC was reported until 2005; beta-linked zinc porphyrins were then reported to show promising device performances with a benchmark efficiency of 7.1% reported in 2007. Meso-linked zinc porphyrin sensitizers in the first series with a push-pull framework appeared in 2009; the best cell performed comparably to that of a N3-based device, and a benchmark 11% was reported for a porphyrin sensitizer of this type in 2010. With a structural design involving long alkoxyl chains to envelop the porphyrin core to suppress the dye aggregation for a push-pull zinc porphyrin, the PSSC achieved a record 12.3% in 2011 with co-sensitization of an organic dye and a cobalt-based electrolyte. The best PSSC system exhibited a panchromatic feature for light harvesting covering the visible spectral region to 700 nm, giving opportunities to many other porphyrins, such as fused and dimeric porphyrins, with near-infrared absorption spectral features, together with the approach of molecular co-sensitization, to enhance the device performance of PSSC. According to this historical trend for the development of prospective porphyrin sensitizers used in PSSC, we review systematically the progress of porphyrins of varied kinds, and their derivatives, applied in PSSC with a focus on reports during 2007-2012 from the point of view of molecular design correlated with photovoltaic performance. PMID:23023240

  16. Alcohol and porphyrin metabolism.

    PubMed

    Doss, M O; Kühnel, A; Gross, U

    2000-01-01

    Alcohol is a porphyrinogenic agent which may cause disturbances in porphyrin metabolism in healthy persons as well as biochemical and clinical manifestations of acute and chronic hepatic porphyrias. After excessive consumption of alcohol, a temporary, clinically asymptomatic secondary hepatic coproporphyrinuria is observable, which can become persistent in cases of alcohol-induced liver damage. Nowadays, the alcohol-liver-porphyrinuria syndrome is the first to be mentioned in secondary hepatic disturbances of porphyrin metabolism. Acute hepatic porphyrias (acute intermittent porphyria, variegate porphyria and hereditary coproporphyria) are considered to be molecular regulatory diseases, in contrast to non-acute, chronic hepatic porphyria, clinically appearing as porphyria cutanea tarda (PCT). Porphyrins do not accumulate in the liver in acute porphyrias, whereas in chronic hepatic porphyrias they do. Thus, chronic hepatic porphyria is a porphyrin-accumulation disease, whereas acute hepatic porphyrias are haem-pathway-dysregulation diseases, characterized in general by induction of delta-aminolevulinic acid synthase in the liver and excessive stimulation of the pathway without storage of porphyrins in the liver. The clinical expression of acute hepatic porphyrias can be triggered by alcohol, because alcohol augments the inducibility of delta-aminolevulinic acid synthase. In chronic hepatic porphyrias, however, which are already associated with liver damage, alcohol potentiates the disturbance of the decarboxylation of uro- and heptacarboxyporphyrinogen, which is followed by a hepatic accumulation of uro- and heptacarboxyporphyrin and their sometimes extreme urinary excretion. Especially in persons with a genetic deficiency of uroporphyrinogen decarboxylase, but also in patients with the so-called sporadic variety of PCT, alcohol is able to transform an asymptomatic coproporphyrinuria into PCT. Alcohol has many biochemical and clinical effects on porphyrin and haem

  17. 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.

  18. 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.

  19. Cyclodextrin-Templated Porphyrin Nanorings**

    PubMed Central

    Liu, Pengpeng; Neuhaus, Patrik; Kondratuk, Dmitry V; Balaban, T Silviu; Anderson, Harry L

    2014-01-01

    α- and β-Cyclodextrins have been used as scaffolds for the synthesis of six- and seven-legged templates by functionalizing every primary CH2OH with a 4-pyridyl moiety. Although these templates are flexible, they are very effective for directing the synthesis of macrocyclic porphyrin oligomers consisting of six or seven porphyrin units. The transfer of chirality from the cyclodextrin templates to their nanoring hosts is evident from NMR and circular dichroism spectroscopy. Surprisingly, the mean effective molarity for binding the flexible α-cyclodextrin-based template within the six-porphyrin nanoring (74 m) is almost as high as for the previously studied rigid hexadentate template (180 m). The discovery that flexible templates are effective in this system, and the availability of a template with a prime number of binding sites, open up many possibilities for the template-directed synthesis of larger macrocycles. PMID:24916813

  20. Cyclodextrin-templated porphyrin nanorings.

    PubMed

    Liu, Pengpeng; Neuhaus, Patrik; Kondratuk, Dmitry V; Balaban, T Silviu; Anderson, Harry L

    2014-07-21

    α- and β-cyclodextrins have been used as scaffolds for the synthesis of six- and seven-legged templates by functionalizing every primary CH2OH with a 4-pyridyl moiety. Although these templates are flexible, they are very effective for directing the synthesis of macrocyclic porphyrin oligomers consisting of six or seven porphyrin units. The transfer of chirality from the cyclodextrin templates to their nanoring hosts is evident from NMR and circular dichroism spectroscopy. Surprisingly, the mean effective molarity for binding the flexible α-cyclodextrin-based template within the six-porphyrin nanoring (74 M) is almost as high as for the previously studied rigid hexadentate template (180 M). The discovery that flexible templates are effective in this system, and the availability of a template with a prime number of binding sites, open up many possibilities for the template-directed synthesis of larger macrocycles. PMID:24916813

  1. 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.

  2. 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

  3. 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.

  4. Unusual aryl-porphyrin rotational barriers in peripherally crowded porphyrins.

    SciTech Connect

    Shyr, David C.; Dooley, Neal R.; Haddad, Raid Edward; Shelnutt, John Allen; Muzzi, Cinzia M.; Ma, Jian-Guo; Olmstead, Marilyn M.; Jaquinod, Laurent A.; Nurco, Daniel J.; Medforth, Craig John; Smith, Kevin M.

    2003-06-01

    Previous studies of 5,10,15,20-tetraarylporphyrins have shown that the barrier for meso aryl-porphyrin rotation ({Delta}G{sub ROT}) varies as a function of the core substituent M and is lower for a small metal (M = Ni) compared to a large metal (M = Zn) and for a dication (M 4H{sup 2+}) versus a free base porphyrin (M = 2H). This has been attributed to changes in the nonplanar distortion of the porphyrin ring and the deformability of the macrocycle caused by the core substituent. In the present work, X-ray crystallography, molecular mechanics (MM) calculations, and variable temperature (VT) {sup 1}H NMR spectroscopy are used to examine the relationship between the aryl-porphyrin rotational barrier and the core substituent M in some novel 2,3,5,7,8,10,12,13,15,17,18,20-dodecaarylporphyrins (DArPs), and specifically in some 5,10,15,20-tetraaryl-2,3,7,8,12,13,17,18-octaphenylporphyrins (TArOPPs), where steric crowding of the peripheral groups always results in a very nonplanar macrocycle. X-ray structures of DArPs indicate differences in the nonplanar conformation of the macrocycle as a function of M, with saddle conformations being observed for M = Zn, 2H or M = 4H{sup 2+} and saddle and/or ruffle conformations for M = Ni. VT NMR studies show that the effect of protonation in the TArOPPs is to increase {Delta}G{sub ROT}, which is the opposite of the effect seen for the TArPs, and MM calculations also predict a strikingly high barrier for the TArOPPs when M = 4H{sup 2+}. These and other findings suggest that the aryl-porphyrin rotational barriers in the DArPs are closely linked to the deformability of the macrocycle along a nonplanar distortion mode which moves the substituent being rotated out of the porphyrin plane.

  5. Oxidation Behavior of Glassy Alloys

    NASA Technical Reports Server (NTRS)

    Yurek, G.

    1985-01-01

    The oxidation behavior of high temperature glassy alloys produced by rapid solidification processing is investigated and the effects of processing and composition on oxidation behavior is studied. Glassy Ta-44.5at%Ir, Ta-40at%Ir-10at%B and Nb-45at%Ir oxidized rapidly at 700 to 800 C at an oxygen partial pressure of .001 atm. The alloys were embrittled during the oxidation process. No apparent oxidation or embrittlement of the Ta-Ir alloy occurred after oxidation for 4h at 500 C at an oxygen partial pressure of .001 atm. Embrittlement occurred, however, after 100h of exposure under the latter conditions. Alloy embrittlement is associated with the partial or full conversion of the metallic glass to a mixture of crystalline beta-Ta2O5 and metallic iridium. Hot compaction of glassy alloys of this type must be limited to relatively low temperatures (approx. 500 C) and short times at the low temperatures unless extremely low oxygen partial pressures can be achieved during the compaction process.

  6. 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.

  7. 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.

  8. 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.

  9. Search for porphyrins in lunar dust.

    PubMed

    Hodgson, G W; Peterson, E; Kvenvolden, K A; Bunnenberg, E; Halpern, B; Ponnamperuma, C

    1970-01-30

    Evidence for porphyrins was obtained in the Apollo 11 bulk sample of lunar dust by fluorescence spectrometry and analytical demetallation. The indicated porphyrins showed major fluorescence excitation at 390 nanometers. Abundance was about 10(-10) gram of porphyrin per gram of dust. Similar pigments were found in exhaust products from tests of a lunar descent engine. The similarity of results suggests that most if not all of the indicated porphyrin aggregate of the lunar sample probably was synthesized from rocket fuel during the landing of the lunar module. These compounds may be the product of a novel high-temperature synthesis of cosmochemical interest. PMID:17781584

  10. Multifunctional Glassy Liquid Crystal for Photonics

    SciTech Connect

    Chen,S.H.

    2004-11-05

    As an emerging class of photonic materials, morphologically stable glassy liquid crystals, were developed following a versatile molecular design approach. Glassy cholesteric liquid crystals with elevated phase-transition temperatures and capability for selective-wavelength reflection and circular polarization were synthesized via determinstic synthesis strategies. Potential applications of glassy cholesteric liquid crystals include high-performance polarizers, optical notch filters and reflectors, and circularly polarized photoluminescence. A glassy nematic liquid crystal comprising a dithienylethene core was also synthesized for the demonstration of nondestructive rewritable optical memory and photonic switching in the sollid state.

  11. New porphyrin glyco-conjugates

    NASA Astrophysics Data System (ADS)

    Drain, Charles M.; Singh, Sunaina; Samaroo, Diana; Thompson, Sebastian; Vinodu, Mikki; Tome, Joao P. C.

    2009-06-01

    Porphyrins bearing sugars and other motifs are proposed for a variety of therapeutic applications. Non-hydrolysable glyco conjugates of porphyrins can be formed in rapid, room temperature reacting in greater than 90% yields from tetraperfluorophenyporphyrin. Additional functional groups can be appended using the same chemistry but different stoichiometries of the reagents. Thus sugars, amines, peptides, and cationic moieties designed to target cancer cells or other diseased or disease-causing cells are made rapidly and cleanly. These compounds can then be rapidly screened for cell uptake, or selected from combinatorial libraries by cell uptake assays using a combination of fluorescence microscopy and mass spectrometry. Modifications of the macrocycle allow fine-tuning of the photonic properties for specific medical, imaging, or biochemical applications.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. Cooperative strings and glassy interfaces

    PubMed Central

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

    2015-01-01

    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

  5. Two-step Mechanochemical Synthesis of Porphyrins

    PubMed Central

    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 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 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 suitable for 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. PMID:25406483

  6. Differential cell photosensitivity following porphyrin photodynamic therapy.

    PubMed

    Gomer, C J; Rucker, N; Murphree, A L

    1988-08-15

    Experiments were performed to determine if differences in porphyrin photosensitivity could be observed for cells with varying efficiency in DNA damage repair, as well as for cells which make up components of the vasculature. Photofrin II is undergoing current clinical evaluation for photodynamic therapy of solid tumors, and therefore the retention, dark toxicity, and photosensitizing effects of this drug on human DNA repair-deficient fibroblasts (ataxia telangiectasia and xeroderma pigmentosum) were compared to normal human fibroblasts. In addition, bovine cells of endothelial, smooth muscle, and fibroblast origin were compared for porphyrin retention, toxicity, and photosensitivity. All human fibroblasts exhibited porphyrin-induced dark toxicity, but there were no significant differences in photosensitization or porphyrin retention for any of these cell lines. However, bovine endothelial cells were considerably more photosensitive than smooth muscle or fibroblast cells treated under identical conditions. All bovine cells accumulated similar levels of porphyrin, and therefore the increased sensitivity of the endothelial cells was not due to differences in porphyrin retention. These results provide additional evidence that nuclear damage and/or repair is not a dominant factor in the cytotoxicity induced by porphyrin photosensitization. In addition, these results indicate that endothelial cell photosensitivity may play a role in the vascular damage observed following photodynamic therapy. PMID:2969280

  7. 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

  8. 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

  9. 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.

  10. Porphyrins as Catalysts in Scalable Organic Reactions.

    PubMed

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

    2016-01-01

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

  11. A dynamic library of porphyrinic true nanorings.

    PubMed

    Pawlicki, Miłosz; Latos-Grażyński, Lechosław

    2012-11-01

    Behind the wheel: a 10 nm diameter nanoring, containing 24 porphyrin units, has been created by a Vernier-templating self-organization of hexa- or octadentate templating units and linear covalently linked porphyrin oligomers. Coordination of a bidentate ligand triggers a conversion of the molecular nanocylinder into a molecular nanoannulus to afford the dimeric species, which can adopt a water wheel structure. PMID:23037988

  12. Urinary porphyrin excretion in hepatitis C infection.

    PubMed

    Vogeser, M; Jacob, K; Zachoval, R

    1999-08-01

    A high prevalence of hepatitis C virus infection in porphyria cutanea tarda in some populations suggests a close link between viral hepatitis and alteration of porphyrin metabolism. Moreover, there is evidence of a role of porphyrinopathies in hepatocarcinogenesis. The aim of our study was to obtain data on the prevalence and patterns of heme metabolism alterations in patients with chronic hepatitis C virus infection. Urinary porphyrin excretion was prospectively studied in 100 consecutive outpatients with chronic hepatitis C infection without signs of photosensitivity, using an ion-pair high-performance liquid chromatography method. Increased total porphyrin excretion was found in 41 patients, with predominant excretion of coproporphyrins (whole study group: mean 146 microg/g creatinine, interquartile range 76-186; normal < 150), in 10 patients excretion exceeded 300 microg/g creatinine. In the majority of all patients studied (75/100) an increased ratio of the relatively hydrophobic coproporphyrin isomer I to isomer III was found. In just one case, urinary porphyrin pattern characteristic for chronic hepatic porphyria was present (uroporphyrin > coproporphyrin, heptacarboxyporphyrin III increased) but the total porphyrin excretion was only slightly elevated in this case. In the whole group, total urinary porphyrin excretion correlated well with serum bilirubin and was inversely correlated with albumin and thrombin time. In conclusion, secondary coproporphyrinuria occurs frequently in heptatitis C infection, whereas in Germany, preclinical porphyria cutanea tarda seems to be rare in these patients. PMID:10536928

  13. 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.

  14. 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. PMID:27250315

  15. 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.

  16. Crazing in Glassy Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Lee, Jong-Young; Zhang, Qingling; Emrick, Todd; Crosby, Alfred

    2006-03-01

    Crazing is a polymer deformation process in which dense arrays of nanoscale fibrils grow prior to the propagation of a crack. Here, we discuss experimental results on the impact of two nanostructured materials on the crazing process: 1) ordered glassy block copolymers and 2) homopolymer/nanoparticle composites. We not only find that an ordered lamellar microstructure leads a lower craze growth rate compared with polystyrene homopolymer, but also nanoscale, surface terraces significantly decrease the failure strain of these advanced materials. For homopolymer/nanoparticle composites, we discover significant alterations in the crazing process. Specifically, nanoparticles in the presence of a craze undergo three stages of rearrangement: 1) Alignment along the precraze (fluid-like region), 2) Expulsion from nanoscale craze fibrils, and 3) Assembly into clusters trapped between craze fibrils. Although nanoparticles have no effect on the initiation strain, fibril breakdown strain, and craze growth rate, the composite failure strain can be increased significantly by nearly 100% compared to neat homopolymer films. These results provide direct evidence for the physical mechanisms that control the mechanical properties of polymer nanocomposites.

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

    NASA Astrophysics Data System (ADS)

    Kalachyova, Yevgeniya; Lyutakov, Oleksiy; Solovyev, Andrey; Slepička, Petr; Švorčík, Vaclav

    2013-12-01

    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.

  18. 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. PMID:26383015

  19. 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.

  20. 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.

  1. Photoinduced electron transfer in a porphyrin dyad

    SciTech Connect

    Gust, D.; Moore, T.A.; Moore, A.L.; Leggett, L.; Lin, S.; DeGraziano, J.M.; Hermant, R.M.; Nicodem, D.; Craig, P.; Seely, G.R.; Nieman, R.A. )

    1993-07-29

    A prophyrin dyad designed to facilitate vectorial interporphyrin electron transfer has been synthesized and studied using steady-state and time-resolved absorption and emission spectroscopies. The dyad features a zinc tetraaylporphyrin bearing electron-donating substituents linked by an amide bond to a free base porphyrin carrying electron-withdrawing groups. Excitation of the zinc porphyrin moiety in dichloromethane solution is followed by singlet energy transfer to the free base and concurrent electron transfer to the same moiety to yield a charge-separated state. The free base first excited singlet state decays by accepting an electron from the zinc porphyrin to form the same charge-separated state. Similar results are observed in butyronitrile. Transient absorption studies in butyronitrile verify the formation of a short-lived (8 ps) charge-separated state from the porphyrin first excited singlet states. The results support the suggestion that fluorescence quenching in related porphyrin dyads and carotenoid--diporphyrin triads is due to photoinduced electron transfer, rather than some other decay process. 17 refs., 8 refs.

  2. 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

  3. 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.

  4. Porphyrin accumulation in mitochondria is mediated by 2-oxoglutarate carrier.

    PubMed

    Kabe, Yasuaki; Ohmori, Masashi; Shinouchi, Kazuya; Tsuboi, Yasunori; Hirao, Satoshi; Azuma, Motoki; Watanabe, Hajime; Okura, Ichiro; Handa, Hiroshi

    2006-10-20

    Heme (Fe-protoporphyrin IX), an endogenous porphyrin derivative, is an essential molecule in living aerobic organisms and plays a role in a variety of physiological processes such as oxygen transport, respiration, and signal transduction. For the biosynthesis of heme or the mitochondrial heme proteins, heme or its biosynthetic precursor porphyrin must be transported into mitochondria from cytosol. The mechanism of porphyrin accumulation in the mitochondrial inner membrane is unclear. In the present study, we analyzed the mechanism of mitochondrial translocation of porphyrin derivatives. We showed that palladium meso-tetra(4-carboxyphenyl)porphyrin (PdTCPP), a phosphorescent porphyrin derivative, accumulated in the mitochondria of several cell lines. Using affinity latex beads, we showed that 2-oxoglutarate carrier (OGC), the mitochondrial transporter of 2-oxoglutarate, bound to PdTCPP, and in vitro PdTCPP inhibited 2-oxoglutarate uptake into mitochondria in a competitive manner (Ki = 15 microM). Interestingly, all types of porphyrin derivatives examined in this study competitively inhibited 2-oxoglutarate uptake into mitochondria, including protoporphyrin IX, coproporphyrin III, and hemin. Furthermore, mitochondrial accumulation of porphyrins was inhibited by 2-oxoglutarate or OGC inhibitor. These results suggested that porphyrin accumulation in mitochondria is mediated by OGC and that porphyrins are able to competitively inhibit 2-oxoglutarate uptake into mitochondria. This is the first report of a putative mechanism for accumulation of porphyrins in the mitochondrial inner membrane. PMID:16920706

  5. 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

  6. Optical properties of porphyrin: graphene oxide composites

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  7. Absorption Of Gases By Glassy Polymers

    NASA Technical Reports Server (NTRS)

    Fedors, Robert F.

    1990-01-01

    Report discusses solubility of gas in glassy polymer, both above and below glass-transition temperature (Tg). Thermodynamic arguments brought to bear on previously-developed mathematical models, result being new model that enables calculation of infinite-dilution partial molar volume of solvent in glass or liquid solvent from data on pressure, volume, and temperature of solute in equilibrium with solvent.

  8. On the cytoskeleton and soft glassy rheology.

    PubMed

    Mandadapu, Kranthi K; Govindjee, Sanjay; Mofrad, Mohammad R K

    2008-01-01

    The cytoskeleton is a complex structure within the cellular corpus that is responsible for the main structural properties and motilities of cells. A wide range of models have been utilized to understand cytoskeletal rheology and mechanics (see e.g. [Mofrad, M., Kamm, R., 2006. Cytoskeletal Mechanics: Models and Measurements. Cambridge University Press, Cambridge]). From this large collection of proposed models, the soft glassy rheological model (originally developed for inert soft glassy materials) has gained a certain traction in the literature due to the close resemblance of its predictions to certain mechanical data measured on cell cultures [Fabry, B., Maksym, G., Butler, J., Glogauer, M., Navajas, D., Fredberg, J., 2001. Scaling the microrheology of living cells. Physical Review Letters 87, 14102]. We first review classical linear rheological theory in a concise fashion followed by an examination of the soft glassy rheological theory. With this background we discuss the observed behavior of the cytoskeleton and the inherent limitations of classical rheological models for the cytoskeleton. This then leads into a discussion of the advantages and disadvantages presented to us by the soft glassy rheological model. We close with some comments of caution and recommendations on future avenues of exploration. PMID:18402964

  9. 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.

  10. 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.

  11. 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.

  12. Self-Assembly of Porphyrin J-Aggregates

    NASA Astrophysics Data System (ADS)

    Snitka, Valentinas; Rackaitis, Mindaugas; Navickaite, Gintare

    2006-03-01

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

  13. 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

  14. The superconducting state parameters of glassy superconductors

    NASA Astrophysics Data System (ADS)

    Vora, Aditya M.

    2011-11-01

    We present theoretical investigations of the superconducting state parameters (SSPs), i.e. the electron-phonon coupling strength, λ, Coulomb pseudopotential, μ*, transition temperature, Tc, isotope effect exponent, α, and effective interaction strength, N0V, of glassy superconductors by employing Ashcroft's well know empty core model potential for the first time using five screening functions proposed by Hartree (H), Taylor, Ichimaru-Utsumi (IU), Farid et al and Sarkar et al. The Tc obtained from the H and IU screening functions is found to be in excellent agreement with available experimental data. Also, the present results confirm the superconducting phase in bulk metallic glass superconductors. A strong dependency of the SSPs of the glassy superconductors on the 'Z' valence is found.

  15. Glassy Spin Dynamics in Buckled Colloidal Crystal

    NASA Astrophysics Data System (ADS)

    Zhou, Di; Wang, Feng; Han, Yilong

    Geometric frustration arises when lattice structure prevents simultaneous minimization of local interaction energies. It leads to highly degenerate ground states and complex behaviors in frustrated magnetic materials. Here we experimentally studied buckled 1.5-layer colloidal NIPA microgel crystals confined between parallel plates. Spheres buckled up and down are analogous to antiferromagnetic Ising spins. These spins on the distorted triangular lattice exhibit glassy dynamics at low temperatures. In particular, a spin only has 13 nearest-neighbor configurations, which enables to reveal the correlation between structures and dynamical heterogeneity. Soft modes also localize at high-energy regions. Further, we compared the colloidal spin system with kinetic constrained models (KCMs) and observed dynamical facilitation behaviors including excitations lines in space-time. Similar structures and glassy dynamics are also observed in our simulation of Coulomb charges on a triangular lattice. The work was supported by Grant RGC-GRF601613.

  16. The viscoelastic behavior of notched glassy polymers

    NASA Technical Reports Server (NTRS)

    Crook, R. A.; Letton, Alan

    1993-01-01

    In the bulk, glassy polymers exhibit a nonlinear viscoelastic response during deformation. Stress or strain induced damage (i.e. crazing, microshear banding) results in the production of nonrecoverable work and observed nonlinearity. Stress or strain dependent shift factors have been used to mathematically model the mechanical behavior of these polymers. Glassy polymers that have been notched, may exhibit very different load displacement response compared to the same material under bulk deformation. If a sharp notch is introduced into the body then loaded, the load displacement trace may appear to be single-valued in the absence of viscoelasticity and crack growth. This suggests the volume of damaged material is small compared to the overall dimensions of the specimen. The ability to produce a single-valued load-load-line displacement trace through the use of the Correspondence Principle may prove to be useful for fracture of viscoelastic materials.

  17. 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.

  18. Vapor Condensed and Supercooled Glassy Nanoclusters.

    PubMed

    Qi, Weikai; Bowles, Richard K

    2016-03-22

    We use molecular simulation to study the structural and dynamic properties of glassy nanoclusters formed both through the direct condensation of the vapor below the glass transition temperature, without the presence of a substrate, and via the slow supercooling of unsupported liquid nanodroplets. An analysis of local structure using Voronoi polyhedra shows that the energetic stability of the clusters is characterized by a large, increasing fraction of bicapped square antiprism motifs. We also show that nanoclusters with similar inherent structure energies are structurally similar, independent of their history, which suggests the supercooled clusters access the same low energy regions of the potential energy landscape as the vapor condensed clusters despite their different methods of formation. By measuring the intermediate scattering function at different radii from the cluster center, we find that the relaxation dynamics of the clusters are inhomogeneous, with the core becoming glassy above the glass transition temperature while the surface remains mobile at low temperatures. This helps the clusters sample the highly stable, low energy structures on the potential energy surface. Our work suggests the nanocluster systems are structurally more stable than the ultrastable glassy thin films, formed through vapor deposition onto a cold substrate, but the nanoclusters do not exhibit the superheating effects characteristic of the ultrastable glass states. PMID:26866858

  19. Hydroxylation of alkanes using sodium hypochlorite catalyzed by iron porphyrins

    SciTech Connect

    Sorokin, A.B.; Khenkin, A.M.

    1988-10-01

    This communication presents data about the oxidation of alkanes to alcohols with hypochlorite in the presence of Fe(III) phenylporphyrin derivatives in the system water-benzene. We used as catalysts the following compounds: tetraphenylporphyrin iron chloride, tetramesitylporphyrin iron chloride, tetra(2-fluorophenyl)porphyrin from chloride, and tetra (2-ntrophenyl)porphyrin iron chloride. The reaction products were analyzed by gas-liquid chromatography. The efficiency of the reaction was determined by the structure of the porphyrin used.

  20. 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

  1. 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.

  2. Surface chemistry of porphyrins and phthalocyanines

    NASA Astrophysics Data System (ADS)

    Gottfried, J. Michael

    2015-11-01

    This review covers the surface chemistry of porphyrins, phthalocyanines, their metal complexes, and related compounds, with particular focus on chemical reactions at solid/vacuum interfaces. Porphyrins are not only important biomolecules, they also find, together with the artificial phthalocyanines, numerous technological and scientific applications, which often involve surface and interface related aspects. After a brief summary of fundamental properties of these molecules in the context of surface science, the following topics will be discussed: (1) Aspects of geometric structure, including self-assembly, conformation, mobility and manipulation of the adsorbed molecules. (2) Surface-related changes of the electronic structure and the magnetic properties. (3) The role of the metal center in the surface chemical bond. (4) On-surface coordination reactions, such as direct metalation and coordination of axial ligands. (5) The influence of axial ligands on the surface chemical bond and the magnetic properties.

  3. Lactoperoxidase haem, an iron-porphyrin thiol.

    PubMed Central

    Nichol, A W; Angel, L A; Moon, T; Clezy, P S

    1987-01-01

    The haem prosthetic group of lactoperoxidase can be prepared from the enzyme in high yield by reductive cleavage with mercaptoethanol in 8 M-urea under mild conditions. The product yields porphyrins, after removal of iron, which show visible spectroscopic properties similar to protoporphyrin but are considerably more polar. In the presence of iodoacetamide, a different product is obtained by reductive cleavage. The proton n.m.r. and mass spectra of this compound indicate that the prosthetic group of the enzyme is the iron complex of 18-mercaptomethyl-2,7,12-trimethyl-3,8-divinylporphyrin-13,17-d ipropionic acid. It is proposed that the unusual strength of binding of the prosthetic group to the apoprotein is due to formation of a disulphide bond from a cysteine residue to the porphyrin thiol. PMID:3689341

  4. Texaphyrins: Tumor Localizing Redox Active Expanded Porphyrins

    PubMed Central

    Arambula, Jonathan F.; Preihs, Christian; Borthwick, Derric; Magda, Darren; Sessler, Jonathan L.

    2011-01-01

    Texaphyrins, a class of tumor selective expanded porphyrins capable of coordinating large metals, have been found to act as redox mediators within biological systems. This review summarizes studies involving their experimentaluse in cancer chemotherapy. Mechanistic insights involving their presumed mode of action are also described, as well as certain structure activity relationships. Finally, newer texaphyrin-based applications associated with targeted drug delivery are presented. PMID:21355841

  5. Synthesis and cellular localization of porphyrinic pigments

    NASA Astrophysics Data System (ADS)

    Sareh, Sarah; Kong, Sarah; Parrales, Lenin; Jung, Anna; Cross, Kara; Röder, Beate; Isaac, Meden; Simonis, Ursula

    2009-06-01

    To determine factors that govern the uptake preference of photosensitizers in cellular organelles of human adenocarcinoma cells, diarginyl-dialkoxy- and diarginyl-dimethoxyphenylporphyrins (TPPs) and two of their corresponding indium(III) complexes were synthesized, characterized and incubated in androgen-sensitive human prostate adenocarcinoma cells LNCaP. The porphyrins revealed properties that are of importance for phototherapy. They are water-soluble, have their fourth Q-band absorbing at ~ 650 nm, are taken up in relatively high concentrations in LNCaP cells, and are phototoxic. Colocalization and phototoxicity studies revealed that all porphyrins localized preferentially to the lysosomes and invoked cell death when excited with 650 nm light. Compared to the corresponding methoxy-substituted TPPs, the diargininyl-dialkoxy-substituted porphyrins localized to a small extent in the mitochondria. The corresponding In(III) chloride complexes that are slightly less water-soluble were also taken up in the lysosomes of LnCaP cells. When the TPPs were compared to a pheophorbide derivative recently synthesized in our laboratory, it was determined that the TPPs have a preference for lysosomal localization, whereas the pheophorbide derivative co-localized to the mitochondria. Phototoxicity studies revealed that the longer chain dialkoxyTPPs were more effective in cell killing and induced greater morphological changes typical of apoptotic cell death than the shorter chain methoxy substituted porphyrins. The In(III) complexes seemed to be the most phototoxic. These results highlight that the type, nature, and substitution pattern of the chromophore modulate the extent of apoptotic cell death and influence cellular targeting.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

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

    PubMed

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

    2004-10-01

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

  12. 21 CFR 862.1595 - Porphyrins test system.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Porphyrins test system. 862.1595 Section 862.1595 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test Systems § 862.1595 Porphyrins test system. (a)...

  13. 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. PMID:24562603

  14. 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

  15. A waterwheel-shaped meso-meso-linked porphyrin pentamer.

    PubMed

    Wu, Chieh-Ao; Chiu, Chien-Lan; Mai, Chi-Lun; Lin, You-Shiang; Yeh, Chen-Yu

    2009-01-01

    Wheels on water? A waterwheel-shaped porphyrin pentamer has been synthesized by palladium-catalyzed cross-coupling reactions. The key intermediate is a boronate porphyrin, in which four boronic ester groups are directly attached to the meso-positions. PMID:19308985

  16. 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

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

    PubMed Central

    Capuano, Rosamaria; Pomarico, Giuseppe; Paolesse, Roberto; Di Natale, Corrado

    2015-01-01

    Porphyrins provide an excellent material for chemical sensors, and they have been used for sensing species both in air and solution. In the gas phase, the broad selectivity of porphyrins is largely dependant on molecular features, such as the metal ion complexed at the core of the aromatic ring and the peripheral substituents. Although these features have been largely exploited to design gas sensor arrays, so far, little attention has been devoted to modify the sensing properties of these macrocycles by variation of the molecular aromatic ring. In this paper, the gas sensing properties of a porphyrin analog, the corrole, are studied in comparison with those of the parent porphyrin. Results show that changes in the aromatic ring have important consequences on the sensitivity and selectivity of the sensors and that porphyrins and corroles can positively cooperate to enhance the performance of sensor arrays. PMID:25856324

  18. 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

  19. 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.

  20. Stimulators and Inhibitors of Hepatic Porphyrin Formation in Human Sera

    PubMed Central

    Rifkind, Arleen B.; Sassa, Shigeru; Merkatz, Irwin R.; Winchester, Robert; Harber, Leonard; Kappas, Attallah

    1974-01-01

    Human sera were found to contain factors that stimulate and factors that inhibit porphyrin formation by cultured avian liver cells. The capacity of sera to stimulate or inhibit porphyrin formation varied in different hormonal states and in the porphyrias. Sera from 31 post partum women, eight of whom were not lactating, inhibited porphyrin formation to a mean level 30% below the level in control cultures and also inhibited drug and steroid stimulation of porphyrin formation. In contrast, mean porphyrin formation compared to control cultures was increased between 9 and 21% by sera from 52 normal subjects, 16 women on oral contraceptives, and 11 pregnant women. It was increased 193% by sera from nine subjects with acute intermittent porphyria and 172% by sera from 13 subjects with porphyria cutanea tarda. Heated sera or ethanol extracts of sera from all groups of subjects further increased the mean porphyrin stimulation by sera and, for the post partum subjects, eliminated the inhibitory effect. Ethanol extracts of sera from 28 oral contraceptive-treated women caused significantly greater mean stimulation of porphyrin formation than did extracts of sera from 30 normal women. While sera from 17 out of 22 porphyric subjects contained both stimulatory and inhibitory factors, 5 out of 22 had no evidence of an inhibitory component. There appeared to be heterogeneity in the occurrence of the factors among porphyrics. The factor(s) in sera responsible for porphyrin stimulation were heat-stable and insensitive to trypsin; were present in the supernates after ethanol precipitation of plasma proteins; were extractable in ethyl acetate and nondialyzable; and they migrated with the albumincontaining fraction of serum during electrophoresis. The factor(s) responsible for porphyrin inhibition were heat labile, sensitive to trypsin, and resistant to neuraminidase; were present in the ethanol precipitates of sera and were nondialyzable; and they migrated with the gamma globulin

  1. Glassy dislocation dynamics in colloidal dimer crystals

    NASA Astrophysics Data System (ADS)

    Gerbode, Sharon

    2012-02-01

    Dislocation mobility is central to both the mechanical response and the relaxation mechanisms of crystalline materials. Recent experiments have explored the role of novel particle anisotropies in affecting the rules of defect motion in crystals. ``Peanut-shaped'' colloidal dimer particles consisting of two connected spherical lobes form densely packed crystals in 2D. In these ``degenerate crystals,'' the particle lobes occupy triangular lattice sites while the particle axes are randomly oriented among the three crystalline directions. One consequence of the random orientations of the dimers is that dislocation glide is severely limited by certain particle arrangements in the degenerate crystals. Using optical tweezers to manipulate single lobe-sized spherical intruder particles, we locally deform the crystal, creating defects. During subsequent relaxation, the dislocations formed during the deformation leave the crystal grain, either via annihilation with other dislocations or by moving to a grain boundary. Interestingly, in large crystalline grains this dislocation relaxation occurs through a two-stage process reminiscent of slow relaxations in glassy systems, suggesting the novel concept that glassy phenomena may be introduced to certain kinds of colloidal crystals via simple anisotropic constituents.

  2. 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.

  3. Approaching theoretical strength in glassy carbon nanolattices

    NASA Astrophysics Data System (ADS)

    Bauer, J.; Schroer, A.; Schwaiger, R.; Kraft, O.

    2016-04-01

    The strength of lightweight mechanical metamaterials, which aim to exploit material-strengthening size effects by their microscale lattice structure, has been limited by the resolution of three-dimensional lithography technologies and their restriction to mainly polymer resins. Here, we demonstrate that pyrolysis of polymeric microlattices can overcome these limitations and create ultra-strong glassy carbon nanolattices with single struts shorter than 1 μm and diameters as small as 200 nm. They represent the smallest lattice structures yet produced--achieved by an 80% shrinkage of the polymer during pyrolysis--and exhibit material strengths of up to 3 GPa, corresponding approximately to the theoretical strength of glassy carbon. The strength-to-density ratios of the nanolattices are six times higher than those of reported microlattices. With a honeycomb topology, effective strengths of 1.2 GPa at 0.6 g cm-3 are achieved. Diamond is the only bulk material with a notably higher strength-to-density ratio.

  4. 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

  5. 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

  6. Detection of volatile organic compounds using porphyrin derivatives.

    PubMed

    Dunbar, A D F; Brittle, S; Richardson, T H; Hutchinson, J; Hunter, C A

    2010-09-16

    Seven different porphyrin compounds have been investigated as colorimetric gas sensors for a wide range of volatile organic compounds. The porphyrins examined were the free base and Mg, Sn, Zn, Au, Co, and Mn derivatives of 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine. Chloroform solutions of these materials were prepared and changes in their absorption spectra induced by exposure to various organic compounds measured. The porphyrins that showed strong responses in solution were selected, and Langmuir-Blodgett films were prepared and exposed to the corresponding analytes. This was done to determine whether they are useful materials for solid state thin film colorimetric vapor sensors. Porphyrins that readily coordinate extra ligands are shown to be suitable materials for colorimetric volatile organic compound detectors. However, porphyrins that already have bound axial ligands when synthesized only show a sensor response to those analytes that can substitute these axial ligands. The Co porphyrin displays a considerably larger response than the other porphyrins investigated which is attributed to a switch between Co(II) and Co(III) resulting in a large spectral change. PMID:20735119

  7. Porphyrins as Theranostic Agents from Prehistoric to Modern Times

    PubMed Central

    Zhang, Yumiao; Lovell, Jonathan F.

    2012-01-01

    Long before humans roamed the planet, porphyrins in blood were serving not only as indispensable oxygen carriers, but also as the bright red contrast agent that unmistakably indicates injury sites. They have proven valuable as whole body imaging modalities have emerged, with endogenous hemoglobin porphyrins being used for new approaches such as functional magnetic resonance imaging and photoacoustic imaging. With the capability for both near infrared fluorescence imaging and phototherapy, porphyrins were the first exogenous agents that were employed with intrinsic multimodal theranostic character. Porphyrins have been used as tumor-specific diagnostic fluorescence imaging agents since 1924, as positron emission agents since 1951, and as magnetic resonance (MR) contrast agents since 1987. Exogenous porphyrins remain in clinical use for photodynamic therapy. Because they can chelate a wide range of metals, exogenous porphyrins have demonstrated potential for use in radiotherapy and multimodal imaging modalities. Going forward, intrinsic porphyrin biocompatibility and multimodality will keep new applications of this class of molecules at the forefront of theranostic research. PMID:23082102

  8. Ubiquitous ``glassy'' relaxation in catalytic reaction networks

    NASA Astrophysics Data System (ADS)

    Awazu, Akinori; Kaneko, Kunihiko

    2009-10-01

    Study of reversible catalytic reaction networks is important not only as an issue for chemical thermodynamics but also for protocells. From extensive numerical simulations and theoretical analysis, slow relaxation dynamics to sustain nonequlibrium states are commonly observed. These dynamics show two types of salient behaviors that are reminiscent of glassy behavior: slow relaxation along with the logarithmic time dependence of the correlation function and the emergence of plateaus in the relaxation-time course. The former behavior is explained by the eigenvalue distribution of a Jacobian matrix around the equilibrium state that depends on the distribution of kinetic coefficients of reactions. The latter behavior is associated with kinetic constraints rather than metastable states and is due to the absence of catalysts for chemicals in excess and the negative correlation between two chemical species. Examples are given and generality is discussed with relevance to bottleneck-type dynamics in biochemical reactions as well.

  9. Glassy dynamics of driven elastic manifolds

    SciTech Connect

    Vinokur, V.M.

    1996-12-31

    We study the low-temperature dynamics of an elastic manifold driven through a random medium. For driving forces well below the zero- temperature depinning force, the manifold advances via thermally activated hops over the energy barriers separating favorable metastable states. We develop a scaling theory of the thermally activated dynamics (creep) and find a nonlinear glassy response for the driven manifold, {upsilon}{approximately}exp(-const{times}F{sup - {mu}}). We consider an exactly solvable 1-D model for random driven dynamics which exhibits a creep-like velocity-force characteristic. We discuss a microscopic mechanism for the creep motion and show that the distribution of waiting times for the hopping processes scales as a power law. This power-law distribution naturally yields an exponential response for the creep of the manifold.

  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. 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.

  12. Shear banding in soft glassy materials.

    PubMed

    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. PMID:25303030

  13. 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

  14. 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

  15. 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.

  16. Group 14 Dithienometallole-Linked Ethynylene-Conjugated Porphyrin Dimers.

    PubMed

    Morisue, Mitsuhiko; Hoshino, Yuki; Nakamura, Masashi; Yumura, Takashi; Machida, Shinjiro; Ooyama, Yousuke; Shimizu, Masaki; Ohshita, Joji

    2016-08-01

    The considerably conjugated π systems of the group 14 dithienometallole-linked ethynylene-conjugated porphyrin dimers (1Ms) were described based on comprehensive experimental and theoretical studies. The electronic absorption spectra of 1M displayed a large splitting in the Soret band and a red-shifted Q-band, indicating that the dithienometallole spacer was effective in facilitating the porphyrin-porphyrin electronic coupling. Torsional planarization behaviors of 1M were observed in the time-resolved fluorescence spectra. Density functional theory (DFT) calculations revealed that the dithienometallole spacer is an ideal partner for the ethynylene-conjugated porphyrin to produce fully delocalized highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels due to their similar HOMO and LUMO levels. Finally, 1M exhibited a strong propensity for the quinoidal-cummulenic conjugation in the dithienometallole spacer when in a photoexcited state. PMID:27410779

  17. 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.

  18. 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

  19. 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.

  20. A Boronic Acid Porphyrin Receptor for Ginsenoside Sensing

    PubMed Central

    Hargrove, Amanda E.; Reyes, Ryan N.; Riddington, Ian; Anslyn, Eric V.; Sessler, Jonathan L.

    2010-01-01

    Ginsenoside detection was pursued through the design of a porphyrin receptor containing two boronic acid units. This receptor was found to undergo different degrees of fluorescence quenching with five ginsenoside guests and an acylated derivative. The trends in the 1:1 binding constants, as well as ESI-HRMS analysis, support a binding mode in which the ginsenoside sugar units are bound to the boronic acid groups while the steroid core and porphyrin ring participate in hydrophobic interactions. PMID:20860384

  1. 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. PMID:26938146

  2. Metagenomics of Glassy-Winged Sharpshooter, Homalodisca vitripennis (Hemiptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A Metagenomics approach was used to identify unknown organisms which live in association with the glassy-winged sharpshooter, Homalodisca vitripennis (Hemiptera: Cicadellidae). Metagenomics combines molecular biology and genetics to identify, and characterize genetic material from unique biological ...

  3. Glassy dislocation dynamics in 2D colloidal dimer crystals.

    PubMed

    Gerbode, Sharon J; Agarwal, Umang; Ong, Desmond C; Liddell, Chekesha M; Escobedo, Fernando; Cohen, Itai

    2010-08-13

    Although glassy relaxation is typically associated with disorder, here we report on a new type of glassy dynamics relating to dislocations within 2D crystals of colloidal dimers. Previous studies have demonstrated that dislocation motion in dimer crystals is restricted by certain particle orientations. Here, we drag an optically trapped particle through such dimer crystals, creating dislocations. We find a two-stage relaxation response where initially dislocations glide until encountering particles that cage their motion. Subsequent relaxation occurs logarithmically slowly through a second process where dislocations hop between caged configurations. Finally, in simulations of sheared dimer crystals, the dislocation mean squared displacement displays a caging plateau typical of glassy dynamics. Together, these results reveal a novel glassy system within a colloidal crystal. PMID:20868079

  4. 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.

  5. 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.

  6. Kinetic studies of porphyrin distribution in suspensions of tumor cells

    NASA Astrophysics Data System (ADS)

    Zorin, Vladimir P.; Mel'nov, Sergey B.; Savitsky, Valery P.; Zorina, Tatyana E.

    1996-12-01

    Using a fluorescence activated cell sorting, we investigated the dynamics of porphyrins in suspensions of tumor cells. In addition to direct studies of the incorporation and output of several porphyrins (hematoporphyrin, hematoporphyrin dimethyl ester, chlorin e6 and its mono-, di-, trimethyl esters) from cells, their transfer between cells was investigated. It was shown that the rate of pigment accumulation by cells correlated with the rate of porphyrin penetration across the plasma membrane. As a result, apolar chlorins and HpDME displayed enhanced staining capacity which was independent on the integrity of plasma membrane of cells. To estimate the rate of pigment redistribution between cells, the suspension of tumor cells loaded with porphyrin had been mixed with unloaded cells and the distribution of all cells according to porphyrin fluorescence was determined in different intervals of time. It was obtained that the highest rate of the pigment transfer between cells was exhibited in the case of moderately apolar pigment. Porphyrins with dominantly hydrophobic and hydrophilic properties had a decreased capacity to intercellular migration. The results of this study indicate that, depending on the photosensitizer used, the processes of its distribution in the bulk of tumor tissue mediated by intercellular exchange may occur with a different rate.

  7. 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.

  8. Topologically protected excitons in porphyrin thin films

    NASA Astrophysics Data System (ADS)

    Yuen-Zhou, Joel; Saikin, Semion K.; Yao, Norman Y.; Aspuru-Guzik, Alán

    2014-11-01

    The control of exciton transport in organic materials is of fundamental importance for the development of efficient light-harvesting systems. This transport is easily deteriorated by traps in the disordered energy landscape. Here, we propose and analyse a system that supports topological Frenkel exciton edge states. Backscattering of these chiral Frenkel excitons is prohibited by symmetry, ensuring that the transport properties of such a system are robust against disorder. To implement our idea, we propose a two-dimensional periodic array of tilted porphyrins interacting with a homogeneous magnetic field. This field serves to break time-reversal symmetry and results in lattice fluxes that mimic the Aharonov-Bohm phase acquired by electrons. Our proposal is the first blueprint for realizing topological phases of matter in molecular aggregates and suggests a paradigm for engineering novel excitonic materials.

  9. Topologically protected excitons in porphyrin thin films.

    PubMed

    Yuen-Zhou, Joel; Saikin, Semion K; Yao, Norman Y; Aspuru-Guzik, Alán

    2014-11-01

    The control of exciton transport in organic materials is of fundamental importance for the development of efficient light-harvesting systems. This transport is easily deteriorated by traps in the disordered energy landscape. Here, we propose and analyse a system that supports topological Frenkel exciton edge states. Backscattering of these chiral Frenkel excitons is prohibited by symmetry, ensuring that the transport properties of such a system are robust against disorder. To implement our idea, we propose a two-dimensional periodic array of tilted porphyrins interacting with a homogeneous magnetic field. This field serves to break time-reversal symmetry and results in lattice fluxes that mimic the Aharonov-Bohm phase acquired by electrons. Our proposal is the first blueprint for realizing topological phases of matter in molecular aggregates and suggests a paradigm for engineering novel excitonic materials. PMID:25242533

  10. 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.

  11. Thermodynamics of porphyrin dimerization in aqueous solutions.

    PubMed Central

    Margalit, R; Rotenberg, M

    1984-01-01

    The dimerization equilibrium of deuteroporphyrin IX and of mesoporphyrin IX in aqueous solutions were studied by fluorimetric techniques over the 0.01-1 microM concentration range, where dimerization is the dominant aggregation process. Deuteroporphyrin IX was studied at several temperatures over the range 22-37 degrees C, and mesoporphyrin at 25 and 37 degrees C. The magnitudes determined for the dimerization equilibrium constants (25 degrees C, neutral pH, phosphate-buffered saline) are 2.3 X 10(6)M-1 and 5.4 X 10(6)M-1 for the deutero and meso derivatives respectively. The meso, deutero and haemato species tested show a similar temperature effect, namely dimerization decreasing with increasing temperature, indicating the involvement of a negative enthalpy change. Van't Hoff isochore of the dimerization constants determined for deuteroporphyrin IX was linear within the temperature range of 22-37 degrees C, allowing the calculation of the thermodynamic parameters. For deuteroporphyrin dimerization, those were found to be delta G0 = -36. 4kJ X mol-1; delta H0 = -46. 0kJ X mol-1 and delta S0 = -32.2J X K-1 X mol-1 (at neutral pH, 25 degrees C, phosphate-buffered saline), showing the process to be enthalpy-driven. Similar trends have been found for porphyrin species other than those studied here. Our data fit with a hypothesis giving a major role to the solvent in driving porphyrins to aggregate in aqueous solution. The magnitudes and directions of the energetic changes fit better with the expectation of the ' solvophobic force' theory predicting enthalpy-driven association, than with the classic hydrophobic bonding, predicting the association to be entropy-driven. PMID:6743228

  12. 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.

  13. 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. PMID:27092716

  14. 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.

  15. Bioconjugatable Porphyrins Bearing a Compact Swallowtail Motif for Water Solubility

    PubMed Central

    Borbas, K. Eszter; Mroz, Pawel; Hamblin, Michael R.; Lindsey, Jonathan S.

    2011-01-01

    A broad range of applications requires access to water-soluble, bioconjugatable porphyrins. Branched alkyl groups attached at the branching site to the porphyrin meso position are known to impart high organic solubility. Such “swallowtail” motifs bearing a polar group (hydroxy, dihydroxyphosphoryl, dihydroxyphosphoryloxy) at the terminus of each branch have now been incorporated at a meso site in trans-AB-porphyrins. The incorporation of the swallowtail motif relies on rational synthetic methods whereby a 1,9-bis(N-propylimino)dipyrromethane (bearing a bioconjugatable tether at the 5-position) is condensed with a dipyrromethane (bearing a protected 1,5-dihydroxypent-3-yl unit at the 5-position). The two hydroxy groups in the swallowtail motif of each of the resulting zinc porphyrins can be transformed to the corresponding diphosphate or diphosphonate product. A 4-(carboxymethyloxy)phenyl group provides the bioconjugatable tether. The six such porphyrins reported here are highly water-soluble (≥20 mM at room temperature in water at pH 7) as determined by visual inspection, UV–vis absorption spectroscopy, or 1H NMR spectroscopy. Covalent attachment was carried out in aqueous solution with the unprotected porphyrin diphosphonate and a monoclonal antibody against the T-cell receptor CD3ε. The resulting conjugate performed comparably to a commercially available fluorescein isothiocyanate-labeled antibody with Jurkat cells in flow cytometry and fluorescence microscopy assays. Taken together, this work enables preparation of useful quantities of water-soluble, bioconjugatable porphyrins in a compact architecture for applications in the life sciences. PMID:16704201

  16. A quinoidal bis-phenalenyl-fused porphyrin with supramolecular organization and broad near-infrared absorption.

    PubMed

    Diev, Vyacheslav V; Femia, Denise; Zhong, Qiwen; Djurovich, Peter I; Haiges, Ralf; Thompson, Mark E

    2016-01-31

    A bis-phenalenyl-fused porphyrin has been synthesized by thermal dehydro-aromatization reaction regioselectively as a single syn-isomer. X-ray crystal structure revealed that both phenalenyl units of this porphyrin have close π-π contacts forming continuous network of interacting porphyrin rings. A broad and intense NIR absorption can be attributed to quinoidal character of bis-phenalenyl-fused porphyrin. PMID:26686757

  17. 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.

  18. 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.

  19. Communication: Substrate induced dehydrogenation: transformation of octa-ethyl-porphyrin into tetra-benzo-porphyrin.

    PubMed

    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. PMID:23758351

  20. β-to-β 2,5-Pyrrolylene-Linked Cyclic Porphyrin Oligomers.

    PubMed

    Rao, Yutao; Kim, Jun Oh; Kim, Woojae; Zhong, Guangming; Yin, Bangshao; Zhou, Mingbo; Shinokubo, Hiroshi; Aratani, Naoki; Tanaka, Takayuki; Liu, Shubin; Osuka, Atsuhiro; Kim, Dongho; Song, Jianxin

    2016-06-20

    β-to-β 2,5-Pyrrolylene linked cyclic porphyrin oligomers have been synthesized by Suzuki-Miyaura coupling of 2,5-diborylpyrrole and 3,7-dibromoporphyrin. The cyclic porphyrin oligomers exhibit roughly coplanar structures, strong excitonic coupling, small electrochemical HOMO-LUMO gaps, and ultrafast excitation energy transfer between the neighboring porphyrins via the pyrrolylene bridge. PMID:27124728

  1. 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

  2. Trimeric and Tetrameric Electron-Deficient Porphyrin Tapes.

    PubMed

    Mori, Hirotaka; Kim, Taeyeon; Kim, Dongho; Osuka, Atsuhiro

    2016-05-01

    New hybrid porphyrin tapes comprising meso-3,5-di-tert-butylphenyl-substituted Zn(II) -porphyrins (D) and meso-pentafluorophenyl-substituted Zn(II) -porphyrins (A) were synthesized via cross-condensation of meso-formyl porphyrins 1, 5, and 9 with oligopyrromethanes 2 and 6 as key steps. These hybrid tapes exhibit improved solubilities and enhanced chemical stability as compared with original Dn porphyrin tapes, and all display remarkably coplanar structures favorable for π-conjugation. The absorption spectrum of ADDA displays Q-like bands at 1400 and 1657 nm with a vibronic structure characteristic of porphyrinoids. The cyclic voltammograms exhibited positively shifted oxidation and reduction waves in the order of DDD

  3. Porphyrin-phospholipid liposomes permeabilized by near-infrared light.

    PubMed

    Carter, Kevin A; Shao, Shuai; Hoopes, Matthew I; Luo, Dandan; Ahsan, Bilal; Grigoryants, Vladimir M; Song, Wentao; Huang, Haoyuan; Zhang, Guojian; Pandey, Ravindra K; Geng, Jumin; Pfeifer, Blaine A; Scholes, Charles P; Ortega, Joaquin; Karttunen, Mikko; Lovell, Jonathan F

    2014-01-01

    The delivery of therapeutic compounds to target tissues is a central challenge in treating disease. Externally controlled drug release systems hold potential to selectively enhance localized delivery. Here we describe liposomes doped with porphyrin-phospholipid that are permeabilized directly by near-infrared light. Molecular dynamics simulations identified a novel light-absorbing monomer esterified from clinically approved components predicted and experimentally demonstrated to give rise to a more stable porphyrin bilayer. Light-induced membrane permeabilization is enabled with liposomal inclusion of 10 molar % porphyrin-phospholipid and occurs in the absence of bulk or nanoscale heating. Liposomes reseal following laser exposure and permeability is modulated by varying porphyrin-phospholipid doping, irradiation intensity or irradiation duration. Porphyrin-phospholipid liposomes demonstrate spatial control of release of entrapped gentamicin and temporal control of release of entrapped fluorophores following intratumoral injection. Following systemic administration, laser irradiation enhances deposition of actively loaded doxorubicin in mouse xenografts, enabling an effective single-treatment antitumour therapy. PMID:24699423

  4. A nonionic porphyrin as a noninterfering DNA antibacterial agent.

    PubMed

    Mendes, Sónia; Camacho, Fábio; Silva, Tito; Calado, Cecília R C; Serra, Arménio Coimbra; Gonsalves, António M d'A Rocha; Roxo-Rosa, Mónica

    2011-01-01

    The increasing interest in clinical bacterial photodynamic inactivation has led to the search for photosensitizers with higher bactericidal efficiency and less side effects on the surrounding tissues. We present a novel nonionic porphyrin, the 5,10,15-tris(2,6-dichlorophenyl)-20-[4-N-(6-amino-hexyl)sulfonamido)phenyl]-porphyrin (ACS769F4) with substantial improvements in the efficiency of nonionic sensitizers. This porphyrin causes eradication of both Escherichia coli and Staphylococcus aureus by the photodynamic effect but in higher concentrations compared with 5,10,15,20-tetrakis (4-N,N,N-trimethylammoniumphenyl)-porphyrin p-tosylate (TTAP(4+)), a known bactericidal tetracationic porphyrin. More important, under such conditions, ACS769F4 proved to be harmless to two mammalian cells lines (human embryonic and baby hamster kidney), causing no reduction in their viability or negative impact on their cytoskeleton, despite its accumulation in cellular structures. On the contrary, TTAP(4+) is shown to accumulate in the nucleus of mammalian cells, in association to DNA, causing chromatin condensation after exposure to light. Furthermore, dark incubation with TTAP(4+) was shown to have a deleterious effect on the microtubule network. Based on its bactericidal efficiency, also observed without exposure to light, and on the low tendency to be harmful or genotoxic to mammalian cells, ACS769F4 should be looked at as an interesting photosensitizer to be evaluated for clinical purposes. PMID:21834867

  5. 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.

  6. Azobenzene-Bridged Porphyrin Nanorings: Syntheses, Structures, and Photophysical Properties.

    PubMed

    Huang, Weiming; Lee, Seung-Kyu; Sung, Young Mo; Peng, Fulei; Yin, Bangshao; Ma, Ming; Chen, Bo; Liu, Shubin; Kirk, Steven Robert; Kim, Dongho; Song, Jianxin

    2015-10-19

    Azobenzene-bridged β-to-β and meso-to-meso porphyrin nanorings were successfully synthesized by a palladium-catalyzed Suzuki-Miyaura coupling reaction in a logical synthesis. The dimeric structure was confirmed by XRD analysis. The azo linkages in di- and tetramers are in the all-trans conformation, whereas in the trimers one azo linkage can be interconverted between cis and trans under external stimulation. When trimeric isomers are heated to 333 K or higher, the azo linkages will be in the all-trans configurations: the pure all-trans trimer can be kept in the dark for several months. Fluorescence anisotropy and pump-power-dependent decay results revealed excitation energy transfer for azobenzene-bridged zinc-porphyrin nanorings. The distances between porphyrin units of these azobenzene-bridged porphyrin arrays are almost the same, but the exciton energy hopping (EEH) times for each wheel are markedly different. The dimer and meso-to-meso tetramer possess relatively short excitation energy transfer (EET) times (1.28 and 2.48 ps, respectively) due to their good planarity and rigidity. In contrast, the EET time for the trimeric zinc(II)-porphyrin array (6.9 ps) is relatively long due to its nonradiative decay pathway (i.e., cis/trans isomerization of azobenzene). Both di- and tetramers exhibit relatively high fluorescence quantum yields, whereas the trimers show weak emission because of structural differences. PMID:26338286

  7. Synthesis and photophysical properties of the photoactivatable cationic porphyrin 5-(4-N-dodecylpyridyl)-10,15,20-tri(4-N-methylpyridyl)-21H,23H-porphyrin tetraiodide for anti-malaria PDT.

    PubMed

    Stallivieri, Aurélie; Le Guern, Florent; Vanderesse, Régis; Meledje, Esme; Jori, Giulio; Frochot, Céline; Acherar, Samir

    2015-07-01

    This article describes a new synthetic method for obtaining three water soluble porphyrins. The more sophisticated porphyrin [5-(4-N-dodecylpyridyl)-10,15,20-tri(4-N-methylpyridyl)-21H,23H-porphyrin tetraiodide], also named C12 porphyrin, was obtained through a three step methodology. The improvements, compared to syntheses described in the literature, mostly concern the purification procedures. The photophysical properties of the three porphyrins are described and the C12 porphyrin presents a very good (1)O2 yield compared to its chemical intermediates. This porphyrin seems to be a very promising candidate for PDT applications. PMID:26066986

  8. 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. PMID:27156996

  9. Dynamical Heterogeneity of the Glassy State

    NASA Astrophysics Data System (ADS)

    Wisitsorasak, Apiwat

    The understanding and the complete description of the glass transition are impeded by the complexity of nature of the glass. Parts of this complexity come from the emergence of long-lived inherent structures of a liquid at a temperature below which the activated reconfiguration events play a dominant role. Molecules in a glass change their locations through the activated process at a rate which varies throughout the glass owing to these local and aperiodic structures. Motions in one location also cause or relieve constrains, thereby altering the rate of transitions of neighboring regions. The key to understanding this problem is the interplay between the activated events that generate mobility and the transport of mobility. In the following we explore fluctuating mobility generation and transport in glasses to understand the dynamics of the glassy state within the framework of the random first order transition theory of glass. Fluctuating mobility generation and transport in the glass that arise from there being a distribution of local stability and thus effective temperature are treated by numerically solving stochastic continuum equations for mobility and fictive temperature fields. Fluctuating spatiotemporal structures in aging and rejuvenating glasses lead to dynamical heterogeneity in glasses with characteristics that are distinct from those found in the equilibrium liquid. We illustrate in this thesis how the heterogeneity in glasses gives rises of a non-Gaussian distribution of activation free energies, the stretching exponent, and the growth of characteristic lengths. These are studied along with the four-point dynamic correlation function. Asymmetric thermodynamic responses upon heating and cooling are also predicted to be the results of the heterogeneity and the out-of-equilibrium behavior of glasses below the glass transition temperature. Moreover the dynamical heterogeneity can lead to a growth front of mobility in rejuvenating glasses that emanates

  10. Thermodynamics of Supercooled and Glassy Water

    NASA Astrophysics Data System (ADS)

    Debenedetti, Pablo G.

    1998-03-01

    The behavior of metastable water at low temperatures is unusual. The isothermal compressibility, the isobaric heat capacity, and the magnitude of the thermal expansion coefficient increase sharply upon supercooling, and structural relaxation becomes extremely sluggish at temperatures far above the glass transition(Angell, C.A., Annu. Rev. Phys. Chem., 34, 593, 1983)(Debenedetti, P.G., Metastable Liquids. Concepts and Principles, Princeton University Press, 1996). Water has two distinct glassy phases, low- and high-density amorphous ice (LDA, HDA). The transition between LDA and HDA is accompanied by sharp volume and enthalpy changes, and appears to be first-order(Mishima, O., L.D.Calvert, and E. Whalley, Nature, 314, 76, 1985)(Mishima, O., J. Chem. Phys., 100, 5910, 1994). The understanding of these observations in terms of an underlying global phase behavior remains incomplete(Speedy, R.J., J. Phys. Chem., 86, 982, 1982)(Poole, P.H., F. Sciortino, U. Essman, and H.E. Stanley, Nature, 360, 324, 1992)(Sastry, S., P.G. Debenedetti, F. Sciortino, and H.E. Stanley, Phys. Rev. E, 53, 6144, 1996)(Tanaka, H., Nature, 380, 328, 1996)(Xie, Y., K.F. Ludwig, G. Morales, D.E. Hare, and C.M. Sorensen, Phys. Rev. Lett., 71, 2050, 1993). Microscopic theories and computer simulations suggest several scenarios that can reproduce some experimental observations. Interesting and novel ideas have resulted from this body of theoretical work, such as the possibility of liquid-liquid immiscibility in a pure substance(Poole, P.H., F.Sciortino, T.Grande, H.E. Stanley, and C.A. Angell, Phys. Rev. Lett., 73, 1632, 1994)(Roberts, C.J., and P.G. Debenedetti, J. Chem. Phys., 105, 658, 1996)(Roberts, C.J., P.G. Debenedetti, and A.Z. Panagiotopoulos, Phys. Rev. Lett., 77, 4386, 1996)(Harrington, S., R. Zhang, P.H. Poole, F. Sciortino, and H.E. Stanley, Phys. Rev. Lett., 78, 2409, 1997). In this talk I will review the experimental facts, discuss their theoretical interpretation, and identify key

  11. Solubility of gases and liquids in glassy polymers.

    PubMed

    De Angelis, Maria Grazia; Sarti, Giulio C

    2011-01-01

    This review discusses a macroscopic thermodynamic procedure to calculate the solubility of gases, vapors, and liquids in glassy polymers that is based on the general procedure provided by the nonequilibrium thermodynamics for glassy polymers (NET-GP) method. Several examples are presented using various nonequilibrium (NE) models including lattice fluid (NELF), statistical associating fluid theory (NE-SAFT), and perturbed hard sphere chain (NE-PHSC). Particular applications illustrate the calculation of infinite-dilution solubility coefficients in different glassy polymers and the prediction of solubility isotherms for different gases and vapors in pure polymers as well as in polymer blends. The determination of model parameters is discussed, and the predictive abilities of the models are illustrated. Attention is also given to the solubility of gas mixtures and solubility isotherms in nanocomposite mixed matrices. The fractional free volume determined from solubility data can be used to correlate solute diffusivities in mixed matrices. PMID:22432612

  12. 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.

  13. Porphyrin shell microbubbles with intrinsic ultrasound and photoacoustic properties.

    PubMed

    Huynh, Elizabeth; Lovell, Jonathan F; Helfield, Brandon L; Jeon, Mansik; Kim, Chulhong; Goertz, David E; Wilson, Brian C; Zheng, Gang

    2012-10-10

    Porphyrin-phospholipid conjugates were used to create photonic microbubbles (MBs) having a porphyrin shell ("porshe"), and their acoustic and photoacoustic properties were investigated. The inclusion of porphyrin-lipid in the MB shell increased the yield, improved the serum stability, and generated a narrow volumetric size distribution with a peak size of 2.7 ± 0.2 μm. Using an acoustic model, we calculated the porshe stiffness to be 3-5 times greater than that of commercial lipid MBs. Porshe MBs were found to be intrinsically suitable for both ultrasound and photoacoustic imaging with a resonance frequency of 9-10 MHz. The distinctive properties of porshe MBs make them potentially advantageous for a broad range of biomedical imaging and therapeutic applications. PMID:22827774

  14. Photophysical properties of monomeric and oligomeric ruthenium (II) porphyrins

    NASA Astrophysics Data System (ADS)

    Ikonen, Marjo; Guez, David; Marvaud, Valérie; Markovitsi, Dimitra

    1994-12-01

    The present Letter deals with three ruthenium(II) porphyrins: RuTBP(CO) (EtOH), RuTBP(pyz) 2 and [RuTBP(pyz)] n where TBP = tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) porphyrin, EtOH = ethanol and pyz = pyrazine. Their photophysical properties are studied by steady-state and time-resolved absorption and emission spectroscopy. Each one of the examined compounds shows weak luminescence originating from a different electronic state: porphyrin triplet 3 (π,π ∗) for RuTBP (CO) (EtOH), equatorial 3LCT for RuTBP(pyz) 2 and axial 1MLCT for [RuTBP(pyz)] n.

  15. Ordered monolayers of free-standing porphyrins on gold.

    PubMed

    Otte, Franziska L; Lemke, Sonja; Schütt, Christian; Krekiehn, Nicolai R; Jung, Ulrich; Magnussen, Olaf M; Herges, Rainer

    2014-08-13

    The controlled attachment of chromophores to metal or semiconducting surfaces is a prerequisite for the construction of photonic devices and artificial surface-based light-harvesting systems. We present an approach to mount porphyrins in ordered monolayers on Au(111) by self-assembly and verify it, employing STM, absorption spectroscopy, and quantum chemical calculations. The usual adsorption geometry of planar chromophores, flat on the surface or densely packed edge-on, is prevented by mounting the porphyrins upright on a molecular platform. An ethynyl unit as spacer and pivot joint provides almost free azimuthal rotation of the unsubstituted porphin. However, rotation of the larger triphenylporphyrin unit is sterically restricted: because the diameter of the substituted porphyrin is larger than the distance to its next neighbors, the phenyl substituents of neigboring molecules interact by dispersion force, which leads to an alignment of the azimuthal rotators. PMID:25053445

  16. Studies of Iron(III) Porphyrinates Containing Silylthiolate Ligands

    PubMed Central

    Meininger, Daniel J.; Caranto, Jonathan D.; Arman, Hadi D.

    2014-01-01

    The chemistry of several iron(III) porphyrinates containing silylthiolate ligands is described. The complexes are prepared by protonolysis reactions of silanethiols with the iron(III) precursors, [Fe(OMe)(TPP)] and [Fe(OH)(H2O)(TMP)] (TPP = dianion of meso-tetraphenylporphine; TMP = dianion of meso-tetramesitylporphine). Each of the compounds has been fully characterized in solution and the solid state. The stability of the silylthiolate complexes versus other iron(III) porphyrinate complexes containing sulfur-based ligands allows for an examination of their reactivity with several biologically relevant small molecules including H2S, NO, and 1-methylimidazole. Electrochemically, the silylthiolate complexes display a quasi-reversible one-electron oxidation event at potentials higher than that observed for an analogous arylthiolate complex. The behavior of these complexes versus other sulfur-ligated iron(III) porphyrinates is discussed. PMID:24138018

  17. 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.

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

    PubMed

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

    2009-10-01

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

  19. 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

  20. 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.

  1. A nonplanar porphyrin-based receptor molecule for chiral amine ligands

    SciTech Connect

    MUZZI,CINZIA M.; MEDFORTH,CRAIG J.; SMITH,KEVIN M.; JIA,SONG-LING; SHELNUTT,JOHN A.

    2000-03-06

    A novel porphyrin-based receptor molecule for chiral amine ligands is described in which nonplanarity of the porphyrin macrocycle is used to orient the ligand and to enhance porphyrin-ligand interactions. The porphyrin macrocycle provides a versatile platform upon which to build elaborate superstructures, and this feature coupled with a rich and well-developed synthetic chemistry has led to the synthesis of many elegant models of heme protein active sites and numerous porphyrin-based receptor molecules. One design feature which is not usually considered in the design of porphyrin-based receptor molecules is nonplanarity of the porphyrin ring, although there are a few systems such as the pyridine sensitive Venus Flytrap and the chirality-memory molecule which illustrate that nonplanar porphyrin-based receptors can display unique and interesting behavior. Given the novel properties of these receptors and the continuing interest in the effects of nonplanarity on the properties of porphyrins the authors decided to investigate in more detail the potential applications of nonplanarity in the design of porphyrin-based receptors. Herein, they describe the design, synthesis, and characterization of a new kind of nonplanar porphyrin-based receptor molecule for chiral amines.

  2. Carbon-13 and proton nuclear magnetic resonance spectroscopy of water-soluble porphyrins and metalloporphyrins.

    PubMed

    Goff, H M; Morgan, L O

    1978-07-01

    Carbon-13 and proton nuclear magnetic resonance (NMR) spectra have been recorded for porphyrins, zinc porphyrins, and iron(III) porphyrin complexes in aqueous media. Spectra of porphyrin-c and hemin-c confirm the structure with thioether linkages at positions alpha to the porphyrin ring. The pattern of NMR isotropic shifts has implications regarding electron transfer in cytochrome-c. Free-base porphyrin-c and meso-substituted porphyrins have been examined for pyrrole nitrogen-hydrogen tautomerism and possible aggregation in aqueous solution. Zinc porphyrin 13C NMR spectra were recorded in order to provide diamagnetic references for paramagnetic iron(III) derivatives. Low-spin iron(III) porphyrin-biscyano complexes in aqueous solution exhibit NMR isotropic shift patterns similar to those previously observed for related compounds in non-aqueous media. The first 13C NMR spectra are reported for mu-oxo-bridged iron(III) porphyrin dimers. A partially resolved spectrum of a high-spin iron(III) porphyrin has also been obtained. Patterns of 13C and proton isotropic shifts are compared, and unpaired spin delocalization mechanisms for 13C resonances are discussed in a qualitative manner. PMID:687673

  3. 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. PMID:26266818

  4. 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.

  5. Layer-by-layer growth of porphyrin supramolecular thin films

    SciTech Connect

    Nishiyama, Fumitaka; Yokoyama, Takashi; Kamikado, Toshiya; Yokoyama, Shiyoshi; Mashiko, Shinro

    2006-06-19

    Multilayer thin film growth of carboxyphenyl-substituted porphyrin on Au(111) was investigated by means of low-temperature scanning tunneling microscopy. The carboxyphenyl-substituted porphyrins are assembled into supramolecular wires on Au(111) by sequential hydrogen bonding between carboxyphenyl groups, and the dense aggregation of the supramolecular wires results in the formation of the first monolayer film. By further molecular deposition, the layer-by-layer growth of the supramolecular wires has been observed, leading to the supramolecular thin film growth.

  6. Time resolved structural dynamics of butadiyne-linked porphyrin dimers

    PubMed Central

    Camargo, Franco V. A.; Hall, Christopher R.; Anderson, Harry L.; Meech, Stephen R.; Heisler, Ismael A.

    2016-01-01

    In this work, the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump/broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through the addition of a ligand, provides conclusive evidence for the twisting motion performed by the porphyrin dimer in solution. PMID:26798839

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

    PubMed

    Khade, Rahul L; Zhang, Yong

    2015-06-24

    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

  8. A method to quantify glassy-winged sharpshooter egg maturation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To identify factors affecting glassy-winged sharpshooter egg production, a method to accurately estimate the number of mature eggs produced during a short-term assay is needed. Egg production is typically quantified by determining the number of eggs deposited during the assay plus the number of matu...

  9. 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

  10. MODELING GLASSY-WINGED SHARPSHOOTER PHENOLOGY AND PIERCE'S DISEASE INCIDENCE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Insect, plant, and bacterial growth are all regulated by environmental factors, such as temperature. Consequently, climate plays an important role in the: 1) ability of glassy winged sharpshooter (GWSS) to survive the winter, 2) development of GWSS populations throughout the year, and 3) propensity...

  11. Fabrication of Bulk Glassy Alloy Foams by High Pressure Hydrogen

    NASA Astrophysics Data System (ADS)

    Wada, Takeshi; Inoue, Akihisa

    Porous Pd42.5Cu30Ni7.5P20 bulk glassy alloy rods with porosities of up to 70% were successfully prepared by high pressure hydrogen of 15 MPa. The melt of Pd42.5Cu30Ni7.5P20 alloy kept under high pressure hydrogen absorbs hydrogen and subsequent water quenching of the melt causes the homogeneous dispersion of hydrogen bubbles, which was resulted from the decrease of hydrogen solubility with decrease of pressure. Annealing the hydrogen bubble containing sample at a supercooled liquid state under vacuum, the bubbles are allowed to expand due to the decrease of viscosity of metallic glass matrix. Pores expansion continues until glassy matrix crystallizes or the equilibration among pressure of the pores, pressure of the atmosphere and surface tension is achieved. By utilizing these phenomena, pores up to 80 m in diameters are homogeneously distributed over the whole cross-sectional area of a fully glassy matrix. Under compressive deformation, the porous alloys with porosities exceeding 40% did not show macroscopic fracture in a wide compressive strain range up to 0.6 whereas the non-porous alloy fractures instantly after elastic limit of about 0.02. Porous bulk glassy alloys exhibit higher plateau stress, lower Young‧s modulus and higher energy absorption capacity compared with the conventional crystalline metal foams.

  12. Immunological detection of glassy-winged sharpshooter saliva in grapevine

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is a major vector for transmission of Xylella fastidiosa (Xf), the causative agent of Pierce’s Disease in grapevine. During the feeding process of stylet penetration and xylem fluid ingestion, GWSS inject saliva into the plant. Inoculation...

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

    PubMed

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

    2016-03-01

    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

  14. 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

  15. 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.

  16. Development of 111In-labeled porphyrins for SPECT imaging

    PubMed Central

    Sadeghi, Shaghayegh; Mirzaei, Mohammad; Rahimi, Mohammad; Jalilian, Amir R.

    2014-01-01

    Objective(s): The aim of this research was the development of 111In-labeled porphyrins as possible radiopharmaceuticals for the imaging of tumors. Methods: Ligands, 5, 10, 15, 20-tetrakis (3, 5-dihydroxyphenyl) porphyrin) (TDHPP), 5, 10, 15, 20-tetrakis (4-hydroxyphenyl) porphyrin (THPP) and 5, 10, 15, 20-tetrakis (3,4-dimethoxyphenyl) porphyrin) (TDMPP) were labeled with 111InCl3 (produced from proton bombardment of natCd target) in 60 min at 80 ºC. Quality control of labeled compounds was performed via RTLC and HPLC followed by stability studies in final formulation and presence of human serum at 37 ºC for 48 h as well as partition coefficient determination. The biodistribution studies performed using tissue dissection and SPECT imaging up to 24h. Results: The complexes were prepared with more than 99% radiochemical purity (HPLC and RTLC) and high stability to 48 h. Partition coefficients (calculated as log P) for 111In-TDHPP, 111In-THPP and 111In-TDMPP were 0.88, 0.8 and 1.63 respectively. Conclusion: Due to urinary excretion with fast clearance for 111In-TDMPP, this complex is probably a suitable candidate for considering as a possible tumor imaging agent. PMID:27408865

  17. 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

  18. 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.

  19. 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. PMID:25640213

  20. 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

  1. 21 CFR 862.1595 - Porphyrins test system.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Porphyrins test system. 862.1595 Section 862.1595 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... metabolism), and other diseases characterized by alterations in the heme pathway. (b) Classification. Class...

  2. 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.

  3. 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

  4. Porphyrins: one ring in the colors of life

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The porphyrin pathway is the source of the "rings of life" and its significance is interwoven in the fabric of the biological world. Protoporphyrinogen oxidase is the last enzyme in the synthesis of the master ring (protoporhyrin) whose fundamental role may have left its mark on King George's legacy...

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    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.

  6. 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

  7. The 5-aminolevulinic acid-induced porphyrin biosynthesis in benign and malignant cells of the skin.

    PubMed

    Lang, K; Bolsen, K; Stahl, W; Ruzicka, T; Sies, H; Lehmann, P; Fritsch, C

    2001-12-01

    In fluorescence diagnosis and photodynamic therapy of neoplastic tissues 5-aminolevulinic acid is used to synthesize endogenous porphyrins as photosensitizers. The efficacy of neoplastic tissues to fluorescence diagnosis and photodynamic therapy is thought to be dependent on the total level of intralesional formed porphyrins. The available profiles of porphyrin metabolites in normal and in neoplastic cell lines after administration of 5-aminolevulinic acid vary considerably. Thus, this is the first in-vitro study which compares the porphyrin biosynthesis in normal skin cells (HaCaT, fibroblasts) with melanoma cells (Bro, SKMel-23, SKMel-28). After incubation with 1 mM 5-aminolevulinic acid, kinetics of porphyrin levels and metabolites were determined in the cells and the corresponding supernatants. Exogenous 5-aminolevulinic acid induced porphyrin formation in all cells with maximum values after an incubation period of 16-36 h. Increase of porphyrin levels varied from 10- to 80-fold (SKMel-28>HaCaT>fibroblasts>SKMel-23>Bro) with minimum 1.5 times higher levels of porphyrins in the supernatants than in the cells. In cells and supernatants protoporphyrin and coproporphyrin were the predominantly formed porphyrin metabolites. Metastatic melanoma cells (SKMel-23, SKMel-28) accumulated much higher porphyrin levels than primary melanoma cells (Bro). In conclusion, by optimizing the treatment modalities, especially the light source, topical photodynamic therapy (PDT) could become a treatment alternative of melanoma metastases in progressive disease. PMID:11748002

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

    SciTech Connect

    Sundararaman, P. ); Moldowan, J.M. )

    1993-03-01

    Correlations are demonstrated between steriod maturity parameters and the porphyrin maturity parameter (PMP) which is based on the ratio of specific vanadyl porphyrins C[sub 28]E/(C[sub 28]E + C[sub 32]D) measured by HPLC. Measurements from a global selection of >100 rock extracts and oils show that PMP parallels changes in the C[sub 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 [open quotes]etio[close quotes] 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. 22 refs., 6 figs., 1 tab.

  9. 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

  10. Porphyrin Biosynthesis Control under Water Stress: Sustained Porphyrin Status Correlates with Drought Tolerance in Transgenic Rice1[W][OA

    PubMed Central

    Phung, Thu-Ha; Jung, Ha-il; Park, Joon-Heum; Kim, Jin-Gil; Back, Kyoungwhan; Jung, Sunyo

    2011-01-01

    A controlled flow of porphyrin metabolites is critical for organisms, but little is known about the control of porphyrin biosynthesis under environmental stress. We monitored transgenic rice (Oryza sativa) plants expressing Myxococcus xanthus protoporphyrinogen oxidase (PPO) for their response to drought stress. Transgenic plants showed significantly improved drought tolerance, as indicated by a higher shoot water potential, less oxidative damage, and a more favorable redox balance compared with wild-type plants. Both transgenic and wild-type plants responded to the onset of drought stress, even prior to changes in shoot water potential and oxidative metabolism, by drastically scavenging porphyrin intermediates in leaves, which was crucial for alleviating reactive oxygen species-induced stress. Protoporphyrin IX, protochlorophyllide, magnesium-protoporphyrin IX, and its methyl ester were absent or hardly detected with the intensification of water stress (–3.1 MPa) in the wild type, whereas transgenic plants retained these intermediates to some extent. Additionally, the expression and activity of most enzymes involved in porphyrin biosynthesis, particularly in the chlorophyll branch, were primarily down-regulated under dehydrating conditions, with stronger repression in the wild type than in transgenic plants. There was up-regulation of Glutamate 1-Semialdehyde Aminotransferase, PPO1, and Fe Chelatase2 transcripts in drought-stressed transgenic plants, enabling the transgenic plants to make larger pools of 5-aminolevulinic acid and protoporphyrin IX available for subsequent steps in the heme branch. Overexpression of PPO ultimately protected the transgenic plants from drought-induced cytotoxicity, demonstrating clearly that manipulation of porphyrin biosynthesis can produce drought-tolerant plants. Our results support a possible role for tetrapyrroles in signaling their metabolic state and in plant protection under drought stress conditions. PMID:22021420

  11. Excitonic Coupling and Femtosecond Relaxation of Zinc Porphyrin Oligomers Linked with Triazole Bridge: Dynamics and Modeling.

    PubMed

    Bukreev, Alexey; Mikhailov, Konstantin; Shelaev, Ivan; Gostev, Fedor; Polevaya, Yuliya; Tyurin, Vladimir; Beletskaya, Irina; Umansky, Stanislav; Nadtochenko, Victor

    2016-03-31

    The synthesis of new zinc porphyrin oligomers linked by a triazole bridge was carried out via "click" reaction. A split in the porphyrin oligomer B-band was observed. It was considered as evidence of exciton-excitonic coupling. The relaxation of excited states in Q-band porphyrin oligomers was studied by the femtosecond laser spectroscopy technique with a 20 fs pump pulse. The transient oscillations of two B-band excitonic peaks have a π-radian shift. For explanation of the coherent oscillation, a theoretical model was developed. The model considered the combination of the exciton-excitonic coupling between porphyrin rings in dimer and weak exciton-vibronic coupling in one porphyrin ring. By varying the values of the structural parameters of porphyrins (the strength values of this couplings and measure of symmetry breaking), we obtained correspondence between the experimental data (phase shift and amplitudes of the spectrum oscillations) and the predictions of the model developed here. PMID:26935579

  12. Two–Photon Oxygen Sensing with Quantum Dot–Porphyrin Conjugates

    PubMed Central

    Lemon, Christopher M.; Karnas, Elizabeth; Bawendi, Moungi G.; Nocera, Daniel G.

    2013-01-01

    Supramolecular assemblies of a quantum dot (QD) associated to palladium(II) porphyrins have been developed to detect oxygen (pO2) in organic solvents. Palladium porphyrins are sensitive in the 0–160 torr range, making them ideal phosphors for in vivo biological oxygen quantification. Porphyrins with meso pyridyl substituents bind to the surface of the QD to produce self–assembled nanosensors. Appreciable overlap between QD emission and porphyrin absorption features results in efficient Förster resonance energy transfer (FRET) for signal transduction in these sensors. The QD serves as a photon antenna, enhancing porphyrin emission under both one– and two–photon excitation, demonstrating that QD–palladium porphyrin conjugates may be used for oxygen sensing over physiological oxygen ranges. PMID:23978247

  13. Energetics and structural consequences of axial ligand coordination in nonplanar nickel porphyrins.

    SciTech Connect

    Pecaut, Jacques; Gazeau, Stephanie; Haddad, Raid Edward; Shelnutt, John Allen; Jia, Song-Ling; Marchon, Jean-Claude; Hok, Saphon; Zhang, Jun; Schore, Neal E.; Ma, Jian-Guo; Olmstead, Marilyn M.; Nurco, Daniel J.; Medforth, Craig John; Smith, Kevin M.; Song, Yujiang

    2004-06-01

    The effects of ruffling on the axial ligation properties of a series of nickel(II) tetra(alkyl)porphyrins have been investigated with UV-visible absorption spectroscopy, resonance Raman spectroscopy, X-ray crystallography, classical molecular mechanics calculations, and normal-coordinate structural decomposition analysis. For the modestly nonplanar porphyrins, porphyrin ruffling is found to cause a decrease in binding affinity for pyrrolidine and piperidine, mainly caused by a decrease in the binding constant for addition of the first axial ligand; ligand binding is completely inhibited for the more nonplanar porphyrins. The lowered affinity, resulting from the large energies required to expand the core and flatten the porphyrin to accommodate the large high-spin nickel(II) ion, has implications for nickel porphyrin-based molecular devices and the function of heme proteins and methyl-coenzyme M reductase.

  14. 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.

  15. From gold porphyrins to gold nanoparticles: catalytic nanomaterials for glucose oxidation.

    PubMed

    Elouarzaki, Kamal; Le Goff, Alan; Holzinger, Michael; Agnès, Charles; Duclairoir, Florence; Putaux, Jean-Luc; Cosnier, Serge

    2014-08-01

    Au(iii) porphyrin was synthesized and evaluated for electrocatalytic oxidation of glucose. These Au(III) porphyrins, immobilized on a multiwalled carbon nanotube matrix, oxidized glucose at low overpotentials. Furthermore, AuNPs were electrogenerated by reduction of the Au(III) porphyrins. The electrocatalytic properties of these compounds towards glucose oxidation were compared and characterized by electrochemistry, electron microscopy and XPS. PMID:24970680

  16. A quest for porphyrins in lunar soil - Samples from Apollo 11, 12 and 14.

    NASA Technical Reports Server (NTRS)

    Hodgson, G. W.; Kvenvolden, K.; Peterson, E.; Ponnamperuma , C.

    1972-01-01

    Analyses for porphyrins in the lunar samples were carried out by extracting the lunar soils as received by organic solvents followed by analytical demetallation using methanesulfonic acid after which free-base porphyrins, if present, were recovered and demonstrably recomplexed with divalent cations. Samples from Apollo 11 showed the presence of fluorescent substances attributed to exhaust from the descent engine. One sample from Apollo 12 showed pigments resembling porphyrins. The Apollo 14 results were negative.

  17. 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

  18. 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.

  19. Nanoparticle Alignment and Repulsion During Failure of Glassy Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Crosby, Alfred; Lee, Jong-Young; Zhang, Qingling; Emrick, Todd

    2007-03-01

    We investigate crazing and failure in a model nanocomposite of surface modified nanoparticles (cadmium selenide, diameter is 5 nm) blended into polystyrene. We demonstrate that nanoparticles undergo three stages of rearrangement during craze formation and propagation in glassy polymer nanocomposites: 1) Alignment along the precraze, 2) Expulsion from craze fibrils, and 3) Assembly into clusters entrapped between craze fibrils. At an optimal volume fraction of nanoparticles, the failure strain of the nanocomposite is increased by nearly 100% relative to unfilled polystyrene. This optimal volume fraction is related to the balance of two mechanisms: 1) the decrease in cross-tie fibril density for craze structures, and 2) the decrease in the probability of craze widening at higher tensile strain by decreasing the number of polymer entanglements at small interparticle lengths. These results offer a clear and detailed understanding of failure mechanism of glassy polymer-nanoparticle composites, and provide predictions for the future design of nanoparticle-based materials.

  20. 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.

  1. 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.

  2. Comparative studies of porphyrin production in Propionibacterium acnes and Propionibacterium granulosum.

    PubMed Central

    Lee, W L; Shalita, A R; Poh-Fitzpatrick, M B

    1978-01-01

    Porphyrin production by Propionibacterium acnes and that by Propionibacterium granulosum were compared. Porphyrin synthesized by both organisms was identified as coproporphyrin III on the bases of absorption and fluorescence spectra and behavior on paper chromatography and thin-layer chromatography. Quantitative, rather than qualitative, differences in production were found between these organisms. In general, P. granulosum produced significantly greater amounts (P less than 0.001) of porphyrin than did P. acnes. delta-Aminolevulinic acid synthetase appeared to be the rate-limiting enzyme of the heme biosynthetic pathway in both organisms. The increased porphyrin production in P. granulosum is apparently associated with increased delta-aminolevulinic acid synthetase activity. PMID:637914

  3. 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

  4. Unique solvatochromism of a membrane composed of a cationic porphyrin-clay complex.

    PubMed

    Takagi, Shinsuke; Shimada, Tetsuya; Masui, Dai; Tachibana, Hiroshi; Ishida, Yohei; Tryk, Donald A; Inoue, Haruo

    2010-04-01

    A novel optically transparent membrane composed of porphyrin-clay mineral complexes was developed. Reversible solvatochromism behavior of the membrane was successfully observed, due to an orientation change of porphyrin in the clay interlayer space. The lambda(max) value of porphyrin was 423 nm in acetone, while it was 464 nm in hexane. The color of the membrane changed from pink to green through to brown, when Sn porphyrin was used. The mechanism for solvatochromism in the present system is very unique compared to those for conventionally reported materials. PMID:20229990

  5. 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.

  6. 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.

  7. The Nature of the Glassy Phase in 4He Crystals

    NASA Astrophysics Data System (ADS)

    Antsygina, T. N.; Poltavskaya, M. I.; Chishko, K. A.

    2015-08-01

    A model of a close-packed polytype with a random stacking fault structure is used to interpret the anomalies of the thermodynamic properties of the disordered (glassy) phase in solid HCP 4He in the so-called supersolid state. The temperature dependence of the phonon pressure is calculated theoretically, and compared to experimental data. A quantitative agreement between the theory and the experiment is achieved.

  8. Liquid and Glassy Water: Two Materials of Interdisciplinary Interest

    NASA Astrophysics Data System (ADS)

    Eugene Stanley, H.

    We can superheat water above its boiling temperature and supercool it below its freezing temperature, down to approximately — 40°C, below which water inevitably crystallizes. In this deeply supercooled region, strange things happen: response functions and transport functions appear as if they might diverge to infinity at a temperature of about-45 °C. These experiments were pioneered by Angell and co-workers over the past 30 years [1-4]. Down in the glassy region of water, additional strange things happen, e.g., there is not just one glassy phase [1]. Rather, just as there is more than one polymorph of crystalline water, so also there appears to be more than one polyamorph of glassy water. The first clear indication of this was a discovery of Mishima in 1985: at low pressure there is one form, called low-density amorphous (LDA) ice [5], while at high pressure Mishima discovered a new form, called highdensity amorphous (HDA) ice [6]. The volume discontinuity separating these two phases is comparable to the volume discontinuity separating low-density and high-density polymorphs of crystalline ice, 25-35 percent [7, 8].

  9. Molecular mechanisms of deformation and failure in glassy materials

    NASA Astrophysics Data System (ADS)

    Rottler, Joerg

    2004-03-01

    Understanding the molecular origins of macroscopic mechanical properties is a fundamental scientific challenge. Fracture of both amorphous and crystalline materials involves many length scales reaching from the continuum to atomic level processes near a crack tip. Using molecular simulations of simple models for amorphous glassy materials, we first study elastoplastic deformation and discuss the nature of the shear yield stress and its dependence on loading conditions, strain rate and temperature. We then focus on the deformation of glassy polymeric systems into crazes at large strains. In the craze, polymers ( 0.5 nm diameter) are bundled into an intricate network of 10 nm diameter fibrils that extends 10 micrometers on either side of a mm crack tip. Analysis of local geometry and stresses provide insight into the real-space nature of the entanglements that control craze formation as well as melt dynamics. Crazes are also shown to share many features with jammed systems such as granular media and foams, but are unique in jamming under a tensile load. This allows explanations for the exponential force distribution in jammed systems to be tested. The force distribution strongly influences the ultimate breakdown of the craze fibrils either through disentanglement or chain scission. We conclude by quantifying the contribution of crazing to the unusually large fracture energy of glassy polymers.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Thermodynamics of water sorption in high performance glassy thermoplastic polymers

    PubMed Central

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

    2014-01-01

    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 from 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 polymers as well as for mean field and for hydrogen bonding interactions, providing a satisfactory quantitative interpretation of the experimental data. PMID:24860802

  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. 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.

  18. Molecular structures of porphyrin-quinone models for electron transfer

    SciTech Connect

    Fajer, J.; Barkigia, K.M.; Melamed, D.; Sweet, R.M.; Kurreck, H.; Gersdorff, J. von; Plato, M.; Rohland, H.C.; Elger, G.; Moebius, K.

    1996-08-15

    Synthetic porphyrin-quinone complexes are commonly used to mimic electron transport in photosynthetic reaction centers and to probe the effects of energetics, distances, and relative orientations on rates of electron transfer between donor-acceptor couples. The structures of two such models have been determined by X-ray diffraction. The redox pairs consist of a zinc porphyrin covalently linked to benzoquinone in cis and trans configurations via a cyclohexanediyl bridge. The crystallographic studies were undertaken to provide a structural foundation for the extensive body of experimental and theoretical results that exists for these compounds in both the ground and photoinduced charge-separated states. The results validate conclusions reached from theoretical calculations, EPR and two-dimensional NMR results for these states. 15 refs., 6 figs., 2 tabs.

  19. Corrole and Porphyrin Amino Acid Conjugates: Synthesis and Physicochemical Properties.

    PubMed

    Karikis, Kostas; Georgilis, Evangelos; Charalambidis, Georgios; Petrou, Athanasia; Vakuliuk, Olena; Chatziioannou, Theodore; Raptaki, Iliana; Tsovola, Sofia; Papakyriacou, Ioanna; Mitraki, Anna; Gryko, Daniel T; Coutsolelos, Athanassios G

    2016-08-01

    A series of conjugates of amino acids with porphyrins and corroles was synthesized. Their self-assembling ability under defined conditions was investigated by scanning electron microscopy. The morphology and photophysical properties of these molecules were studied by absorption and fluorescence spectroscopy in solid, liquid, and self-assembled forms. We observed that both corrole and porphyrin conjugated with the l-phenylalanine-l-phenylalanine peptide to form spherical nanostructures with bathochromic shifts in the emission spectra, indicating the formation of aggregates. These aggregates are characterized by the impressive absorption of light over nearly the whole visible range. The broadening of all bands was particularly strong in the case of corroles. The fluorescence lifetimes of self-assembled species were longer as compared to the solid-state form. PMID:27356185

  20. Porphyrin Analogues of a Trityl Cation and Anion.

    PubMed

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

    2016-05-17

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

  1. Site-isolated porphyrin catalysts in imprinted polymers.

    PubMed

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

    2005-08-19

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

  2. 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).

  3. 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.

  4. 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. PMID

  5. Extraordinary enhancement of porphyrin photocurrent utilizing plasmonic silver arrays.

    PubMed

    Sugawa, Kosuke; Uchida, Koji; Takeshima, Naoto; Jin, Shota; Tsunenari, Natsumi; Takeda, Hideyuki; Kida, Yuki; Akiyama, Tsuyoshi; Otsuki, Joe; Takase, Kouichi; Yamada, Sunao

    2016-08-25

    We demonstrate up to ∼630-fold enhancement of the photocurrent from a porphyrin monolayer on a plasmonic Ag-array electrode showing plasmon absorption in the Q-band region relative to that on a planar Ag electrode. The photocurrent obtained by the Q-band excitation in the plasmonic electrodes even exceeded that obtained by the Soret-band excitation in a normal, nonplasmonic electrode. PMID:27420651

  6. 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.

  7. {sup 19}F NMR spectra and structures of halogenated porphyrins

    SciTech Connect

    Birnbaum, E.R.; Hodge, J.A.; Grinstaff, M.W.

    1995-07-05

    Fluorine-19 NMR spectra of a series of halogenated porphyrins have been used to create a spectral library of different types of fluorine splitting patterns for tetrakis(pentafluorophenyl) porphyrins (TFPP) complexed with diamagnetic and paramagnetic metal ions. The paramagnetic shift, line broadening, and fine structure of the resonances form the peripheral pentafluorophenyl rings are dependent on the symmetry and core environment of the porphyrin macrocycles. In combination with crystal structure data, {sup 19}F NMR helps define the behavior of halogenated porphyrins in solution. Six new crystal structures for TFPP and octahalo-TFPP derivatives are reported: H{sub 2}TFPP in rhombohedral space group R3, a = 20.327(4) {Angstrom}, c = 15.261(2) {Angstrom}, {beta} = 103.87(2){degrees}, V = 2227.6(13) {Angstrom}{sup 3}, Z = 2; CuTFPP in rhombohedral space group R3, a = 20.358(5), c = 14.678(2) {Angstrom}, {alpha} = 88.97(1), {beta}=76.05(1){degrees}, {gamma} = 71.29(1){degrees}, V = 2181.4(6) {Angstrom}{sup 3}, Z = 2; ZnTFPPCl{sub 8} in tetragonal space group P42, c, a = 19.502(20), c = 10.916(8) {Angstrom}, V = 4152(6) {Angstrom}{sup 3}, Z = 2; H{sub 2}TFPPBr{sub 8} in monoclinic space group C2, a = 27.634(6) {Angstrom}, b = 6.926(2) {Angstrom}, c = 14.844(3) {Angstrom}, {beta} = 109.64(2){degrees}, V = 2675.8(11) {Angstrom}{sup 3}, Z = 2.

  8. 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.

  9. Synthesis and Characterization of a New Perhalogenated Porphyrin

    SciTech Connect

    Jia, Songling; Medforth, Craig J.; Nelson, Nora Y.; Nurco, Daniel J.; Shelnutt, John; Smith, Kevin M.

    1999-05-19

    The first synthesis of an octahalotetraalkylporphyrin [2,3,7,8,12,13,17,18 -octabromo-5,10,15,20- tetrakis(trifluoromethyl)porphinato nickel(II)] is reported; this perhalogenated porphyrin has several novel properties including a very nonplanar ruffled structure with an unusually short Ni- N distance, an extremely red-shifted optical spectrum, and hindered rotation of the trifluoromethyl groups ({Delta}G278K =47 kJ mol-1).

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

    PubMed

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

    2015-01-01

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

  12. 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.

  13. Porphyrins as Molecular Electronic Components of Functional Devices

    PubMed Central

    Jurow, Matthew; Schuckman, Amanda E.; Batteas, James D.; Drain, Charles Michael

    2010-01-01

    The proposal that molecules can perform electronic functions in devices such as diodes, rectifiers, wires, capacitors, or serve as functional materials for electronic or magnetic memory, has stimulated intense research across physics, chemistry, and engineering for over 35 years. Because biology uses porphyrins and metalloporphyrins as catalysts, small molecule transporters, electrical conduits, and energy transducers in photosynthesis, porphyrins are an obvious class of molecules to investigate for molecular electronic functions. Of the numerous kinds of molecules under investigation for molecular electronics applications, porphyrins and their related macrocycles are of particular interest because they are robust and their electronic properties can be tuned by chelation of a metal ion and substitution on the macrocycle. The other porphyrinoids have equally variable and adjustable photophysical properties, thus photonic applications are potentiated. At least in the near term, realistic architectures for molecular electronics will require self-organization or nanoprinting on surfaces. This review concentrates on self-organized porphyrinoids as components of working electronic devices on electronically active substrates with particular emphasis on the effect of surface, molecular design, molecular orientation and matrix on the detailed electronic properties of single molecules. PMID:20936084

  14. Cationic porphyrin derivatives for application in photodynamic therapy of cancer

    NASA Astrophysics Data System (ADS)

    Prack McCormick, Bárbara P.; Florencia Pansa, M.; Milla Sanabria, Laura N.; Carvalho, Carla M. B.; Faustino, M. Amparo F.; Neves, Maria Graça P. M. S.; Cavaleiro, José A. S.; Rumie Vittar, Natalia B.; Rivarola, Viviana A.

    2014-04-01

    Current studies in photodynamic therapy (PDT) against cancer are focused on the development of new photosensitizers (PSs), with higher phototoxic action. The aim of this study was to compare the therapeutic efficiency of tri-cationic meso-substituted porphyrin derivatives (Tri-Py+-Me-PF, Tri-Py+-Me-Ph, Tri-Py+-Me-CO2Me and Tri-Py+-Me-CO2H) with the well-known tetra-cationic T4PM. The phototoxic action of these derivatives was assessed in human colon adenocarcinoma cells by cell viability, intracellular localization and nuclear morphology analysis. In the experimental conditions used we determined that after light activation -PF, -Ph and -CO2Me cause a more significant decline of cell viability compared to -CO2H and T4PM. These results suggest that the nature of the peripheral substituent influences the extent of cell photodamage. Moreover, we have demonstrated that PS concentration, physicochemical properties and further light activation determine the PDT response. All porphyrins were clearly localized as a punctuated pattern in the cytoplasm of the cells, and the PDT scheme resulted in apoptotic cell death after 3 h post-PDT. The tri-cationic porphyrin derivatives Tri-Py+-Me-PF, Tri-Py+-Me-Ph and Tri-Py+-Me-CO2Me showed a promising ability, making them good photosensitizer candidates for oncological PDT.

  15. 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.

  16. Ruthenocene-Type Complexes of N-Fused Porphyrins.

    PubMed

    Toganoh, Motoki; Matsuo, Hideaki; Sato, Ayumi; Furuta, Hiroyuki

    2016-06-01

    Ruthenocene-type hybrid complexes with N-fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N-fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X-ray crystallography. [Ru(NFp)Cp] is a common low-spin ruthenium(II) complex and shows strong aromaticity. The Ru-Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp2 ] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three-dimensional d-π conjugated system. The HOMO-LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N-fused porphyrin, in which the HOMO-LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles. PMID:27135204

  17. 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%.

  18. Synthesis of direct β-to-β linked porphyrin arrays with large electronic interactions: branched and cyclic oligomers.

    PubMed

    Cai, Hao; Fujimoto, Keisuke; Lim, Jong Min; Wang, Chaojie; Huang, Weiming; Rao, Yutao; Zhang, Senmiao; Shi, Hui; Yin, Bangshao; Chen, Bo; Ma, Ming; Song, Jianxin; Kim, Dongho; Osuka, Atsuhiro

    2014-10-01

    Direct β-to-β linked branched and cyclic porphyrin trimers and pentamers have been synthesized by the Suzuki-Miyaura coupling of β-borylporphyrins and β-bromoporphyrins. The cyclic porphyrin trimer, the smallest directly linked cyclic porphyrin wheel to date, and its twined pentamer, exhibit small electrochemical HOMO-LUMO gaps, broad nonsplit Soret bands, and red-shifted Q-bands, thus indicating large electronic interactions between the constituent porphyrin units. PMID:25156866

  19. The conserved active-site loop residues of ferrochelatase induce porphyrin conformational changes necessary for catalysis.

    SciTech Connect

    Haddad, Raid Edward; Shelnutt, John Allen; Shi, Zhen; Ferreira, Gloria C.; Franco, Ricardo T.

    2005-05-01

    Binding of porphyrin to murine ferrochelatase, the terminal enzyme of the heme biosynthetic pathway, is investigated by employing a set of variants harboring mutations in a putative porphyrin-binding loop. Using resonance Raman (RR) spectroscopy, the structural properties of the ferrochelatase-bound porphyrins are examined, especially with respect to the porphyrin deformation occurring in the environment of the active site. This deformation is thought to be a key step in the enzymatic insertion of ferrous iron into the porphyrin ring to make heme. Our previous RR spectroscopic studies of binding of porphyrin to murine ferrochelatase led us to propose that the wild-type enzyme induces porphyrin distortion even in the absence of the metal ion substrate. Here, we broaden this view by presenting evidence that the degree of a specific nonplanar porphyrin deformation contributes to the catalytic efficiency of ferrochelatase and its variants. The results also suggest that the conserved Trp256 (murine ferrochelatase numbering) is partially responsible for the observed porphyrin deformation. Binding of porphyrin to the ferrochelatase variants causes a decrease in the intensity of RR out-of-plane vibrational mode {gamma}{sub 15}, a saddling-like mode that is strong in the wild-type enzyme. In particular, the variant with a catalytic efficiency 1 order of magnitude lower than that of the wild-type enzyme is estimated to produce less than 30% of the wild-type saddling deformation. These results suggest that specific conserved loop residues (especially Trp256) are directly involved in the saddling of the porphyrin substrate.

  20. 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.

  1. Effectiveness of porphyrin-like compounds in photodynamic damage of atherosclerotic plaque

    NASA Astrophysics Data System (ADS)

    Zalessky, Viacheslav N.; Bobrov, Vladimir; Michalkin, Igor; Trunov, Vitaliy

    1991-06-01

    Porphyrin-like compounds such as tetra-(4 sulfonatophenyl) porphine (TSPP), chlorin-e6 derivative (CED) and tetrasulfophthalocyanin (TSPC) are photosensitizing agents that absorbed light at 630 nm, 657 nm and 625 nm, respectively, and bind preferentially to atherosclerotic plaque. Porphyrin-treated human cadaveric aorta was compared with untreated aorta using several techniques: the absorptive spectrophotometry which has demonstrated the distinct absorptive peaks at 630 nm, 657 nm, 625 nm in porphyrin-treated plaque which were absent in untreated normal aorta; the fluorescence microscopy, which has shown that the treated atheroma acquired the characteristic fluorescence of porphyrin under ultraviolet light. Because of the porphyrin''s unique property, porphyrin-treated and untreated aorta was exposed to red laser radiation at a wavelength of 632.8 nm. It was found that enhanced photoalteration of porphyrin-treated compared with untreated atheroma. Histologic analysis of the depth of tissue penetration of equal amounts of laser radiation has demonstrated more pronounced photosensitizing effect in TSPC-treated plaque compared with CED-, TSPP-, and untreated plaques. This study demonstrates a potential of tetrasulfophthalocyanin for selective alteration of atheroma by He-Ne laser radiation.

  2. 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.

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

    PubMed

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

    2008-09-15

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

  4. 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

  5. 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

  6. The direct synthesis of organic-containing clays and thermal analysis of porphyrin-clay complexes

    SciTech Connect

    Carrado, K.A.; Anderson, K.B.; Grutkoski, P.S.

    1991-01-01

    Synthetic TMA-montmorillonites have now been made in conjunction with synthetic porphyrin-hectorites reported earlier. In order to help progress towards preparation of porphyrin-containing aluminosilicate clays, the thermal stability of porphyrin-clay systems has been examined in detail. Results from TGA and Py-GC-MS indicate that the porphyrin nucleus is extremely stable in the present of clay minerals. Substituents on the nucleus such as pyridinium or anilinium are, on the other hand, slightly destabilized. In addition, the presence of transition metals like Fe(III) in metalloporphyrins appears to catalyze decomposition of the porphyrin nucleus to some degree. The use of Py-GC-MS in conjunction with TGA results greatly clarified the assignment of weight loss peaks. 18 refs., 3 figs.

  7. Interactions of dicarboxylic porphyrins with membranes in relation to their ionization state.

    PubMed

    Brault, D; Vever-Bizet, C; Kuzelova, K

    1993-10-01

    The interactions of dicarboxylic porphyrins with membrane systems are discussed with particular emphasis on the effect of the charge of the porphyrin and the nature of the side-chains. The incorporation of hematoporphyrin or related dicarboxylic porphyrins within small unilamellar vesicles as membrane models is favored by a decrease of the pH in the range of physiological pH values. This effect might play an important role in the retention of porphyrins by tumors, which are more acidic than normal tissues. Kinetics studies also show that the partition of the porphyrin between the lipidic bilayer and the aqueous phase is governed by its release rate rather than by its incorporation rate. PMID:8271119

  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. The chemistry of rhenium and tungsten porphyrin complexes in low oxidation states. Synthesis and characterization of rhenium and tungsten porphyrin dimers containing metal-metal multiple bonds

    SciTech Connect

    Collmann, J.P.; Garner, J.M.; Woo, L.K. )

    1989-10-11

    The coordination chemistry of rhenium and tungsten porphyrin complexes in low oxidation states is presented. W{sup IV}(Por)(Cl){sub 2}, W{sup II}(Por)(H{sub 5}C{sub 6}C{identical to}CC{sub 6}H{sub 5}) and W{sup II}(OEP)(PEt{sub 3}){sub 2} complexes (Por = 5,10,15,20-tetra(4-tolyl)porphyrin (TTP) or 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) dianions) were found to be similar to the analogous molybdenum porphyrin complexes by spectroscopic and magnetic measurements. UV-visible and vibrational spectroscopies indicate that these oxidations occur at the metal-metal bond rather than the porphyrin ligand.

  10. 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.

  11. 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.

  12. Linear Response Theory for Hard and Soft Glassy Materials

    SciTech Connect

    Langer, J.; Bouchbinder, Eran

    2011-01-01

    Despite qualitative differences in their underlying physics, both hard and soft glassy materials exhibit almost identical linear rheological behaviors. We show that these nearly universal properties emerge naturally in a shear-transformation-zone (STZ) theory of amorphous plasticity, extended to include a broad distribution of internal thermal-activation barriers. The principal features of this barrier distribution are predicted by nonequilibrium, effective-temperature thermodynamics. Our theoretical loss modulus G{double_prime}({omega}) has a peak at the {alpha} relaxation rate, and a power law decay of the form {omega}{sup -{zeta}} for higher frequencies, in quantitative agreement with experimental data.

  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. Nonequilibrium thermodynamics of the soft glassy rheology model.

    PubMed

    Fuereder, Ingo; Ilg, Patrick

    2013-10-01

    The soft glassy rheology (SGR) model is a mesoscopic framework which proved to be very successful in describing flow and deformation of various amorphous materials phenomenologically (e.g., pastes, slurries, foams, etc.). In this paper, we cast SGR in a general, model-independent framework for nonequilibrium thermodynamics called general equation for the nonequilibrium reversible-irreversible coupling. This leads to a formulation of SGR which clarifies how it can properly be coupled to hydrodynamic fields, resulting in a thermodynamically consistent, local, continuum version of SGR. Additionally, we find that compliance with thermodynamics imposes the existence of a modification to the stress tensor as predicted by SGR. PMID:24229142

  15. Evaluation of urinary porphyrin excretion in neonates born to mothers exposed to airborne hexachlorobenzene.

    PubMed Central

    Ozalla, Dolores; Herrero, Carmen; Ribas-Fitó, Núria; To-Figueras, Jordi; Toll, Agustí; Sala, Maria; Grimalt, Joan; Basagaña, Xavier; Lecha, Màrius; Sunyer, Jordi

    2002-01-01

    The existence of a link between hexachlorobenzene (HCB) and porphyria cutanea tarda has been known for a long time. However, the epidemiologic data on effects on health caused by prenatal exposure have not provided convincing evidence that HCB alters porphyrin metabolism. Our objectives were to analyze urinary porphyrin excretion and HCB in maternal serum and fetal cord blood in neonates born in a village (Flix) near a chlorinated solvent factory, to detect possible adverse effects in urinary porphyrin excretion caused by prenatal exposure, and to assess their relationship with HCB blood levels. We conducted a cross-sectional study in the Porphyria Unit at a tertiary care facility in Barcelona, Spain, and the Pediatric Unit of the Móra d'Ebre Hospital, the reference hospital of the study area. We included in the study all neonates (n = 68) born in Móra d'Ebre Hospital 1997-1999 and their mothers. We obtained 68 urine specimens of singleton neonates on the third day after birth to test for urinary porphyrin excretion. We obtained 52 fetal cord blood and 56 maternal serum samples for HCB analysis. Total urinary porphyrins were quantified using spectrofluorometry. Porphyrin profile was determined by HPLC. Serum HCB was analyzed by gas chromatography coupled with electron capture detection. In total population, median HCB levels were 1.08 ng/mL in cord blood and 3.31 ng/mL in maternal serum. Total urinary porphyrin concentration was 37.87 micromol/mol creatinine. Coproporphyrin I and coproporphyrin III were the major porphyrins excreted. We found no positive relationship between urinary porphyrin excretion and HCB levels. However, we observed an association between maternal smoking and coproporphyrin excretion. Although high environmental levels of HCB are reported in the town of Flix, we found no alteration in urinary porphyrin excretion. PMID:11836151

  16. Confined glassy dynamics at grain boundaries in colloidal crystals

    PubMed Central

    Nagamanasa, K. Hima; Gokhale, Shreyas; Ganapathy, Rajesh; Sood, A. K.

    2011-01-01

    Grain boundary (GB) microstructure and dynamics dictate the macroscopic properties of polycrystalline materials. Although GBs have been investigated extensively in conventional materials, it is only recently that molecular dynamics simulations have shown that GBs exhibit features similar to those of glass-forming liquids. However, current simulation techniques to probe GBs are limited to temperatures and driving forces much higher than those typically encountered in atomic experiments. Further, the short spatial and temporal scales in atomic systems preclude direct experimental access to GB dynamics. Here, we have used confocal microscopy to investigate the dynamics of high misorientation angle GBs in a three-dimensional colloidal polycrystal, with single-particle resolution, in the zero-driving force limit. We show quantitatively that glassy behavior is inherent to GBs as exemplified by the slowing down of particle dynamics due to transient cages formed by their nearest neighbors, non-Gaussian probability distribution of particle displacements and string-like cooperative rearrangements of particles. Remarkably, geometric confinement of the GB region by adjacent crystallites decreases with the misorientation angle and results in an increase in the size of cooperatively rearranging regions and hence the fragility of the glassy GBs. PMID:21705662

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    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-Ag2O-[(1-x)B2O3-xTeO2] (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 TeO2 as well as with temperature. The conductivity of the present glass system is found to be of the order of 10-2 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.

  18. 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.

  19. Modeling VOC Sorption and Transport in Glassy Polymeric Membranes

    NASA Astrophysics Data System (ADS)

    De Angelis, Maria Grazia; Olivieri, Luca; Sarti, G. C.

    2010-06-01

    In this work we evaluated the sorption, diffusion and permeation of a series of volatile organic compounds (VOCs) (acetone, n-butane, n-pentane, n-hexane, ethanol, methanol, chloroform and toluene) into glassy polymers of increasing fractional free volume (FFV): Polycarbonate (PC), Amorphous Teflon AF1600 and AF2400, poly-trimethylsilyl norbornene (PTMSN) and poly[1-(trimethylsilyl)-1-propyne] (PTMSP). Based on some experimental data of sorption and diffusion, and on theoretical and empirical models for the solubility and diffusion coefficients, the permeability for vapor/N2 mixtures was evaluated. These parameters are useful for the membrane separation processes and for other applications such as chemical sensors. The ideal separation factors of glassy polymeric membranes versus mixtures of VOCs and N2 were estimated at various pressures and compositions and at 25° C. The selectivity vs. permeability maps for the mixtures considered were plotted, showing that some of these materials show potentially the same selective ability of rubbery polymeric films. In particular it is shown that, the higher the FFV, the better the vapor/gas selectivity.

  20. TOPICAL REVIEW: Fracture in glassy polymers: a molecular modeling perspective

    NASA Astrophysics Data System (ADS)

    Rottler, Jörg

    2009-11-01

    Over the past 25 years, molecular modeling and simulations have provided important insights into the physics of deformation and fracture of glassy polymers. This review presents an overview of key results discussed in the context of experimentally observed polymer behavior. Both atomistic and coarse-grained polymer models have been used in different deformation protocols to study elastic properties, shear yielding, creep, physical aging, strain hardening and crazing. Simulations reproduce most of the macroscopic features of plasticity in polymer glasses such as stress-strain relations and creep response, and reveal information about the underlying atomistic processes. Trends of the shear yield stress with loading conditions, temperature and strain rate, and the atomistic dynamics under load have been systematically explored. Most polymers undergo physical aging, which leads to a history-dependent mechanical response. Simulations of strain hardening and crazing demonstrate the nature of polymer entanglements in the glassy state and the role of local plasticity and provide insight into the origin of fracture toughness of amorphous polymers.

  1. Fracture in glassy polymers: a molecular modeling perspective.

    PubMed

    Rottler, Jörg

    2009-11-18

    Over the past 25 years, molecular modeling and simulations have provided important insights into the physics of deformation and fracture of glassy polymers. This review presents an overview of key results discussed in the context of experimentally observed polymer behavior. Both atomistic and coarse-grained polymer models have been used in different deformation protocols to study elastic properties, shear yielding, creep, physical aging, strain hardening and crazing. Simulations reproduce most of the macroscopic features of plasticity in polymer glasses such as stress-strain relations and creep response, and reveal information about the underlying atomistic processes. Trends of the shear yield stress with loading conditions, temperature and strain rate, and the atomistic dynamics under load have been systematically explored. Most polymers undergo physical aging, which leads to a history-dependent mechanical response. Simulations of strain hardening and crazing demonstrate the nature of polymer entanglements in the glassy state and the role of local plasticity and provide insight into the origin of fracture toughness of amorphous polymers. PMID:21715863

  2. Zeolitization of glassy Topopah Spring tuff under hydrothermal conditions

    SciTech Connect

    Knauss, K.G.

    1987-01-01

    In support of the Nevada Nuclear Waste Storage Investigations Project experiments were conducted to study the effects of heat generated by a nuclear waste repository in densely welded, devitrified tuff on the underlying, compositionally-equivalent glassy tuff at Yucca Mtn. Solid wafers of glassy tuff were reacted with a dilute ground water for several months at 150{sup 0}C and 250{sup 0}C at 100 bars pressure in Dickson-type, gold-bag rocking autoclaves. The in-situ chemistry of the hydrothermal fluids was modeled and the chemical affinities for all possible mineral precipitation reactions were calculated using the EQ3/6 program. In the 250{sup 0}C experiment the calculations suggest that a zeolite mineral would be expected to form. Analyses of the run products showed that not only had the wafer been extensively corroded and the glass shards replaced by clinoptilolite, but pure clinoptilolite had precipitated directly from solution. In the 150{sup 0}C experiment, although clay minerals were thermodynamically favored to form in the first half of the experiment, by the end of the run a zeolite mineral was predicted to form. Analyses of the run products showed no well-formed secondary minerals (clays or zeolites) had formed. At the lower temperature the effects of precipitation kinetics may preclude the formation of the zeolite within the time span of this experiment. In general the observations are in relatively good agreement with the geochemical model calculations.

  3. Approaching theoretical strength in glassy carbon nanolattices.

    PubMed

    Bauer, J; Schroer, A; Schwaiger, R; Kraft, O

    2016-04-01

    The strength of lightweight mechanical metamaterials, which aim to exploit material-strengthening size effects by their microscale lattice structure, has been limited by the resolution of three-dimensional lithography technologies and their restriction to mainly polymer resins. Here, we demonstrate that pyrolysis of polymeric microlattices can overcome these limitations and create ultra-strong glassy carbon nanolattices with single struts shorter than 1 μm and diameters as small as 200 nm. They represent the smallest lattice structures yet produced--achieved by an 80% shrinkage of the polymer during pyrolysis--and exhibit material strengths of up to 3 GPa, corresponding approximately to the theoretical strength of glassy carbon. The strength-to-density ratios of the nanolattices are six times higher than those of reported microlattices. With a honeycomb topology, effective strengths of 1.2 GPa at 0.6 g cm(-3) are achieved. Diamond is the only bulk material with a notably higher strength-to-density ratio. PMID:26828314

  4. 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.

  5. 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...

  6. Glassy-winged sharpshooter excreta production and egg maturation on grapevines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To better understand glassy-winged sharpshooter movement and reproduction in vineyards, studies evaluating glassy-winged sharpshooter feeding (as measured by excreta production) and egg maturation on grapevines were conducted. In 2010, studies compared excreta production and egg maturation of femal...

  7. 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.

  8. 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

  9. 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...

  10. Manganese Porphyrins Catalyze Selective C-H Bond Halogenations

    SciTech Connect

    Liu, Wei; Groves, John T.

    2010-08-31

    We report a manganese porphyrin mediated aliphatic C-H bond chlorination using sodium hypochlorite as the chlorine source. In the presence of catalytic amounts of phase transfer catalyst and manganese porphyrin Mn(TPP)Cl 1, reaction of sodium hypochlorite with different unactivated alkanes afforded alkyl chlorides as the major products with only trace amounts of oxygenation products. Substrates with strong C-H bonds, such as neopentane (BDE =~100 kcal/mol) can be also chlorinated with moderate yield. Chlorination of a diagnostic substrate, norcarane, afforded rearranged products indicating a long-lived carbon radical intermediate. Moreover, regioselective chlorination was achieved by using a hindered catalyst, Mn(TMP)Cl, 2. Chlorination of trans-decalin with 2 provided 95% selectivity for methylene-chlorinated products as well as a preference for the C2 position. This novel chlorination system was also applied to complex substrates. With 5α-cholestane as the substrate, we observed chlorination only at the C2 and C3 positions in a net 55% yield, corresponding to the least sterically hindered methylene positions in the A-ring. Similarly, chlorination of sclareolide afforded the equatorial C2 chloride in a 42% isolated yield. Regarding the mechanism, reaction of sodium hypochlorite with the MnIII porphyrin is expected to afford a reactive MnV=O complex that abstracts a hydrogen atom from the substrate, resulting in a free alkyl radical and a MnIV—OH complex. We suggest that this carbon radical then reacts with a MnIV—OCl species, providing the alkyl chloride and regenerating the reactive MnV=O complex. The regioselectivity and the preference for CH2 groups can be attributed to nonbonded interactions between the alkyl groups on the substrates and the aryl groups of the manganese porphyrin. The results are indicative of a bent [Mnv=O---H---C] geometry due to the C—H approach to the Mn

  11. Hole burning on porphyrin centers in langmuir-blodgett films

    NASA Astrophysics Data System (ADS)

    Bernard, J.; Orrit, M.; Personov, R. I.; Samoilenko, A. D.

    1989-12-01

    Spectral holes were burnt in the excitation spectra of porphyrin centers imbedded in a multilayer assembly of poly-heptyl-cyanoacrylate Langmuir-Blodgett films. We found a strong dependence of the hole width on the burning wavelength and attributed it to energy transfer to lower energy centers in our concentrated sample. The temperature dependence of the hole width was measured between 1.7 and 10 K for two wavelengths and found steeper than in glasses but weaker than in most crystals. The holes were shallower and broader in a monolayer sample.

  12. 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.

  13. 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.

  14. Heterogeneous nucleation of ice particles on glassy aerosols modifies TTL cirrus

    NASA Astrophysics Data System (ADS)

    Wilson, T. W.; Murray, B. J.; Dobbie, S.; Al-Jumur, S. M.; Cui, Z.; Wagner, R.; Moehler, O.; Schnaiter, M.; Benz, S.; Niemand, M.; Saathoff, H.; Skrotzki, J.; Ebert, V.; Wagner, S.; Karcher, B.

    2010-12-01

    Experiments at the AIDA chamber, Karlsruhe Institute of Technology, have shown that glassy aqueous citric acid aerosol can nucleate ice at temperatures relevant to the tropical tropopause layer (TTL)(1). Modelling suggests this new route to the formation of TTL cirrus can provide an explanation for the very low ice particle number density observed in cirrus clouds in this region and may lead to high in-cloud supersaturations(1). Nucleation of ice on glassy aerosol is consistent with the absence of traditional ice nuclei in sampled TTL cirrus residue(2). In addition, we will present new data from experiments performed in July 2010 at the AIDA chamber using glassy aerosols composed of other atmospherically relevant compounds (levoglucosan, raffinose) and an internal mixture of five dicarboxylic acids and ammonium sulphate (raffinose/M5AS)(3). All four systems tested nucleate ice when in a glassy state. This indicates that heterogeneous ice nucleation is a general property of glassy aerosols and that natural aerosols which are composed of similar molecules will also nucleate ice if glassy. Glassy aqueous levoglucosan and raffinose/M5AS aerosol nucleated ice at temperatures similar to those found for glassy aqueous citric acid aerosol (<202 K). Whereas raffinose, which forms a glass at much higher temperatures, nucleated ice heterogeneously at up to ~220 K. This activity at higher temperatures suggests that ice nucleation by glassy aerosol may also play a role in the formation of warmer ice clouds. (1)B. J. Murray et al., Heterogeneous nucleation of ice particles on glassy aerosols under cirrus conditions, Nature Geosci, 2010, 3, 233-237. (2)K. D. Froyd et al., Aerosols that form subvisible cirrus at the tropical tropopause, Atmos. Chem. Phys., 2010, 10, 209-218. (3)B. Zobrist et al., Do atmospheric aerosols form glasses?, Atmos. Chem. Phys., 2008, 8, 5221-5244.

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

    PubMed

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

    2006-11-10

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

  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. Facile synthesis and enhanced nonlinear optical properties of porphyrin-functionalized multi-walled carbon nanotubes.

    PubMed

    Wang, Aijian; Fang, Yu; Long, Lingliang; Song, Yinglin; Yu, Wang; Zhao, Wei; Cifuentes, Marie P; Humphrey, Mark G; Zhang, Chi

    2013-10-11

    Two multi-walled carbon nanotube (MWCNT)-based nanohybrids, MWCNT-ZnTPP and MWCNT-TPP (TPP=5-[4-{2-(4-formylphenoxy)- ethyloxy}phenyl]-10,15,20-triphenylporphyrin, ZnTPP=5-[4-{(4-formylphenyl)ethynyl}phenyl]-10,15,20-triphenylporphinatozinc(II)), were prepared directly from pristine MWCNTs through 1,3-dipolar cycloaddition reactions. Covalent attachment of the porphyrins to the surfaces of the MWCNTs was confirmed by Fourier transform infrared spectroscopy, ultraviolet/visible absorption, fluorescence, Raman, and X-ray photoelectron spectroscopy, elemental analysis, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin moieties to the surface of the MWCNTs significantly improves the solubility and ease of processing of these MWCNT-porphyrin composite materials. Z-scan studies reveal that these MWCNT-porphyrin nanohybrids exhibit enhanced nonlinear optical properties under both nanosecond and picosecond laser pulses at λ=532 nm in comparison with free MWCNTs and the free porphyrin chromophores, whereas superior optical limiting performance was displayed by MWCNT-porphyrin composite materials rather than MWCNTs/ZnTPP and MWCNTs/TPP blends, which is consistent with a remarkable accumulation effect as a result of the covalent linkage between the porphyrin and the MWCNTs. PMID:24038312

  18. 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

  19. 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

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

    PubMed

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

    2015-09-24

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

  1. Novel porphyrin-preparation, characterization, and applications in solar energy conversion.

    PubMed

    Lu, Jianfeng; Li, Hao; Liu, Shuangshuang; Chang, Yu-Cheng; Wu, Hui-Ping; Cheng, Yibing; Wei-Guang Diau, Eric; Wang, Mingkui

    2016-03-01

    Porphyrins have been demonstrated as one of the most efficient sensitizers in dye-sensitized solar cells (DSSC). Herein, we investigated a series of porphyrin sensitizers functionalized with various π-spacers, such as phenyl for LD14, thiophene for LW4, thiophene-phenyl for LW5, and 2,1,3-benzothiadiazole (BTD)-phenyl for LW24. Photo-physical investigation by means of time-resolved fluorescence and nanosecond transient absorption spectroscopy revealed an accelerated inner charge transfer in porphyrins containing the BTD-phenyl π-spacer. Implementation of an auxiliary electron-deficient BTD unit to the porphyrin spacer also results in a broad light-harvesting ability extending up to 840 nm, contributing to an enhanced charge transfer character from the porphyrin ring to the anchoring group. When utilized as a sensitizer in DSSCs, the LW24 device achieved a power conversion efficiency of 9.2%, higher than those based on LD14 or LW5 porphyrins (PCE 9.0% or 8.2%, respectively) but lower than that of the LW4 device (PCE 9.5%). Measurements of transient photovoltage decays demonstrate that the LW24 device features the up-shifted potential band edge of the conduction band of TiO2, but involves serious charge recombination in the dye/TiO2 interface. The findings provide insights into the molecular structure and the charge-transfer characteristics for designing efficient porphyrin sensitizers for DSSC applications. PMID:26878900

  2. Nickel(II) Chelatase Variants Directly Evolved from Murine Ferrochelatase: Porphyrin Distortion and Kinetic Mechanism†

    PubMed Central

    McIntyre, Neil R.; Franco, Ricardo; Shelnutt, John A.; Ferreira, Gloria C.

    2011-01-01

    The heme biosynthetic pathway culminates with the ferrochelatase-catalyzed ferrous iron chelation into protoporphyrin IX to form protoheme. The catalytic mechanism of ferrochelatase has been proposed to involve the stabilization of a nonplanar porphyrin to present the pyrrole nitrogens to the metal ion substrate. Previously, we hypothesized that the ferrochelatase-induced nonplanar distortions of the porphyrin substrate impose selectivity for the divalent metal ion incorporated into the porphyrin ring and facilitate the release of the metalated porphyrin through its reduced affinity for the enzyme. Using resonance Raman spectroscopy, the structural properties of porphyrins bound to the active site of directly evolved Ni-chelatase variants are now examined with regard to the mode and extent of porphyrin deformation and related to the catalytic properties of the enzymes. The Ni2+-chelatase variants (S143T, F323L, and S143T/F323L), which were directly evolved to exhibit an enhanced Ni2+-chelatase activity over that of the parent wild-type ferrochelatase, induced a weaker saddling deformation of the porphyrin substrate. Steady-state kinetic parameters of the evolved variants for Ni2+- and Fe2+-chelatase activities increased compared to those of wild-type ferrochelatase. In particular, the reduced porphyrin saddling deformation correlated with increased catalytic efficiency toward the metal ion substrate (Ni2+ or Fe2+). The results lead us to propose that the decrease in the induced protoporphyrin IX saddling mode is associated with a less stringent metal ion preference by ferrochelatase and a slower porphyrin chelation step. PMID:21222436

  3. Evaluation of porphyrin C analogues for photodynamic therapy of cerebral glioma.

    PubMed Central

    Karagianis, G.; Hill, J. S.; Stylli, S. S.; Kaye, A. H.; Varadaxis, N. J.; Reiss, J. A.; Phillips, D. R.

    1996-01-01

    A series of monomeric porphyrins (2-8) based on porphyrin C (1) have been tested as sensitisers for photodynamic therapy (PDT) of cerebral glioma using the in vitro/in vivo C6 intracerebral animal tumour model. The in vivo screening, consisting of cytotoxicity, phototoxicity (red light) and subcellular localisation studies, revealed two sensitisers (porphyrin 7, molecular weight 863 Da and porphyrin 8, molecular weight 889 Da), which had greater photoactivity than porphyrin C and similar photoactivity to haematoporphyrin derivative (HpD) although at a 5-fold higher dose than HpD. Both sensitisers showed intracellular localisation to discrete organelle sites and exhibited considerably less 'dark' cytotoxicity than HpD. The kinetics of uptake of porphyrins 7 and 8 was studied in the mouse C6 glioma model as well as in biopsy samples from normal brain, liver, spleen and blood. Maximal drug uptake levels in tumour occurred 9 and 6 h after intraperitoneal injection for 7 and 8 respectively, at which time the tumour to normal brain ratios were 15:1 and 13:1 respectively. The effect of PDT using porphyrin 7 activated by the gold metal vapour laser tuned to 627.8 nm was studied in Wistar rats bearing intracerebral C6 glioma. At a drug dose of 10 mg porphyrin 7 kg-1 body weight and laser doses of up to 400 J cm-2 light, selective tumour kill with sparing of normal brain was achieved, with a maximal depth of tumour kill of 1.77+/-0.40. mm. Irradiation following a higher drug dose of 75 mg porphyrin 7 kg-1 body weight resulted in a greater depth of tumour kill, but also significantly increased the likelihood and extent of necrosis in normal brain. Images Figure 3 Figure 4 Figure 6 PMID:8595167

  4. 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.

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

    NASA Astrophysics Data System (ADS)

    Zheng, Jia-Jia; Li, Qiao-Zhi; Dang, Jing-Shuang; Wang, Wei-Wei; Zhao, Xiang

    2016-01-01

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

  6. 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. PMID:26663758

  7. Surface-confined Ullmann coupling of thiophene substituted porphyrins

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  8. Surface-confined Ullmann coupling of thiophene substituted porphyrins.

    PubMed

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

    2015-09-11

    The covalent coupling of (5,10,15,20-tetrabromothien-2-ylporphyrinato)zinc(II) (TBrThP) molecules on the Ag(111) surface has been investigated under ultra-high-vacuum conditions, using scanning tunnelling microscopy and x-ray photoelectron spectroscopy. The findings provide atomic-level insight into surface-confined Ullmann coupling of thiophene substituted porphyrins, analyzing the progression of organometallic intermediate to final coupled state. Adsorption of the TBrThP molecules on the Ag(111) surface at room temperature is found to result in the reductive dehalogenation of the bromothienyl substituents and the subsequent formation of single strand and crosslinked coordination networks. The coordinated substrate atoms bridge the proximal thienyl groups of the organometallic intermediate, while the cleaved bromine atoms are bound on the adjacent Ag(111) surface. The intermediate complex displays a thermal lability at ∼423 K that results in the dissociation of the proximal thienyl groups with the concomitant loss of the surface bound bromine. At the thermally induced dissociation of the intermediate complex the resultant thienylporphyrin derivatives covalently couple, leading to the formation of a polymeric network of thiophene linked and meso-meso fused porphyrins. PMID:26294321

  9. 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.

  10. Self-Assembly of Russian Doll Concentric Porphyrin Nanorings.

    PubMed

    Rousseaux, Sophie A L; Gong, Juliane Q; Haver, Renée; Odell, Barbara; Claridge, Tim D W; Herz, Laura M; Anderson, Harry L

    2015-10-01

    Electronic communication between concentric macrocycles with wave functions that extend around their circumferences can lead to remarkable behavior, as illustrated by multiwalled carbon nanotubes and photosynthetic chlorophyll arrays. However, it is difficult to hold one π-conjugated molecular ring inside another. Here, we show that ring-in-ring complexes, consisting of a 6-porphyrin ring locked inside a 12-porphyrin ring, can be assembled by placing different metals in the two rings (zinc and aluminum). A bridging ligand with carboxylate and imidazole binding sites forms spokes between the two rings, resulting in a highly cooperative supramolecular self-assembly process. Excitation is transferred from the inner 6-ring to the outer 12-ring of this Russian doll complex within 40 ps. These complexes lead to a form of template-directed synthesis in which one nanoring promotes formation of a larger concentric homologous ring; here, the effective template is an eight-component noncovalent assembly. Russian doll templating provides a new approach to amplifying the size of a covalent nanostructure. PMID:26378660

  11. Self-Assembly of Russian Doll Concentric Porphyrin Nanorings

    PubMed Central

    2015-01-01

    Electronic communication between concentric macrocycles with wave functions that extend around their circumferences can lead to remarkable behavior, as illustrated by multiwalled carbon nanotubes and photosynthetic chlorophyll arrays. However, it is difficult to hold one π-conjugated molecular ring inside another. Here, we show that ring-in-ring complexes, consisting of a 6-porphyrin ring locked inside a 12-porphyrin ring, can be assembled by placing different metals in the two rings (zinc and aluminum). A bridging ligand with carboxylate and imidazole binding sites forms spokes between the two rings, resulting in a highly cooperative supramolecular self-assembly process. Excitation is transferred from the inner 6-ring to the outer 12-ring of this Russian doll complex within 40 ps. These complexes lead to a form of template-directed synthesis in which one nanoring promotes formation of a larger concentric homologous ring; here, the effective template is an eight-component noncovalent assembly. Russian doll templating provides a new approach to amplifying the size of a covalent nanostructure. PMID:26378660

  12. 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 .

  13. Aggregation of asphaltene model compounds using a porphyrin tethered to a carboxylic acid.

    PubMed

    Schulze, Matthias; Lechner, Marc P; Stryker, Jeffrey M; Tykwinski, Rik R

    2015-07-01

    A Ni(II) porphyrin functionalized with an alkyl carboxylic acid (3) has been synthesized to model the chemical behavior of the heaviest portion of petroleum, the asphaltenes. Specifically, porphyrin 3 is used in spectroscopic studies to probe aggregation with a second asphaltene model compound containing basic nitrogen (4), designed to mimic asphaltene behavior. NMR spectroscopy documents self-association of the porphyrin and aggregation with the second model compound in solution, and a Job's plot suggests a 1 : 2 stoichiometry for compounds 3 and 4. PMID:26024486

  14. Recent advances in the template-directed synthesis of porphyrin nanorings.

    PubMed

    Wang, Shu-Ping; Shen, Yan-Feng; Zhu, Ben-Yue; Wu, Jing; Li, Shijun

    2016-08-11

    The template-directed strategy is a powerful method to construct porphyrin nanorings with high complexities, wherein metalloporphyrin precursors pre-organize via supramolecular interactions of the porphyrin or its central metal with a carefully selected template, and then react with each other to deliver a final cyclic multiporphyrin structure. In this article, we review the recent breakthroughs in the template-directed synthesis methods and new structures of porphyrin or metalloporphyrin nanorings, as well as their applications in host-guest chemistry and artificial light-harvesting. PMID:27378382

  15. Fluorenyl porphyrins for combined two-photon excited fluorescence and photosensitization

    NASA Astrophysics Data System (ADS)

    Mongin, Olivier; Hugues, Vincent; Blanchard-Desce, Mireille; Merhi, Areej; Drouet, Samuel; Yao, Dandan; Paul-Roth, Christine

    2015-04-01

    The two-photon absorption (2PA), the luminescence and the photosensitization properties of porphyrin-cored fluorenyl dendrimers and meso-substituted fluorenylporphyrin monomer, dimer and trimer are described. In comparison with model tetraphenylporphyrin, these compounds combine enhanced (non-resonant) 2PA cross-sections in the near infrared and enhanced fluorescence quantum yields, together with maintained singlet oxygen generation quantum yields. 'Semi-disconnection' between fluorenyl groups and porphyrins (i.e. direct meso substitution) proved to be more efficient than non-conjugated systems (based on efficient FRET between fluorenyl antennae and porphyrins). These results are of interest for combined two-photon imaging and photodynamic therapy.

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. 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

  1. 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

  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. 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).

  4. 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

  5. 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.

  6. 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.

  7. 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

  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. Target-selective degradation of proteins by porphyrins upon visible photo-irradiation.

    PubMed

    Tanimoto, Shuho; Matsumura, Shuichi; Toshima, Kazunobu

    2008-08-21

    A porphyrin derivative effectively and selectively degraded the target transcription factor, human estrogen receptor-alpha (hER-alpha), upon visible light irradiation, in the absence of additives and under neutral conditions. PMID:18665297

  10. Photocurrent in Multilayered Assemblies of Porphyrin-Fullerene Covalent Dyads: Evidence for Channels for Charge Transport.

    PubMed

    Konev, Alexander S; Khlebnikov, Alexander F; Levin, Oleg V; Lukyanov, Daniil A; Zorin, Ivan M

    2016-04-01

    Specially designed porphyrin-fullerene dyads have been synthesized to verify literature predictions based on quantum chemistry calculations that certain porphyrin-fullerene dyads are able to self-arrange into specific structures providing channels for charge transport in a bulk mass of organic compound. According to AFM and SEM data, the newly synthesized compounds were indeed prone to some kind of self-arrangement, although to a lesser degree than was expected. A dispersion corrected DFT study of the molecular non-covalent interactions performed at the DFT-D3 (B3LYP, 6-31G*) level of theory showed that the least energy corresponded to head-to-head dimers, with close contacts of porphyrin-porphyrin and fullerene-fullerene fragments, thus providing a unit building block of the channel for charge transport. Experimental proof for the existence of channels for charge transport was obtained by observing a photocurrent in a simple photovoltaic cell. PMID:26893269

  11. Light induced catalytic intramolecular hydrofunctionalization of allylphenols mediated by porphyrin rhodium(iii) complexes.

    PubMed

    Liu, Xu; Wang, Zikuan; Fu, Xuefeng

    2016-09-14

    Catalytic intramolecular hydrofunctionalization of allylphenols to heterocyclic compounds mediated by rhodium(iii) porphyrin complexes was described. The Wacker-type intermediate β-heterocyclic alkyl rhodium complex was independently synthesized and crystallized. PMID:27482840

  12. Pd-porphyrin-cross-linked implantable hydrogels with oxygen-responsive phosphorescence.

    PubMed

    Huang, Haoyuan; Song, Wentao; Chen, Guanying; Reynard, Justin M; Ohulchanskyy, Tymish Y; Prasad, Paras N; Bright, Frank V; Lovell, Jonathan F

    2014-06-01

    Development of long-term implantable luminescent biosensors for subcutaneous oxygen has proved challenging due to difficulties in immobilizing a biocompatible matrix that prevents sensor aggregation yet maintains sufficient concentration for transdermal optical detection. Here, Pd-porphyrins can be used as PEG cross-linkers to generate a polyamide hydrogel with extreme porphyrin density (≈5 × 10(-3) m). Dye aggregation is avoided due to the spatially constraining 3D mesh formed by the porphyrins themselves. The hydrogel exhibits oxygen-responsive phosphorescence and can be stably implanted subcutaneously in mice for weeks without degradation, bleaching, or host rejection. To further facilitate oxygen detection using steady-state techniques, an oxygen-non-responsive companion hydrogel is developed by blending copper and free base porphyrins to yield intensity-matched luminescence for ratiometric detection. PMID:24259519

  13. Highly-efficient synthesis of covalent porphyrinic cages via DABCO-templated imine condensation reactions.

    PubMed

    Ding, Huimin; Meng, Xiangshi; Cui, Xu; Yang, Yihui; Zhou, Tailin; Wang, Caixing; Zeller, Matthias; Wang, Cheng

    2014-10-01

    We report a new approach to construct covalent porphyrinic cages with different spacer lengths, in which the cage compounds have been conveniently synthesized in quantitative yields, via DABCO-templated imine condensation reactions. PMID:25111246

  14. Six-Coordinate Zinc Porphyrins for Template-Directed Synthesis of Spiro-Fused Nanorings

    PubMed Central

    2015-01-01

    Five-coordinate geometry is the standard binding mode of zinc porphyrins with pyridine ligands. Here we show that pseudo-octahedral six-coordinate zinc porphyrin complexes can also be formed in solution, by taking advantage of the chelate effect. UV–vis–NIR titrations indicate that the strength of this second coordination is ca. 6–8 kJ mol–1. We have used the formation of six-coordinate zinc porphyrin complexes to achieve the template-directed synthesis of a 3D π-conjugated spiro-fused array of 11 porphyrin units, covalently connected in a nontrivial topology. Time-resolved fluorescence anisotropy experiments show that electronic excitation delocalizes between the two perpendicular nanorings of this spiro-system within the experimental time-resolution of 270 fs. PMID:26536147

  15. 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.

  16. Mechanothermally induced conformational switch of a porphyrin dimer in a polymer film.

    PubMed

    Doan, Hung; Raut, Sangram L; Yale, David; Balaz, Milan; Dzyuba, Sergei V; Gryczynski, Zygmunt

    2016-07-21

    Stretching a polymer film induces a conformational change (from the twisted to planar state) in the embedded porphyrin dimer, as evidenced by steady-state and time-resolved emission spectra. PMID:27294828

  17. 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...

  18. XAFS and crystallographic studies of Ni(II) porphyrins in single crystals and in solution

    SciTech Connect

    Renner, M.W.; Furenlid, L.R.; Barkigia, K.M.; Fajer, J.

    1996-09-01

    Abstract. Nickel porphyrins serve as models for the active sites of several biological processes. Crystallographic and EXAFS results for a Ni meso-tetrapropyl porphyrin (NiTPrP) yield different Ni-N distances in solution and in the solid state. The Ni-N distances determined by single crystal polarized XAS and X-ray diffraction agree well. Polarized XANES experiments further establish that the pre-edge feature observed in square planar Ni(II) complexes is a ls-4pz transition. The single crystal and solution EXAFS results demonstrate that conformational variations of the porphyrin macrocycle can readily be imposed by environmental and/or packing forces and can thereby modulate the chemical and physical properties of porphyrinic chromophores and prosthetic groups.

  19. Six-Coordinate Zinc Porphyrins for Template-Directed Synthesis of Spiro-Fused Nanorings.

    PubMed

    Favereau, Ludovic; Cnossen, Arjen; Kelber, Julien B; Gong, Juliane Q; Oetterli, René M; Cremers, Jonathan; Herz, Laura M; Anderson, Harry L

    2015-11-18

    Five-coordinate geometry is the standard binding mode of zinc porphyrins with pyridine ligands. Here we show that pseudo-octahedral six-coordinate zinc porphyrin complexes can also be formed in solution, by taking advantage of the chelate effect. UV-vis-NIR titrations indicate that the strength of this second coordination is ca. 6-8 kJ mol(-1). We have used the formation of six-coordinate zinc porphyrin complexes to achieve the template-directed synthesis of a 3D π-conjugated spiro-fused array of 11 porphyrin units, covalently connected in a nontrivial topology. Time-resolved fluorescence anisotropy experiments show that electronic excitation delocalizes between the two perpendicular nanorings of this spiro-system within the experimental time-resolution of 270 fs. PMID:26536147

  20. Pd-Porphyrin-Crosslinked Implantable Hydrogels with Oxygen-Responsive Phosphorescence

    PubMed Central

    Huang, Haoyuan; Song, Wentao; Chen, Guanying; Reynard, Justin M.; Ohulchanskyy, Tymish Y.; Prasad, Paras N.; Bright, Frank V.

    2014-01-01

    Development of long-term implantable luminescent biosensors for subcutaneous oxygen has proved challenging due to difficulties in immobilizing a biocompatible matrix that prevents sensor aggregation yet maintains sufficient concentration for transdermal optical detection. Here, we demonstrate that Pd-porphyrins can be used as PEG crosslinkers to generate a polyamide hydrogel with extreme porphyrin density (~5 mM). Dye aggregation was avoided due to the spatially constraining 3-D mesh formed by the porphyrins themselves. The hydrogel exhibited oxygen-responsive phosphorescence and could be stably implanted subcutaneously in mice for weeks without degradation, bleaching or host rejection. To further facilitate oxygen detection using steady state techniques, we developed an oxygen non-responsive companion hydrogel by blending copper and free base porphyrins to yield intensity-matched luminescence for ratiometric detection. PMID:24259519

  1. Increased Porphyrins in Primary Liver Cancer Mainly Reflect a Parallel Liver Disease

    PubMed Central

    Kaczynski, Jerzy; Hansson, Göran; Wallerstedt, Sven

    2009-01-01

    Hepatic porphyries have been associated with an increased risk of primary liver cancer (PLC), which on the other hand may cause an increased porphyrin production. To evaluate the role of an underlying liver disorder we analyzed porphyrins in patients with hepatocellular carcinoma (HCC) (n = 65), cholangiocellular carcinoma (n = 3), or suspected PLC, which turned out to be metastases (n = 18) or a benign disorder (n = 11). None of the patients had a family history of porphyry or clinical signs of porphyry. Increased aminolevulinic acid or porphyrin values were common not only in patients with PLC (43%) but also in metastatic (50%) and benign (64%) liver disorders. The corresponding proportion for HCC patients with liver cirrhosis (55%) was higher (P < .05) than in those without cirrhosis (17%). We conclude that symptomatic porphyries are unusual in PLC, whereas elevated urinary and/or faecal porphyrins are common, primarily reflecting a parallel liver disease and not the PLC. PMID:19841684

  2. Energy transfer on demand: photoswitch-directed behavior of metal-porphyrin frameworks.

    PubMed

    Williams, Derek E; Rietman, Joseph A; Maier, Josef M; Tan, Rui; Greytak, Andrew B; Smith, Mark D; Krause, Jeanette A; Shustova, Natalia B

    2014-08-27

    In this paper, a photochromic diarylethene-based derivative that is coordinatively immobilized within an extended porphyrin framework is shown to maintain its photoswitchable behavior and to direct the photophysical properties of the host. In particular, emission of a framework composed of bis(5-pyridyl-2-methyl-3-thienyl)cyclopentene (BPMTC) and tetrakis(4-carboxyphenyl)porphyrin (H4TCPP) ligands anchored by Zn(2+) ions can be altered as a function of incident light. We attribute the observed cyclic fluorescence behavior of the synthesized porphyrin-BPMTC array to activation of energy transfer (ET) pathways through BPMTC photoisomerization. Time-resolved photoluminescence measurements show a decrease in average porphyrin emission lifetime upon BPMTC insertion, consistent with an ET-based mechanism. These studies portend the possible utilization of photochromic ligands to direct chromophore behavior in large light-harvesting ensembles. PMID:25116646

  3. 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).

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

    PubMed Central

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

    2015-01-01

    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). PMID:25716054

  5. Au nanoparticles and graphene quantum dots co-modified glassy carbon electrode for catechol sensing

    NASA Astrophysics Data System (ADS)

    Zhao, Xuan; He, Dawei; Wang, Yongsheng; Hu, Yin; Fu, Chen

    2016-03-01

    In this letter, the gold nanoparticles and graphene quantum dots were applied to the modification of glassy carbon electrode for the detection of catechol. The synergist cooperation between gold nanoparticles and graphene quantum dots can increase specific surface area and enhance electronic and catalytic properties of glassy carbon electrode. The detection limit of catechol is 0.869 μmol/L, demonstrating the superior detection efficiency of the gold nanoparticles and graphene quantum dots co-modified glassy carbon electrode as a new sensing platform.

  6. 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

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

    PubMed

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

    2015-08-13

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

  8. 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

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

    PubMed

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

    2015-07-01

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

  10. 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.

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

    PubMed

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

    2015-10-10

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

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

    NASA Astrophysics Data System (ADS)

    Mongwaketsi, N.; Khamlich, S.; Klumperman, B.; Sparrow, R.; Maaza, M.

    2012-05-01

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

  14. Structural consequences of spin conversion in a sterically encumbered Ni(II) porphyrin

    SciTech Connect

    Barkigia, K.M.; Nelson, N.Y.; Renner, M.W.; Smith, K.M.; Fajer, J.

    1999-10-14

    The crystal structure of a pyridine-ligated, high-spin Ni(II) complex of 2,3,7,8,12,13,17,18-octabromo-5, 15-bis(isopropyl)-10,20-bis(isopropylidenyl) porphyrin, is reported and compared to the unligated, low-spin Ni(II) complex previously reported. The results demonstrate that conversion to high-spin Ni(II) in nonplanar, sterically encumbered porphyrins induces a significant core expansion about the Ni while nonplanarity is still retained. The expansion of the core parameters (Ni-N, Ct-C{alpha}, Ct-Cmexo) and the Ni-N{sub axial} distances are characteristic of the d{sub x{sup 2}{minus}y{sup 2}} orbital occupancies in high-spin Ni(II) porphyrins and document the structural consequences of the spin conversion in severely nonplanar Ni(II) porphyrins. The stereochemical results are particularly relevant to ligation effects in nonplanar Ni biomolecules and synthetic porphyrins increasingly used as biomimetic models of conformational effects in chromophores and prosthetic groups in vivo, and to the remarkably wide range of lifetimes observed for excited (d,d) states in nonplanar, sterically constrained Ni(II) porphyrins in which the d{sub x{sup 2}{minus}y{sup 2}} and d{sub z{sup 2}} orbitals are also populated.

  15. Two-photon Absorption Enhancement of Polymer-templated Porphyrin-based J-Aggregates

    PubMed Central

    Biswas, Sanchita; Ahn, Hyo-Yang; Bondar, Mykhailo V.; Belfield, Kevin D.

    2011-01-01

    Supramolecular structures based on organized assemblies of macrocyclic chromophores, particularly porphyrin-based dyes, have attracted widespread interest as components of molecular devices with potential applications in molecular electronics, artificial light harvesting, and pharmacology. We report the formation of J-aggregates of two porphyrin-based dyes, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TSPP, 4) and an amino tris-sulfonate analog (5) in water using a functionalized norbornene-based homopolymer, synthesized by ring opening metathesis polymerization (ROMP). Ionic interactions of the cationic side chains (ammonium groups) of the polymer under acidic conditions with the negatively charged sulfonate groups of the porphyrins facilitated polymer template enhanced J-aggregation of the porphyrin dyes. J-aggregation behavior was investigated photophysically by UV-vis absorption along with steady-state and time-resolved fluorescence studies. Two-photon absorption (2PA) was enhanced by about an order of magnitude for the J-aggregated TSPP relative to its free base. Significantly, the 2PA cross section of the polymer-templated TSPP J-aggregate was up to three times higher than the J-aggregated TSPP in the absence of the polymer template while the 2PA cross section for polymer-templated J-aggregates of 5 increased substantially, up to ca. 10,000 GM, suggesting a prominent role of polymer-templating to facilitate porphyrin aggregation and greatly enhance nonlinear absorption. PMID:22188399

  16. 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

  17. Optical limiting processes in derivatized fullerenes and porphyrins/phthalocyanines

    SciTech Connect

    Kohlman, R.; Klimov, V.; Shi, X.

    1998-07-01

    The authors review their results from spectral studies of the ultrafast excited-state absorption in fullerenes and derivatized fullerenes. These results allow determination of both the spectral response of reverse saturable absorption (RSA) nonlinearities such as optical limiting (OL) in fullerenes, and the dynamical response for different morphologies. The authors have investigated the effects of thin film and various sol-gel glass environments on the nanosecond OL and femtosecond dynamics of derivatized fullerenes. These data provide evidence of decay pathways which compete with the intersystem crossing to a triplet from the initial singlet states. With appropriate processing, however, the OL response of derivatized-fullerene sol-gel glasses can be enhanced to approach that of the same molecule in solution, while significantly enhancing the optical damage threshold. The optical limiting of these derivatized fullerenes is compared with that of various porphyrin and phthalocyanine molecules.

  18. 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.

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

    PubMed

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

    2009-07-01

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

  20. 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

  1. Respiratory Monitoring by Porphyrin Modified Quartz Crystal Microbalance Sensors

    PubMed Central

    Selyanchyn, Roman; Korposh, Serhiy; Wakamatsu, Shunichi; Lee, Seung-Woo

    2011-01-01

    A respiratory monitoring system based on a quartz crystal microbalance (QCM) sensor with a functional film was designed and investigated. Porphyrins 5,10,15,20-tetrakis-(4-sulfophenyl)-21H,23H-porphine (TSPP) and 5,10,15,20-tetrakis-(4-sulfophenyl)-21H, 23H-porphine manganese (III) chloride (MnTSPP) used as sensitive elements were assembled with a poly(diallyldimethyl ammonium chloride) (PDDA). Films were deposited on the QCM resonators using layer-by-layer method in order to develop the sensor. The developed system, in which the sensor response reflects lung movements, was able to track human respiration providing respiratory rate (RR) and respiratory pattern (RP). The sensor system was tested on healthy volunteers to compare RPs and calculate RRs. The operation principle of the proposed system is based on the fast adsorption/desorption behavior of water originated from human breath into the sensor films deposited on the QCM electrode. PMID:22346621

  2. Reduction of porphyrins to porphyrinogens with palladium on carbon

    PubMed Central

    Bergonia, Hector A.; Phillips, John D.; Kushner, James P.

    2008-01-01

    Porphyrinogens serve as substrates for three heme biosynthetic enzymes. Porphyrinogens are highly unstable and must be generated as an integral part of enzyme assays. Methods commonly utilized to generate porphyrinogens include chemical reduction using sodium amalgam or sodium borohydride and enzymatic generation from porphobilinogen. Chemical reduction yields porphyrinogens in highly alkaline solutions with high ionic strength, while enzymatic generation requires purified enzymes, deproteination and complete buffer replacement. This report describes an improved method for reducing porphyrins to porphyrinogens using palladium on carbon as a catalyst under hydrogen at ambient temperature and pressure in the dark. The palladium catalyst is removed by filtration, the filtrate blown dry with an inert gas and the dried porphyrinogen can be dissolved in a buffer compatible with biological studies. PMID:18845122

  3. Jump in the electrical conductivity of shock-compressed glassy carbon

    NASA Astrophysics Data System (ADS)

    Molodets, A. M.; Golyshev, A. A.; Emel'yanov, A. N.; Shul'ga, Yu. M.; Fortov, V. E.

    2014-04-01

    The effect of high dynamic pressures on the electrical conductivity of the amorphous conducting carbon phase (glassy carbon) has been studied. The electrical conductivity of glassy carbon samples has been measured under the condition of shock compression and subsequent release wave. The history of the shock loading of glassy carbon has been calculated with the developed semiempirical equations of state. It has been shown the electrical conductivity of glassy carbon samples in the compression phase at a pressure of 45(5) GPa decreases abruptly by two orders of magnitude. In the relief phase, partially reversible change in the electrical conductivity of an amorphous carbon sample occurs. The recorded effect has been treated as a result of a partially reversible physicochemical transformation of shock-compressed amorphous carbon.

  4. Sub-nanoscale nanoimprint fabrication of atomically stepped glassy substrates of silicate glass and acryl polymer

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Mamoru

    2015-11-01

    In the nanoimprint process, the resolution limit of patterning has attracted much attention from both scientific and industrial aspects. In this article, we briefly review the main achievements of our research group on sub-nanoscale nanoimprint fabrication of atomically patterned glassy substrates of oxide glass and polymer. By applying the sapphire (α-Al2O3 single crystal) wafers with self-organized nanopatterns of atomic steps as thermal nanoimprinting molds, we successfully transferred their nanoscale patterns onto the surfaces of glassy substrates such as soda-lime silicate glasses and poly(methyl methacrylate) polymers. The surfaces of nanoimprinted glassy materials exhibited regularly arrayed atomic stairs with 0.2-0.3 nm step height, which were in good agreement with the sub-nanopatterns of sapphire molds. These atomically stepped morphologies on the glassy substrates were found to be stable for about 1 year.

  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. Synthesis of porphyrins bearing 1-4 hydroxymethyl groups and other one-carbon oxygenic substituents in distinct patterns

    PubMed Central

    Yao, Zhen; Bhaumik, Jayeeta; Dhanalekshmi, Savithri; Ptaszek, Marcin; Rodriguez, Phillip A.; Lindsey, Jonathan S.

    2007-01-01

    Porphyrins that bear one-carbon oxygenic substituents (hydroxymethyl, formyl, ester) directly attached to the macrocycle afford a compact architecture that is attractive for diverse applications. Routes to 9 porphyrins bearing such groups in distinct architectures (A4-, trans-A2-, trans-A2B2-, trans-AB- and trans-AB2C-porphyrins) have been explored (A = hydroxymethyl), including porphyrins bearing two one-carbon units in different oxidation states (hydroxymethyl/ester, formyl/ester). The hydroxymethyl group was introduced via TBDMS-protected dipyrromethane precursors. PMID:18037972

  7. Robust organic lasers comprising glassy-cholesteric pentafluorene doped with a red-emitting oligofluorene

    NASA Astrophysics Data System (ADS)

    Wei, Simon K. H.; Chen, Shaw H.; Dolgaleva, Ksenia; Lukishova, Svetlana G.; Boyd, Robert W.

    2009-01-01

    Doped with a red-emitting oligofluorene, fluid and glassy cholesteric liquid crystal (CLC) films are characterized by similar lasing thresholds and efficiencies. With picosecond excitations the output from a glassy CLC laser is temporally stable, but that from a fluid CLC laser decays with time. The difference in stability is attributable to external perturbations on supramolecular structure in the fluid but not the solid state, such as heating through optical pumping, light-induced pitch dilation, and laser-induced flow.

  8. Structural and thermodynamic aspects of plasticization and antiplasticization in glassy encapsulation and biostabilization matrices.

    PubMed

    Ubbink, Job

    2016-05-01

    The structural and thermodynamic properties of glassy carbohydrate matrices for the encapsulation and biostabilization of sensitive bioactive compounds, such as pharmaceutically active proteins and oxidation-sensitive compounds, are reviewed in the context of the plasticization and antiplasticization of glassy carbohydrates of intermediate and high molecular weight by low molecular weight diluents. Plasticization and antiplasticization may be monitored either by dynamic measures or by structural and thermodynamic features of the glassy matrices. Specifically, it is demonstrated that the decrease in size of the molecular free volume holes with increasing diluent content, as determined by positron annihilation lifetime spectroscopy (PALS), is related to the antiplasticization of glassy carbohydrate matrices, resulting in increased barrier properties of the glassy matrix. As far as could be ascertained from the available data, the regimes as identified by PALS map on those detected by neutron scattering and dielectric spectroscopy for glassy matrices consisting of trehalose and the diluent glycerol. The review is concluded by a survey of the published results on the stability of bioactive compounds encapsulated in carbohydrate glasses and an overview of outstanding questions. PMID:26748258

  9. 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.

  10. Growth, microstructure, and failure of crazes in glassy polymers

    NASA Astrophysics Data System (ADS)

    Rottler, Jörg; Robbins, Mark O.

    2003-07-01

    We report on an extensive study of craze formation in glassy polymers. Molecular dynamics simulations of a coarse-grained bead-spring model were employed to investigate the molecular level processes during craze nucleation, widening, and breakdown for a wide range of temperature, polymer chain length N, entanglement length Ne, and strength of adhesive interactions between polymer chains. Craze widening proceeds via a fibril-drawing process at constant drawing stress. The extension ratio is determined by the entanglement length, and the characteristic length of stretched chain segments in the polymer craze is Ne/3. In the craze, tension is mostly carried by the covalent backbone bonds, and the force distribution develops an exponential tail at large tensile forces. The failure mode of crazes changes from disentanglement to scission for N/Ne˜10, and breakdown through scission is governed by large stress fluctuations. The simulations also reveal inconsistencies with previous theoretical models of craze widening, which were based on continuum level hydrodynamics.

  11. Gamma ray attenuation in a developed borate glassy system

    NASA Astrophysics Data System (ADS)

    Saeed, Aly; El shazly, R. M.; Elbashar, Y. H.; Abou El-azm, A. M.; El-Okr, M. M.; Comsan, M. N. H.; Osman, A. M.; Abdal-monem, A. M.; El-Sersy, A. R.

    2014-09-01

    Measurements and calculations of gamma ray attenuation coefficients in glass barriers of xBaO-5ZnO-5MgO-14Na2O--1Li2O-(75-x)B2O3, previously prepared by the melt-quenching technique [1], were performed for γ-ray of energies 121.8, 244.7, 344.14, 661.66, 778.7, 974, 1086.7, 1173.24, 1332.5, and 1407.9 keV; which emitted from 152Eu, 137Cs, and 60Co radioactive gamma ray sources. The transmitted γ-rays were detected by 3″×3″ and 5″×5″ NaI (Tl) scintillation γ-ray spectrometers, and a highly calibrated survey meter. The mass attenuation coefficients of γ-rays (σ(E) were deduced from the attenuation curves, while the WinXCom computer program (version 3.1) was used to calculate the mass attenuation coefficients of γ-rays for such energies at different barium concentrations of a glassy system. A good agreement between both experimental and theoretical results was achieved as well as results obtained by other workers in similar field.

  12. CO2 reduction catalyzed by mercaptopteridine on glassy carbon.

    PubMed

    Xiang, Dongmei; Magana, Donny; Dyer, R Brian

    2014-10-01

    The catalytic reduction of CO2 is of great current interest because of its role in climate change and the energy cycle. We report a pterin electrocatalyst, 6,7-dimethyl-4-hydroxy-2-mercaptopteridine (PTE), that catalyzes the reduction of CO2 and formic acid on a glassy carbon electrode. Pterins are natural cofactors for a wide range of enzymes, functioning as redox mediators and C1 carriers, but they have not been exploited as electrocatalysts. Bulk electrolysis of a saturated CO2 solution in the presence of the PTE catalyst produces methanol, as confirmed by gas chromatography and (13)C NMR spectroscopy, with a Faradaic efficiency of 10-23%. FTIR spectroelectrochemistry detected a progression of two-electron reduction products during bulk electrolysis, including formate, aqueous formaldehyde, and methanol. A transient intermediate was also detected by FTIR and tentatively assigned as a PTE carbamate. The results demonstrate that PTE catalyzes the reduction of CO2 at low overpotential and without the involvement of any metal. PMID:25259884

  13. 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.

  14. Real-time nonequilibrium dynamics of quantum glassy systems

    NASA Astrophysics Data System (ADS)

    Cugliandolo, Leticia F.; Lozano, Gustavo

    1999-01-01

    We develop a systematic analytic approach to aging effects in quantum disordered systems in contact with an environment. Within the closed-time path-integral formalism we include dissipation by coupling the system to a set of independent harmonic oscillators that mimic a quantum thermal bath. After integrating over the bath variables and averaging over disorder we obtain an effective action that determines the real-time dynamics of the system. The classical limit yields the Martin-Siggia-Rose generating functional associated to a colored noise. We apply this general formalism to a prototype model related to the p spin glass. We show that the model has a dynamic phase transition separating the paramagnetic from the spin-glass phase and that quantum fluctuations depress the transition temperature until a quantum critical point is reached. We show that the dynamics in the paramagnetic phase is stationary but presents an interesting crossover from a region controlled by the classical critical point to another one controlled by the quantum critical point. The most characteristic property of the dynamics in a glassy phase, namely, aging, survives the quantum fluctuations. In the subcritical region the quantum fluctuation-dissipation theorem is modified in a way that is consistent with the notion of effective temperatures introduced for the classical case. We discuss these results in connection with recent experiments in dipolar quantum spin glasses and the relevance of the effective temperatures with respect to the understanding of the low-temperature dynamics.

  15. Evolution of Entanglements During Crazing of Glassy Polymers

    NASA Astrophysics Data System (ADS)

    Ge, Ting; Robbins, Mark O.; Hoy, Robert; Anogiannakis, Stefanos; Tzoumanekas, Christos; Theodorou, Doros

    2011-03-01

    Craze formation increases the fracture energy of glassy polymers by orders of magnitude. The polymer volume expands by an extension ratio which is assumed to be determined by the entanglement network. We test this assumption with molecular simulations that use the Contour Reduction Topological Analysis (CReTA) algorithm to follow topological constraints (TCs) associated with the entanglement network. The TCs are identified with contacts between chains after applying CReTA. Within systematic errors, crazing does not change the number of TCs or the distribution of chemical distances between them. Moreover, about 75% of the contacts remain between the same chains at nearly the same location. The 25% of contacts that change do not reflect a comparable loss of entanglements. Instead, small displacements within the tube change which chains contact after CReTA. This interpretation is tested by adding fixed crosslinks to a sparse entanglement network and crazing preoriented samples. This material is based upon work supported by NSF Grant DMR 108474.

  16. Entanglements and the Mechanical Properties of Glassy Polymers

    NASA Astrophysics Data System (ADS)

    Robbins, Mark

    2011-03-01

    The response of glassy polymers to shear or tensile strain is strongly influenced by the entanglement network that is inherited from the melt. Molecular dynamics simulations are used to probe the microscopic origins of stress-strain curves and their connection to entanglements. The latter are identified in real space by examining topological constraints along the primitive path. The first part of the talk will consider the process of craze formation, where the entanglement density is correlated to the volume increase during crazing. Simulations show that entanglements are preserved during crazing, but the craze density does not correspond to pulling chains taut between entanglements. The second part of the talk will examine the effect of entanglements on strain hardening under uniaxial strain. The stress is directly associated with the degree of orientational order along the strain axis, and nearly independent of order along perpendicular directions. Studies with mixtures of short and long chains show that the degree of order is independent of the surrounding chains. The final part of the talk will examine the strength of welds formed by diffusion across polymer interfaces. The shear stress follows the bulk response until chains are pulled taut on the scale of the length of segments that have diffused across the interface. When this length is several times the entanglement length, the maximum shear stress saturates at the bulk value and chains fail through scission. Similar trends are found for the fracture energy in tensile loading. This material is based upon work supported by NSF Grant DMR 108474.

  17. 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

  18. 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.

  19. Glassy Dynamics versus Thermodynamics: The Case of 2-Adamantanone.

    PubMed

    Szewczyk, D; Jeżowski, A; Vdovichenko, G A; Krivchikov, A I; Bermejo, F J; Tamarit, J Ll; Pardo, L C; Taylor, J W

    2015-07-01

    The heat capacity and thermal conductivity of the monoclinic and the fully ordered orthorhombic phases of 2-adamantanone (C10H14O) have been measured for temperatures between 2 and 150 K. The heat capacities for both phases are shown to be strikingly close regardless of the site disorder present in the monoclinic crystal which arises from the occupancy of three nonequivalent sites for the oxygen atom. The heat capacity curves are also well accounted for by an evaluation carried out within the harmonic approximation in terms of the g(ω) vibrational frequency distributions measured by means of inelastic neutron scattering. Such spectral functions show however a significant excess of low frequency modes for the crystal showing statistical disorder. In contrast, large differences are found for the thermal conductivity which contrary to what could be expected, shows the substitutionally disordered crystal to exhibit better heat transport properties than the fully ordered orthorhombic phase. Such an anomalous behavior is understood from examination of the crystalline structure of the orthorhombic phase which leads to very strong scattering of heat-carrying phonons due to grain boundary effects able to yield a largely reduced value of the conductivity as well as to a plateau-like feature at intermediate temperatures which contrasts with a bell-shaped maximum shown by data pertaining the disordered crystal. The relevance of the present findings within the context of glassy dynamics of the orientational glass state is finally discussed. PMID:26073682

  20. 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

  1. 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.

  2. Electrochemical determination of mesotrione at organoclay modified glassy carbon electrodes.

    PubMed

    Kamga Wagheu, Josephine; Forano, Claude; Besse-Hoggan, Pascale; Tonle, Ignas K; Ngameni, Emmanuel; Mousty, Christine

    2013-01-15

    A natural Cameroonian smectite-type clay (SaNa) was exchanged with cationic surfactants, namely cetyltrimethylammonium (CTA) and didodecyldimethyl ammonium (DDA) modifying its physico-chemical properties. The resulting organoclays that have higher adsorption capacity for mesotrione than the pristine SaNa clay, have been used as modifiers of glassy carbon electrode for the electrochemical detection of this herbicide by square wave voltammetry. The stripping performances of SaNa, SaCTA and SaDDA modified electrodes were therefore evaluated and the experimental parameters were optimized. SaDDA gives the best results in deoxygenated acetate buffer solution (pH 6.0) after 2 min accumulation under open circuit conditions. Under optimal conditions, the reduction current is proportional to mesotrione concentration in the range from 0.25 to 2.5 μM with a detection limit of 0.26 μM. The fabricated electrode was also applied for the commercial formulation CALLISTO, used in European maize market. PMID:23200396

  3. Frequency-dependent conductivity in bismuth-vanadate glassy semiconductors

    NASA Astrophysics Data System (ADS)

    Ghosh, Aswini

    1990-01-01

    The first measurements are reported for the frequency-dependent (ac) conductivity (real as well as imaginary parts) for various compositions of the bismuth-vanadate glassy semiconductors in the frequency range 102-105 Hz and in the temperature range 77-420 K. The behavior of the ac conductivity is broadly similar to what has been observed previously in many other types of amorphous semiconductors, namely, nearly linear frequency dependence and weak temperature dependence. The experimental results are analyzed with reference to various theoretical models based on quantum-mechanical tunneling and classical hopping over barriers. The analysis shows that the temperature dependence of the ac conductivity is consistent with the simple quantum-mechanical tunneling model at low temperatures; however, this model completely fails to predict the observed temperature dependence of the frequency exponent. The overlapping-large-polaron tunneling model can explain the temperature dependence of the frequency exponent at low temperatures. Fitting of this model to the low-temperature data yields a reasonable value of the wave-function decay constant. However, this model predicts the temperature dependence of the ac conductivity much higher than what actual data showed. The correlated barrier hopping model is consistent with the temperature dependence of both the ac conductivity and its frequency exponent. This model provides reasonable values of the maximum barrier heights but higher values of characteristic relaxation times.

  4. 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.

  5. 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

  6. 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

  7. 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

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

    PubMed

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

    2005-05-13

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  10. 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

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

    EPA Science Inventory

    Abstract

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

  12. 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

  13. 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.

  14. 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.

  15. 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.

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

    PubMed

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

    2005-04-01

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

  17. Synthesis, Characterization, and Reactivities of Manganese(V)-Oxo Porphyrin Complexes

    PubMed Central

    Song, Woon Ju; Seo, Mi Sook; George, Serena DeBeer; Ohta, Takehiro; Song, Rita; Kang, Min-Jung; Tosha, Takehiko; Kitagawa, Teizo; Solomon, Edward I.; Nam, Wonwoo

    2010-01-01

    The reactions of manganese(III) porphyrin complexes with terminal oxidants, such as m-chloroperbenzoic acid, iodosylarenes, and H2O2, produced high-valent manganese(V)-oxo porphyrins in the presence of base in organic solvents at room temperature. The manganese(V)-oxo porphyrins have been characterized with various spectroscopic techniques, including UV-vis, EPR, 1H and 19F NMR, resonance Raman, and X-ray absorption spectroscopy. The combined spectroscopic results indicate that the manganese(V)-oxo porphyrins are diamagnetic low-spin (S = 0) species with a longer, weaker Mn-O bond than in previously reported Mn(V)-oxo complexes of non-porphyrin ligands. This is indicative of double bond character between the manganese(V) ion and the oxygen atom, and may be attributed to the presence of a trans-axial ligand. The [(Porp)MnV=O]+ species are stable in the presence of base at room temperature. The stability of the intermediates is dependent on base concentration. In the absence of base, (Porp)MnIV=O is generated instead of the [(Porp)MnV=O]+ species. The stability of the [(Porp)MnV=O]+ species also depends on the electronic nature of porphyrin ligands; [(Porp)MnV=O]+ complexes bearing electron-deficient porphyrin ligands are more stable than those bearing electron-rich porphyrins. Reactivity studies of manganese(V)-oxo porphyrins revealed that the intermediates are capable of oxygenating PPh3 and thioanisoles, but not olefins and alkanes at room temperature. These results indicate that the oxidizing power of [(Porp)MnV=O]+ is low in the presence of base. However, when the [(Porp)MnV=O]+ complexes were associated with iodosylbenzene in the presence of olefins and alkanes, high yields of oxygenated products were obtained in the catalytic olefin epoxidation and alkane hydroxylation reactions. Mechanistic aspects, such as oxygen exchange between [(Porp)MnV=16O]+ and H218O, are also discussed. PMID:17263410

  18. Synthesis, characterization, and reactivities of manganese(V)-oxo porphyrin complexes.

    PubMed

    Song, Woon Ju; Seo, Mi Sook; George, Serena Debeer; Ohta, Takehiro; Song, Rita; Kang, Min-Jung; Tosha, Takehiko; Kitagawa, Teizo; Solomon, Edward I; Nam, Wonwoo

    2007-02-01

    The reactions of manganese(III) porphyrin complexes with terminal oxidants, such as m-chloroperbenzoic acid, iodosylarenes, and H(2)O(2), produced high-valent manganese(V)-oxo porphyrins in the presence of base in organic solvents at room temperature. The manganese(V)-oxo porphyrins have been characterized with various spectroscopic techniques, including UV-vis, EPR, 1H and 19F NMR, resonance Raman, and X-ray absorption spectroscopy. The combined spectroscopic results indicate that the manganese(V)-oxo porphyrins are diamagnetic low-spin (S = 0) species with a longer, weaker Mn-O bond than in previously reported Mn(V)-oxo complexes of non-porphyrin ligands. This is indicative of double-bond character between the manganese(V) ion and the oxygen atom and may be attributed to the presence of a trans axial ligand. The [(Porp)Mn(V)=O](+) species are stable in the presence of base at room temperature. The stability of the intermediates is dependent on base concentration. In the absence of base, (Porp)Mn(IV)=O is generated instead of the [(Porp)Mn(V)=O](+) species. The stability of the [(Porp)Mn(V)=O](+) species also depends on the electronic nature of the porphyrin ligands: [(Porp)Mn(V)=O](+) complexes bearing electron-deficient porphyrin ligands are more stable than those bearing electron-rich porphyrins. Reactivity studies of manganese(V)-oxo porphyrins revealed that the intermediates are capable of oxygenating PPh(3) and thioanisoles, but not olefins and alkanes at room temperature. These results indicate that the oxidizing power of [(Porp)Mn(V)=O](+) is low in the presence of base. However, when the [(Porp)Mn(V)=O](+) complexes were associated with iodosylbenzene in the presence of olefins and alkanes, high yields of oxygenated products were obtained in the catalytic olefin epoxidation and alkane hydroxylation reactions. Mechanistic aspects, such as oxygen exchange between [(Porp)Mn(V)=16O](+) and H(2)(18)O, are also discussed. PMID:17263410

  19. 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).

  20. 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.

  1. 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

  2. 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

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

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

    1990-06-01

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

  5. 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

  6. 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

  7. Intercalative and nonintercalative binding of large cationic porphyrin ligands to calf thymus DNA.

    PubMed Central

    Carvlin, M J; Fiel, R J

    1983-01-01

    The large meso-substituted porphine, meso-tetra(4-N-methylpyridyl)porphine has been identified as a DNA-interactive ligand with a capacity for intercalation (1,2). Subsequently, the 2-N-methyl, 3-N-methyl and N-trimethylanilinium analogues of this porphyrin intercalator have been obtained for physico-chemical analyses (absorption spectroscopy, viscometry, circular dichroism, unwinding of supercoiled DNA). In this paper we discuss the factors affecting the character of porphyrin binding (intercalative, as is the case for the 4-N-methyl and 3-N-methyl porphines, versus non-intercalative, as is the case for the 2-N-methyl and N-trimethylanilinium porphines) and the impact that porphyrins' binding has upon the structure of DNA. The molecular conformation of the porphyrin ligand varies slightly within this series so that the ability of a given porphyrin to intercalate may be correlated with the arrangement of charged groups, the planarity of the porphine ring and the effective width of the individual molecules. The results from these studies indicate that sequence selective binding occurs within a small aperture of solution conditions. Images PMID:6889138

  8. First insight into catalytic activity of anionic iron porphyrins immobilized on exfoliated layered double hydroxides.

    PubMed

    Nakagaki, Shirley; Halma, Matilte; Bail, Alesandro; Arízaga, Gregório Guadalupe Carbajal; Wypych, Fernando

    2005-01-15

    Mg-Al layered double hydroxide (LDH) intercalated with glycinate anions was synthesized through co-precipitation and exfoliated in formamide and the single-layer suspension was reacted with aqueous iron porphyrin solutions (Fe(TDFSPP) and Fe(TCFSPP)). The obtained materials were characterized by X-ray powder diffraction, UV-vis, and electron paramagnetic resonance and investigated in the oxidation reaction of cyclooctene and cyclohexane using iodosylbenzene as oxidant. The iron porphyrin seems to be immobilized at the surface of the glycinate intercalated LDH. The catalytic activities obtained in heterogeneous media for iron porphyrin, Fe(TDFSPP), was superior to the results obtained under homogeneous conditions, but the opposite effect was observed on the Fe(TCFSPP), indicating that, instead of the structural similarity of both iron porphyrins (second-generation porphyrins), the immobilization of each one produced different catalysts. The best catalytic activity of the Fe(TDFSPP)/Gly-LDH, compared to Fe(TCFSPP)/Gly-LDH, can be explained by the easy access of the oxidant and the substrate to the catalytic sites in the former, probably located at the surface of the layered double hydroxide pillared with glycinate anions. A model for the immobilization and a mechanism for the oxidation reaction will be discussed. PMID:15571697

  9. Conformational effects of peripheral substituents and axial ligands in sterically crowded porphyrins

    SciTech Connect

    Nurco, D.J.; Smith, K.M.; Fajer, J.

    1997-12-31

    Crystallographic results for peripherally substituted porphyrins illustrate effects of steric crowding, axial ligation and {pi}-{pi} interactions on the structures of metalloporphyrins that begin to resemble the architectures found for porphyrinic prosthetic groups and chromophores in vivo. (1) Metalloporphyrins with multiple peripheral substituents can adopt planar, saddled, ruffled or {open_quotes}wavy{close_quotes} conformations that persist upon axial ligation of the metal. (2) In porphyrins with substituents at all peripheral positions, the substituents form pockets that force the axial ligands to align in specific orientations relative to each other and to the axes defined by the porphyrin estrogens. (3) The enforced alignment of the axial ligands caused by the substituent pocket prevents aromatic ligands from rotating around the coordination axis with intriguing consequences: the axial ligands can be forced to tip off axis because of steric crowding by adjacent molecules in the crystal lattice. (4) In porphyrins with meso substituents only, the axial ligands are free to rotate but {pi}-{pi} interactions and collacial stacking between adjacent molecules in the crystal also induce off-axis ligand tilts.

  10. 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

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

    SciTech Connect

    Ocampo, R.; Bauder, C.; Callot, H.J.; Albrecht, P. )

    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.

  12. 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.

  13. Electrochemical oxidation of butein at glassy carbon electrodes.

    PubMed

    Tesio, Alvaro Yamil; Robledo, Sebastián Noel; Fernández, Héctor; Zon, María Alicia

    2013-06-01

    The electrochemical oxidation of flavonoid butein is studied at glassy carbon electrodes in phosphate and citrate buffer solutions of different pH values, and 1M perchloric acid aqueous solutions by cyclic and square wave voltammetries. The oxidation peak corresponds to the 2e(-), 2H(+) oxidation of the 3,4-dihydroxy group in B ring of butein, given the corresponding quinone species. The overall electrode process shows a quasi-reversible behavior and an adsorption/diffusion mixed control at high butein bulk concentrations. At low butein concentrations, the electrode process shows mainly an adsorption control. Butein surface concentration values were obtained from the charge associated with the adsorbed butein oxidation peaks, which are in agreement with those values expected for the formation of a monolayer of adsorbate in the concentration range from 1 to 5μM. Square wave voltammetry was used to perform a full thermodynamic and kinetics characterization of the butein surface redox couple. Therefore, from the combination of the "quasi-reversible maximum" and the "splitting of the net square wave voltammetric peak" methods, values of (0.386±0.003) V, (0.46±0.04), and 2.7×10(2)s(-1) were calculated for the formal potential, the anodic transfer coefficient, and the formal rate constant, respectively, of the butein overall surface redox process in pH4.00 citrate buffer solutions. These results will be then used to study the interaction of butein, and other flavonoids with the deoxyribonucleic acid, in order to better understand the potential therapeutic applications of these compounds. PMID:23434740

  14. 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.

  15. 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. PMID:22082024

  16. Meso-substituted cationic porphyrins as efficient photosensitizers of gram-positive and gram-negative bacteria.

    PubMed

    Merchat, M; Bertolini, G; Giacomini, P; Villanueva, A; Jori, G

    1996-02-01

    Previous studies on the photosensitization of bacterial cells with different neutral or negatively charged porphyrins and phthalocyanines have demonstrated that, although Gram-positive bacteria are efficiently photoinactivated, Gram-negative bacteria become photosensitive only after modification of the permeability of their outer membrane. The results described in this paper show that two meso-substituted cationic porphyrins, namely tetra(4N-methyl-pyridyl)porphine tetraiodide and tetra(4N,N,N-trimethyl-anilinium)porphine, efficiently photosensitize the inactivation of Gram-negative bacteria, such as Vibrio anguillarum and Escherichia coli. A negatively charged meso-substituted porphyrin, tetra(4-sulphonatophenyl)porphine, has no appreciable photosensitizing activity towards Gram-negative bacteria, although all three porphyrins exhibit a similar subcellular distribution pattern, being mainly localized in the protoplasts or spheroplasts. Moreover, the three porphyrins show similar efficiency in the photoinactivation of the Gram-positive bacterium Entorecoccus seriolicida. PMID:8622178

  17. 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".

  18. 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

  19. 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.

  20. A manganese porphyrin superoxide dismutase mimetic enhances tumor radioresponsiveness

    SciTech Connect

    Moeller, Benjamin J.; Batinic-Haberle, Ines; Spasojevic, Ivan; Rabbani, Zahid N.; Anscher, Mitchell S.; Vujaskovic, Zeljko; Dewhirst, Mark W. D.V.M. . E-mail: dewhirst@radonc.duke.edu

    2005-10-01

    Purpose: To determine the effect of the superoxide dismutase mimetic Mn(III) tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP{sup 5+}) on tumor radioresponsiveness. Methods and Materials: Various rodent tumor (4T1, R3230, B16) and endothelial (SVEC) cell lines were exposed to MnTE-2-PyP{sup 5+} and assayed for viability and radiosensitivity in vitro. Next, tumors were treated with radiation and MnTE-2-PyP{sup 5+} in vivo, and the effects on tumor growth and vascularity were monitored. Results: In vitro, MnTE-2-PyP{sup 5+} was not significantly cytotoxic. However, at concentrations as low as 2 {mu}mol/L it caused 100% inhibition of secretion by tumor cells of cytokines protective of irradiated endothelial cells. In vivo, combined treatment with radiation and MnTE-2-PyP{sup 5+} achieved synergistic tumor devascularization, reducing vascular density by 78.7% within 72 h of radiotherapy (p < 0.05 vs. radiation or drug alone). Co-treatment of tumors also resulted in synergistic antitumor effects, extending tumor growth delay by 9 days (p < 0.01). Conclusions: These studies support the conclusion that MnTE-2-PyP{sup 5+}, which has been shown to protect normal tissues from radiation injury, can also improve tumor control through augmenting radiation-induced damage to the tumor vasculature.

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

    PubMed

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

    2014-09-01

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

  2. 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. PMID:26754271

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

    PubMed Central

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

    1998-01-01

    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. PMID:9533688

  4. Photoinitiated destruction of composite porphyrin-protein polymersomes.

    PubMed

    Robbins, Gregory P; Jimbo, Masaya; Swift, Joe; Therien, Michael J; Hammer, Daniel A; Dmochowski, Ivan J

    2009-03-25

    Bilayer vesicles assembled from amphiphilic diblock copolymers (polymersomes) adopt asymmetric structures when loaded with moderate concentrations (>or=1.5 mg/mL) of horse spleen ferritin (HSF) or its iron-free variant (HSAF). Incorporation of both ferritin and a zinc porphyrin dimer (PZn(2)) generates photoresponsive vesicles: irradiation with focused light of near-UV to near-IR wavelengths induces polymersome deformation and destruction on the minute time scale. To investigate this phenomenon, polymersomes were loaded with dye-labeled ferritin and PZn(2). Confocal microscopy identified BODIPY-FL-labeled ferritin at the membrane, whereas Cy3-labeled ferritin was found both at the membrane and throughout the aqueous core. Fluorescence recovery after photobleaching (FRAP) experiments confirmed that Cy3- and BODIPY-FL-labeled ferritin and PZn(2) exhibited slow diffusion at the membrane, consistent with membrane association. Furthermore, micropipette aspiration experiments revealed increased elastic moduli and altered bending rigidity in vesicles incorporating HSAF. Finally, a small molecule (biocytin) was encapsulated within the ferritin-PZn(2) vesicles and released upon exposure to light. These data indicate synergy between ferritin, whose membrane association lowers the barrier to deformation, and PZn(2), which embeds in the membrane, harvests light energy and produces local heating that may lead to membrane budding. This appears to be a general protein-polymer membrane phenomenon, as replacement of ferritin with bovine serum albumin or equine skeletal myoglobin resulted in vesicles with similar asymmetric morphology and photosensitivity. PMID:19249827

  5. 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.

  6. 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.

  7. Sorption of water by bidisperse mixtures of carbohydrates in glassy and rubbery states.

    PubMed

    Ubbink, Job; Giardiello, Maria-Isabelle; Limbach, Hans-Jörg

    2007-09-01

    Water sorption by bidisperse carbohydrate mixtures consisting of varying ratios of a narrow-molecular-weight distribution maltopolymer and the disaccharide maltose is investigated to establish a quantitative relation between the composition of the carbohydrate system and the water sorption isotherm. The sorption of water is approached from two limiting cases: the glassy state at low water content and the dilute aqueous carbohydrate solution. In the glassy state, the water content at a given water activity decreases with increasing maltose content of the matrix, whereas in the rubbery state it increases with increasing maltose content. The water sorption behavior in the glassy state is quantified using a variety of models, including the often-utilized but physically poorly founded Guggenheim-Anderson-de Boer model, several variants of the free-volume theory of sorption by glassy polymers, and a two-state sorption model introduced in the present paper. It is demonstrated that both the free-volume models and the two-state sorption model, which all encompass the Flory-Huggins theory for the rubbery-state sorption but which differ in their modeling of the glassy-state sorption, provide a physically consistent foundation for the analysis of water sorption by the carbohydrate matrixes. PMID:17691841

  8. Relaxation dynamics and crystallization study of sildenafil in the liquid and glassy states.

    PubMed

    Kolodziejczyk, K; Paluch, M; Grzybowska, K; Grzybowski, A; Wojnarowska, Z; Hawelek, L; Ziolo, J D

    2013-06-01

    In this paper, the physical stability and molecular dynamics of amorphous sildenafil are investigated in both the liquid and glassy states. We have established that the amorphous sildenafil is resistant to recrystallization at temperatures below the glass transition temperature Tg during the experimental period of its storage (i.e., above 6 months), however, it easily undergoes cold crystallization at T > Tg. To determine the crystallization mechanism, the isothermal and non-isothermal studies of the cold crystallization kinetics of the drug are performed by using the broadband dielectric spectroscopy (BDS) and the differential scanning calorimetry (DSC), respectively. The cold crystallization mechanism has been found to be similar in both the isothermal and non-isothermal cases. This mechanism has been analyzed from the point of view of the molecular mobility of sildenafil investigated in the supercooled liquid and glassy states by using the BDS measurements in the wide temperature range. This analysis has been enriched with a new approach based on a recently reported measure of dynamic heterogeneity given by a four-point dynamic susceptibility function. No tendency to recrystallization of glassy sildenafil at T < Tg is also discussed in relation to molecular dynamics of sildenafil in the glassy state. The relatively small molecular mobility reflected in one secondary relaxation as well as the predicted large time scale of structural relaxation of glassy sildenafil suggests that amorphous sildenafil should not recrystallize during its long-term storage at room temperature. PMID:23594226

  9. Understanding the Physical Aging Behavior of Glassy Polystyrene Layers in Close Contact with Rubbery Domains

    NASA Astrophysics Data System (ADS)

    Roth, Connie; Rauscher, Phil; Pye, Justin; Baglay, Roman

    2014-03-01

    Recent advances in synthesis strategies and processing methods have led to new nanostructured polymer blend and block-copolymer materials containing domain sizes less than 100 nm with glassy and rubbery domains in close proximity. Given the outsized role interfacial perturbations have played in causing large changes in the glass transition temperature Tg and physical aging of ultrathin single-layer films, we are interested in studying how the presence of glassy-rubbery interfaces between neighboring polymer domains may alter the local stability and physical aging of confined glassy layers. Using a polystyrene (PS) / poly(n-butyl methacrylate) (PnBMA) weakly immiscible system with 7 nm interfacial width, we demonstrate how ellipsometry can be used to isolate the physical aging rate of thin PS layers atop rubbery PnBMA layers. Despite a 25-30 K reduction in the average Tg of 84 nm thick PS layers atop PnBMA as measured by fluorescence, we observe no change in the PS aging rate relative to bulk. These results are in contrast with previous works on single-layer polymer films that have found the local aging rate to often be correlated with local Tg changes. This appears not to be the case for glassy PS layers atop rubbery PnBMA suggesting some additional factor is affecting the structural relaxation occurring near the glassy-rubbery interface.

  10. Mechanisms of crazing in glassy polymers revealed by molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mahajan, Dhiraj K.; Hartmaier, Alexander

    2012-08-01

    Mechanisms leading to initiation of crazing type failure in a glassy polymer are not clearly understood. This is mainly due to the difficulty in characterizing the stress state and polymer configuration sufficiently locally at the craze initiation site. Using molecular dynamics simulations, we have now been able to access this information and have shown that the local heterogeneous deformation leads to craze initiation in glassy polymers. We found that zones of high plastic activity are constrained by their neighborhood and become unstable, initiating crazing from these sites. Furthermore, based on the constant flow stresses observed in the unstable zones, we conclude that microcavitation is the essential local deformation mode to trigger crazing in glassy polymers. Our results demonstrate the basic difference in the local deformation mode as well as the conditions that lead to either shear-yielding or crazing type failures in glassy polymers. We anticipate our paper to help in devising a new criterion for craze initiation that not only considers the stress state, but also considers local deformation heterogeneities that form the necessary condition for crazing in glassy polymers.

  11. Mechanisms of crazing in glassy polymers revealed by molecular dynamics simulations.

    PubMed

    Mahajan, Dhiraj K; Hartmaier, Alexander

    2012-08-01

    Mechanisms leading to initiation of crazing type failure in a glassy polymer are not clearly understood. This is mainly due to the difficulty in characterizing the stress state and polymer configuration sufficiently locally at the craze initiation site. Using molecular dynamics simulations, we have now been able to access this information and have shown that the local heterogeneous deformation leads to craze initiation in glassy polymers. We found that zones of high plastic activity are constrained by their neighborhood and become unstable, initiating crazing from these sites. Furthermore, based on the constant flow stresses observed in the unstable zones, we conclude that microcavitation is the essential local deformation mode to trigger crazing in glassy polymers. Our results demonstrate the basic difference in the local deformation mode as well as the conditions that lead to either shear-yielding or crazing type failures in glassy polymers. We anticipate our paper to help in devising a new criterion for craze initiation that not only considers the stress state, but also considers local deformation heterogeneities that form the necessary condition for crazing in glassy polymers. PMID:23005778

  12. Comparative analysis of the conformations of symmetrically and asymmetrically deca- and undecasubstituted porphyrins bearing meso-alkyl or -aryl groups

    SciTech Connect

    Senge, M.O.; Medforth, C.J.; Forsyth, T.P.

    1997-03-12

    Conformational analysis of highly substituted porphyrins, has potential implications for modeling the behavior of macrocycles in tetrapyrrole-containing protein complexes and during catalytic reactions. In order to study the influence of different substituent patterns of the conformation of the porphyrin macrocycle, a series of metal free and nickel(II) decasubstituted porphyrins bearing aryl or ethyl groups at opposite meso positions and alkyl groups at the pyrrole positions have been synthesized and characterized by X-ray crystallography. Crystal structures of the free-base porphyrins with 5,15-diaryl substituents showed negligible out-of-plane distortion but a large amount of in-plane distortion along the 5,15-axis accompanied by large bond angle changes similar to those previously seen for related porphyrins with 5,15-dialkyl substituents. Nickel(II) complexes of the 5,15-diaryl-substituted porphyrins show planar or modestly nonplanar conformations, suggesting that these complexes are not intrinsically nonplanar, whereas a complex with 5,15-diethyl substituents has a very ruffled conformation similar to those observed for related complexes with other metals. The nickel(II) complexes are also elongated along the 5,15-axis in a qualitatively similar but less dramatic fashion than are the free-base porphyrins. Spectroscopic studies ({sup 1}H NMR, optical, and resonance Raman spectroscopy) suggest that conformations similar to those determined by X-ray crystallography are present in solution for the 5,15-disubstituted porphyrins containing both aryl and alkyl mesosubstituents were also investigated. Metal-free 5,15-dialkyl- and 5,15-diaryl-substituted porphyrins. Several asymmetric nickel(II) and metal-free deca- and undecasubstituted porphyrins containing both aryl and alkyl mesosubstituents were also investigated.

  13. 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.

  14. 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.

  15. Surface functionalization and electronic interactions of ZnO nanorods with a porphyrin derivative.

    PubMed

    Klaumünzer, Martin; Kahnt, Axel; Burger, Alexandra; Mačković, Mirza; Münzel, Corinna; Srikantharajah, Rubitha; Spiecker, Erdmann; Hirsch, Andreas; Peukert, Wolfgang; Guldi, Dirk M

    2014-05-14

    To optimize electron transfer and optoelectronic properties in nanoparticulate thin films for electronics we show the surface functionalization of ZnO nanorods by means of replacing surface active 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (TODA) by a redoxactive organic component, that is, 5,10,15,20-(phenoxyacetat)-porphyrin bearing four carboxylic acids as possible ZnO anchors. Microscopy-transmission electron microscopy-and spectroscopy-optical spectroscopy-verifies the successful and homogenous integration of the porphyrin onto the surface of ZnO nanorods, a process that is facilitated by the four anchoring groups. Photophysical investigations based on emission and absorption spectroscopy prompt to distinct electronic interactions between ZnO nanorods and the porphyrins. Consequently, we performed further photophysical studies flanked by pulse radiolysis assays to corroborate the nature of the electronic interactions. PMID:24665864

  16. 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.

  17. 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

  18. Fluorescent nanogel based on four-arm PEG-PCL copolymer with porphyrin core for bioimaging.

    PubMed

    Dong, Xia; Wei, Chang; Lu, Li; Liu, Tianjun; Lv, Feng

    2016-04-01

    Four-arm PEG-PCL copolymer with porphyrin core (POR-PEG-PCL) exhibits beneficial fluorescence ability in vivo. To further develop an application of thermosensitive porphyrin hydrogel based on four-arm PEG-PCL copolymer as a drug carrier, a POR-PEG-PCL nanogel was tracked and located to tumor tissue with porphyrin as a fluorescence tag via intravenous injection. The structure and function of the nanogel were evaluated by TEM, DLS, H-NMR, UV-vis and fluorescence spectra. The fluorescent nanogel was monitored by an in vivo imaging system with hepatoma tumor-bearing mice. Good biocompatibility and safety in vitro and in vivo show that the POR-PEG-PCL nanogel is a potential drug carrier that targets tumor tissues with fluorescence bioimaging. PMID:26838843

  19. 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

  20. 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.

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

    PubMed

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

    2007-02-22

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

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

    PubMed

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

    2016-06-01

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

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

    PubMed

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

    2015-11-16

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

  4. Porphyrin overproduction by Pseudomonas denitrificans: essentiality of betaine and stimulation by ethionine.

    PubMed

    Demain, A L; White, R F

    1971-08-01

    Ethionine supplementation of a defined medium for growth of Pseudomonas denitrificans inhibited vitamin B(12) overproduction and led to the elaboration of a red pigment. The pigment was shown to be coproporphyrin III. Inhibition by ethionine of cobalamin synthesis is probably due to interference of methylation of the corrin nucleus by methionine. Accumulation of coproporphyrin III is thought to result from interference by ethionine with the activity of methionine in the coproporphyrinogenase reaction; this would inhibit formation of heme, the feedback inhibitor and corepressor of delta-aminolevulinate synthetase, thus allowing unregulated synthesis of coproporphyrinogen III and its degradation product, coproporphyrin III. Betaine, known to be required for vitamin B12 overproduction, was found to be an essential requirement for porphyrin overproduction in the presence of ethionine. Low-level production of porphyrin, which occurs in the absence of ethionine, also required betaine supplementation. Betaine is thus required for overproduction of both corrins and porphyrins in P. denitrificans. PMID:5113597

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

    PubMed

    Marbach, Hubertus

    2015-09-15

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

  6. Direct X-ray observation of trapped CO₂ in a predesigned porphyrinic metal-organic framework.

    PubMed

    Johnson, Jacob A; Chen, Shuang; Reeson, Tyler C; Chen, Yu-Sheng; Zeng, Xiao Cheng; Zhang, Jian

    2014-06-16

    Metal-organic frameworks (MOFs) are emerging microporous materials that are promising for capture and sequestration of CO2 due to their tailorable binding properties. However, it remains a grand challenge to pre-design a MOF with a precise, multivalent binding environment at the molecular level to enhance CO2 capture. Here, we report the design, synthesis, and direct X-ray crystallographic observation of a porphyrinic MOF, UNLPF-2, that contains CO2-specific single molecular traps. Assembled from an octatopic porphyrin ligand with [Co2(COO)4] paddlewheel clusters, UNLPF-2 provides an appropriate distance between the coordinatively unsaturated metal centers, which serve as the ideal binding sites for in situ generated CO2. The coordination of Co(II) in the porphyrin macrocycle is crucial and responsible for the formation of the required topology to trap CO2. By repeatedly releasing and recapturing CO2, UNLPL-2 also exhibits recyclability. PMID:24861568

  7. 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

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

    PubMed

    Malinski, T; Huk, I

    2001-05-01

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

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

    PubMed

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

    2015-06-24

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

  10. Effect of halogenation on the nonlinear optical properties of porthyrin and substituted porphyrins

    NASA Technical Reports Server (NTRS)

    Cardelino, Beatriz H.; Moore, Craig E.; Benloss, Angela; Thompson, Albert N., Jr.; Richards, Rosalie A.; Roney, Celeste A.; Sanghadasa, Mohan

    1998-01-01

    The effect that fluorine and chlorine substitution has on the nonlinear optical properties of porphyrin, tetramethylporphyrin and tetraphenylporphyrin has been theoretically studied. The calculations of nonlinear optical properties have been obtained by performing finite-field calculations on structures determined by semiempirical methods. In addition, tetra(p-chlorophenyl)porphyrin and tetra(p-bromophenyl)porphyrin were synthesized by the condensation of pyrrol and the appropriate aldehyde. Thin films of polymethylmethacrylate were obtained containing these materials, by spin coating onto glass substrates. The films were characterized by third-harmonic generation. It was determined that the experimental conditions enhance the third-order polarizability of the tetraphenylporphyrins by a factor of about 1.6.

  11. 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

  12. DFT-D studies of single porphyrin molecule on doped boron silicon surfaces.

    PubMed

    Boukari, Khaoula; Sonnet, Philippe; Duverger, Eric

    2012-12-01

    We present a theoretical study in the framework of density functional calculations, taking into account the van der Waals interactions (DFT-D) of isolated Cu-5,10,15,20-tetrakis(3,5-di-tert-butyl-phenyl) porphyrin (Cu-TBPP) molecules in a C2v conformation adsorbed on a Si(111)√3x√3R30°-boron surface [denoted Si(111)-B]. With this approach, we investigate interactions between perfect or boron-defect Si(111)-B substrates and the Cu-TBPP molecule as well as the consequences of demetallation of Cu-TBPP. For each model, we determine the structural equilibrium, the spatial charge-density distribution and the electronic properties of the ground state. We conclude that there is potential for Si adatom capture by a porphyrin without strong modification of the porphyrin response, as seen from simulated scanning tunneling microscopy (STM) images. PMID:23055297

  13. 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.

  14. 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.

  15. 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.

  16. Novel amphiphilic cationic porphyrin and its Ag(II) complex as potential anticancer agents

    PubMed Central

    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

    2015-01-01

    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), 1H 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. PMID:25086237

  17. 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.

  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. 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.

  20. 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

  1. 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. PMID:27213825

  2. 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

  3. Observation of kinetic tritium isotope effects by dynamic NMR. The tautomerism of porphyrin

    SciTech Connect

    Braun, J.; Limbach, H.H.; Williams, P.G.; Morimoto, Hiromi; Wemmer, D.E.

    1996-07-31

    As the knowledge of tritium isotope effects is desirable from a theoretical standpoint, we have applied {sup 3}H NMR in order to study these effects in the case of the double-hydron tautomerism of {sup 15} N-labeled porphyrin. In conclusion, the determination of kinetic tritium isotope effects is a powerful application of dynamic {sup 3}H NMR. In the case of the tautomerism of porphyrin, these effects support the stepwise hydron-tunneling mechanism and can serve to test multidimensional tunneling models in the future. 10 refs., 2 figs.

  4. Ferryl Protonation in Oxoiron(IV) Porphyrins and Its Role in Oxygen Transfer

    PubMed Central

    Boaz, Nicholas C.; Bell, Seth R.

    2015-01-01

    Ferryl porphyrins, P−FeIV=O, are central reactive intermediates in the catalytic cycles of numerous heme proteins and a variety of model systems. There has been considerable interest in elucidating factors, such as terminal oxo basicity, that may control ferryl reactivity. Here, the sulfonated, water-soluble ferryl porphyrin complexes tetramesitylporphyrin, oxoFeIVTMPS (FeTMPS-II), its 2,6-dichlorophenyl analogue, oxoFeIVTDClPS (FeTDClPS-II), and two other analogues are shown to be protonated under turnover conditions to produce the corresponding bis-aqua-iron(III) porphyrin cation radicals. The results reveal a novel internal electromeric equilibrium, P−FeIV=O ⇆ P+−FeIII(OH2)2. Reversible pKa values in the range of 4–6.3 have been measured for this process by pH-jump, UV–vis spectroscopy. Ferryl protonation has important ramifications for C–H bond cleavage reactions mediated by oxoiron(IV) porphyrin cation radicals in protic media. Both solvent O–H and substrate C–H deuterium kinetic isotope effects are observed for these reactions, indicating that hydrocarbon oxidation by these oxoiron(IV) porphyrin cation radicals occurs via a solvent proton-coupled hydrogen atom transfer from the substrate that has not been previously described. The effective FeO–H bond dissociation energies for FeTMPS-II and FeTDClPS-II were estimated from similar kinetic reactivities of the corresponding oxoFeIVTMPS+ and oxoFeIVTDClPS+ species to be ~92–94 kcal/mol. Similar values were calculated from the two-proton P+−FeIII(OH2)2 pKaobs and the porphyrin oxidation potentials, despite a 230 mV range for the iron porphyrins examined. Thus, the iron porphyrin with the lower ring oxidation potential has a compensating higher basicity of the ferryl oxygen. The solvent-derived proton adds significantly to the driving force for C–H bond scission. PMID:25651467

  5. Porphyrin-doped solgel-lined structured optical fibers for local and remote sensing.

    PubMed

    Huyang, George; Canning, John; Åslund, Mattias L; Naqshbandi, Masood; Gibson, Brant; Petermann, Ingemar; Stocks, Danial; Crossley, Maxwell J

    2011-06-01

    We constructed a type of sensor by depositing a solgel layer within the interior holes of a silica-structured fiber and, subsequently, coating this with an acid-responsive porphyrin. Protonation of the porphyrin by an acidic gas (HCl in this case), is detected by a large change in the visible spectrum. Compared to previous work on a liquid-core sensor in a structured optical fiber, the signal-to-noise ratio of this gas sensor shows a reduced signal strength, but the detection rate is increased about fortyfold. PMID:21633420

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

    SciTech Connect

    Zeng, Jing; Chen, Ke-Qiu

    2014-01-20

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

  7. [Accumulation of porphyrins in cells of system of blood induced by 5-aminolaevulinic acid].

    PubMed

    Lobanok, E S; Vasilevich, I B; Vorobeĭ, A V

    2011-01-01

    The levels and rates of accumulation of porphyrins in lymphoid cells and bone marrow cells treated with exogenous 5-aminolaevulinic acid (ALA) were studied. The dependence of the quantity of porphyrins accumulated in cell on ALA concentrations in the medium had maximum at 0.7-1.0 mM ALA for all the cell types studied (splenocytes, thymocytes, peripheral blood lymphocytes and bone marrow cells). The rate of accumulation of uro-, copro- and protoporphyrins depended on cell types. The lowest and the highest levels were found in splenocytes and highest in bone marrow cells respectively. It is suggested that photodynamic therapy employing ALA is potentially dangerous for blood cells. PMID:21870605

  8. 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

  9. Pattern formation in polymer via electrohydrodynamic instabilities and glassy fracture

    NASA Astrophysics Data System (ADS)

    Pease, Leonard Franklin, III

    Fabrication of micro and nano structures from polymeric materials has attracted significant attention due to their promise of inexpensive, fast throughput and ease of integration into existing fabrication processes. This dissertation describes our contributions to two such processes. In the first process, electrohydrodynamic flow drives a thin polymer film sandwiched between electrodes with an intervening gap into multidomained, hexagonally packed pillars or concentric rings. We model the initial stages of formation by performing a linear stability analysis under the lubrication approximation. We find the presence of free charge at the free interface both decreases the pillar-to-pillars spacing and increases the growth rate. We examined the possible sources of electrostatic field in the absence of an applied voltage to find static charge to be the most likely candidate. In practice, however, the lubrication approximation may not strictly apply in the situations of greatest interest. Accordingly, we contrasted results of the linear stability analysis with and without the lubrication approximation to show that the approximation fails where surface tension is small and electric fields are large, typical of experiments with a polymer/organic liquid instead of air in the gap---precisely the conditions that predict the smallest pillar arrays. Motivated by the discovery of concentric rings, we adapted the form of the perturbation from sinusoids to Bessel functions to predict constant ring-to-ring spacings, constant annular widths and growth rates in agreement with experiment. In the second patterning technique, a thin film sandwiched between two substrates fractures into periodic ridges upon insertion of a razor blade. We investigated the conditions that selected for the presence or absence of the gratings, their fractional coverage, their period, and their alignment. Our key findings indicated that the gratings form from all glassy materials tested with periods of

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. Nature of ThF bonding in crystalline and glassy states using EXAFS and XANES

    NASA Astrophysics Data System (ADS)

    Rao, K. J.; Wong, J.; Shafer, M. W.

    1984-11-01

    A binary glass of thorium and hafnium tetrafluorides (with dopant concentrations of LaF 3) has been investigated using EXAFS and XANES analysis of the L Ill edge spectra of thorium. Results of EXAFS analysis indicate that there is no change in the number of nearest neighbors of thorium ions. However, the intensity of the white line in XANES is significantly higher in the glass. This increase in intensity has been explained semiquantitatively in terms of enhanced covalency of ThF bonding. Since the coordination number of Th 4+ remains constant in both crystalline and glassy states, covalency enhancement seems to be a general characteristic of glassy state of ionic materials.

  16. 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.

  17. Characterization of molecular mobility within the glassy matrix of dry seeds using mechanical properties: pea cotyledon as a test study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seed glasses form during maturation drying and regulate seed longevity. Seeds continue to age within the glassy state and, even during cryogenic storage, viability eventually declines. Inevitability of aging suggests some level of molecular motion within the glassy matrix and quantifying these “rel...

  18. Tuning the thermoelectric properties of metallo-porphyrins

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    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.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

  19. 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

  20. 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

  1. 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

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

    PubMed Central

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

    2015-01-01

    Summary Cu,H2-bis-porphyrin (Cu,H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir–Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase) to a surface plasmon resonance (SPR) substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions. PMID:26665088

  3. Electronic and fluorescence spectral studies of a novel porphyrin-polypyridyl ruthenium(II) hybrid linked by a butyl chain

    NASA Astrophysics Data System (ADS)

    Liu, Jie; Huang, Jin-Wang; Fu, Bo; Zhao, Ping; Yu, Han-Cheng; Ji, Liang-Nian

    2007-06-01

    The electronic and fluorescence spectroscopic properties of a novel porphyrin-polypyridyl ruthenium(II) hybrid, [C 4-TPP-(ip)Ru(phen) 2](ClO 4) 2 (TPP = 5,10,15,20-tetraphenylporphyrin, ip = imidazo[4,5-f][1,10]phenanthroline and phen = 1,10-Phenanthroline), in which a polypyridyl ruthenium(II) moiety is linked to a porphyrin moiety by a butyl chain have been investigated and compared to its corresponding reference compounds. The studies of electronic absorption spectra have shown that there is an electronic interaction between the porphyrin moiety and the polypyridyl ruthenium(II) moiety in the hybrid. It can be found that intramolecular photoinduced electron and energy transfer processes may occur in the hybrid from the fluorescence spectra. When exciting in Soret band and Q band of porphyrin, the fluorescence quenching of the porphyrin moiety of the hybrid takes place due to electron transfer from the lowest singlet excited state (S 1) to the appended polypyridyl rutherium(II) moiety, while the decay of S 2 (the second-excited singlet state) of the porphyrin moiety is mainly contributed to internal conversion to S 1. When exciting in MLCT band of the polypyridyl ruthenium(II) moiety, fluorescence corresponding to the polypyridyl ruthenium(II) moiety is quenched by intramolecular energy transfer from 3MLCT of the ruthenium moiety to the lowest-energy triplet state localized on the porphyrin moiety.

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

    PubMed

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

    2015-01-01

    Cu,H2-bis-porphyrin (Cu,H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir-Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase) to a surface plasmon resonance (SPR) substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions. PMID:26665088

  5. Novel methodology to control the adsorption structure of cationic porphyrins on the clay surface using the "size-matching rule".

    PubMed

    Egawa, Tsuyoshi; Watanabe, Hajime; Fujimura, Takuya; Ishida, Yohei; Yamato, Masafumi; Masui, Dai; Shimada, Tetsuya; Tachibana, Hiroshi; Yoshida, Hirohisa; Inoue, Haruo; Takagi, Shinsuke

    2011-09-01

    Saponite-type clays that have different cation exchange capacities were successfully synthesized by hydrothermal synthesis. The structure and properties were analyzed by X-ray diffraction, X-ray fluorescence, (27)Al NMR, FT-IR, thermogravimetric and differential thermal analysis, atomic force microscopy, and cation exchange capacity measurement. The intercharge distances on the synthetic saponite (SS) surfaces were calculated to be 0.8-1.9 nm on the basis of a hexagonal array. The complex formation behavior between SS and cationic porphyrins was examined. It turns out that the average intermolecular distance between porphyrin molecules on the SS surface can be controlled, depending on the charge density of the SS. In the case of tetrakis(1-methylpyridinium-4-yl)porphyrin (H(2)TMPyP(4+)), the average intermolecular distances on the SS surface can be controlled from 2.3 to 3.0 nm on the basis of a hexagonal array. It was also found that absorption maxima of porphyrins depend on the charge density of the SS. The adsorption behavior of porphyrin on the SS surface can be rationally understood by the previously reported "size-matching rule". This methodology using host-guest interaction can realize a unique adsorption structure control of the porphyrin molecule on the SS surface, where the gap distance between guest porphyrin molecules is rather large. These findings will be highly valuable to construct photochemical reaction systems such as energy transfer in the complexes. PMID:21774506

  6. 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

  7. Soft magnetic properties of bulk FeCoMoPCBSi glassy core prepared by copper mold casting

    NASA Astrophysics Data System (ADS)

    Zhang, Mingxiao; Kong, Fanli; Wang, Anding; Chang, Chuntao; Shen, Baolong

    2012-04-01

    Bulk Fe66Co10Mo3.5P10C4B4Si2.5 glassy core of 10 mm in outer diameter, 6 mm in inner diameter, and 1 mm in thickness was successfully prepared by copper mold casting. The effects of annealing treatments on magnetic properties and microstructure of these cores were investigated. After an optimum annealing treatment, the resulting bulk glassy core exhibits good magnetic properties, i.e., high saturation magnetic flux density of 1.23 T, low coercive force of 1.0 A/m, high maximum permeability of 450 000, respectively. In addition, the glassy core also shows low core loss of 0.4 W/kg at 50 Hz and at maximum magnetic flux density of 1 T. The synthesis of bulk glassy core with excellent magnetic properties is encouraging for enlarging the application field of ferromagnetic bulk glassy alloys.

  8. 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

  9. Transient EPR Reveals Triplet State Delocalization in a Series of Cyclic and Linear π-Conjugated Porphyrin Oligomers

    PubMed Central

    2015-01-01

    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

  10. Development of novel formulations for photodynamic therapy on the basis of amphiphilic polymers and porphyrin photosensitizers. Pluronic influence on photocatalytic activity of porphyrins

    NASA Astrophysics Data System (ADS)

    Solovieva, A. B.; Melik-Nubarov, N. S.; Zhiyentayev, T. M.; Tolstih, P. I.; Kuleshov, I. I.; Aksenova, N. A.; Litmanovich, E. A.; Glagolev, N. N.; Timofeeva, V. A.; Ivanov, A. V.

    2009-04-01

    Effect of ethylene and propylene oxide tri-block copolymers (Pluronics) on the photocatalytic activity of tree porphyrins differing by their hydrophobicity was studied. It was shown that Pluronics induce considerable increase in the photocatalytic activity of the tetraphenylporphyrin, hematoporphyrin disodium salt (Dimegine) and relatively hydrophilic N-methyl-bis-glucamine salt of chlorine e6 (Photoditazine) in the reaction of photooxidation of tryptophan in water solution. This effect was maximal for Pluronics F127 and P85 with intermediate hydrophobicity, while more hydrophilic F68 and more hydrophobic L61 were less effective. Pluronic effect on the photocatalytic activity of tetraphenylporphyrin and dimegine is attributed to their disaggregation in water solution, while PD activity is elevated due to the local concentrating of the photocatalyst and the substrate within micellar volume. It was found by AFM that the structure of Pluronic F127 thin films prepared by water solution evaporation on mica surface significantly changed in the presence of porphyrin. This effect can be attributed to the interaction of Pluronics with porphyrins in water solution.

  11. 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

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

    PubMed

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

    2012-01-01

    Cardanol is a natural and renewable organic raw material obtained as the major chemical component by vacuum distillation of cashew nut shell liquid. In this work a new sustainable procedure for producing cardanol-based micellar nanodispersions having an embedded lipophilic porphyrin itself peripherally functionalized with cardanol substituents (porphyrin-cardanol hybrid) has been described for the first time. In particular, cardanol acts as the solvent of the cardanol hybrid porphyrin and cholesterol as well as being the main component of the nanodispersions. In this way a "green" micellar nanodispersion, in which a high percentage of the micellar system is derived from renewable "functional" molecules, has been produced. PMID:23079496

  13. Interaction peculiarities of 5,10,15,20-tetrakis(4-N-methylpyridil) tetra iodide porphyrin with albumin

    NASA Astrophysics Data System (ADS)

    Lebedeva, N. Sh.; Malkova, E. A.; Popova, T. E.; Kutyrev, A. E.; Syrbu, S. A.; Parfenyuk, E. V.; Vyugin, A. I.

    2014-01-01

    In present work interactions of bovine serum albumin with 5,10,15,20-tetrakis(4-N-methylpyridil) tetra iodide porphyrin have been studied by electron absorption and fluorescence spectroscopy. The studies were carried out in aqueous media at different pH and in water-dimethylformamide mixtures containing up to 0.19 M of the organic solvent. It has been demonstrated that the porphyrin forms stable complexes with BSA in which the porphyrin is located subdomains IB and IIA. The stability constants of the complexes is practically independent of pH.

  14. 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.

  15. Improved antibacterial phototoxicity of a neutral porphyrin in natural deep eutectic solvents.

    PubMed

    Wikene, Kristine Opsvik; Bruzell, Ellen; Tønnesen, Hanne Hjorth

    2015-07-01

    Neutral porphyrins for antibacterial photodynamic therapy (aPDT) have received little attention due to their tendency to aggregate in aqueous media and reports of low phototoxic effect. These compounds may be less toxic to cells than positively and negatively charged photosensitisers. The preparation of highly bacterial phototoxic formulations of neutral porphyrins remains an open field of research with great potential if achievable. The purpose of this study was to develop novel hydrophilic formulations of the neutral porphyrin 5,10,15,20-tetrakis(4-hydroxyphenyl)-porphyrin (THPP) by use of natural deep eutectic solvents (NADES) prepared by the solvent evaporation method. Physical and photochemical stability and in vitro photoinactivation of Enterococcus faecalis and Escherichia coli were investigated. Two of the 15 NADES investigated demonstrated superior solubilising properties of THPP. The photostability of THPP was higher in NADES than in methanol. A 100-fold dilution of the preparations with buffer to a final concentration of 0.5-5 nM THPP resulted in complete photoinactivation of E. faecalis and E. coli both in their exponential and stationary phase. THPP demonstrated significantly higher phototoxicity when formulated in NADES than in other aqueous preparations like phosphate buffered saline. NADES as a formulation concept for photosensitisers shows a great potential in aPDT. PMID:25966307

  16. 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. PMID:25989424

  17. 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.

  18. 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

  19. 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

  20. 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.

  1. 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

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

    PubMed

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

    2011-03-14

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

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

    PubMed

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

    2015-07-01

    Binding of a novel cationic porphyrin-imidazophenazine conjugate, TMPyP(3+)-ImPzn, to four-stranded poly(G) was investigated in aqueous solutions of neutral pH under near physiological ionic conditions using absorption, polarized fluorescent spectroscopy and fluorescence titration techniques. In absence of the polymer the conjugate folds into stable internal heterodimer with stacking between the porphyrin and phenazine chromophores. Binding of TMPyP(3+)-ImPzn to poly(G) is realized by two competing ways. At low polymer-to-dye ratio (P/D < 6) outside electrostatic binding of the cationic porphyrin moieties of the conjugate to anionic polynucleotide backbone with their self-stacking is predominant. It is accompanied by heterodimer dissociation and distancing of phenazine moieties from the polymer. This binding mode is characterized by strong quenching of the conjugate fluorescence. Increase of P/D results in the disintegration of the porphyrin stacks and redistribution of the bound conjugate molecules along the polymer chain. At P/D > 10 another binding mode becomes dominant, embedding of TMPyP(3+)-ImPzn heterodimers into poly(G) groove as a whole is occurred. PMID:26076929

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

    PubMed

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

    2008-04-01

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

  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. Quantum dot effects upon the interaction between porphyrins and phospholipids in cell membrane models.

    PubMed

    Parra, Gustavo G; Borissevitch, Galina; Borissevitch, Iouri; Ramos, Ana P

    2016-04-01

    This study employed surface pressure isotherms and spectroscopic techniques to investigate the effect of quantum dots on the interaction between porphyrins and phospholipids using Langmuir monolayers and Langmuir-Blodgett films formed from negatively charged DMPA (the sodium salt of dimyristoyl-sn-glycero-phosphatidyl acid) and zwitterionic DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) as cell membrane models in the presence of 5,10,15,20-tetrakis(4-N-tetradecyl-pyridyl) porphyrin (TMPyP), 5,10,15,20-tetrakis(p-sulfonato-phenyl) porphyrin (TPPS4) and PEG-coated CdSe/ZnS quantum dots (QD). The porphyrins present at the monolayer subphase affected the organization of the lipids at the air/liquid interface, as shown by the changes in the surface pressure-surface area isotherms. QDs enhanced the interaction of TMPyP with DMPA, improving their transference from the liquid monolayers to solid supports. A higher amount of TMPyP was transferred to DMPA-Langmuir-Blodgett films when the QDs were present in the subphase as evidenced by the UV-Vis data. For DPPC the surface effects due to the presence of QDs are less evident. PMID:26518694

  7. 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…

  8. Electrocatalytic reduction of dioxygen to water by iridium porphyrins adsorbed on edge plane graphite electrodes

    SciTech Connect

    Collman, J.P.; Chng, Leng Leng; Tyvoll, D.A.

    1995-03-15

    Electrocatalytic effects of adsorbed iridium porphyrin complexes for the reduction of oxygen to water was studied. The Ir(II) metal center is proposed as the active catalytic center and catalytic effects can be attributed to transformation to Ir(II) centers.

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

    PubMed

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

    2009-09-30

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

  10. Azoimidazole functionalized Ni-porphyrins for molecular spin switching and light responsive MRI contrast agents.

    PubMed

    Heitmann, Gernot; Schütt, Christian; Gröbner, Jens; Huber, Lukas; Herges, Rainer

    2016-07-28

    Azo-N-methylimidazole functionalized Ni(ii)porphyrins were rationally designed and synthesized and their performance as molecular spin switches was investigated. They perform intramolecular light-driven coordination-induced spin state switching (LD-CISSS) in the presence of water and therefore are an important step towards spin switches for medicinal applications, particularly functional MRI contrast agents. PMID:27334263

  11. 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.

  12. Crystal Structure of Two Anti-Porphyrin Antibodies with Peroxidase Activity

    PubMed Central

    Maréchal, Jean-Didier; Bahloul, Amel; Sari, Marie-Agnès; Mahy, Jean-Pierre

    2012-01-01

    We report the crystal structures at 2.05 and 2.45 Å resolution of two antibodies, 13G10 and 14H7, directed against an iron(III)-αααβ-carboxyphenylporphyrin, which display some peroxidase activity. Although these two antibodies differ by only one amino acid in their variable λ-light chain and display 86% sequence identity in their variable heavy chain, their complementary determining regions (CDR) CDRH1 and CDRH3 adopt very different conformations. The presence of Met or Leu residues at positions preceding residue H101 in CDRH3 in 13G10 and 14H7, respectively, yields to shallow combining sites pockets with different shapes that are mainly hydrophobic. The hapten and other carboxyphenyl-derivatized iron(III)-porphyrins have been modeled in the active sites of both antibodies using protein ligand docking with the program GOLD. The hapten is maintained in the antibody pockets of 13G10 and 14H7 by a strong network of hydrogen bonds with two or three carboxylates of the carboxyphenyl substituents of the porphyrin, respectively, as well as numerous stacking and van der Waals interactions with the very hydrophobic CDRH3. However, no amino acid residue was found to chelate the iron. Modeling also allows us to rationalize the recognition of alternative porphyrinic cofactors by the 13G10 and 14H7 antibodies and the effect of imidazole binding on the peroxidase activity of the 13G10/porphyrin complexes. PMID:23240001

  13. Organisation and ordering of 1D porphyrin polymers synthesised by on-surface Glaser coupling.

    PubMed

    Saywell, Alex; Browning, Abigail S; Rahe, Philipp; Anderson, Harry L; Beton, Peter H

    2016-08-16

    One-dimensional polymer chains consisting of π-conjugated porphyrin units are formed via Glaser coupling on a Ag(111) surface. Scanning probe microscopy reveals the covalent structure of the products and their ordering. The conformational flexibility within the chains is investigated via a comparision of room temperature and cryogenic measurements. PMID:27348050

  14. Theoretical Study of High-Valent Vanadium Oxo-Porphyrins as a Dopant of Crude Oil

    SciTech Connect

    Salcedo, Roberto; Martinez, LMR; Martinez-Magadan, Jose M.

    2001-06-15

    The role played by the vanadyl porphyrinate as a dopant for zeolites in the refinement process of crude oil is analyzed using DFT calculations. The pair formed by the vanadium atom and its bonded oxygen atoms seems to be the responsible items in the dopant reaction. However, the present paper shows the participation of the vanadium atom as being the most important.

  15. 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

  16. Active loading into extracellular vesicles significantly improves the cellular uptake and photodynamic effect of porphyrins.

    PubMed

    Fuhrmann, Gregor; Serio, Andrea; Mazo, Manuel; Nair, Rekha; Stevens, Molly M

    2015-05-10

    Extracellular vesicles (EVs) are phospholipid-based particles endogenously produced by cells. Their natural composition and selective cell interactions make them promising drug carriers. However, in order to harness their properties, efficient exogenous drug encapsulation methods need to be investigated. Here, EVs from various cellular origins (endothelial, cancer and stem cells) were produced and characterised for size and composition. Porphyrins of different hydrophobicities were employed as model drugs and encapsulated into EVs using various passive and active methods (electroporation, saponin, extrusion and dialysis). Hydrophobic compounds loaded very efficiently into EVs and at significantly higher amounts than into standard liposomes composed of phosphocholine and cholesterol using passive incubation. Moreover, loading into EVs significantly increased the cellular uptake by >60% and the photodynamic effect of hydrophobic porphyrins in vitro compared to free or liposome encapsulated drug. The active encapsulation techniques, with the saponin-assisted method in particular, allowed an up to 11 fold higher drug loading of hydrophilic porphyrins compared to passive methods. EVs loaded with hydrophilic porphyrins induced a stronger phototoxic effect than free drug in a cancer cell model. Our findings create a firm basis for the development of EVs as smart drug carriers based on straightforward and transferable methods. PMID:25483424

  17. 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

  18. 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

  19. Anisotropic Iron Motion in Nitrosyl Iron Porphyrinates: Natural and Synthetic Hemes

    PubMed Central

    2015-01-01

    The vibrational spectra of two five-coordinate nitrosyl iron porphyrinates, [Fe(OEP)(NO)] (OEP = dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin) and [Fe(DPIX)(NO)] (DPIX = deuteroporphyrin IX), have been studied by oriented single-crystal nuclear resonance vibrational spectroscopy. Single crystals (both are in the triclinic crystal system) were oriented to give vibrational spectra perpendicular to the porphyrin plane. Additionally, two orthogonal in-plane measurements that were also either perpendicular or parallel to the projection of the FeNO plane onto the porphyrin plane yield the complete set of vibrations with iron motion. In addition to cleanly enabling the assignment of the FeNO bending and stretching modes, the measurements reveal that the two in-plane spectra from the parallel and perpendicular in-plane directions for both compounds have substantial differences. The assignment of these in-plane vibrations were aided by density functional theory predictions. The differences in the two in-plane directions result from the strongly bonded axial NO ligand. The direction of the in-plane iron motion is thus found to be largely parallel and perpendicular to the projection of the FeNO plane on the porphyrin plane. These axial ligand effects on the in-plane iron motion are related to the strength of the axial ligand-to-iron bond. PMID:24528178

  20. Examination of Apollo 17 surface fines for porphyrins and aromatic hydrocarbons

    NASA Technical Reports Server (NTRS)

    Rho, J. H.

    1974-01-01

    An Apollo 17 surface fines sample 75081,78, collected from Station 5, was extracted and examined fluorometrically. No porphyrins were found with fluorometric methods capable of detecting 2 times 10 to the minus 14th moles/g of Ni-mesoporphyrin IX in the sample. Also aromatic hydrocarbons were undetected.