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Sample records for perylene monoimide derivative

  1. Pi-Stack Engineering of Semiconducting Perylene Tetracarboxylic Derivatives

    NASA Astrophysics Data System (ADS)

    Xue, Chenming

    In the past decades, there has been intensive research in generating novel perylene tetracarboxylic derivatives because of a vast number of applications based on their semiconducting characteristics. The properties of the new materials rely heavily on not only the single molecular structure, but also the way of molecular packing in condensed states. The formation of effective pi-stacking structures is the key issue. In this thesis, I focused in synthesizing novel perylene tetracarboxylic derivatives by attaching various substituents at the imide nitrogens. Consequently different phases appeared and exhibited different way of molecular packing. In Chapter 1, it is the general background of perylene tetracarboxylic derivatives including (a) synthesis routes, (b) optical and electronic properties, (c) the molecular packing in condensed phases or assembling in solutions; and also the introduction of condensed state phases including amorphous, crystalline and liquid crystalline (LC) phases. In Chapter 2, a series of solution processible amorphous glassy perylene tetracarboxylic diimides (PDIs) has been designed, synthesized and characterized. The pi-stacking order in the amorphous glass phase was successfully tailored by the steric means and qualitatively evaluated. In Chapter 3, the n-alkyl chain length dependence of a series of two-dimensional (2D) smectic LC PDIs has been explored. When the n-alkyl chain is no shorter than decyl group, the PDI could exhibit a novel 2D crystalline smectic LC phase. In this phase, the PDI cores microphase separate from flexible n-alkyl chains forming 2D crystalline layers. Thermoanalysis data quantitatively reveal that the n-alkyl chains in this phase have the essentially the same order as that in the isotropic liquid state. Such truly disordered n-alkyl chains effectively decouple the inter-layer molecular correlation and make the phase genuine LC. The PDI pi-stacking order in this LC phase is crystalline because it is a part of the 2

  2. Perylene Derivatives As Useful SERRS Reporters, Including Multiplexing Analysis.

    PubMed

    Tenori, Eleonora; Colusso, Andrea; Syrgiannis, Zois; Bonasera, Aurelio; Osella, Silvio; Ostric, Adrian; Lazzaroni, Roberto; Meneghetti, Moreno; Prato, Maurizio

    2015-12-30

    Five perylene bisimide (PBI) derivatives were designed and synthesized, on the basis of quantum-chemical calculations. The influence of halogen substituents on the shape and energy of the frontier orbitals and the Raman spectra were calculated, in the prospect use in surface-enhanced resonance Raman scattering (SERRS) studies. The corresponding experiments confirmed a very strong SERRS response in the presence of pristine (i.e., uncoated) gold nanoparticles. These spectra can be used for multiplexing measurements, namely measurements in which, by using a single laser excitation, one can recognize the simultaneous presence of several analytes. PMID:26252443

  3. Effect of nitrogen-containing substituents on fragmentation of perylene derivatives under laser irradiation

    NASA Astrophysics Data System (ADS)

    Komolov, A. S.; Komolov, S. A.; Lazneva, E. F.; Turiev, A. M.

    2012-01-01

    The effect of nitrogen-containing substituents such as phenyl imide and actyl imide on the character of fragmentation of perylene derivative molecules under laser irradiation has been studied by laser desorption (LD) mass spectrometry. Replacement of the central oxygen atom by a nitrogen atom in anhydride carboxy groups in perylene tetracarboxylic dianhydride (PTCDA) molecule results in the suppression of CO2 desorption and predominant desorption of CO. The LD mass spectrum exhibits peaks that correspond to fragments of the perylene nucleus and those of the aromatic and aliphatic substituents. Intact PTCDA molecules are present in the desorbed flux in insignificant amounts.

  4. Perylene derivatives produced by Alternaria alternata, an endophytic fungus isolated from Laurencia species.

    PubMed

    Gao, Shu-Shan; Li, Xiao-Ming; Wang, Bin-Gui

    2009-11-01

    Two new perylene derivatives, 7-epi-8-hydroxyaltertoxin I (1) and 6-epi-stemphytriol (2), along with two known compounds stemphyperylenol (3) and altertoxin I (4) were isolated from Alternaria alternata, a marine endophytic fungus derived from an unidentified algal species of the genus Laurencia. Structures of compounds 1-4 were determined on the basis of detailed spectroscopic analysis, as well as by comparison with literature reports. The antimicrobial activities of compounds 1 and 3 against Staphylococcus aureus, Escherichia coli, and Aspergillus niger were evaluated; neither showed obvious activity. PMID:19967977

  5. Morphology-controlled growth of perylene derivative induced by double-hydrophilic block copolymers

    NASA Astrophysics Data System (ADS)

    Huang, Minghua; Antonietti, Markus; Cölfen, Helmut

    2016-01-01

    Controlled growth of technically relevant perylene derivative 3, 4, 9, 10-perylenetetracarboxylic acid potassium salt (PTCAPS), with tuneable morpologies, has been successfully realized by a recrystallization method using a double-hydrophilic block copolymer poly (ethylene glycol)-block poly (ethyleneimine) (PEG-b-PEI) as the structure directing agent. The {001} faces of PTCAPS are most polar and adsorb the oppositively charged polymer additive PEG-b-PEI well by electrostatic attraction. By simply adjusting the PEG-b-PEI concentration, systematic morphogenesis of PTCAPS from plates to microparticles composed of various plates splaying outwards could be realized. Furthermore, the variation of pH value of the recrystallization solution could induce the change of the interaction strength between PEG-b-PEI additive and PTCAPS and thus modify the morphology of PTCAPS from microparticles composed of various plates to ultralong microbelts.

  6. Photophysical characterization of perylene derivatives and their interaction with human serum albumin

    NASA Astrophysics Data System (ADS)

    Farooqi, Mohammed Junaid

    The study of the binding and effects of polyaromatic hydro-carbons (PAH) to proteins remains one of the fundamental aspects of research in biophysics. Among other processes, ligand binding can regulate the function of proteins including inhibiting their action. Binding to small ligands remains a very important aspect in the study of the function of many proteins. We have investigated a number of novel perylene analogues. The investigation includes the photophysical characterization of perylene diimides and their interaction with HSA. In this study we have shown that 3,9-disubstitutes perylenes show weak affinity to binding with HSA and their irradiation produces no observable structural effects on the bound protein. Perylene Diimides were photophysically characterized in organic solvents. PDI phenylalanine and leucine are the only PDIs spectroscopically observable in aqueous solution and bind with HSA with great affinity. Resonance energy transfer was observed in PDIF bound to HSA with an energy efficiency of 0.268.

  7. The perylene derivative BASF-241 solution as a new tunable dye laser in the visible

    NASA Astrophysics Data System (ADS)

    Ivri, J.; Burshtein, Z.; Miron, E.; Reisfeld, R.; Eyal, M.

    1990-09-01

    Basic optical properties of the perylene derivative BASF-241 solution in chloroform relevant to its application as a dye laser were measured. The fluorescence spectrum, excited by frequency-doubled (532-nm) Nd:YAG laser pulses, shows three pronounced peaks centered at 540, 580, and 630 nm, with a Stokes shift and mirror image in relation to the absorption spectrum. The quantum yield was about a unity, with a lifetime of 5.0 +/- 0.5 ns. Addition of trichloroacetic acid (CCl3COOH) causes a red shift of absorption and fluorescence spectra by about 750/cm-L/mol. In a cavity consisting of a about 100 percent reflecting back mirror and an 8 percent reflecting output coupler, lasing was obtained at 577 nm, with a threshold of about 10 micro-J/pulse, and a slope efficiency of about 8 percent. Medium losses were attributed to excited singlet-singlet absorption of cross section 1-2 x 10 to the -16th sq cm. Using a grating, a tuning range of almost 20 nm was obtained, centered at the 0-1 fluorescence emission peak. The laser range shifted to the red when the dye was dissolved in chloroform with an increasing concentration of trichloroacetic acid. The BASF-241 solution in chloroform thus appears to be a new, promising material for a dye laser.

  8. Single-Molecule Break Junctions Based on a Perylene-Diimide Cyano-Functionalized (PDI8-CN2) Derivative

    NASA Astrophysics Data System (ADS)

    Frisenda, Riccardo; Parlato, Loredana; Barra, Mario; van der Zant, Herre S. J.; Cassinese, Antonio

    2015-07-01

    In this letter, we report the single-molecule conductance properties of a cyano-functionalized perylene-diimide derivative (PDI8-CN2) investigated with gold nano-electrodes. This molecule is of large interest for the fabrication of high-performance and air-stable n-type organic field-effect transistors. Low-bias experiments performed on mechanically controllable break junctions reveal the presence of two different values of the single-molecule conductance, which differ by about two orders of magnitudes. Up to date, this feature was never observed for other perylene-diimide compounds having alternative chemical moieties attached to the basic aromatic core. Theoretical calculations suggest that the highest single-molecule conductance value here observed, comprised between 10-2 and 10-3 G0, is related to a charge transport path directly linking the two cyano groups.

  9. Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach.

    PubMed

    Navarro, Amparo; Fernández-Liencres, M Paz; Peña-Ruiz, Tomás; García, Gregorio; Granadino-Roldán, José M; Fernández-Gómez, Manuel

    2016-08-01

    Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ∼0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier compared to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integral values ∼0.3 eV with a relative disc orientation of 25°, which is the preferred angle according to the dimer energy profile. All the results indicate that the tetraselenium-substituted derivative, not synthetized so far, could be a promising candidate among those studied in this work for the fabrication of n-type semiconductors based on columnar discotic liquid crystals materials. PMID:27497578

  10. Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach

    NASA Astrophysics Data System (ADS)

    Navarro, Amparo; Fernández-Liencres, M. Paz; Peña-Ruiz, Tomás; García, Gregorio; Granadino-Roldán, José M.; Fernández-Gómez, Manuel

    2016-08-01

    Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ˜0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier compared to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integral values ˜0.3 eV with a relative disc orientation of 25°, which is the preferred angle according to the dimer energy profile. All the results indicate that the tetraselenium-substituted derivative, not synthetized so far, could be a promising candidate among those studied in this work for the fabrication of n-type semiconductors based on columnar discotic liquid crystals materials.

  11. Fabrication and humidity sensing performance studies of a fluorescent film based on a cholesteryl derivative of perylene bisimide.

    PubMed

    Zhang, Shujuan; Zhou, Feng; Peng, Haonan; Liu, Taihong; Ding, Liping; Fang, Yu

    2016-08-01

    A fluorescent film based on a cholesteryl derivative of perylene bisimide (PTCDI-co-CholDEA) was fabricated via utilization of an electrostatic spinning technique on a glass plate surface. SEM studies revealed that the film was characterized by fibrous network structure. It is the structure and the chemical composition that make the fluorescence emission of the film sensitive to the variation of local environmental humidity. The sensitivity of the sensing is 0.1497 (×10(4)a.u. of the intensity)/1% RH, of which RH is the abbreviation of relative humidity. The maximum quenching efficiency of the film is 55.4% when humidity reaches 97% RH. Furthermore, the sensing process is fully reversible, and presence of other commonly found liquids shows little effect to the monitoring process. PMID:27131145

  12. STM-induced light emission from thin films of perylene derivatives on the HOPG and Au substrates

    PubMed Central

    2011-01-01

    We have investigated the emission properties of N,N'-diheptyl-3,4,9,10-perylenetetracarboxylic diimide thin films by the tunneling-electron-induced light emission technique. A fluorescence peak with vibronic progressions with large Stokes shifts was observed on both highly ordered pyrolytic graphite (HOPG) and Au substrates, indicating that the emission was derived from the isolated-molecule-like film condition with sufficient π-π interaction of the perylene rings of perylenetetracarboxylic diimide molecules. The upconversion emission mechanism of the tunneling-electron-induced emission was discussed in terms of inelastic tunneling including multiexcitation processes. The wavelength-selective enhanced emission due to a localized tip-induced surface plasmon on the Au substrate was also obtained. PMID:21711870

  13. Fabrication and humidity sensing performance studies of a fluorescent film based on a cholesteryl derivative of perylene bisimide

    NASA Astrophysics Data System (ADS)

    Zhang, Shujuan; Zhou, Feng; Peng, Haonan; Liu, Taihong; Ding, Liping; Fang, Yu

    2016-08-01

    A fluorescent film based on a cholesteryl derivative of perylene bisimide (PTCDI-co-CholDEA) was fabricated via utilization of an electrostatic spinning technique on a glass plate surface. SEM studies revealed that the film was characterized by fibrous network structure. It is the structure and the chemical composition that make the fluorescence emission of the film sensitive to the variation of local environmental humidity. The sensitivity of the sensing is 0.1497 (× 104 a.u. of the intensity)/1% RH, of which RH is the abbreviation of relative humidity. The maximum quenching efficiency of the film is 55.4% when humidity reaches 97% RH. Furthermore, the sensing process is fully reversible, and presence of other commonly found liquids shows little effect to the monitoring process.

  14. A sensitive electrochemiluminescent aptasensor based on perylene derivatives as a novel co-reaction accelerator for signal amplification.

    PubMed

    Yu, Yan-Qing; Zhang, Hai-Yu; Chai, Ya-Qin; Yuan, Ruo; Zhuo, Ying

    2016-11-15

    Herein, a novel signal amplification strategy was designed using the perylene derivative as the co-reaction accelerator toward graphene-CdTe quantum dots (G-CdTe)/S2O8(2-) system to construct a highly sensitive electrochemiluminescent (ECL) aptasensor for thrombin (TB) detection. Firstly, the G-CdTe nanocomposites were prepared by one-step method of in situ generating CdTe quantum dots onto the surface of the graphene oxide by using 3-mercaptopropionic acid as the CdTe QDs stabilizer. Then, a kind of perylene derivative (PTC-Lys), was synthesized by covalently binding L-lysine to 3,4,9,10-perylenetetracarboxylic acid, which was further immobilized onto the G-CdTe by the π-π* stacking and cross-linked the detection thrombin aptamer (TBA II) to obtain the TBA II/PTC-Lys/G-CdTe signal probes. It is worth pointing out that PTC-Lys acting as an efficient co-reaction accelerator interacted with the co-reactant of S2O8(2-) rather than G-CdTe to promote the more oxidant mediators of SO4(•-), which could further react with G-CdTe to produce excited state species G-CdTe* for emitting light. Compared with the G-CdTe/S2O8(2-) ECL system, our proposed strategy with the introduction of co-reaction accelerator of PTC-Lys exhibited ultra-high sensitivity to quantify the concentration of TB from 1.0×10(-7)nM to 10nM with a detection limit of 34aM. PMID:27148827

  15. Perylene-derived single-component organic nanoparticles with tunable emission: efficient anticancer drug carriers with real-time monitoring of drug release.

    PubMed

    Jana, Avijit; Nguyen, Kim Truc; Li, Xin; Zhu, Pengcheng; Tan, Nguan Soon; Ågren, Hans; Zhao, Yanli

    2014-06-24

    An organic nanoparticle-based drug delivery system with high drug loading efficacy (∼79 wt %) was developed using a perylene-derived photoremovable protecting group, namely, perylene-3,4,9,10-tetrayltetramethanol (Pe(OH)4). The anticancer drug chlorambucil was protected by coupling with Pe(OH)4 to form photocaged nanoparticles (Pe(Cbl)4). The photorelease mechanism of chlorambucil from the Pe(Cbl)4 conjugate was investigated experimentally by high-resolution mass spectrometry and theoretically by density functional theory calculations. The Pe(Cbl)4 nanoparticles perform four important roles: (i) a nanocarrier for drug delivery, (ii) a phototrigger for drug release, (iii) a fluorescent chromophore for cell imaging, and (iv) a photoswitchable fluorophore for real-time monitoring of drug release. Tunable emission of the perylene-derived nanoparticles was demonstrated by comparing the emission properties of the Pe(OH)4 and Pe(Cbl)4 nanoparticles with perylene-3-ylmethanol. These nanoparticles were subsequently employed in cell imaging for investigating their intracellular localization. Furthermore, the in vivo toxicity of the Pe(OH)4 nanoparticles was investigated using the mouse model. Histological tissue analysis of five major organs, i.e., heart, kidney, spleen, liver, and lung, indicates that the nanoparticles did not show any obvious damage to these major organs under the experimental conditions. The current research presents a successful example of integrating multiple functions into single-component organic nanoparticles for drug delivery. PMID:24824959

  16. Single-molecule redox blinking of perylene diimide derivatives in water.

    PubMed

    Cordes, Thorben; Vogelsang, Jan; Anaya, Milena; Spagnuolo, Carla; Gietl, Andreas; Summerer, Wolfram; Herrmann, Andreas; Müllen, Klaus; Tinnefeld, Philip

    2010-02-24

    Dynamic developments in ultrasensitive and superresolution fluorescence microscopy call for improved fluorescence markers with increased photostability and new functionalities. We used single-molecule spectroscopy to study water-soluble perylene dicarboximide fluorophores (PDI), which were immobilized in aqueous buffer by attaching the fluorophore to DNA. Under these conditions bright fluorescence, comparable to that of single-molecule compatible organic fluorophores, is observed with homogeneous spectral and fluorescence decay time distributions. We additionally show how the fluorescence of the PDI can be controlled through photoinduced electron-transfer reactions by using different concentrations of reductants and oxidants, yielding either blinking or stable emission. We explain these properties by the redox potentials of PDI and the recently introduced ROXS (reducing and oxidizing system) concept. Finally, we evaluate how this fluorescence control of PDIs can be used for superresolution "Blink-Microscopy" in aqueous or organic media and more generally for single-molecule spectroscopy. PMID:20121094

  17. Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

    PubMed

    Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

    2009-01-01

    Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide. PMID:19197929

  18. Phosphorescent perylene imides.

    PubMed

    Ventura, Barbara; Langhals, Heinz; Böck, Bernd; Flamigni, Lucia

    2012-05-01

    Asymmetrically substituted perylene imide derivatives PIa and PIx display phosphorescence in glassy matrices at 77 K. The lifetime is 49.0 ms for PIa and 13.5 ms for PIx. The triplet energy is 1.79 eV for PIa and 1.68 eV for PIx as confirmed by sensitization experiments of the C(60) triplet. PMID:22436977

  19. Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives

    PubMed Central

    Vagnini, Michael T.; Smeigh, Amanda L.; Blakemore, James D.; Eaton, Samuel W.; Schley, Nathan D.; D’Souza, Francis; Crabtree, Robert H.; Brudvig, Gary W.; Co, Dick T.; Wasielewski, Michael R.

    2012-01-01

    Photodriving the activity of water-oxidation catalysts is a critical step toward generating fuel from sunlight. The design of a system with optimal energetics and kinetics requires a mechanistic understanding of the single-electron transfer events in catalyst activation. To this end, we report here the synthesis and photophysical characterization of two covalently bound chromophore-catalyst electron transfer dyads, in which the dyes are derivatives of the strong photooxidant perylene-3,4:9,10-bis(dicarboximide) (PDI) and the molecular catalyst is the Cp∗Ir(ppy)Cl metal complex, where ppy = 2-phenylpyridine. Photoexcitation of the PDI in each dyad results in reduction of the chromophore to PDI•- in less than 10 ps, a process that outcompetes any generation of 3∗PDI by spin-orbit-induced intersystem crossing. Biexponential charge recombination largely to the PDI-Ir(III) ground state is suggestive of multiple populations of the PDI•--Ir(IV) ion-pair, whose relative abundance varies with solvent polarity. Electrochemical studies of the dyads show strong irreversible oxidation current similar to that seen for model catalysts, indicating that the catalytic integrity of the metal complex is maintained upon attachment to the high molecular weight photosensitizer. PMID:22586073

  20. Visible-light driven oxidation of gaseous aliphatic alcohols to the corresponding carbonyls via TiO2 sensitized by a perylene derivative.

    PubMed

    Guarisco, Chiara; Palmisano, Giovanni; Calogero, Giuseppe; Ciriminna, Rosaria; Di Marco, Gaetano; Loddo, Vittorio; Pagliaro, Mario; Parrino, Francesco

    2014-10-01

    Sensitized P25 TiO2 was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N'-bis(2-(1-piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO2 allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2-propanol. The reaction was carried out under cut-off (λ > 400 nm) simulated solar radiation in O2 atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was evaluated by cyclic voltammetry. The optimal organic sensitizing amount was found to be 5.6 % w/w in terms of yield in carbonyl derivatives. Moreover, no change in reactivity/selectivity was observed after 10-h irradiation thus confirming the catalyst stability. Yields into formaldehyde, acetaldehyde, and acetone were 67, 70, and 96 %, respectively. No significant amounts of organic byproducts were detected but for methanol oxidation, whereas a minor amount of the substrate degraded to CO2. PMID:24469771

  1. Perylene and coronene derivatives binding to G-rich promoter oncogene sequences efficiently reduce their expression in cancer cells.

    PubMed

    Micheli, Emanuela; Altieri, Alessandro; Cianni, Lorenzo; Cingolani, Chiara; Iachettini, Sara; Bianco, Armandodoriano; Leonetti, Carlo; Cacchione, Stefano; Biroccio, Annamaria; Franceschin, Marco; Rizzo, Angela

    2016-06-01

    A novel approach to cancer therapeutics is emerging in the field of G-quadruplex (G4) ligands, small molecules designed to stabilize four-stranded structures that can form at telomeres as well as in other genomic sequences, including oncogene promoter sequences, 5'-UTR regions and introns. In this study, we investigated the binding activity of perylene and coronene derivatives PPL3C, CORON and EMICORON to G4 structures formed within the promoter regions of two important cancer-related genes, c-MYC and BCL-2, and their biochemical effects on gene and protein expression. In order to fully characterize the ability of the selected ligands to bind and stabilize the G4 structures originated by the c-MYC and BCL-2 promoter sequences, we performed electrospray ionization mass spectrometry (ESI-MS), Fluorescence Resonance Energy Transfer (FRET) measurements, Circular Dichroism (CD) spectra and polymerase stop assay. Altogether our results showed that the ligands had a high capacity in binding and stabilizing the G4 structures within the c-MYC and BCL-2 promoter sequences in vitro. Notably, when we evaluated by quantitative real-time PCR and western blotting analysis, the effects of treatment with the different G4 ligands on c-MYC and BCL2 expression in a human melanoma cell line, EMICORON appeared the most effective compound in reducing the mRNA and protein levels of both genes. These results encourage to consider EMICORON as a promising example of multimodal class of an antineoplastic drug, affecting different tumor crucial pathways simultaneously: telomere maintenance (as previously described), cell proliferation and apoptosis via down-regulation of both c-MYC and BCL-2 (this paper). PMID:27086081

  2. Operating longevity of organic light-emitting diodes with perylene derivatives as aggregating light-emitting-layer additives: Expansion of the emission zone

    NASA Astrophysics Data System (ADS)

    Jarikov, Viktor V.; Young, Ralph H.; Vargas, J. Ramon; Brown, Christopher T.; Klubek, Kevin P.; Liao, Liang-Sheng

    2006-11-01

    We describe aggregating perylene derivatives as light-emitting-layer (LEL) additives in organic light-emitting diodes (OLEDs). These molecules readily form emissive aggregates when added to the LEL. In the resulting devices, the aggregates show moderate external quantum efficiencies of 0.9%-1.7%, which can be improved to 2.7%-4.0% by further adding a proper dopant. Importantly, addition of these polycyclic aromatic hydrocarbons increases the half-life (t50) of undoped and doped OLEDs by 30-150 times. Thus, 11cd/A green and 5.2cd/A red devices are produced that have pure color, Commission Internationale de l'Eclairage 1931 2° color chromaticity coordinates (CIEx ,y) 0.32, 0.63 and 0.64, 0.36, respectively, and t50 of 30 000 and 200 000h, respectively, upon operation at 40mA/cm2. A possible link between the thickness of the emission zone and the lifetime increase is illustrated by comparing aluminum 8-hydroxyquinoline chelate (Alq3) as an LEL host versus an Alq3+dibenzo[b ,k]perylene mixed host using C545T as an emissive probe. The comparison suggests that the emission zone and probably the electron-hole recombination zone are expanded for the mixed host.

  3. Time-dependent aggregation-induced enhanced emission, absorption spectral broadening, and aggregation morphology of a novel perylene derivative with a large D-π-A structure.

    PubMed

    Yang, Long; Yu, Yuyan; Zhang, Jin; Ge, Feijie; Zhang, Jianling; Jiang, Long; Gao, Fang; Dan, Yi

    2015-05-01

    Strong aggregation-caused quenching of perylene diimides (PDI) is changed successfully by simple chemical modification with two quinoline moieties through C=C at the bay positions to obtain aggregation-induced enhanced emission (AIEE) of a perylene derivative (Cya-PDI) with a large π-conjugation system. Cya-PDI is weakly luminescent in the well-dispersed CH(3)CN or THF solutions and exhibits an evident time-dependent AIEE and absorption spectra broadening in the aggregated state. In addition, morphological inspection demonstrates that the morphology of the aggregated form of Cya-PDI molecules changed from plate-shaped to rod-like aggregates under the co-effects of time and water. An edge-to-face arrangement of aggregation was proposed and discussed. The fact that the Cya-PDI aggregates show a broad absorption covering the whole visible-light range and strong intermolecular interaction through π-π stacking in the solid state makes them promising materials for optoelectric applications. PMID:25643930

  4. Monolayer Phases of a Dipolar Perylene Derivative on Au(111) and Surface Potential Build-Up in Multilayers.

    PubMed

    Niederhausen, Jens; Kersell, Heath R; Christodoulou, Christos; Heimel, Georg; Wonneberger, Henrike; Müllen, Klaus; Rabe, Jürgen P; Hla, Saw-Wai; Koch, Norbert

    2016-04-19

    9-(Bis-p-tert-octylphenyl)-amino-perylene-3,4-dicarboxy anhydride (BOPA-PDCA) is a strongly dipolar molecule representing a group of asymmetrically substituted perylenes that are employed in dye-sensitized solar cells and hold great promise for discotic liquid crystal applications. Thin BOPA-PDCA films with orientated dipole moments can potentially be used to tune the energy-level alignment in electronic devices and store information. To help assessing these prospects, we here elucidate the molecular self-assembly and electronic structure of BOPA-PCDA employing room temperature scanning tunneling microscopy and spectroscopy in combination with ultraviolet and X-ray photoelectron spectroscopies. BOPA-PCDA monolayers on Au(111) exclusively form in-plane antiferroelectric phases. The molecular arrangements, the increase of the average number of molecules per unit cell via ripening, and the rearrangement upon manipulation with the STM tip indicate an influence of the dipole moment on the molecular assembly and the rearrangement. A slightly preferred out-of-plane orientation of the molecules in the multilayer induces a surface potential of 1.2 eV. This resembles the giant surface potential effect that was reported for vacuum-deposited tris(8-hydroxyquinoline)aluminum and deemed applicable for data storage. Notably, the surface potential in the case of BOPA-PDCA can in part be reversibly removed by visible light irradiation. PMID:26991048

  5. Host-Guest Chemistry between Perylene Diimide (PDI) Derivatives and 18-Crown-6: Enhancement in Luminescence Quantum Yield and Electrical Conductivity.

    PubMed

    Lasitha, P; Prasad, Edamana

    2016-07-18

    Perylene diimide (PDI) derivatives exhibit a high propensity for aggregation, which causes the aggregation-induced quenching of emission from the system. Host-guest chemistry is one of the best-known methods for preventing aggregation through the encapsulation of guest molecules. Herein we report the use of 18-crown-6 (18-C-6) as a host system to disaggregate suitably substituted PDI derivatives in methanol. 18-C-6 formed complexes with amino-substituted PDIs in methanol, which led to disaggregation and enhanced emission from the systems. Furthermore, the embedding of the PDI⋅18-C-6 complexes in poly(vinyl alcohol) (PVA) films generated remarkably high emission quantum yields (60-70 %) from the PDI derivatives. More importantly, the host-guest systems were tested for their ability to conduct electricity in PVA films. The electrical conductivities of the self-assembled systems in PVA were measured by electrochemical impedance spectroscopy (EIS) and the highest conductivity observed was 2.42×10(-5)  S cm(-1) . PMID:27319975

  6. A model for triple helix formation on human telomerase reverse transcriptase (hTERT) promoter and stabilization by specific interactions with the water soluble perylene derivative, DAPER.

    PubMed

    Rossetti, Luigi; D'Isa, Giuliana; Mauriello, Clementina; Varra, Michela; De Santis, Pasquale; Mayol, Luciano; Savino, Maria

    2007-08-01

    The promoter of human telomerase reverse transcriptase (hTERT) gene, in the region from -1000 to +1, contains two homopurine-homopyrimidine sequences (-835/-814 and -108/-90), that can be considered as potential targets to triple helix forming oligonucleotides (TFOs) for applying antigene strategy. We have chosen the sequence (-108/-90) on the basis of its unfavorable chromatin organization, evaluated by theoretical nucleosome positioning and nuclease hypersensitive sites mapping. On this sequence, anti-parallel triplex with satisfactory thermodynamic stability is formed by two TFOs, having different lengths. Triplex stability is significantly increased by specific interactions with the perylene derivative N,N'-bis[3,3'-(dimethylamino) propylamine]-3,4,9,10-perylenetetracarboxylic diimide (DAPER). Since DAPER is a symmetric molecule, the induced Circular Dichroism (CD) spectra in the range 400-600 nm allows us to obtain information on drug binding to triplex and duplex DNA. The drug-induced ellipticity is significantly higher in the case of triplex with respect to duplex and, surprisingly, it increases at decreasing of DNA. A model is proposed where self-stacked DAPER binds to triplex or to duplex narrow grooves. PMID:17560709

  7. A derivative photoelectrochemical sensing platform for 4-nitrophenolate contained organophosphates pesticide based on carboxylated perylene sensitized nano-TiO2.

    PubMed

    Li, Hongbo; Li, Jing; Xu, Qin; Yang, Zhanjun; Hu, Xiaoya

    2013-03-01

    A novel visible light sensitized photoelectrochemical sensing platform was constructed based on the perylene-3,4,9,10-tetracarboxylic acid/titanium dioxide (PTCA/TiO(2)) heterojunction as the photoelectric beacon. PTCA was synthesized via facile steps of hydrolysis and neutralization reaction, and then the PTCA/TiO(2) heterojunction was easily prepared by coating PTCA on nano-TiO(2) surface. The resulting photoelectric beacon was characterized by transmission electron microscope, scanning electron microscopy, X-ray diffractometry, FTIR spectroscopy, and ultraviolet and visible spectrophotometer. Using parathion-methyl as a model, after a simple hydrolyzation process, p-nitrophenol as the hydrolysate of parathion-methyl could be obtained, the fabricated derivative photoelectrochemical sensor showed good performances with a rapid response, instrument simple and portable, low detection limit (0.08 nmol L(-1)) at a signal-to-noise ratio of 3, and good selectivity against other pesticides and possible interferences. It had been successfully applied to the detection of parathion-methyl in green vegetables and the results agreed well with that by GC-MS. This strategy not only extends the application of PTCA, but also presents a simple, economic and novel methodology for photoelectrochemical sensing. PMID:23427799

  8. Bay-Annulated Perylene Tetraesters: A New Class of Discotic Liquid Crystals.

    PubMed

    Gupta, Ravindra Kumar; Pathak, Suraj Kumar; Pradhan, Balaram; Gupta, Monika; Pal, Santanu Kumar; Sudhakar, Achalkumar Ammathnadu

    2016-03-16

    Selenium-annulated perylene tetraesters that stabilize the hexagonal columnar phase have been synthesized and characterized, and their thermal and photophysical behavior has been determined. The mesophase range decreased with an increase in chain length. A comparative account of the structure-property relationships of this series of compounds with respect to parent perylene tetraesters, N- and S-annulated perylene tetraesters, in terms of their thermal, photophysical and electrochemical behavior is provided. The bay-annulation of perylene tetraesters is a good option to modify the thermal and photophysical properties of perylene derivatives and it can provide a new avenue for the synthesis of several technologically important self-assembling perylene derivatives. PMID:26748430

  9. New insights into the origin of perylene in geological samples

    NASA Astrophysics Data System (ADS)

    Grice, Kliti; Lu, Hong; Atahan, Pia; Asif, Muhammad; Hallmann, Christian; Greenwood, Paul; Maslen, Ercin; Tulipani, Svenja; Williford, Kenneth; Dodson, John

    2009-11-01

    The origin of the polycyclic aromatic hydrocarbon (PAH) perylene in sediments and petroleum has been a matter of continued debate. Reported to occur in Phanerozoic organic matter (OM), fossil crinoids and tropical termite mounds, its mechanism of formation remains unclear. While a combustion source can be excluded, structural similarities to perylene quinone-like components present in e.g. fungi, plants, crinoids and insects, potentially suggest a product-precursor relationship. Here, we report perylene concentrations, 13C/ 12C, and D/H ratios from a Holocene sediment profile from the Qingpu trench, Yangtze Delta region, China. Perylene concentrations differ from those of pyrogenic PAHs, and rise to prominence in a stratigraphic interval that was dominated by woody vegetation as determined by palynology including fungal spores. In this zone, perylene concentrations exhibit an inverse relationship to the lignin marker guaiacol, D/H ratios between -284‰ and -317‰, similar to the methoxy groups in lignin, as well as co-variation with spores from wood-degrading fungi. 13C/ 12C of perylene differs from that of land plant wax alkanes and falls in the fractionation range expected for saprophytic fungi that utilise lignin, which is isotopically lighter than cellulose and whole wood. During progressive lignin degradation, the relative carbon isotopic ratio of the perylene decreases. We therefore hypothesise a relationship of perylene to the activity of wood-degrading fungi. To support our hypothesis, we analysed a wide range of Phanerozoic sediments and oils, and found perylene to generally be present in subordinate amounts before the evolutionary rise of vascular plants, and to be generally absent from marine-sourced oils, few exceptions being attributed perhaps to a contribution of marine and/or terrestrial-derived fungi, anoxia (especially under marine conditions) and/or contamination of core material by fungi. A series of low-molecular-weight aromatic quinones

  10. Perylene and its geochemical significance.

    NASA Technical Reports Server (NTRS)

    Aizenshtat, Z.

    1973-01-01

    Perylene was found in a variety of marine sediments, in a shale and in peat. It is suggested that its precursors arise predominantly from land organisms and are carried into oceanic traps along with detrital minerals. When rates of deposition are fast, and reducing conditions are established within the sediment, biogenic pigment precursors of perylene are converted to the polycyclic aromatic hydrocarbon, which is then stabilized by pi-bonding with metals and protected from degradation.

  11. Thermodynamic properties of Langmuir layers created of monoimide perylenetetracarboxylic acid derivatives

    NASA Astrophysics Data System (ADS)

    Hertmanowski, R.; Piosik, E.; Martyński, T.

    2016-04-01

    Langmuir films formed of some fluorescent dyes, 3,4-bis-pentyl ester of 9,10-N-(n-pentylimide)-perylenetetracarboxylic acid, as well as their mixtures with arachidic acid, were studied. Surface pressure versus mean molecular area isotherms for Langmuir films were reordered and the alignment of molecules at the air-water interface was estimated. The isotherms show that the dye molecules do not lie flat onto the water surface but are tilted with respect to the normal to the interface. The surface pressure-area isotherms of Langmuir films formed from the dye/arachidic acid mixture provide evidence for phase separation of the components within almost the entire range of mole fractions. A repulsive interaction between molecules was observed in all two components of Langmuir films.

  12. Electronic structure of p-type perylene monoimide-based donor-acceptor dyes on the nickel oxide (100) surface: a DFT approach.

    PubMed

    Kontkanen, O V; Niskanen, M; Hukka, T I; Rantala, T T

    2016-05-25

    A p-type dye-sensitized solar cell, where the dye injects a hole into the semiconductor, could be combined with a typical Grätzel cell to create an efficient tandem device. However, the current p-type devices suffer from low efficiency. Here, geometries and electronic structures of four perylenemonoimide-based dyes () both as free and adsorbed on the NiO(100) semiconductor surface have been investigated to gain a better understanding of the p-type devices. In particular, the electronic transitions relevant to charge transfer between the dye and the surface have been identified. Excitations have been evaluated using the time-dependent DFT calculations, and the roles of frontier orbitals and band edges in transitions have been assessed. The adsorbed dyes can adopt either upright or slightly tilted geometries depending on the structure of the anchoring group and the binding mode of the dye. The adsorption slightly lowers the NiO band gap, from 4.06 eV to 3.90-3.96 eV, depending on the surface-adsorbate system and the band gaps of the dye molecules by 0.1-0.2 eV. Additionally, the adsorption mode of dye moves the LUMO+1 level down by 0.5 eV. The effective mass of charge carrier holes is significantly smaller at the NiO surface than in the bulk indicating the importance of surface conductivity. We also found that the potential drop, i.e. the driving force for charge transfer from NiO to the dye molecule, depends on the adsorption mode of . PMID:27224900

  13. Comparison of the electronic structure of different perylene-based dye-aggregates.

    PubMed

    Settels, Volker; Liu, Wenlan; Pflaum, Jens; Fink, Reinhold F; Engels, Bernd

    2012-07-01

    Aggregates of functionalized polycyclic aromatic molecules like perylene derivatives differ in important optoelectronic properties such as absorption and emission spectra or exciton diffusion lengths. Although those differences are well known, it is not fully understood if they are caused by variations in the geometrical orientation of the molecules within the aggregates, variations in the electronic structures of the dye aggregates or interplay of both. As this knowledge is of interest for the development of materials with optimized functionalities, we investigate this question by comparing the electronic structures of dimer systems of representative perylene-based chromophores. The study comprises dimers of perylene, 3,4,9,10-perylene tetracarboxylic acid bisimide (PBI), 3,4,9,10-perylene tetracarboxylic acid dianhydride (PTCDA), and diindeno perylene (DIP). Potential energy curves (PECs) and characters of those electronic states are investigated which determine the optoelectronic properties. The computations use the spin-component-scaled approximate coupled-cluster second-order method (SCS-CC2), which describes electronic states of predominately neutral excited (NE) and charge transfer (CT) character equally well. Our results show that the characters of the excited states change significantly with the intermolecular orientation and often represent significant mixtures of NE and CT characters. However, PECs and electronic structures of the investigated perylene derivatives are almost independent of the substitution patterns of the perylene core indicating that the observed differences in the optoelectronic properties mainly result from the geometrical structure of the dye aggregate. It also hints at the fact that optical properties can be computed from less-substituted model compounds if a proper aggregate geometry is chosen. PMID:22514040

  14. Pedogenic Formation of Perylene in a Terrestrial Soil Profile: Evidence From Carbon Isotopic Ratios

    NASA Astrophysics Data System (ADS)

    Gocht, T.; Jochmann, M. A.; Blessing, M.; Barth, J.; Schmidt, T. C.; Grathwohl, P.

    2005-12-01

    Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POP), which are introduced into the environment mainly due to combustion of fossil fuel. Perylene is one compound of the PAHs that consists of 5 condensed rings like the well known carcinogenic benzo(a)pyrene. Apart from the pyrogenic formation, there are strong indications that it is produced biologically and/or diagenetically under anaerobic conditions. This conclusion was derived from the presence of perylene in deeper parts of marine and lacustrine sediment profiles, where the combustion-derived PAHs are almost absent ( Lima et al., 2003). 13C/12C compound-specific stable isotopic ratios were successfully applied for the differentiation of probably biologically generated perylene in tropical termite nests and pyrolytic perylene from surface soils of temperate regions ( Wilcke et al., 2002). Our study is the first aiming on the determination of the different processes of perylene formation at one location using carbon isotopic ratios such as 13C/12C. We determined PAHs in natural soils of southern Germany. At one location in the Black Forest we found for the first time evidence for natural perylene production in the subsoil of terrestrial environments. Apart from the combustion derived PAHs that accumulate at the top of all soil profiles, the depth distribution of perylene shows the highest peak in the subsoil about 1 m below the surface. Due to its very low solubility (0.4 μg l-1 at 25 °C) vertical transport of perylene with seepage water is very unlikely. Thus, we suggest atmospheric deposition of pyrogenic perylene at the top of the profile and in-situ generation in the subsoil, probably due to microbial activities. In order to distinguish between the pyrogenic and natural generation we employed 13C/12C compound-specific stable isotope analysis of perylene in soil samples from the top of the profile as well as from the subsoil. Preliminary measurements with soil extracts show strong

  15. Self-assembly of luminescent N-annulated perylene tetraesters into fluid columnar phases.

    PubMed

    Gupta, Ravindra Kumar; Pathak, Suraj Kumar; Pradhan, Balaram; Shankar Rao, D S; Krishna Prasad, S; Achalkumar, Ammathnadu S

    2015-05-14

    A new class of N-annulated perylene tetraesters and their N-alkylated derivatives has been synthesized. N-Annulated perylene tetraesters stabilize a hexagonal columnar phase over a broad temperature range. The hexagonal columnar phase exhibited by these compounds shows good homeotropic alignment with few defects. Annulation in the bay region of the perylene tetraesters enhanced the width of the mesophase compared with the parent tetraesters. N-Alkylation of these compounds perturbed the self-assembly behaviour and the resulting compounds were non-mesomorphic. A bright green luminescence was visible under long wavelength UV light. These properties suggest that these materials may have promising applications in organic electronics. PMID:25812168

  16. Benzo[g,h,i]perylene

    Integrated Risk Information System (IRIS)

    Benzo [ g , h , i ] perylene ; CASRN 191 - 24 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Nonc

  17. The initial growth behavior of perylene on Cu(100)

    NASA Astrophysics Data System (ADS)

    Hu, Fang; Zhang, Hanjie; Mao, Hongying; Liao, Qing; He, Pimo

    2011-05-01

    Using scanning tunneling microscopy (STM) together with density functional theory (DFT) the growth behavior of perylene on the Cu(100) substrate has been investigated. As revealed by STM images, perylene molecules prefer to adopt lying configuration with their molecular plane parallel to the substrate, and two symmetrically equivalent ordered domains were observed. DFT calculations show that perylene molecule prefers to adsorb on the top site of substrate Cu atoms with its long molecular axis aligning along the [011] or [01-1] azimuth of the substrate which is the most stable adsorption geometry according to its highest binding energy. Consequently, two adsorption structures of c(8×4) and c(8×6), each containing two perylene molecules per unit cell, are proposed based on our STM images. The growth mechanism for ordered perylene domains on Cu(100) can be attributed to the balance between weak adsorbate-adsorbate interaction and comparable adsorbate-substrate interaction.

  18. Photoinduced electron transfer in perylene-TiO2 nanoassemblies.

    PubMed

    Llansola-Portoles, Manuel J; Bergkamp, Jesse J; Tomlin, John; Moore, Thomas A; Kodis, Gerdenis; Moore, Ana L; Cosa, Gonzalo; Palacios, Rodrigo E

    2013-01-01

    The photosensitization effect of three perylene dye derivatives on titanium dioxide nanoparticles (TiO2 NPs) has been investigated. The dyes used, 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2) and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10-tetracarboxy dianhydride (3) have in common bisanhydride groups that convert into TiO2 binding groups upon hydrolysis. The different substituents on the bay position of the dyes enable tuning of their redox properties to yield significantly different driving forces for photoinduced electron transfer (PeT). Recently developed TiO2 NPs having a small average size and a narrow distribution (4 ± 1 nm) are used in this work to prepare the dye-TiO2 systems under study. Whereas successful sensitization was obtained with 1 and 2 as evidenced by steady-state spectral shifts and transient absorption results, no evidence for the attachment of 3 to TiO2 was observed. The comparison of the rates of PeT (kPeT ) for 1- and 2-TiO2 systems studied in this work with those obtained for previously reported analogous systems, having TiO2 NPs covered by a surfactant layer (Hernandez et al. [2012] J. Phys. Chem. B., 117, 4568-4581), indicates that kPeT for the former systems is slower than that for the later. These results are interpreted in terms of the different energy values of the conduction band edge in each system. PMID:23742178

  19. Source identification of perylene in surface sediments and waterbird eggs in the Anzali Wetland, Iran.

    PubMed

    Zamani, Mojtaba; Khorasani, Nematollah; Bakhtiari, Alireza Riyahi; Rezaei, Karamatollah

    2015-10-01

    Following the marked increase of perylene concentration in southern coast of Caspian Sea, waterbird eggs were used as biomonitoring agents. Surface sediments and eggs of five bird species were collected from colonies in Anzali Wetland in the above coast for perylene analysis. The perylene concentrations in sediment and egg samples ranged within 70.6-204.4 and 25.5-43.2 ng/g dw, respectively. Diagnostic perylene ratios showed that the perylene found in all samples was of biogenic origin, possibly developing from terrestrial materials. The combination pattern of perylene was found to be similar in all samples. Conclusively, perylene observed in the area was transmitted from sediments in breeding areas into the eggs, so the eggs are biomonitoring agents and the prevalence of oxic conditions in surface sediments limits formation of perylene, reflecting perylene formation in the catchment area. We found that perylene distribution in surface sediments follows irregular patterns, representing significant effects from local inputs. PMID:26000756

  20. Interaction of albumin with perylene-diimides with aromatic substituents

    NASA Astrophysics Data System (ADS)

    Farooqi, Mohammed; Penick, Mark; Burch, Jessica; Negrete, George; Brancaleon, Lorenzo

    2015-03-01

    Polyaromatic hydrocarbons (PAH) binding to proteins remains one of the fundamental aspects of research in biophysics. Ligand binding can regulate the function of proteins. Binding to small ligands remains a very important aspect in the study of the function of many proteins. Perylene diimide or PDI derivatives have attracted initial interest as industrial dyes and pigments. Recently, much attention has been focused on their strong π - π stacks resulting from the large PDI aromatic core. These PDI stacks have distinct optical properties, and provide informative models that mimic the light-harvesting system and initial charge separation and charge transfer in the photosynthetic system. The absorption property of PDI derivatives may be largely tuned from visible to near-infrared region by chemical modifications at the bay-positions. We are currently studying a new class of PDI derivatives with substituents made of the side chains of aromatic amino acids (Tyrosine, Tryptophan and Phenylalanine). We have looked at the fluorescence absorption and emission of these PDIs in water and other organic solvents. PDIs show evidence of dimerization and possible aggregation. We also present binding studies of these PDIs with Human Serum Albumin (HSA). The binding was studied using fluorescence emission quenching of the HSA Tryptophan residue. Stern-Volmer equation is used to derive the quenching constants. PDI binding to HSA also has an effect on the fluorescence emission of the PDIs themselves by red shifting the spectra. Funded by RCMI grant.

  1. Regioselective functionalization of core-persubstituted perylene diimides.

    PubMed

    Yue, Wan; Jiang, Wei; Böckmann, Marcus; Doltsinis, Nikos L; Wang, Zhaohui

    2014-04-25

    Regioselective functionalization of core per-substituted perylene diimides has been achieved efficiently based on a new versatile building block, named tetrabromotetrachloro-perylene-3,4:9,10-tetracarboxylic acid dianhydride (Br4Cl4-PTCDA), which affords a series of novel chromophores with impressive optoelectronic properties. Direct palladium-catalyzed fourfold intramolecular ring fusion affords successfully unique propeller-shaped biscarbazole[2,3-b]carbazole diimides with six annulated rings. PMID:24687914

  2. Highly fluorescent complexes with 3-isocyanoperylene and N-(2,5-di-tert-butylphenyl)-9-isocyano-perylene-3,4-dicarboximide.

    PubMed

    Lentijo, S; Expósito, J E; Aullón, G; Miguel, J A; Espinet, P

    2014-07-28

    The perylene derivatives 3-isocyanoperylene (Per-N≡C) (4a) and N-(2,5-di-tert-butylphenyl)-9-isocyano-perylene-3,4-dicarboximide (PMI-N≡C) (4b) were prepared and used to synthesize gold complexes [AuX(CNR)] (X = C6F5 (5a,b), C6F4-O(n)Bu-p (6b)). The reaction of 5b and 6b with HNEt2 led to the carbene complexes [AuX{C(NEt2)(NHR)}] (7b, 8b), respectively. The molecular structure of complexes 7b and 8b have been determined by X-ray diffraction analysis showing intermolecular π-stacking of the perylene groups and C6F5 rings and no Au···Au interactions. The derivative compounds [M(CO)5(CNR)] (M = Cr (9a,b), Mo (10a,b) or W (11a,b)) and trans-[Pd(CNR)2(C6F3Cl2)2] (12a,b) were also prepared. All complexes exhibit fluorescence associated with the perylene fragment with emission quantum yields, in solution at room temperature, in the range 0.05-0.93 and emission lifetimes ~ 4 ns. DFT calculations were performed of the absorption spectra of the ligands Per-N≡C and PMI-N≡C and representative complexes [Au(C6F5)(CNR)], [Cr(CO)5(CNR)], showing a perylene-dominated intraligand π-π* emissive state, from the HOMO and LUMO orbitals of the perylene chromophore, but with significantly different absorption maxima by the influence of the metal fragment, particularly significant in the Per-N≡C derivatives. PMID:24901028

  3. Chiral Perylene Diimides: Building Blocks for Ionic Self‐Assembly

    PubMed Central

    Echue, Geraldine; Lloyd‐Jones, Guy C.

    2015-01-01

    Abstract A chiral perylene diimide building block has been prepared based on an amine derivative of the amino acid l‐phenylalanine. Detailed studies were carried out into the self‐assembly behaviour of the material in solution and the solid state using UV/Vis, circular dichroism (CD) and fluorescence spectroscopy. For the charged building block BTPPP, the molecular chirality of the side chains is translated into the chiral supramolecular structure in the form of right‐handed helical aggregates in aqueous solution. Temperature‐dependent UV/Vis studies of BTPPP in aqueous solution showed that the self‐assembly behaviour of this dye can be well described by an isodesmic model in which aggregation occurs to generate short stacks in a reversible manner. Wide‐angle X‐ray diffraction studies (WXRD) revealed that this material self‐organises into aggregates with π–π stacking distances typical for π‐conjugated materials. TEM investigations revealed the formation of self‐assembled structures of low order and with no expression of chirality evident. Differential scanning calorimetry (DSC) and polarised optical microscopy (POM) were used to investigate the mesophase properties. Optical textures representative of columnar liquid–crystalline phases were observed for solvent‐annealed samples of BTPPP. The high solubility, tunable self‐assembly and chiral ordering of these materials demonstrate their potential as new molecular building blocks for use in the construction of chiro‐optical structures and devices. PMID:25689392

  4. Improving the photoinduced charge separation parameters in corrole-perylene carboximide dyads by tuning the redox and spectroscopic properties of the components.

    PubMed

    Flamigni, Lucia; Ciuciu, Adina I; Langhals, Heinz; Böck, Bernd; Gryko, Daniel T

    2012-03-01

    A couple of corrole-perylene carboximide dyads (C2-PIa and C2-PIx) have been synthesized and their photoreactivity has been evaluated. We aimed at obtaining better performances for photoinduced charge separation, both in terms of efficiency and in terms of lifetime, with respect to formerly studied systems. The energy level of the charge-separated state was tuned by selecting perylene and corrole components with diverse redox and spectroscopic properties. High spectroscopic energy levels of the perylene carboximide derivatives (PIs) allow a fast charge separation to be maintained in competition with an energy-transfer process from the PI to the corrole unit. Yields and lifetimes of charge separation in toluene are, respectively, 75% and 2.5 μs for C2-PIa and 65% and 24 ns for C2-PIx. The results and the effect of solvent polarity are discussed in the framework of current energy- and electron-transfer theories. PMID:22234895

  5. Understanding and optimising the packing density of perylene bisimide layers on CVD-grown graphene

    NASA Astrophysics Data System (ADS)

    Berner, Nina C.; Winters, Sinéad; Backes, Claudia; Yim, Chanyoung; Dümbgen, Kim C.; Kaminska, Izabela; Mackowski, Sebastian; Cafolla, Attilio A.; Hirsch, Andreas; Duesberg, Georg S.

    2015-10-01

    The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale.The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale. Electronic supplementary information (ESI) available

  6. Amphiphilic tribranched scaffolds with polyaromatic panels that wrap perylene stacks displaying unusual emissions.

    PubMed

    Suzuki, Akira; Akita, Munetaka; Yoshizawa, Michito

    2016-08-21

    A rigid tribranched scaffold with three anthracene panels was synthesized using a stereocontrolled 1,3,5-triphenylbenzene core. Grinding a mixture of the rigid scaffold and perylene leads to the quantitative formation of a spherical assembly containing stacked perylene molecules in water. The wrapped perylenes exhibit unusual Y-type excimer-like emission (λmax = ∼500 nm) at room temperature. In contrast, an analogous assembly from a flexible tribranched scaffold and perylene shows E-type emission (λmax = ∼610 nm) from the wrapped perylenes under the same conditions. PMID:27444246

  7. Dinitro and mononitrobenzo(ghi)perylenes and mononitrocoronene are highly mutagenic in the Ames Salmonella assay

    SciTech Connect

    Vance, W.A.; Chan, R.

    1983-01-01

    Benzo(ghi)perylene (B(ghi)Per, (191-24-2)) and coronene (Cor, (191-07-1)) are major constituents of the polycyclic aromatic hydrocarbons (PAH) found in automobile exhaust and polluted air. Nitration of these PAH by NO/sub 2/ and traces of HNO/sub 3/, which are also formed in automobile exhaust, seems highly probable. To identify the presence of these nitroarenes in environmental samples and to examine their mutagenic potencies the authors synthesized and characterized nitro derivatives of both PAH. 5-NO/sub 2/B(ghi)Per(81316-87-2) and 1-NO/sub 2/Cor(81316-84-9) produced 405 and 340 reverants/nmole, respectively, in TA98 in the presence of 0.6 mg of microsomal enzymes (S-9) per plate in the Ames test. 5,8-diNO/sub 2/B(ghi)Per (83292-25-5) and 5,10-diNO/sub 2/B(ghi)Per (83292-26-6) produced 21,500 and 4000 revertants/nmole in TA98NR without microsomal activation. Mutagenicity for the dinitrobenzo(ghi)perylenes was also high in TA98NR and TA97 but was reduced by 97% in TA98-1,8DNP. There is close similarity in the orientation and distances between reactive sites (nitronium ion and carbocation) on the dinitrobenzo(ghi)perylenes and 1,6 dinitropyrene (42397-64-8) and 1,8-dinitropyrene (42397-65-9).

  8. Fluorene-Perylene Diimide Arrays onto Graphene Sheets for Photocatalysis.

    PubMed

    Stergiou, Anastasios; Tagmatarchis, Nikos

    2016-08-24

    A facile approach for introducing photoactive poly(fluorene-perylene diimide) arrays (PFPDI) onto graphene sheets was accomplished. Noncovalent PFPDI/graphene ensembles formed via π-π stacking interactions between the two components and covalent PFPDI-graphene hybrids realized upon a Stille polycondensation reaction between an iodobenzyl-functionalized graphene, a 9,9-dialkyl substituted fluorene diboronic acid, and a 1,7-dibromo-PDI derivative were prepared. The morphology of PFPDI/graphene and PFPDI-graphene was evaluated by high-resolution transmission electron microscopy (HR-TEM), revealing the presence of even monolayered graphene sheets. Moreover, their photophysical and redox properties as assessed by electronic absorption spectroscopy and steady-state as well as time-resolved photoluminescence assays and electrochemistry, respectively, disclosed charge-transfer characteristics owing to the high photoluminescence quenching of PFPDI in the presence of graphene and the fast component attributed to the decay of the emission intensity of the singlet excited state of PFPDI in both PFPDI/graphene and PFPDI-graphene. Next, testing their ability to operate in energy conversion schemes, the PFPDI-graphene was successfully employed as catalyst for the reduction of 4-nitrophenol to 4-aminophenol. Notably, the kinetics for the reduction were enhanced by visible light photoirradiation as compared to dark conditions as well as the presence of PFPDI-graphene, contrasting the case where only PFPDI, in the absence of graphene, was employed. Finally, recycling of the catalyst PFPDI-graphene was achieved and reutilization in successive reduction reactions of 4-nitrophenol was found to proceed with the same efficiency. PMID:27483330

  9. Miscibility between differently shaped mesogens: structural and morphological study of a phthalocyanine-perylene binary system.

    PubMed

    Zucchi, Gaël; Viville, Pascal; Donnio, Bertrand; Vlad, Alexandru; Melinte, Sorin; Mondeshki, Mihail; Graf, Robert; Spiess, Hans Wolfgang; Geerts, Yves H; Lazzaroni, Roberto

    2009-04-23

    The thermotropic, structural, and morphological properties of blends of a disk-like liquid crystalline phthalocyanine derivative and a lath-shaped perylenetetracarboxidiimide mesogen derivative have been studied by combining differential scanning calorimetry, thermal polarized optical microscopy, X-ray diffraction, solid-state nuclear magnetic resonance, and atomic force microscopy. The two compounds are fully miscible for blends containing at least 60 mol % of the disk-like molecule. In such composition range, the homogeneous blends form a columnar hexagonal (Col(h)) mesophase for which the thermal stability is enhanced compared to that of the corresponding mesophase of the pure phthalocyanine. The miscible blends self-align homeotropically between two glass slides. For blends containing between 55 and 40 mol % of the disk-shaped molecule, the two components are fully miscible at high temperature but the perylene derivative forms a separate crystalline phase when the temperature is decreased. Phase separation is systematically observed in blends containing less than 40 mol % of the discotic molecule. In this case, the resulting Col(h) mesophase is less stabilized compared to the blends containing a larger amount of the phthalocyanine derivative. These phase-separated blends do not show any homeotropic alignment. AFM investigations confirm the formation of a single columnar morphology in the phthalocyanine-rich blends, consistent with the full miscibility between the two compounds. Solid-state NMR measurements on the mixed phase show the influence of the presence of the perylene molecules on the molecular dynamics of the molecules; remarkably, the presence of the host molecules improves the local order parameter in the phthalocyanine columnar phase. PMID:19301888

  10. Effect of the ortho alkylation of perylene bisimides on the alignment and self-assembly properties.

    PubMed

    Dasgupta, Debarshi; Kendhale, Amol M; Debije, Michael G; Ter Schiphorst, Jeroen; Shishmanova, Ivelina K; Portale, Giuseppe; Schenning, Albertus P H J

    2014-08-01

    The effect of the ortho alkylation of perylene bisimides on the alignment and self-assembly properties has been studied. It was found that the dichroic properties of perylene bisimides in a liquid crystal host can be reversed with a single synthetic step by ortho alkylation. Furthermore, a solvent-induced growth of ultralong organic n-type semiconducting fibrils from non-ortho-alkylated perylene bisimide was observed. Ortho substitution of the perylene bisimide core alters the mode of fibrillar growth, leading to isotropic crystallization. PMID:25478308

  11. Chiral Perylene Materials by Ionic Self-Assembly.

    PubMed

    Echue, Geraldine; Hamley, Ian; Lloyd Jones, Guy C; Faul, Charl F J

    2016-09-01

    Two chiral complexes (1-SDS and 1-SDBS) were prepared via the ionic self-assembly of a chiral perylene diimide tecton with oppositely charged surfactants. The effect of surfactant tail architecture on the self-assembly properties and supramolecular structure was investigated in detail using UV-vis, IR, circular dichroism, light microscopy, X-ray diffraction studies, and electron microscopy. The results obtained revealed the molecular chirality of the parent perylene tecton could be translated into supramolecular helical chirality of the resulting complexes via primary ionic interactions through careful choice of solvent and concentration. Differing solvent-dependent aggregation behavior was observed for these complexes as a result of the different possible noncovalent interactions via the surfactant alkyl tails. The results presented in this study demonstrate that ionic self-assembly (ISA) is a facile strategy for the production of chiral supramolecular materials based on perylene diimides. The structure-function relationship is easily explored here due to the wide selection and easy availability of common surfactants. PMID:27486788

  12. Theoretical Determination of The Optimum Thickness of Perylene Layer in Bilayer Phthalocyanine/Perylene Photovoltaic Device

    NASA Astrophysics Data System (ADS)

    Pratiwi, Herlina; Siahaan, Timothy; Satriawan, Mirza; Nurwantoro, Pekik; Triyana, Kuwat

    2009-09-01

    We do theoretical study on thickness of the active layers in a heterojunction bilayer thin film photovoltaic device based on copper phthalocyanine (CuPc)/perylene that gives the highest Incident Photon to Current Efficiency (IPCE). The device we study consists Glass (1 mm)/ITO (Indium Tin Oxide, 120 nm)/CuPc (50 nm)/PTCDA (3, 4, 9, 10-perylenetetracarboxylic dianhydride, x nm)/Ag (40 nm), where x is the thickness of the PTCDA layer that we calculate here. The calculation is based on assumption that the photocurrent generation process is the result of the creation of photogenerated excitons, which difuse before dissociated at the CuPc/PTCDA interface following the diffusion equation, by internal optical electric field that comes from light exposure. We also assume that almost all photocurrent is created in the CuPc/PTCDA interface. Because the order of the thickness of the active layers is the same or smaller than of the wavelength of visible light, we take into account the effect of reflection and interference in the calculation of internal optical electric field distribution inside the device by making use complex indices of refraction of the active materials in our calculation. The modulus of it is proportional with the number generated excitons. The general solution of the exciton diffusion equation was used for calculating the photocurrent and the IPCE. Here, we find the optimum thickness of PTCDA layer that gives greatest IPCE at the wavelength of 344 nm and 467 nm, which are the wavelengths at which the absorption coefficients of CuPc and PTCDA, respectively, reach the maximum values.

  13. 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

  14. Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes.

    PubMed

    Hernández, Laura I; Godin, Robert; Bergkamp, Jesse J; Llansola Portolés, Manuel J; Sherman, Benjamin D; Tomlin, John; Kodis, Gerdenis; Méndez-Hernández, Dalvin D; Bertolotti, Sonia; Chesta, Carlos A; Mariño-Ochoa, Ernesto; Moore, Ana L; Moore, Thomas A; Cosa, Gonzalo; Palacios, Rodrigo E

    2013-04-25

    We report on the photosensitization of titanium dioxide nanoparticles (TiO2 NPs) synthesized inside AOT (bis(2-ethylhexyl) sulfosuccinate sodium salt) reverse micelles following photoexcitation of perylene derivatives with dicarboxylate anchoring groups. The dyes, 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2), and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10-tetracarboxy dianhydride (3), have considerably different driving forces for photoinduced electron injection into the TiO2 conduction band, as estimated by electrochemical measurements and quantum mechanical calculations. Fluorescence anisotropy measurements indicate that dyes 1 and 2 are preferentially solubilized in the micellar structure, creating a relatively large local concentration that favors the attachment of the dye to the TiO2 surface. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time for 1 and 2. Photoinduced electron transfer from the singlet excited state of 1 and 2 to the TiO2 conduction band (CB) is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2 semiconductor. Steady state and transient spectroscopy indicate that dye 3 does not bind to the TiO2 NPs and does not photosensitize the semiconductor. This observation was rationalized as a consequence of the bulky t-butylphenyloxy groups which create a strong steric impediment for deep access of the dye within the micelle structure to reach the semiconductor oxide surface. PMID:23189921

  15. Formation of ohmic contacts to perylene molecular crystals

    NASA Astrophysics Data System (ADS)

    Hiramoto, Masahiro; Tomioka, Akinori; Suemori, Kouji; Yokoyama, Masaaki

    2004-09-01

    Ohmic contacts to perylene molecular crystals were successfully formed at bromine-doped p-type crystal/platinum junctions and sodium-doped n-type crystal/aluminum junctions to enable hole and electron injection, respectively. Charge-carrier doping of the organic semiconductor surface that was in direct contact with the metal electrodes was revealed as being a requirement for fabricating organic/metal junctions that were ohmic in character. The fabrication of ohmic contacts would be applicable to carrier injection in organic electroluminescent devices and carrier extraction from organic solar cells.

  16. Characterization of novel perylene diimides containing aromatic amino acid side chains.

    PubMed

    Farooqi, Mohammed J; Penick, Mark A; Burch, Jessica; Negrete, George R; Brancaleon, Lorenzo

    2016-01-15

    Perylene diimide derivatives have attracted initial interest as industrial dyes. Recently, much attention has been focused on their strong π-π stacks resulting from the large PDI aromatic core. These PDI stacks have distinct optical properties, and provide informative models that could mimic light-harvesting systems and initial charge transfer typical of photosynthetic systems. The absorption property of PDI derivatives may be tuned from visible to near-infrared region by peripheral substitution. We have studied a new class of PDI derivatives with aryl substituents derived from the side chains of aromatic aminoacids (Tyrosine, Tryptophan and Phenylalanine). We have investigated their absorption and the fluorescence properties in a set of organic solvents and established their different tendencies to aggregate in solution despite their solubility. Most aggregation appears to be unordered. One PDI analogue (the one formed from Tyr) in Methanol, however, appears to form J-type aggregates. Based on our results the compounds appear to be promising for future investigations regarding the interaction of these dyes with biomolecules. PMID:26298679

  17. Perylene in Lake Biwa sediments originating from Cenococcum geophilum in its catchment area

    NASA Astrophysics Data System (ADS)

    Itoh, Nobuyasu; Sakagami, Nobuo; Torimura, Masaki; Watanabe, Makiko

    2012-10-01

    Perylene, which is composed of five benzene rings, is commonly found in sediments throughout the world at concentrations and distributions that are different from those of other polycyclic aromatic hydrocarbons. The only information available on the origin of perylene comes from 4,9-dihydroxyperylene-3,10-quinone (DHPQ), which originates from fungal component symbiosis or from parasites on plants; however, there is no direct evidence of a mechanism of perylene formation. In this study, we examined the relationship between sedimentary perylene and Cenococcum geophilum (C. geophilum) in a catchment area at Lake Biwa. Sclerotium grains of C. geophilum containing DHPQ were found in this catchment area (approximately 40 balls kg-1 dried soil for >1 mm-ϕ), and small sclerotium grains were frequently found in the sediment. In the sediment sample, we also found broken particles containing perylene, and they had a porous structure characteristic of sclerotium grains. Furthermore, the particles contained DHPQ in different transformation stages to perylene via 3,10-perylenequinone (3,10-PQ). This finding was consistent with results from elemental analysis (oxygen/carbon). Because a remarkable amount of DHPQ originating from C. geophilum also exists in the humic acids of soils and because the inputs of compounds to the lake depend strongly on the rivers, perylene in the Lake Biwa sediment originates mainly from the DHPQ of C. geophilum in its catchment area.

  18. Femtosecond Pump-Probe Microspectroscopy of Single Perylene Nanoparticles.

    PubMed

    Ishibashi, Yukihide; Asahi, Tsuyoshi

    2016-08-01

    We have developed a femtosecond pump-probe light scattering microspectroscopic system in which the output of a femtosecond Ti:sapphire oscillator (1 W, 82 MHz) was used as a light source; the pump light is the second harmonics (395 nm) of the laser output, and the probe light is a femtosecond white-light continuum (490-900 nm) generated with a photonic crystal fiber. Detection of the backscattered light from single nanoparticle on a glass substrate allowed us to obtain higher gain of the transient signals by ∼20 times in comparison with the conventional transmittance-mode experiment. This high-sensitivity of the backscattering detection makes it possible to examine ultrafast relaxation dynamics of excited states in organic nanoparticles, which, in general, are lower photodurability than the inorganic one. We applied the system to single nanocrystals of α-form perylene and then succeeded in direct observation of the excimer formation dynamics on a picosecond time scale. Single nanoparticle measurements for the perylene nanocrystals having a size range of 100 to 500 nm suggested that the excimer formation time became short from 2 ps to <0.3 ps for decreasing of the size. PMID:27420175

  19. Perylene bisimides with rigid 2,2'-biphenol bridges at bay area as conjugated chiral platforms.

    PubMed

    Xie, Zengqi; Würthner, Frank

    2010-07-16

    Facile nucleophilic substitution of two chlorine atoms by 2,2'-biphenol at one of the two bay areas (1,12- and 6,7-positions) of core-tetrachlorinated perylene bisimide afforded a novel, completely desymmetrized perylene bisimide building block, which could be further functionalized by substitution of the remaining two chlorine atoms. The atropisomers (P- and M-enantiomers) of the core twisted perylene bisimides were resolved by HPLC on a chiral column at room temperature, and the activation parameters for racemization were elucidated. PMID:20560541

  20. Development of novel fluorescent probe 3-perylene diphenylphosphine for determination of lipid hydroperoxide with fluorescent image analysis

    SciTech Connect

    Chotimarkorn, Chatchawan; Nagasaka, Reiko; Ushio, Hideki . E-mail: hushio@s.kaiyodai.ac.jp; Ohshima, Toshiaki; Matsunaga, Shigeki

    2005-12-16

    A novel fluorescent probe 3-perylene diphenylphosphine (3-PeDPP) was synthesized for the direct analysis of lipid hydroperoxides. The structure of 3-PeDPP was identified by the spectroscopic data, FAB-MS, {sup 1}H NMR, and {sup 13}C NMR. The reactivities of 3-PeDPP with lipid hydroperoxides were investigated in chloroform/MeOH homogeneous solutions and PC liposome model systems oxidized by either 2,2'-azobis(2-amidinopropane)dihydrochloride and photosensitized oxidation. The fluorescence intensity derived from 3-perylene diphenylphosphineoxide (3-PeDPPO) increased proportionally with amount of hydroperoxides produced in homogeneous solutions and liposome model systems. 3-PeDPP was easily incorporated into mouse myeloma SP2 cells and thin tissue section for dynamic membrane lipid peroxidation studies. Linear correlations between fluorescence intensity and amount of hydroperoxides in the cell membrane and tissue sections were obtained. The fluorescence intensity from 2-dimensional image analysis was also well correlated with lipid hydroperoxide level in these models. Thus, the novel probe 3-PeDPP is useful for the direct determination of lipid hydroperoxides in biological materials.

  1. Loss mechanisms in organic solar cells based on perylene diimide acceptors studied by time-resolved photoluminescence

    NASA Astrophysics Data System (ADS)

    Gerhard, Marina; Gehrig, Dominik; Howard, Ian A.; Arndt, Andreas P.; Bilal, Mühenad; Rahimi-Iman, Arash; Lemmer, Uli; Laquai, Frédéric; Koch, Martin

    2016-04-01

    In organic photovoltaics (OPV), perylene diimide (PDI) acceptor materials are promising candidates to replace the commonly used, but more expensive fullerene derivatives. The use of alternative acceptor materials however implies new design guidelines for OPV devices. It is therefore important to understand the underlying photophysical processes, which either lead to charge generation or geminate recombination. In this contribution, we investigate radiative losses in a series of OPV materials based on two polymers, P3HT and PTB7, respectively, which were blended with different PDI derivatives. Our time-resolved photoluminescence measurements (TRPL) allow us to identify different loss mechanisms by the decay characteristics of several excitonic species. In particular, we find evidence for unfavorable morphologies in terms of large-scale pure domains, inhibited exciton transport and incomplete charge transfer. Furthermore, in one of the P3HT-blends, an interfacial emissive charge transfer (CT) state with strong trapping character is identified.

  2. Photoinduced Fluorescence from the Perylene Cation Isolated in Ne and Ar Matrices

    NASA Technical Reports Server (NTRS)

    Joblin, C.; Salama, F.; Allamandola, L.

    1995-01-01

    The fluorescence and fluorescence excitation spectra of the perylene cation isolated in neon and argon matrices are reported. This is the first report of the fluorescence spectrum of a polycyclic aromatic hydrocarbon ion in any phase.

  3. Room-temperature Y-type emission of perylenes by encapsulation within single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Tange, Masayoshi; Okazaki, Toshiya; Liu, Zheng; Suenaga, Kazu; Iijima, Sumio

    2016-04-01

    Fluorescent materials that exhibit large Stokes shifts are useful for suppressing aggregation-caused quenching. Controlling the self-trapped exciton (STE) states in organic dyes with a dimeric structure is one way of tuning Stokes shifts. However, this leads to the spectral broadening of the emissions at room temperature owing to the effects of the surrounding materials on the excited dimers. Here, we demonstrate the effects of confining organic dyes on their optical properties via the encapsulation of perylene molecules within single-walled carbon nanotubes. The encapsulated dimeric perylene exhibits fluorescence with large Stokes shifts and long lifetimes through the STE states. In particular, a noticeable emission of dimeric perylene is observed with a vibronic structure at room temperature; this resembles the Y-type emission of dimeric α-perylene crystals observed only at low temperatures. The results suggest that the isolation of the excited perylene dimers plays an important role in the occurrence of the room-temperature Y-emission.Fluorescent materials that exhibit large Stokes shifts are useful for suppressing aggregation-caused quenching. Controlling the self-trapped exciton (STE) states in organic dyes with a dimeric structure is one way of tuning Stokes shifts. However, this leads to the spectral broadening of the emissions at room temperature owing to the effects of the surrounding materials on the excited dimers. Here, we demonstrate the effects of confining organic dyes on their optical properties via the encapsulation of perylene molecules within single-walled carbon nanotubes. The encapsulated dimeric perylene exhibits fluorescence with large Stokes shifts and long lifetimes through the STE states. In particular, a noticeable emission of dimeric perylene is observed with a vibronic structure at room temperature; this resembles the Y-type emission of dimeric α-perylene crystals observed only at low temperatures. The results suggest that the

  4. Cross-shaped photoluminescence of excimers in perylene crystals

    NASA Astrophysics Data System (ADS)

    Tanaka, Daichi; Numata, Yudai; Nakagawa, Kazuya; Kobayashi, Takayoshi; Tokunaga, Eiji

    2016-04-01

    Cross-shaped excimer (self-trapped exciton) luminescence from α- and β-perylene single crystals of 50-100 μm was found when they were excited at the center of the crystals with a continuous-wave (cw) laser resonant with the exciton absorption. The cross shape is formed by the two lines which intersect at the excited position and are perpendicular to the sides of the crystals of parallelogram shape. Luminescence is emitted from the excited spot and 4 side edges in the cross shape. The most striking feature is that the luminescence intensity at the edges was as high as or higher than at the excited spot. The possibility of the exciton propagation or the waveguide effect is rejected both experimentally and theoretically. This phenomenon can be reasonably explained only when the radiative transition probability of excimers is significantly enhanced at the crystals side edges than at the center due to the lower symmetry.

  5. Cross-shaped photoluminescence of excimers in perylene crystals

    NASA Astrophysics Data System (ADS)

    Tanaka, Daichi; Numata, Yudai; Nakagawa, Kazuya; Kobayashi, Takayoshi; Tokunaga, Eiji

    2016-06-01

    Cross-shaped excimer (self-trapped exciton) luminescence from α- and β-perylene single crystals of 50-100 μm was found when they were excited at the center of the crystals with a continuous-wave (cw) laser resonant with the exciton absorption. The cross shape is formed by the two lines which intersect at the excited position and are perpendicular to the sides of the crystals of parallelogram shape. Luminescence is emitted from the excited spot and 4 side edges in the cross shape. The most striking feature is that the luminescence intensity at the edges was as high as or higher than at the excited spot. The possibility of the exciton propagation or the waveguide effect is rejected both experimentally and theoretically. This phenomenon can be reasonably explained only when the radiative transition probability of excimers is significantly enhanced at the crystals side edges than at the center due to the lower symmetry.

  6. PL and FT-IR characterization of novel polymer thin films: PVCz mixed with perylene and fatty acids

    NASA Astrophysics Data System (ADS)

    Kusano, Hiroyuki; Kuruma, Ichiro; Kitagawa, Masahiko; Ichino, Kunio; Kobayashi, Hiroshi

    1997-04-01

    We have investigated the effect of addition of stearic acid in poly( N-vinylcarbazole) (PVCz) films doped with perylene. Samples were prepared by spin coating technique and characterized by photoluminescence (PL) and Fourier transform-infrared (FT-IR) absorption. It was elucidated that PL emission due to perylene at 450 nm and 480 nm was enhanced and the concentration quenching of the perylene emission was reduced by the addition of stearic acid. Orientation ordering of carbazole base plane and/or perylene ring plane was suggested from IR measurement.

  7. Effect of crystalline microstructure on the photophysical performance of polymer/perylene composite films

    NASA Astrophysics Data System (ADS)

    Feng, Wei; Xu, You-Long; Yi, Wen-Hui; Zhou, Feng; Wang, Xiao-Gong; Katsumi, Yoshino

    2003-04-01

    To obtain high carrier mobility, better charge injection capability and high photovoltaic device conversion efficiency, a powerful strategy is to improve the morphology of the polymer/dye composite films. Conjugated conducting polymer (CP) thin films doped with perylene derivative (PV) of various concentrations were prepared by spin-casting method and their morphology and photovoltaic characteristics were examined. The change in morphology and molecular reorientation occurring in CP-PV composite films upon annealing at different temperatures was investigated using scanning electron microscopy, x-ray diffraction, Fourier transform infrared and UV-vis absorption. By changing the annealing temperature, PV microcrystallines of 8-10µm in size lying parallel to the substrate surface can be obtained. Annealing effect improved the photovoltaic performance of ITO/CP-PV/Al Schottky-type solar cells, which can be attributed to the formation of an electron conducting PV crystal network. Preliminary studies indicate that the morphological structure in CP-PV composite films has an important influence to their photovoltaic properties.

  8. Controllable and stepwise synthesis of soluble ladder-conjugated bis(perylene imide) fluorenebisimidazole as a multifunctional optoelectronic material.

    PubMed

    Chen, Lingcheng; Zhang, Kaichen; Tang, Changquan; Zheng, Qingdong; Xiao, Yi

    2015-02-01

    By a controllable and stepwise strategy, a soluble ladder-conjugated perylene derivative BPI-FBI as the only product has been synthesized, which avoids the tough work to isolate regioisomers generated by a conventional one-step condensation method. BPI-FBI exhibits broad absorption spectra covering the whole visible region from 300 to 700 nm because of the large π-conjugation skeleton and has a low LUMO level inheriting the prototype PDI. In the steady-state space-charge-limited current (SCLC) devices, BPI-FBI exhibits an intrinsic electron mobility of 1.01 × 10(-5) cm(2) V(-1) s(-1). With a high two photon absorbing activity in the near-infrared region from 1200 to 1400 nm, BPI-FBI also exhibits good optical limiting performance, which will be useful for sensor or human eye protection and stabilization of light sources for optical communications. PMID:25574830

  9. Solution Processable n-Type Perylene Diimide Copolymers for Organic Photovoltaics

    SciTech Connect

    Liang, Z.; Cormier, R. A.; Nardes, A. M.; Gregg, B. A.

    2011-01-01

    Perylene diimides are known as promising n-type semiconductor building blocks. Here we report the synthesis and characterization of a set of three soluble poly(perylene diimide)s and their preliminary characterization in organic photovoltaic cells. These polymers are made through the polycondensation of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) with a variety of poly(ethylene glycol) (PEG)- or poly(propylene glycol) (PPG)-based diamine comonomers. The flexible spacer offers increased solubility in organic solvents and allows the perylene core to assume a conformation that promotes favorable cofacial {pi}-{pi} interactions. Mixtures of these polymers with the hole-transporting polymer, poly(3-hexylthiophene) (P3HT) result in significant fluorescence quenching. However, the phase separation occurs on a scale too large for a bulk heterojunction solar cell. The PPGylated poly(perylene diimide) shows an unusually low free electron concentration ({approx}1.0 x 10{sup 12} cm{sup -3}) and therefore makes an excellent model system for future doping studies. These new polymers may have promise as stable electron-conductive layers with large light-absorptivities in solution-processable applications of organic electronics.

  10. Random copolyesters containing perylene bisimide: flexible films and fluorescent fibers.

    PubMed

    Nisha, S Kumari; Asha, S K

    2014-08-13

    Random copolyesters of poly(l-lactic acid) (PLLA) and [poly(1,4-cyclohexylenedimethylene-1,4- cyclohexanedicarboxylate)] (PCCD) incorporating varying mol ratios of perylene bisimide (PBI) were developed via a high-temperature solution-blending approach. PCCD incorporating PBI was developed by melt polycondenzation followed by a polyester-polyester transesterification reaction between PCCD-PBI and PLLA. The polymers exhibited good solubility in common organic solvents and formed free-standing films, which showed bright red emission upon irradiation with ultraviolet radiation. A solid state fluorescence quantum yield of 10% was observed for this PBI based polyester, which was much higher than that reported in literature for PBI based polymers in the solid state (<1%). Strong red fluorescent nanofibers of these polymers were successfully constructed by electrospinning technique. A random copolyester incorporating donor based on oligo(p-pheneylenevinylene) (OPV) and PBI as acceptor chromophore was also synthesized and fluorescence microscopy images of the electrospun fibers of this polymer exhibited blue, green and red emission upon excitation at different wavelengths. The high temperature solution blending approach involving a high molecular weight polymer and a suitably functionalized π conjugated molecule described here is a unique method by which 1D nanostructures of a wide range of π-conjugated chromophores could be fabricated having strong fluorescence, with the scope of application in nanoscale optoelectronics, biological devices, as well as sensing. PMID:25055318

  11. Perylene Diimide Based ``Nanofabric'' Thin Films for Organic Photovoltaic Cells

    NASA Astrophysics Data System (ADS)

    Carter, Austin; Park, June Hyoung; Min, Yong; Epstein, Arthur

    2011-03-01

    We report progress in using a perylene diimide (PDI) nanofabric as an effective electron accepting nanostructure for organic photovoltaics (OPV). A key challenge in OPV continues to be the recovery of electrons after charge separation due to the relatively poor mobility of C60 and related materials. A series of PDI compounds and complexes have been synthesized and used to fabricate nanofibers and thin films using solution and vacuum deposition techniques. Overlaping PDI-based nanofibers form a fast electron-transporting ``nanofabric'' that has been characterized (AFM, PL, UV-vis, etc.) and can be blended with electron donating materials. A solution-processible OPV configuration containing a nanofabric heterojunction (FHJ) of poly(3-hexylthiophene) and the PDI nanofabric was investigated. We observed a significant improvement in power-conversion efficiency due in part to expansion of the interfacial area and the presence of high mobility electron pathways to the LiF/Al electrode. This work is supported by the Wright Center for Photovoltaic Innovation and Commercialization, the Institute for Materials Research and the Center for Affordable Nanoengineering of Polymeric Biomedical Devices.

  12. White organic light-emitting diodes based on incomplete energy transfer from perylene to rubrene

    NASA Astrophysics Data System (ADS)

    Ding, Bangdong; Zhu, Wenqing; Jiang, Xueyin; Zhang, Zhilin

    2008-11-01

    This paper presents organic light-emitting diodes which generate white emission based on both perylene and rubrene doped in 9,10-di(2-naphthyl)anthracene (ADN). In this doping system, the blue dopant perylene not only emitted but also assisted the energy transfer from ADN to rubrene, which contributes to a lower doping concentration of rubrene. The optimal configuration of the device is ITO/TPD(50 nm)/ADN:0.5 wt% perylene:0.006 wt% rubrene(40 nm)/Bphen(25 nm)/LiF(1 nm)/Al. The maximum luminance of 11 665 cd/m 2 at 14 V according to a luminance efficiency of 2.9 cd/A was obtained. A CIE color coordinate of (0.30, 0.37) at 4 mA/cm 2 was also achieved.

  13. Patterned Growth of Organic Semiconductors: Selective Nucleation of Perylene on Self-Assembled Monolayers.

    PubMed

    Pick, André; Witte, Gregor

    2016-08-16

    Organic semiconductors (OSC) have received a large amount of attention because they afford the fabrication of flexible electronic devices. However, the limited resistance to radiation and etching of such materials does not permit their patterning by photolithography, which has been a driving force for the development of integrated circuits and therefore requires alternative structuring techniques. One approach is based on precoating the substrate with self-assembled monolayers (SAMs) to control the nucleation of subsequently deposited OSC layers, but the underlying mechanism is barely understood. Here, we used alkanethiols with different chemical terminations to prepare SAMs on gold substrates serving as model systems to identify the mechanism of selective nucleation for the case of the OSC perylene. Using atomic force microscopy and fluorescence microscopy, we demonstrate that the chemical functionalization of the SAMs determines the adhesion forces for the OSC that are smallest for CF3-terminated and largest for OH-terminated SAMs, hence yielding distinctly different sticking probabilities upon perylene deposition at room temperature. Microcontact printing and immersion were employed to prepare SAM patterns that enable the selective growth of polycrystalline perylene films. A quite different situation is found upon printing long-chain thiols with low vapor pressure, which leads to the transfer of multilayers and favors the growth of perylene single crystallites. In a more abstract scenario, patterns of silicone oil droplets were printed on a gold substrate, which was previously covered with a repelling fluorinated SAM. Such droplets provide nucleation centers for liquid-mediated growth, often yielding platelet-shaped perylene single crystallites without unwanted perylene nucleation on the remaining surface. PMID:27441921

  14. Dispersing perylene diimide/SWCNT hybrids: structural insights at the molecular level and fabricating advanced materials.

    PubMed

    Tsarfati, Yael; Strauss, Volker; Kuhri, Susanne; Krieg, Elisha; Weissman, Haim; Shimoni, Eyal; Baram, Jonathan; Guldi, Dirk M; Rybtchinski, Boris

    2015-06-17

    The unique properties of carbon nanotubes (CNT) are advantageous for emerging applications. Yet, the CNT insolubility hampers their potential. Approaches based on covalent and noncovalent methodologies have been tested to realize stable dispersions of CNTs. Noncovalent approaches are of particular interest as they preserve the CNT's structures and properties. We report on hybrids, in which perylene diimide (PDI) amphiphiles are noncovalently immobilized onto single wall carbon nanotubes (SWCNT). The resulting hybrids were dispersed and exfoliated both in water and organic solvents in the presence of two different PDI derivatives, PP2b and PP3a. The dispersions were investigated using cryogenic transmission electron microscopy (cryo-TEM), providing unique structural insights into the exfoliation. A helical arrangement of PP2b assemblies on SWCNTs dominates in aqueous dispersions, while a single layer of PP2b and PP3a was found on SWCNTs in organic dispersions. The dispersions were probed by steady-state and time-resolved spectroscopies, revealing appreciable charge redistribution in the ground state, and an efficient electron transfer from SWCNTs to PDIs in the excited state. We also fabricated hybrid materials from the PP2b/SWCNT dispersions. A supramolecular membrane was prepared from aqueous dispersions and used for size-selective separation of gold nanoparticles. Hybrid buckypaper films were prepared from the organic dispersions. In the latter, high conductivity results from enhanced electronic communication and favorable morphology within the hybrid material. Our findings shed light onto SWCNT/dispersant molecular interactions, and introduce a versatile approach toward universal solution processing of SWCNT-based materials. PMID:25977989

  15. Design of Acceptors with Suitable Frontier Molecular Orbitals to Match Donors via Substitutions on Perylene Diimide for Organic Solar Cells

    PubMed Central

    Lv, Xiaoli; Li, Zhuoxin; Li, Songyang; Luan, Guoyou; Liang, Dadong; Tang, Shanshan; Jin, Ruifa

    2016-01-01

    A series of perylene diimide (PDI) derivatives have been investigated at the CAM-B3LYP/6-31G(d) and the TD-B3LYP/6-31+G(d,p) levels to design solar cell acceptors with high performance in areas such as suitable frontier molecular orbital (FMO) energies to match oligo(thienylenevinylene) derivatives and improved charge transfer properties. The calculated results reveal that the substituents slightly affect the distribution patterns of FMOs for PDI-BI. The electron withdrawing group substituents decrease the FMO energies of PDI-BI, and the electron donating group substituents slightly affect the FMO energies of PDI-BI. The di-electron withdrawing group substituents can tune the FMOs of PDI-BI to be more suitable for the oligo(thienylenevinylene) derivatives. The electron withdrawing group substituents result in red shifts of absorption spectra and electron donating group substituents result in blue shifts for PDI-BI. The –CN substituent can improve the electron transport properties of PDI-BI. The –CH3 group in different positions slightly affects the electron transport properties of PDI-BI. PMID:27187370

  16. Time-resolved electron transfer from the excited singlet state of anchored perylene into Ag(1 1 0)

    NASA Astrophysics Data System (ADS)

    Gundlach, Lars; Willig, Frank

    2007-11-01

    Perylene chromophores were adsorbed on the Ag(1 1 0) surface via surface bond formation of the -CH 2-SH group that was covalently attached to the perylene moieties. The lowest excited singlet state of perylene was populated with a laser pulse of 440 nm wavelength. The decay of this donor state due to ultrafast electron transfer to the Ag electrode was probed with a second, delayed laser pulse centered at 280 nm that gave rise to a photoemission signal detected in ultra-high-vacuum by a spectrometer. The fit to the measured data revealed a time constant of 15 fs for the electron injection reaction.

  17. Photoinduced processes in self-assembled porphyrin/perylene bisimide metallosupramolecular boxes.

    PubMed

    Indelli, M Teresa; Chiorboli, Claudio; Scandola, Franco; Iengo, Elisabetta; Osswald, Peter; Würthner, Frank

    2010-11-18

    Two new supramolecular boxes, (ZnMC)(2)(rPBI)(2) and (ZnMC)(2)(gPBI)(2), have been obtained by axial coordination of N,N'-dipyridyl-functionalized perylene bisimide (PBI) dyes to the zinc ion centers of two 2+2 porphyrin metallacycles (ZnMC = [trans,cis,cis-RuCl(2)(CO)(2)(Zn·4'-cis-DPyP)](2)). The two molecular boxes involve PBI pillars with different substituents at the bay area: the "red" PBI (rPBI = N,N'-di(4-pyridyl)-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide) containing tert-butylphenoxy substituents and the "green" PBI (gPBI = N,N'-di(4-pyridyl)-1,7-bis(pyrrolidin-1-yl)perylene-3,4:9,10-tetracarboxylic acid bisimide) bearing pyrrolidinyl substituents. Due to the rigidity of the modules and the simultaneous formation of four pyridine-zinc bonds, these discrete adducts self-assemble quantitatively and are remarkably stable in dichloromethane solution. The photophysical behavior of the new supramolecular boxes has been studied in dichloromethane by emission spectroscopy and ultrafast absorption techniques. A different photophysical behavior is observed for the two systems. In (ZnMC)(2)(rPBI)(2), efficient electron transfer quenching of both perylene bisimide and zinc porphyrin chromophores is observed, leading to a charge separated state, PBI(-)-Zn(+), in which a perylene bisimide unit is reduced and zinc porphyrin is oxidized. In the deactivation of the perylene bisimide localized excited state, an intermediate zwitterionic charge transfer state of type PBI(-)-PBI(+) seems to play a relevant role. In (ZnMC)(2)(gPBI)(2), singlet energy transfer from the Zn porphyrin chromophores to the perylene bisimide units occurs with an efficiency of 0.7. This lower than unity value is due to a competing electron transfer quenching, leading to the charge separated state PBI(-)-Zn(+). The distinct photophysical behavior of these two supramolecular boxes is interpreted in terms of energy changes occurring upon replacement of the "red" r

  18. Direct Arylation of Pyrroles via Indirect Electroreductive C-H Functionalization Using Perylene Bisimide as an Electron-Transfer Mediator.

    PubMed

    Sun, Guoquan; Ren, Shuya; Zhu, Xinhai; Huang, Manna; Wan, Yiqian

    2016-02-01

    The indirect electroreductive coupling of aryl halides and pyrroles was successfully conducted using a catalytic amount of perylene bisimide as a mediator in 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([EMIM]NTf2)/DMSO. PMID:26800089

  19. Intersystem crossing rates of single perylene molecules in ortho-dichlorobenzene.

    PubMed

    Verhart, Nico R; Navarro, Pedro; Faez, Sanli; Orrit, Michel

    2016-06-29

    Triplet states can be interesting for optical switching of molecular fluorescence as well as quantum experiments relying on the manipulation of spin states. However, the ground state of molecules is usually a singlet state. It is therefore interesting to study the intersystem crossing (ISC) rates between singlet and triplet states. We have measured the autocorrelation function of the fluorescence from single perylene molecules in an ortho-dichlorobenzene host matrix at cryogenic temperatures (1.3 K). We observed two time scales in the autocorrelation function corresponding to intersystem crossing to two indistinguishable triplet states (TX and TY) and a third triplet state (TZ). By studying the power dependence of the correlation times and contrasts in the autocorrelation functions of single molecules, we determine the ISC rates of perylene for the first time. PMID:27306477

  20. Energy and Electron Transfer Dynamics within a Series of Perylene Diimide/Cyclophane Systems.

    PubMed

    Ryan, Seán T J; Young, Ryan M; Henkelis, James J; Hafezi, Nema; Vermeulen, Nicolaas A; Hennig, Andreas; Dale, Edward J; Wu, Yilei; Krzyaniak, Matthew D; Fox, Athan; Nau, Werner M; Wasielewski, Michael R; Stoddart, J Fraser; Scherman, Oren A

    2015-12-01

    Artificial photosynthetic systems for solar energy conversion exploit both covalent and supramolecular chemistry to produce favorable arrangements of light-harvesting and redox-active chromophores in space. An understanding of the interplay between key processes for photosynthesis, namely light-harvesting, energy transfer, and photoinduced charge separation and the design of novel, self-assembling components capable of these processes are imperative for the realization of multifunctional integrated systems. We report our investigations on the potential of extended tetracationic cyclophane/perylene diimide systems as components for artificial photosynthetic applications. We show how the selection of appropriate heterocycles, as extending units, allows for tuning of the electron accumulation and photophysical properties of the extended tetracationic cyclophanes. Spectroscopic techniques confirm energy transfer between the extended tetracationic cyclophanes and perylene diimide is ultrafast and quantitative, while the heterocycle specifically influences the energy transfer related parameters and the acceptor excited state. PMID:26551041

  1. Stretchable photo sensor using perylene/graphene composite on ridged polydimethylsiloxane substrate.

    PubMed

    Ali, Shawkat; Bae, Jinho; Lee, Chong Hyun

    2015-11-30

    To apply in wearable electronics, we propose a stretchable photo sensor that detects an inversely changed resistance by varying light intensity, which is stably operated up to 25% axial strain. Especially, the stretchabity of the proposed photo sensor is achived by using a uniform ridged substrate made of polydimethylsiloxane (PDMS). The proposed device is composed of a thin film of perylene/graphene composite, which is sandwiched between bottom and top indium tin oxide (ITO) transparent electrodes fabricated through electro-hydrodynamic (EHD) technique. The electrical conductivity of perylene is improved by blending graphene with it. The resistance of the proposed photo sensor changes from 108 MΩ to 87 MΩ within the light intensity range of 0 to 400 lux, respectively. Furthermore, the flexibility is verified through a bendability test from 16 mm down to 0 mm and a bending endurance test for more than 1000 cycles. Uniform and smooth deposition of the active layer is tested through surface morphology characterization. PMID:26698691

  2. Magnetic induced vertical crystal growth of perylene cation radicals on ITO glass surface

    NASA Astrophysics Data System (ADS)

    Micheletto, Ruggero; Matsui, Jun; Oyama, Munetaka; El-Hami, Khalil; Matsushige, Kazumi; Kawakami, Yoichi

    2005-03-01

    Perylene-acetonitrile solution with tetra- n-butyl-ammonium perchlorate (TBAP) is a substance that tends to electro-crystallize and form particular needle-like structures. These perylene materials are studied extensively for their peculiar electrical and optical properties and for the interest in the fundamental phenomena occurring in the electro crystallization process. We introduce here a novel methodology to orient the needle-like crystals by means of electro crystallization in presence of a weak magnetic field. We report details on the technique we used and we present several exceptional SEM pictures of the aggregates growing vertically from the substrate by the effect of the magnetic field. The method introduce a new simple way to control the growth of these intriguing materials and the approach is potentially the basis for the fabrication of new miniaturized devices.

  3. Highly Fluorescent Nanotubes with Tunable Diameter and Wall Thickness Self-Assembled from Asymmetric Perylene Diimides.

    PubMed

    Peng, Cheng; Zhang, Yibin; Zhang, Yifan; Hu, Yanyong; Che, Yanke; Zhao, Jincai

    2016-08-01

    Highly fluorescent bilayer-walled and monolayer-walled nanotubes are assembled from elaborately designed asymmetric perylene diimide (PDI) molecules. The diameter of bilayer-walled nanotubes increases with the size of the branched substituents at the meta-position of the phenyl moiety of PDI molecules, whereas that of monolayer-walled nanotubes remains unchanged regardless of the size of branched substituents. PMID:27375155

  4. Cationic-perylene-G-quadruplex complex based fluorescent biosensor for label-free detection of Pb(2+).

    PubMed

    Zhao, Xu-Hua; Gong, Liang; Wu, Yuan; Zhang, Xiao-Bing; Xie, Jun

    2016-03-01

    In this work we use a water-soluble cationic perylene derivative (compound 1) as the G-quadruplex (G4) structure fluorescence indicator to construct a fluorescent biosensor for simple, rapid and label-free detection of Pb(2+). In the absence of Pb(2+), strong electrostatic interactions between compound 1 and the G-rich DNA probe (PW17) induced the aggregation of compound 1 and resulted in the fluorescence quenching. In the presence of Pb(2+), the PW17 formed Pb(2+)-stabilized G4 structure, which reduced the aggregation of compound 1 and gave rise to high fluorescence. This allowed us to use convenient "mix-and-detect" protocol for quantitative analysis of Pb(2+). Since Pb(2+) can specially induce PW17 to form compact DNA fold, our proposed biosensor displayed high selectivity for Pb(2+). It also exhibited a high sensitivity to Pb(2+), with a limit of detection of 5.0nM observed. Furthermore, the biosensor was applied for the detection of Pb(2+) in urine and paint samples, and both showed satisfactory results. PMID:26717819

  5. Understanding ground- and excited-state properties of perylene tetracarboxylic acid bisimide crystals by means of quantum chemical computations.

    PubMed

    Zhao, Hong-Mei; Pfister, Johannes; Settels, Volker; Renz, Manuel; Kaupp, Martin; Dehm, Volker C; Würthner, Frank; Fink, Reinhold F; Engels, Bernd

    2009-11-01

    Quantum chemical protocols explaining the crystal structures and the visible light absorption properties of 3,4:9,10-perylene tetracarboxylic acid bisimide (PBI) derivates are proposed. Dispersion-corrected density functional theory has provided an intermolecular potential energy of PBI dimers showing several energetically low-lying minima, which corresponds well with the packing of different PBI dyes in the solid state. While the dispersion interaction is found to be crucial for the binding strength, the minimum structures of the PESs are best explained by electrostatic interactions. Furthermore, a method is introduced, which reproduces the photon energies at the absorption maxima of PBI pigments within 0.1 eV. It is based on time-dependent Hartree-Fock (TD-HF) excitation energies calculated for PBI dimers with the next-neighbor arrangement in the pigment and incorporates crystal packing effects. This success provides clear evidence that the electronically excited states, which determine the color of these pigments, have no significant charge-transfer character. The developed protocols can be applied in a routine manner to understand and to predict the properties of such pigments, which are important materials for organic solar cells and (opto-)electronic devices. PMID:19860479

  6. A simple and sensitive label-free fluorescent approach for protein detection based on a Perylene probe and aptamer.

    PubMed

    Lv, Zhenzhen; Liu, Jinchuan; Bai, Wenhui; Yang, Shuming; Chen, Ailiang

    2015-02-15

    Highly sensitive detection of proteins is of great importance for effective clinical diagnosis and biomedical research. However, so far most detection methods rely on antibody-based immunoassays and are usually laborious and time-consuming with poor sensitivity. Here, we developed a simple and ultra-sensitive method to detect a biomarker protein-thrombin by taking advantage of the fluorescent probe Perylene tetracarboxylic acid diimide (PTCDI) derivatives and thrombin aptamer. The water-soluble dye PTCDI shows strong fluorescence in buffer solution for the existence of free dye monomer, but becomes weak after aggregation through self-assembly on nucleic acid aptamer. In the presence of thrombin, it specifically binds to thrombin aptamer which causes the conformational transition between aptamer and PTCDI and results in a significant fluorescence recovery. The results showed that as low as 40 pM of thrombin could be detected by this method. The high sensitivity of the developed sensing system mainly attributes to the ultra-sensitivity of the fluorescence intensity changes of PTCDI. With the specificity of aptamer, the assay exhibited high selectivity for thrombin against three other proteins (bovine serum albumin, lysozyme, mouse IgG) and 1% diluted fetal bovine serum. The detection method might be extended to sensitive detection of a variety of proteins for its advantages of isothermal conditions required, simple and rapid without multiple separation and washing steps. PMID:25310484

  7. Highly Soluble Monoamino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties

    PubMed Central

    Chen, Kew-Yu; Chang, Che-Wei

    2014-01-01

    Three dialkylamino-substituted perylene tetracarboxylic dianhydrides with different n-alkyl chain lengths (n = 6, 12 or 18), 1a–1c, were synthesized under mild conditions in high yields and were characterized by 1H NMR, 13C NMR and high resolution mass spectroscopy. Their optical and electrochemical properties were measured using UV-Vis and emission spectroscopic techniques, as well as cyclic voltammetry (CV). This is the first time that the structures and the properties of monoamino-substituted perylene tetracarboxylic dianhydrides have been reported. These molecules show a deep green color in both solution and the solid state and are soluble in most organic solvents. They all show a unique charge transfer emission in the near-infrared region, and the associated peaks exhibit solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show slightly larger dipole moment changes than those of corresponding perylene diimides, 2a–2c. Additionally, Compounds 1a–1c undergo two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to gain more insight into their molecular structures and optical properties. PMID:25493474

  8. XPS and STEM Study of the Interface Formation between Ultra-Thin Ru and Ir OER Catalyst Layers and Perylene Red Support Whiskers

    SciTech Connect

    Atanasoska, Liliana; Cullen, David A; Hester, Amy E; Atanasoski, Radoslav

    2013-01-01

    The interface formation between perylene red (PR) and ruthenium or iridium OER catalysts has been studied systematically by XPS and STEM. The OER catalyst over-layers with thicknesses ranging from ~0.1 to ~50 nm were vapor deposited onto PR ex-situ. As seen by STEM, Ru and Ir form into nanoparticles, which agglomerate with increased loading. XPS data show a strong interaction between Ru and PR. Ir also interacts with PR although not to the extent seen for Ru. At low coverages, the entire Ru deposit is in the reacted state while a small portion of the deposited Ir remains metallic. Ru and Ir bonding occur at the PR carbonyl sites as evidenced by the attenuation of carbonyl photoemission and the emergence of new peak assigned to C-O single bond. The curve fitting analysis and the derived stoichiometry indicates the formation of metallo-organic bonds. The co-existence of oxide bonds is also apparent.

  9. Core Perylene Diimide Designs via Direct Bay and Ortho (Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties

    SciTech Connect

    Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue B.; Chen, Yu-Sheng; Rumbles, Garry; Strauss, Steven H.; Boltalina, Olga V.

    2015-09-22

    We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay and ortho substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Analysis of the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects of electron withdrawing group substitution at all three positions.

  10. Core Perylene Diimide Designs via Direct Bay- and ortho-(Poly)trifluoromethylation: Synthesis, Isolation, X-Ray Structures, Optical and Electronic Properties

    SciTech Connect

    Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue-Bin; Chen, Yu-Sheng; Rumbles, Garry; Strauss, Steven H.; Boltalina, Olga V.

    2015-09-22

    We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay- and ortho-substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Moreover, analysis of the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects from substituting electron-withdrawing groups at all three positions.

  11. Photo-initiated multi-step electron transfer in donor-acceptor systems using a novel bi-functionalized perylene chromophore

    NASA Astrophysics Data System (ADS)

    Dyar, Scott M.; Smeigh, Amanda L.; Karlen, Steven D.; Young, Ryan M.; Wasielewski, Michael R.

    2015-06-01

    The excited state and redox properties of a new bi-functional perylene redox chromophore, 2,3-dihydro-1-azabenzo[cd]perylene (DABP), are described. Perylene has been widely used in electron donor-acceptor molecules in fields ranging from artificial photosynthesis to molecular spintronics. However, attaching multiple redox components to perylene to carry out multi-step electron transfer reactions often produces hard to separate regioisomers, which complicate data analysis. The use of DABP provides a strategy to retain the electronic properties of perylene, yet eliminate regioisomers. Ultrafast photo-initiated single- and two-step electron transfer reactions in three linear electron donor-acceptor systems incorporating DABP are described to illustrate its utility.

  12. Color Bricks: Building Highly Organized and Strongly Absorbing Multicomponent Arrays of Terpyridyl Perylenes on Metal Oxide Surfaces.

    PubMed

    Sariola-Leikas, Essi; Ahmed, Zafar; Vivo, Paola; Ojanperä, Anniina; Lahtonen, Kimmo; Saari, Jesse; Valden, Mika; Lemmetyinen, Helge; Efimov, Alexander

    2016-01-22

    Terpyridine-substituted perylenes containing cyclic anhydrides in the peri position were synthesized. The anhydride group served as an anchor for assembly of the terpyridyl-crowned chromophores as monomolecular layers on metal oxide surfaces. Further coordination with Zn(2+) ions allowed for layer-by-layer formation of supramolecular assemblies of perylene imides on the solid substrates. With properly selected anchor and linker molecules it was possible to build high quality structures of greater than ten successive layers by a simple and straightforward procedure. The prepared films were stable and had a broad spectral coverage and high absorbance. To demonstrate their potential use, the synthesized dyes were employed in solid-state dye-sensitized solar cells, and electron injection from the perylene antennas to titanium dioxide was observed. PMID:26632758

  13. Evaluation of anisotropic charge carrier mobility of perylene single crystals by time-of-flight method

    NASA Astrophysics Data System (ADS)

    Kougo, Junichi; Ishikawa, Ken

    2016-03-01

    The charge carrier mobilities along the vertical and lateral directions of perylene platelet single crystals were measured by the time-of-flight (TOF) method. In the lateral directional measurement, the entire region between electrodes was irradiated to obtain measurable signals. The transient photocurrent was different from the conventional TOF measurements; hence, we developed an analytic method for lateral directional measurement. The electron mobilities along the thickness and lateral directions were 0.33 and 2.0 cm2·V-1·s-1 and the hole mobilities were 0.12 and 0.6 cm2·V-1·s-1, respectively.

  14. A highly sensitive aptasensor for OTA detection based on hybridization chain reaction and fluorescent perylene probe.

    PubMed

    Wang, Bin; Wu, Yuanya; Chen, Yanfen; Weng, Bo; Xu, Liqun; Li, Changming

    2016-07-15

    An optical aptasensor was developed for ultrasensitive detection of ochratoxin A (OTA) based on hybridization chain reaction (HCR) amplification strategy and fluorescent perylene probe (PAPDI)/DNA composites. Dendritic DNA concatamers were synthesized by HCR strategy and modified on magnetic nanoparticles through aptamer as medium. A large amount of PAPDI probe aggregated under the induction of DNA concatamers and caused fluorescence quenching. In the presence of OTA, the PAPDI/DNA composites were released from magnetic nanoparticles due to the strong affinity between aptamer and OTA. In ethanol, PAPDI monomers disaggregated and produced strong fluorescence. The present method displays excellent sensitivity and selectivity towards OTA. PMID:26938491

  15. Tuning the color and photostability of perylene diimides inside polymer nanoparticles: towards biodegradable substitutes of quantum dots

    NASA Astrophysics Data System (ADS)

    Trofymchuk, Kateryna; Reisch, Andreas; Shulov, Ievgen; Mély, Yves; Klymchenko, Andrey S.

    2014-10-01

    Fluorescent organic nanoparticles (NPs) are attractive alternatives to quantum dots due to their potential biodegradability. However, preparation of fluorescent organic NPs is challenging due to the problem of self-quenching of the encapsulated dyes. Moreover, the photostability of organic dyes is much lower than that of quantum dots. To address both problems, we studied encapsulation into biodegradable polymer PLGA NPs of perylene diimide (PDI) derivatives, which are among the most photostable dyes reported to date. Two PDIs were tested, one bearing bulky hydrophobic groups at the imides, while the other was substituted in both imide and bay regions (Lumogen Red). Encapsulation of the former resulted in aggregation, which was accompanied by the emission color change from green to red, some decrease in the fluorescence quantum yield and a significant drop in the photostability, unexpected for PDI dyes. In contrast, Lumogen Red showed nearly no aggregation inside polymer NPs and maintained high quantum yield and photostability. According to wide-field fluorescence microscopy with a 532 nm excitation laser, our 40 nm PLGA NPs loaded with 1 wt% Lumogen Red were >10-fold brighter than quantum dots (QD-585). These NPs were stable in biological media, including serum, and entered spontaneously into HeLa cells by endocytosis showing no sign of cytotoxicity. Due to excellent photostability, these nanoparticles could be considered as biodegradable substitutes of quantum dots in bioimaging.Fluorescent organic nanoparticles (NPs) are attractive alternatives to quantum dots due to their potential biodegradability. However, preparation of fluorescent organic NPs is challenging due to the problem of self-quenching of the encapsulated dyes. Moreover, the photostability of organic dyes is much lower than that of quantum dots. To address both problems, we studied encapsulation into biodegradable polymer PLGA NPs of perylene diimide (PDI) derivatives, which are among the most

  16. Thermo-reversible gelation of rod-coil and coil-rod-coil molecules based on poly(dimethyl siloxane) and perylene imides and self-sorting of the homologous pair.

    PubMed

    Dahan, Elianne; Sundararajan, Pudupadi R

    2014-08-01

    Organogels with perylene derivatives and phthalocyanines reported in the literature so far involve self-assembly promoted by hydrogen bonds, in addition to aromatic and van der Waals interactions. Although the self assembly of these types of molecules without a hydrogen bonding group in the structure occurs in solution or during crystallization, the gelation studies reported so far incorporated a hydrogen bonding pair of the type N-H···O=C in the structure of the molecule. We present a case of thermo-reversible gelation without a hydrogen bonding group in the structure of (1) a coil-rod-coil molecule based on perylenetetracarboxylic diimide (PTCDI) and poly(dimethyl siloxane) (PDMS) and (2) a rod-coil molecule with perylene dicarboxylic imide (PDI) and PDMS. However IR spectroscopy shows the presence of multiple types of hydrogen bonding between the solvents and the gelator molecules. In addition, publications so far on gelation of perylene diimide based molecules involve groups attached to both imide nitrogens and with or without substitution in the bay position. We discuss here the gelation with a Mono-substituted perylene imide. The PDMS segment was attached to one side of PDI (Mono-PDMS) or to both imide nitrogens of PTCDI (Di-PDMS). The Mono-PDMS is an inverse macromolecular surfactant applicable to non-aqueous systems, and the Di-PDMS is a Gemini surfactant. The PDMS segment that we attached to PTCDI here is longer than most substituents used by other authors. These molecules gel propylamine, as well as mixed solvents of hexane-water and diisopropylamine-water. Both hexane and diisopropylamine dissolve Mono-PDMS and Di-PDMS at room temperature and addition of water results in precipitation. However, heating the solution to about 70 °C, adding water (5-15 wt%) and slowly cooling the solution, lead to gelation. The Di-PDMS forms fibers which are not flat but curved as an eaves trough. The Mono-PDMS forms hollow spheres. Although the Mono-PDMS and Di

  17. Influence of a polarizable surrounding on the electronically excited states of aggregated perylene materials.

    PubMed

    Bellinger, Daniel; Settels, Volker; Liu, Wenlan; Fink, Reinhold F; Engels, Bernd

    2016-06-30

    To tune the efficiency of organic semiconductor devices it is important to understand limiting factors as trapping mechanisms for excitons or charges. An understanding of such mechanisms deserves an accurate description of the involved electronical states in the given environment. In this study, we investigate how a polarizable surrounding influences the relative positions of electronically excited states of dimers of different perylene dyes. Polarization effects are particularly interesting for these systems, because gas phase computations predict that the CT states lie slightly above the corresponding Frenkel states. A polarizable environment may change this energy order because CT states are thought to be more sensitive to a polarizable surrounding than Frenkel states. A first insight we got via a TD-HF approach in combination with a polarizable continuum model (PCM). These give limited insights because TD-HF overestimates excitation energies of CT states. However, SCS-CC2 approaches, which are sufficiently accurate, cannot easily be used in combination with continuum solvent models. Hence, we developed two approaches to combine gas phase SCS-CC2 results with solvent effects based on TD-HF computations. Their accuracies were finally checked via ADC(2)//COSMO computations. The results show that for perylene dyes a polarizable surrounding alone does not influence the energetic ordering of CT and Frenkel states. Variations in the energy order of the states only result from nuclear relaxation effects after the excitation process. © 2016 Wiley Periodicals, Inc. PMID:27030658

  18. Photophysical properties of new bis-perylene dyads for potential upconversion use

    NASA Astrophysics Data System (ADS)

    Ribas, Marcos R.; Steer, Ronald P.; Rüther, Ricardo

    2014-06-01

    Two new bis-perylenes, BPC with a meta-disubstituted benzene linker, and BPD with a p,p‧-disubstituted biphenyl linker, have been synthesized and their photophysical parameters measured. Their singlet and triplet energies decrease incrementally in the order perylene, BPC, BPD, making them ideally matched with C60 for triplet-triplet energy transfer in sensitized photon upconversion schemes. Following photosensitization by triplet C60, BPC exhibits strong fluorescence upconversion by triplet-triplet annihilation, indicating that these bis-perylene dyads (and the multimers that can be constructed from them) will be interesting candidates for use in organic devices such as bulk-heterojunction and dye-sensitized solar cells employing non-coherent photon upconversion. Excitation of C60 at 532 nm will produce its long-lived lowest triplet state with near unit quantum efficiency under the conditions of this experiment [33]. The thermal energy loss usually associated with triplet-triplet energy transfer, Eq. (2), is minimal in this system as the triplet energies of the donor and acceptor are nearly identical at ca. 1.5 eV. In the absence of self-quenching of the fluorescing singlet state, increasing the relative concentrations of acceptor to donor can raise the overall efficiency of the sensitization process to nearly 100%, even if their triplet energies are the same, due to entropic assistance [34]. This was confirmed by measuring the upconversion intensity as a function of dyad concentration at constant absorbed power (Supplementary Information), and by transient absorption measurements of C60 (T1) at 740 nm (Supplementary Information). The latter show that C60(T1) decays with a lifetime on the order of 400 ns for equimolar C60 + BPC concentrations, i.e. at a rate at least 100 times faster (due to quenching by energy transfer) than it would decay in the absence of the BPC triplet energy acceptor. Note also that the dimers with their slightly lower triplet energies are

  19. Manipulating single-wall carbon nanotubes by chemical doping and charge transfer with perylene dyes.

    PubMed

    Ehli, Christian; Oelsner, Christian; Guldi, Dirk M; Mateo-Alonso, Aurelio; Prato, Maurizio; Schmidt, Cordula; Backes, Claudia; Hauke, Frank; Hirsch, Andreas

    2009-06-01

    Single-wall carbon nanotubes (SWNTs) are emerging as materials with much potential in several disciplines, in particular in electronics and photovoltaics. The combination of SWNTs with electron donors or acceptors generates active materials, which can produce electrical energy when irradiated. However, SWNTs are very elusive species when characterization of their metastable states is required. This problem mainly arises because of the polydispersive nature of SWNT samples and the inevitable presence of SWNTs in bundles of different sizes. Here, we report the complete and thorough characterization of an SWNT radical ion-pair state induced by complexation with a perylene dye, which combines excellent electron-accepting and -conducting features with a five-fused ring π-system. At the same time, the perylene dye enables the dispersion of SWNTs by means of π-π interactions, which gives individual SWNTs in solution. This work clears a path towards electronic and optoelectronic devices in which regulated electrical transport properties are important. PMID:21378855

  20. Fluorescence turn-on detection of glucose via the Ag nanoparticle mediated release of a perylene probe.

    PubMed

    Li, Juanmin; Li, Yongxin; Shahzad, Sohail Anjum; Chen, Jian; Chen, Yang; Wang, Yan; Yang, Meiding; Yu, Cong

    2015-04-14

    A novel fluorescence turn-on strategy for glucose sensing is demonstrated. The fluorescence of a perylene probe could be quenched by the silver nanoparticles (Ag NPs). The Ag NPs could be etched by H2O2 generated from the enzymatic oxidation of glucose. And efficient probe fluorescence recovery was detected. PMID:25763414

  1. Enantiomeric perylene-glycerolipids as fluorogenic substrates for a dual wavelength assay of lipase activity and stereoselectivity.

    PubMed

    Zandonella, G; Haalck, L; Spener, F; Faber, K; Paltauf, F; Hermetter, A

    1996-01-01

    A new type of fluorogenic alkyldiacyl glycerols was synthesized and used as fluorogenic substrates for the analysis of lipase activities and stereoselectivities. These compounds contain perylene as a fluorophore and the trinitrophenylamino (TNP) residue as a quencher. Both substituents are covalently bound to the omega-ends of the sn-2 and sn-1 (3) acyl chains, respectively. Upon glycerolipid hydrolysis, the residues are separated from each other thus allowing determination of lipase activity by the continuous increase in fluorescence intensity which is caused by dequenching. Using enantiomeric pairs of these compounds, we were able to analyze lipase stereoselectivity depending on the reaction medium. Mixtures of enantiomeric fluorogenic alkyldiacyl glycerols, selectively labelled with pyrene or perylene as fluorophores, can be used for a dual-wavelength "stereoassay" of lipases. Since absorption and emission maxima of both labels are clearly separated, hydrolysis of the respective enantiomeric substrates can be determined simultaneously, and the difference in the rates of hydrolysis can be taken as a parameter for the stereopreference of a lipase. Hydrolysis rates measured with perylene-substituted lipids are generally lower than those obtained with the pyrene analogs. Thus, with a mixture of perylene and pyrene-substituted lipids, we observe a higher apparent stereoselectivity of lipases since we measure a combination of stereo- and substrate selectivity. In the presence of albumin, all microbial lipases tested so far exhibit stereopreference for the sn-1 glycerol position. In our assay, the apparent stereoselectivities are highest if in the presence of albumin, the sn-1 position carries pyrene and the sn-3 position is substituted with perylene. The lipase stereoselectivity assay described here requires the simultaneous measurement of the fluorescence intensities at two different wavelengths in a single cuvette and can thus be carried out using existing and cheap

  2. Core-perfluoroalkylated perylene diimides and naphthalene diimides: versatile synthesis, solubility, electrochemistry, and optical properties.

    PubMed

    Yuan, Zhongyi; Li, Jing; Xiao, Yi; Li, Zheng; Qian, Xuhong

    2010-05-01

    By a strategy featuring perfluoroalkylation of the highly soluble intermediates and their further efficient transformations to target compounds, a versatile synthesis of core-perfluoroalkylated perylene diimides (PDIs) and naphthalene diimides (NDIs) was developed, and PDIs perfluoroalkylated at 1-position or 1,6-positions and core-perfluoroalkylated NDIs were first obtained. By esterification, perfluoroalkylation, hydrolysis, and condensation with amine, 1-perfluorooctyl-PDIs (7b, 7c, and 7e), 1,7-bis(perfluorooctyl)-PDIs (8a-c and 8e-g), 1,6-bis(perfluorooctyl)-PDIs (8'e), a mixture of 1,7-bis(trifluoromethyl)-PDIs and 1,6-bis(trifluoromethyl)-PDIs (11b and 11'b, 11d and 11'd, in a ratio of 19:1), 2-perfluorooctyl-NDIs (20a-d), and 2,6-bis(perfluorooctyl)-NDIs (21a-21d) were efficiently synthesized. Five valuable intermediates--1-perfluorooctylperylene dianhydride (5), 1,7-bis(perfluorooctyl)perylene dianhydride (6) 1,6-bis(perfluorooctyl)perylene dianhydride (6'), 2-perfluorooctylnaphthalene dianhydride (18), and 2,6-bis(perfluorooctyl) naphthalene dianhydride (19)--were also obtained, and they can condense with many amines to produce PDIs containing different functional side chains on the imide nitrogen atoms. Solubility, electrochemistry, and optical properties of the above core-perfluoroalkylated PDIs and NDIs were investigated. Core-perfluoroalkylated 8e, 8f, 8'e, mixture of 11d and 11'd, 20b, and 20d with excellent solubility in common organic solvents are competitive as candidates as solution processable semiconductors. Core-perfluoroalkylated PDIs and NDIs with experimental LUMO energy of 4.04-4.34 eV demonstrate strong electron accepting ability. For core-perfluoroalkylated PDIs, the maximum absorptions display blue shifts of 6-18 nm and the maximum molar extinction coefficients decrease obviously relative to those of unsubstituted PDIs, and they inherit the strong fluorescence from the PDIs family, which makes them promising fluorescent dyes. PMID

  3. Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst.

    PubMed

    Theriot, Jordan C; Ryan, Matthew D; French, Tracy A; Pearson, Ryan M; Miyake, Garret M

    2016-01-01

    A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism. PMID:27166728

  4. Entropically Driven Self-Assembly of Bolaamphiphilic Perylene Dyes in Water.

    PubMed

    Görl, Daniel; Würthner, Frank

    2016-09-19

    The specific hydrophobic effect involved in the self-assembly of a bolaamphiphilic perylene bisimide (PBI) dye bearing oligoethylene glycol (OEG) chains has been identified. In pure water, the self-assembly is entropically driven and enthalpically disfavored, as explored by optical spectroscopy and isothermal titration calorimetry studies. Besides strong π-π interactions between the PBI units that are primarily of enthalpic nature, the major contribution to the self-assembly is the gain of entropy by release of confined water molecules from the hydration shell of the hydrophilic OEG moieties. Both contributions favor self-assembly, but their countervailing thermodynamic parameters are reflected in an uncommon temperature dependence, which can be inverted upon gradual addition of an organic cosolvent that makes the π-π interaction increasingly dominant. PMID:27558471

  5. Circularly Polarized Luminescence of Chiral Perylene Diimide Based Enantiomers Triggered by Supramolecular Self-Assembly.

    PubMed

    Li, Fei; Li, Yunzhi; Wei, Guo; Wang, Yuxiang; Li, Shuhua; Cheng, Yixiang

    2016-08-26

    Two perylene diimide (PDI) enantiomers (d/l-PDI) incorporating the d/l-alanine moiety have been designed and synthesized. d/l-PDI in chloroform displays bright-yellow fluorescence that is redshifted to orange-red when the solvent contains a methanol fraction of 99 vol %. No circular dichroism (CD) or circularly polarized luminescence (CPL) signals were observed for d/l-PDI enantiomers in CHCl3 . Interestingly, the d/l-PDI enantiomers exhibit clear mirror-image Cotton effects and CPL emission in the aggregate state. The optical anisotropy factor (glum ) is as high as 0.02 at fm =99 %, which can be attributed to self-assembly through intermolecular π-π interactions in the aggregate state. PMID:27470269

  6. Rapid Energy Transfer Enabling Control of Emission Polarization in Perylene Bisimide Donor-Acceptor Triads.

    PubMed

    Menelaou, Christopher; ter Schiphorst, Jeroen; Kendhale, Amol M; Parkinson, Patrick; Debije, Michael G; Schenning, Albertus P H J; Herz, Laura M

    2015-04-01

    Materials showing rapid intramolecular energy transfer and polarization switching are of interest for both their fundamental photophysics and potential for use in real-world applications. Here, we report two donor-acceptor-donor triad dyes based on perylene-bisimide subunits, with the long axis of the donors arranged either parallel or perpendicular to that of the central acceptor. We observe rapid energy transfer (<2 ps) and effective polarization control in both dye molecules in solution. A distributed-dipole Förster model predicts the excitation energy transfer rate for the linearly arranged triad but severely underestimates it for the orthogonal case. We show that the rapid energy transfer arises from a combination of through-bond coupling and through-space transfer between donor and acceptor units. As they allow energy cascading to an excited state with controllable polarization, these triad dyes show high potential for use in luminescent solar concentrator devices. PMID:26262968

  7. Quenching of the perylene fluorophore by stable nitroxide radical-containing macromolecules.

    PubMed

    Hughes, Barbara K; Braunecker, Wade A; Ferguson, Andrew J; Kemper, Travis W; Larsen, Ross E; Gennett, Thomas

    2014-10-30

    Stable nitroxide radical bearing organic polymer materials are attracting much attention for their application as next generation energy storage materials. A greater understanding of the inherent charge transfer mechanisms in such systems will ultimately be paramount to further advancements in the understanding of both intrafilm and interfacial ion- and electron-transfer reactions. This work is focused on advancing the fundamental understanding of these dynamic charge transfer properties by exploiting the fact that these species are efficient fluorescence quenchers. We systematically incorporated fluorescent perylene dyes into solutions containing the 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) radical and controlled their interaction by binding the TEMPO moiety into macromolecules with varying morphologies (e.g., chain length, density of radical pendant groups). In the case of the model compound, 4-oxo-TEMPO, quenching of the perylene excited state was found to be dominated by a dynamic (collisional) process, with a contribution from an apparent static process that is described by an ∼2 nm quenching sphere of action. When we incorporated the TEMPO unit into a macromolecule, the quenching behavior was altered significantly. The results can be described by using two models: (A) a collisional quenching process that becomes less efficient, presumably due to a reduction in the diffusion constant of the quenching entity, with a quenching sphere of action similar to 4-oxo-TEMPO or (B) a collisional quenching process that becomes more efficient as the radius of interaction grows larger with increasing oligomer length. This is the first study that definitively illustrates that fluorophore quenching by a polymer system cannot be explained using merely a classical Stern-Volmer approach but rather necessitates a more complex model. PMID:25329883

  8. Synergetic Solvent Engineering of Film Nanomorphology to Enhance Planar Perylene Diimide-Based Organic Photovoltaics.

    PubMed

    Wang, Jialin; Liang, Ziqi

    2016-08-31

    Solvent additive has proven as a useful protocol for improving the film nanomorphology of polymer donor (D): fullerene acceptor (A) blends in bulk heterojunction (BHJ) photovoltaic cells. By contrast, the effect of such solvent additive on nonfullerene BHJ cells based on perylene diimide acceptor, for instance, is less effective because of their highly planar structure and strong π-aggregation in solid state. Here we choose N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (PDI) and thieno[3,4-b]thiophene-alt-benzodithiophene (PTB7) as a model D:A blend system to investigate how solvent engineering strategy synergistically impacts the blend film nanomorphology. Based on the differences of solvent volatility and solubility, various host solvents-chloroform (CF) and chlorobenzene (CB) and solvent additives-chloronaphthalene (CN) and 1,8-diiodooctane (DIO) are selected for comparative studies. It is found that the π-aggregation of PDIs can be largely suppressed by using low-boiling point (Tb) CF solvent, yet enlarged by using high-Tb CB. Moreover, CN additive provides good solubility of PDI molecules and hence reduces large PDI aggregates in CB system, while DIO exhibiting poor solubility works oppositely. By contrast, DIO that presents larger Tb difference with CF prolongs the film-forming, which assists in optimizing the PDI aggregation and increases the intermixed PTB7:PDI phases more significantly than CN in CF system, yielding the finest phase-separation morphology and balanced charge mobility. Consequently, the inverted BHJ cells based on CF-processed PTB7:PDI blend film with 0.4 vol % DIO exhibit the highest PCE of 3.55% with a fill factor of 56%, both of which are among the best performance for such a paradigm PTB7:PDI blend-based BHJ cells. PMID:27513281

  9. Photoinduced Charge and Energy Transfer within meta- and para-Linked Chlorophyll a-Perylene-3,4:9,10-bis(dicarboximide) Donor-Acceptor Dyads.

    PubMed

    Huang, Guan-Jhih; Harris, Michelle A; Krzyaniak, Matthew D; Margulies, Eric A; Dyar, Scott M; Lindquist, Rebecca J; Wu, Yilei; Roznyatovskiy, Vladimir V; Wu, Yi-Lin; Young, Ryan M; Wasielewski, Michael R

    2016-02-01

    Connecting electron donors and acceptors to a benzene ring in a meta or para relationship results in quantum interference effects that can strongly influence charge separation (CS) and charge recombination (CR) processes in these systems. We report on the energy and electron transfer behavior of chlorophyll-based para- and meta-linked donor-bridge-acceptor (D-B-A) dyads, where the semisynthetic chlorophyll a derivative, zinc methyl 3-ethyl-pyrochlorophyllide a (D), is covalently attached at its 20-position to the para position of one phenyl of diphenylacetylene (B). The meta or para position of the phenyl in B distal to the donor is in turn attached to perylene-3,4:9,10-bis(dicarboximide) (PDI) (A). Photoexcitation of the D-B-A dyads produces long-lived radical ion pairs D(•+)-B-A(•-), which recombine to the ground state and to both (3*)D-B-A and D-B-(3*)A. Time-resolved optical and electron paramagnetic resonance spectroscopies were used to monitor the charge transfer and triplet energy transfer (TEnT) processes. At longer times, TEnT occurs from (3*)D-B-A to D-B-(3*)A. Surprisingly, the D-B-A molecules linked via the meta linkage exhibit faster CS, CR, and TEnT rates than do those with the para linkage in contrast to most other meta/para-linked D-B-A molecules previously examined. PMID:26731377

  10. Pentadecyl phenol- and cardanol-functionalized fluorescent, room-temperature liquid-crystalline perylene bisimides: effect of pendant chain unsaturation on self-assembly.

    PubMed

    Bhavsar, Ghanashyam A; Asha, S K

    2011-11-01

    A new perylene bisimide (PBI) building block based on pentadecyl phenol (PDP) or cardanol was developed, which upon esterification with 3,4,5-tridodecyloxy gallate resulted in highly emissive, room-temperature liquid-crystalline (LC) molecules. The self assembly in solution was studied in detail by NMR spectroscopy, UV/Vis absorption, and fluorescence spectroscopy. In solution both PDP- and cardanol-based PBI exhibited similar behavior. They were molecularly dissolved in chloroform (CHCl(3)) but formed rotationally displaced H-type aggregates that emitted at 640 nm in methylcyclohexane (MCH). Surface morphology in dropcast films were characterized using microscopic techniques such as SEM, TEM, and atomic force microscopy (AFM). The liquid-crystalline properties were studied using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and variable-temperature X-ray (small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WXRD)) studies. Variable-temperature X-ray studies in the LC phase indicated strong π-π stacking interaction present in the PDP-based PBI derivative, whereas the stacking was absent in the LC phase of the cardanol-based PBI. The latter formed self-organized structures of extremely short length due to the presence of cis double bonds in the C15 alkyl side chain, whereas the saturated alkyl side chain in PDP could pack efficiently, thereby resulting in nanofibers that were several micrometers in length. PMID:21956257

  11. Visible-light-assisted photoelectrochemical water oxidation by thin films of a phosphonate-functionalized perylene diimide plus CoOx cocatalyst.

    PubMed

    Kirner, Joel T; Stracke, Jordan J; Gregg, Brian A; Finke, Richard G

    2014-08-27

    A novel perylene diimide dye functionalized with phosphonate groups, N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI), is synthesized and characterized. Thin films of PMPDI spin-coated onto indium tin oxide (ITO) substrates are further characterized, augmented by photoelectrochemically depositing a CoOx catalyst, and then investigated as photoanodes for water oxidation. These ITO/PMPDI/CoOx electrodes show visible-light-assisted water oxidation with photocurrents in excess of 150 μA/cm(2) at 1.0 V applied bias vs. Ag/AgCl. Water oxidation is confirmed by the direct detection of O2, with a faradaic efficiency of 80 ± 15% measured under 900 mV applied bias vs. Ag/AgCl. Analogous photoanodes prepared with another PDI derivative with alkyl groups in place of PMPDI's phosphonate groups do not function, providing evidence that PMPDI's phosphonate groups may be important for efficient coupling between the inorganic CoOx catalyst and the organic dye. Our ITO/PMPDI/CoOx anodes achieve internal quantum efficiencies for water oxidation ∼1%, and for hydroquinone oxidation of up to ∼6%. The novelty of our system is that, to the best of our knowledge, it is the first device to achieve photoelectrochemically driven water oxidation by a single-layer molecular organic semiconductor thin film coupled to a water-oxidation catalyst. PMID:24654796

  12. Two-photon photoemission spectra related to an ultrafast heterogeneous electron transfer from perylene to TiO2

    NASA Astrophysics Data System (ADS)

    Tsivlin, Dmitry V.; Willig, Frank; May, Volkhard

    2008-01-01

    Two-photon photoemission (2PPE) spectra related to sub- 100-fs heterogeneous electron transfer from perylene to TiO2 are calculated. The approach accounts for the dominant intramolecular vibration of perylene as well as for the band structure of TiO2 described in a tight-binding model. The focus is on the influence of the pump and probe laser pulse duration, with the pump laser originating charge injection and the probe laser causing the photoemission process. The latter may proceed directly from the photoexcited molecule or, after charge injection, from the TiO2 conduction band. The time-dependent Schrödinger equation which describes charge injection and accounts for the pump pulse is solved exactly within a time interval of about 250fs . The action of the probe pulse is considered in linear response theory. While the vibrational structure in the 2PPE spectra broadens with decreasing pump pulse length, it is found that this structure is largely preserved when varying the probe pulse duration. In order to estimate dephasing caused by intramolecular vibrational energy redistribution in perylene and electron phonon coupling in TiO2 , a density matrix scheme is also introduced describing heterogeneous electron transfer and the photoelectron emission processes. A finite escape depth for electrons at the TiO2 surface is finally taken into account to evaluate its influence on the spectra.

  13. Identification of ultrafast relaxation processes as a major reason for inefficient exciton diffusion in perylene-based organic semiconductors.

    PubMed

    Settels, Volker; Schubert, Alexander; Tafipolski, Maxim; Liu, Wenlan; Stehr, Vera; Topczak, Anna K; Pflaum, Jens; Deibel, Carsten; Fink, Reinhold F; Engel, Volker; Engels, Bernd

    2014-07-01

    The exciton diffusion length (LD) is a key parameter for the efficiency of organic optoelectronic devices. Its limitation to the nm length scale causes the need of complex bulk-heterojunction solar cells incorporating difficulties in long-term stability and reproducibility. A comprehensive model providing an atomistic understanding of processes that limit exciton trasport is therefore highly desirable and will be proposed here for perylene-based materials. Our model is based on simulations with a hybrid approach which combines high-level ab initio computations for the part of the system directly involved in the described processes with a force field to include environmental effects. The adequacy of the model is shown by detailed comparison with available experimental results. The model indicates that the short exciton diffusion lengths of α-perylene tetracarboxylicdianhydride (PTCDA) are due to ultrafast relaxation processes of the optical excitation via intermolecular motions leading to a state from which further exciton diffusion is hampered. As the efficiency of this mechanism depends strongly on molecular arrangement and environment, the model explains the strong dependence of LD on the morphology of the materials, for example, the differences between α-PTCDA and diindenoperylene. Our findings indicate how relaxation processes can be diminished in perylene-based materials. This model can be generalized to other organic compounds. PMID:24909402

  14. Perylene, pyrromethene and grafted rhodamine-doped xerogels for tunable solid state laser

    NASA Astrophysics Data System (ADS)

    Canva, Michael; Dubois, Arnaud; Georges, Patrick M.; Brun, Alain; Chaput, Frederic; Ranger, Agnes; Boilot, Jean-Pierre

    1994-10-01

    Organic dye molecules have been widely used in solution as amplifying media in tunable lasers. The possibility of trapping these molecules in a solid state matrix may lead to a new field of application outside the laboratory. Many types of matrices can be used. We present results with new hybrid organic/inorganic xerogels prepared by hydrolysis-condensation of the methyl- or vinyl-triethoxysilane precursor under acid-catalyzed hydrolysis and basic-catalyzed condensation. Organic methyl or vinyl groups attached to the silica network provide a favorable environment to dye fluorescence. We have studied the effect induced by using different basic catalysts: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 3- aminopropyltriethoxysilane are found to lead to the best matrix characteristics. Perylenes and pyrromethenes were chosen because of their thermal- and photo-stability. After gelation, 10 mm thick samples, polished to a surface roughness of about 4 nm, are placed in a plano- concave cavity as gain media and pumped by a frequency doubled nanosecond Q:switched Nd:YAG laser. Efficiency is the greatest with a pyrromethene 597 doped sample: more than 6 mJ output energy for a 10 mJ pump energy (2 J/cm2 fluence) leading to a slope efficiency of 63%. The lifetime of the laser emission when the same point of the sample is sequentially used is also an important characteristic. Best results are obtained with perylene red dye: for a pump energy of 0.7 mJ at 1 Hz repetition rate, the output energy is still 50% of the initial value (0.1 mJ) after 80,000 shots. For a pyrromethene 597 doped MTEOS sample, it appears that the measured lifetimes are independent of the operating frequency in the 0.2 - 20 Hz range, indicating a reasonable heat conductivity for this type of matrix. We have also studied tunability by adding a grating or prism to the cavity: a typical tunability of over 50 nm or more is obtained with many of these dyes. Finally we report laser activity obtained with

  15. Charge versus Energy Transfer Effects in High-Performance Perylene Diimide Photovoltaic Blend Films.

    PubMed

    Singh, Ranbir; Shivanna, Ravichandran; Iosifidis, Agathaggelos; Butt, Hans-Jürgen; Floudas, George; Narayan, K S; Keivanidis, Panagiotis E

    2015-11-11

    Perylene diimide (PDI)-based organic photovoltaic devices can potentially deliver high power conversion efficiency values provided the photon energy absorbed is utilized efficiently in charge transfer (CT) reactions instead of being consumed in nonradiative energy transfer (ET) steps. Hitherto, it remains unclear whether ET or CT primarily drives the photoluminescence (PL) quenching of the PDI excimer state in PDI-based blend films. Here, we affirm the key role of the thermally assisted PDI excimer diffusion and subsequent CT reaction in the process of PDI excimer PL deactivation. For our study we perform PL quenching experiments in the model PDI-based composite made of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene)-2-6-diyl] (PBDTTT-CT) polymeric donor mixed with the N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (PDI) acceptor. Despite the strong spectral overlap between the PDI excimer PL emission and UV-vis absorption of PBDTTT-CT, two main observations indicate that no significant ET component operates in the overall PL quenching: the PL intensity of the PDI excimer (i) increases with decreasing temperature and (ii) remains unaffected even in the presence of 10 wt % content of the PBDTTT-CT quencher. Temperature-dependent wide-angle X-ray scattering experiments further indicate that nonradiative resonance ET is highly improbable due to the large size of PDI domains. The dominance of the CT over the ET process is verified by the high performance of devices with an optimum composition of 30:70 PBDTTT-CT:PDI. By adding 0.4 vol % of 1,8-diiodooctane we verify the plasticization of the polymer side chains that balances the charge transport properties of the PBDTTT-CT:PDI composite and results in additional improvement in the device efficiency. The temperature-dependent spectral width of the PDI excimer PL band suggests the presence of energetic disorder in the

  16. Fluorescence Quenching of Perylene DBPI Dye by Colloidal Low-Dimensional Gold Nanoparticles.

    PubMed

    El-Daly, Samy A; Rahman, Mohammed M; Alamry, Kalid A; Asiri, Abdullah M

    2015-07-01

    The interaction of a perylene DBPI dye [N,N-bis(2,5-di-tert-butylphenyl)-3,4:9,10-perylenebis(dicarboximide)] with aqueous colloidal gold nanoparticles (AuNPs) was studied using steady state fluorescence quenching measurements. The Stern-Volmer quenching rate constant (Ksv) was calculated as ~2.2 × 10(8) and ~1.072 × 10(9) M(-1) in ethanol and ethylene glycol respectively. From fluorescence quenching data, the static quenching and energy transfer play a significant role in the fluorescence quenching of DBPI with AuNPs. The apparent association constant (Kapp) was calculated as ~1.4 × 10(9) (EtOH)and ~3.7 × 10(9) M(-1) (ethylene). Due to AuNPs interaction with DBPI, the average aggregated colloidal AuNPs size is increased from ~53.39 nm (before interaction) to ~94.12 nm (after interaction). PMID:25982950

  17. Photophysical properties and semiempirical calculations of perylene-3,4,9,10-tetracarboxylic tetramethylester (PTME).

    PubMed

    El-Daly, Samy A; Awad, Mohamed K; Abdel-Halim, Shakir T; Dowidar, Dina A

    2008-12-01

    The spectral behavior and fluorescence quantum yield of perylene-3,4,9,10-tetracarboxylic tetramethylester (PTME) have been measured in different solvents. Both electronic absorption and fluorescence spectra are not sensitive to medium polarity. The dye exhibits high fluorescence quantum yield and high photostable. Crystalline solid of PTME gives excimer-like emission at 530 nm. The laser activity of PTME has been investigated. The dye solution in N,N-dimethylformamide (DMF) gives laser emission around 480 nm upon excitation by 337.1 nm nitrogen laser pulse. The excitation energy transfer from 7-dimethylamino-4-methylcoumarine (DMC) to PTME has also has been studied and the value of energy transfer rate constant, k(ET), and critical transfer distance, R(0) indicate a Förster-type mechanism. The photodecomposition of PTME in chloromethane solvents has been also studied. We applied semiempirical MO calculations using (PM3 and ZINDO-CI) calculations to explain the geometric and electronic behaviors of the PTME molecule in both ground and excited states and make a correlation with the experimental observations. PMID:18436473

  18. Cavity ring-down spectroscopy and vibronic activity of benzo[ghi]perylene.

    PubMed

    Tan, Xiaofeng; Salama, Farid

    2005-07-01

    Gas-phase cavity ring-down spectroscopy of jet-cooled benzo[ghi]perylene (C22H12) in the 26 950-28 600-cm(-1) spectral range is reported for the first time. This study is part of our extensive laboratory astrophysics program for the study of interstellar polycyclic aromatic hydrocarbons. The observed spectrum shows an intermediate level structure and significant broadening and is associated with the vibronically coupled S1(1A1)<--S0(1A1) and S2(1B1)<--S0(1A1) electronic transitions. Time-dependent density-functional calculations were performed to calculate the energetics, vibrational frequencies, and normal coordinates of the S1 and S2 states. A simple vibronic model was employed to account for the vibronic interaction between the vibronic levels of the S1 and S2 states. The calculated vibronic spectrum is found to be in good agreement with the experimental spectrum. PMID:16035840

  19. Optical gain characterization of Perylene Red-doped PMMA for different pump configurations.

    PubMed

    Kaysir, Md Rejvi; Fleming, Simon; MacQueen, Rowan W; Schmidt, Timothy W; Argyros, Alexander

    2016-01-01

    The optical gain is measured in Perylene Red (PR)-doped polymethyl methacrylate (PMMA) slabs for copropagating and transverse pumping configurations based on a single-pass pump-probe method where a small signal is used as a probe beam. The gain is characterized in terms of the stimulated gain coefficient (g(S)) for both pump configurations. This material property determines the strength of pump absorption and coupling to the probe signal beam through stimulated emission. For copropagating pumping, g(S) was found to be (3.05±0.17)×10(-3) m/W for ∼0.05  mM PR-doped PMMA using a 633 nm probe laser, pumping with a 532 nm CW laser. For transverse pumping, g(S) was found to be (3.28±0.09)×10(-3)  m/W for a ∼0.15  mM sample. The small difference in the gain coefficient is attributed to the difference in concentration. The stimulated gain coefficient, a material property of the gain medium independent of the pump configuration and experimental setup, offers a useful and convenient way to characterize the optical gain for solid-state lasers or amplifiers. PMID:26835639

  20. Interaction of alkali metals with perylene-3,4,9,10- tetracarboxylic-dianhydride thin films

    SciTech Connect

    Wuesten, J.; Berger, S.; Heimer, K.; Lach, S.; Ziegler, Ch.

    2005-07-01

    n doping of the molecular organic semiconductor perylene-3,4,9,10-tetracarboxylic-dianhydride (PTCDA) is often achieved by use of alkali metals as dopants. This doping process is commonly performed in two steps. In the first the dopant is evaporated onto the surface of the PTCDA film. As it has been believed that the dopant shows an inhomogeneous diffusion profile through the layer with most of the dopant accumulated in the first few layers, a subsequent annealing step has been performed in order to reach a homogeneous distribution of the dopant in the whole layer. In this paper experimental results concerning chemical composition ((angle resolved) X-ray photoemission spectroscopy, secondary-ion-mass spectrometry, Fourier transform infrared spectroscopy), electronic structure (ultraviolet photoemission spectroscopy, inverse photoemission spectroscopy), as well as electrical properties (conductivity, Seebeck coefficient) are shown before and after doping and before and after annealing. These results suggest that the deposited dopant is redistributed and partially removed during the annealing step. A model for the dopant distribution is suggested.

  1. Flexible and Patterned Thin Film Polarizer: Photopolymerization of Perylene-based Lyotropic Chromonic Reactive Mesogens.

    PubMed

    Im, Pureun; Kang, Dong-Gue; Kim, Dae-Yoon; Choi, Yu-Jin; Yoon, Won-Jin; Lee, Myong-Hoon; Lee, In-Hwan; Lee, Cheul-Ro; Jeong, Kwang-Un

    2016-01-13

    A perylene-based reactive mesogen (DAPDI) forming a lyotropic chromonic liquid crystal (LCLC) phase was newly designed and synthesized for the fabrication of macroscopically oriented and patterned thin film polarizer (TFP) on the flexible polymer substrates. The anisotropic optical property and molecular self-assembly of DAPDI were investigated by the combination of microscopic, scattering and spectroscopic techniques. The main driving forces of molecular self-assembly were the face-to-face π-π intermolecular interaction among aromatic cores and the nanophase separation between hydrophilic ionic groups and hydrophobic aromatic cores. Degree of polarization for the macroscopically oriented and photopolymerized DAPDI TFP was estimated to be 99.81% at the λmax = 491 nm. After mechanically shearing the DAPDI LCLC aqueous solution on the flexible polymer substrates, we successfully fabricated the patterned DAPDI TFP by etching the unpolymerized regions selectively blocked by a photomask during the photopolymerization process. Chemical and mechanical stabilities were confirmed by the solvent and pencil hardness tests, and its surface morphology was further investigated by optical microscopy, atomic force microscopy, and three-dimensional surface nanoprofiler. The flexible and patterned DAPDI TFP with robust chemical and mechanical stabilities can be a stepping stone for the advanced flexible optoelectronic devices. PMID:26616135

  2. Modifying growth of perylene diimide nanocrystals with poly(3-hexyl thiophene) as additives

    NASA Astrophysics Data System (ADS)

    Bu, Laju; Hayward, Ryan

    2014-03-01

    The shape, size, and crystallinity of organic semiconductors play vital roles in their applications in optoelectronics. Various methods to control crystallization of organic semiconductors, including thermal/solvent annealing, addition of poor solvents, and chemical structure modification, have been applied to improve the performance of organic photovoltaics. While soluble additives controlled crystallization are commonly found in biomineralization, pharmaceutics, and food science, they have rarely been applied to organic semiconductors. Here, we show that a p-type polymer, P3HT, serves as a soluble additive in crystallization of a n-type semiconductor, perylene diimide (PDI), by preferentially adsorbing on lateral crystal faces, which reduce lateral growth of PDI crystals relative to longitudinal growth, yielding extended 1-D nanofibers. Upon subsequent crystallization of P3HT, the PDI nanofibers serve as efficient nucleation sties, resulting in shish-kebab like p/n heterostuctures. Using ultrasound to enhance nucleation of PDI crystals, variations in P3HT molecular weight and concentration, and sonication temperature, allow PDI nanocrystal size and uniformity to be tuned. The uniform PDI nanocrystals can act as seeds to crystallize additional PDI to get segmented nanocrystals.

  3. Excited-State Vibrational Coherence in Perylene Bisimide Probed by Femtosecond Broadband Pump-Probe Spectroscopy.

    PubMed

    Son, Minjung; Park, Kyu Hyung; Yoon, Min-Chul; Kim, Pyosang; Kim, Dongho

    2015-06-18

    Broadband laser pulses with ultrashort duration are capable of triggering impulsive excitation of the superposition of vibrational eigenstates, giving rise to quantum beating signals originating from coherent wave packet motions along the potential energy surface. In this work, coherent vibrational wave packet dynamics of an N,N'-bis(2,6-dimethylphenyl)perylene bisimide (DMP-PBI) were investigated by femtosecond broadband pump-probe spectroscopy which features fast and balanced data acquisition with a wide spectral coverage of >200 nm. Clear modulations were observed in the envelope of the stimulated emission decay profiles of DMP-PBI with the oscillation frequencies of 140 and 275 cm(-1). Fast Fourier transform analysis of each oscillatory mode revealed characteristic phase jumps near the maxima of the steady-state fluorescence, indicating that the observed vibrational coherence originates from an excited-state wave packet motion. Quantum calculations of the normal modes at the low-frequency region suggest that low-frequency C-C (C═C) stretching motions accompanied by deformation of the dimethylphenyl substituents are responsible for the manifestation of such coherent wave packet dynamics. PMID:25992707

  4. Ionomers based on multisulfonated perylene dianhydride: Synthesis and properties of water resistant sulfonated polyimides

    NASA Astrophysics Data System (ADS)

    Zhang, Feng; Li, Nanwen; Zhang, Suobo; Li, Shenghai

    A novel locally and densely sulfonated dianhydride with four sulfonic acid groups, 1,6,7,12-tetra[4-(sulfonic acid)phenoxy]perylene-3,4,9,10-tetracarboxylic dianhydride (SPTDA), was successfully synthesized by direct sulfonation of the parent dianhydride, 1,6,7,12-tetraphenoxyperylene-3,4,9,10-tetracarboxylic dianhydride (PTDA). Sulfonated copolyimides were prepared from SPTDA, nonsulfonated dianhydride 4,4‧-binaphthyl-1,1‧,8,8‧-tetracarboxylic dianydride, 4,4‧-diaminodiphenyl ether (a) or dodecane-1,12-diamine (b). The synthesized copolymers, with the -SO 3H group on the polymer side chain, possess high molecular weights and high viscosities, and they form tough, flexible membranes. The copolymer membrane with an ion exchange capacity of 2.69 mequiv. g -1 had a proton conductivity of 0.126 S cm -1 at 20 °C and 0.292 S cm -1 at 100 °C; the latter is much higher than that of Nafion ® 117 under the same conditions. The mechanical properties of the copolymer membranes were almost unchanged after accelerated water stability testing at 140 °C for 100 h; this indicates excellent hydrolytic stability of the synthesized copolyimides.

  5. Ultrafast electron transfer reactions initiated by excited CT states of push pull perylenes

    NASA Astrophysics Data System (ADS)

    Miller, Scott E.; Zhao, Yongyu; Schaller, Richard; Mulloni, Viviana; Just, Eric M.; Johnson, Robert C.; Wasielewski, Michael R.

    2002-01-01

    Two new chromophores that absorb in the visible spectrum, the 9-( N-pyrrolidinyl)- and 9-( N-piperidinyl)perylene-3,4-dicarboximides, 5PMI and 6PMI, respectively, were synthesized and shown to possess lowest excited singlet states with about 70% charge transfer (CT) character. Changing the ring size of the cyclic amine from 5 to 6 significantly changes the energies of the CT states, as well as the redox potentials of the chromophores. These chromophores were linked to pyromellitimide (PI) and 1,8:4,5-naphthalenediimide (NI) electron acceptors using a single N-N bond between their respective imides to yield the corresponding donor-acceptor dyads 5PMI-PI, 5PMI-NI, 6PMI-PI, and 6PMI-NI. The donors and acceptors in these molecules are positioned relative to one another in a rod-like arrangement at fixed distances and restricted orientations. The rates of charge separation and recombination were measured using transient absorption spectroscopy. These chromophores were also used to prepare rigid donor-acceptor triads 5PMI-PI-NI and 6PMI-PI-NI, which display one- or two-step electron transfer mechanisms that depend on solvent polarity. These compounds exhibit a broad range of structure and media driven changes in electron transfer mechanism.

  6. Competition between singlet fission and charge separation in solution-processed blend films of 6,13-bis(triisopropylsilylethynyl)pentacene with sterically-encumbered perylene-3,4:9,10-bis(dicarboximide)s.

    PubMed

    Ramanan, Charusheela; Smeigh, Amanda L; Anthony, John E; Marks, Tobin J; Wasielewski, Michael R

    2012-01-11

    The photophysics and morphology of thin films of N,N-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-bis(dicarboximide) (1) and the 1,7-diphenyl (2) and 1,7-bis(3,5-di-tert-butylphenyl) (3) derivatives blended with 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) were studied for their potential use as photoactive layers in organic photovoltaic (OPV) devices. Increasing the steric bulk of the 1,7-substituents of the perylene-3,4:9,10-bis(dicarboximide) (PDI) impedes aggregation in the solid state. Film characterization data using both atomic force microscopy and X-ray diffraction showed that decreasing the PDI aggregation by increasing the steric bulk in the order 1 < 2 < 3 correlates with a decrease in the density/size of crystalline TIPS-Pn domains. Transient absorption spectroscopy was performed on ~100 nm solution-processed TIPS-Pn:PDI blend films to characterize the charge separation dynamics. These results showed that selective excitation of the TIPS-Pn results in competition between ultrafast singlet fission ((1*)TIPS-Pn + TIPS-Pn → 2 (3*)TIPS-Pn) and charge transfer from (1*)TIPS-Pn to PDIs 1-3. As the blend films become more homogeneous across the series TIPS-Pn:PDI 1 → 2 → 3, charge separation becomes competitive with singlet fission. Ultrafast charge separation forms the geminate radical ion pair state (1)(TIPS-Pn(+•)-PDI(-•)) that undergoes radical pair intersystem crossing to form (3)(TIPS-Pn(+•)-PDI(-•)), which then undergoes charge recombination to yield either (3*)PDI or (3*)TIPS-Pn. Energy transfer from (3*)PDI to TIPS-Pn also yields (3*)TIPS-Pn. These results show that multiple pathways produce the (3*)TIPS-Pn state, so that OPV design strategies based on this system must utilize this triplet state for charge separation. PMID:22111926

  7. Hole-transfer induced energy transfer in perylene diimide dyads with a donor-spacer-acceptor motif.

    PubMed

    Kölle, Patrick; Pugliesi, Igor; Langhals, Heinz; Wilcken, Roland; Esterbauer, Andreas J; de Vivie-Riedle, Regina; Riedle, Eberhard

    2015-10-14

    We investigate the photoinduced dynamics of perylene diimide dyads based on a donor-spacer-acceptor motif with polyyne spacers of varying length by pump-probe spectroscopy, time resolved fluorescence, chemical variation and quantum chemistry. While the dyads with pyridine based polyyne spacers undergo energy transfer with near-unity quantum efficiency, in the dyads with phenyl based polyyne spacers the energy transfer efficiency drops below 50%. This suggests the presence of a competing electron transfer process from the spacer to the energy donor as the excitation sink. Transient absorption spectra, however, reveal that the spacer actually mediates the energy transfer dynamics. The ground state bleach features of the polyyne spacers appear due to the electron transfer decay with the same time constant present in the rise of the ground state bleach and stimulated emission of the perylene energy acceptor. Although the electron transfer process initially quenches the fluorescence of the donor it does not inhibit energy transfer to the perylene energy acceptor. The transient signatures reveal that electron and energy transfer processes are sequential and indicate that the donor-spacer electron transfer state itself is responsible for the energy transfer. Through the introduction of a Dexter blocker unit into the spacer we can clearly exclude any through bond Dexter-type energy transfer. Ab initio calculations on the donor-spacer and the donor-spacer-acceptor systems reveal the existence of a bright charge transfer state that is close in energy to the locally excited state of the acceptor. Multipole-multipole interactions between the bright charge transfer state and the acceptor state enable the energy transfer. We term this mechanism coupled hole-transfer FRET. These dyads represent a first example that shows how electron transfer can be connected to energy transfer for use in novel photovoltaic and optoelectronic devices. PMID:26347443

  8. Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene)n, n = 1,2.

    PubMed

    Balmer, Franziska A; Ottiger, Philipp; Leutwyler, Samuel

    2015-10-22

    The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = -451 and -858 cm(-1) relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm(-1) in S0 and 55 cm(-1) in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of -D0 = 28-35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2

  9. Infrared study on the molecular orientation in bulk-heterojunction films based on perylene and 3,4,9,10-perylenetetracarboxylic dianhydride

    NASA Astrophysics Data System (ADS)

    Seto, Keisuke; Pham, John; Furukawa, Yukio

    2012-03-01

    Solid-state structures of thin blend films of perylene and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) formed on the Au surface have been studied by a combination of infrared reflection-absorption spectroscopy and the RATIO method of Debe. In the blend films, PTCDA molecules take the face-on orientation in the whole range of PTCDA contents from 7.5 to 88 mol%. On the other hand, the molecular orientation of perylene molecules changes from edge-on toward random as the PTCDA content increases.

  10. New M- and V-shaped perylene diimide small molecules for high-performance nonfullerene polymer solar cells.

    PubMed

    Park, Gi Eun; Kim, Hyung Jong; Choi, Suna; Lee, Dae Hee; Uddin, Mohammad Afsar; Woo, Han Young; Cho, Min Ju; Choi, Dong Hoon

    2016-07-01

    New M- and V-shaped perylene diimide (PDI)-based small molecules using a non-conjugated 1,1-diphenylcyclohexane linker (CP-M and CP-V, respectively) were designed and synthesized as new n-type acceptors for nonfullerene-based polymer solar cells. The blended film with poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT) and CP-V displayed a higher power conversion efficiency of 5.28% due to higher short circuit current and fill factor values. PMID:27351371

  11. Ionic compound mediated rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride molecules on Ag(100) surface

    NASA Astrophysics Data System (ADS)

    Guo, Qinmin; Huang, Min; Lu, Shuangzan; Cao, Gengyu

    2015-07-01

    Tailoring of the assembly structure of organic molecular monolayer is of great importance to improve the performance of molecular devices. In this work, a typical ionic compound, namely KCl, was used to mediate the rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride (PTCDA) monolayer on Ag(100). Combined scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) results indicate that both molecule and molecular superlattice would rotate after the dosing of KCl. The density functional theory calculation shows that KCl would exist in the form of molecules rather than ions on Ag(100) and demonstrates that experimentally observed structural transition induced by KCl molecules is energetically favored.

  12. Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays

    DOEpatents

    Loewe, Robert S.; Tomizaki, Kin-ya; Lindsey, Jonathan S.

    2005-07-12

    The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I: wherein m is at least 1; X.sup.1 is a charge separation group, and X.sup.2 through X.sup.m+1 are chromophores. At least one of X.sup.2 through X.sup.m+1 has at least one perylene group coupled thereto.

  13. Ionic compound mediated rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride molecules on Ag(100) surface.

    PubMed

    Guo, Qinmin; Huang, Min; Lu, Shuangzan; Cao, Gengyu

    2015-07-10

    Tailoring of the assembly structure of organic molecular monolayer is of great importance to improve the performance of molecular devices. In this work, a typical ionic compound, namely KCl, was used to mediate the rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride (PTCDA) monolayer on Ag(100). Combined scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) results indicate that both molecule and molecular superlattice would rotate after the dosing of KCl. The density functional theory calculation shows that KCl would exist in the form of molecules rather than ions on Ag(100) and demonstrates that experimentally observed structural transition induced by KCl molecules is energetically favored. PMID:26080855

  14. Photoluminescence and conductivity of self-assembled pi-pi stacks of perylene bisimide dyes.

    PubMed

    Chen, Zhijian; Stepanenko, Vladimir; Dehm, Volker; Prins, Paulette; Siebbeles, Laurens D A; Seibt, Joachim; Marquetand, Philipp; Engel, Volker; Würthner, Frank

    2007-01-01

    The self-assembly of a new, highly fluorescent perylene bisimide dye 2 into pi stacks, both in solution and condensed phase, has been studied in detail by NMR spectroscopy, vapor pressure osmometry (VPO), UV/Vis and fluorescence spectroscopy, differential scanning calorimetry (DSC), optical polarizing microscopy (OPM) and X-ray diffraction. The NMR and VPO measurements revealed the formation of extended pi-pi stacks of the dye molecules in solution. The aggregate size determined from VPO and DOSY NMR measurements agree well with that obtained from the concentration and temperature-dependent UV/Vis spectral data by employing the isodesmic model (equal K model). In the condensed state, dye 2 possesses a hexagonal columnar liquid crystalline (LC) phase as confirmed by X-ray diffraction analysis. The columnar stacking of this dye has been further explored by atomic force microscopy (AFM). Well-resolved columnar nanostructures of the compound are observed on graphite surface. A color-tunable luminescence from green to red has been observed upon aggregation which is accompanied by an increase of the fluorescence lifetime and depolarization. The observed absorption properties can be explained in terms of molecular exciton theory. The charge transport properties of dye 2 have been investigated by pulse radiolysis-time resolved microwave conductivity measurements and a 1D charge carrier mobility up to 0.42 cm(2) V(-1) s(-1) is obtained. Considering the promising self-assembly, semiconducting, and luminescence properties of this dye, it might serve as a useful functional material for nano(opto)electronics. PMID:17143925

  15. Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

    SciTech Connect

    Hestand, Nicholas J.; Spano, Frank C.

    2015-12-28

    The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (t{sub e}) and hole (t{sub h}) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product t{sub e}t{sub h} and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in “null-aggregates” which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.

  16. Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

    NASA Astrophysics Data System (ADS)

    Hestand, Nicholas J.; Spano, Frank C.

    2015-12-01

    The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (te) and hole (th) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product teth and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in "null-aggregates" which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.

  17. Label-free multimodal protease detection based on protein/perylene dye coassembly and enzyme-triggered disassembly.

    PubMed

    Lin, Yiyang; Chapman, Robert; Stevens, Molly M

    2014-07-01

    The development of novel assays for protease sensing plays an important role in clinical diagnostics and therapeutics. Herein, we report a supramolecular platform for label-free protease detection, based on protein/dye self-assembly and enzyme-triggered disassembly. In a typical case, coassembly of protamine sulfate and perylene dye via electrostatic attractions and π-π interactions caused significant colorimetric and fluorescent responses. Subsequent addition of trypsin was found to cleave the amide bonds of protein, triggering the dissociation of protein/dye aggregates and the release of perylene dyes. The enzyme-triggered disassembly was transduced into multiple readouts including absorption, fluorescence, and polarization, which were exploited for trypsin detection and inhibitor testing. This assay was also used for turn-on fluorescence detection of cathepsin B, an enzyme known to be overexpressed in mammalian cancer cells. The integration of supramolecular self-assembly into enzyme detection in this work has provided a novel label-free biosensing platform which is highly sensitive with multimodal readouts. The relative simplicity of the approach avoids the need for time-consuming substrate synthesis, and is also amenable to naked eye detection. PMID:24914622

  18. Real-Time Visualization of Perylene Nanoclusters in Water and Their Partitioning to Graphene Surface and Macrophage Cells.

    PubMed

    Guo, Xuejun; Jin, Xin; Lv, Xiaofang; Pu, Yingying; Bai, Fan

    2015-07-01

    Hydrophobic organic chemicals (HOCs) are of special ecotoxicological concern because they can be directly incorporated and bioconcentrated in living organisms. However, the effects of self-clustering of HOCs on their environmental behavior and toxicology have not yet received enough attention. With the use of a recently developed technique, single-molecule fluorescence microscopy, the motion and distribution of perylene nanoclusters (PNCs) formed in water at very low concentration (1 μM) were visualized with high temporal and spatial resolution. The liquid-solid interface process of PNCs adsorbing onto graphene was also recorded. Instead of the traditional view of HOC adsorption as a single molecule, our study revealed the characteristic of irreversible adsorption of perylene onto the carbonaceous surface in the form of nanoclusters, exhibiting random sequential "car-parking" events. More interestingly, the transport of PNCs across the cell membrane was also captured in real time, demonstrating that they entered macrophage cells by endocytosis. Supplementing the well-recognized routine of passive diffusion through a membrane lipid bilayer, the uptake of HOCs in the form of nanoclusters by endocytosis is proposed to be an additional but important mechanism for their uptake into living cells. The distribution of HOCs in environmental systems in the form of nanoclusters, exemplified by PNCs in this study, may have significant implications for understanding their environmental fate and potential toxicological effects. PMID:26055420

  19. Influence of the preparation conditions on the morphology of perylene thin films on Si(111) and Si(100)

    SciTech Connect

    Casu, M. B.; Yu, X.; Schmitt, S.; Heske, C.; Umbach, E.

    2008-12-28

    Thin films of perylene on Si(111) and Si(100) substrates have been investigated using a variety of experimental techniques. We find that the structural and morphological properties as well as the growth modes strongly depend on the preparation parameters. In general, we observe the existence of a relatively weak coupling between perylene and the two single crystal substrates. However, under special preparation conditions, it is possible to obtain a multilayer phase on the Si(111) substrate that is characterized by flat-lying, parallel-oriented molecules, and strong coupling with the substrate in the first layer. This phase has different structural, electronic, and intermolecular bonding properties as compared to the known crystalline phases. On Si(100), by varying the deposition rate between 0.1 and 10 nm/min, it is possible to observe a transition from island growth mode, with large and isolated crystallites, to homogeneous film growth. These findings contribute to the basic knowledge for film engineering. Thus, the film morphology could be designed ranging from the growth of very large single grains suitable for a complete nanodevice to homogenous films for application in large displays.

  20. Coordination-driven self-assembly of PEO-functionalized perylene bisimides: supramolecular diversity from a limited set of molecular building blocks.

    PubMed

    Gebers, Jan; Rolland, Damien; Frauenrath, Holger

    2009-01-01

    A limited number of poly(ethylene oxide)-substituted perylene bisimides, some of which are equipped with terpyridine ligands for transition-metal coordination (see structure), combine different types of noncovalent interactions to yield optoelectronically active organic materials with different types of supramolecular morphologies. PMID:19455536

  1. 21 CFR 73.3120 - 16,17-Dimethoxydinaphtho [1,2,3-cd:3′,2′,1′-lm] perylene-5,10-dione.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false 16,17-Dimethoxydinaphtho perylene-5,10-dione. 73.3120 Section 73.3120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3120...

  2. 21 CFR 73.3120 - 16,17-Dimethoxydinaphtho [1,2,3-cd:3′,2′,1′-lm] perylene-5,10-dione.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false 16,17-Dimethoxydinaphtho perylene-5,10-dione. 73.3120 Section 73.3120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3120...

  3. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

    NASA Astrophysics Data System (ADS)

    Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

    2015-05-01

    New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating.

  4. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

    PubMed Central

    Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

    2015-01-01

    New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

  5. Novel nanosized water soluble fluorescent micelles with embedded perylene diimide fluorophores for potential biomedical applications: cell permeability, localization and cytotoxicity.

    PubMed

    Bryaskova, Rayna; Georgiev, Nikolai I; Dimov, Stefan M; Tzoneva, Rumiana; Detrembleur, Christophe; Asiri, Abdullah M; Alamry, Khalid A; Bojinov, Vladimir B

    2015-06-01

    Novel biocompatible water-soluble fluorescent micelles with embedded perylene diimides (PDI) for intracellular applications have been prepared by self assembling of amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) (PVA-b-PAN) copolymers in the presence of synthesized fluorophores. Amphiphilic PVA-b-PAN copolymers were obtained by selective hydrolysis of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) (PVAc-b-PAN) copolymer. The preparation of the novel fluorescence micelles consisting of PVA hydrophilic shell and PAN hydrophobic core with incorporated PDI fluorophores has been confirmed by DLS and TEM analysis. The cytotoxicity of the water-soluble fluorophores and their internalization into living cells depending on the micellar concentration have been tested. It was shown that they could successfully enter in living cells without destroying their morphology. The results obtained indicate that the novel water-soluble fluorescent micelles with embedded PDI fluorophores would be suitable for potential intracellular biomedical applications. PMID:25842102

  6. Switch-On Fluorescence of a Perylene-Dye-Functionalized Metal-Organic Framework through Postsynthetic Modification.

    PubMed

    Dietl, Christian; Hintz, Henrik; Rühle, Bastian; Schmedt Auf der Günne, Jörn; Langhals, Heinz; Wuttke, Stefan

    2015-07-20

    A perylene dye was introduced directly as a linker into a metal-organic framework (MOF) during synthesis. Depending on the dye concentration in the MOF synthesis mixture, different fluorescent materials were generated. The successful incorporation of the dye was proven by using (13) C and (27) Al MAS NMR spectroscopy, by solution NMR spectroscopy after digestion of the MOF sample, and by synthesizing a reference dye without connecting groups, which could coordinate on the metal-oxo cluster inside the MOF. Fluorescence quenching effects of the MOF linker, 2-aminoterephthalate, were observed and overcome by postsynthetic modification with acetic anhydride. We show here for the first time that amino groups, which can be used as anchoring points for covalent attachment of other molecules, are responsible for fluorescence quenching. Thus, a very promising strategy to implement switchable fluorescence into MOFs is shown here. PMID:26037475

  7. Synthesis, photophysics of two new perylene bisimides and their photovoltaic performances in quasi solid state dye sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Mikroyannidis, John A.; Stylianakis, Minas M.; Roy, M. S.; Suresh, P.; Sharma, G. D.

    Two new symmetrical compounds A and P based on perylene-anthracene and perylene-pyrene, respectively, were synthesized and characterized by FT-IR, 1H NMR, TGA and TMA. These compounds contained tert-butyl groups which enhanced their solubility, decomposed above 400 °C and gave char yields of 46-65% at 800 °C in N 2. Compound A showed significantly higher glass transition temperature (124 °C) than P (75 °C). Their absorption spectra were broad with longer wavelength absorption at 467-525 nm and optical band gap of 2.05 eV. The solutions of the compounds emitted green-yellow light with maximum at 555 nm, while their films were not photoluminescent. The compound A shows better photovoltaic response than compound P. Quasi solid state dye sensitized solar cells (DSSCs) have been fabricated employing compound A as sensitizer and polymer sol gel as electrolyte and characterized through the current-voltage characteristics in dark as well as under illumination and electrochemical impedance spectra. We found that the Al 2O 3 modification of TiO 2 layer significantly improves the dye absorption resulting in enhancement of power conversion efficiency (PCE) (from 1.15 to 2.13%) which is attributed to the increase in electron lifetime and reduction in back transfer of electrons. Finally, the TiO 2 has been incorporated into the polymer electrolyte gel to improve the power conversion efficiency (3.42%) of the quasi solid state DSSC. The faster electron diffusion in the device, the high ionic conductivity and the low activation energy of the polymer electrolyte are also responsible for enhanced PCE, when TiO 2 nano-particles are incorporated in the polymer electrolyte.

  8. Molecular metals based on 1,2,7,8-tetrahydrodicyclopenta[cd:lm]perylene and iodine, (CPP){sub 2}(I{sub 3}){sub 1-{delta}}

    SciTech Connect

    Morgado, J. |; Santos, I.C.; Henriques, R.T.; Almeida, M.; Fourmigue, M.; Matias, P.; Veiros, L.F.; Duarte, M.T.; Alcacer, L.; Calhorda, M.J. |

    1994-12-01

    The synthesis and characterization of molecular metals derived from 1,2,7,8-tetrahydrodicyclopenta[cd:lm]perylene (CPP) by partial oxidation with iodine and with general formula (CPP){sub 2}(I{sub 3}){sub 1-{delta}}, {delta} = 0-0.13, are reported. Single crystals, obtained either by electrocrystallization or by diffusion-controlled iodine oxidation of CPP, present two types of morphologies, elongated diamond or thinner needle-shaped crystals, both with a monoclinic cell, space group P2{sub 1}/a, a = 4.3757(9), b = 19.3681(11), c = 10.0860(11) {angstrom}, {beta} = 98.050(8){degrees}, V = 846.4(2) {angstrom}{sup 3}, Z = 2. The structure of the diamond-shaped crystal was solved by X-ray diffraction to a final R(F) = 0.096, R{sub w}(F) = 0.069. It consists of regular stacks of CPP molecules along a with a 3.41 {angstrom} spacing and uncorrected one-dimensional chains of I{sub 3}{sup {minus}} located in channels between four CPP stacks corresponding to (CPP){sub 2}(I{sub 3}){sub 0.892}. The thin needle crystals have the same unit cell but an unspecified and slightly different iodine content. Band structure calculations in this structure by the extended Hueckel method indicate a one-dimensional conduction band 0.55 eV wide. These thin needle crystals present, at room temperature, an electrical conductivity along the a axis {alpha}{sub a}(RT) = 200 S/cm and thermopower S{sub a}(RT) = 30 {mu}V/K, while for the diamond-shaped crystals {alpha}{sub a}(RT) = 2 S/cm and S{sub a}(RT) = -8 {mu}V/K. These transport coefficients for both types of crystals indicate a metallic behavior from room temperature down to {approx_equal}63 K, where a metal-to-insular (M-I) transition takes place. EPR studies in single crystals show an almost isotropic line at g = 2.0044 and with a width of {approx_equal}6 G in the range 80-300 K and without significant differences between the two types of crystals. 53 refs., 9 figs., 4 tabs.

  9. Fluorescence turn-on detection of mercury ions based on the controlled adsorption of a perylene probe onto the gold nanoparticles.

    PubMed

    Li, Juanmin; Chen, Jian; Chen, Yang; Li, Yongxin; Shahzad, Sohail Anjum; Wang, Yan; Yang, Meiding; Yu, Cong

    2016-01-01

    A novel fluorescence turn-on strategy based on Au nanoparticles and a perylene probe for the sensing of Hg(2+) ions has been developed. It was observed that a perylene probe could be adsorbed onto the surface of Au NPs through strong electrostatic and hydrophobic interactions. Its fluorescence was efficiently quenched by the Au nanoparticles. However, in the presence of Hg(2+) and NaBH4, Hg(2+) was reduced and an Au/Hg amalgam was formed on the surface of the Au nanoparticles. The perylene probe could hardly be adsorbed and quenched by the Au/Hg amalgam. A turn on fluorescence signal was therefore detected. The assay is quite sensitive, and 5 nM Hg(2+) could be easily detected. It is also very selective, a number of metal ions were tested and no noticeable interference was observed. The assay was also successfully applied for the determination of Hg(2+) in lake water samples. A simple, fast, inexpensive, highly sensitive and selective Hg(2+) sensing strategy is therefore established. PMID:26618370

  10. Electronic energy and electron transfer processes in photoexcited donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units.

    PubMed

    Lee, K J; Woo, J H; Kim, E; Xiao, Y; Su, X; Mazur, L M; Attias, A-J; Fages, F; Cregut, O; Barsella, A; Mathevet, F; Mager, L; Wu, J W; D'Aléo, A; Ribierre, J-C

    2016-03-01

    We investigate the photophysical properties of organic donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units linked by a non-conjugated flexible bridge in solution using complementary optical spectroscopy techniques. When these molecules are diluted in dichloromethane solution, energy transfer from the triphenylene to the perylene diimide excited moieties is evidenced by time-resolved fluorescence measurements resulting in a quenching of the emission from the triphenylene moieties. Simultaneously, another quenching process that affects the emission from both donor and acceptor units is observed. Solution ultrafast transient absorption measurements provide evidence of photo-induced charge transfer from either the donor or the acceptor depending upon the excitation. Overall, the analysis of the detailed time-resolved spectroscopic measurements carried out in the dyad and triad systems as well as in the triphenylene and perylene diimide units alone provides useful information both to better understand the relations between energy and charge transfer processes with molecular structures, and for the design of future functional dyad and triad architectures based on donor and acceptor moieties for organic optoelectronic applications. PMID:26911420

  11. In situ-generated nano-gold plasmon-enhanced photoelectrochemical aptasensing based on carboxylated perylene-functionalized graphene.

    PubMed

    Li, Jing; Tu, Wenwen; Li, Hongbo; Han, Min; Lan, Yaqian; Dai, Zhihui; Bao, Jianchun

    2014-01-21

    A novel in situ-generated nanogold plasmon-enhanced photoelectrochemical aptasensor for Hg(2+) ions was fabricated using a perylene-3,4,9,10-tetracarboxylic acid/graphene (PTCA-GR) heterojunction. The fabricated photoelectrochemical aptasensor was based on thymine-Hg(2+)-thymine coordination chemistry and the plasmonic near-field absorption enhancement effect of the subsequent specific catalytic formation of nanogold. The energetic electrons from the surface plasmons of the nanogold were injected into the LUMO orbit of the organic PTCA semiconductor and then rapidly transferred to the electrode through GR due to the possible Hg(2+)-DNA molecular wires following irradiation with the visible light (λ > 450 nm) and at a bias voltage of 0.2 V. The fabricated aptasensor was linear in its response to the concentration of Hg(2+) ions in the range of 5-500 pmol L(-1), with a detection limit of 2 pmol L(-1). The presence of up to 200-fold greater concentrations of other common metal ions did not interfere with the detection of Hg(2+) ions in an aqueous system, and the results corresponded well with those obtained by ICP-MS. This novel plasmon-enhanced photoelectrochemical aptasensor exhibited good performance with its high sensitivity, good selectivity, low cost, and portable features. The strategy of the localized surface plasmon resonance through the in situ generation of noble metal nanoparticles paves the way for improvements in PEC aptasensor performance. PMID:24377281

  12. Donor-linked di(perylene bisimide)s: arrays exhibiting fast electron transfer for photosynthesis mimics.

    PubMed

    Wu, Yishi; Zhen, Yonggang; Wang, Zhaohui; Fu, Hongbing

    2013-02-28

    The first example of donor-linked di(perylene bisimide)s is reported. UV-vis absorption spectra of these newly synthesized dyads showed intense absorption across the entire visible region, demonstrating their excellent light-harvesting activities. The severe fluorescence quenching event probed by steady-state fluorescence spectroscopy and the free-energy calculations suggested the possibility of electron transfer (ET) in these arrays upon photoexcitation. Further femtosecond transient absorption spectra clarified that the fluorescence quenching was due to fast intramolecular ET. The rate of the charge separation (CS) was found to be as high as 10(12) s(-1) in CH(2)Cl(2). It was suggested that the large ET driving forces, strong donor-acceptor electronic coupling, and relatively small reorganization energy of diPBI accounted for the rapid ET process in a synergic manner. The fate of the generated radical ion pair depended on the solvent used. Rapid charge recombination to ground state occurred for the dyads in polar CH(2)Cl(2) and for diPBI-TPA in nonpolar toluene. However, sufficient (3)diPBI* population was attained via efficient spin-orbit coupled intersystem crossing from the charge-separated state for diPBI-PdTPP in toluene. These photophysical properties are interpreted as the cooperation between thermodynamic feasibility and kinetic manipulation. PMID:23391220

  13. Improving the layer morphology of solution-processed perylene diimide organic solar cells with the use of a polymeric interlayer

    NASA Astrophysics Data System (ADS)

    Singh, Ranbir; Mróz, Marta M.; Di Fonzo, Fabio; Cabanillas-Gonzalez, Juan; Marchi, Enrico; Bergamini, Giacomo; Müllen, Klaus; Jacob, Josemon; Keivanidis, Panagiotis E.

    2013-10-01

    Herein we demonstrate a method to improve the power conversion efficiency (PCE) parameter of organic photovoltaic (OPV) devices based on the electron acceptor N,N'-bis(1- ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (PDI) blended with the electron donor poly(indenofluorene)-aryloctyl (PIF-Aryl). The device parameters of the short-circuit current, open-circuit voltage and fill factor are found increased after the insertion of a thin poly [9, 9-dioctylfluorene-co-N- [4-(3-methylpropyl)]-diphenylamine] (TFB) photoactive interlayer between the hole-collecting electrode and the photoactive layer of the device. Unlike to most of the cases where interlayers serve as charge extractors, in our system the polymeric interlayer serves as a morphology modifying agent that drives the PDI component to segregate better at the interface with the device cathode; that is at the carrier-collecting electrode interface, which is not in physical contact with the interlayer. The processes of energy/charge transfer of the TFB excitons to/with the PIF-Aryl:PDI top-layer are also addressed. Charge transfer reactions dominate at the TFB/PIF-Aryl:PDI interface but no significant contribution in the photocurrent generation is seen in the photoaction spectra of the bilayer device.

  14. Direct observation of ultrafast coherent exciton dynamics in helical π-stacks of self-assembled perylene bisimides

    PubMed Central

    Sung, Jooyoung; Kim, Pyosang; Fimmel, Benjamin; Würthner, Frank; Kim, Dongho

    2015-01-01

    Ever since the discovery of dye self-assemblies in nature, there have been tremendous efforts to exploit biomimetic supramolecular assemblies for tailored artificial photon processing materials. This feature necessarily has resulted in an increasing demand for understanding exciton dynamics in the dye self-assemblies. In a sharp contrast with J-type aggregates, however, the detailed observation of exciton dynamics in H-type aggregates has remained challenging. In this study, as we succeed in measuring transient fluorescence from Frenkel state of π-stacked perylene tetracarboxylic acid bisimide dimer and oligomer aggregates, we present an experimental demonstration on Frenkel exciton dynamics of archetypal columnar π–π stacks of dyes. The analysis of the vibronic peak ratio of the transient fluorescence spectra reveals that unlike the simple π-stacked dimer, the photoexcitation energy in the columnar π-stacked oligomer aggregates is initially delocalized over at least three molecular units and moves coherently along the chain in tens of femtoseconds, preceding excimer formation process. PMID:26492820

  15. Synthesis, characterization and binding interactions of amino acids coupled perylene diimides with colloidal doped and undoped TiO2

    NASA Astrophysics Data System (ADS)

    Kavery, E.; Nagarajan, N.; Paramaguru, G.; Renganathan, R.

    2015-07-01

    Two sensitizers based on amino acids coupled with perylene moiety having absorption in the visible region have been designed and their interaction with doped and undoped TiO2 for the application of dye sensitized solar cells (DSSCs) has been studied. The synthesized compounds PDI-PA and PDI-AA were characterized using 1H and 13C NMR, Mass and FT-IR spectroscopic techniques. The optical properties and lifetime measurements of the sensitizers were analyzed using various solvents with different polarity. The solvatochromism effect was studied using Lippert-Mataga plot. The electrochemical studies of both dyes were investigated in DMF with various scan rate ranging from 200 to 1000 mV s-1. Colloidal doped and undoped TiO2 was prepared and characterized by using absorption measurements. Binding ability of the sensitizers with the nanoparticles was studied through absorption, fluorescence quenching, cyclic voltammetry and FT-IR measurements. Results obtained from all the above analysis suggest the mode of quenching may be static. The binding constant values were calculated using Kamat-Fox equation indicates the binding behavior of the sensitizers with the nanoparticles. The fluorescence quenching was mainly attributed to electron transfer from the excited state of PDI's to the conduction band of colloidal semiconductors. The electron transfer mechanism was explained based on the Rehm-Weller equation as well as the energy level diagram.

  16. Modification of nanocrystalline WO3 with a dicationic perylene bisimide: applications to molecular level solar water splitting.

    PubMed

    Ronconi, Federico; Syrgiannis, Zois; Bonasera, Aurelio; Prato, Maurizio; Argazzi, Roberto; Caramori, Stefano; Cristino, Vito; Bignozzi, Carlo Alberto

    2015-04-15

    [(N,N'-Bis(2-(trimethylammonium)ethylene) perylene 3,4,9,10-tetracarboxylic acid bisimide)(PF6)2] (1) was observed to spontaneously adsorb on nanocrystalline WO3 surfaces via aggregation/hydrophobic forces. Under visible irradiation (λ > 435 nm), the excited state of 1 underwent oxidative quenching by electron injection (kinj > 10(8) s(-1)) to WO3, leaving a strongly positive hole (Eox ≈ 1.7 V vs SCE), which allows to drive demanding photo-oxidation reactions in photoelectrochemical cells (PECs). The casting of IrO2 nanoparticles (NPs), acting as water oxidation catalysts (WOCs) on the sensitized electrodes, led to a 4-fold enhancement in photoanodic current, consistent with hole transfer from oxidized dye to IrO2 occurring on the microsecond time scale. Once the interaction of the sensitizer with suitable WOCs is optimized, 1/WO3 photoanodes may hold potentialities for the straightforward building of molecular level devices for solar fuel production. PMID:25837588

  17. Electronic structure at the perylene-tetracarboxylic acid dianhydride/Ag(111) interface studied with two-photon photoelectron spectroscopy.

    PubMed

    Sachs, Sönke; Schwalb, Christian H; Marks, Manuel; Schöll, Achim; Reinert, Friedrich; Umbach, Eberhard; Höfer, Ulrich

    2009-10-14

    The electronic structure of the prototype metal/organic contact 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) on a Ag(111)-surface has been investigated using time- and angle-resolved two-photon photoelectron spectroscopy (2PPE). Our analysis addresses particularly the nature of the interface state (IS) emerging at the interface due to the substrate-adsorbate interaction [C. H. Schwalb, S. Sachs, M. Marks et al., Phys. Rev. Lett. 101, 146801 (2008)]. Its free-electron-like dispersion and a possible backfolding at the surface Brillouin zone boundaries are discussed. Time-resolved pump-probe experiments reveal the inelastic electron lifetime along the dispersion parabola and show its decrease for increasing parallel momentum. The temperature dependence of the peak linewidth indicates a coupling of the IS to molecular vibrations. Moreover, additional aspects are addressed, such as the determination of the electron attenuation length of photoelectrons for low kinetic energy originating from the IS and the work function change of the sample upon PTCDA adsorption with very high energy resolution. PMID:19831458

  18. Molecular Packing Determines Charge Separation in a Liquid Crystalline Bisthiophene-Perylene Diimide Donor-Acceptor Material.

    PubMed

    Polkehn, Matthias; Tamura, Hiroyuki; Eisenbrandt, Pierre; Haacke, Stefan; Méry, Stéphane; Burghardt, Irene

    2016-04-01

    Combined electronic structure and quantum dynamical calculations are employed to investigate charge separation in a novel class of covalently bound bisthiophene-perylene diimide type donor-acceptor (DA) co-oligomer aggregates. In an earlier spectroscopic study of this DA system in a smectic liquid crystalline (LC) film, efficient and ultrafast (subpicosecond) initial charge separation was found to be followed by rapid recombination. By comparison, the same DA system in solution exhibits ultrafast resonant energy transfer followed by slower (picosecond scale) charge separation. The present first-principles study explains these contrasting observations, highlighting the role of an efficient intermolecular charge-transfer pathway that results from the molecular packing in the LC phase. Despite the efficiency of this primary charge-transfer step, long-range charge separation is impeded by a comparatively high Coulomb barrier in conjunction with small electron- and hole-transfer integrals. Quantum dynamical calculations are carried out for a fragment-based model Hamiltonian, parametrized by ab initio second-order Algebraic Diagrammatic Construction (ADC(2)) and Time-Dependent Density Functional Theory (TDDFT) electronic structure calculations. Simulations of coherent vibronic quantum dynamics for up to 156 electronic states and 48 modes are performed using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method. Excellent agreement with experimentally determined charge separation time scales is obtained, and the spatially coherent nature of the dynamics is analyzed. PMID:26987362

  19. Synthesis, characterization and optoelectronic properties of a new perylene diimide-benzimidazole type solar light harvesting dye

    NASA Astrophysics Data System (ADS)

    Dinçalp, Haluk; Çimen, Oguzhan; Ameri, Tayebeh; Brabec, Christoph J.; İçli, Sıddık

    2014-07-01

    A perylene diimide type small molecule (BI-PDI) has been synthesized through Suzuki coupling reaction between N,N‧-bis(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4,9,10-tetracarboxylic diimide and 2-(2-hydroxyphenyl)-7-phenyl-1H-benzimidazole-4-boronic acid. BI-PDI small molecule has showed an absorption band between 350 and 750 nm on thin films. HOMO and LUMO energy levels of BI-PDI dye have been calculated to be about -5.92 eV and -3.82 eV, respectively. Solution-processed bulk heterojunction (BHJ) solar cells have been constructed using BI-PDI as donor and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor or poly(3-hexylthiophene) (P3HT) as donor and BI-PDI as acceptor. The external quantum efficiencies (EQE) of the devices cover the most of the visible region between 400 and 700 nm for both configurations. Photovoltaic performances of BI-PDI-based organic solar cells are limited by the aggregation tendency of PDI structure and poor hole/electron mobilities of the active layer.

  20. Interfacial spectroscopic characterization of organic/ferromagnet hetero-junction of 3,4,9,10-perylene-teracarboxylic dianhydride-based organic spin valves

    NASA Astrophysics Data System (ADS)

    Hong, Jhen-Yong; Ou Yang, Kui-Hon; Wang, Bo-Yao; Li, Kai-Shin; Shiu, Hung-Wei; Chen, Chia-Hao; Chan, Yuet-Loy; Wei, Der-Hsin; Chang, Fan-Hsiu; Lin, Hong-Ji; Chiang, Wen-Chung; Lin, Minn-Tsong

    2014-02-01

    We report interfacial characterization of 3,4,9,10-perylene-teracarboxylic dianhydride (PTCDA)-based organic spin valves (OSV) dusted with a thin layer of partially oxidized alumina at the organic semiconductor (OSC)/ferromagnet (FM) interfaces. Up to 13.5% magnetoresistance is achieved at room temperature. X-ray photoelectron spectroscopy measurements reveal interfacial electronic interaction between PTCDA and FM while the application of a thin alumina layer at the PTCDA/FM interfaces prevents the electronic hybridization and effectively preserves the spin injection into the OSC spacer. This finding demonstrates the critical effect of interfacial structure on magnetotransport behavior in OSV.

  1. Charge transfer dynamics of 3,4,9,10-perylene-tetracarboxylic-dianhydride molecules on Au(111) probed by resonant photoemission spectroscopy.

    PubMed

    Cao, Liang; Wang, Yu-Zhan; Chen, Tie-Xin; Zhang, Wen-Hua; Yu, Xiao-Jiang; Ibrahim, Kurash; Wang, Jia-Ou; Qian, Hai-Jie; Xu, Fa-Qiang; Qi, Dong-Chen; Wee, Andrew T S

    2011-11-01

    Charge transfer dynamics across the lying-down 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) organic semiconductor molecules on Au(111) interface has been investigated using the core-hole clock implementation of resonant photoemission spectroscopy. It is found that the charge transfer time scale at the PTCDA∕Au(111) interface is much larger than the C 1s core-hole lifetime of 6 fs, indicating weak electronic coupling between PTCDA and the gold substrate due to the absence of chemical reaction and∕or bonding. PMID:22070311

  2. Fluorescence of the perylene radical cation and an inaccessible D0/D1 conical intersection: An MMVB, RASSCF, and TD-DFT computational study

    NASA Astrophysics Data System (ADS)

    Tokmachev, Andrei M.; Boggio-Pasqua, Martial; Mendive-Tapia, David; Bearpark, Michael J.; Robb, Michael A.

    2010-01-01

    The photophysics of the perylene radical cation (Pe•+) was studied using the molecular mechanics-valence bond (MMVB) hybrid force field. Potential energy surfaces of the first three electronic states were investigated. Geometry optimizations of critical points—including conical intersections between the relevant electronic states—were performed using the MMVB analytical energy gradient for cations. No accessible planar conical intersection between the D0 and D1 states of Pe•+ was found; this is consistent with the experimentally observed D1 lifetimes and the observation of D1 emission from this cation in the condensed phase. Benchmark RASSCF and TD-DFT calculations support the reliability of the MMVB results.

  3. Benzo[ghi]perylene activates the AHR pathway to exert biological effects on the NL-20 human bronchial cell line.

    PubMed

    Zaragoza-Ojeda, Montserrat; Eguía-Aguilar, Pilar; Perezpeña-Díazconti, Mario; Arenas-Huertero, Francisco

    2016-08-10

    Polycyclic aromatic hydrocarbons (PAH) are produced by incomplete combustion of organic material. In the Mexico City atmosphere, the most abundant PAH is benzo[ghi]perylene (BghiP), a gasoline combustion marker. At present, there are no reports of the effects of BghiP on human bronchial cells, so the aim of the study was to evaluate the effects in vitro of BghiP on the NL-20 cell line. Results showed that BghiP induced the formation of small vesicles throughout the cytoplasm, with absence of nuclear fragmentation. At 48h exposition, damage in cell membrane increased significantly at 1.24μg/mL of BghiP (p<0.05). Immunocytochemistry revealed that BghiP provokes nuclear translocation of AhR receptor, which indicates that this compound can induce transcription of genes via receptor binding (AhR pathway activation). BghiP induced a two-fold increase (p<0.05) in the expression of AhR and CYP4B1 (a lung-specific pathway effector). In the presence of the receptor antagonist CH-223191, the loss of viability, the nuclear translocation and the overexpression of genes decreased, though this did not prevent the formation of vesicles. BghiP induced oxidative stress and in presence of the receptor antagonist this increased significantly. In conclusion, BghiP can activate the overexpression of AhR and CYP4B1, and the effects are abated by the AhR receptor antagonist. This is the first report to prove that BghiP utilizes the AhR pathway to exert its toxic effects on the NL-20 human bronchial cell line . PMID:27234499

  4. Aromatization of Benzannulated Perylene-3,9-diones: Unexpected Photophysical Properties and Reactivity.

    PubMed

    Rao, M Rajeswara; Johnson, Shea; Perepichka, Dmitrii F

    2016-08-01

    Highly unusual properties of acene-based quinones 1A and 1T are reported. They undergo an unexpected combination of Michael and carbonyl additions of aryllithium leading to new triarylated benzoperylenes 3A and 3T. Uncharacteristically for quinones, 1A and 1T display vibronically split absorption bands and small Stokes shifts. The absorption/emission spectra of the highly emissive 1A are almost indistinguishable from those of the aromatized 3A. Additional benzene rings cause a counterintuitive blue shift of the aromatic derivatives (2T/3T), but an expected red shift was observed for the quinone (1T). This behavior is fully supported by DFT calculations and rationalized by considering the longest conjugation path. PMID:27404491

  5. Photophysics and redox properties of rylene imide and diimide dyes alkylated ortho to the imide groups.

    PubMed

    Bullock, Joseph E; Vagnini, Michael T; Ramanan, Charusheela; Co, Dick T; Wilson, Thea M; Dicke, Jay W; Marks, Tobin J; Wasielewski, Michael R

    2010-02-11

    Ruthenium-catalyzed C-H bond activation was used to directly attach phenethyl groups derived from styrene to positions ortho to the imide groups in a variety of rylene imides and diimides including naphthalene-1,8-dicarboximide (NMI), naphthalene-1,4:5,8-bis(dicarboximide) (NI), perylene-3,4-dicarboximide (PMI), perylene-3,4:9,10-bis(dicarboximide) (PDI), and terrylene-3,4:11,12-bis(dicarboximide) (TDI). The monoimides were dialkylated, while the diimides were tetraalkylated, with the exception of NI, which could only be dialkylated due to steric hindrance. The absorption, fluorescence, transient absorption spectra, and lowest excited singlet state lifetimes of these chromophores, with the exception of NI, are nearly identical to those of their unsubstituted parent chromophores. The reduction potentials of the dialkylated chromophores are approximately 100 mV more negative and oxidation potentials are approximately 40 mV less positive than those of the parent compounds, while the corresponding potentials of the tetraalkylated compounds are approximately 200 mV more negative and approximately 100 mV less positive than those of their parent compounds, respectively. Continuous wave electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) data on the radical anion of PDI reveals spin density on the perylene-core protons as well as on the beta-protons of the phenethyl groups. The phenethyl groups enhance the otherwise poor solubility of the bis(dicarboximide) chromophores and only weakly perturb the photophysical and redox properties of the parent molecules, rendering these derivatives and related molecules of significant interest to solar energy conversion. PMID:20073517

  6. Photophysics of new photostable rylene derivatives: applications in single-molecule studies and membrane labelling.

    PubMed

    Davies, Melari; Jung, Christophe; Wallis, Philipp; Schnitzler, Tobias; Li, Chen; Müllen, Klaus; Bräuchle, Christoph

    2011-06-01

    Three new photostable rylene dyes for applications in single molecule studies and membrane labelling have been synthesized and their photophysical properties were characterized. These dyes differ in the number of polyethylene glycol (PEG) chains attached to the core structure which is either a perylene derivate or a terrylene derivate. One perylene and one terrylene dye is modified with two PEG chains, and another terrylene derivate has four PEG chains. The results show that the terrylene dye with four PEG chains (4-PEG-TDI) forms soluble nonfluorescing H-aggregates in water, so that the absorption bands are blue-shifted with respect to those of the fluorescing monomeric form. The presence of a surfactant such as Pluronic P123 leads to the disruption of the aggregates due to the formation of monomers in micelles and a strong increase in fluorescence. Application for labelling cell membranes can be considered for this dye since it adsorbs in a similar way as monomer to a lipid bilayer. Furthermore a single-molecule study of all three rylene dyes in polymeric films of PMMA showed excellent photostability with respect to photobleaching, far above the photostability of other common water-soluble dyes, such as Oxazine-1, Atto647N, Cy5, Alexa647 and Rhodamin6G. Especially 4-PEG-TDI seems to be a promising dye for membrane labelling with its high photostability. PMID:21154947

  7. Determination of the individual atomic site contribution to the electronic structure of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA)

    NASA Astrophysics Data System (ADS)

    Cho, S. W.; Newby, D.; DeMasi, A.; Smith, K. E.; Piper, L. F. J.; Jones, T. S.

    2013-11-01

    We have studied the element and orbital-specific electronic structure of thin films of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) using a combination of synchrotron radiation-exited resonant x-ray emission spectroscopy, x-ray absorption spectroscopy, x-ray photoelectron spectroscopy, as well as density functional theory calculations. Resonant and non-resonant x-ray emission spectroscopies were used to measure the C and O 2p partial densities of state in PTCDA. Furthermore, resonant x-ray emission at the C and O K-edges is shown to be able to measure the partial densities of states associated with individual atomic sites. The flat molecular orientation of PTCDA on various substrates is explained in terms of the carbonyl O atom acting as a hydrogen-bond acceptor leading to multiple in-plane intermolecular C=O...H-C hydrogen bonding between carbonyl groups and the perylene core of the neighboring PTCDA molecules. We support this conclusion by comparison of our calculations to measurements of the electronic structure using element-, site-, and orbital-selective C and O K-edge resonant x-ray emission spectroscopy, and photoemission spectroscopy.

  8. Formation of the conduction band electronic structure during deposition of ultrathin dicarboximide-substituted perylene films on the oxidized silicon surface

    NASA Astrophysics Data System (ADS)

    Komolov, A. S.; Lazneva, E. F.; Gerasimova, N. B.; Panina, Yu. A.; Baramygin, A. V.; Ovsyannikov, A. D.

    2015-07-01

    The results of the investigation of the conduction band electronic structure and the interfacial potential barrier during deposition of ultrathin dicarboximide-substituted perylene films (PTCBI-C8) on the oxidized silicon surface have been presented. The measurements have been performed using the very low energy electron diffraction (VLEED) technique implemented in the total current spectroscopy (TCS) mode with a variation in the incident electron energy from 0 to 25 eV. Changes in the intensities of the maxima from the deposited PTCBI-C8 film and from the substrate with an increase in the organic coating thickness to 7 nm have been analyzed using TCS measurements. A comparison of the structure of the maxima of PTCBI-C8 and perylene-tetracarboxylic-dianhydride (PTCDA) films has made it possible to distinguish the energy range (8-13 eV above E F) in which distinct differences in the structures of maxima for PTCDA and PTCBI-C8 films are observed. This energy range corresponds to low-lying σ*-states of the conduction band of the films studied. The formation of the interfacial region of the PTCBI-C8 film and (SiO2) n-Si substrate is accompanied by an increase in the surface work function by 0.6 eV, which corresponds to the electron density charge transfer from the (SiO2) n-Si substrate to the PTCBI-C8 film.

  9. Determination of the individual atomic site contribution to the electronic structure of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA).

    PubMed

    Cho, S W; Newby, D; DeMasi, A; Smith, K E; Piper, L F J; Jones, T S

    2013-11-14

    We have studied the element and orbital-specific electronic structure of thin films of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) using a combination of synchrotron radiation-exited resonant x-ray emission spectroscopy, x-ray absorption spectroscopy, x-ray photoelectron spectroscopy, as well as density functional theory calculations. Resonant and non-resonant x-ray emission spectroscopies were used to measure the C and O 2p partial densities of state in PTCDA. Furthermore, resonant x-ray emission at the C and O K-edges is shown to be able to measure the partial densities of states associated with individual atomic sites. The flat molecular orientation of PTCDA on various substrates is explained in terms of the carbonyl O atom acting as a hydrogen-bond acceptor leading to multiple in-plane intermolecular C=O···H-C hydrogen bonding between carbonyl groups and the perylene core of the neighboring PTCDA molecules. We support this conclusion by comparison of our calculations to measurements of the electronic structure using element-, site-, and orbital-selective C and O K-edge resonant x-ray emission spectroscopy, and photoemission spectroscopy. PMID:24320295

  10. Structure of vacant electronic states of an oxidized germanium surface upon deposition of perylene tetracarboxylic dianhydride films

    NASA Astrophysics Data System (ADS)

    Komolov, A. S.; Lazneva, E. F.; Gerasimova, N. B.; Panina, Yu. A.; Baramygin, A. V.; Zashikhin, G. D.; Pshenichnyuk, S. A.

    2016-02-01

    This paper presents the results of the investigation of the interface potential barrier and vacant electronic states in the energy range of 5 to 20 eV above the Fermi level ( E F) in the deposition of perylene tetracarboxylic dianhydride (PTCDA) films on the oxidized germanium surface ((GeO2)Ge). The concentration of oxide on the (GeO2)Ge surface was determined by X-ray photoelectron spectroscopy. In the experiments, we used the recording of the reflection of a test low-energy electron beam from the surface, implemented in the mode of total current spectroscopy. The theoretical analysis involves the calculation of the energy and spatial distribution of the orbitals of PTCDA molecules by the density functional theory (DFT) using B3LYP functional with the basis 6-31G(d), followed by the scaling of the calculated values of the orbital energy according to the procedure well-proven in the studies of small organic conjugated molecules. The pattern of changes in the fine structure of the total current spectra with increasing thickness of the PTCDA coating on the (GeO2)Ge surface to 6 nm was studied. At energies below 9 eV above E F, there is a maximum of the density of unoccupied electron states in the PTCDA film, formed mainly by π* molecular orbitals. The higher density maxima of unoccupied states are of σ* nature. The formation of the interface potential barrier in the deposition of PTCDA at the (GeO2)Ge surface is accompanied by an increase in the work function of the surface, E vac- E F, from 4.6 ± 0.1 to 4.9 ± 0.1 eV. This occurs when the PTCDA coating thickness increases to 3 nm, and upon further deposition of PTCDA, the work function of the surface does not change, which corresponds to the model of formation of a limited polarization layer in the deposited organic film.

  11. Microsomal biotransformation of benzo[ghi]perylene, a mutagenic polycyclic aromatic hydrocarbon without a "classic" bay region.

    PubMed

    Platt, Karl L; Grupe, Stefanie

    2005-04-01

    Carcinogenic polycyclic aromatic hydrocarbons (PAH), e.g., benzo[a]pyrene (BaP), possess a bay region comprising an ortho-fused benzene ring. Benzo[ghi]perylene (BghiP) represents the group of PAHs lacking such a "classic" bay region and hence cannot be metabolically converted like BaP to bay region dihydrodiol epoxides considered as ultimate mutagenic and carcinogenic metabolites of PAH. BghiP exhibits bacterial mutagenicity in strains TA98 (1.3 his(+)-revertant colonies/nmol) and TA100 (4.3 his(+)-revertant colonies/nmol) of Salmonella typhimurium after metabolic activation by the postmitochondrial hepatic fraction of CD rats treated with 3-methylcholanthrene. Inhibition of microsomal epoxide hydrolase (mEH) with 1,1,1-trichloro-2-propene oxide raised the bacterial mutagenicity of BghiP in TA98 almost 4-fold indicating arene oxides as ultimate mutagens. To confirm this assumption, the biotransformation of BghiP was elucidated. Incubation of BghiP with liver microsomes of CD rats treated with Aroclor 1254 yielded 17 ethyl acetate extractable metabolic products. Twelve metabolites were identified by a combination of chromatographic, spectroscopic, and biochemical methods. The microsomal biotransformation of BghiP proceeds by two pathways: Pathway I starts with the monooxygenase attack at the 7-position leading to the 7-phenol, which is transformed to the 7,8- and 7,10-diphenols followed by oxidation to the 7,8- and 7,10-quinones. On pathway II, the K regions of BghiP are successively converted to arene oxides yielding the indirectly identified 3,4-oxide and the 3,4,11,12-bisoxides. Enzymatic hydrolysis of the 3,4-oxide leads to the trans-3,4-dihydrodiol, which is oxidized to the 3,4-quinone. Similarly, the trans-3,4-trans-11,12-bisdihydrodiols and the trans-3,4-dihydrodiol 11,12-quinone are generated from the 3,4,11,12-bisoxides. The trans-3,4-dihydrodiol and the trans-3,4-trans-11,12-bisdihydrodiols are preferentially formed as R,R and R,R,R,R enantiomers

  12. The modification of Schottky barrier height of Au/p-Si Schottky devices by perylene-diimide

    NASA Astrophysics Data System (ADS)

    Yüksel, Ö. F.; Tuǧluoǧlu, N.; Şafak, H.; Kuş, M.

    2013-01-01

    Perylene-diimide (PDI) thin film was fabricated by spin coating method on p-Si single-crystal substrate to prepare Au/PDI/p-Si Schottky device. The electrical properties of the Au/PDI/p-Si Schottky device were investigated by current-voltage (I-V) measurements in the temperature range 80-300 K and room temperature capacitance-voltage (C-V) measurement. Results showed a rectification behavior. Junction parameters such as ideality factor (n), barrier height (ϕB0), series resistance (Rs) interface state density (Nss), built-in potential (Vbi), carrier concentration (NA), and the width of the depletion layer (WD) were obtained from the I-V and C-V measurements. The values of ideality factor (n) and barrier height (BH) for the Au/PDI/p-Si structure from the I-V measurements were obtained as 1.77 and 0.584 eV at 300 K, 7.78 and 0.176 eV at 80 K, respectively. It was seen that the BH value of 0.584 eV calculated for the Au/PDI/p-Si structure was significantly larger than the value of 0.34 eV of conventional Au/p-Si Schottky diodes at room temperature. Thus, modification of the interfacial potential barrier for Au/p-Si diodes has been achieved using a thin interlayer of the peryleen-diimide organic semiconductor; this has been ascribed to the fact that the peryleen-diimide interlayer increases the effective barrier height because of the interface dipole induced by passivation of the organic layer. Furthermore, the energy distribution of the interface state density determined from I-V characteristics increases exponentially with bias from 1.11 × 1012 eV-1 cm-2 at (0.556-Ev) eV to 11.01 × 1013 eV-1 cm-2 at (0.449-Ev) eV.

  13. Air-stable n-channel organic field-effect transistors based on N,N‧-bis(4-trifluoromethylbenzyl)perylene-3,4,9,10-tetracarboxylic diimide

    NASA Astrophysics Data System (ADS)

    Hosoi, Yoshinobu; Tsunami, Daisuke; Ishii, Hisao; Furukawa, Yukio

    2007-02-01

    Air-stable n-channel field-effect transistors based on thin films of the compound, N, N'-bis(4-trifluoromethylbenzyl)perylene-3,4,9,10-tetracarboxylic diimide (PTCDI-TFB), were fabricated, and the effects of surface treatment and substrate temperature at the film deposition on the electron mobility of the transistors were studied. The maximum mobility, 4.1 × 10 -2 cm 2 V -1 s -1 in the saturation region (1.7 × 10 -2 cm 2 V -1 s -1 in the linear region), was obtained in air for the film deposited at 95 °C on the SiO 2 surface modified with hexamethyldisilazane. The high electron affinity of PTCDI-TFB estimated at 4.8 eV by photoelectron yield spectroscopy and UV-Vis absorption spectroscopy, which is ascribable to the trifluoromethylbenzyl groups, is likely to result in the observed stable transistor operation in air.

  14. Effects of Side-Chain and Electron Exchange Correlation on the Band Structure of Perylene Diimide Liquid Crystals: A Density Functional Study

    SciTech Connect

    Arantes, J. T.; Lima, M. P.; Fazzio, A.; Xiang, H.; Wei, S. H.; Dalpian, G. M.

    2009-04-01

    The structural and electronic properties of perylene diimide liquid crystal PPEEB are studied using ab initio methods based on the density functional theory (DFT). Using available experimental crystallographic data as a guide, we propose a detailed structural model for the packing of solid PPEEB. We find that due to the localized nature of the band edge wave function, theoretical approaches beyond the standard method, such as hybrid functional (PBE0), are required to correctly characterize the band structure of this material. Moreover, unlike previous assumptions, we observe the formation of hydrogen bonds between the side chains of different molecules, which leads to a dispersion of the energy levels. This result indicates that the side chains of the molecular crystal not only are responsible for its structural conformation but also can be used for tuning the electronic and optical properties of these materials.

  15. Morphology and molecular arrangement of perylene-3,4,9,10-(n-pentylester) in thin layers obtained by zone-casting

    NASA Astrophysics Data System (ADS)

    Adamski, Adrian; Nowicka, Ariadna B.; Barszcz, Bolesław; Szybowicz, Mirosław; Piosik, Emilia; Wolarz, Eryk

    2016-08-01

    Liquid-crystalline perylene-3,4,9,10-tetra-(n-pentylester) zone-casted on hydrophilic glass substrates forms characteristic belt-like structures which are observed under optical microscope and atomic force microscope. Polarised Raman scattering spectra reveal the presence of anisotropic alignment of the molecules inside the obtained structures. Moreover, the absorption and fluorescence spectra confirm molecular aggregation in the belt-like structures. The research shows, that the belt-like structures are created by columns of molecules with the edge-on alignment on the glass substrate. Such organisation of the molecules is confirmed by spectroscopic methods. These structures can be interesting from the point of view of organic electronics.

  16. Morphology and molecular arrangement of perylene-3,4,9,10-(n-pentylester) in thin layers obtained by zone-casting.

    PubMed

    Adamski, Adrian; Nowicka, Ariadna B; Barszcz, Bolesław; Szybowicz, Mirosław; Piosik, Emilia; Wolarz, Eryk

    2016-08-01

    Liquid-crystalline perylene-3,4,9,10-tetra-(n-pentylester) zone-casted on hydrophilic glass substrates forms characteristic belt-like structures which are observed under optical microscope and atomic force microscope. Polarised Raman scattering spectra reveal the presence of anisotropic alignment of the molecules inside the obtained structures. Moreover, the absorption and fluorescence spectra confirm molecular aggregation in the belt-like structures. The research shows, that the belt-like structures are created by columns of molecules with the edge-on alignment on the glass substrate. Such organisation of the molecules is confirmed by spectroscopic methods. These structures can be interesting from the point of view of organic electronics. PMID:27104675

  17. A novel water-soluble fluorescent polymer based on perylene bisimides dyes: one-pot preparation and its bio-imaging.

    PubMed

    Tan, Haijian; Liu, Hongmei; Liu, Yaojun; Duan, Wenfeng; Yi, Xuegang; Wu, Yonggang; Zhao, Hongchi; Bai, Libin

    2016-04-01

    Perylene bisimides dye-based water-soluble fluorescent polymer P3, N,N'-bis(3-amyl)-1-bromo-7-{4'-[3''-(S-poly(N-acryloyl ethylene diamine hydrochloride)-2'''-methyl propionic acid)propionyloxy hexyloxy]phenyl} perylene-3,4:9,10-tetracarboxylic bisimides, was synthesized with polyelectrolyte modification via one-pot reaction (the reduction reaction of trithioester and click reaction between the thiol group and carbon-carbon double bond were simultaneously conducted in one pot with high conversion). One-pot method can overcome the limitation that usual click reaction between thiol and other groups has low conversion because thiol group is subject to rapid oxidation during purification and storage. Chemical, structural, and optical properties of P3 and intermediate products were fully characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared, gel permeation chromatograph, UV-vis spectra, and fluorescence spectra, respectively. The results revealed that P3 displayed excellent water solubility and not only exhibited red strong fluorescence emission band in water but also had the similar photoluminescent spectra to those of intermediate products (M4 and P2) in chloroform. Allowing for the potential application in biological detection field, cell viability and live cell imaging with the presence of P3 were further investigated with Hela cells. The results showed that P3 had low cytotoxicity with strong intracellular fluorescence entry. Meanwhile, with the augment of concentration of P3 (0-0.500 mg mL(-1)), the cell uptake and accumulation of P3 increased and thereby result in enhancement of the intracellular fluorescence. These experiment results suggested that P3 had enormous potential as a fluorescence probe to be an important component in biological detection field. PMID:26719068

  18. An amplified electrochemiluminescent aptasensor using Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites as a signal enhancement tag.

    PubMed

    Ma, Meng-Nan; Zhang, Xia; Zhuo, Ying; Chai, Ya-Qin; Yuan, Ruo

    2015-02-01

    A novel electrochemiluminescent (ECL) signal tag of Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites (AuNPs/TSC-PTC/C60NPs) was developed for thrombin (TB) aptasensor construction based on the peroxydisulfate/oxygen (S2O8(2-)/O2) system. For signal tag fabrication, the C60 nanoparticles (C60NPs) were prepared and then coated with 3,4,9,10-perylene tetracarboxylic acid (PTCA) by π-π stacking interactions. Afterwards, thiosemicarbazide (TSC) was linked with PTCA functionalized C60NPs via amidation for further assembling Au nanoparticles (AuNPs). Finally, detection aptamer of thrombin (TBA 2) was labeled on the ECL signal amplification tag of AuNPs/TSC-PTC/C60NPs. Herein, TSC, with the active groups of -NH2 and -SH, was selected and introduced into the ECL S2O8(2-)/O2 system for the first time, which could not only offer the active groups of -SH to absorb AuNPs for TBA 2 anchoring but also remarkably enhance the ECL signal of the S2O8(2-)/O2 system by the formation of TSC-PTC/C60NPs for signal amplification. Meanwhile, the sensing interface of a glassy carbon electrode (GCE) was modified by AuNPs/graphene (AuNPs/GR) nanocomposites with the large specific surface area and the active sites, followed by immobilization of thiol-terminated thrombin capture aptamer (TBA 1). With the formation of the sandwich-type structure of TBA 1, TB, and TBA 2 signal probes, a desirable enhanced ECL signal was measured in the testing buffer of an S2O8(2-)/O2 solution for detecting TB. The aptasensor exhibited a good linear relationship for TB detection in the range of 1 × 10(-5)-10 nM with a detection limit of 3.3 fM. PMID:25559492

  19. High-mobility, air stable bottom-contact n-channel thin film transistors based on N,N′-ditridecyl perylene diimide

    SciTech Connect

    Ma, Lanchao; University of Chinese Academy of Sciences, Beijing 100049 ; Guo, Yunlong; Wen, Yugeng; Liu, Yunqi E-mail: liuyq@iccas.ac.cn; Zhan, Xiaowei E-mail: liuyq@iccas.ac.cn; Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871

    2013-11-11

    Bottom-gate bottom-contact (BGBC) organic thin film transistors (OTFTs) based on N,N′-ditridecyl perylene diimide exhibit electron mobility as high as 3.54 cm{sup 2} V{sup −1} s{sup −1} in nitrogen, higher than that (1 cm{sup 2} V{sup −1} s{sup −1}) of bottom-gate top-contact devices. The better performance of BGBC configuration in N{sub 2} is attributed to lower contact resistance, which is further reduced by thermal annealing. After thermally annealing the BGBC OTFTs at 180 °C, electron mobility as high as 3.5 cm{sup 2} V{sup −1} s{sup −1}, current on/off ratio of 10{sup 6} and threshold voltage of 9 V are achieved in air, and the mobility retains above 1 cm{sup 2} V{sup −1} s{sup −1} after storage for two months in air. Thermal treatment enhanced crystalline grains, reduced grain boundaries, and suppressed the adsorption of H{sub 2}O and O{sub 2}, leading to excellent performance in air.

  20. Enhanced Photocurrent Density by Spin-Coated NiO Photocathodes for N-Annulated Perylene-Based p-Type Dye-Sensitized Solar Cells.

    PubMed

    Li, Xing; Yu, Fengtao; Stappert, Sebastian; Li, Chen; Zhou, Ying; Yu, Ying; Li, Xin; Ågren, Hans; Hua, Jianli; Tian, He

    2016-08-01

    The low photocurrent density of p-type dye-sensitized solar cells (p-DSSCs) has limited the development of high-efficiency tandem cells due to the inadequate light-harvesting ability of sensitizers and the low hole mobility of semiconductors. Hereby, two new "push-pull" type organic dyes (PQ-1 and PQ-2) containing N-annulated perylene as electron donor have been synthesized, where the PQ-2-based p-DSSCs show higher photoelectric conversion efficiency (PCE) of 0.316% owing to the higher molar extinction compared to of that PQ-1. Additionally, the photocurrent densities were remarkably increased from 2.20 to 5.85 mA cm(-2) for PQ-1 and 2.45 to 6.69 mA cm(-2) for PQ-2 by spin-coated NiO photocathode based-p-DSSCs, respectively. This results are ascribed to the enhancement of hole transport rate, dye-loading amounts and transparency of NiO films in comparison to that prepared by screen-printing method. Electrochemical impedance spectroscopy and theoretical calculations studies indicate that the molecular dipole moment approaching closer to the NiO surface shifts the quasi-Fermi level to more positive levels, improving open-circuit voltage (Voc). Intensity-modulated photocurrent spectroscopy illustrates that the hole transit time in NiO films prepared in spin-coating is shorter than that prepared by screen-printing method. PMID:27416960

  1. Push-Pull Type Oligo(N-annulated perylene)quinodimethanes: Chain Length and Solvent-Dependent Ground States and Physical Properties.

    PubMed

    Zeng, Zebing; Lee, Sangsu; Son, Minjung; Fukuda, Kotaro; Burrezo, Paula Mayorga; Zhu, Xiaojian; Qi, Qingbiao; Li, Run-Wei; Navarrete, Juan T López; Ding, Jun; Casado, Juan; Nakano, Masayoshi; Kim, Dongho; Wu, Jishan

    2015-07-01

    Research on stable open-shell singlet diradicaloids recently became a hot topic because of their unique optical, electronic, and magnetic properties and promising applications in materials science. So far, most reported singlet diradicaloid molecules have a symmetric structure, while asymmetric diradicaloids with an additional contribution of a dipolar zwitterionic form to the ground state were rarely studied. In this Article, a series of new push-pull type oligo(N-annulated perylene)quinodimethanes were synthesized. Their chain length and solvent-dependent ground states and physical properties were systematically investigated by various experimental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device, Raman spectroscopy, and electrochemistry. It was found that with extension of the chain length, the diradical character increases while the contribution of the zwitterionic form to the ground state becomes smaller. Because of the intramolecular charge transfer character, the physical properties of this push-pull system showed solvent dependence. In addition, density functional theory calculations on the diradical character and Hirshfeld charge were conducted to understand the chain length and solvent dependence of both symmetric and asymmetric systems. Our studies provided a comprehensive understanding on the fundamental structure- and environment-property relationships in the new asymmetric diradicaloid systems. PMID:26062868

  2. An amplified electrochemiluminescent aptasensor using Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites as a signal enhancement tag

    NASA Astrophysics Data System (ADS)

    Ma, Meng-Nan; Zhang, Xia; Zhuo, Ying; Chai, Ya-Qin; Yuan, Ruo

    2015-01-01

    A novel electrochemiluminescent (ECL) signal tag of Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites (AuNPs/TSC-PTC/C60NPs) was developed for thrombin (TB) aptasensor construction based on the peroxydisulfate/oxygen (S2O82-/O2) system. For signal tag fabrication, the C60 nanoparticles (C60NPs) were prepared and then coated with 3,4,9,10-perylene tetracarboxylic acid (PTCA) by π-π stacking interactions. Afterwards, thiosemicarbazide (TSC) was linked with PTCA functionalized C60NPs via amidation for further assembling Au nanoparticles (AuNPs). Finally, detection aptamer of thrombin (TBA 2) was labeled on the ECL signal amplification tag of AuNPs/TSC-PTC/C60NPs. Herein, TSC, with the active groups of -NH2 and -SH, was selected and introduced into the ECL S2O82-/O2 system for the first time, which could not only offer the active groups of -SH to absorb AuNPs for TBA 2 anchoring but also remarkably enhance the ECL signal of the S2O82-/O2 system by the formation of TSC-PTC/C60NPs for signal amplification. Meanwhile, the sensing interface of a glassy carbon electrode (GCE) was modified by AuNPs/graphene (AuNPs/GR) nanocomposites with the large specific surface area and the active sites, followed by immobilization of thiol-terminated thrombin capture aptamer (TBA 1). With the formation of the sandwich-type structure of TBA 1, TB, and TBA 2 signal probes, a desirable enhanced ECL signal was measured in the testing buffer of an S2O82-/O2 solution for detecting TB. The aptasensor exhibited a good linear relationship for TB detection in the range of 1 × 10-5-10 nM with a detection limit of 3.3 fM.A novel electrochemiluminescent (ECL) signal tag of Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites (AuNPs/TSC-PTC/C60NPs) was developed for thrombin (TB) aptasensor construction based on the peroxydisulfate/oxygen (S2O82-/O2) system. For signal

  3. Characterization of perylene diimide dye self-assemblies and their use as templates for the synthesis of hybrid and supermicroporous nanotubules.

    PubMed

    Rodríguez-Abreu, Carlos; Aubery-Torres, Carolina; Solans, Conxita; López-Quintela, Arturo; Tiddy, Gordon J T

    2011-10-01

    The self-organizing structures formed by a water-soluble perylene diimide dye (PDI) have been studied by several experimental techniques as potential templates for the preparation of hybrid nanomaterials. The dye forms chromonic-nematic and hexagonal liquid crystals in water. The aggregates in liquid crystals consist of one-molecule-wide stacks. From the changes in the solution proton NMR chemical shifts with concentration, it appears that adjacent molecules are twisted. There is significant broadening of the aromatic resonances at higher concentrations, arising from nonmotionally averaged dipole-dipole coupling between adjacent aromatic hydrogens. This is attributed to slow overall rotation of the aggregates in solution, suggesting that they grow up to several tens of nanometers. Dye aggregates serve as templates for the formation of silica tubules (1-5 μm length, average diameter ≈300 nm), with aligned and very thin (1-2 nm) dye nanostripes embedded in the walls. The silica tubes precipitated from solution are formed by the cooperative interaction between PDI and silica species during the sol-gel reaction. Upon calcination, silica nanotubules with supermicroporous walls are obtained. In comparison with conventional surfactant systems, the use of π-π stacked chromonic aggregates brings new possibilities for the templated fabrication of pores with sizes below the mesoporous range. Materials could find applications in photovoltaics as well as in shape selective catalysis and adsorption. PMID:21942535

  4. Substituent effect on supramolecular motifs in series of succinimide polycyclic keto derivatives - Spectroscopic, theoretical and crystallographic studies

    NASA Astrophysics Data System (ADS)

    Miroslaw, Barbara; Koziol, Anna E.; Bielenica, Anna; Dziuba, Kamil; Struga, Marta

    2014-09-01

    The substituent effect on the supramolecular arrangement in a series of polycyclic monoimide keto derivatives crystals was studied. Single crystal X-ray diffraction and IR spectroscopic experiments were performed for seven related compounds, as well as the Hirshfeld surface analysis and quantum chemical calculations at HF and DFT levels in vacuo, in solution and for small clusters. The presence of Cdbnd O group at the bridge of the main hydrocarbon skeleton implied the catemer motif of the Nimidesbnd H⋯Oimide hydrogen bond in case of smaller substituents (Hsbnd , MeOsbnd , EtOsbnd ). For more voluminous groups (iBuOsbnd ) or additional hydrogen bond acceptors (AcOsbnd , Odbnd ) the steric hindrance increased and the imide⋯imide interactions were no longer present in the solid state. The Nimidesbnd H⋯Oketo or Nimidesbnd H⋯Oester hydrogen bonds were formed instead. The binding energy per one Nsbnd H⋯O interaction calculated for supramolecular clusters at HF/6-31G(d,p) level was ca. 20 kJ mol-1, indicating moderate strength of this hydrogen bond. The solvation free energies and induced dipole moments were computed at B3LYP/6-311+G(d,p) level using the integral equation formalism model (IEF PCM) considering three solvents of various polarity: non-polar chloroform, polar aprotic dimethyl sulfoxide (DMSO) and polar protic water. The relations between the vibrational spectra and the crystal structure have been discussed. The following sequence of carbonyl stretching modes in IR spectra has been derived from quantum chemical calculations: (1) at the highest frequencies - the symmetric vibration of two imide Cdbnd O bonds, (2) the vibrations of keto Cdbnd O bonds attached directly to the polycyclic hydrocarbon skeleton, (3) the asymmetric vibration of two imide Cdbnd O bonds, and (4) at the lowest frequencies - the vibration of ester Cdbnd O group. The characteristic peaks observed in imide experimental IR spectra at about 3080 cm-1 have been

  5. Water-Soluble NIR-Absorbing Rylene Chromophores for Selective Staining of Cellular Organelles.

    PubMed

    Kaloyanova, Stefka; Zagranyarski, Yulian; Ritz, Sandra; Hanulová, Mária; Koynov, Kaloian; Vonderheit, Andreas; Müllen, Klaus; Peneva, Kalina

    2016-03-01

    Biocompatible organic dyes emitting in the near-infrared are highly desirable in fluorescence imaging techniques. Herein we report a synthetic approach for building novel small peri-guanidine-fused naphthalene monoimide and perylene monoimide chromophores. The presented structures possess near-infrared absorption and emission, high photostability, and good water solubility. After a fast cellular uptake, they selectively stain mitochondria with a low background in live and fixed cells. They can be additionally modified in a one-step reaction with functional groups for covalent labeling of proteins. The low cytotoxicity allows a long time exposure of live cells to the dyes without the necessity of washing. Successful application in localization super-resolution microscopy was demonstrated in phosphate-buffered saline without any reducing or oxidizing additives. PMID:26891229

  6. Electronic Absorption Spectra of Neutral Perylene (C20H12), Terrylene (C30H16), and Quaterrylene (C40H20) and their Positive and Negative Ions: Ne Matrix-Isolation Spectroscopy and Time Dependent Density Functional Theory Calculations

    NASA Technical Reports Server (NTRS)

    Halasinski, Thomas M.; Weisman, Jennifer L.; Lee, Timothy J.; Salama, Farid; Head-Gordon, Martin; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We present a full experimental and theoretical study of an interesting series of polycyclic aromatic hydrocarbons, the oligorylenes. The absorption spectra of perylene, terrylene and quaterrylene in neutral, cationic and anionic charge states are obtained by matrix-isolation spectroscopy in Ne. The experimental spectra are dominated by a bright state that red shifts with growing molecular size. Excitation energies and state symmetry assignments are supported by calculations using time dependent density functional theory methods. These calculations also provide new insight into the observed trends in oscillator strength and excitation energy for the bright states: the oscillator strength per unit mass of carbon increases along the series.

  7. Nanoparticle Self-Assembled Grain Like Curcumin Conjugated ZnO: Curcumin Conjugation Enhances Removal of Perylene, Fluoranthene, and Chrysene by ZnO

    NASA Astrophysics Data System (ADS)

    Moussawi, Rasha N.; Patra, Digambara

    2016-04-01

    Curcumin conjugated ZnO, referred as Zn(cur)O, nanostructures have been successfully synthesized, these sub-micro grain-like structures are actually self-assemblies of individual needle-shaped nanoparticles. The nanostructures as synthesized possess the wurtzite hexagonal crystal structure of ZnO and exhibit very good crystalline quality. FT-Raman and TGA analysis establish that Zn(cur)O is different from curcumin anchored ZnO (ZnO@cur), which is prepared by physically adsorbing curcumin on ZnO surfaces. Chemically Zn(cur)O is more stable than ZnO@cur. Diffuse reflectance spectroscopy indicates Zn(cur)O have more impurities compared to ZnO@cur. The solid-state photoluminescence of Zn(cur)O has been investigated, which demonstrates that increase of curcumin concentration in Zn(cur)O suppresses visible emission of ZnO prepared through the same method, this implies filling ZnO defects by curcumin. However, at excitation wavelength 425 nm the emission is dominated by fluorescence from curcumin. The study reveals that Zn(cur)O can remove to a far extent high concentrations of perylene, fluoranthene, and chrysene faster than ZnO. The removal depends on the extent of curcumin conjugation and is found to be faster for PAHs having smaller number of aromatic rings, particularly, it is exceptional for fluoranthene with 93% removal after 10 minutes in the present conditions. The high rate of removal is related to photo-degradation and a mechanism has been proposed.

  8. Nanoparticle Self-Assembled Grain Like Curcumin Conjugated ZnO: Curcumin Conjugation Enhances Removal of Perylene, Fluoranthene, and Chrysene by ZnO.

    PubMed

    Moussawi, Rasha N; Patra, Digambara

    2016-01-01

    Curcumin conjugated ZnO, referred as Zn(cur)O, nanostructures have been successfully synthesized, these sub-micro grain-like structures are actually self-assemblies of individual needle-shaped nanoparticles. The nanostructures as synthesized possess the wurtzite hexagonal crystal structure of ZnO and exhibit very good crystalline quality. FT-Raman and TGA analysis establish that Zn(cur)O is different from curcumin anchored ZnO (ZnO@cur), which is prepared by physically adsorbing curcumin on ZnO surfaces. Chemically Zn(cur)O is more stable than ZnO@cur. Diffuse reflectance spectroscopy indicates Zn(cur)O have more impurities compared to ZnO@cur. The solid-state photoluminescence of Zn(cur)O has been investigated, which demonstrates that increase of curcumin concentration in Zn(cur)O suppresses visible emission of ZnO prepared through the same method, this implies filling ZnO defects by curcumin. However, at excitation wavelength 425 nm the emission is dominated by fluorescence from curcumin. The study reveals that Zn(cur)O can remove to a far extent high concentrations of perylene, fluoranthene, and chrysene faster than ZnO. The removal depends on the extent of curcumin conjugation and is found to be faster for PAHs having smaller number of aromatic rings, particularly, it is exceptional for fluoranthene with 93% removal after 10 minutes in the present conditions. The high rate of removal is related to photo-degradation and a mechanism has been proposed. PMID:27080002

  9. Increasing 3D Supramolecular Order by Decreasing Molecular Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated and Tetrachlorinated Perylene Bisimides.

    PubMed

    Partridge, Benjamin E; Leowanawat, Pawaret; Aqad, Emad; Imam, Mohammad R; Sun, Hao-Jan; Peterca, Mihai; Heiney, Paul A; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Ungar, Goran; Percec, Virgil

    2015-04-22

    A nonplanar, twisted, and flexible tetrachlorinated perylene bisimide (Cl4PBI) was functionalized with two AB3 minidendrons containing hydrogenated or semifluorinated dodecyl groups. The hydrogenated dendron was attached to the imide groups of Cl4PBI via m = 0, 1, and 2 methylenic units, whereas the dendron containing semifluorinated groups was attached via m = 3 or a di(ethylene oxide) linker (m = 2EO). The supramolecular structures of these compounds, determined by a combination of differential scanning calorimetry, X-ray diffraction, and solid-state NMR, were compared with those of nonchlorinated planar and rigid PBI reported previously, which demonstrated the thermodynamically controlled formation of 2D periodic arrays at high temperatures and 3D arrays at low temperatures. The molecularly less ordered Cl4PBI containing hydrogenated dendrons self-organize into exclusively 3D crystalline periodic arrays under thermodynamic control for m = 0 and 2, while the more highly molecularly ordered PBI produced less stable and ordered 3D crystals and also 2D assemblies. This induction of a higher degree of 3D order in supramolecular assemblies of the less well-ordered molecular building blocks was unanticipated. The semifluorinated dendronized Cl4PBI with m = 3 formed a 2D columnar hexagonal array under kinetic control, whereas the compound with m = 2EO formed an unusual 2D honeycomb-like hexagonal phase under thermodynamic control. These Cl4PBI compounds provide a new route to stable crystalline assemblies via thermodynamic control at lower temperatures than previously obtained with PBI, thus generating 3D order in an accessible range of temperature of interest for structural analysis and for technological applications. PMID:25830346

  10. Nanoparticle Self-Assembled Grain Like Curcumin Conjugated ZnO: Curcumin Conjugation Enhances Removal of Perylene, Fluoranthene, and Chrysene by ZnO

    PubMed Central

    Moussawi, Rasha N.; Patra, Digambara

    2016-01-01

    Curcumin conjugated ZnO, referred as Zn(cur)O, nanostructures have been successfully synthesized, these sub-micro grain-like structures are actually self-assemblies of individual needle-shaped nanoparticles. The nanostructures as synthesized possess the wurtzite hexagonal crystal structure of ZnO and exhibit very good crystalline quality. FT-Raman and TGA analysis establish that Zn(cur)O is different from curcumin anchored ZnO (ZnO@cur), which is prepared by physically adsorbing curcumin on ZnO surfaces. Chemically Zn(cur)O is more stable than ZnO@cur. Diffuse reflectance spectroscopy indicates Zn(cur)O have more impurities compared to ZnO@cur. The solid-state photoluminescence of Zn(cur)O has been investigated, which demonstrates that increase of curcumin concentration in Zn(cur)O suppresses visible emission of ZnO prepared through the same method, this implies filling ZnO defects by curcumin. However, at excitation wavelength 425 nm the emission is dominated by fluorescence from curcumin. The study reveals that Zn(cur)O can remove to a far extent high concentrations of perylene, fluoranthene, and chrysene faster than ZnO. The removal depends on the extent of curcumin conjugation and is found to be faster for PAHs having smaller number of aromatic rings, particularly, it is exceptional for fluoranthene with 93% removal after 10 minutes in the present conditions. The high rate of removal is related to photo-degradation and a mechanism has been proposed. PMID:27080002

  11. Single molecular detection of a perylene dye dispersed in a Langmuir-Blodgett fatty acid monolayer using surface-enhanced resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    Constantino, C. J. L.; Lemma, T.; Antunes, P. A.; Aroca, R.

    2002-02-01

    The Langmuir-Blodgett (LB) monolayer technique was used to fabricate single molecule LB monolayer containing bis(phenethylimido)perylene (PhPTCD), a red dye dispersed in arachidic acid (AA) with an average doping of 1 molecule per μm 2. The monolayer was transferred onto Ag island films to obtain spatially resolved surface-enhanced resonance Raman scattering (SERRS) spectra. The mixed LB monolayers were fabricated with a concentration, on average, of 1, 6, 19 and 118 PhPTCD molecules per μm 2 in AA. The AA provides a two-dimensional host matrix whose background signal does not interfere with the detection of the probe molecule's SERRS signal. The properties of the single molecule detection were investigated using micro-Raman with a 514.5-nm laser line. The Ag island surfaces coated with the LB monolayer were mapped with spatial steps of 3 μm and global chemical imaging of the most intense SERRS band in the spectrum was also recorded. The SERRS and surface-enhanced fluorescence (SEF) of the neat and single molecule LB monolayer were recorded in a temperature range from liquid nitrogen to +200°C. Neat PhPTCD LB monolayer spectra served as reference for the identification of characteristic signatures of the single molecule behavior. The spatial resolution of Raman-microscopy experiments, the multiplicative effect of resonance Raman and SERRS, and the high sensitivity of the new dispersive Raman instruments, allow SERRS to be part of the family of single molecular spectroscopies.

  12. Recognition of Double-Stranded DNA Using Energetically Activated Duplexes Modified with N2'-Pyrene-, Perylene-, or Coronene-Functionalized 2'-N-Methyl-2'-amino-DNA Monomers.

    PubMed

    Anderson, Brooke A; Onley, Jared J; Hrdlicka, Patrick J

    2015-06-01

    Invader probes have been proposed as alternatives to polyamides, triplex-forming oligonucleotides, and peptide nucleic acids for recognition of chromosomal DNA targets. These double-stranded probes are activated for DNA recognition by +1 interstrand zippers of pyrene-functionalized nucleotides. This particular motif forces the intercalating pyrene moieties into the same region, resulting in perturbation and destabilization of the probe duplex. In contrast, the two probe strands display very high affinity toward complementary DNA. The energy difference between the probe duplexes and recognition complexes provides the driving force for DNA recognition. In the present study, we explore the properties of Invader probes based on larger intercalators, i.e., perylene and coronene, expecting that the larger π-surface area will result in additional destabilization of the probe duplex and further stabilization of probe-target duplexes, in effect increasing the thermodynamic driving force for DNA recognition. Toward this end, we developed protocols for 2'-N-methyl-2'-amino-2'-deoxyuridine phosphoramidites that are functionalized at the N2'-position with pyrene, perylene, or coronene moieties and incorporated these monomers into oligodeoxyribonucleotides (ONs). The resulting ONs and Invader probes are characterized by thermal denaturation experiments, analysis of thermodynamic parameters, absorption and fluorescence spectroscopy, and DNA recognition experiments. Invader probes based on large intercalators efficiently recognize model targets. PMID:25984765

  13. Complex derivatives

    NASA Astrophysics Data System (ADS)

    Battiston, Stefano; Caldarelli, Guido; Georg, Co-Pierre; May, Robert; Stiglitz, Joseph

    2013-03-01

    The intrinsic complexity of the financial derivatives market has emerged as both an incentive to engage in it, and a key source of its inherent instability. Regulators now faced with the challenge of taming this beast may find inspiration in the budding science of complex systems.

  14. Swallow-tailed alkyl and linear alkoxy-substituted dibenzocoronene tetracarboxdiimide derivatives: synthesis, photophysical properties, and thermotropic behaviors.

    PubMed

    Yang, Tengzhou; Pu, Jialing; Zhang, Jun; Wang, Wenguang

    2013-05-17

    A series of dibenzocoronene tetracarboxdiimide derivatives decorated with alkyl swallow-tail and alkoxy moieties were synthesized, and their structures were characterized. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an effective oxidant was first used in the benzannulation of perylene diimides with the almost quantitative yield. The thermotropic behavior was investigated using differential scanning calorimetry (DSC) and polarization optical microscopy (POM). The introduction of alkyl swallow-tail and alkoxy substituents facilitates thermotropic liquid crystalline behavior. The branching site of alkyl swallow-tail units at the α position and the longer alkoxy chains played a similar role in lowering the mesophase transition as well as isotropization transition temperatures. The UV-vis absorption spectra of all compounds appeared as absorption in 425-600 nm region, and POM images of certain compounds exhibited characteristic columnar hexagonal (Col(h)) packing and readily self-assembled into a homeotropic alignment toward the substrate. PMID:23600443

  15. Hierarchical supramolecular assembly of sterically demanding π-systems by conjugation with oligoprolines.

    PubMed

    Lewandowska, Urszula; Zajaczkowski, Wojciech; Chen, Long; Bouillière, Francelin; Wang, Dapeng; Koynov, Kaloian; Pisula, Wojciech; Müllen, Klaus; Wennemers, Helma

    2014-11-10

    Self-assembly from flexible worm-like threads via bundles of rigid fibers to nanosheets and nanotubes was achieved by covalent conjugation of perylene monoimide (PMI) chromophores with oligoprolines of increasing length. Whereas the chromophoric π-system and the peptidic building block do not self-aggregate, the covalent conjugates furnish well-ordered supramolecular structures with a common wall/fiber thickness. Their morphology is controlled by the number of repeat units and can be tuned by seemingly subtle structural modifications. PMID:25303332

  16. Optical absorption and dispersion analysis of nanocrystalline perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride film prepared by dip coating and its optoelectronic application

    NASA Astrophysics Data System (ADS)

    Farag, A. A. M.; Fadel, M.

    2013-02-01

    High uniform and good adhesion of nanocrystalline films of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) were successfully deposited by dip coating technique. The surface morphology characteristic of the film was studied by scanning electron microscopy (SEM). The X-ray diffraction patterns of PTCDA film is characterized by a single wide peak along (102) orientation. The absorption spectrum of the film shows an intense band in the UV region followed by Q-band in the visible region. The onset optical and transport energy gaps were found to be 1.76 and 3.16 eV, respectively. The dispersion parameters and the ratio of free carrier concentration to the effective mass were also estimated. The photovoltaic characteristics of the device based PTCDA under illumination of 100 mW/cm2 were also considered.

  17. CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: Air-stable ambipolar organic field effect transistors with heterojunction of pentacene and N,N' -bis(4-trifluoromethylben-zyl) perylene-3,4,9,10-tetracarboxylic diimide

    NASA Astrophysics Data System (ADS)

    Li, Jian-Feng; Chang, Wen-Li; Ou, Gu-Ping; Zhang, Fu-Jia

    2009-07-01

    Fabrication of ambipolar organic field-effect transistors (OFETs) is essential for the achievement of an organic complementary logic circuit. Ambipolar transports in OFETs with heterojunction structures are realized. We select pentacene as a P-type material and N,N'-bis(4-trifluoromethylben-zyl)perylene-3,4,9,10-tetracarboxylic diimide (PTCDI-TFB) as a n-type material in the active layer of the OFETs. The field-effect transistor shows highly air-stable ambipolar characteristics with a field-effect hole mobility of 0.18 cm2/(V.s) and field-effect electron mobility of 0.031 cm2/(V.s). Furthermore the mobility only slightly decreases after being exposed to air and remains stable even for exposure to air for more than 60 days. The high electron affinity of PTCDI-TFB and the octadecyltrichlorosilane (OTS) self-assembly monolayer between the SiO2 gate dielectric and the organic active layer result in the observed air-stable characteristics of OFETs with high mobility. The results demonstrate that using the OTS as a modified gate insulator layer and using high electron affinity semiconductor materials are two effective methods to fabricate OFETs with air-stable characteristics and high mobility.

  18. Highly sensitive electrochemical sensor based on β-cyclodextrin-gold@3, 4, 9, 10-perylene tetracarboxylic acid functionalized single-walled carbon nanohorns for simultaneous determination of myricetin and rutin.

    PubMed

    Ran, Xin; Yang, Long; Zhang, Jianqiang; Deng, Guogang; Li, Yucong; Xie, Xiaoguang; Zhao, Hui; Li, Can-Peng

    2015-09-10

    The application of macrocyclic hosts for construction of different electrochemical devices and separation matrices has attracted much attentions due to their benign biocompatibility and simplicity of synthesis. Myricetin and rutin are considered two of the most bioactive flavonoids, which have been proved to exhibit various physiological functions. This work reports a simple and facile approach for the synthesis of β-cyclodextrin-gold@3, 4, 9, 10-perylene tetracarboxylic acid functionalized single-walled carbon nanohorns (β-CD-Au@PTCA-SWCNHs) nanohybrids. The simultaneous electrochemical determination of myricetin and rutin using a β-CD-Au@PTCA-SWCNHs-modified glassy carbon electrode was established. The results show that the β-CD-Au@PTCA-SWCNHs-modified electrode displayed electrochemical signal superior to those of Au@PTCA-;SWCNHs and SWCNHs towards myricetin and rutin. The proposed modified electrode has a linear response range of 0.01-10.00 μM both for myricetin and rutin with relatively low detection limits of 0.0038 μM for myricetin and 0.0044 μM (S/N = 3) for rutin, respectively. The excellent performance of the sensing platform is considered to be the synergic effects of the SWCNHs (e.g. their good electrochemical properties and large surface area) and β-CD (e.g. a hydrophilic external surface, a high supramolecular recognition, and a good enrichment capability). PMID:26388478

  19. Franck-Condon factors perturbed by damped harmonic oscillators: Solvent enhanced X {sup 1}A{sub g} ↔ A{sup 1}B{sub 1u} absorption and fluorescence spectra of perylene

    SciTech Connect

    Wang, Chen-Wen; Zhu, Chaoyuan Lin, Sheng-Hsien; Yang, Ling; Yu, Jian-Guo

    2014-08-28

    Damped harmonic oscillators are utilized to calculate Franck-Condon factors within displaced harmonic oscillator approximation. This is practically done by scaling unperturbed Hessian matrix that represents local modes of force constants for molecule in gaseous phase, and then by diagonalizing perturbed Hessian matrix it results in direct modification of Huang–Rhys factors which represent normal modes of solute molecule perturbed by solvent environment. Scaling parameters are empirically introduced for simulating absorption and fluorescence spectra of an isolated solute molecule in solution. The present method is especially useful for simulating vibronic spectra of polycyclic aromatic hydrocarbon molecules in which hydrogen atom vibrations in solution can be scaled equally, namely the same scaling factor being applied to all hydrogen atoms in polycyclic aromatic hydrocarbons. The present method is demonstrated in simulating solvent enhanced X {sup 1}A{sub g} ↔ A{sup 1}B{sub 1u} absorption and fluorescence spectra of perylene (medium-sized polycyclic aromatic hydrocarbon) in benzene solution. It is found that one of six active normal modes v{sub 10} is actually responsible to the solvent enhancement of spectra observed in experiment. Simulations from all functionals (TD) B3LYP, (TD) B3LYP35, (TD) B3LYP50, and (TD) B3LYP100 draw the same conclusion. Hence, the present method is able to adequately reproduce experimental absorption and fluorescence spectra in both gas and solution phases.

  20. Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air-Insensitive Electron Acceptors for Artificial Photosynthesis.

    PubMed

    Chen, Hung-Cheng; Hsu, Chao-Ping; Reek, Joost N H; Williams, René M; Brouwer, Albert M

    2015-11-01

    A series of new benzo[ghi]perylenetriimide (BPTI) derivatives has been synthesized and characterized. These remarkably soluble BPTI derivatives show strong optical absorption in the range of λ=300-500 nm and have a high triplet-state energy of 1.67 eV. A cyanophenyl substituent renders BPTI such a strong electron acceptor (Ered =-0.11 V vs. the normal hydrogen electrode) that electron-trapping reactions with O2 and H2 O do not occur. The BPTI radical anion on a fluorine-doped tin oxide|TiO2 electrode is persistent up to tens of seconds (t1/2 =39 s) in air-saturated buffer solution. As a result of favorable packing, theoretical electron mobilities (10(-2) ∼10(-1) cm(2) V(-1) s(-1)) are high and similar to the experimental values observed for perylene diimide and C60 derivatives. Our studies show the potential of the cyanophenyl-modified BPTI compounds as electron acceptors in devices for artificial photosynthesis in water splitting that are also very promising nonfullerene electron-transport materials for organic solar cells. PMID:26395847

  1. Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air-Insensitive Electron Acceptors for Artificial Photosynthesis

    PubMed Central

    Chen, Hung-Cheng; Hsu, Chao-Ping; Reek, Joost N H; Williams, René M; Brouwer, Albert M

    2015-01-01

    A series of new benzo[ghi]perylenetriimide (BPTI) derivatives has been synthesized and characterized. These remarkably soluble BPTI derivatives show strong optical absorption in the range of λ=300–500 nm and have a high triplet-state energy of 1.67 eV. A cyanophenyl substituent renders BPTI such a strong electron acceptor (Ered=−0.11 V vs. the normal hydrogen electrode) that electron-trapping reactions with O2 and H2O do not occur. The BPTI radical anion on a fluorine-doped tin oxide|TiO2 electrode is persistent up to tens of seconds (t1/2=39 s) in air-saturated buffer solution. As a result of favorable packing, theoretical electron mobilities (10−2∼10−1 cm2 V−1 s−1) are high and similar to the experimental values observed for perylene diimide and C60 derivatives. Our studies show the potential of the cyanophenyl-modified BPTI compounds as electron acceptors in devices for artificial photosynthesis in water splitting that are also very promising nonfullerene electron-transport materials for organic solar cells. PMID:26395847

  2. Synthetic Bioluminescent Coelenterazine Derivatives.

    PubMed

    Nishihara, Ryo; Citterio, Daniel; Suzuki, Koji

    2016-01-01

    The development of coelenterazine (CTZ) derivatives resulting in superior optical characteristics is an efficient method to extend the range of its possible applications. Here, we describe the synthesis of three C-6 substituted CTZ derivatives retaining the recognition by Renilla luciferase (RLuc) and its derivatives. The novel derivatives are useful as bright blue-shifted CTZ derivatives, which can be used as an alternative to hitherto reported compound DeepBlueC™. PMID:27424892

  3. A general route to labile niobium and tantalum d{sup 0} monoimides. Discussion of metal-nitrogen vibrational modes

    SciTech Connect

    Korolev, A.V.; Rheingold, A.L.; Williams, D.S.

    1997-06-04

    Reaction of TaCl{sub 5} with 2 equiv of an amine in the presence of sodium silicate and pyridine affords Ta(NR)Cl{sub 3}(py){sub 2} in good yield. Reaction of NbCl{sub 5} with ZnCl{sub 2} followed by addition of an amine RNH{sub 2} and pyridine affords M(NR)Cl{sub 3}(dme) (dme is 1,2-dimethoxyethane). For niobium this reaction proceeds smoothly regardless of the amine but is ineffective with tantalum and alkyl amines. An alternative route involves reaction of TaCl{sub 5} with 3 equiv of RNH{sub 2} to form [RNH{sub 3}]{sub 2}[Ta(NR)Cl{sub 5}], followed by reaction of this salt with ZnCl{sub 2} in the presence of dme. The molecular structure of Nb(N{sup t}Bu)Cl{sub 3}(dme) (formula C{sub 8}H{sub 19}Cl{sub 3}NNbO{sub 2}) was determined by X-ray crystallography (monoclinic space group Cc with a = 30.565(4) {angstrom}, b = 7.2406(13) {angstrom}, c = 13.915(2) {angstrom}, {beta} = 90.626(7){degrees}, V = 3079.4(8) {angstrom}{sup 3}, Z = 8). The Nb-N bond length is 1.72 {angstrom} with a Nb-N-C bond angle of 177{degrees} in a distorted octahedral structure. In order to characterize the M-N stretching frequencies in these compounds, IR data for each compound are compared with calculated stretching frequencies using the commercially available Sparten calculation package. These experiments reveal that there is no real M-N stretching frequency in these imidos. Rather, the M-N modes are strongly coupled to N-C and C-H or C-C modes in these imidos. IR active modes are observed at {approximately}1260 cm{sup -1} for tantalum alkyl imidos and {approximately}1350 cm{sup -1} for tantalum aryl imidos. These correspond to a Ta-(N-C) stretch coupled to the CR{sub 3} umbrella deformation. 28 refs., 2 figs., 4 tabs.

  4. Direct Density Derivative Estimation.

    PubMed

    Sasaki, Hiroaki; Noh, Yung-Kyun; Niu, Gang; Sugiyama, Masashi

    2016-06-01

    Estimating the derivatives of probability density functions is an essential step in statistical data analysis. A naive approach to estimate the derivatives is to first perform density estimation and then compute its derivatives. However, this approach can be unreliable because a good density estimator does not necessarily mean a good density derivative estimator. To cope with this problem, in this letter, we propose a novel method that directly estimates density derivatives without going through density estimation. The proposed method provides computationally efficient estimation for the derivatives of any order on multidimensional data with a hyperparameter tuning method and achieves the optimal parametric convergence rate. We further discuss an extension of the proposed method by applying regularized multitask learning and a general framework for density derivative estimation based on Bregman divergences. Applications of the proposed method to nonparametric Kullback-Leibler divergence approximation and bandwidth matrix selection in kernel density estimation are also explored. PMID:27140943

  5. Study on copper phthalocyanine and perylene-based ambipolar organic light-emitting field-effect transistors produced using neutral beam deposition method

    SciTech Connect

    Kim, Dae-Kyu; Oh, Jeong-Do; Shin, Eun-Sol; Seo, Hoon-Seok; Choi, Jong-Ho

    2014-04-28

    The neutral cluster beam deposition (NCBD) method has been applied to the production and characterization of ambipolar, heterojunction-based organic light-emitting field-effect transistors (OLEFETs) with a top-contact, multi-digitated, long-channel geometry. Organic thin films of n-type N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide and p-type copper phthalocyanine were successively deposited on the hydroxyl-free polymethyl-methacrylate (PMMA)-coated SiO{sub 2} dielectrics using the NCBD method. Characterization of the morphological and structural properties of the organic active layers was performed using atomic force microscopy and X-ray diffraction. Various device parameters such as hole- and electron-carrier mobilities, threshold voltages, and electroluminescence (EL) were derived from the fits of the observed current-voltage and current-voltage-light emission characteristics of OLEFETs. The OLEFETs demonstrated good field-effect characteristics, well-balanced ambipolarity, and substantial EL under ambient conditions. The device performance, which is strongly correlated with the surface morphology and the structural properties of the organic active layers, is discussed along with the operating conduction mechanism.

  6. Weakly coupled molecular photonic wires: synthesis and excited-state energy-transfer dynamics.

    PubMed

    Ambroise, Arounaguiry; Kirmaier, Christine; Wagner, Richard W; Loewe, Robert S; Bocian, David F; Holten, Dewey; Lindsey, Jonathan S

    2002-05-31

    Molecular photonic wires, which absorb light and undergo excited-state energy transfer, are of interest as biomimetic models for photosynthetic light-harvesting systems and as molecular devices with potential applications in materials chemistry. We describe the stepwise synthesis of four molecular photonic wires. Each wire consists of an input unit, transmission element, and output unit. The input unit consists of a boron-dipyrrin dye or a perylene-monoimide dye (linked either at the N-imide or the C9 position); the transmission element consists of one or three zinc porphyrins affording short or long wires, respectively; and the output unit consists of a free base (Fb) porphyrin. The components in the arrays are joined in a linear architecture via diarylethyne linkers (an ethynylphenyl linker is attached to the C9-linked perylene). The wires have been examined by static absorption, static fluorescence, and time-resolved absorption spectroscopy. Each wire (with the exception of the C9-linked perylene wire) exhibits a visible absorption spectrum that is the sum of the spectra of the component parts, indicating the relatively weak electronic coupling between the components. Excitation of each wire at the wavelength where the input unit absorbs preferentially (typically 480-520 nm) results in emission almost exclusively from the Fb porphyrin. The static emission and time-resolved data indicate that the overall rate constants and quantum efficiencies for end-to-end (i.e., input to output) energy transfer are as follows: perylene-(N-imide)-linked short wire, (33 ps)(-1) and >99%; perylene-(C9)-linked short wire, (26 ps)(-1) and >99%; boron-dipyrrin-based long wire, (190 ps)(-1) and 81%; perylene-(N-imide)-linked long wire, (175 ps)(-1) and 86%. Collectively, the studies provide valuable insight into the singlet-singlet excited-state energy-transfer properties in weakly coupled molecular photonic wires. PMID:12027698

  7. Endohedral Metallofullerene Derivatives

    NASA Technical Reports Server (NTRS)

    Dorn, Harry C. (Inventor); Iezzi, Erick B. (Inventor); Duchamp, James (Inventor)

    2008-01-01

    Trimetallic nitride endohedral metallofullerene derivatives and their preparation are described. The trimetallic nitride endohedral metallofullerene derivatives have the general formula A(sub 3-n)X(sub n)@C(sub m)(R) where n ranges from 0 to 3, A and X may be trivalent metals and may be either rare earth metal or group IIIB metals, m is between about 60 and about 200, and R is preferably an organic group. Derivatives where the R group forms cyclized derivatives with the fullerene cage are also described.

  8. Genotoxicity-Related Chemistry of Human Metabolites of Benzo[ghi]perylene (B[ghi]P) Investigated using Electro-optical Arrays and DNA/Microsome Biocolloid Reactors with LC-MS/MS

    PubMed Central

    Pan, Shenmin; Li, Dandan; Zhao, Linlin; Schenkman, John B.; Rusling, James F.

    2013-01-01

    There is limited and sometimes contradictory information about the genotoxicity of polycyclic aromatic hydrocarbon benzo[ghi]perylene (B[ghi]P). Using recently developed metabolic toxicity screening arrays and a biocolloid reactor-LC-MS/MS approach, both featuring films of DNA and human metabolic enzymes, we demonstrated relatively low reactivity of metabolically activated B[ghi]P towards DNA. Electro-optical toxicity screening arrays showed that B[ghi]P metabolites damage DNA at a 3-fold lower rate than benzo[a]pyrene (B[a]P), whose metabolites have a strong and well-understood propensity for DNA damage. Metabolic studies using magnetic bead biocolloid reactors coated with microsomal enzymes in 96-well plates showed that cyt P450s 1A1 and 1B1 provide high activity for B[ghi]P and B[a]P conversion. Consistent with published results, the major metabolism of B[ghi]P involved oxidations at 3,4 and 11,12 positions, leading to formation of B[ghi]P 3,4-oxide and B[ghi]P 3,4,11,12-bisoxide. B[ghi]P 3,4-oxide was synthesized and reacted with deoxyadenosine at N6 and N7 positions and with deoxyguanosine at the N2 position. B[ghi]P 3,4-oxide is hydrolytically unstable and transforms into the 3,4-diol or converts to 3- or 4-hydroxy B[ghi]P. LC-MS/MS of reaction products from the magnetic biocolloid reactor particles coated with DNA and human enzymes revealed for the first time that a major DNA adduct results from reaction between B[ghi]P 3,4,11,12-bisoxide and deoxyguanosine. Results also demonstrated 5-fold lower formation rates of the major DNA adduct for B[ghi]P metabolites compared to B[a]P. Overall, results from both ECL array and biocolloid reactor-LC-MS/MS consistently suggest a lower human genotoxicity profile of B[ghi]P than B[a]P. PMID:23879290

  9. Irregularities in Imperfective Derivation

    ERIC Educational Resources Information Center

    Levin, Maurice I.

    1977-01-01

    This article discusses presentation of Russian conjugation via the one-stem system advocated by Lipson and Townsend, and attempts a more unified and complete presentation of irregularities in imperfect derivation. Two major irregularities are occurrence of an unexpected suffix and unpredictable alternation in the root of the derived imperfective.…

  10. The Dangers of Derivatives.

    ERIC Educational Resources Information Center

    Blumenstyk, Goldie

    1994-01-01

    Heavy investment in derivatives, whose value derives from the price movement of some underlying security, has meant heavy losses for some colleges and universities despite the fact that institutional investors are required to assure that they understand the risks of such investment. (MSE)

  11. DERIVE in Slovenian Schools.

    ERIC Educational Resources Information Center

    Lokar, Matija

    This paper describes several projects concerning the use of the DERIVE programming language for symbolic computation in Slovenia. The main topics discussed include preparing books and materials using DERIVE in Slovenian language, and a survey on the use of programs for symbolic computation by mathematics teachers in Slovenian secondary schools.…

  12. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1984-01-01

    Flame-resistant reinforced bodies are disclosed which are composed of reinforcing fibers, filaments or fabrics in a cured body of bis- and tris-imide resins derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, or of addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride.

  13. The azobenzene derivatives

    NASA Astrophysics Data System (ADS)

    Ionita, Ionica; Radulescu, Cristiana; Poinescu, Aurora Anca; Anghelina, Florina Violeta; Bunghez, Raluca; Ion, Rodica-Mariana

    2015-02-01

    Azobenzene derivatives constitute a group of dyes which have photochromic properties and have been investigated as promising systems for diverse applications in the unconventional optic area, their properties can be moulded with help of light.

  14. Synthesis of phenoxatellurine derivatives

    SciTech Connect

    Maksimenko, A.A.; Rivkin, B.B.; Sadekov, I.D.; Minkin, V.I.

    1985-12-01

    The reaction of dimedon enol acetate with tellurium tetrachloride gives derivatives of octahydrophenoxatellurine. The reaction of cyclohexanone enol acetate and methyl ethyl ketone with tellurium tetrachloride or aryltellurium trichloride gives the respective organotellurium trichloride and diorganotellurium dichloride.

  15. [Derivative fluorescence probe recognition results of the light physical mechanism of metal ions].

    PubMed

    Dai, Yu-mei; Hu, Xiao-jun; Li, Fu-jun; Xie, Yu-meng; Zhao, Yang-yang; Zhou, Qiao

    2015-02-01

    As people deeply study the electronic spectra of fluorescent compounds and photophysical behavior, enormous progress has been made in the aspect of changes and states of different systems in the use of fluorescent molecules as probes. PTC-DA is a kind of typical fluorescent molecular probe that is highly sensitive and selective in water environment. This paper makes a research on the physical mechanism of light of PTCDA by TDF (Density Functional Theory), calculates the optimal configuration the charge population and excitation spectra of PTCDA molecules under ideal condition and acquires PTCDA fluorescence emission spectra then analyses that PTCDA is a kind of quenching and dual colorimetric signal probe response. Its optical signal response mechanism belongs to ICT (Intramolecular Charge Transfer) mechanism. According to the results, this perylene derivatives is fitted with Cu2+ excited state absorption spectra. Before and after the combination with Cu2+, the peak shape of absorption spectrum is similar. When copper is added, the overall absorption peak position occurred redshift, quenching discoloration happens. By comparing with experimental values, the calculated molecular configuration is reasonable and effective and the peak of excitation spectra is realistic. Analysis shows that: PTCDA molecules divalent copper ions have better fluorescence detection activity, the optical signal response mechanisms are intramolecular charge transfer (ICT) mechanisms. When a molecule receives divalent copper ions, the absorption spectrum peak position redshifts, intramolecular charge transfer direction and intensity changes. There occur both quenching signal and discoloration signal. It is a kind of fluorescent probe material with double quenching and discoloration fluorescent signal, which has great potential for development. This paper makes an early-stage exploration of the physical mechanism of light response mechanism analysis in molecular fluorescent probe field and

  16. D1((2)B2g) to D0((2)Au) Fluorescence from the Matrix-Isolated Perylene Cation Following Laser Excitation into the D5(2)B3g) and D2 ((2)B3g) Electronic States

    NASA Technical Reports Server (NTRS)

    Chillier, Xavier D. F.; Stone, Bradley M.; Joblin, Christine; Salama, Farid; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    Fluorescence spectra of the perylene cation, pumped by direct laser excitation via the D(sub 2)((2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) and D(sub 5)(2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) transitions, are presented. Direct excitation into the D5 or D2 states is followed by rapid non-radiative relaxation to D1 that, in turn,relaxes radiatively. Excitation spectroscopy across the D(sub 2)((2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) transition near 730 nm shows that site splitting plays little or no role in determining the spectral substructure in the ion spectra. Tentative assignments for ground state vibrational frequencies are made by comparison of spectral intervals with calculated normal mode frequencies.

  17. D1(2B2g)→D0(2Au) fluorescence from the matrix-isolated perylene cation following laser excitation into the D5(2B3g) and D2(2B3g) electronic states

    NASA Astrophysics Data System (ADS)

    Chillier, Xavier D. F.; Stone, Bradley M.; Joblin, Christine; Salama, Farid; Allamandola, Louis J.

    2002-04-01

    Fluorescence spectra of the perylene cation, isolated in an argon matrix and pumped by direct laser excitation via the D2(2B3g)←D0(2Au) and D5(2B3g)←D0(2Au) transitions, are presented. Direct excitation into the D5 or D2 states is followed by rapid nonradiative relaxation to D1 that, in turn, relaxes radiatively. Excitation spectroscopy across the D2(2B3g)←D0(2Au) transition near 731 nm shows that site splitting plays little or no role in determining the spectral substructure in the ion spectra. Tentative assignments for ground state vibrational frequencies are made by a comparison of spectral intervals with calculated normal mode frequencies, with the strongest IR bands leading to the most intense vibronic bands.

  18. Semisynthetic Derivatives of Epothilones

    NASA Astrophysics Data System (ADS)

    Altmann, Karl-Heinz

    Semisynthetic derivatives of natural products traditionally occupy a prominent space in natural-product-based drug discovery (1, 2). As many biologically active natural products exhibit a high degree of structural complexity (3), the chemical derivatization of material isolated from natural sources often represents the only feasible means (or at least the only economically viable approach) to explore structure-activity-relationships (SAR) and to produce analogs with more favorable pharmacokinetic and pharmacological properties than the natural product lead. Examples of clinically important drugs that are semisynthetic derivatives of natural products exist in virtually all disease areas (1, 2); in the treatment of cancer this includes compounds such as etoposide or teniposide (derived from podophyllotoxin) (4-6), irinotecan and topotecan (derived from camptothecin) (7-9), or docetaxel (derived from 10-deacetylbaccatin III) (10, 11). Even for taxol (11), which is a natural product (12), the sustained supply of sufficient quantities of material for widespread clinical use could only be secured through the development of a semisynthetic production process from another natural product, namely, 10-deacetylbaccatin III (13). In light of these facts, it is not surprising that semisynthesis approaches have also featured prominently in the elucidation of the SAR for epothilones and in the discovery of a number of clinical development candidates.

  19. Ferroelectricity in corundum derivatives

    NASA Astrophysics Data System (ADS)

    Ye, Meng; Vanderbilt, David

    The search for new ferroelectric (FE) materials holds promise for broadening our understanding of FE mechanisms and extending the range of application of FE materials. The known FE materials LiNbO3 can be regarded as derived from the A2O3 corundum structure with cation ordering. Here we consider more general binary (AB O3) and ternary (A2 BB' O6) corundum derivatives as an extended class of potential FE materials, motivated by the fact that some members of this class have recently been synthesized. There are four structure types for these corundum derivatives, and the number of cation combinations is enormous, but in many cases the energy barriers for polarization reversal may be too large to allow FE behavior. Here we present a first-principles study of the polar structure, coherent FE barrier, and domain-wall switching barrier for a representative set of polar corundum derivatives, allowing us to identify several potentially new FE materials. We also discuss the conditions under which ferroelectricity is compatible with magnetic ordering. Finally, we identify several empirical measures that can provide a rule of thumb for estimating the barrier energies. Our results should assist in the experimental search for new FE materials in the corundum derivative family. This work is supported by ONR Grant No. N-00014-12-1-1035.

  20. Myeloid derived suppressor cells

    PubMed Central

    Waldron, Todd J.; Quatromoni, Jon G.; Karakasheva, Tatiana A.; Singhal, Sunil; Rustgi, Anil K.

    2013-01-01

    The goal of achieving measurable response with cancer immunotherapy requires counteracting the immunosuppressive characteristics of tumors. One of the mechanisms that tumors utilize to escape immunosurveillance is the activation of myeloid derived suppressor cells (MDSCs). Upon activation by tumor-derived signals, MDSCs inhibit the ability of the host to mount an anti-tumor immune response via their capacity to suppress both the innate and adaptive immune systems. Despite their relatively recent discovery and characterization, anti-MDSC agents have been identified, which may improve immunotherapy efficacy. PMID:23734336

  1. Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

    NASA Astrophysics Data System (ADS)

    Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.; McClendon, Mark; Koltonow, Andrew R.; Samuel, Amanda P. S.; Kiebala, Derek J.; Wasielewski, Michael R.; Stupp, Samuel I.

    2014-11-01

    Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.

  2. Effect of Structural Modifications on the Self-Assembly of Oligoprolines Conjugated with Sterically Demanding Chromophores.

    PubMed

    Lewandowska, Urszula; Zajaczkowski, Wojciech; Pisula, Wojciech; Ma, Yingjie; Li, Chen; Müllen, Klaus; Wennemers, Helma

    2016-03-01

    Conjugates between oligoprolines and sterically demanding perylene monoimides (PMIs) form hierarchical supramolecular self-assemblies. The influence of the length and stereochemistry at the attachment site between the peptide backbone and the chromophore on the self-assembly properties of the conjugates was explored. Comparison between oligoprolines bearing 4R- or 4S-configured azidoprolines (Azp) for the conjugation with the PMIs revealed that diastereoisomers with 4R configuration guide the self-assembly consistently better than conjugates with 4S configuration. Elongating the peptide chain beyond nine proline residues or introducing structural "errors", by altering the absolute configuration of one stereogenic center at the outside of the functionalizable oligoproline helix, lowered the efficacy of self-assembly significantly, both in solution phase and in the solid state. The results showed how subtle structural modifications allow for tuning the self-assembly of chromophores and provided further design principles for the development of peptide-chromophore conjugates into nanostructured materials. PMID:26891419

  3. Tuning the Electron Acceptor in Phthalocyanine-Based Electron Donor-Acceptor Conjugates.

    PubMed

    Sekita, Michael; Jiménez, Ángel J; Marcos, M Luisa; Caballero, Esmeralda; Rodríguez-Morgade, M Salomé; Guldi, Dirk M; Torres, Tomás

    2015-12-21

    Zinc phthalocyanines (ZnPc) have been attached to the peri-position of a perylenemonoimide (PMI) and a perylenemonoanhydride (PMA), affording electron donor-acceptor conjugates 1 and 2, respectively. In addition, a perylene-monoimide-monoanhydride (PMIMA) has been connected to a ZnPc through its imido position to yield the ZnPc-PMIMA conjugate 10. The three conjugates have been studied for photoinduced electron transfer. For ZnPc-PMIMA 10, electron transfer occurs upon both ZnPc and PMIMA excitation, giving rise to a long-lived (340 ps) charge-separated state. For ZnPc-PMI 1 and ZnPc-PMA 2, stabilization of the radical ion pair states by using polar media is necessary. In THF, photoexcitation of either ZnPc or PMI/PMA produces charge-separated states with lifetimes of 375 and 163 ps, respectively. PMID:26593778

  4. Oxygenated Derivatives of Hydrocarbons

    Technology Transfer Automated Retrieval System (TEKTRAN)

    For the book entitled “Insect Hydrocarbons: Biology, Biochemistry and Chemical Ecology”, this chapter presents a comprehensive review of the occurrence, structure and function of oxygenated derivatives of hydrocarbons. The book chapter focuses on the occurrence, structural identification and functi...

  5. 78 FR 32191 - Derivatives

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-29

    ... alternatives. \\5\\ 71 FR 5155 (February 2, 2012). C. 1998 IRPS This proposed rule is consistent with a 1998... promulgation of this proposed rule. \\7\\ 76 FR 37030 (June 24, 2011). First, the Board asked if it should... derivatives transactions independently. \\9\\ 77 FR 5416 (Feb. 3, 2012). Question One. The Board asked if...

  6. Biotechnology and derived products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Microorganisms able to infect and kill insect pests, metabolites from plants and microorganisms, and transgenic crops are biotechnologically derived products that are being promoted for use to control insect pests in lieu of chemical insecticides. Products based on these technologies effectively co...

  7. Ferroelectricity in corundum derivatives

    NASA Astrophysics Data System (ADS)

    Ye, Meng; Vanderbilt, David

    2016-04-01

    The search for new ferroelectric (FE) materials holds promise for broadening our understanding of FE mechanisms and extending the range of application of FE materials. Here we investigate a class of A B O3 and A2B B'O6 materials that can be derived from the X2O3 corundum structure by mixing two or three ordered cations on the X site. Most such corundum derivatives have a polar structure, but it is unclear whether the polarization is reversible, which is a requirement for a FE material. In this paper, we propose a method to study the FE reversal path of materials in the corundum derivative family. We first categorize the corundum derivatives into four classes and show that only two of these allow for the possibility of FE reversal. We then calculate the energy profile and energy barrier of the FE reversal path using first-principles density functional methods with a structural constraint. Furthermore, we identify several empirical measures that can provide a rule of thumb for estimating the energy barriers. Finally, the conditions under which the magnetic ordering is compatible with ferroelectricity are determined. These results lead us to predict several potentially new FE materials.

  8. Fundamental Studies of Hydroporphyrin Architectures for Solar-Energy Applications

    SciTech Connect

    Lindsey, Jonathan S.; Bocian, David F.; Holten, Dewey; Kirmaier, Christine

    2013-10-30

    The long-term objective of the Bocian/Holten&Kirmaier/Lindsey research program is to design, synthesize, and characterize tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy, and separate charge with high efficiency and in a manner compatible with current and future solar-energy conversion schemes. The synthetic tetrapyrroles include porphyrins and hydroporphyrins; the latter classes of molecules encompass analogues of the naturally occurring chlorophylls and bacteriochlorophylls (e.g., chlorins, bacteriochlorins, and their derivatives). The attainment of the goals of the research program requires the close interplay of molecular design and synthesis (Lindsey group), static and time-resolved optical spectroscopic measurements (Holten&Kirmaier group), and electrochemical, electron paramagnetic resonance, resonance Raman, and infrared studies, as well as density functional theory calculations (Bocian Group). The proposed research encompasses four interrelated themes: (i) Gain a deeper understanding of the spectral and electronic properties of bacteriochlorins, with a subsidiary aim of learning how to shift the long-wavelength absorption band deeper into the NIR region. Bacteriochlorins bearing diverse substituents, including annulated rings, will be prepared and examined. A set of bacteriochlorins with site-specific isotopic (13C, 2H) substitution patterns about the macrocycle perimeter will be prepared for studies of vibrational and electronic properties. (ii) Examine the underlying electronic origin of panchromatic absorption and excited-state behavior of strongly coupled rylene–tetrapyrrole arrays. The rylene constituents include a perylene-monoimide and a terrylene-monoimide. The tetrapyrroles include porphyrins (meso- or β-linked) and bacteriochlorins (β-linked). The objective is to achieve panchromatic absorption while preserving a viable, long-lived excited singlet state. (iii) Determine the rates of ground-state hole

  9. Derived enriched uranium market

    SciTech Connect

    Rutkowski, E.

    1996-12-01

    The potential impact on the uranium market of highly enriched uranium from nuclear weapons dismantling in the Russian Federation and the USA is analyzed. Uranium supply, conversion, and enrichment factors are outlined for each country; inventories are also listed. The enrichment component and conversion components are expected to cause little disruption to uranium markets. The uranium component of Russian derived enriched uranium hexafluoride is unresolved; US legislation places constraints on its introduction into the US market.

  10. Space Derived Air Monitor

    NASA Technical Reports Server (NTRS)

    1983-01-01

    COPAMS, Commonwealth of Pennsylvania Air Monitoring System, derives from technology involved in building unmanned spacecraft. The Nimbus spacecraft carried experimental sensors to measure temperature, pressure, ozone, and water vapor, and instruments for studying solar radiation and telemetry. The process which relayed these findings to Earth formed the basis for COPAMS. The COPAMS system consists of data acquisition units which measure and record pollution level, and sense wind speed and direction, etc. The findings are relayed to a central station where the information is computerized. The system is automatic and supplemented by PAQSS, PA Air Quality Surveillance System.

  11. In defense of derivations

    NASA Astrophysics Data System (ADS)

    Mungan, Carl E.

    2016-05-01

    At the 2015 AAPT Summer Meeting, I presented four derivations of the formula for motional emf. Such physics derivations involve the construction of explanatory frameworks involving diagrams and mathematical models. Although textbooks devote considerable space to such explanations, many teachers and students spend their time on worksheets, end-of-chapter problems, and the like. The book is reduced to a bank of solved (i.e., example) and unsolved (i.e., homework) questions, along with equations in colored boxes that presumably are to be used to answer those questions. Such an approach encourages fragmentation of knowledge, the view that there is only one right answer to a problem with the goal of physics being to find that answer (neatly boxed of course), and the inability to reason about even a slightly different (much less a novel) situation. If we are to develop scientific literacy, significant course time must be devoted to explaining the structure of and support for the models and equations we use.

  12. Acquiring Knowledge of Derived Nominals and Derived Adjectives in Context

    ERIC Educational Resources Information Center

    Marinellie, Sally A.; Kneile, Lynn A.

    2012-01-01

    Purpose: This research investigated children's ability to acquire semantic and syntactic knowledge of derived nominals and derived adjectives in the context of short passages. The study also investigated the relation of morphological awareness and the ability to acquire knowledge of derived words in context. Method: A total of 106 children in…

  13. Experts' Understanding of Partial Derivatives Using the Partial Derivative Machine

    ERIC Educational Resources Information Center

    Roundy, David; Weber, Eric; Dray, Tevian; Bajracharya, Rabindra R.; Dorko, Allison; Smith, Emily M.; Manogue, Corinne A.

    2015-01-01

    Partial derivatives are used in a variety of different ways within physics. Thermodynamics, in particular, uses partial derivatives in ways that students often find especially confusing. We are at the beginning of a study of the teaching of partial derivatives, with a goal of better aligning the teaching of multivariable calculus with the needs of…

  14. Algae Derived Biofuel

    SciTech Connect

    Jahan, Kauser

    2015-03-31

    One of the most promising fuel alternatives is algae biodiesel. Algae reproduce quickly, produce oils more efficiently than crop plants, and require relatively few nutrients for growth. These nutrients can potentially be derived from inexpensive waste sources such as flue gas and wastewater, providing a mutual benefit of helping to mitigate carbon dioxide waste. Algae can also be grown on land unsuitable for agricultural purposes, eliminating competition with food sources. This project focused on cultivating select algae species under various environmental conditions to optimize oil yield. Membrane studies were also conducted to transfer carbon di-oxide more efficiently. An LCA study was also conducted to investigate the energy intensive steps in algae cultivation.

  15. 6-Bromocholesterol derivatives

    SciTech Connect

    Flanagan, R.J.

    1984-02-07

    Novel 6-bromo derivatives of cholesterol have the formula 3-(R-O-),6-BR,17-((H3C-)2-HC-H2C-H2C-H2C-HC(-CH3)-)-ESTR-5-ENE Such compounds are prepared from the known 6-iodocholesterol by treatment with cuprous bromide. These compounds, labelled with radioisotopes of Br-82 or Br-77, are localized in the adrenal, mammary and ovary tissue of female mammals and in the adrenal or prostate tissue of males when administered to such individuals. This provides a method for imaging adrenal, ovary or prostate tissue which is superior to use of the prior art 6-iodo-cholesterol.

  16. Experts' understanding of partial derivatives using the partial derivative machine

    NASA Astrophysics Data System (ADS)

    Roundy, David; Weber, Eric; Dray, Tevian; Bajracharya, Rabindra R.; Dorko, Allison; Smith, Emily M.; Manogue, Corinne A.

    2015-12-01

    [This paper is part of the Focused Collection on Upper Division Physics Courses.] Partial derivatives are used in a variety of different ways within physics. Thermodynamics, in particular, uses partial derivatives in ways that students often find especially confusing. We are at the beginning of a study of the teaching of partial derivatives, with a goal of better aligning the teaching of multivariable calculus with the needs of students in STEM disciplines. In this paper, we report on an initial study of expert understanding of partial derivatives across three disciplines: physics, engineering, and mathematics. We report on the central research question of how disciplinary experts understand partial derivatives, and how their concept images of partial derivatives differ, with a focus on experimentally measured quantities. Using the partial derivative machine (PDM), we probed expert understanding of partial derivatives in an experimental context without a known functional form. In particular, we investigated which representations were cued by the experts' interactions with the PDM. Whereas the physicists and engineers were quick to use measurements to find a numeric approximation for a derivative, the mathematicians repeatedly returned to speculation as to the functional form; although they were comfortable drawing qualitative conclusions about the system from measurements, they were reluctant to approximate the derivative through measurement. On a theoretical front, we found ways in which existing frameworks for the concept of derivative could be expanded to include numerical approximation.

  17. DRS: Derivational Reasoning System

    NASA Technical Reports Server (NTRS)

    Bose, Bhaskar

    1995-01-01

    The high reliability requirements for airborne systems requires fault-tolerant architectures to address failures in the presence of physical faults, and the elimination of design flaws during the specification and validation phase of the design cycle. Although much progress has been made in developing methods to address physical faults, design flaws remain a serious problem. Formal methods provides a mathematical basis for removing design flaws from digital systems. DRS (Derivational Reasoning System) is a formal design tool based on advanced research in mathematical modeling and formal synthesis. The system implements a basic design algebra for synthesizing digital circuit descriptions from high level functional specifications. DRS incorporates an executable specification language, a set of correctness preserving transformations, verification interface, and a logic synthesis interface, making it a powerful tool for realizing hardware from abstract specifications. DRS integrates recent advances in transformational reasoning, automated theorem proving and high-level CAD synthesis systems in order to provide enhanced reliability in designs with reduced time and cost.

  18. Piroxicam derivatives THz classification

    NASA Astrophysics Data System (ADS)

    Sterczewski, Lukasz A.; Grzelczak, Michal P.; Nowak, Kacper; Szlachetko, Bogusław; Plinska, Stanislawa; Szczesniak-Siega, Berenika; Malinka, Wieslaw; Plinski, Edward F.

    2016-02-01

    In this paper we report a new approach to linking the terahertz spectral shapes of drug candidates having a similar molecular structure to their chemical and physical parameters. We examined 27 newly-synthesized derivatives of a well-known nonsteroidal anti-inflammatory drug Piroxicam used for treatment of inflammatory arthritis and chemoprevention of colon cancer. The testing was carried out by means of terahertz pulsed spectroscopy (TPS). Using chemometric techniques we evaluated their spectral similarity in the terahertz range and attempted to link the position on the principal component analysis (PCA) score map to the similarity of molecular descriptors. A simplified spectral model preserved 75% and 85.1% of the variance in 2 and 3 dimensions respectively, compared to the input 1137. We have found that in 85% of the investigated samples a similarity of the physical and chemical parameters corresponds to a similarity in the terahertz spectra. The effects of data preprocessing on the generated maps are also discussed. The technique presented can support the choice of the most promising drug candidates for clinical trials in pharmacological research.

  19. Vaccine-derived polioviruses.

    PubMed

    Burns, Cara C; Diop, Ousmane M; Sutter, Roland W; Kew, Olen M

    2014-11-01

    The attenuated oral poliovirus vaccine (OPV) has many properties favoring its use in polio eradication: ease of administration, efficient induction of intestinal immunity, induction of durable humoral immunity, and low cost. Despite these advantages, OPV has the disadvantage of genetic instability, resulting in rare and sporadic cases of vaccine-associated paralytic poliomyelitis (VAPP) and the emergence of genetically divergent vaccine-derived polioviruses (VDPVs). Whereas VAPP is an adverse event following exposure to OPV, VDPVs are polioviruses whose genetic properties indicate prolonged replication or transmission. Three categories of VDPVs are recognized: (1) circulating VDPVs (cVDPVs) from outbreaks in settings of low OPV coverage, (2) immunodeficiency-associated VDPVs (iVDPVs) from individuals with primary immunodeficiencies, and (3) ambiguous VDPVs (aVDPVs), which cannot be definitively assigned to either of the first 2 categories. Because most VDPVs are type 2, the World Health Organization's plans call for coordinated worldwide replacement of trivalent OPV with bivalent OPV containing poliovirus types 1 and 3. PMID:25316847

  20. Synthesis of 2-carbethoxybenzofuran derivatives

    SciTech Connect

    Prewysz-Kwinto, A.

    1987-12-01

    A mixture of 3-formyl and 3-acetoxymethyl derivatives is formed in the oxidation of 2-carbethoxy-3-methyl-7-ethylbenzofuran with selenium dioxide. Reduction with lithium aluminum hydride gives 2,3-dihydroxymethyl derivatives, which are converted to 2,3-diformyl derivatives by successive oxidation. A number of derivatives of 3-methyl-7-ethylbenzofurancarboxylic acid were obtained. The PMR spectra of solutions of the compounds in CDCl/sub 3/ were recorded with a Tesla B-487 spectrometer (80 Hz) with hexamethyldisiloxane (HMDS) as the internal standard. The IR spectra of KBr pellets of the compounds were obtained with a UR-10 spectrometer.

  1. Buckybowls: Corannulene and Its Derivatives.

    PubMed

    Li, Xu; Kang, Feiyu; Inagaki, Michio

    2016-06-01

    Corannulene, a kind of bowl like polycyclic aromatic hydrocarbon (PAH), whose molecule is composed of a central pentagon and five closely adjacent hexagons on the pentagon's five sides, has received great scientific interest among research groups. In this review, the syntheses, characteristic molecule structure and properties of corannulene are clarified, as well as its derivatives with different substituted groups, fused derivatives, metal complex, and derivatives for host guest chemistry. On the basis of reviewing the applications and properties of corannulene together with its derivatives, the potential applications in hydrogen storage and lithium storage were highlighted and prospected. PMID:27136669

  2. Alternative algebras admitting derivations with invertible values and invertible derivations

    NASA Astrophysics Data System (ADS)

    Kaygorodov, I. B.; Popov, Yu S.

    2014-10-01

    We prove an analogue of the Bergen-Herstein-Lanski theorem for alternative algebras: describe all alternative algebras that admit derivations with invertible values. We also prove an analogue of Moens' theorem for alternative algebras (a finite-dimensional alternative algebra over a field of characteristic zero is nilpotent if and only if it admits an invertible Leibniz derivation).

  3. Bone Marrow Derived Eosinophil Cultures

    PubMed Central

    Lu, Thomas X.; Rothenberg, Marc E.

    2016-01-01

    Eosinophils are multifunctional effector cells implicated in the pathogenesis of a variety of diseases including asthma, eosinophil gastrointestinal disorders and helminth infection. Mouse bone marrow derived progenitor cells can be differentiated into eosinophils following IL-5 exposure. These bone marrow derived eosinophils are fully differentiated at the end of a 14 day culture based on morphology and expression of molecular markers.

  4. Elevation Derivatives for National Applications

    USGS Publications Warehouse

    U.S. Geological Survey

    2005-01-01

    The Elevation Derivatives for National Applications (EDNA) project is a multi-agency effort to develop standard topographically derived layers for use in hydrologic and environmental modeling. The EDNA takes advantage of the seamless and filtered characteristics for the National Elevation Dataset (NED) to create a hydrologically conditioned Digital Elevation Model (DEM) useful for modeling applications. The goals of the project are to create a hydrologically conditioned DEM and systematically extract a set of standard derivatives that can be used to facilitate data integration with other U.S. Geological Survey (USGS) framework data sets such as the National Hydrography Dataset (NHD) and the Watershed Boundaries Dataset (WBD).

  5. Quinazoline derivatives: synthesis and bioactivities

    PubMed Central

    2013-01-01

    Owing to the significant biological activities, quinazoline derivatives have drawn more and more attention in the synthesis and bioactivities research. This review summarizes the recent advances in the synthesis and biological activities investigations of quinazoline derivatives. According to the main method the authors adopted in their research design, those synthetic methods were divided into five main classifications, including Aza-reaction, Microwave-assisted reaction, Metal-mediated reaction, Ultrasound-promoted reaction and Phase-transfer catalysis reaction. The biological activities of the synthesized quinazoline derivatives also are discussed. PMID:23731671

  6. Microscopic derivation of discrete hydrodynamics.

    PubMed

    Español, Pep; Anero, Jesús G; Zúñiga, Ignacio

    2009-12-28

    By using the standard theory of coarse graining based on Zwanzig's projection operator, we derive the dynamic equations for discrete hydrodynamic variables. These hydrodynamic variables are defined in terms of the Delaunay triangulation. The resulting microscopically derived equations can be understood, a posteriori, as a discretization on an arbitrary irregular grid of the Navier-Stokes equations. The microscopic derivation provides a set of discrete equations that exactly conserves mass, momentum, and energy and the dissipative part of the dynamics produces strict entropy increase. In addition, the microscopic derivation provides a practical implementation of thermal fluctuations in a way that the fluctuation-dissipation theorem is satisfied exactly. This paper points toward a close connection between coarse-graining procedures from microscopic dynamics and discretization schemes for partial differential equations. PMID:20059064

  7. Fullerene Derivatives for Medical Applications

    NASA Astrophysics Data System (ADS)

    Hirsch, Andreas

    2005-09-01

    Water-soluble fullerene derivatives have a potential for a variety of medical applications. This is due to the unique structural-, electronic and chemical properties of the fullerene core. The biological properties of suitably functionalized fullerenes range from enzyme inhibition/receptor binding, anticancer and antiviral activity, cell signalling, DNA- and genomic applications, photodynamic activation and most importantly antioxidant properties. This review focusses on the anti-HIV and antioxidant properties of a couple of water soluble fullerene derivatives.

  8. What is a fractional derivative?

    NASA Astrophysics Data System (ADS)

    Ortigueira, Manuel D.; Tenreiro Machado, J. A.

    2015-07-01

    This paper discusses the concepts underlying the formulation of operators capable of being interpreted as fractional derivatives or fractional integrals. Two criteria for required by a fractional operator are formulated. The Grünwald-Letnikov, Riemann-Liouville and Caputo fractional derivatives and the Riesz potential are accessed in the light of the proposed criteria. A Leibniz rule is also obtained for the Riesz potential.

  9. Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygenated-PAHs, nitrated-PAHs and azaarenes) in size-fractionated particles emitted in an urban road tunnel

    NASA Astrophysics Data System (ADS)

    Alves, C. A.; Vicente, A. M. P.; Gomes, J.; Nunes, T.; Duarte, M.; Bandowe, B. A. M.

    2016-11-01

    A sampling campaign of size segregated particulate matter (PM0.5, PM0.5-1, PM1-2.5 and PM2.5-10) was carried out at two sites, one in a road tunnel (Braga, Portugal) and another at an urban background location in the neighbourhood. Particle-bound polycyclic aromatic compounds were extracted with organic solvents and analysed by gas chromatography-mass spectrometry. Twenty six parent and alkyl-polycyclic aromatic hydrocarbons (PAHs), 4 azaarenes (AZAs), 15 nitrated and 15 oxygenated derivatives (NPAHs and OPAHs) were analysed. On average, submicron particles (PM1) in the tunnel comprised 93, 91, 96 and 71% of the total PAHs, OPAHs, NPAHs and AZAs mass in PM10, respectively. Tunnel to outdoor PAH concentration ratios between 10 and 14 reveal the strong contribution of fresh exhaust emissions to the PM loads. The dominant PAHs in the tunnel were pyrene, retene and benzo[ghi]perylene, accounting for 20, 17 and 8% of the total PAH levels in PM10, respectively. Isomer ratios indicated the importance of unburnt fuel as a significant PAH source. The only NPAH consistently present in all samples was 5-nitroacenaphthene. Indanone and 1,8-naphthalic anhydride were the most abundant OPAHs, accounting for 25 and 17% of the total concentrations of this organic class, respectively. Other abundant OPAHs were 1,4-naphthoquinone, 9-fluorenone, 1,2-acenaphthylenequinone and 7H-benz[de]anthracene-7-one. Individual emission factors (μg veh- 1 km- 1) were estimated and compared with those obtained in other tunnel studies.

  10. Bioactive steroid derivatives and butyrolactone derivatives from a gorgonian-derived Aspergillus sp. fungus.

    PubMed

    Chen, Min; Wang, Kai-Ling; Liu, Min; She, Zhi-Gang; Wang, Chang-Yun

    2015-09-01

    Six steroid derivatives, 1-6, and five butyrolactone derivatives, 7-11, were isolated from the fermentation broth of a gorgonian-derived Aspergillus sp. fungus. Their structures were elucidated on the basis of NMR and MS spectral data. Compound 1 is a new, highly conjugated steroid. The NMR and MS data of 7 and 8 are reported for the first time, as their structures were listed in SciFinder Scholar with no associated reference. Compounds 1, 4, 5, and 8-11 inhibited the larval settlement of barnacle Balanus amphitrite with EC50 values ranging from 0.63 to 18.4 μg ml(-1) . Butyrolactone derivatives 7 and 8 showed pronounced antibacterial activities against Staphylococcus aureus with the same MIC values as the positive control ciprofloxacin (MIC 1.56 μM for all three compounds). PMID:26363883

  11. Nucleoside derivatives from the marine-derived fungus Aspergillus versicolor.

    PubMed

    Chen, Min; Fu, Xiu-Mei; Kong, Chui-Jian; Wang, Chang-Yun

    2014-01-01

    Four nucleoside derivatives (1-4) were isolated from the fungus Aspergillus versicolor derived from the gorgonian Dichotella gemmacea collected in the South China Sea. Their structures were elucidated by comprehensive spectroscopic method of NMR and MS analysis. All isolated metabolites were evaluated for their cytotoxicity, antibacterial activity and lethality towards brine shrimp Artemia salina. Compounds 1/2 exhibited selective antibacterial activity against Staphylococcus epidermidis with an MIC value of 12.5 μM. It should be noted that 1 and 2, whose structures were listed in SciFinder Scholar, had no associated reference. This is the first report about their isolation, structure elucidation and biological activities. PMID:24670197

  12. 12 CFR 390.352 - Financial derivatives.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 12 Banks and Banking 5 2013-01-01 2013-01-01 false Financial derivatives. 390.352 Section 390.352... Financial derivatives. (a) What is a financial derivative? A financial derivative is a financial contract... common types of financial derivatives are futures, forward commitments, options, and swaps. A...

  13. 12 CFR 390.352 - Financial derivatives.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 12 Banks and Banking 5 2012-01-01 2012-01-01 false Financial derivatives. 390.352 Section 390.352... Financial derivatives. (a) What is a financial derivative? A financial derivative is a financial contract... common types of financial derivatives are futures, forward commitments, options, and swaps. A...

  14. Sol-gel derived sorbents

    DOEpatents

    Sigman, Michael E.; Dindal, Amy B.

    2003-11-11

    Described is a method for producing copolymerized sol-gel derived sorbent particles for the production of copolymerized sol-gel derived sorbent material. The method for producing copolymerized sol-gel derived sorbent particles comprises adding a basic solution to an aqueous metal alkoxide mixture for a pH.ltoreq.8 to hydrolyze the metal alkoxides. Then, allowing the mixture to react at room temperature for a precalculated period of time for the mixture to undergo an increased in viscosity to obtain a desired pore size and surface area. The copolymerized mixture is then added to an immiscible, nonpolar solvent that has been heated to a sufficient temperature wherein the copolymerized mixture forms a solid upon the addition. The solid is recovered from the mixture, and is ready for use in an active sampling trap or activated for use in a passive sampling trap.

  15. Variational approach and deformed derivatives

    NASA Astrophysics Data System (ADS)

    Weberszpil, J.; Helayël-Neto, J. A.

    2016-05-01

    Recently, we have demonstrated that there exists a possible relationship between q-deformed algebras in two different contexts of Statistical Mechanics, namely, the Tsallis' framework and the Kaniadakis' scenario, with a local form of fractional-derivative operators for fractal media, the so-called Hausdorff derivatives, mapped into a continuous medium with a fractal measure. Here, in this paper, we present an extension of the traditional calculus of variations for systems containing deformed-derivatives embedded into the Lagrangian and the Lagrangian densities for classical and field systems. The results extend the classical Euler-Lagrange equations and the Hamiltonian formalism. The resulting dynamical equations seem to be compatible with those found in the literature, specially with mass-dependent and with nonlinear equations for systems in classical and quantum mechanics. Examples are presented to illustrate applications of the formulation. Also, the conserved ​Noether current is worked out.

  16. Relieving of Misconceptions of Derivative Concept with Derive

    ERIC Educational Resources Information Center

    Kaplan, Abdullah; Ozturk, Mesut; Ocal, Mehmet Fatih

    2015-01-01

    The purpose of this study is to determine students' learning levels in derivative subjects and their misconceptions. In addition, this study aims to compared to the effects of the computer based instruction and traditional instruction in resolving these misconceptions. For this purpose, 12th grade 70 students were chosen from high schools in Agri…

  17. Relieving of Misconceptions of Derivative Concept with Derive

    ERIC Educational Resources Information Center

    Kaplan, Abdullah; Ozturk, Mesut; Ocal, Mehmet Fatih

    2015-01-01

    The purpose of this study is to determine students' learning levels in derivative subjects and their misconceptions. In addition, this study aims to compared to the effects of the computer based instruction and traditional instruction in resolving these misconceptions. For this purpose, 70 12th grade students were chosen from high schools in Agri…

  18. Magnetic cellulose-derivative structures

    DOEpatents

    Walsh, Myles A.; Morris, Robert S.

    1986-09-16

    Structures to serve as selective magnetic sorbents are formed by dissolving a cellulose derivative such as cellulose triacetate in a solvent containing magnetic particles. The resulting solution is sprayed as a fine mist into a chamber containing a liquid coagulant such as n-hexane in which the cellulose derivative is insoluble but in which the coagulant is soluble or miscible. On contact with the coagulant, the mist forms free-flowing porous magnetic microspheric structures. These structures act as containers for the ion-selective or organic-selective sorption agent of choice. Some sorbtion agents can be incorporated during the manufacture of the structure.

  19. Empirically derived injury prevention rules.

    PubMed Central

    Peterson, L; Schick, B

    1993-01-01

    This study describes a set of empirically derived safety rules that if followed, would have prevented the occurrence of minor injuries. Epidemiologists have criticized behavioral interventions as increasing "safe" behavior but failing to demonstrate a decrease in injury. The present study documents retrospectively the link between safe behavior and injury. It demonstrates that these empirically derived rules are very similar to rules for the prevention of serious injury. The study also shows that these rules are not widely accepted and implemented by parents. Suggestions for future research in this area are advanced. PMID:8307829

  20. Characterization of Soluble Anthradithiophene Derivatives

    NASA Astrophysics Data System (ADS)

    Conrad, Brad; Chan, Calvin; Loth, Marsha; Anthony, John; Gundlach, David

    2010-03-01

    We will discuss the growth and electrical measurements of a newly developed, partially fluorinated anthradithiophene (F-ADT) derivative with tert-butyldiphenylsilyl (TBDMS) side groups. Single crystals of the material can be readily grown and device hole mobility is shown to exceed 0.05 cm^2/Vs with on/off ratios of 10^7. F- TBDMS ADT is also observed to be readily soluble with films spun cast onto surface treated SiO2 displaying a mobility >0.002 cm^2/Vs. These electrical measurements will be correlated with growth, morphology, and the performance of related F-ADT derivatives.

  1. Synthesis of 2-phosphaadamantane derivatives

    SciTech Connect

    Zemlyanoi, V.N.; Aleksandrov, A.M.; Kukhar', V.P.

    1986-05-20

    The authors describe the synthesis and properties of 2-phosphadamantane derivatives. For the synthesis of 2-phosphaadamantane derivatives they decided to use the methodology of the synthesis of 2-thiaadamantane. The IR spectra were determined on CHCl/sub 3/ solutions with a Specord 711R spectrometer, the PMR spectra were determined on Tesla BS-467 (60 MHz) and Bruker WP-200 (200 MHz) spectrometers, external standard hexamethyldisiloxane, the /sup 31/P NMR spectra were determined on Tesla BS-487 C (30 MHz) and Bruker WP-200 (81 MHz) spectrometers, external standard 85% phosphoric acid, and the mass spectra were determined on an MS-1302 spectrometer.

  2. Magnetic cellulose-derivative structures

    DOEpatents

    Walsh, M.A.; Morris, R.S.

    1986-09-16

    Structures to serve as selective magnetic sorbents are formed by dissolving a cellulose derivative such as cellulose triacetate in a solvent containing magnetic particles. The resulting solution is sprayed as a fine mist into a chamber containing a liquid coagulant such as n-hexane in which the cellulose derivative is insoluble but in which the coagulant is soluble or miscible. On contact with the coagulant, the mist forms free-flowing porous magnetic microspheric structures. These structures act as containers for the ion-selective or organic-selective sorption agent of choice. Some sorption agents can be incorporated during the manufacture of the structure. 3 figs.

  3. Some Active Derivatives of Penicillin

    PubMed Central

    Brown, Loman D.; Zygmunt, Walter A.; Stavely, Homer E.

    1969-01-01

    The antibacterial activities of a number of amide derivatives of penicillin against both penicillin-sensitive and penicillin-resistant cultures were determined. Several of them were found to possess significant inhibitory activity against certain gram-positive bacteria. The amides, although resistant to the destructive action of β-lactamase, did not protect G in competitive experiments. One derivative, the O-benzylhydroxamide of penicillin G, was active against six or eight penicillin-resistant strains of Staphylococcus aureus (minimal inhibitory concentration, 0.2 μg/ml or less), but was found to have only a minimal in vivo activity against mouse Streptococcus infections. PMID:5780394

  4. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1985-01-01

    Cured polymers of bis and tris-imides derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a monoimide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride prior to curing are disclosed and claimed. Such polymers are flame resistant. Also disclosed are an improved method of producing tris(m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst and fiber reinforced cured resin composites.

  5. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1983-01-01

    Bis- and tris-imides derived from tris (m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride. Such monomers or their oligomes may be used to impregnate fibers and fabrics which when cured, are flame resistant. Also an improved method of producing tris (m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst is described.

  6. Informational derivation of quantum theory

    NASA Astrophysics Data System (ADS)

    Chiribella, Giulio; D'Ariano, Giacomo Mauro; Perinotti, Paolo

    2011-07-01

    We derive quantum theory from purely informational principles. Five elementary axioms—causality, perfect distinguishability, ideal compression, local distinguishability, and pure conditioning—define a broad class of theories of information processing that can be regarded as standard. One postulate—purification—singles out quantum theory within this class.

  7. Derivative couplings in massive bigravity

    NASA Astrophysics Data System (ADS)

    Gao, Xian; Heisenberg, Lavinia

    2016-03-01

    In this work we study the cosmological perturbations in massive bigravity in the presence of non-minimal derivative couplings. For this purpose we consider a specific subclass of Horndeski scalar-tensor interactions that live on the unique composite effective metric. For the viability of the model both metrics have to be dynamical. Nevertheless, the number of allowed kinetic terms is crucial. We adapt to the restriction of having one single kinetic term. After deriving the full set of equations of motion for flat Friedmann-Lemaitre-Robertson-Walker background, we study linear perturbations on top of it. We show explicitly that only four tensor, two vector and two scalar degrees of freedom propagate, one of which being the Horndeski scalar, while the Boulware-Deser ghost can be integrated out.

  8. Derivation of aerodynamic kernel functions

    NASA Technical Reports Server (NTRS)

    Dowell, E. H.; Ventres, C. S.

    1973-01-01

    The method of Fourier transforms is used to determine the kernel function which relates the pressure on a lifting surface to the prescribed downwash within the framework of Dowell's (1971) shear flow model. This model is intended to improve upon the potential flow aerodynamic model by allowing for the aerodynamic boundary layer effects neglected in the potential flow model. For simplicity, incompressible, steady flow is considered. The proposed method is illustrated by deriving known results from potential flow theory.

  9. Position Estimation Using Image Derivative

    NASA Technical Reports Server (NTRS)

    Mortari, Daniele; deDilectis, Francesco; Zanetti, Renato

    2015-01-01

    This paper describes an image processing algorithm to process Moon and/or Earth images. The theory presented is based on the fact that Moon hard edge points are characterized by the highest values of the image derivative. Outliers are eliminated by two sequential filters. Moon center and radius are then estimated by nonlinear least-squares using circular sigmoid functions. The proposed image processing has been applied and validated using real and synthetic Moon images.

  10. 12 CFR 563.172 - Financial derivatives.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 12 Banks and Banking 5 2011-01-01 2011-01-01 false Financial derivatives. 563.172 Section 563.172...-OPERATIONS Financial Management Policies § 563.172 Financial derivatives. (a) What is a financial derivative? A financial derivative is a financial contract whose value depends on the value of one or...

  11. 12 CFR 563.172 - Financial derivatives.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 12 Banks and Banking 6 2013-01-01 2012-01-01 true Financial derivatives. 563.172 Section 563.172...-OPERATIONS Financial Management Policies § 563.172 Financial derivatives. (a) What is a financial derivative? A financial derivative is a financial contract whose value depends on the value of one or...

  12. 12 CFR 163.172 - Financial derivatives.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 12 Banks and Banking 1 2012-01-01 2012-01-01 false Financial derivatives. 163.172 Section 163.172...-OPERATIONS Financial Management Policies § 163.172 Financial derivatives. (a) What is a financial derivative? A financial derivative is a financial contract whose value depends on the value of one or...

  13. 12 CFR 563.172 - Financial derivatives.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 12 Banks and Banking 6 2012-01-01 2012-01-01 false Financial derivatives. 563.172 Section 563.172...-OPERATIONS Financial Management Policies § 563.172 Financial derivatives. (a) What is a financial derivative? A financial derivative is a financial contract whose value depends on the value of one or...

  14. 12 CFR 563.172 - Financial derivatives.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 12 Banks and Banking 6 2014-01-01 2012-01-01 true Financial derivatives. 563.172 Section 563.172...-OPERATIONS Financial Management Policies § 563.172 Financial derivatives. (a) What is a financial derivative? A financial derivative is a financial contract whose value depends on the value of one or...

  15. Stable Hemiaminals: 2-Aminopyrimidine Derivatives.

    PubMed

    Kwiecień, Anna; Ciunik, Zbigniew

    2015-01-01

    Stable hemiaminals can be obtained in the one-pot reaction between 2-aminopyrimidine and nitrobenzaldehyde derivatives. Ten new hemiaminals have been obtained, six of them in crystal state. The molecular stability of these intermediates results from the presence of both electron-withdrawing nitro groups as substituents on the phenyl ring and pyrimidine ring, so no further stabilisation by intramolecular interaction is required. Hemiaminal molecules possess a tetrahedral carbon atom constituting a stereogenic centre. As the result of crystallisation in centrosymmetric space groups both enantiomers are present in the crystal structure. PMID:26258772

  16. Asymptotic vacua with higher derivatives

    NASA Astrophysics Data System (ADS)

    Cotsakis, Spiros; Kadry, Seifedine; Kolionis, Georgios; Tsokaros, Antonios

    2016-04-01

    We study limits of vacuum, isotropic universes in the full, effective, four-dimensional theory with higher derivatives. We show that all flat vacua as well as general curved ones are globally attracted by the standard, square root scaling solution at early times. Open vacua asymptote to horizon-free, Milne states in both directions while closed universes exhibit more complex logarithmic singularities, starting from initial data sets of a possibly smaller dimension. We also discuss the relation of our results to the asymptotic stability of the passage through the singularity in ekpyrotic and cyclic cosmologies.

  17. Binder enhanced refuse derived fuel

    DOEpatents

    Daugherty, Kenneth E.; Venables, Barney J.; Ohlsson, Oscar O.

    1996-01-01

    A refuse derived fuel (RDF) pellet having about 11% or more particulate calcium hydroxide which is utilized in a combustionable mixture. The pellets are used in a particulate fuel bring a mixture of 10% or more, on a heat equivalent basis, of the RDF pellet which contains calcium hydroxide as a binder, with 50% or more, on a heat equivalent basis, of a sulphur containing coal. Combustion of the mixture is effective to produce an effluent gas from the combustion zone having a reduced SO.sub.2 and polycyclic aromatic hydrocarbon content of effluent gas from similar combustion materials not containing the calcium hydroxide.

  18. Iron and iron derived radicals

    SciTech Connect

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fastexclamation Think smallexclamation In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab.

  19. Fourth order spatial derivative gravity

    NASA Astrophysics Data System (ADS)

    Bemfica, F. S.; Gomes, M.

    2011-10-01

    In this work, we study a modified theory of gravity that contains up to fourth order spatial derivatives as a model for the Hořava-Lifshitz gravity. The propagator is evaluated and, as a result, one extra pole is obtained, corresponding to a spin-2 nonrelativistic massless particle, an extra term which jeopardizes renormalizability, besides the unexpected general relativity unmodified propagator. Then unitarity is proved at the tree level, where the general relativity pole has been shown to have no dynamics, remaining only the 2 degrees of freedom of the new pole. Next, the nonrelativistic effective potential is determined from a scattering process of two identical massive gravitationally interacting bosons. In this limit, Newton’s potential is obtained, together with a Darwin-like term that comes from the extra nonpole term in the propagator. Regarding renormalizability, this extra term may be harmful by power counting, but it can be eliminated by adjusting the free parameters of the model. This adjustment is in accord with the detailed balance condition suggested in the literature and shows that the way in which extra spatial derivative terms are added is of fundamental importance.

  20. Fourth order spatial derivative gravity

    SciTech Connect

    Bemfica, F. S.; Gomes, M.

    2011-10-15

    In this work, we study a modified theory of gravity that contains up to fourth order spatial derivatives as a model for the Horava-Lifshitz gravity. The propagator is evaluated and, as a result, one extra pole is obtained, corresponding to a spin-2 nonrelativistic massless particle, an extra term which jeopardizes renormalizability, besides the unexpected general relativity unmodified propagator. Then unitarity is proved at the tree level, where the general relativity pole has been shown to have no dynamics, remaining only the 2 degrees of freedom of the new pole. Next, the nonrelativistic effective potential is determined from a scattering process of two identical massive gravitationally interacting bosons. In this limit, Newton's potential is obtained, together with a Darwin-like term that comes from the extra nonpole term in the propagator. Regarding renormalizability, this extra term may be harmful by power counting, but it can be eliminated by adjusting the free parameters of the model. This adjustment is in accord with the detailed balance condition suggested in the literature and shows that the way in which extra spatial derivative terms are added is of fundamental importance.

  1. Deriving Laws from Ordering Relations

    NASA Technical Reports Server (NTRS)

    Knuth, Kevin H.

    2004-01-01

    The effect of Richard T. Cox's contribution to probability theory was to generalize Boolean implication among logical statements to degrees of implication, which are manipulated using rules derived from consistency with Boolean algebra. These rules are known as the sum rule, the product rule and Bayes Theorem, and the measure resulting from this generalization is probability. In this paper, I will describe how Cox s technique can be further generalized to include other algebras and hence other problems in science and mathematics. The result is a methodology that can be used to generalize an algebra to a calculus by relying on consistency with order theory to derive the laws of the calculus. My goals are to clear up the mysteries as to why the same basic structure found in probability theory appears in other contexts, to better understand the foundations of probability theory, and to extend these ideas to other areas by developing new mathematics and new physics. The relevance of this methodology will be demonstrated using examples from probability theory, number theory, geometry, information theory, and quantum mechanics.

  2. Food-derived immunomodulatory peptides.

    PubMed

    Santiago-López, Lourdes; Hernández-Mendoza, Adrián; Vallejo-Cordoba, Belinda; Mata-Haro, Verónica; González-Córdova, Aarón F

    2016-08-01

    Food proteins contain specific amino acid sequences within their structures that may positively impact bodily functions and have multiple immunomodulatory effects. The functional properties of these specific sequences, also referred to as bioactive peptides, are revealed only after the degradation of native proteins during digestion processes. Currently, milk proteins have been the most explored source of bioactive peptides, which presents an interesting opportunity for the dairy industry. However, plant- and animal-derived proteins have also been shown to be important sources of bioactive peptides. This review summarizes the in vitro and in vivo evidence of the role of various food proteins as sources of immunomodulatory peptides and discusses the possible pathways involving these properties. © 2016 Society of Chemical Industry. PMID:26940008

  3. Derivatives of Black Knight Technology

    NASA Astrophysics Data System (ADS)

    Hill, N.; Wright, D.

    This paper traces the line of descent from Black Knight to Black Arrow, and at the same time looks at various proposed projects, both civil and military, which were to be Black Knight derivatives, but which for one reason or another never saw the light of day. Research in this area is rather akin to anthropological work, tracing fossils from Homo erectus (Black Knight) to Homo sapiens (Black Arrow), knowing that a lot of the fossils found will not be on the direct line of descent, but represent branches that became extinct. This article attempts to cover designs, which, although they never made it to hardware, are none the less interesting technically, or shine light on the evolution of design philosophy.

  4. Derivative Sign Patterns in Two Dimensions

    ERIC Educational Resources Information Center

    Schilling, Kenneth

    2013-01-01

    Given a function defined on a subset of the plane whose partial derivatives never change sign, the signs of the partial derivatives form a two-dimensional pattern. We explore what patterns are possible for various planar domains.

  5. 22 CFR 9.6 - Derivative classification.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... CFR 2001.22. (c) Department of State Classification Guide. The Department of State Classification... Foreign Relations DEPARTMENT OF STATE GENERAL SECURITY INFORMATION REGULATIONS § 9.6 Derivative...'s classified Web site....

  6. 22 CFR 9.6 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... CFR 2001.22. (c) Department of State Classification Guide. The Department of State Classification... Foreign Relations DEPARTMENT OF STATE GENERAL SECURITY INFORMATION REGULATIONS § 9.6 Derivative...'s classified Web site....

  7. 5 CFR 1312.7 - Derivative classification.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ..., DOWNGRADING, DECLASSIFICATION AND SAFEGUARDING OF NATIONAL SECURITY INFORMATION Classification and Declassification of National Security Information § 1312.7 Derivative classification. A derivative classification means that the information is in substance the same information that is currently classified, usually...

  8. 5 CFR 1312.7 - Derivative classification.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ..., DOWNGRADING, DECLASSIFICATION AND SAFEGUARDING OF NATIONAL SECURITY INFORMATION Classification and Declassification of National Security Information § 1312.7 Derivative classification. A derivative classification means that the information is in substance the same information that is currently classified, usually...

  9. 5 CFR 1312.7 - Derivative classification.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ..., DOWNGRADING, DECLASSIFICATION AND SAFEGUARDING OF NATIONAL SECURITY INFORMATION Classification and Declassification of National Security Information § 1312.7 Derivative classification. A derivative classification means that the information is in substance the same information that is currently classified, usually...

  10. 5 CFR 1312.7 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ..., DOWNGRADING, DECLASSIFICATION AND SAFEGUARDING OF NATIONAL SECURITY INFORMATION Classification and Declassification of National Security Information § 1312.7 Derivative classification. A derivative classification means that the information is in substance the same information that is currently classified, usually...

  11. 5 CFR 1312.7 - Derivative classification.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ..., DOWNGRADING, DECLASSIFICATION AND SAFEGUARDING OF NATIONAL SECURITY INFORMATION Classification and Declassification of National Security Information § 1312.7 Derivative classification. A derivative classification means that the information is in substance the same information that is currently classified, usually...

  12. Polymer-Derived Ceramic Fibers

    NASA Astrophysics Data System (ADS)

    Ichikawa, Hiroshi

    2016-07-01

    SiC-based ceramic fibers are derived from polycarbosilane or polymetallocarbosilane precursors and are classified into three groups according to their chemical composition, oxygen content, and C/Si atomic ratio. The first-generation fibers are Si-C-O (Nicalon) fibers and Si-Ti-C-O (Tyranno Lox M) fibers. Both fibers contain more than 10-wt% oxygen owing to oxidation during curing and lead to degradation in strength at temperatures exceeding 1,300°C. The maximum use temperature is 1,100°C. The second-generation fibers are SiC (Hi-Nicalon) fibers and Si-Zr-C-O (Tyranno ZMI) fibers. The oxygen content of these fibers is reduced to less than 1 wt% by electron beam irradiation curing in He. The thermal stability of these fibers is improved (they are stable up to 1,500°C), but their creep resistance is limited to a maximum of 1,150°C because their C/Si atomic ratio results in excess carbon. The third-generation fibers are stoichiometric SiC fibers, i.e., Hi-Nicalon Type S (hereafter Type S), Tyranno SA, and Sylramic™ fibers. They exhibit improved thermal stability and creep resistance up to 1,400°C. Stoichiometric SiC fibers meet many of the requirements for the use of ceramic matrix composites for high-temperature structural application. SiBN3C fibers derived from polyborosilazane also show promise for structural applications, remain in the amorphous state up to 1,800°C, and have good high-temperature creep resistance.

  13. Deriving Laws from Ordering Relations

    NASA Technical Reports Server (NTRS)

    Knuth, Kevin H.

    2003-01-01

    It took much effort in the early days of non-Euclidean geometry to break away from the mindset that all spaces are flat and that two distinct parallel lines do not cross. Up to that point, all that was known was Euclidean geometry, and it was difficult to imagine anything else. We have suffered a similar handicap brought on by the enormous relevance of Boolean algebra to the problems of our age-logic and set theory. Previously, I demonstrated that the algebra of questions is not Boolean, but rather is described by the free distributive algebra. To get to this stage took much effort, as many obstacles-most self-placed-had to be overcome. As Boolean algebras were all I had ever known, it was almost impossible for me to imagine working with an algebra where elements do not have complements. With this realization, it became very clear that the sum and product rules of probability theory at the most basic level had absolutely nothing to do with the Boolean algebra of logical statements. Instead, a measure of degree of inclusion can be invented for many different partially ordered sets, and the sum and product rules fall out of the associativity and distributivity of the algebra. To reinforce this very important idea, this paper will go over how these constructions are made, while focusing on the underlying assumptions. I will derive the sum and product rules for a distributive lattice in general and demonstrate how this leads to probability theory on the Boolean lattice and is related to the calculus of quantum mechanical amplitudes on the partially ordered set of experimental setups. I will also discuss the rules that can be derived from modular lattices and their relevance to the cross-ratio of projective geometry.

  14. Complex order fractional derivatives in viscoelasticity

    NASA Astrophysics Data System (ADS)

    Atanacković, Teodor M.; Konjik, Sanja; Pilipović, Stevan; Zorica, Dušan

    2016-06-01

    We introduce complex order fractional derivatives in models that describe viscoelastic materials. This cannot be carried out unrestrictedly, and therefore we derive, for the first time, real valued compatibility constraints, as well as physical constraints that lead to acceptable models. As a result, we introduce a new form of complex order fractional derivative. Also, we consider a fractional differential equation with complex derivatives, and study its solvability. Results obtained for stress relaxation and creep are illustrated by several numerical examples.

  15. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  16. Bioactive Terpenes from Marine-Derived Fungi

    PubMed Central

    Elissawy, Ahmed M.; El-Shazly, Mohamed; Ebada, Sherif S.; Singab, AbdelNasser B.; Proksch, Peter

    2015-01-01

    Marine-derived fungi continue to be a prolific source of secondary metabolites showing diverse bioactivities. Terpenoids from marine-derived fungi exhibit wide structural diversity including numerous compounds with pronounced biological activities. In this review, we survey the last five years’ reports on terpenoidal metabolites from marine-derived fungi with particular attention on those showing marked biological activities. PMID:25854644

  17. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  18. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  19. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  20. Improved Second Derivative Test for Relative Extrema

    ERIC Educational Resources Information Center

    Wu, Yan

    2007-01-01

    In this note, a modified Second Derivative Test is introduced for the relative extrema of a single variable function. This improved test overcomes the difficulty of the second derivative vanishing at the critical point, while in contrast the traditional test fails for this case. A proof for this improved Second Derivative Test is presented,…

  1. 32 CFR 2001.22 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 32 National Defense 6 2010-07-01 2010-07-01 false Derivative classification. 2001.22 Section 2001... Identification and Markings § 2001.22 Derivative classification. (a) General. Information classified derivatively on the basis of source documents or classification guides shall bear all markings prescribed...

  2. Partial Derivatives of the Lambert Problem

    NASA Technical Reports Server (NTRS)

    Arora, Nitin; Russell, Ryan P.; Strange, Nathan

    2014-01-01

    A procedure for deriving analytic partial derivatives of the Lambert problem is presented. Using the universal, cosine based Lambert formulation; first order partial derivatives of the velocities with respect to the positions and times are developed. Taking advantage of inherent symmetries and intermediate variables, the derivatives are expressed in a computationally efficient form. The added cost of computing these partials is found to be approximately 10% to approximately 60% of the Lambert compute cost. The availability of analytic partial derivatives increases optimization speed, efficiency and allows for trajectory optimization formulations that implicitly enforce continuity constraints via embedded Lambert problems.

  3. Optical gating of perylene bisimide fluorescence using dithienylcyclopentene photochromic switches

    SciTech Connect

    Pärs, Martti; Köhler, Jürgen; Gräf, Katja; Bauer, Peter; Thelakkat, Mukundan

    2013-11-25

    The emission of millions of fluorescence photons from a chromophore is controlled by the absorption of a few tens of photons in a photochromic molecule. The parameters that determine the efficiency of this process are investigated, providing insights for the development of an all-optical gate.

  4. Optical gating of perylene bisimide fluorescence using dithienylcyclopentene photochromic switches

    NASA Astrophysics Data System (ADS)

    Pärs, Martti; Gräf, Katja; Bauer, Peter; Thelakkat, Mukundan; Köhler, Jürgen

    2013-11-01

    The emission of millions of fluorescence photons from a chromophore is controlled by the absorption of a few tens of photons in a photochromic molecule. The parameters that determine the efficiency of this process are investigated, providing insights for the development of an all-optical gate.

  5. Boron-nitrogen substituted perylene obtained through photocyclisation.

    PubMed

    Müller, Matthias; Behnle, Stefan; Maichle-Mössmer, Cäcilia; Bettinger, Holger F

    2014-07-25

    A BN substituted hexabenzotriphenylene (B3N3) closes one C-C-bond upon irradiation with light of 280-400 nm in the presence of iodine to yield a phenanthrene annelated B3N3 tribenzoperylene. Upon hydrolysis a B2N2 dibenzoperylene is obtained. PMID:24905718

  6. Space-Derived Sewer Monitor

    NASA Technical Reports Server (NTRS)

    1982-01-01

    The QuadraScan Longterm Flow Monitoring System is a second generation sewer monitor developed by American Digital Systems, Inc.'s founder Peter Petroff. Petroff, a former spacecraft instrumentation designer at Marshall Space Flight Center, used expertise based on principles acquired in Apollo and other NASA programs. QuadraScan borrows even more heavily from space technology, for example in its data acquisition and memory system derived from NASA satellites. "One-time" measurements are often plagued with substantial errors due to the flow of groundwater absorbed into the system. These system sizing errors stem from a basic informational deficiency: accurate, reliable data on how much water flows through a sewer system over a long period of time is very difficult to obtain. City officials are turning to "permanent," or long-term sewer monitoring systems. QuadraScan offers many advantages to city officials such as the early warning capability to effectively plan for city growth in order to avoid the crippling economic impact of bans on new sewer connections in effect in many cities today.

  7. STS Derived Exploration Launch Operations

    NASA Technical Reports Server (NTRS)

    Best, Joel; Sorge, L.; Siders, J.; Sias, Dave

    2004-01-01

    A key aspect of the new space exploration programs will be the approach to optimize launch operations. A STS Derived Launch Vehicle (SDLV) Program can provide a cost effective, low risk, and logical step to launch all of the elements of the exploration program. Many benefits can be gained by utilizing the synergy of a common launch site as an exploration spaceport as well as evolving the resources of the current Space Shuttle Program (SSP) to meet the challenges of the Vision for Space Exploration. In particular, the launch operation resources of the SSP can be transitioned to the exploration program and combined with the operations efficiencies of unmanned EELVs to obtain the best of both worlds, resulting in lean launch operations for crew and cargo missions of the exploration program. The SDLV Program would then not only capture the extensive human space flight launch operations knowledge, but also provide for the safe fly-out of the SSP through continuity of system critical skills, manufacturing infrastructure, and ability to maintain and attract critical skill personnel. Thus, a SDLV Program can smoothly transition resources from the SSP and meet the transportation needs to continue the voyage of discovery of the space exploration program.

  8. Eburnamine derivatives and the brain.

    PubMed

    Vas, Adám; Gulyás, Balázs

    2005-11-01

    The Apocynaceae plant family contains a great number of so called eburnamine-vincamine alkaloids. Quite a few of these alkaloids exert varied pharmacological activities on the cell multiplication, cardiovascular system, and brain functions. Many derivatives were also synthesized to find pharmacologically active compounds better characterized and safer to be administered than the natural plant alkaloids themselves. We concentrate on the eburnamine structures with cerebral activities in this review. Vincamine, vinburnine, vindeburnol, apovincaminate, and vinpocetine (cis-ethyl-apovincaminate) all share modulatory effects on brain circulation and neuronal homeostasis, bear antihypoxic and neuroprotective potencies to various degrees. The most eminent compound of this class of alkaloids is vinpocetine. Since its introduction to the market as a neuroprotective agent many non clinical and clinical studies proved vinpocetine's effects on calmodulin dependent phosphodiesterase E1, on sodium, calcium channels, peripheral benzodiazepine receptor, and glutamate receptors as well as its clinical usefulness in the treatment of post-ischaemic stroke disease states and various disorders of cerebrovascular origin. Lately, positron emission tomography studies proved that vinpocetine has a rapid uptake in the primate and human brain with a heterogeneous distribution pattern (preference areas: thalamus, basal ganglia, and visual cortex) both after intravenous and oral administration. Vinpocetine exerts beneficial effects in cerebral glucose metabolism and regional cerebral blood flow in chronic post-stroke patients. PMID:16158388

  9. Unconventional fuel: Tire derived fuel

    SciTech Connect

    Hope, M.W.

    1995-09-01

    Material recovery of scrap tires for their fuel value has moved from a pioneering concept in the early 1980`s to a proven and continuous use in the United States` pulp and paper, utility, industrial, and cement industry. Pulp and paper`s use of tire derived fuel (TDF) is currently consuming tires at the rate of 35 million passenger tire equivalents (PTEs) per year. Twenty mills are known to be burning TDF on a continuous basis. The utility industry is currently consuming tires at the rate of 48 million PTEs per year. Thirteen utilities are known to be burning TDF on a continuous basis. The cement industry is currently consuming tires at the rate of 28 million PTEs per year. Twenty two cement plants are known to be burning TDF on a continuous basis. Other industrial boilers are currently consuming tires at the rate of 6.5 million PTEs per year. Four industrial boilers are known to be burning TDF on a continuous basis. In total, 59 facilities are currently burning over 117 million PTEs per year. Although 93% of these facilities were not engineered to burn TDF, it has become clear that TDF has found acceptance as a supplemental fuel when blending with conventional fuels in existing combustion devices designed for normal operating conditions. The issues of TDF as a supplemental fuel and its proper specifications are critical to the successful development of this fuel alternative. This paper will focus primarily on TDF`s use in a boiler type unit.

  10. Acute overdosage with benzodiazepine derivatives.

    PubMed

    Greenblatt, D J; Allen, M D; Noel, B J; Shader, R I

    1977-04-01

    A total of 773 admissions to Massachusetts General Hospital between 1962 and 1975 were due to acute overdosage with one or more psychotropic drugs. Benzodiazepine overdosage, particularly with diazepam, increased relative to other psychotropic drugs over the years. Only 12 admissions were due to benzodiazepine overdosage alone, and none of these patients were seriously ill or had significant complications. Multiple drugs were ingested in the other 87 cases, and the frequency and severity of complications among these individuals depended upon the type and quantity of other nonbenzodiazepines taken. For example, 21 of 31 patients who ingested benzodiazepines together with barbiturates experienced severe central nervous system (CNS) depression, and 14 of 31 required assisted ventilation. However, the frequency of such complications was nearly identical in a group of patients who ingested barbiturates alone. This report and a review of the literature suggest that serious intoxication following overdosage with a benzodiazepine derivative alone is unusual. Ingestion of benzodiazepines together with other drugs appears to be considerably more common than benzodiazepine overdosage alone as a cause of intoxication. The severity of intoxication in such cases of multiple drug ingestion probably depends largely on the type and quantity of nonbenzodiazepines. PMID:14802

  11. Clinical status of benzoporphyrin derivative

    NASA Astrophysics Data System (ADS)

    Levy, Julia G.; Chan, Agnes H.; Strong, H. Andrew

    1996-01-01

    Benzoporphyrin derivative monoacid ring A (BPD) is currently in Phase II clinical trials for the treatment of cutaneous malignancies (basal cell carcinoma and cutaneous metastases) and psoriasis. Results to date suggest that this photosensitizer has potential in both of these areas. Recently, a clinical trial with BPD was initiated for the treatment of age related macular degeneration, a neovascular condition in the eye which leads to blindness. BPD is a lipophilic photosensitizer which is rapidly taken up by activated cells and the vascular endothelium of neovasculature. The PDT effects seen with BPD appear to be a combination of vascular occlusion and direct killing of target cells. Since many diseases involve either activated cells and/or neovasculature, PDT with photosensitizer with characteristics like those of BPD, has applications far wider than oncology. A new area of interest involving photosensitizers is that of immune modulation. A number of photosensitizers have been shown to effect immune modulation in animal models of immune dysfunction including autoimmunity (rheumatoid arthritis, lupus), cutaneous hypersensitivity and allografts. BPD and PHOTOFRINR have both been shown to be effective in ameliorating arthritic symptoms in a number of animal models. The mechanisms by which immune modulation is affected in these studies still remains to be resolved.

  12. Satellite-Derived Management Zones

    NASA Technical Reports Server (NTRS)

    Lepoutre, Damien; Layrol, Laurent

    2005-01-01

    The term "satellite-derived management zones" (SAMZ) denotes agricultural management zones that are subdivisions of large fields and that are derived from images of the fields acquired by instruments aboard Earth-orbiting satellites during approximately the past 15 years. "SAMZ" also denotes the methodology and the software that implements the methodology for creating such zones. The SAMZ approach is one of several products of continuing efforts to realize a concept of precision agriculture, which involves optimal variations in seeding, in application of chemicals, and in irrigation, plus decisions to farm or not to farm certain portions of fields, all in an effort to maximize profitability in view of spatial and temporal variations in the growth and health of crops, and in the chemical and physical conditions of soils. As used here, "management zone" signifies, more precisely, a subdivision of a field within which the crop-production behavior is regarded as homogeneous. From the perspective of precision agriculture, management zones are the smallest subdivisions between which the seeding, application of chemicals, and other management parameters are to be varied. In the SAMZ approach, the main sources of data are the archives of satellite imagery that have been collected over the years for diverse purposes. One of the main advantages afforded by the SAMZ approach is that the data in these archives can be reused for purposes of precision agriculture at low cost. De facto, these archives contain information on all sources of variability within a field, including weather, crop types, crop management, soil types, and water drainage patterns. The SAMZ methodology involves the establishment of a Web-based interface based on an algorithm that generates management zones automatically and quickly from archival satellite image data in response to requests from farmers. A farmer can make a request by either uploading data describing a field boundary to the Web site or else

  13. Longipinane derivatives from Stevia connata.

    PubMed

    Sánchez-Arreola, E; Cerda-García-Rojas, C M; Román, L U; Hernández, J D; Joseph-Nathan, P

    2000-01-01

    The hexane extracts of the roots of Stevia connata afforded three new longipinene derivatives, longipinane-7beta,8alpha, 9alpha-triol-1-one 7-angelate-8-methylbutyrate (1), longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 8,9-diangelate (6), and longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 8-angelate-9-methylbutyrate (8), together with the known longipinane-7beta,8alpha,9alpha-triol-1-one 8,9-diangelate (2), longipinane-7beta,8alpha,9alpha-triol-1-one 7,9-diangelate (3), longipinane-7beta,8alpha,9alpha-triol-1-one 7,8-diangelate (4), longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 7,8-diangelate (5), longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 7-angelate-8-methylbutyrate (12), and stigmasterol. The structures of the new compounds were determined by chemical transformations and spectral methods including 2D NMR measurements. Spontaneous intramolecular transesterifications starting from the 8-angelate-9-methylbutyrate 8 provided an equilibrated mixture of the 7-angelate-9-methylbutyrate 10, the 7-angelate-8-methylbutyrate 12 and the starting material when stored in MeOH-H(2)O solution, while the 8,9-diangelate 6 only provided a binary mixture of the 7, 9-diangelate 7 and the starting material under the same conditions. The structures of 6-8, 10, and 12 and those of the nonisolable reaction intermediates 9, 11, and 14 were further evaluated by AM1 semiempirical calculations. PMID:10650070

  14. Drug laws and the 'derivative' problem.

    PubMed

    King, Leslie A; Ujváry, István; Brandt, Simon D

    2014-01-01

    The concept of a 'derivative' is used widely in chemistry, where its precise meaning depends on the circumstances. However, numerous examples of derivative also occur in domestic drugs legislation, some of which stem from the 1961 United Nations Single Convention on Narcotic Drugs. There is a commonly held view that only 'first-order' derivatives should be considered: substances that can be created from a parent structure in a single chemical reaction. In other words, 'derivatives of derivatives' are excluded. However, some substances related to ecgonine (e.g. 2-carbomethoxytropinone) are clearly convertible to cocaine, even though this may require more than one reaction step. It follows that 2-carbomethoxytropinone is a controlled drug, a situation that most chemists would regard as perverse. A more extreme example of the complexity of 'derivative' is shown by the conversion of thebaine to buprenorphine. Even though this requires six or more stages, the US Drug Enforcement Administration successfully argued in a 1986 case that for the purposes of the Controlled Substances Act, the number of steps required was irrelevant; buprenorphine was a derivative of thebaine. Because the term derivative is rarely defined in statutes, the legal status of some substances, such as 2-bromo-LSD, is uncertain. Although a number of definitions of derivative can be found in the chemical literature, no single definition is adequate to describe all situations where it occurs in legislation. Unless qualified, it is suggested that the term derivative should be avoided in any future legislation. PMID:23949903

  15. Drug Nanoparticle Formulation Using Ascorbic Acid Derivatives

    PubMed Central

    Moribe, Kunikazu; Limwikrant, Waree; Higashi, Kenjirou; Yamamoto, Keiji

    2011-01-01

    Drug nanoparticle formulation using ascorbic acid derivatives and its therapeutic uses have recently been introduced. Hydrophilic ascorbic acid derivatives such as ascorbyl glycoside have been used not only as antioxidants but also as food and pharmaceutical excipients. In addition to drug solubilization, drug nanoparticle formation was observed using ascorbyl glycoside. Hydrophobic ascorbic acid derivatives such as ascorbyl mono- and di-n-alkyl fatty acid derivatives are used either as drugs or carrier components. Ascorbyl n-alkyl fatty acid derivatives have been formulated as antioxidants or anticancer drugs for nanoparticle formulations such as micelles, microemulsions, and liposomes. ASC-P vesicles called aspasomes are submicron-sized particles that can encapsulate hydrophilic drugs. Several transdermal and injectable formulations of ascorbyl n-alkyl fatty acid derivatives were used, including ascorbyl palmitate. PMID:21603195

  16. Transportation Planning with Immune System Derived Approach

    NASA Astrophysics Data System (ADS)

    Sugiyama, Kenji; Yaji, Yasuhito; Ootsuki, John Takuya; Fujimoto, Yasutaka; Sekiguchi, Takashi

    This paper presents an immune system derived approach for planning transportation of materials between manufacturing processes in the factory. Transportation operations are modeled by Petri Net, and divided into submodels. Transportation orders are derived from the firing sequences of those submodels through convergence calculation by the immune system derived excitation and suppression operations. Basic evaluation of this approach is conducted by simulation-based investigation.

  17. Variational Lie derivative and cohomology classes

    NASA Astrophysics Data System (ADS)

    Palese, Marcella; Winterroth, Ekkehart

    2011-07-01

    We relate cohomology defined by a system of local Lagrangian with the cohomology class of the system of local variational Lie derivative, which is in turn a local variational problem; we show that the latter cohomology class is zero, since the variational Lie derivative `trivializes' cohomology classes defined by variational forms. As a consequence, conservation laws associated with symmetries of the second variational derivative of a local variational problem are globally defined.

  18. Anisotropic higher derivative gravity and inflationary universe

    SciTech Connect

    Kao, W. F.

    2006-08-15

    Stability analysis of the Kantowski-Sachs type universe in pure higher derivative gravity theory is studied in detail. The nonredundant generalized Friedmann equation of the system is derived by introducing a reduced one-dimensional generalized Kantowski-Sachs type action. Existence and stability of inflationary solution in the presence of higher derivative terms are also studied in detail. Implications to the choice of physical theories are discussed in detail in this paper.

  19. Generalized gravitational entropy from total derivative action

    NASA Astrophysics Data System (ADS)

    Dong, Xi; Miao, Rong-Xin

    2015-12-01

    We investigate the generalized gravitational entropy from total derivative terms in the gravitational action. Following the method of Lewkowycz and Maldacena, we find that the generalized gravitational entropy from total derivatives vanishes. We compare our results with the work of Astaneh, Patrushev, and Solodukhin. We find that if total derivatives produced nonzero entropy, the holographic and the field-theoretic universal terms of entanglement entropy would not match. Furthermore, the second law of thermodynamics could be violated if the entropy of total derivatives did not vanish.

  20. Mantle derived economic sulfide mineralization?

    NASA Astrophysics Data System (ADS)

    Krivolutskaya, Nadezda; Gongalskiy, Bronislav; Svirskaya, Natalia

    2014-05-01

    Sulfide ores of the unique Pt-Cu-Ni Noril'sk deposits are characterized by heavy sulfur isotopic composition (d34S = 6-18 ‰ ; Grinenko, 1985). These data are traditionally explained by the crustal contamination of the mantle melts by Devonian sedimentary rocks with anhydrites at certain depths or in a chamber of crystallization (Naldrett, 1992; Li et al., 2009). However, data on the distribution of major and trace elements and isotopic composition (their eNd, 87Sr/86Sr, d34S) in the contact zones of the intrusions with the host rocks are at variance with any significant in-situ contamination. Moreover , the mechanism of the "digestion" of this high-temperature material (Tm = 1430ºC) by the lower temperature magma (1250ºC) has never been analyzed and questioned. Our pioneering data on the sulfur radiogenic isotopes in the anhydrite are in conflict with the hypothesis that this mineral could serve as a sulfur source for the Noril'sk ores. The fact that the average composition of the intrusions is independent on the stratigraphic setting of these intrusions, which can be hosted by limestone, sandstone, and/or basalt, provides further support for the idea that no assimilation took place at the depths of the chambers in which the melts crystallized.The reason for the heavy sulfur isotopic composition of ores in the Noril'sk district is still uncertain. Last data obtained on the sulfur isotopic composition of basalts and ores from some intrusions in the Taimyr Peninsula likely provide a clue to this problem. The highest d34S values in rocks of all of the trap formations were detected in the Gudchikhinsky picrites (d34S = +8,7; Ripley et al., 2003) formed from a primitive mantle magma. They are geochemically similar to the rocks from the Dyumtaleysky Massif (d34S = 12.2; Krivolutskaya and Gongalsky, 2013) which crystallized from a primitive mantle-derived magma (with no Ta-Nb and Pb anomalies and high Gd/Yb ratio) too. This intrusion comprises economic important

  1. 17 CFR 200.507 - Declassification dates on derivative documents.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... documents. (a) A document that derives its classification from information classified under Executive Order... derivative document that derives its classification from the approved use of the classification guide...

  2. 17 CFR 200.507 - Declassification dates on derivative documents.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... documents. (a) A document that derives its classification from information classified under Executive Order... derivative document that derives its classification from the approved use of the classification guide...

  3. 17 CFR 200.507 - Declassification dates on derivative documents.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... documents. (a) A document that derives its classification from information classified under Executive Order... derivative document that derives its classification from the approved use of the classification guide...

  4. 5 CFR 2500.5 - Derivative classification.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 5 Administrative Personnel 3 2012-01-01 2012-01-01 false Derivative classification. 2500.5 Section 2500.5 Administrative Personnel OFFICE OF ADMINISTRATION, EXECUTIVE OFFICE OF THE PRESIDENT INFORMATION SECURITY REGULATION § 2500.5 Derivative classification. The Office of Administration serves only as...

  5. 5 CFR 2500.5 - Derivative classification.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 5 Administrative Personnel 3 2011-01-01 2011-01-01 false Derivative classification. 2500.5 Section 2500.5 Administrative Personnel OFFICE OF ADMINISTRATION, EXECUTIVE OFFICE OF THE PRESIDENT INFORMATION SECURITY REGULATION § 2500.5 Derivative classification. The Office of Administration serves only as...

  6. 5 CFR 2500.5 - Derivative classification.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 5 Administrative Personnel 3 2013-01-01 2013-01-01 false Derivative classification. 2500.5 Section 2500.5 Administrative Personnel OFFICE OF ADMINISTRATION, EXECUTIVE OFFICE OF THE PRESIDENT INFORMATION SECURITY REGULATION § 2500.5 Derivative classification. The Office of Administration serves only as...

  7. 5 CFR 2500.5 - Derivative classification.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 5 Administrative Personnel 3 2014-01-01 2014-01-01 false Derivative classification. 2500.5 Section 2500.5 Administrative Personnel OFFICE OF ADMINISTRATION, EXECUTIVE OFFICE OF THE PRESIDENT INFORMATION SECURITY REGULATION § 2500.5 Derivative classification. The Office of Administration serves only as...

  8. Analysis of Blackbody Radiation with Derivative Spectroscopy.

    ERIC Educational Resources Information Center

    Dusek, J.; And Others

    1980-01-01

    Describes an undergraduate experiment which uses derivative spectroscopy to investigate the validity of the Planck function appearing in the blackbody radiation law. These measurements allow a critical examination of this function and also serve as an introduction to derivative spectroscopy techniques. (Author/HM)

  9. Understanding the Derivative through the Calculus Triangle

    ERIC Educational Resources Information Center

    Weber, Eric; Tallman, Michael; Byerley, Cameron; Thompson, Patrick W.

    2012-01-01

    Typical treatments of the derivative do not clearly convey the idea that the derivative function represents the original function's rate of change. Revealing the relationship between a function and its rate-of-change function for static values of "x" does not facilitate productive ways of thinking about generating the rate-of-change function or…

  10. Inflation with non-minimally derivative coupling

    NASA Astrophysics Data System (ADS)

    Yang, Nan; Gao, Qing; Gong, Yungui

    2015-10-01

    We derive the second order correction to the scalar and tensor spectral tilts for the inflationary models with non-minimally derivative coupling. In the high friction limit, the quartic power law potential is consistent with the observational constraint at 95% CL because the amplitude of the primordial gravitational waves is smaller, and the inflaton excursion is sub-Planckian.

  11. Tilt/Integral/Derivative Compensators For Controllers

    NASA Technical Reports Server (NTRS)

    Lurie, Boris J.

    1995-01-01

    Tilt/integral/derivative (TID) compensators for tunable feedback control systems offer advantages over proportional/integral/derivative compensators. Designed and adjusted more easily, and made to reject disturbances more strongly and less sensitive to variations in parameters of controlled system.

  12. 45 CFR 601.5 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 45 Public Welfare 3 2010-10-01 2010-10-01 false Derivative classification. 601.5 Section 601.5 Public Welfare Regulations Relating to Public Welfare (Continued) NATIONAL SCIENCE FOUNDATION..., or who only apply classification markings derived from source material or as directed by...

  13. 12 CFR 403.4 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 12 Banks and Banking 4 2010-01-01 2010-01-01 false Derivative classification. 403.4 Section 403.4 Banks and Banking EXPORT-IMPORT BANK OF THE UNITED STATES CLASSIFICATION, DECLASSIFICATION, AND SAFEGUARDING OF NATIONAL SECURITY INFORMATION § 403.4 Derivative classification. (a) Use of...

  14. 28 CFR 17.26 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., the ISOO implementing directives in 32 CFR 2001.22, and internal Department directions provided by the... 28 Judicial Administration 1 2010-07-01 2010-07-01 false Derivative classification. 17.26 Section... ACCESS TO CLASSIFIED INFORMATION Classified Information § 17.26 Derivative classification. (a)...

  15. 17 CFR 200.506 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 17 Commodity and Securities Exchanges 2 2010-04-01 2010-04-01 false Derivative classification. 200...; CONDUCT AND ETHICS; AND INFORMATION AND REQUESTS Classification and Declassification of National Security Information and Material § 200.506 Derivative classification. Any document that includes...

  16. 12 CFR 563.172 - Financial derivatives.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... Interest Rate Risk, Investment Securities, and Derivatives Activities,” and other applicable agency... chapter), and other applicable agency guidance on implementing a sound risk management program. (e) What..., forward commitments, options, and swaps. A mortgage derivative security, such as a collateralized...

  17. Eulerian derivation of the Coriolis force

    NASA Astrophysics Data System (ADS)

    Kageyama, Akira; Hyodo, Mamoru

    2006-02-01

    In textbooks of geophysical fluid dynamics, the Coriolis force and the centrifugal force in a rotating fluid system are derived by making use of the fluid parcel concept. In contrast to this intuitive derivation to the apparent forces, more rigorous derivation would be useful not only for the pedagogical purpose but also for the applications to other kinds of rotating geophysical systems rather than the fluid. The purpose of this paper is to show a general procedure to derive the transformed equations in the rotating frame of reference based on the local Galilean transformation and rotational coordinate transformation of field quantities. The generality and usefulness of this Eulerian approach is demonstrated in the derivation of apparent forces in rotating fluids as well as the transformed electromagnetic field equation in the rotating system.

  18. Integrating weather derivatives for managing risks

    SciTech Connect

    Bilski, B.

    1999-11-01

    As deregulation and customer choice loom on the horizon, many energy utilities and other energy suppliers are scrambling to find new services that add value for consumers. Many are also seeking opportunities for increasing efficiency to ensure that costs remain competitive. Integrating weather derivatives with marketing programs and financial management can produce attractive new services and increase efficiency. Weather derivatives can be used to create innovative consumer services, such as a guaranteed annual energy bill which is unaffected by weather and energy price changes. They can also be used to protect the earnings of energy suppliers from one of their most significant financial risks, unpredictable weather. There are three basic types of weather derivatives available today. Option or insurance based derivatives (options), swaps or hedge based derivatives (swaps) and packages where other services are combined with one or both of the above.

  19. Stability-Derivative Determination from Flight Data

    NASA Technical Reports Server (NTRS)

    Holowicz, Chester H.; Holleman, Euclid C.

    1958-01-01

    A comprehensive discussion of the various factors affecting the determination of stability and control derivatives from flight data is presented based on the experience of the NASA High-Speed Flight Station. Factors relating to test techniques, determination of mass characteristics, instrumentation, and methods of analysis are discussed. For most longitudinal-stability-derivative analyses simple equations utilizing period and damping have been found to be as satisfactory as more comprehensive methods. The graphical time-vector method has been the basis of lateral-derivative analysis, although simple approximate methods can be useful If applied with caution. Control effectiveness has been generally obtained by relating the peak acceleration to the rapid control input, and consideration must be given to aerodynamic contributions if reasonable accuracy is to be realized.. Because of the many factors involved In the determination of stability derivatives, It is believed that the primary stability and control derivatives are probably accurate to within 10 to 25 percent, depending upon the specific derivative. Static-stability derivatives at low angle of attack show the greatest accuracy.

  20. Risk management, derivatives and shariah compliance

    NASA Astrophysics Data System (ADS)

    Bacha, Obiyathulla Ismath

    2013-04-01

    Despite the impressive growth of Islamic Banking and Finance (IBF), a number of weaknesses remain. The most important of this is perhaps the lack of shariah compliant risk management tools. While the risk sharing philosophy of Islamic Finance requires the acceptance of risk to justify returns, the shariah also requires adherents to avoid unnecessary risk-maysir. The requirement to avoid maysir is in essence a call for the prudent management of risk. Contemporary risk management revolves around financial engineering, the building blocks of which are financial derivatives. Despite the proven efficacy of derivatives in the management of risk in the conventional space, shariah scholars appear to be suspicious and uneasy with their use in IBF. Some have imposed outright prohibition of their use. This paper re-examines the issue of contemporary derivative instruments and shariah compliance. The shariah compatibility of derivatives is shown in a number of ways. First, by way of qualitative evaluation of whether derivatives can be made to comply with the key prohibitions of the sharia. Second, by way of comparing the payoff profiles of derivatives with risk sharing finance and Bai Salam contracts. Finally, the equivalence between shariah compliant derivatives like the IPRS and Islamic FX Currency Forwards with conventional ones is presented.

  1. ADIFOR: Fortran source translation for efficient derivatives

    SciTech Connect

    Bischof, C.; Corliss, G.; Griewank, A.; Hovland, P. ); Carle, A. . Center for Research on Parallel Computation)

    1992-01-01

    The numerical methods employed in the solution of many scientific computing problems require the computation of derivatives of a function f: R{sup n} {yields} R{sup m}. Both the accuracy and the computational requirements of the derivative computation are usually of critical importance for the robustness and speed of the numerical method. ADIFOR (Automatic Differentiation In FORtran) is a source translation tool implemented using the data abstractions and program analysis capabilities of the ParaScope Parallel Programming Environment. ADIFOR accepts arbitrary Fortran-77 code defining the computation of a function and writes portable Fortran-77 code for the computation of its derivatives. In contrast to previous approaches, ADIFOR views automatic differentiation as a process of source translation that exploits computational context to reduce the cost of derivative computations. Experimental results show that ADIFOR can handle real-life codes, providing exact derivatives with a running time that is competitive with the standard divided-difference approximations of derivatives and which may perform orders of magnitude faster than divided-differences in cases. The computational scientist using ADIFOR is freed from worrying about the accurate and efficient computation of derivatives, even for complicated functions,'' and hence, is able to concentrate on the more important issues of algorithm design or system modeling. 35 refs.

  2. [Mechanism of Platinum Derivatives Induced Kidney Injury].

    PubMed

    Yan, Feifei; Duan, Jianchun; Wang, Jie

    2015-09-20

    Platinum derivatives are the most widely used chemotherapeutic agents to treat solid tumors including ovarian, head and neck, and testicular germ cell tumors, lung cancer, and colorectal cancer. Two major problems exist, however, in the clinic use of platinum derivatives. One is the development of tumor resistance to the drug during therapy, leading to treatment failure. The other is the drug's toxicity such as the cisplatin's nephrotoxicity, which limits the dose that can be administered. This paper describes the mechanism of platinum derivatives induced kidney injury. PMID:26383983

  3. A new Bisabolane Derivative of Leontopodium andersonii

    PubMed Central

    Schwaiger, Stefan; Hehenberger, Stefanie; Ellmerer, Ernst P.; Stuppner, Hermann

    2012-01-01

    Phytochemical investigations of the roots of Leontopodium andersonii C. B. Clarke (Asteraceae) resulted in the isolation of a new bisabolane sesquiterpene derivative. The structure of the highly substituted derivative (1R*, 5S*, 6S*)-5-(acetyloxy)-6-[3-(acetyloxy)-1,5-dimethylhex-4-enyl]-3-methylcyclohex-2-en-4-on-1-yl (2Z)-2-methyl-but-2-enoate was established by 1- and 2-D-NMR spectroscopy and is the first report of a bisabolone derivative of the genus Leontopodium. PMID:20521527

  4. Four new bibenzyl derivatives from Dendrobium candidum.

    PubMed

    Li, Yan; Wang, Chun-Lan; Wang, Ya-Jun; Wang, Fang-Fei; Guo, Shun-Xing; Yang, Jun-Shan; Xiao, Pei-Gen

    2009-09-01

    Four new bibenzyl derivatives, namely, dendrocandins F-I (1-4), were isolated from the stems of Dendrobium candidum. Their structures were elucidated by the analysis of spectroscopic data. Dendrocandins F and G represent the fourth and fifth example of bisbibenzyl derivates with a dibenzopyran ring between two units, respectively. Dendrocandin H represents the first example of a bibenzyl derivative formed by a bibenzyl and a 1,4-phenanthraquinone unit via a dibenzopyran ring. Compounds 1-4 were examined for antioxidant activity by 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging assay. PMID:19721264

  5. Theory of Financial Risk and Derivative Pricing

    NASA Astrophysics Data System (ADS)

    Bouchaud, Jean-Philippe; Potters, Marc

    2004-02-01

    Summarizing market data developments, some inspired by statistical physics, this book explains how to better predict the actual behavior of financial markets with respect to asset allocation, derivative pricing and hedging, and risk control. Risk control and derivative pricing are major concerns to financial institutions. The need for adequate statistical tools to measure and anticipate amplitude of potential moves of financial markets is clearly expressed, in particular for derivative markets. Classical theories, however, are based on assumptions leading to systematic (sometimes dramatic) underestimation of risks. First edition Hb (2000): 0-521-78232-5

  6. The Theory of Quaternion Matrix Derivatives

    NASA Astrophysics Data System (ADS)

    Xu, Dongpo; Mandic, Danilo P.

    2015-03-01

    A systematic theory is introduced for calculating the derivatives of quaternion matrix function with respect to quaternion matrix variables. The proposed methodology is equipped with the matrix product rule and chain rule and it is able to handle both analytic and nonanalytic functions. This corrects a flaw in the existing methods, that is, the incorrect use of the traditional product rule. In the framework introduced, the derivatives of quaternion matrix functions can be calculated directly without the differential of this function. Key results are summarized in tables. Several examples show how the quaternion matrix derivatives can be used as an important tool for solving problems related to signal processing.

  7. Synthesis of new polysialic acid derivatives.

    PubMed

    Su, Yi; Kasper, Cornelia; Kirschning, Andreas; Dräger, Gerald; Berski, Silke

    2010-09-01

    In this paper we report the first synthesis of novel polysialic acid derivatives which is initiated by treatment of polysialic acid with EDC-HCl to yield the inter-residual delta-lactone. Subsequent reaction with amines or hydrazine gives the corresponding polysialic acid amides and hydrazide. Alkylation of the tetrabutylammonium salt of polysialic acid yields polysialic acid esters. In contrast a variety of N-derivatives of polysialic acid can be prepared starting from deacetylated polysialic acid. The N-derivatives prepared in this communication can be used for the Cu-catalyzed as well as Cu-free "click" chemistry. PMID:20602419

  8. Derivation of GFDM Based on OFDM Principles

    SciTech Connect

    Hussein Moradi; Behrouz Farhang-Boroujeny

    2015-06-01

    This paper starts with discussing the principle based on which the celebrated orthogonal frequency division multiplexing (OFDM) signals are constructed. It then extends the same principle to construct the newly introduced generalized frequency division multiplexing (GFDM) signals. This novel derivation sheds light on some interesting properties of GFDM. In particular, our derivation seamlessly leads to an implementation of GFDM transmitter which has significantly lower complexity than what has been reported so far. Our derivation also facilitates a trivial understanding of how GFDM (similar to OFDM) can be applied in MIMO channels.

  9. Supramolecular Packing Controls H2 Photocatalysis in Chromophore Amphiphile Hydrogels

    PubMed Central

    2015-01-01

    Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap. PMID:26593389

  10. Supramolecular Packing Controls H₂ Photocatalysis in Chromophore Amphiphile Hydrogels.

    PubMed

    Weingarten, Adam S; Kazantsev, Roman V; Palmer, Liam C; Fairfield, Daniel J; Koltonow, Andrew R; Stupp, Samuel I

    2015-12-01

    Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap. PMID:26593389

  11. A naphthoquinone derivative from Tectona grandis (Linn.).

    PubMed

    Gupta, Pradeep K; Singh, Pahup

    2004-09-01

    A new naphthoquinone derivative has been isolated, along with a number of prenylnaphthoquinone congeners, from the heartwood of Tectona grandis (Linn.). It was characterized as dehydro-alpha-isodunnione (1) by careful analysis of its spectral data. PMID:15224424

  12. MANGROVE-DERIVED NUTRIENTS AND CORAL REEFS

    EPA Science Inventory

    Understanding the consequences of the declining global cover of mangroves due to anthropogenic disturbance necessitates consideration of how mangrove-derived nutrients contribute to threatened coral reef systems. We sampled potential sources of organic matter and a suite of sessi...

  13. 45 CFR 601.5 - Derivative classification.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... Public Welfare Regulations Relating to Public Welfare (Continued) NATIONAL SCIENCE FOUNDATION... information that is already classified, and marking the newly developed material consistent with the marking..., or who only apply classification markings derived from source material or as directed by...

  14. 45 CFR 601.5 - Derivative classification.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... Public Welfare Regulations Relating to Public Welfare (Continued) NATIONAL SCIENCE FOUNDATION... information that is already classified, and marking the newly developed material consistent with the marking..., or who only apply classification markings derived from source material or as directed by...

  15. 45 CFR 601.5 - Derivative classification.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... Public Welfare Regulations Relating to Public Welfare (Continued) NATIONAL SCIENCE FOUNDATION... information that is already classified, and marking the newly developed material consistent with the marking..., or who only apply classification markings derived from source material or as directed by...

  16. 45 CFR 601.5 - Derivative classification.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... Public Welfare Regulations Relating to Public Welfare (Continued) NATIONAL SCIENCE FOUNDATION... information that is already classified, and marking the newly developed material consistent with the marking..., or who only apply classification markings derived from source material or as directed by...

  17. Patient-Derived Antibody Targets Tumor Cells

    Cancer.gov

    An NCI Cancer Currents blog on an antibody derived from patients that killed tumor cells in cell lines of several cancer types and slowed tumor growth in mouse models of brain and lung cancer without evidence of side effects.

  18. Casimir Energy Associated With Fractional Derivative Field

    SciTech Connect

    Lim, S. C.

    2007-04-28

    Casimir energy associated with fractional derivative scalar massless field at zero and positive temperature can be obtained using the regularization based on generalized Riemann zeta function of Epstein-Hurwitz type.

  19. Sums and Differences vs. Integrals and Derivatives.

    ERIC Educational Resources Information Center

    Strang, Gilbert

    1990-01-01

    Offers an approach to the understanding and to the teaching of the fundamental theorem of calculus. Stresses teaching the relation between a function and its derivative and the functions themselves. (YP)

  20. SCM Forcing Data Derived from NWP Analyses

    DOE Data Explorer

    Jakob, Christian

    2008-01-15

    Forcing data, suitable for use with single column models (SCMs) and cloud resolving models (CRMs), have been derived from NWP analyses for the ARM (Atmospheric Radiation Measurement) Tropical Western Pacific (TWP) sites of Manus Island and Nauru.

  1. Perspectives on Biologically Active Camptothecin Derivatives

    PubMed Central

    Liu, Ying-Qian; Li, Wen-Qun; Morris-Natschke, Susan L.; Qian, Keduo; Yang, Liu; Zhu, Gao-Xiang; Wu, Xiao-Bing; Chen, An-Liang; Zhang, Shao-Yong; Song, Zi-Long; Lee, Kuo-Hsiung

    2015-01-01

    Camptothecins (CPTs) are cytotoxic natural alkaloids that specifically target DNA topoisomerase I. Research on CPTs has undergone a significant evolution from the initial discovery of CPT in the late 1960s through the study of synthetic small molecule derivatives to investigation of macromolecular constructs and formulations. Over the past years, intensive medicinal chemistry efforts have generated numerous CPT derivatives. Three derivatives, topotecan, irinotecan, and belotecan, are currently prescribed as anticancer drugs, and several related compounds are now in clinical trials. Interest in other biological effects, besides anticancer activity, of CPTs is also growing exponentially, as indicated by the large number of publications on the subject during the last decades. Therefore, the main focus of the present review is to provide an ample but condensed overview on various biological activities of CPT derivatives, in addition to continued up-to-date coverage of anticancer effects. PMID:25808858

  2. Derivatives of the Stochastic Growth Rate

    PubMed Central

    Steinsaltz, David; Tuljapurkar, Shripad; Horvitz, Carol

    2011-01-01

    We consider stochastic matrix models for population driven by random environments which form a Markov chain. The top Lyapunov exponent a, which describes the long-term growth rate, depends smoothly on the demographic parameters (represented as matrix entries) and on the parameters that define the stochastic matrix of the driving Markov chain. The derivatives of a — the “stochastic elasticities” — with respect to changes in the demographic parameters were derived by Tuljapurkar (1990). These results are here extended to a formula for the derivatives with respect to changes in the Markov chain driving the environments. We supplement these formulas with rigorous bounds on computational estimation errors, and with rigorous derivations of both the new and the old formulas. PMID:21463645

  3. 28 CFR 17.26 - Derivative classification.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., the ISOO implementing directives in 32 CFR 2001.22, and internal Department directions provided by the... need not possess original classification authority to derivatively classify information based on...

  4. Entanglement entropy in higher derivative holography

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Arpan; Kaviraj, Apratim; Sinha, Aninda

    2013-08-01

    We consider holographic entanglement entropy in higher derivative gravity theories. Recently Lewkowycz and Maldacena [1] have provided a method to derive the equations for the entangling surface from first principles. We use this method to compute the entangling surface in four derivative gravity. Certain interesting differences compared to the two derivative case are pointed out. For Gauss-Bonnet gravity, we show that in the regime where this method is applicable, the resulting equations coincide with proposals in the literature as well as with what follows from considerations of the stress tensor on the entangling surface. Finally we demonstrate that the area functional in Gauss-Bonnet holography arises as a counterterm needed to make the Euclidean action free of power law divergences.

  5. Polyimides Derived from Novel Asymmetric Benzophenone Dianhydrides

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2015-01-01

    This invention relates to the composition and processes for preparing thermoset polyimides derived from an asymmetric dianhydride, namely 2,3,3',4'-benzophenone dianhydride (a-BTDA) with at least one diamine, and a monofunctional terminal endcaps. The monofunctional terminating groups include 4-phenylethynylphthalic anhydride ester-acid derivatives, phenylethyl trimellitic anhydride (PETA) and its ester derivatives as well as 3-phenylethynylaniline. The process of polyimide composite comprises impregnating monomer reactants of dianhydride or its ester-acid derivatives, diamine and with monofunctional reactive endcaps into glass, carbon, quartz or synthetic fibers and fabrics, and then stack up into laminates and subsequently heated to between 150-375.degree. C. either at atmosphere or under pressure to promote the curing and crosslinking of the reactive endcaps to form a network of thermoset polyimides.

  6. Frequency analysis of photoplethysmogram and its derivatives.

    PubMed

    Elgendi, Mohamed; Fletcher, Richard R; Norton, Ian; Brearley, Matt; Abbott, Derek; Lovell, Nigel H; Schuurmans, Dale

    2015-12-01

    There are a limited number of studies on heat stress dynamics during exercise using the photoplethysmogram (PPG). We investigate the PPG signal and its derivatives for heat stress assessment using Welch (non-parametric) and autoregressive (parametric) spectral estimation methods. The preliminary results of this study indicate that applying the first and second derivatives to PPG waveforms is useful for determining heat stress level using 20-s recordings. Interestingly, Welch's and Yule-Walker's methods in agreement that the second derivative is an improved detector for heat stress. In fact, both spectral estimation methods showed a clear separation in the frequency domain between measurements before and after simulated heat-stress induction when the second derivative is applied. Moreover, the results demonstrate superior performance of the Welch's method over the Yule-Walker's method in separating before and after the three simulated heat-stress inductions. PMID:26498064

  7. Drilling fluid containing crosslinked polysaccharide derivative

    SciTech Connect

    Demott, D.N.; Kucera, C.H.

    1981-03-24

    A drilling fluid having extremely desirable physical properties which comprises an aqueous solution of a hydroxyalkyl polysaccharide derivative and a water soluble ionic aluminum crosslinking agent, preferably sodium aluminate.

  8. Plant-derived nanostructures: types and applications

    EPA Science Inventory

    Plant-derived nanostructures and nanoparticles (NPs) have functional applications in numerous disciplines such as health care, food and feed, cosmetics, biomedical science, energy science, drug-gene delivery, environmental health, and so on. Consequently, it is imperative for res...

  9. Analysis and the Derivation of Valid Objectives

    ERIC Educational Resources Information Center

    Tiemann, Philip W.

    1973-01-01

    Author states that "to the extent that behavioral objectives are derived from an analysis of relatively broad objectives, they can serve as valid criteria which enable our students to avoid trivia." (Author)

  10. Catalytic combustion of coal-derived liquids

    NASA Technical Reports Server (NTRS)

    Bulzan, D. L.; Tacina, R. R.

    1981-01-01

    A noble metal catalytic reactor was tested with three grades of SRC 2 coal derived liquids, naphtha, middle distillate, and a blend of three parts middle distillate to one part heavy distillate. A petroleum derived number 2 diesel fuel was also tested to provide a direct comparison. The catalytic reactor was tested at inlet temperatures from 600 to 800 K, reference velocities from 10 to 20 m/s, lean fuel air ratios, and a pressure of 3 x 10 to the 5th power Pa. Compared to the diesel, the naphtha gave slightly better combustion efficiency, the middle distillate was almost identical, and the middle heavy blend was slightly poorer. The coal derived liquid fuels contained from 0.58 to 0.95 percent nitrogen by weight. Conversion of fuel nitrogen to NOx was approximately 75 percent for all three grades of the coal derived liquids.

  11. Computer derivation of some dolphin echolocation signals.

    PubMed

    Altes, R A

    1971-09-01

    Recent advances in radar theory have given rise to a straightforward method of sonar signal design. The method involves computer maximization of a signal-to-interference ratio. The procedure has been used to derive sonar signals that can accurately measure target velocity. When two dolphins were placed in a situation conducive to the utilization of such signals, their waveforms were similar to those that had been theoretically derived. PMID:17751313

  12. On computing Laplace's coefficients and their derivatives.

    NASA Astrophysics Data System (ADS)

    Gerasimov, I. A.; Vinnikov, E. L.

    The algorithm of computing Laplace's coefficients and their derivatives is proposed with application of recurrent relations. The A.G.M.-method is used for the calculation of values L0(0), L0(1). The FORTRAN-program corresponding to the algorithm is given. The precision control was provided with numerical integrating by Simpsons method. The behavior of Laplace's coefficients and their third derivatives whith varying indices K, n for fixed values of the α-parameter is presented graphically.

  13. Analytical second derivatives for effective core potentials

    NASA Astrophysics Data System (ADS)

    Breidung, Jürgen; Thiel, Walter; Komornicki, Andrew

    1988-12-01

    Analytical first and second derivatives for effective core potentials are reported. The computational implementation of the derivative formulas makes use of new integral routines which take advantage of the shell concept. Test calculations for H 3SnBr and F 3AsS demonstrate the efficiency of the analytical determination of harmonic force fields using effective core potentials. The spectroscopic constants of the unknown molecule F 3AsS are predicted.

  14. Crystal structure of (2,11-di­aza­[3.3](2,6)pyridino­phane-κ 4 N,N′,N′′,N′′′)(1,6,7,12-tetra­aza­perylene-κ 2 N 1,N 12)ruthenium(II) bis­(hexa­fluorido­phosphate) aceto­nitrile 1.422-solvate

    PubMed Central

    Brietzke, Thomas; Rottke, Falko Otto; Kelling, Alexandra; Schilde, Uwe; Holdt, Hans-Jürgen

    2014-01-01

    In the title compound, [Ru(C14H16N4)(C16H8N4)](PF6)2·1.422CH3CN, discrete dimers of complex cations, [Ru(L–N4H2)tape]2+ are formed {L–N4H2 = 2,11-di­aza­[3.3](2,6)pyridino­phane; tape = 1,6,7,12-tetra­aza­perylene}, held together by π–π stacking inter­actions via the tape ligand moieties with a centroid–centroid distance of 3.49 (2) Å, assisted by hydrogen bonds between the non-coordinating tape ligand α,α′-di­imine unit and the amine proton of a 2,11-di­aza­[3.3](2,6)-pyridino­phane ligand of the opposite complex cation. The combination of these inter­actions leads to an unusual nearly face-to-face π–π stacking mode. Additional weak C—H⋯N, C—H⋯F, N—H⋯F and P—F⋯π-ring (tape, py) (with F⋯centroid distances of 2.925–3.984 Å) inter­actions are found, leading to a three-dimensional architecture. The RuII atom is coordinated in a distorted octa­hedral geometry, particularly manifested by the Namine—Ru—Namine angle of 153.79 (10)°. The counter-charge is provided by two hexa­fluorido­phosphate anions and the asymmetric unit is completed by aceto­nitrile solvent mol­ecules of crystallization. Disorder was observed for both the hexa­fluorido­phosphate anions as well as the aceto­nitrile solvate mol­ecules, with occupancies for the major moieties of 0.801 (6) for one of the PF6 anions, and a shared occupancy of 0.9215 (17) for the second PF6 anion and a partially occupied aceto­nitrile mol­ecule. A second CH3CN mol­ecule is fully occupied, but 1:1 disordered across a crystallographic inversion center. PMID:25484670

  15. Analytic computation of energy derivatives - Relationships among partial derivatives of a variationally determined function

    NASA Technical Reports Server (NTRS)

    King, H. F.; Komornicki, A.

    1986-01-01

    Formulas are presented relating Taylor series expansion coefficients of three functions of several variables, the energy of the trial wave function (W), the energy computed using the optimized variational wave function (E), and the response function (lambda), under certain conditions. Partial derivatives of lambda are obtained through solution of a recursive system of linear equations, and solution through order n yields derivatives of E through order 2n + 1, extending Puley's application of Wigner's 2n + 1 rule to partial derivatives in couple perturbation theory. An examination of numerical accuracy shows that the usual two-term second derivative formula is less stable than an alternative four-term formula, and that previous claims that energy derivatives are stationary properties of the wave function are fallacious. The results have application to quantum theoretical methods for the computation of derivative properties such as infrared frequencies and intensities.

  16. New steroid derivative with hypoglycemic activity

    PubMed Central

    Lauro, Figueroa-Valverde; Francisco, Díaz-Cedillo; Lenin, Hau-Heredia; Elodia, García-Cervera; Eduardo, Pool-Gómez; Marcela, Rosas-Nexticapa; Bety, Sarabia-Alcocer

    2014-01-01

    Data indicates that some steroid derivatives may induce changes on glucose levels; nevertheless, data are very confusing. Therefore, more pharmacological data are needed to characterize the activity induced by the steroid derivatives on glucose levels. The aim of this study was to synthesize a new steroid derivative for evaluate its hypoglycemic activity. The effects of steroid derivative on glucose concentration were evaluated in a diabetic animal model using glibenclamide and metformin as controls. In addition, the pregnenolone-dihydrotestosterone conjugate was bound to Tc-99m using radioimmunoassay methods, to evaluate the pharmacokinetics of the steroid derivative over time. The results showed that the pregnenolone-dihydrotestosterone conjugate induces changes on the glucose levels in similar form than glibenclamide. Other data showed that the biodistribution of Tc-99m-steroid derivativein brain was higher in comparison with spleen, stomach, intestine liver and kidney. In conclusion, the pregnenolone-dihydrotestosterone conjugate exerts hypoglycemic activity and this phenomenon could depend of its physicochemical properties which could be related to the degree of lipophilicity of the steroidderivative. PMID:25550906

  17. Microscopically derived free energy of dislocations

    NASA Astrophysics Data System (ADS)

    Kooiman, M.; Hütter, M.; Geers, M. G. D.

    2015-05-01

    The dynamics of large amounts of dislocations is the governing mechanism in metal plasticity. The free energy of a continuous dislocation density profile plays a crucial role in the description of the dynamics of dislocations, as free energy derivatives act as the driving forces of dislocation dynamics. In this contribution, an explicit expression for the free energy of straight and parallel dislocations with different Burgers vectors is derived. The free energy is determined using systematic coarse-graining techniques from statistical mechanics. The starting point of the derivation is the grand-canonical partition function derived in an earlier work, in which we accounted for the finite system size, discrete glide planes and multiple slip systems. In this paper, the explicit free energy functional of the dislocation density is calculated and has, to the best of our knowledge, not been derived before in the present form. The free energy consists of a mean-field elastic contribution and a local defect energy, that can be split into a statistical and a many-body contribution. These depend on the density of positive and negative dislocations on each slip system separately, instead of GND-based quantities only. Consequently, a crystal plasticity model based on the here obtained free energy, should account for both statistically stored and geometrically necessary dislocations.

  18. Derivative expansion of the effective action

    SciTech Connect

    Cheyette, O.

    1987-04-01

    This paper describes some methods for calculating derivative terms in the one loop effective action for a quantum field theory. The functional approach and background field method are first used to derive the general form of the one loop determinant. Then the determinant is expanded in powers of derivatives of the background fields. The form of this expansion is described for the simple case of an interacting scalar field, and then for the more complicated problem of a non-abelian gauge field. Finally, the expansion is applied to the task of calculating Higgs mass dependent effects in the Glashow-Weinberg-Salam model, and all terms which grow with the Higgs mass M/sub H/ are found in the one loop approximation. The result of this calculation is used to find the dependence of the gauge boson mass ratio rho on M/sub H/, and also to estimate the size of corrections to W and Z scattering theorems.

  19. Understanding, Deriving, and Computing Buffer Capacity

    NASA Astrophysics Data System (ADS)

    Urbansky, Edward T.; Schock, Michael R.

    2000-12-01

    The concept of buffer capacity appears in varied disciplines, including bio-, geo-, analytical, and environmental chemistry, physiology, medicine, dentistry, and agriculture. Unfortunately, however, derivation and systematic calculation of buffer capacity is a topic that seems to be neglected in the undergraduate analytical chemistry curriculum. In this work, we give an account of the development of the buffer capacity concept and derive the buffer capacity contribution equations for buffer systems containing mono-, di-, and triprotic weak acids (and their conjugate bases) and aluminum(III), which undergoes hydrolysis. A brief review of pH is provided because pH is involved in applying buffer capacity to the real world. In addition, we discuss evaluation of the equations, numerical approximation of buffer capacity when an analytic solution is not derived, and the mathematical properties of the buffer capacity expressions.

  20. Real-time cosmography with redshift derivatives

    NASA Astrophysics Data System (ADS)

    Martins, C. J. A. P.; Martinelli, M.; Calabrese, E.; Ramos, M. P. L. P.

    2016-08-01

    The drift in the redshift of objects passively following the cosmological expansion has long been recognized as a key model-independent probe of cosmology. Here, we study the cosmological relevance of measurements of time or redshift derivatives of this drift, arguing that the combination of first and second redshift derivatives is a powerful test of the Λ CDM cosmological model. In particular, the latter can be obtained numerically from a set of measurements of the drift at different redshifts. We show that, in the low-redshift limit, a measurement of the derivative of the drift can provide a constraint on the jerk parameter, which is j =1 for flat Λ CDM , while generically j ≠1 for other models. We emphasize that such a measurement is well within the reach of the ELT-HIRES and SKA Phase 2 array surveys.

  1. Inequalities for angular derivatives and boundary interpolation

    NASA Astrophysics Data System (ADS)

    Bolotnikov, Vladimir; Elin, Mark; Shoikhet, David

    2013-03-01

    The classical Julia-Wolff-Carathéodory theorem asserts that the angular derivative of a holomorphic self-mapping of the open unit disk (Schur function) at its boundary fixed point is a positive number. Cowen and Pommerenke (J Lond Math Soc 26:271-289, 1982) proved that if a Schur function has several boundary regular fixed (or mutual contact) points, then the angular derivatives at these points are subject to certain inequalities. We develop a unified approach to establish relations between angular derivatives of Schur functions with a prescribed (possibly, infinite) collection of either mutual contact points or boundary fixed points. This approach yields diverse inequalities improving both classical and more recent results. We apply them to study the Nevanlinna-Pick interpolation problem with boundary data. Our methods lead to fairly explicit formulas describing the set of solutions.

  2. Analytics of Quinine and its Derivatives.

    PubMed

    Kluska, Mariusz; Marciniuk-Kluska, Anna; Prukała, Dorota; Prukała, Wiesław

    2016-01-01

    The objective of this study was to perform a synthesis and analysis of the most important information on quinine and its derivatives, which are still very important in the treatment of malaria. The analysis of stereoisomers of quinine and its derivatives was conducted using two techniques, high-performance liquid chromatography and capillary electrophoresis. Particularly noteworthy is the technique used for the determination of isotachophoresis, referred to as one of the so-called green chemistry techniques. Particular attention was paid to properties and the use of quinine and its derivatives in the treatment of malaria. The analytical part will supplement knowledge about quinidine, quinine, and cinchonidine, and will contribute to the growth of research on the so-much-needed drugs against malaria. PMID:25831406

  3. Second derivatives for approximate spin projection methods

    SciTech Connect

    Thompson, Lee M.; Hratchian, Hrant P.

    2015-02-07

    The use of broken-symmetry electronic structure methods is required in order to obtain correct behavior of electronically strained open-shell systems, such as transition states, biradicals, and transition metals. This approach often has issues with spin contamination, which can lead to significant errors in predicted energies, geometries, and properties. Approximate projection schemes are able to correct for spin contamination and can often yield improved results. To fully make use of these methods and to carry out exploration of the potential energy surface, it is desirable to develop an efficient second energy derivative theory. In this paper, we formulate the analytical second derivatives for the Yamaguchi approximate projection scheme, building on recent work that has yielded an efficient implementation of the analytical first derivatives.

  4. Phase retrieval from one partial derivative.

    PubMed

    Matías Di Martino, J; Flores, Jorge L; Pfeiffer, Franz; Scherer, Kai; Ayubi, Gastón A; Ferrari, José A

    2013-11-15

    Phase objects can be characterized using well-known methods such as shear interferometry and deflectometry, which provide information on the partial derivatives of the phase. It is often believed that for phase retrieval it is strictly necessary to have knowledge of two partial derivatives in orthogonal directions. In the praxis, this implies that the measurements have to be performed along two dimensions, which often requires a rotation of the object or rotation of the shear direction. This is time consuming and errors can be easily generated from the process of rotation, especially for image registration in the axial direction. In the present Letter, we will demonstrate that only one partial derivative often suffices to recover the phase, and we will discuss under which conditions that is possible. Simulations and validation experiments are presented. PMID:24322139

  5. Halogenated coumarin derivatives as novel seed protectants.

    PubMed

    Brooker, N; Windorski, J; Bluml, E

    2008-01-01

    Development of new and improved antifungal compounds that are target-specific is backed by a strong Federal, public and commercial mandate. Many plant-derived chemicals have proven fungicidal properties, including the coumarins (1,2-Benzopyrone) found in a variety of plants such as clover, sweet woodruff and grasses. Preliminary research has shown the coumarins to be a highly active group of molecules with a wide range of antimicrobial activity against both fungi and bacteria. It is believed that these cyclic compounds behave as natural pesticidal defence molecules for plants and they represent a starting point for the exploration of new derivative compounds possessing a range of improved antifungal activity. Within this study, derivatives of coumarin that were modified with halogenated side groups were screened for their antifungal activity against a range of soil-borne plant pathogenic fungi. Fungi included in this in vitro screen included Macrophomina phaseolina (charcoal rot), Phytophthora spp. (damping off and seedling rot), Rhizoctonia spp. (damping off and root rot) and Pythium spp. (seedling blight), four phylogenetically diverse and economically important plant pathogens. Studies indicate that these halogenated coumarin derivatives work very effectively in vitro to inhibit fungal growth and some coumarin derivatives have higher antifungal activity and stability as compared to the original coumarin compound alone. The highly active coumarin derivatives are brominated, iodinated and chlorinated compounds and results suggest that besides being highly active, very small amounts can be used to achieve LD100 rates. In addition to the in vitro fungal inhibition assays, results of polymer seed coating compatibility and phytotoxicity testing using these compounds as seed treatments will also be reported. These results support additional research in this area of natural pesticide development. PMID:19226745

  6. Synthesis of Amaryllidaceae Constituents and Unnatural Derivatives.

    PubMed

    Ghavre, Mukund; Froese, Jordan; Pour, Milan; Hudlicky, Tomas

    2016-05-01

    This update covers the syntheses of Amaryllidaceae alkaloids since the publication of the last major review in 2008. A short summary of past syntheses and their step count is provided for the major constituents; pancratistatin, 7-deoxypancratistatin, narciclasine, lycoricidine, lycorine, and for other natural constituents, as well as for unnatural derivatives. Discussion of biological activities is provided for unnatural derivatives. Future prospects and further developments in this area are covered at the end of the review. The literature is covered to the end of August 2015. PMID:26969844

  7. The derivative of a continued fraction

    SciTech Connect

    Bowman, Kimiko o

    2009-01-01

    The paper considers second order continued fractions associated with (I) the Psi function {psi}(z), (II) the continued fraction component in ln {Gamma}(z) due to Stieltjes. The second order sequences k*{sub s}/k{sub s} provide approximants, some of which are remarkably close. In addition a series form for the convergent {chi}{sub s}={omega}{sub s} associated with a continued fraction provides an expression for the derivatives of a continued fraction. The implementation uses a Maple code for derivatives.

  8. Water-soluble derivatives of 1 -tetrahydrocannabinol.

    PubMed

    Zitko, B A; Howes, J F; Razdan, R K; Dalzell, B C; Dalzell, H C; Sheehan, J C; Pars, H G; Dewey, W L; Harris, L S

    1972-08-01

    Delta1-Tetrahydrocannabinol, which is resinous and insoluble in water and therefore difficult to study pharmacologically, can be converted to a watersoluble derivative without loss of its biological activity. This has been achieved by preparing esters bearing a nitrogen moiety with the use of carbodiimide as the condensing agent. The availability of such water-soluble derivatives will allow the evaluation of Delta1-tetrahydrocannabinol in self-administration studies in monkeys for its addiction liability potential in man. This technique of water solubilization is also applicable to other compounds of chemical and biological significance. PMID:5043146

  9. Photoluminescence in anthracene and it's derivatives

    NASA Astrophysics Data System (ADS)

    Vyas, Arpita; Mirgane, Nitin A.; Moharil, S. V.; Muley, Aarti Iyer

    2016-05-01

    The anthracene and it's derivative 9-chloro acridine and Anthracene-9-ylmethylacetate have prepared in Poly vinyl alcohol(PVOH). Their photoluminescence properties have studied. The pure anthracene has an emission at 424 and 443nm. The intense peak is observed at 465nm and shoulder at 407nm. The derivatives of anthracene Anthracene-9-ylmethylacetate shows an emission around 440nm for the excitation at 393nm and 9-chloro acridine shows emission around 360nm for the excitation at 290nm. The major problem of this organic material is the stability. The composites prepared in the medium of PVOH are more stable.

  10. Passerini Reactions on Biocatalytically Derived Chiral Azetidines.

    PubMed

    Moni, Lisa; Banfi, Luca; Basso, Andrea; Bozzano, Andrea; Spallarossa, Martina; Wessjohann, Ludger; Riva, Renata

    2016-01-01

    The purpose of this study was to explore a series of Passerini reactions on a biocatalytically derived enantiopure azetidine-2-carboxyaldehyde in order to obtain, in a diastereoselective manner, polyfunctionalised derivatives having the potential to be cyclized to chiral bridged bicyclic nitrogen heterocycles. While diastereoselectivity was poor under classical Passerini conditions, a significant increase of diastereoselectivity (up to 76:24) was gained by the use of zinc bromide as promoter. The methodology has a broad scope and yields are always good. PMID:27589709

  11. High ethanol producing derivatives of Thermoanaerobacter ethanolicus

    DOEpatents

    Ljungdahl, Lars G.; Carriera, Laura H.

    1983-01-01

    Derivatives of the newly discovered microorganism Thermoanaerobacter ethanolicus which under anaerobic and thermophilic conditions continuously ferment substrates such as starch, cellobiose, glucose, xylose and other sugars to produce recoverable amounts of ethanol solving the problem of fermentations yielding low concentrations of ethanol using the parent strain of the microorganism Thermoanaerobacter ethanolicus are disclosed. These new derivatives are ethanol tolerant up to 10% (v/v) ethanol during fermentation. The process includes the use of an aqueous fermentation medium, containing the substrate at a substrate concentration greater than 1% (w/v).

  12. Hydrogermylation of itaconic and sorbic derivatives

    SciTech Connect

    Gar, T.K.; Viktorov, N.A.; Nosova, V.M.; Kisin, A.V.; Ivashchenko, D.A.; Popkov, M.K.; Mironov, V.F.

    1987-10-10

    We have investigated the reactions of trichlorogermane with itaconic acid and its derivatives and also with derivatives of sorbic acid. It was shown that the acid chlorides and the anhydride of itaconic acid readily undergo addition with the trichlorogermane ether complex. The structures of the compounds obtained were determined by means of /sup 1/H and /sup 13/C NMR spectroscopy with the use of model compounds: 3-butenoyl chloride, methyl 3-butenoate, crotonoyl chloride, methyl crotonate, and products of the addition of trichlorogermane ether complex to the latter.

  13. Special Relativity Derived from Spacetime Magma

    PubMed Central

    Greensite, Fred

    2014-01-01

    We present a derivation of relativistic spacetime largely untethered from specific physical considerations, in constrast to the many physically-based derivations that have appeared in the last few decades. The argument proceeds from the inherent magma (groupoid) existing on the union of spacetime frame components and Euclidean which is consistent with an “inversion symmetry” constraint from which the Minkowski norm results. In this context, the latter is also characterized as one member of a class of “inverse norms” which play major roles with respect to various unital -algebras more generally. PMID:24959889

  14. Quantum mechanics of 4-derivative theories

    NASA Astrophysics Data System (ADS)

    Salvio, Alberto; Strumia, Alessandro

    2016-04-01

    A renormalizable theory of gravity is obtained if the dimension-less 4-derivative kinetic term of the graviton, which classically suffers from negative unbounded energy, admits a sensible quantization. We find that a 4-derivative degree of freedom involves a canonical coordinate with unusual time-inversion parity, and that a correspondingly unusual representation must be employed for the relative quantum operator. The resulting theory has positive energy eigenvalues, normalizable wavefunctions, unitary evolution in a negative-norm configuration space. We present a formalism for quantum mechanics with a generic norm.

  15. Bistacrine derivatives as new potent antimalarials.

    PubMed

    Schmidt, Ines; Pradel, Gabriele; Sologub, Ludmilla; Golzmann, Alexandra; Ngwa, Che J; Kucharski, Anna; Schirmeister, Tanja; Holzgrabe, Ulrike

    2016-08-15

    Linking two tacrine molecules results in a tremendous increase of activity against Plasmodia in comparison to the monomer. This finding prompted the synthesis of a library of monomeric and dimeric tacrine derivatives in order to derive structure-activity relationships. The most active compounds towards chloroquine sensitive Plasmodium strain 3D7 and chloroquine resistant strain Dd2 show IC50 values in the nanomolar range of concentration, low cytotoxicity and target the cysteine protease falcipain-2, which is essential for parasite growth. PMID:27316542

  16. Elevation Derivatives for Mojave Desert Tortoise Habitat

    USGS Publications Warehouse

    Wallace, Cynthia S.A.; Gass, Leila

    2008-01-01

    This report describes the methods used to derive various elevation-derivative grids that were inputted to the Mojave Desert Tortoise Habitat model (L. Gass and others, unpub. data). These grids, which capture information on surface roughness and topographic characteristics, are a subset of the environmental datasets evaluated for the tortoise habitat model. This habitat model is of major importance to the U.S. Fish and Wildlife Service, which is charged with management of this threatened population, including relocating displaced tortoises to areas identified as suitable habitat.

  17. Special relativity derived from spacetime magma.

    PubMed

    Greensite, Fred

    2014-01-01

    We present a derivation of relativistic spacetime largely untethered from specific physical considerations, in constrast to the many physically-based derivations that have appeared in the last few decades. The argument proceeds from the inherent magma (groupoid) existing on the union of spacetime frame components [Formula: see text] and Euclidean [Formula: see text] which is consistent with an "inversion symmetry" constraint from which the Minkowski norm results. In this context, the latter is also characterized as one member of a class of "inverse norms" which play major roles with respect to various unital [Formula: see text]-algebras more generally. PMID:24959889

  18. Structural studies of 4-aminoantipyrine derivatives

    NASA Astrophysics Data System (ADS)

    Cunha, Silvio; Oliveira, Shana M.; Rodrigues, Manoel T.; Bastos, Rodrigo M.; Ferrari, Jailton; de Oliveira, Cecília M. A.; Kato, Lucília; Napolitano, Hamilton B.; Vencato, Ivo; Lariucci, Carlito

    2005-10-01

    Reaction of 4-aminoantipyrine with acetylacetone, ethyl acetoacetate, benzoyl isothiocyanate, phenyl isothiocyanate, maleic anhydride and methoxymethylene Meldrum's acid afforded a series of new antipyrine derivatives. The antibacterial activity of the synthesized compounds against Micrococcus luteus ATCC 9341, Staphilococcus aureus ATCC 29737, and Escherichia coli ATCC 8739 was evaluated and the minimal inhibitory concentration determined. Modest activity was found only to the maleamic acid obtained from the reaction of 4-aminoantipyrine and maleic anhydride. 1H NMR investigation of this maleamic acid showed that it is slowly converted to the corresponding toxic maleimide. The structures of three derivatives were determined by X-ray diffraction analysis.

  19. Terpenes from Marine-Derived Fungi

    PubMed Central

    Ebel, Rainer

    2010-01-01

    Terpenes from marine-derived fungi show a pronounced degree of structural diversity, and due to their interesting biological and pharmacological properties many of them have aroused interest from synthetic chemists and the pharmaceutical industry alike. The aim of this paper is to give an overview of the structural diversity of terpenes from marine-derived fungi, highlighting individual examples of chemical structures and placing them in a context of other terpenes of fungal origin. Wherever possible, information regarding the biological activity is presented. PMID:20948911

  20. Geometric derivation of the quantum speed limit

    SciTech Connect

    Jones, Philip J.; Kok, Pieter

    2010-08-15

    The Mandelstam-Tamm and Margolus-Levitin inequalities play an important role in the study of quantum-mechanical processes in nature since they provide general limits on the speed of dynamical evolution. However, to date there has been only one derivation of the Margolus-Levitin inequality. In this paper, alternative geometric derivations for both inequalities are obtained from the statistical distance between quantum states. The inequalities are shown to hold for unitary evolution of pure and mixed states, and a counterexample to the inequalities is given for evolution described by completely positive trace-preserving maps. The counterexample shows that there is no quantum speed limit for nonunitary evolution.

  1. High ethanol producing derivatives of Thermoanaerobacter ethanolicus

    DOEpatents

    Ljungdahl, L.G.; Carriera, L.H.

    1983-05-24

    Derivatives of the newly discovered microorganism Thermoanaerobacter ethanolicus which under anaerobic and thermophilic conditions continuously ferment substrates such as starch, cellobiose, glucose, xylose and other sugars to produce recoverable amounts of ethanol solving the problem of fermentations yielding low concentrations of ethanol using the parent strain of the microorganism Thermoanaerobacter ethanolicus are disclosed. These new derivatives are ethanol tolerant up to 10% (v/v) ethanol during fermentation. The process includes the use of an aqueous fermentation medium, containing the substrate at a substrate concentration greater than 1% (w/v).

  2. Optimal economic order quantity for buyer-distributor-vendor supply chain with backlogging derived without derivatives

    NASA Astrophysics Data System (ADS)

    Teng, Jinn-Tsair; Cárdenas-Barrón, Leopoldo Eduardo; Lou, Kuo-Ren; Wee, Hui Ming

    2013-05-01

    In this article, we first complement an inappropriate mathematical error on the total cost in the previously published paper by Chung and Wee [2007, 'Optimal the Economic Lot Size of a Three-stage Supply Chain With Backlogging Derived Without Derivatives', European Journal of Operational Research, 183, 933-943] related to buyer-distributor-vendor three-stage supply chain with backlogging derived without derivatives. Then, an arithmetic-geometric inequality method is proposed not only to simplify the algebraic method of completing prefect squares, but also to complement their shortcomings. In addition, we provide a closed-form solution to integral number of deliveries for the distributor and the vendor without using complex derivatives. Furthermore, our method can solve many cases in which their method cannot, because they did not consider that a squared root of a negative number does not exist. Finally, we use some numerical examples to show that our proposed optimal solution is cheaper to operate than theirs.

  3. Antibacterial anthraquinone derivatives from a sea anemone-derived fungus Nigrospora sp.

    PubMed

    Yang, Kai-Lin; Wei, Mei-Yan; Shao, Chang-Lun; Fu, Xiu-Mei; Guo, Zhi-Yong; Xu, Ru-Fang; Zheng, Cai-Juan; She, Zhi-Gang; Lin, Yong-Cheng; Wang, Chang-Yun

    2012-05-25

    Chemical investigation of a marine-derived fungus Nigrospora sp., isolated from an unidentified sea anemone, yielded two new hydroanthraquinone analogues, 4a-epi-9α-methoxydihydrodeoxybostrycin (1) and 10-deoxybostrycin (2), together with seven known anthraquinone derivatives (3-9). The structures of the two new compounds were established through extensive NMR spectroscopy as well as a single-crystal X-ray diffraction analysis using Cu Kα radiation. The antibacterial activities of compounds 1-9 and 10 acetyl derivatives (6a, 7a, 8a-8g, 9a) were evaluated in vitro. Compound 6a, the acetylated derivative of 6, exhibited promising activity against Bacillus cereus with an MIC value of 48.8 nM, which was stronger than that of the positive control ciprofloxacin (MIC = 1250 nM). Analysis of the antibacterial screening data for the metabolites and their acetyl derivatives revealed the key structural features required for this activity. PMID:22545792

  4. Ecosystem Services Derived from Headwater Catchments

    EPA Science Inventory

    We used data from the USEPA’s wadeable streams assessment (WSA), US Forest Service’s forest inventory and analysis (FIA), and select USFS experimental forests (EF) to investigate potential ecosystems services derived from headwater catchments. C, N, and P inputs to these catchmen...

  5. Alternative Derivations for the Poisson Integral Formula

    ERIC Educational Resources Information Center

    Chen, J. T.; Wu, C. S.

    2006-01-01

    Poisson integral formula is revisited. The kernel in the Poisson integral formula can be derived in a series form through the direct BEM free of the concept of image point by using the null-field integral equation in conjunction with the degenerate kernels. The degenerate kernels for the closed-form Green's function and the series form of Poisson…

  6. A new benzofuran derivative from Nicotiana tabacum.

    PubMed

    Xia, Jian-Jun; Li, Yuan-Dong; Liu, Xiu-Ming; Lu, Yuan; Wu, Yi-Qin; Qin, Yun-Hua

    2016-08-01

    A new benzofuran derivative, methyl 3-acetyl-7-hydroxy-6-methoxy-2-methylbenzofuran-4-carboxylate (1), and a known compound pyrrolezanthine (2), were isolated from leaves of Nicotiana tabacum. Compound 1 was elucidated by means of spectroscopic methods, as well as X-ray diffraction. Both compounds 1 and 2 exhibited moderate inhibitory activities on human cancer cell lines. PMID:26982907

  7. Constraining higher derivative supergravity with scattering amplitudes

    SciTech Connect

    Wang, Yifan; Yin, Xi

    2015-08-31

    We study supersymmetry constraints on higher derivative deformations of type IIB supergravity by consideration of superamplitudes. Thus, combining constraints of on-shell supervertices and basic results from string perturbation theory, we give a simple argument for the non-renormalization theorem of Green and Sethi, and some of its generalizations.

  8. 18 CFR 1301.65 - Derivative classification.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... classification. 1301.65 Section 1301.65 Conservation of Power and Water Resources TENNESSEE VALLEY AUTHORITY... record copy. (c) Documents classified derivatively shall bear all markings prescribed by 32 CFR 2001.20 through 2001.23 and shall otherwise conform to the requirements of 32 CFR 2001.20 through 2001.23....

  9. 18 CFR 1301.65 - Derivative classification.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... classification. 1301.65 Section 1301.65 Conservation of Power and Water Resources TENNESSEE VALLEY AUTHORITY... record copy. (c) Documents classified derivatively shall bear all markings prescribed by 32 CFR 2001.20 through 2001.23 and shall otherwise conform to the requirements of 32 CFR 2001.20 through 2001.23....

  10. 18 CFR 1301.65 - Derivative classification.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... classification. 1301.65 Section 1301.65 Conservation of Power and Water Resources TENNESSEE VALLEY AUTHORITY... record copy. (c) Documents classified derivatively shall bear all markings prescribed by 32 CFR 2001.20 through 2001.23 and shall otherwise conform to the requirements of 32 CFR 2001.20 through 2001.23....

  11. Robust Derivation of Risk Reduction Strategies

    NASA Technical Reports Server (NTRS)

    Richardson, Julian; Port, Daniel; Feather, Martin

    2007-01-01

    Effective risk reduction strategies can be derived mechanically given sufficient characterization of the risks present in the system and the effectiveness of available risk reduction techniques. In this paper, we address an important question: can we reliably expect mechanically derived risk reduction strategies to be better than fixed or hand-selected risk reduction strategies, given that the quantitative assessment of risks and risk reduction techniques upon which mechanical derivation is based is difficult and likely to be inaccurate? We consider this question relative to two methods for deriving effective risk reduction strategies: the strategic method defined by Kazman, Port et al [Port et al, 2005], and the Defect Detection and Prevention (DDP) tool [Feather & Cornford, 2003]. We performed a number of sensitivity experiments to evaluate how inaccurate knowledge of risk and risk reduction techniques affect the performance of the strategies computed by the Strategic Method compared to a variety of alternative strategies. The experimental results indicate that strategies computed by the Strategic Method were significantly more effective than the alternative risk reduction strategies, even when knowledge of risk and risk reduction techniques was very inaccurate. The robustness of the Strategic Method suggests that its use should be considered in a wide range of projects.

  12. 5 CFR 2500.5 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 2500.5 Administrative Personnel OFFICE OF ADMINISTRATION, EXECUTIVE OFFICE OF THE PRESIDENT INFORMATION SECURITY REGULATION § 2500.5 Derivative classification. The Office of Administration serves only as the temporary physical custodian of classified information which originated in other agencies of the...

  13. 76 FR 4751 - Position Limits for Derivatives

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-01-26

    ...Title VII of the Dodd-Frank Wall Street Reform and Consumer Protection Act of 2010 (``Dodd-Frank Act'') requires the Commodity Futures Trading Commission (``Commission'' or ``CFTC'') to establish position limits for certain physical commodity derivatives. The Commission is proposing to simultaneously establish position limits and limit formulas for certain physical commodity futures and option......

  14. UNDERSTANDING, DERIVING, AND COMPUTING BUFFER CAPACITY

    EPA Science Inventory

    Derivation and systematic calculation of buffer capacity is a topic that seems often to be neglected in chemistry courses and given minimal treatment in most texts. However, buffer capacity is very important in the chemistry of natural waters and potable water. It affects corro...

  15. Enabling quaternion derivatives: the generalized HR calculus.

    PubMed

    Xu, Dongpo; Jahanchahi, Cyrus; Took, Clive C; Mandic, Danilo P

    2015-08-01

    Quaternion derivatives exist only for a very restricted class of analytic (regular) functions; however, in many applications, functions of interest are real-valued and hence not analytic, a typical case being the standard real mean square error objective function. The recent HR calculus is a step forward and provides a way to calculate derivatives and gradients of both analytic and non-analytic functions of quaternion variables; however, the HR calculus can become cumbersome in complex optimization problems due to the lack of rigorous product and chain rules, a consequence of the non-commutativity of quaternion algebra. To address this issue, we introduce the generalized HR (GHR) derivatives which employ quaternion rotations in a general orthogonal system and provide the left- and right-hand versions of the quaternion derivative of general functions. The GHR calculus also solves the long-standing problems of product and chain rules, mean-value theorem and Taylor's theorem in the quaternion field. At the core of the proposed GHR calculus is quaternion rotation, which makes it possible to extend the principle to other functional calculi in non-commutative settings. Examples in statistical learning theory and adaptive signal processing support the analysis. PMID:26361555

  16. Enabling quaternion derivatives: the generalized HR calculus

    PubMed Central

    Xu, Dongpo; Jahanchahi, Cyrus; Took, Clive C.; Mandic, Danilo P.

    2015-01-01

    Quaternion derivatives exist only for a very restricted class of analytic (regular) functions; however, in many applications, functions of interest are real-valued and hence not analytic, a typical case being the standard real mean square error objective function. The recent HR calculus is a step forward and provides a way to calculate derivatives and gradients of both analytic and non-analytic functions of quaternion variables; however, the HR calculus can become cumbersome in complex optimization problems due to the lack of rigorous product and chain rules, a consequence of the non-commutativity of quaternion algebra. To address this issue, we introduce the generalized HR (GHR) derivatives which employ quaternion rotations in a general orthogonal system and provide the left- and right-hand versions of the quaternion derivative of general functions. The GHR calculus also solves the long-standing problems of product and chain rules, mean-value theorem and Taylor's theorem in the quaternion field. At the core of the proposed GHR calculus is quaternion rotation, which makes it possible to extend the principle to other functional calculi in non-commutative settings. Examples in statistical learning theory and adaptive signal processing support the analysis. PMID:26361555

  17. Dynamic derivative UV spectroscopy for combustion monitoring

    NASA Astrophysics Data System (ADS)

    Sassenscheid, Karsten; Klocke, Ulrich; Marb, C.; Riedel, H.; Schmidtke, Gerhard; Tacke, Maurus

    1999-01-01

    Derivative UV-absorption spectroscopy is a powerful spectroscopic technique for multicomponent gas analysis, particularly in combustion and process controlling applications. It offers enhanced selectivity and sensitivity compared to conventional techniques. We here report on a test of a special system with optical derivative generation in a waste incineration plant. Gas analysis is performed by transmission spectroscopy. A deuterium lamp is used as UV- source. Spectroscopic filtering is provided by a special grating monochromator. The grating is mounted on a galvanometer scanner, thus allowing a computer controlled wavelength scan and modulation. Signal analysis is performed with lock-in amplifier. The is from of detection for derivative spectra with a movable optical component is the origin of the term DYnamic Derivative Spectroscopy (DDS). The performance of this spectroscopic technique was demonstrated in a measurement campaign at a municipal solid waste incineration plant. The sensitivity for relevant gases is blow ppm level with an optical cell length of 10cm. The basics of the DDS and its performance will be explained, and data on NO, SO2 and NO2 will be reported.

  18. Synthesis of hydroxy derivatives of limonene

    NASA Astrophysics Data System (ADS)

    Ardashov, O. V.; Volcho, K. P.; Salakhutdinov, N. F.

    2014-04-01

    Synthetic routes to mono-, di- and trihydroxy derivatives of limonene are presented. Emphasis is given to the problems of regio- and stereoselectivity of transformations. Data on the isolation from natural sources and on the biological activities of the title compounds are given. The bibliography includes 107 references.

  19. Polyprenylated benzophenone derivatives from Cuban propolis.

    PubMed

    Hernández, Ingrid Márquez; Fernandez, Mercedes Campo; Cuesta-Rubio, Osmany; Piccinelli, Anna Lisa; Rastrelli, Luca

    2005-06-01

    Three new polyprenylated benzophenone derivatives, propolones B-D (5-7), together with garcinielliptone I (8) and hyperibone B (9), were isolated from Cuban propolis. All the structures, including relative configurations, were elucidated by spectroscopic methods and computer-generated molecular modeling. PMID:15974622

  20. Three new bibenzyl derivatives from Dendrobium nobile.

    PubMed

    Zhang, Xue; Gao, Hao; Wang, Nai-Li; Yao, Xin-Sheng

    2006-01-01

    Three new bibenzyl derivatives have been isolated from the stems of Dendrobium nobile Lindl. (Orchidaceae). Their structures were established as 4,5-dihydroxy-3,3',alpha-trimethoxybibenzyl (1), 4,4'-dihydroxy-3,3',5,alpha-tetramethoxybibenzyl (2) and 4-hydroxy-3,3',4',5,alpha-pentamethoxybibenzyl (3) on the basis of spectroscopic analysis. PMID:16753791

  1. An accelerated subspace iteration for eigenvector derivatives

    NASA Technical Reports Server (NTRS)

    Ting, Tienko

    1991-01-01

    An accelerated subspace iteration method for calculating eigenvector derivatives has been developed. Factors affecting the effectiveness and the reliability of the subspace iteration are identified, and effective strategies concerning these factors are presented. The method has been implemented, and the results of a demonstration problem are presented.

  2. Cellulose Derivatives for Water Repellent Properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this poster presentation, we will discuss the synthesis and structural characterizations of nitro-benzyl cellulose (1), amino-benzyl cellulose (2) and pentafluoro –benzyl cellulose (3). All cellulose derivatives are synthesized by etherification process in lithium chloride/N,N-dimethylacetamide h...

  3. Cellulose Derivatives for Water Repellent Properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Synthesis and structural characterizations of nitro-benzyl cellulose, amino-benzyl cellulose and pentafluoro –benzyl cellulose were carried out. Cellulose derivatives were synthesized by etherification process in lithium chloride/N,N-dimethylacetamide homogeneous solution. Nitrobenzylation was effec...

  4. Sol-Gel Derived Hafnia Coatings

    NASA Technical Reports Server (NTRS)

    Feldman, Jay D.; Stackpoole, Mairead; Blum, Yigal; Sacks, Michael; Ellerby, Don; Johnson, Sylvia M.; Venkatapathy, Ethiras (Technical Monitor)

    2002-01-01

    Sol-gel derived hafnia coatings are being developed to provide an oxidation protection layer on ultra-high temperature ceramics for potential use in turbine engines (ultra-efficient engine technology being developed by NASA). Coatings using hafnia sol hafnia filler particles will be discussed along with sol synthesis and characterization.

  5. Partial Derivative Automata Formalized in Coq

    NASA Astrophysics Data System (ADS)

    Almeida, José Bacelar; Moreira, Nelma; Pereira, David; de Sousa, Simão Melo

    In this paper we present a computer assisted proof of the correctness of a partial derivative automata construction from a regular expression within the Coq proof assistant. This proof is part of a formalization of Kleene algebra and regular languages in Coq towards their usage in program certification.

  6. Two-point derivative dispersion relations

    NASA Astrophysics Data System (ADS)

    Ferreira, Erasmo; Sesma, Javier

    2013-03-01

    A new derivation is given for the representation, under certain conditions, of the integral dispersion relations of scattering theory through local forms. The resulting expressions have been obtained through an independent procedure to construct the real part and consist of new mathematical structures of double infinite summations of derivatives. In this new form the derivatives are calculated at the generic value of the energy E and separately at the reference point E = m that is the lower limit of the integration. This new form may be more interesting in certain circumstances and directly shows the origin of the difficulties in convergence that were present in the old truncated forms called standard-derivative dispersion relations (DDR). For all cases in which the reductions of the double to single sums were obtained in our previous work, leading to explicit demonstration of convergence, these new expressions are seen to be identical to the previous ones. We present, as a glossary, the most simplified explicit results for the DDR's in the cases of imaginary amplitudes of forms (E/m)λ[ln (E/m)]n that cover the cases of practical interest in particle physics phenomenology at high energies. We explicitly study the expressions for the cases with λ negative odd integers, that require identification of cancelation of singularities, and provide the corresponding final results.

  7. Radioimmunoassay of tuberculoprotein derived from Mycobacterium tuberculosis.

    PubMed Central

    Straus, E; Wu, N

    1980-01-01

    A radioimmunoassay was developed for constituent of the purified-protein derivative obtained from cultures of Mycobacterium tuberculosis. Crossreacting immunoreactive material was detected in cultures of other mycobacterial species, but no immunoreactivity was present in cultures of various fungal and bacterial species. The development of specific radioimmunoassays for tuberculoproteins offers a new research and diagnostic approach. Images PMID:6933481

  8. Derivative luminescence spectra in lanthanide analysis

    SciTech Connect

    Bel'tyukova, S.V.; Poluektov, N.S.; Tochidlovskaya, T.L.; Kucher, A.A.

    1987-06-01

    This communication presents the results of derivative spectroscopic study of luminescence of complex compounds of europium and terbium. Solutions of complexes of europium with ethylenediaminetetraacetate, thenoyltrifluoroacetone, dibenzoylmethane, salicylate and 1,10-phenanthroline, and of terbium with phenyl ester of salicyclic acid and nalidixic acid were investigated.

  9. Facile synthesis of acacetin and its derivatives.

    PubMed

    Zhao, Yuan; Cai, Li; Sui, Qiang; Lin, Feng; Jiang, Wen; Chen, Jianli; Lu, Weigeng; Gao, Qi

    2016-08-01

    Acacetin, a O-methylated bioflavonoid isolated from the traditional Chinese medicine Xuelianhua (Saussurea tridactyla), is a promising orally effective atrium-selective antiarrhythmic agent for the treatment of atrial fibrillation (AF). Here we describe an efficient two-component method for the synthesis of acacetin and its derivatives. PMID:27321812

  10. Simple Derivation of the Lindblad Equation

    ERIC Educational Resources Information Center

    Pearle, Philip

    2012-01-01

    The Lindblad equation is an evolution equation for the density matrix in quantum theory. It is the general linear, Markovian, form which ensures that the density matrix is Hermitian, trace 1, positive and completely positive. Some elementary examples of the Lindblad equation are given. The derivation of the Lindblad equation presented here is…

  11. Derivation of the Ideal Gas Law

    ERIC Educational Resources Information Center

    Laugier, Alexander; Garai, Jozsef

    2007-01-01

    Undergraduate and graduate physics and chemistry books usually state that combining the gas laws results in the ideal gas law. Leaving the derivation to the students implies that this should be a simple task, most likely a substitution. Boyle's law, Charles's law, and the Avogadro's principle are given under certain conditions; therefore, direct…

  12. Computing Airplane Stopping Distance: Applications of Derivatives.

    ERIC Educational Resources Information Center

    Tylee, J. Louis

    1997-01-01

    Presents two real world applications that use derivatives and are related to computing the distance required to stop an airplane. Examines the curve-fitting techniques used to develop an equation for braking force and develops equations for the deceleration and speed. (DDR)

  13. Derived Transformation of Children's Pregambling Game Playing

    ERIC Educational Resources Information Center

    Dymond, Simon; Bateman, Helena; Dixon, Mark R.

    2010-01-01

    Contemporary behavior-analytic perspectives on gambling emphasize the impact of verbal relations, or derived relational responding and the transformation of stimulus functions, on the initiation and maintenance of gambling. Approached in this way, it is possible to undertake experimental analysis of the role of verbal/mediational variables in…

  14. Deriving a Pedagogy of Educational Foundations

    ERIC Educational Resources Information Center

    Fenstermacher, Gary D.

    2007-01-01

    This sixth and last paper in the series describes four elements believed to be crucial to a high quality pedagogy for educational foundations. These four elements are derived from a close reading of the previous papers. The work of Osguthorpe, Sanger, Haniford, and Mucher, four of the authors in this series, is cited as both a source for these…

  15. 6 CFR 7.26 - Derivative classification.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... amended, 32 CFR 2001.22, and internal DHS guidance provided by the Chief Security Officer. ... 6 Domestic Security 1 2010-01-01 2010-01-01 false Derivative classification. 7.26 Section 7.26 Domestic Security DEPARTMENT OF HOMELAND SECURITY, OFFICE OF THE SECRETARY CLASSIFIED NATIONAL...

  16. 22 CFR 9.6 - Derivative classification.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Foreign Relations DEPARTMENT OF STATE GENERAL SECURITY INFORMATION REGULATIONS § 9.6 Derivative... CFR 2001.22. (c) Department of State Classification Guide. The Department of State Classification... generating in new form information that is already classified and the marking of the new material...

  17. 6 CFR 7.26 - Derivative classification.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... amended, 32 CFR 2001.22, and internal DHS guidance provided by the Chief Security Officer. ... 6 Domestic Security 1 2012-01-01 2012-01-01 false Derivative classification. 7.26 Section 7.26 Domestic Security DEPARTMENT OF HOMELAND SECURITY, OFFICE OF THE SECRETARY CLASSIFIED NATIONAL...

  18. 28 CFR 17.26 - Derivative classification.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 17.26 Judicial Administration DEPARTMENT OF JUSTICE CLASSIFIED NATIONAL SECURITY INFORMATION AND ACCESS TO CLASSIFIED INFORMATION Classified Information § 17.26 Derivative classification. (a) Persons..., the ISOO implementing directives in 32 CFR 2001.22, and internal Department directions provided by...

  19. 22 CFR 9.6 - Derivative classification.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Foreign Relations DEPARTMENT OF STATE GENERAL SECURITY INFORMATION REGULATIONS § 9.6 Derivative... CFR 2001.22. (c) Department of State Classification Guide. The Department of State Classification... generating in new form information that is already classified and the marking of the new material...

  20. 22 CFR 9.6 - Derivative classification.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Foreign Relations DEPARTMENT OF STATE GENERAL SECURITY INFORMATION REGULATIONS § 9.6 Derivative... CFR 2001.22. (c) Department of State Classification Guide. The Department of State Classification... generating in new form information that is already classified and the marking of the new material...

  1. 6 CFR 7.26 - Derivative classification.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... amended, 32 CFR 2001.22, and internal DHS guidance provided by the Chief Security Officer. ... 6 Domestic Security 1 2014-01-01 2014-01-01 false Derivative classification. 7.26 Section 7.26 Domestic Security DEPARTMENT OF HOMELAND SECURITY, OFFICE OF THE SECRETARY CLASSIFIED NATIONAL...

  2. High speed point derivative microseismic detector

    DOEpatents

    Uhl, James Eugene; Warpinski, Norman Raymond; Whetten, Ernest Blayne

    1998-01-01

    A high speed microseismic event detector constructed in accordance with the present invention uses a point derivative comb to quickly and accurately detect microseismic events. Compressional and shear waves impinging upon microseismic receiver stations disposed to collect waves are converted into digital data and analyzed using a point derivative comb including assurance of quiet periods prior to declaration of microseismic events. If a sufficient number of quiet periods have passed, the square of a two point derivative of the incoming digital signal is compared to a trip level threshold exceeding the determined noise level to declare a valid trial event. The squaring of the derivative emphasizes the differences between noise and signal, and the valid event is preferably declared when the trip threshold has been exceeded over a temporal comb width to realize a comb over a given time period. Once a trial event has been declared, the event is verified through a spatial comb, which applies the temporal event comb to additional stations. The detector according to the present invention quickly and accurately detects initial compressional waves indicative of a microseismic event which typically exceed the ambient cultural noise level by a small amount, and distinguishes the waves from subsequent larger amplitude shear waves.

  3. High speed point derivative microseismic detector

    DOEpatents

    Uhl, J.E.; Warpinski, N.R.; Whetten, E.B.

    1998-06-30

    A high speed microseismic event detector constructed in accordance with the present invention uses a point derivative comb to quickly and accurately detect microseismic events. Compressional and shear waves impinging upon microseismic receiver stations disposed to collect waves are converted into digital data and analyzed using a point derivative comb including assurance of quiet periods prior to declaration of microseismic events. If a sufficient number of quiet periods have passed, the square of a two point derivative of the incoming digital signal is compared to a trip level threshold exceeding the determined noise level to declare a valid trial event. The squaring of the derivative emphasizes the differences between noise and signal, and the valid event is preferably declared when the trip threshold has been exceeded over a temporal comb width to realize a comb over a given time period. Once a trial event has been declared, the event is verified through a spatial comb, which applies the temporal event comb to additional stations. The detector according to the present invention quickly and accurately detects initial compressional waves indicative of a microseismic event which typically exceed the ambient cultural noise level by a small amount, and distinguishes the waves from subsequent larger amplitude shear waves. 9 figs.

  4. 14 CFR 1203.501 - Applying derivative classification markings.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... INFORMATION SECURITY PROGRAM Derivative Classification § 1203.501 Applying derivative classification markings... classification decisions: (b) Verify the information's current level of classification so far as...

  5. A derivative standard for polarimeter calibration

    SciTech Connect

    Mulhollan, G.; Clendenin, J.; Saez, P.

    1996-10-01

    A long-standing problem in polarized electron physics is the lack of a traceable standard for calibrating electron spin polarimeters. While several polarimeters are absolutely calibrated to better than 2%, the typical instrument has an inherent accuracy no better than 10%. This variability among polarimeters makes it difficult to compare advances in polarized electron sources between laboratories. The authors have undertaken an effort to establish 100 nm thick molecular beam epitaxy grown GaAs(110) as a material which may be used as a derivative standard for calibrating systems possessing a solid state polarized electron source. The near-bandgap spin polarization of photoelectrons emitted from this material has been characterized for a variety of conditions and several laboratories which possess well calibrated polarimeters have measured the photoelectron polarization of cathodes cut from a common wafer. Despite instrumentation differences, the spread in the measurements is sufficiently small that this material may be used as a derivative calibration standard.

  6. Rheological properties of sulfoacetate derivatives of cellulose.

    PubMed

    Chauvelon, Gaëlle; Doublier, Jean-Louis; Buléon, Alain; Thibault, Jean-François; Saulnier, Luc

    2003-04-01

    Water-soluble cellulose acetate sulfate derivatives (CAS) have been prepared through chemical reaction involving sulfuric acid as a catalyst. These CAS have been obtained from cellulosic materials of different origins (pure cellulose, wheat bran, maize bran) and their rheological behavior in salt-free aqueous solution has been estimated in dilute and semi-dilute regime using dynamic viscoelastic and viscosity measurements. Influence of concentration, temperature of solubilization and temperature of measurement has been investigated. Weak gel-like properties were exhibited at elevated concentration (typically above 7-8 g/L). These systems also exhibited thixotropic properties: the structure was partly broken down upon shearing and recovered at rest. They also displayed thermoreversibility with large hysteresis, the melting temperature being approximately 15 degrees C higher than the temperature at which gelation took place. These overall observations clearly indicate that these distinctive properties arise from intermolecular association of the macromolecular chains of the cellulose derivative. PMID:12668095

  7. Inequalities for a polynomial and its derivative

    NASA Astrophysics Data System (ADS)

    Chanam, Barchand; Dewan, K. K.

    2007-12-01

    Let , 1[less-than-or-equals, slant][mu][less-than-or-equals, slant]n, be a polynomial of degree n such that p(z)[not equal to]0 in z0, then for 0derivative, Math. Inequal. Appl. 2 (2) (1999) 203-205] proved Equality holds for the polynomial where n is a multiple of [mu]E In this paper, we obtain an improvement of the above inequality by involving some of the coefficients. As an application of our result, we further improve upon a result recently proved by Aziz and Shah [A. Aziz, W.M. Shah, Inequalities for a polynomial and its derivative, Math. Inequal. Appl. 7 (3) (2004) 379-391].

  8. Sulfated triterpene derivatives from Fagonia arabica.

    PubMed

    Perrone, Angela; Masullo, Milena; Bassarello, Carla; Hamed, Arafa I; Belisario, Maria Antonietta; Pizza, Cosimo; Piacente, Sonia

    2007-04-01

    Two new sulfated triterpenes (1, 6) and four new sulfated triterpene glycosides (2-5) have been isolated from the aerial parts of Fagonia arabica. Their structures were established by spectroscopic data analysis. Compounds 1/2 and 3/4 are sulfated derivatives of the rare sapogenins 3beta,27-dihydroxyolean-12-en-28-oic acid and 3beta,27-dihydroxyurs-12-en-28-oic acid, respectively. Compound 5 is an unusual disulfated oleanene derivative characterized by the occurrence of a 13,18-double bond, while compound 6 is the first reported naturally occurring saturated and sulfated pentacyclic triterpene of the taraxastane series with a C-20,28 lactone unit. PMID:17338564

  9. Developmental derivation of embryonic and adult macrophages.

    PubMed

    Shepard, J L; Zon, L I

    2000-01-01

    The macrophage cell lineage continually arises from hematopoietic stem cells during embryonic, fetal, and adult life. Previous theories proposed that macrophages are the recent progeny of bone marrow-derived monocytes and that they function primarily in phagocytosis. More recently, however, observations have shown that the ontogeny of macrophages in early mouse and human embryos is different from that occurring during adult development, and that the embryonic macrophages do not follow the monocyte pathway. Fetal macrophages are thought to differentiate from yolk sac-derived primitive macrophages before the development of adult monocytes. Further support for a separate lineage of fetal macrophages has come from studies of several species, including chicken, zebrafish, Xenopus, Drosophila, and C. elegans. The presence of fetal macrophages in PU.1-null mice indicates their independence from monocyte precursors and their existence as an alternative macrophage lineage. PMID:10608497

  10. Synthesis and Antidiabetic Evaluation of Benzenesulfonamide Derivatives

    PubMed Central

    Hosseinzadeh, Nouraddin; Seraj, Soodeh; Bakhshi-Dezffoli, Mohamad Ebrahim; Hasani, Mohammad; Khoshneviszadeh, Mehdi; Fallah-Bonekohal, Saeed; Abdollahi, Mohammad; Foroumadi, Alireza; Shafiee, Abbas

    2013-01-01

    The complex metabolic syndrome, diabetes mellitus, is a major human health concern in the world and is estimated to affect 300 million people by the year 2025. Several drugs such as sulfonylureas and biguanides are presently available to reduce hyperglycemia in diabetes mellitus. These drugs have side effects and thus searching for a new class of compounds is essential to overcome this problems. A series of seven novel N-(4-phenylthiazol-2-yl)benzenesulfonamides derivatives were synthesized and assayed in-vivo to investigate their antidiabetic activities by streptozotocin-induced model in rat. These derivatives showed considerable biological efficacy when compared to glibenclamide, a potent and well-known antidiabetic agent, as a reference drug. Four of the compounds were effective, amongst which 13 show more prominent activity at 100 mg/Kg p.o. The experimental results are statistically significant at p < 0.05 level. PMID:24250607

  11. Hydrocarbon and nonhydrocarbon derivatives of cyclopropane

    NASA Technical Reports Server (NTRS)

    Slabey, Vernon A; Wise, Paul H; Gibbons, Louis C

    1953-01-01

    The methods used to prepare and purify 19 hydrocarbon derivatives of cyclopropane are discussed. Of these hydrocarbons, 13 were synthesized for the first time. In addition to the hydrocarbons, six cyclopropylcarbinols, five alkyl cyclopropyl ketones, three cyclopropyl chlorides, and one cyclopropanedicarboxylate were prepared as synthesis intermediates. The melting points, boiling points, refractive indices, densities, and, in some instances, heats of combustion of both the hydrocarbon and nonhydrocarbon derivatives of cyclopropane were determined. These data and the infrared spectrum of each of the 34 cyclopropane compounds are presented in this report. The infrared absorption bands characteristic of the cyclopropyl ring are discussed, and some observations are made on the contribution of the cyclopropyl ring to the molecular refractions of cyclopropane compounds.

  12. Tissue-Derived Stem and Progenitor Cells

    PubMed Central

    Tesche, Leora J.; Gerber, David A.

    2010-01-01

    The characterization and isolation of various stem cell populations, from embryonic through tissue-derived stem cells, have led a rapid growth in the field of stem cell research. These research efforts have often been interrelated as to the markers that identify a select cell population are frequently analyzed to determine their expression in cells of distinct organs/tissues. In this review, we will expand the current state of research involving select tissue-derived stem cell populations including the liver, central nervous system, and cardiac tissues as examples of the success and challenges in this field of research. Lastly, the challenges of clinical therapies will be discussed as it applies to these unique cell populations. PMID:21048854

  13. Bacterial degradation of chlorophenols and their derivatives

    PubMed Central

    2014-01-01

    Chlorophenols (CPs) and their derivatives are persistent environmental pollutants which are used in the manufacture of dyes, drugs, pesticides and other industrial products. CPs, which include monochlorophenols, polychlorophenols, chloronitrophenols, chloroaminophenols and chloromethylphenols, are highly toxic to living beings due to their carcinogenic, mutagenic and cytotoxic properties. Several physico-chemical and biological methods have been used for removal of CPs from the environment. Bacterial degradation has been considered a cost-effective and eco-friendly method of removing CPs from the environment. Several bacteria that use CPs as their sole carbon and energy sources have been isolated and characterized. Additionally, the metabolic pathways for degradation of CPs have been studied in bacteria and the genes and enzymes involved in the degradation of various CPs have been identified and characterized. This review describes the biochemical and genetic basis of the degradation of CPs and their derivatives. PMID:24589366

  14. Platelet-derived microparticles - an updated perspective.

    PubMed

    Siljander, Pia R M

    2011-01-01

    Platelet-derived microparticles (PMP) are a heterogeneous population of vesicles (< 1 mm) generated from the plasma membrane upon platelet activation by various stimuli. They are a discrete population differing from the exosomes which originate from the intracellular multivesicular bodies. PMP also differ from the microparticles derived from megakaryocytes despite the presence of several identical surface markers on the latter. The molecular properties and the functional roles of the PMP are beginning to be elucidated by the rapidly evolving research interest, but novel questions are simultaneously raised. This updated perspective discusses the most recent highlights in the PMP research in context with the methodological problems and the paradoxical role of the PMP in health and disease. PMID:21193112

  15. Cosmology with higher-derivative matter fields

    NASA Astrophysics Data System (ADS)

    Harko, Tiberiu; Lobo, Francisco S. N.; Saridakis, Emmanuel N.

    2016-06-01

    We investigate the cosmological implications of a new class of modified gravity, where the field equations generically include higher-order derivatives of the matter fields, arising from the introduction of non-dynamical auxiliary fields in the action. Imposing a flat, homogeneous and isotropic geometry, we extract the Friedmann equations, obtaining an effective dark-energy sector containing higher-derivatives of the matter energy density and pressure. For the cases of dust, radiation and stiff matter, we analyze the cosmological behavior, finding accelerating, de Sitter and non-accelerating phases, dominated by matter or dark-energy. Additionally, the effective dark-energy equation-of-state parameter can be quintessence-like, cosmological-constant-like or even phantom-like. The detailed study of these scenarios may provide signatures, that could distinguish them from other candidates of modified gravity.

  16. New phenanthrene derivatives from maxillaria densa(1)

    PubMed

    Estrada; Toscano; Mata

    1999-08-01

    Two new phenanthrene derivatives, 2,5-dihydroxy-3, 4-dimethoxyphenanthrene (1) and 9,10-dihydro-2,5-dihydroxy-3, 4-dimethoxyphenanthrene (2), were isolated from an extract prepared from the whole plant of the orchid Maxillaria densa with spasmolytic activity. In addition, four known compounds, namely 2,7-dihydroxy-3, 4-dimethoxyphenanthrene, 9,10-dihydro-2,7-dihydroxy-3, 4-dimethoxyphenanthrene (3), 2,5-dihydroxy-3,4, 9-trimethoxyphe-nanthrene, and 2,7-dihydroxy-3,4, 9-trimethoxyphenanthrene, were obtained. The structures of the isolated compounds were elucidated by spectroscopic methods. In the case of phenanthrene derivatives 1 and 3, the structures were unambiguously assigned by X-ray analysis. PMID:10479332

  17. Novel harmine derivatives for tumor targeted therapy

    PubMed Central

    Gu, Fan; Wang, Zhaohui; Tian, Caiping; Qian, Zhiyu; Tang, Liping; Gu, Yueqing

    2015-01-01

    Harmine is a beta-carboline alkaloid found in medicinal plant PeganumHarmala, which has served as a folk anticancer medicine. However, clinical applications of harmine were limited by its low pharmacological effects and noticeable neurotoxicity. In this study, we modified harmine to increase the therapeutic efficacy and to decrease the systemic toxicity. Specifically, two tumor targeting harmine derivatives 2DG-Har-01 and MET-Har-02 were synthesized by modifying substituent in position-2, -7 and -9 of harmine ring with two different targeting group2-amino-2-deoxy-D-glucose (2DG) and Methionine (Met), respectively. Their therapeutic efficacy and toxicity were investigated both in vitro and in vivo. Results suggested that the two newharmine derivatives displayed much higher therapeutic effects than non-modified harmine. In particular, MET-Har-02 was more potent than 2DG-Har-01 with promising potential for targeted cancer therapy. PMID:25940702

  18. An Inverse Problem of Derivative Security Pricing

    NASA Astrophysics Data System (ADS)

    Zhang, Guanquan; Li, Peijun

    2003-04-01

    Suppose that interest rate is governed by a stochastic differential equation, a partial differential equation for the price of bond can be derived in a similar way to the derivation of the Black-Scholes equation. Valuation of bond with implied function in the equation, which is called the risk market price of interest rate, is known as the model of bond pricing. An inverse problem of bond pricing is to determined the risk market price of interest rate implied by current prices of bonds with different expirations. In this paper, numerical algorithm to solve this system is constructed and some numerical experiments are performed. The numerical results show that the algorithm is quite efficient and robust.

  19. Piperidine derivatives as nonprostanoid IP receptor agonists.

    PubMed

    Hayashi, Ryoji; Sakagami, Hideki; Koiwa, Masakazu; Ito, Hiroaki; Miyamoto, Mitsuko; Isogaya, Masafumi

    2016-05-01

    The discovery of a new class of nonprostanoid prostaglandin I2 receptor (IP receptor) agonists is reported. Among them, the unique piperidine derivative 31b (2-((1-(2-(N-(4-tolyl)benzamido)ethyl)piperidin-4-yl)oxy)acetic acid) was a good IP receptor agonist and was 50-fold more selective for the human IP receptor than for other human prostanoid receptors. This compound showed good pharmacokinetic properties in dog. PMID:26996371

  20. Triamine chelants, their derivatives, complexes and conjugates

    DOEpatents

    Troutner, D.E.; John, C.S.; Pillai, M.R.A.

    1995-03-07

    A group of functionalized triamine chelants and their derivatives that form complexes with radioactive metal ions are disclosed. The complexes can be covalently attached to a protein or an antibody or antibody fragment and used for therapeutic and/or diagnostic purposes. The chelants are of the formula, as shown in the accompanying diagrams, wherein n, m, R, R{sup 1}, R{sup 2} and L are defined in the specification.

  1. Uncertainty estimates for derivatives and intercepts

    SciTech Connect

    Clark, E.L.

    1994-09-01

    Straight line least squares fits of experimental data are widely used in the analysis of test results to provide derivatives and intercepts. A method for evaluating the uncertainty in these parameters is described. The method utilizes conventional least squares results and is applicable to experiments where the independent variable is controlled, but not necessarily free of error. A Monte Carlo verification of the method is given.

  2. Nile Blue derivatives as lysosomotropic photosensitizers

    NASA Astrophysics Data System (ADS)

    Lin, Chi-Wei; Shulok, Janine R.; Kirley, S. D.; Cincotta, Louis; Foley, James W.

    1991-06-01

    The benzophenoxazines, including several Nile blue analogues, are a unique group of dyes that localize selectively in animal tumors. Chemical modifications of Nile blue A can yield derivatives with high 1O2 quantum yields. These derivatives represent a group of potentially effective photosensitizers for selective phototherapy of malignant tumors. In vitro evaluation of these derivatives has indicated that those with high 1O2 yields are very effective in mediating the photocytotoxicity of tumor cells. This photodynamic effect is most likely mediated through the action of 1O2, since photoirradiation under D2O enhanced and under hypoxic conditions diminished the photocytotoxic action. The subcellular localization of these photosensitizers in bladder tumor cells in culture was examined by light and fluorescence microscopies as well as by histochemical and biochemical studies. The results indicate that these dyes are localized primarily in the lysosome. The cellular uptake and retention of these dyes is energy- and pH-dependent. Agents such as nigericin, which alter the transmembrane pH gradient, reduced uptake and enhanced efflux of the dyes, while agents such as valinomycin, which reduce cellular membrane potential, had no effect on the uptake. These findings are consistent with having ion-trapping as the mechanism for the uptake of these dyes. Photoirradiation of sensitizer-treated cells obliterated lysosomes in a light-dose and drug-dose dependent fashion. Release of the hydrolytic enzymes may be the main cause for subsequent cell death since the cytolytic effect was reduced by a specific inhibitor of lysosomal proteolytic enzyme. A lysosomotropic photosensitization mechanism is therefore proposed for the photocytotoxic action of the Nile blue derivatives. This mechanism may provide an approach to the development of new photosensitizers for the effective and selective destruction of malignant tumors.

  3. Tetrahydroquinoline derivatives as opioid receptor antagonists.

    PubMed

    Zhang, Cunyu; Westaway, Susan M; Speake, Jason D; Bishop, Michael J; Goetz, Aaron S; Carballo, Luz Helena; Hu, Mike; Epperly, Andrea H

    2011-01-15

    Opioid receptors play an important role in both behavioral and homeostatic functions. We herein report tetrahydroquinoline derivatives as opioid receptor antagonists. SAR studies led to the identification of the potent antagonist 2v, endowed with 1.58nM (K(i)) functional activity against the μ opioid receptor. DMPK data suggest that novel tetrahydroquinoline analogs may be advantageous in peripheral applications. PMID:21193310

  4. Triamine chelants, their derivatives, complexes and conjugates

    DOEpatents

    Troutner, David E.; John, Christy S.; Pillai, Maroor R. A.

    1995-01-01

    A group of functionalized triamine chelants and their derivatives that form complexes with radioactive metal ions are disclosed. The complexes can be covalently attached to a protein or an antibody or antibody fragment and used for therapeutic and/or diagnostic purposes. The chelants are of the formula: ##STR1## wherein n, m, R, R.sup.1, R.sup.2 and L are defined in the specification.

  5. Follicular cell-derived thyroid cancer.

    PubMed

    Dralle, Henning; Machens, Andreas; Basa, Johanna; Fatourechi, Vahab; Franceschi, Silvia; Hay, Ian D; Nikiforov, Yuri E; Pacini, Furio; Pasieka, Janice L; Sherman, Steven I

    2015-01-01

    Follicular cell-derived thyroid cancers are derived from the follicular cells in the thyroid gland, which secrete the iodine-containing thyroid hormones. Follicular cell-derived thyroid cancers can be classified into papillary thyroid cancer (80-85%), follicular thyroid cancer (10-15%), poorly differentiated thyroid cancer (<2%) and undifferentiated (anaplastic) thyroid cancer (<2%), and these have an excellent prognosis with the exception of undifferentiated thyroid cancer. The advent and expansion of advanced diagnostic techniques has driven and continues to drive the epidemic of occult papillary thyroid cancer, owing to overdiagnosis of clinically irrelevant nodules. This transformation of the thyroid cancer landscape at molecular and clinical levels calls for the modification of management strategies towards personalized medicine based on individual risk assessment to deliver the most effective but least aggressive treatment. In thyroid cancer surgery, for instance, injuries to structures outside the thyroid gland, such as the recurrent laryngeal nerve in 2-5% of surgeries or the parathyroid glands in 5-10% of surgeries, negatively affect quality of life more than loss of the expendable thyroid gland. Furthermore, the risks associated with radioiodine ablation may outweigh the risks of persistent or recurrent disease and disease-specific mortality. Improvement in the health-related quality of life of survivors of follicular cell-derived thyroid cancer, which is decreased despite the generally favourable outcome, hinges on early tumour detection and minimization of treatment-related sequelae. Future opportunities include more widespread adoption of molecular and clinical risk stratification and identification of actionable targets for individualized therapies. PMID:27188261

  6. Antidepressant activity of aspartic acid derivatives.

    PubMed

    Petrov, V I; Sergeev, V S; Onishchenko, N V; Piotrovskii, L B

    2001-04-01

    Antidepressant activity of N-phenyl(benzyl)amino derivatives of aspartic acid was studied on various experimental models of depression. IEM-1770 (30 mg/kg) and IEM-1944 (20 mg/kg) exhibited antidepressant activity after single injection in the forced swimming and tail suspension tests. Antidepressant effect of 14-day administration of these compounds and reference drugs maprotiline (10 mg/kg) and citalopram (10 mg/kg) was confirmed on the model of learned helplessness. PMID:11550022

  7. Chemo-Enzymatic Synthesis of Oligoglycerol Derivatives.

    PubMed

    Singh, Abhishek K; Nguyen, Remi; Galy, Nicolas; Haag, Rainer; Sharma, Sunil K; Len, Christophe

    2016-01-01

    A cleaner and greener method has been developed and used to synthesize 14 different functionalized oligomer derivatives of glycerol in moderate 29%-39% yields over three steps. After successive regioselective enzymatic acylation of the primary hydroxyl groups, etherification or esterification of the secondary hydroxyl groups and chemoselective enzymatic saponification, the target compounds can efficiently be used as versatile building blocks in organic and supramolecular chemistry. PMID:27517886

  8. Systematic Enumeration and Symmetries of Cubane Derivatives.

    PubMed

    Fujita, Shinsaku

    2016-06-01

    The feasibilities of Fujita's unit-subduced-cycle-index (USCI) approach, Fujita's proligand method, and Fujita's stereoisogram approach have been demonstrated by applying them to cubane derivatives as probes. They provide us with a new set of theoretical foundations for comprehensive investigation of geometric and stereoisomeric features of stereochemistry. The new set of theoretical foundations is based on mathematical formulations so as to explore mathematical stereochemistry as a new interdisciplinary field of stereochemistry. PMID:27027497

  9. Solgel-derived photosensitive germanosilicate glass monoliths.

    PubMed

    Heaney, A D; Erdogan, T

    2000-12-15

    We demonstrate volume gratings written in solgel-derived, Ge-doped silica monoliths. Glass was fabricated both with and without germanium oxygen deficient center (GODC) defects. The UV absorption and UV-induced index changes of these glasses, with and without hydrogen loading, are reported. The presence of GODC defects greatly enhances the photosensitivity of Ge-doped silica with and without the presence of hydrogen. PMID:18066337

  10. [Analgesic properties of morpholinoethylimidazobenzimidazole derivative RU-1205].

    PubMed

    Spasov, A A; Grechko, O Iu; Shtareva, D M; Anisimova, V A

    2013-01-01

    We have studied the analgesic activity of a morpholinoethylimidazobenzimidazole derivative (RU-1205) in comparison to butorphanol. It is established that the test compound exhibits a pronounced analgesic activity, which exceeded that ofbutorphanol six times in the hot-plate test and was comparable to the reference drug effect in the tail-flick and acetic acid-induced writhing tests. It is established that the analgesic action of RU-1205 is based on the kappa-opioidergic mechanism. PMID:24432563

  11. Antiaggregant activity of a new benzimidazole derivative.

    PubMed

    Kucheryavenko, A F; Spasov, A A; Petrov, V I; Anisimova, V A

    2014-04-01

    Antiaggregant activity of a new tricyclic benzimidazole derivative, RU-891 compound, was studied on the model of ADP-induced platelet aggregation in vitro and intravascular platelet aggregation in vivo. We evaluated the effect of this substance on blood coagulation potential. Antiaggregant agent acetylsalicylic acid was used as the reference drug. RU-891 produced a dose-dependent antiaggregant effect in vivo and in vitro that exceeded the effect of the reference drug. This compound did not modulate blood coagulation potential. PMID:24824700

  12. Healthy degenerate theories with higher derivatives

    NASA Astrophysics Data System (ADS)

    Motohashi, Hayato; Noui, Karim; Suyama, Teruaki; Yamaguchi, Masahide; Langlois, David

    2016-07-01

    In the context of classical mechanics, we study the conditions under which higher-order derivative theories can evade the so-called Ostrogradsky instability. More precisely, we consider general Lagrangians with second order time derivatives, of the form L(̈phia, dot phia, phia; qi, qi) with a = 1,⋯,n and i = 1,⋯,m. For n = 1, assuming that the qi's form a nondegenerate subsystem, we confirm that the degeneracy of the kinetic matrix eliminates the Ostrogradsky instability. The degeneracy implies, in the Hamiltonian formulation of the theory, the existence of a primary constraint, which generates a secondary constraint, thus eliminating the Ostrogradsky ghost. For n > 1, we show that, in addition to the degeneracy of the kinetic matrix, one needs to impose extra conditions to ensure the presence of a sufficient number of secondary constraints that can eliminate all the Ostrogradsky ghosts. When these conditions that ensure the disappearance of the Ostrogradsky instability are satisfied, we show that the Euler-Lagrange equations, which involve a priori higher order derivatives, can be reduced to a second order system.

  13. Oxygen derived variables in acute respiratory failure.

    PubMed

    Covelli, H D; Nessan, V J; Tuttle, W K

    1983-08-01

    The clinical course of 33 patients with acute respiratory distress syndrome (ARDS) was monitored by noninvasive oxygen derived variables and compared to data obtained by invasive monitoring. A total of 350 data points were used to compare the physiologic shunt fraction (Qsp/Qt) with the ratio of arterial oxygen to inspired oxygen concentration (PaO2/FIO2), the alveolar-arterial oxygen pressure difference [P(A-a)O2], the respiratory index (RI)-[P(A-a)O2/PaO2], and the ratio of arterial oxygen to alveolar oxygen (a/A). The PaO2/FIO2 ratio, the RI and the aA ratio correlated well with Qsp/Qt (r = 0.87 to 0.94). The P(A-a)O2 correlated less well (r = 0.68). Changes in the cardiac index (CI) and the arteriovenous oxygen content difference C(a-v)O2 had only a minimal effect on the correlation of the oxygen derived variables with Qsp/Qt, although a higher correlation resulted when these extrapulmonary factors were within normal range. We conclude that a number of oxygen derived variables may accurately reflect the degree of Qsp/Qt. The PaO2/FIO2 ratio is the easiest of these variables to calculate, yet accurately predicts the degree of Qsp/Qt throughout a course of acute respiratory failure. PMID:6409506

  14. Perturbative unitarity of Higgs derivative interactions

    NASA Astrophysics Data System (ADS)

    Kikuta, Yohei; Yamamoto, Yasuhiro

    2013-05-01

    We study the perturbative unitarity bound given by dimension six derivative interactions consisting of Higgs doublets. These interactions emerge from kinetic terms of composite Higgs models or integrating out heavy particles that interact with Higgs doublets. They lead to new phenomena beyond the Standard Model. One of characteristic contributions from derivative interactions appear in vector boson scattering processes. Longitudinal modes of massive vector bosons can be regarded as Nambu Goldstone bosons eaten by each vector field. Since their effects become larger and larger as the collision energy of vector bosons increases, vector boson scattering processes become important in the high energy region around the TeV scale. On the other hand, in such a high energy region, we have to take into account the unitarity of amplitudes. We have obtained the unitarity condition in terms of the parameter included in the effective Lagrangian for one Higgs doublet models. Applying it to some models, we have found that contributions of derivative interactions are not so large enough to clearly discriminate them from the Standard Model ones. We also study the unitarity bound in two Higgs doublet models. Because they are too complex to obtain it in the general effective Lagrangian, we have calculated it in explicit models. These analyses tell that the perturbative unitarity bounds are highly model dependent.

  15. Carbon nanomaterials: Biologically active fullerene derivatives.

    PubMed

    Bogdanović, Gordana; Djordjević, Aleksandar

    2016-01-01

    Since their discovery, fullerenes, carbon nanotubes, and graphene attract significant attention of researches in various scientific fields including biomedicine. Nano-scale size and a possibility for diverse surface modifications allow carbon nanoallotropes to become an indispensable nanostructured material in nanotechnologies, including nanomedicine. Manipulation of surface chemistry has created diverse populations of water-soluble derivatives of fullerenes, which exhibit different behaviors. Both non-derivatized and derivatized fullerenes show various biological activities. Cellular processes that underline their toxicity are oxidative, genotoxic, and cytotoxic responses.The antioxidant/cytoprotective properties of fullerenes and derivatives have been considered in the prevention of organ oxidative damage and treatment. The same unique physiochemical properties of nanomaterials may also be associated with potential health hazards. Non-biodegradability and toxicity of carbon nanoparticles still remain a great concern in the area of biomedical application. In this review, we report on basic physical and chemical properties of carbon nano-clusters--fullerenes, nanotubes, and grapheme--their specificities, activities, and potential application in biological systems. Special emphasis is given to our most important results obtained in vitro and in vivo using polyhydroxylated fullerene derivative C₆₀(OH)₂₄. PMID:27483572

  16. Long-memory volatility in derivative hedging

    NASA Astrophysics Data System (ADS)

    Tan, Abby

    2006-10-01

    The aim of this work is to take into account the effects of long memory in volatility on derivative hedging. This idea is an extension of the work by Fedotov and Tan [Stochastic long memory process in option pricing, Int. J. Theor. Appl. Finance 8 (2005) 381-392] where they incorporate long-memory stochastic volatility in option pricing and derive pricing bands for option values. The starting point is the stochastic Black-Scholes hedging strategy which involves volatility with a long-range dependence. The stochastic hedging strategy is the sum of its deterministic term that is classical Black-Scholes hedging strategy with a constant volatility and a random deviation term which describes the risk arising from the random volatility. Using the fact that stock price and volatility fluctuate on different time scales, we derive an asymptotic equation for this deviation in terms of the Green's function and the fractional Brownian motion. The solution to this equation allows us to find hedging confidence intervals.

  17. Affinity of guanosine derivatives for polycytidylate revisited

    NASA Technical Reports Server (NTRS)

    Kanavarioti, A.; Hurley, T. B.; Baird, E. E.

    1995-01-01

    Evidence is presented for complexation of guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) with polycytidylate (poly(C)) at pH 8.0 and 23 degrees C in the presence of 1.0 M NaCl2 and 0.2 M MgCl2 in water. The association of 2-MeImpG with poly(C) was investigated using UV-vis spectroscopy as well as by monitoring the kinetics of the nucleophilic substitution reaction of the imidazole moiety by amines. The results of both methods are consistent with moderately strong poly(C) 2-MeImpG complexation and the spectrophotometric measurements allowed the construction of a binding isotherm with a concentration of 2-MeImpG equal to 5.55 +/- 0.15 mM at half occupancy. UV spectroscopy was employed to establish the binding of other guanosine derivatives on poly(C). These derivatives are guanosine 5'-monophosphate (5'GMP), guanosine 5'-monophosphate imidazolide (ImpG), and guanosine 5'-monophosphate morpholidate (morpG). Within experimental error these guanosine derivatives exhibit the same affinity for poly(C) as 2-MeImpG.

  18. Forest Area Derivation from SENTINEL-1 Data

    NASA Astrophysics Data System (ADS)

    Dostálová, Alena; Hollaus, Markus; Milenković, Milutin; Wagner, Wolfgang

    2016-06-01

    The recently launched Sentinel-1A provides the high resolution Synthetic Aperture Radar (SAR) data with very high temporal coverage over large parts of European continent. Short revisit time and dual polarization availability supports its usability for forestry applications. The following study presents an analysis of the potential of the multi-temporal dual-polarization Sentinel-1A data for the forest area derivation using the standard methods based on Otsu thresholding and K-means clustering. Sentinel-1 data collected in winter season 2014-2015 over a test area in eastern Austria were used to derive forest area mask with spatial resolution of 10m and minimum mapping unit of 500 m2. The validation with reference forest mask derived from airborne full-waveform laser scanning data revealed overall accuracy of 92 % and kappa statistics of 0.81. Even better results can be achieved when using external mask for urban areas, which might be misclassified as forests when using the introduced approach based on SAR data only. The Sentinel-1 data and the described methods are well suited for forest change detection between consecutive years.

  19. Facile Preparation of 4-Substituted Quinazoline Derivatives.

    PubMed

    Wang, Daniel Z; Yan, Lesong; Ma, Lingmei

    2016-01-01

    Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted 2-aminobenzophenones and thiourea in the presence of dimethyl sulfoxide (DMSO). This is a unique complementary reaction system in which thiourea undergoes thermal decomposition to form carbodiimide and hydrogen sulfide, where the former reacts with 2-aminobenzophenone to form 4-phenylquinazolin-2(1H)-imine intermediate, whilst hydrogen sulfide reacts with DMSO to give methanethiol or other sulfur-containing molecule which then functions as a complementary reducing agent to reduce 4-phenylquinazolin-2(1H)-imine intermediate into 4-phenyl-1,2-dihydroquinazolin-2-amine. Subsequently, the elimination of ammonia from 4-phenyl-1,2-dihydroquinazolin-2-amine affords substituted quinazoline derivative. This reaction usually gives quinazoline derivative as a single product arising from 2-aminobenzophenone as monitored by GC/MS analysis, along with small amount of sulfur-containing molecules such as dimethyl disulfide, dimethyl trisulfide, etc. The reaction usually completes in 4-6 hr at 160 ºC in small scale but may last over 24 hr when carried out in large scale. The reaction product can be easily purified by means of washing off DMSO with water followed by column chromatography or thin layer chromatography. PMID:26967553

  20. Novel isoquinoline derivatives as antimicrobial agents.

    PubMed

    Galán, Abraham; Moreno, Laura; Párraga, Javier; Serrano, Ángel; Sanz, Ma Jesús; Cortes, Diego; Cabedo, Nuria

    2013-06-01

    The wide variety of potent biological activities of natural and synthetic isoquinoline alkaloids encouraged us to develop novel antimicrobial isoquinoline compounds. We synthesized a variety of differently functionalized 1-pentyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolines (THIQs), including dihydroisoquinolinium salts (2 and 5), methyl pentanoate-THIQ (6), 1-pentanol-THIQ (7), ester derivatives (8-15) and carbamate derivatives (16-23). We employed classic intramolecular Bischler-Napieralski cyclodehydration to generate the isoquinoline core. All the structures were characterized by nuclear magnetic resonance and mass spectrometry. The bactericide and fungicide activities were evaluated for all the synthesized compounds and structure-activity relationships were established. Many compounds exhibited high and broad-range bactericidal activity. Fluorophenylpropanoate ester 13 and the halogenated phenyl- (17, 18) and phenethyl carbamates (21, 22) exerted the most remarkable bactericidal activity. However, few compounds displayed antifungal activity against most of the fungi tested. Among them, chlorinated derivatives like chlorobenzoate and chlorophenylpropanoate esters (10 and 14, respectively) and chlorophenethyl carbamate 22, exhibited the greatest antifungal activity. PMID:23601815

  1. Non-Derivable Item Set and Non-Derivable Literal Set Representations of Patterns Admitting Negation

    NASA Astrophysics Data System (ADS)

    Kryszkiewicz, Marzena

    The discovery of frequent patterns has attracted a lot of attention of the data mining community. While an extensive research has been carried out for discovering positive patterns, little has been offered for discovering patterns with negation. The main hindrance to the progress of such research is huge amount of frequent patterns with negation, which exceeds the number of frequent positive patterns by orders of magnitude. In this paper, we examine properties of derivable and non-derivable patterns, including those with negated items. In particular, we establish important relationships among patterns admitting negation that have the same canonical variant. By analogy to frequent non-derivable itemsets, which constitute a concise lossless representation NDR of frequent positive patterns, we introduce frequent non-derivable literal sets lossless representation NDRL of frequent positive patterns admitting negation. Then we use the derived properties of literal sets to offer a concise representation NDIR of frequent patterns admitting negation that is built only from positive non-derivable itemsets. The relationships between the three representations are identified. The transformation of the new representations into not less concise lossless closure representations is discussed.

  2. Biologic rhythms derived from Siberian mammoths' hairs.

    PubMed

    Spilde, Mike; Lanzirotti, Antonio; Qualls, Clifford; Phillips, Genevieve; Ali, Abdul-Mehdi; Agenbroad, Larry; Appenzeller, Otto

    2011-01-01

    Hair is preserved for millennia in permafrost; it enshrines a record of biologic rhythms and offers a glimpse at chronobiology as it was in extinct animals. Here we compare biologic rhythms gleaned from mammoth's hairs with those of modern human hair. Four mammoths' hairs came from varying locations in Siberia 4600 km, four time zones, apart ranging in age between 18,000 and 20,000 years before present. We used two contemporaneous human hairs for comparison. Power spectra derived from hydrogen isotope ratios along the length of the hairs gave insight into biologic rhythms, which were different in the mammoths depending on location and differed from humans. Hair growth for mammoths was ∼31 cms/year and ∼16 cms/year for humans. Recurrent annual rhythms of slow and fast growth varying from 3.4 weeks/cycles to 8.7 weeks/cycles for slow periods and 1.2 weeks/cycles to 2.2 weeks/cycles for fast periods were identified in mammoth's hairs. The mineral content of mammoth's hairs was measured by electron microprobe analysis (k-ratios), which showed no differences in sulfur amongst the mammoth hairs but significantly more iron then in human hair. The fractal nature of the data derived from the hairs became evident in Mandelbrot sets derived from hydrogen isotope ratios, mineral content and geographic location. Confocal microscopy and scanning electron microscopy showed varied degrees of preservation of the cuticle largely independent of age but not location of the specimens. X-ray fluorescence microprobe and fluorescence computed micro-tomography analyses allowed evaluation of metal distribution and visualization of hollow tubes in the mammoth's hairs. Seasonal variations in iron and copper content combined with spectral analyses gave insights into variation in food intake of the animals. Biologic rhythms gleaned from power spectral plots obtained by modern methods revealed life style and behavior of extinct mega-fauna. PMID:21747920

  3. Biologic Rhythms Derived from Siberian Mammoths' Hairs

    PubMed Central

    Spilde, Mike; Lanzirotti, Antonio; Qualls, Clifford; Phillips, Genevieve; Ali, Abdul-Mehdi; Agenbroad, Larry; Appenzeller, Otto

    2011-01-01

    Hair is preserved for millennia in permafrost; it enshrines a record of biologic rhythms and offers a glimpse at chronobiology as it was in extinct animals. Here we compare biologic rhythms gleaned from mammoth's hairs with those of modern human hair. Four mammoths' hairs came from varying locations in Siberia 4600 km, four time zones, apart ranging in age between 18,000 and 20,000 years before present. We used two contemporaneous human hairs for comparison. Power spectra derived from hydrogen isotope ratios along the length of the hairs gave insight into biologic rhythms, which were different in the mammoths depending on location and differed from humans. Hair growth for mammoths was ∼31 cms/year and ∼16 cms/year for humans. Recurrent annual rhythms of slow and fast growth varying from 3.4 weeks/cycles to 8.7 weeks/cycles for slow periods and 1.2 weeks/cycles to 2.2 weeks/cycles for fast periods were identified in mammoth's hairs. The mineral content of mammoth's hairs was measured by electron microprobe analysis (k-ratios), which showed no differences in sulfur amongst the mammoth hairs but significantly more iron then in human hair. The fractal nature of the data derived from the hairs became evident in Mandelbrot sets derived from hydrogen isotope ratios, mineral content and geographic location. Confocal microscopy and scanning electron microscopy showed varied degrees of preservation of the cuticle largely independent of age but not location of the specimens. X-ray fluorescence microprobe and fluorescence computed micro-tomography analyses allowed evaluation of metal distribution and visualization of hollow tubes in the mammoth's hairs. Seasonal variations in iron and copper content combined with spectral analyses gave insights into variation in food intake of the animals. Biologic rhythms gleaned from power spectral plots obtained by modern methods revealed life style and behavior of extinct mega-fauna. PMID:21747920

  4. Vibrational Relaxation in Several Derivatives of Benzene

    NASA Astrophysics Data System (ADS)

    Linde, Bogumił B. J.; Skrodzka, Ewa B.; Lezhnev, Nikołaj B.

    2012-04-01

    Acoustical spectroscopy at frequencies up to 10 GHz gives the possibility of the investigation of liquid substances, where the relaxation process observed is caused by energy transfer between translational and vibrational degrees of freedom. The compounds presented in this article belong to this group of liquids. The acoustic investigations in the group of benzene derivatives, particularly research of the dependencies of acoustic parameters and the structure of organic liquids, demonstrated some interesting regularities in the group of these compounds in gas and liquid states. In this article, the results of research on five cyclic liquids: bromo-, chloro-, fluoro-, iodo-, and nitrobenzene as well as toluene and aniline are discussed and compared to benzene. The acoustic relaxation observed in all these compounds was found to result from Kneser's processes (vibrational relaxation). Based on investigations reported in this article, as well as by other authors, and taking into account experimental and literature data concerning a great number of compounds, one can draw a conclusion that almost all acoustic relaxation (Kneser-type) processes in liquids can be described using a single relaxation time. It also seems that all vibrational degrees of freedom of the molecule take part in this process. It is known that the appearance of differences in transition probabilities could be caused by additional attraction in interactions of molecules having dipole moments. Halogen derivatives have higher values of dipole moments than benzene. This difference could be responsible for the difference of transition probabilities and changes in the relaxation times. However, benzene derivatives with amino, nitro, and methyl groups and halides show the other type of relaxation.

  5. Novel sphingolipid derivatives promote keratinocyte differentiation.

    PubMed

    Paragh, György; Schling, Petra; Ugocsai, Peter; Kel, Alexander E; Liebisch, Gerhard; Heimerl, Susanne; Moehle, Christoph; Schiemann, Yvonne; Wegmann, Michael; Farwick, Mike; Wikonkál, Norbert M; Mandl, József; Langmann, Thomas; Schmitz, Gerd

    2008-12-01

    Sphingolipids are important components of the water permeability barrier of the skin. Moreover, ceramides were also shown to influence keratinocyte differentiation and regulate cellular signalling. A confluence-induced differentiation model of normal human keratinocytes was established to allow evaluation of pro- and anti-differentiation effects of exogenous compounds. The effects of phytosphingosine (PS), sphingosine (SO), sphinganine (SA) and their hexanoyl (-C6), stearoyl (-C18) and salicyl (-SLC) derivatives, C12-alkylamine-salicylate (C12-SLC), salicylate (SLC) along with vitamin D3 (VD3) and retinol as control substances were tested in this system. Cytotoxicity assays were carried out to optimize the incubation conditions of compounds and whole genome expression changes were monitored by DNA-microarray on days 0, 1 and 4. Geometric means of gene expression levels of a subset of known keratinocyte differentiation-related genes were calculated from the microarray data to compare effects of the sphingolipid derivatives. Compound treatment-induced transcriptional changes were analysed by the ExPlain software (BIOBASE GmbH). Five of the assayed substances (SA, SO-C6, PS-C6, SO-SLC, PS-SLC) were found to be potent promoters of keratinocyte differentiation compared with VD3, and C12-SLC revealed potential anti-differentiation properties. ExPlain analysis found a different regulatory profile in the computed transcriptional networks of the sphingoid bases versus their -C6 and especially -SLC derivatives suggesting that the change in their keratinocyte differentiation modifying potential is due to a unique effect of the covalent attachment of the salicylic acid. Taken together, these results demonstrate the gene regulatory potential of sphingolipid species that could be valuable for dermatological or cosmetic applications. PMID:18631249

  6. CYP450-derived oxylipins mediate inflammatory resolution

    PubMed Central

    Gilroy, Derek W.; De Maeyer, Roel P. H.; Bystrom, Jonas; Newson, Justine; Lih, Fred B.; Stables, Melanie; Zeldin, Darryl C.; Bishop-Bailey, David

    2016-01-01

    Resolution of inflammation has emerged as an active process in immunobiology, with cells of the mononuclear phagocyte system being critical in mediating efferocytosis and wound debridement and bridging the gap between innate and adaptive immunity. Here we investigated the roles of cytochrome P450 (CYP)-derived epoxy-oxylipins in a well-characterized model of sterile resolving peritonitis in the mouse. Epoxy-oxylipins were produced in a biphasic manner during the peaks of acute (4 h) and resolution phases (24–48 h) of the response. The epoxygenase inhibitor SKF525A (epoxI) given at 24 h selectively inhibited arachidonic acid- and linoleic acid-derived CYP450-epoxy-oxlipins and resulted in a dramatic influx in monocytes. The epoxI-recruited monocytes were strongly GR1+, Ly6chi, CCR2hi, CCL2hi, and CX3CR1lo. In addition, expression of F4/80 and the recruitment of T cells, B cells, and dendritic cells were suppressed. sEH (Ephx2)−/− mice, which have elevated epoxy-oxylipins, demonstrated opposing effects to epoxI-treated mice: reduced Ly6chi monocytes and elevated F4/80hi macrophages and B, T, and dendritic cells. Ly6chi and Ly6clo monocytes, resident macrophages, and recruited dendritic cells all showed a dramatic change in their resolution signature following in vivo epoxI treatment. Markers of macrophage differentiation CD11b, MerTK, and CD103 were reduced, and monocyte-derived macrophages and resident macrophages ex vivo showed greatly impaired phagocytosis of zymosan and efferocytosis of apoptotic thymocytes following epoxI treatment. These findings demonstrate that epoxy-oxylipins have a critical role in monocyte lineage recruitment and activity to promote inflammatory resolution and represent a previously unidentified internal regulatory system governing the establishment of adaptive immunity. PMID:27226306

  7. CYP450-derived oxylipins mediate inflammatory resolution.

    PubMed

    Gilroy, Derek W; Edin, Matthew L; De Maeyer, Roel P H; Bystrom, Jonas; Newson, Justine; Lih, Fred B; Stables, Melanie; Zeldin, Darryl C; Bishop-Bailey, David

    2016-06-01

    Resolution of inflammation has emerged as an active process in immunobiology, with cells of the mononuclear phagocyte system being critical in mediating efferocytosis and wound debridement and bridging the gap between innate and adaptive immunity. Here we investigated the roles of cytochrome P450 (CYP)-derived epoxy-oxylipins in a well-characterized model of sterile resolving peritonitis in the mouse. Epoxy-oxylipins were produced in a biphasic manner during the peaks of acute (4 h) and resolution phases (24-48 h) of the response. The epoxygenase inhibitor SKF525A (epoxI) given at 24 h selectively inhibited arachidonic acid- and linoleic acid-derived CYP450-epoxy-oxlipins and resulted in a dramatic influx in monocytes. The epoxI-recruited monocytes were strongly GR1(+), Ly6c(hi), CCR2(hi), CCL2(hi), and CX3CR1(lo) In addition, expression of F4/80 and the recruitment of T cells, B cells, and dendritic cells were suppressed. sEH (Ephx2)(-/-) mice, which have elevated epoxy-oxylipins, demonstrated opposing effects to epoxI-treated mice: reduced Ly6c(hi) monocytes and elevated F4/80(hi) macrophages and B, T, and dendritic cells. Ly6c(hi) and Ly6c(lo) monocytes, resident macrophages, and recruited dendritic cells all showed a dramatic change in their resolution signature following in vivo epoxI treatment. Markers of macrophage differentiation CD11b, MerTK, and CD103 were reduced, and monocyte-derived macrophages and resident macrophages ex vivo showed greatly impaired phagocytosis of zymosan and efferocytosis of apoptotic thymocytes following epoxI treatment. These findings demonstrate that epoxy-oxylipins have a critical role in monocyte lineage recruitment and activity to promote inflammatory resolution and represent a previously unidentified internal regulatory system governing the establishment of adaptive immunity. PMID:27226306

  8. Biologic Rhythms Derived from Siberian Mammoths Hairs

    SciTech Connect

    M Spilde; A Lanzirotti; C Qualls; G Phillips; A Ali; L Agenbroad; O Appenzeller

    2011-12-31

    Hair is preserved for millennia in permafrost; it enshrines a record of biologic rhythms and offers a glimpse at chronobiology as it was in extinct animals. Here we compare biologic rhythms gleaned from mammoth's hairs with those of modern human hair. Four mammoths' hairs came from varying locations in Siberia 4600 km, four time zones, apart ranging in age between 18,000 and 20,000 years before present. We used two contemporaneous human hairs for comparison. Power spectra derived from hydrogen isotope ratios along the length of the hairs gave insight into biologic rhythms, which were different in the mammoths depending on location and differed from humans. Hair growth for mammoths was {approx}31 cms/year and {approx}16 cms/year for humans. Recurrent annual rhythms of slow and fast growth varying from 3.4 weeks/cycles to 8.7 weeks/cycles for slow periods and 1.2 weeks/cycles to 2.2 weeks/cycles for fast periods were identified in mammoth's hairs. The mineral content of mammoth's hairs was measured by electron microprobe analysis (k-ratios), which showed no differences in sulfur amongst the mammoth hairs but significantly more iron then in human hair. The fractal nature of the data derived from the hairs became evident in Mandelbrot sets derived from hydrogen isotope ratios, mineral content and geographic location. Confocal microscopy and scanning electron microscopy showed varied degrees of preservation of the cuticle largely independent of age but not location of the specimens. X-ray fluorescence microprobe and fluorescence computed micro-tomography analyses allowed evaluation of metal distribution and visualization of hollow tubes in the mammoth's hairs. Seasonal variations in iron and copper content combined with spectral analyses gave insights into variation in food intake of the animals. Biologic rhythms gleaned from power spectral plots obtained by modern methods revealed life style and behavior of extinct mega-fauna.

  9. Studies on some derivatives of oxamniquine

    SciTech Connect

    el-Hamouly, W.; Pica-Mattoccia, L.; Cioli, D.; Schwartz, H.M.; Archer, S.

    1988-08-01

    On the basis of the remarkable biological similarities between hycanthone and oxamniquine and as a sequel to our finding that some esters of hycanthone are active against hycanthone-resistant schistosomes, we prepared oxamniquine acetate, oxamniquine N-methylcarbamate, and four substituted phenylsulfonohydrazones of oxamniquine aldehyde. These compounds were tested for their effect on survival of and on (/sup 3/H)uridine incorporation into hycanthone-sensitive and -resistant Schistosoma mansoni. All of these derivatives were effective to a greater or lesser degree in killing worms and in inhibiting (/sup 3/H)uridine incorporation in the sensitive strain, but none was effective in the resistant strain.

  10. Optimized Derivative Kernels for Gamma Ray Spectroscopy

    SciTech Connect

    Vlachos, D. S.; Kosmas, O. T.; Simos, T. E.

    2007-12-26

    In gamma ray spectroscopy, the photon detectors measure the number of photons with energy that lies in an interval which is called a channel. This accumulation of counts produce a measuring function that its deviation from the ideal one may produce high noise in the unfolded spectrum. In order to deal with this problem, the ideal accumulation function is interpolated with the use of special designed derivative kernels. Simulation results are presented which show that this approach is very effective even in spectra with low statistics.

  11. Lignin-Derived Advanced Carbon Materials

    SciTech Connect

    Chatterjee, Sabornie; Saito, Tomonori

    2015-01-01

    Lignin is a highly abundant source of renewable carbon that can be considered as a valuable sustainable source of biobased materials. By application specific pretreatments and manufacturing method, lignin can be converted to a variety of value added carbon materials. However, the physical and chemical heterogenitites in lignin complicate its use as a feedstock. In this review, lignin manufacturing process, effects of pretreatments and manufacturing methods on the properties of lignin, properties and applications of various lignin derived carbon materials such as carbon fibers, carbon mats, activated carbons, carbon films; are discussed.

  12. Derivation of an Applied Nonlinear Schroedinger Equation.

    SciTech Connect

    Pitts, Todd Alan; Laine, Mark Richard; Schwarz, Jens; Rambo, Patrick K.; Karelitz, David B.

    2015-01-01

    We derive from first principles a mathematical physics model useful for understanding nonlinear optical propagation (including filamentation). All assumptions necessary for the development are clearly explained. We include the Kerr effect, Raman scattering, and ionization (as well as linear and nonlinear shock, diffraction and dispersion). We explain the phenomenological sub-models and each assumption required to arrive at a complete and consistent theoretical description. The development includes the relationship between shock and ionization and demonstrates why inclusion of Drude model impedance effects alters the nature of the shock operator. Unclassified Unlimited Release

  13. Anticoagulant activity of original synthetic peptide derivatives.

    PubMed

    Drozd, N N; Tolstenkov, A S; Makarov, V A; Miphtakhova, N T; Voyushina, T L; Sergeev, M E

    2008-01-01

    Original synthetic peptide derivatives exhibit anticoagulant activity in vitro and in vivo. They delayed fibrin clot formation from human blood plasma in tests for the intrinsic coagulation pathway (activated partial thromboplastin time) and final stage of plasma coagulation (thrombin time) and inhibited amidolytic activity of thrombin. We determined the minimum effective dose of the most active compound providing a 2-fold lengthening of blood clotting time (activated partial thromboplastin time test and thrombin time test), which persisted for 2-3 h. PMID:19024001

  14. Stable Tricyclic Antitubercular Ozonides Derived from Artemisinin.

    PubMed

    Chaudhary, Sandeep; Sharma, Vashundhra; Jaiswal, Pradeep K; Gaikwad, Anil N; Sinha, Sudhir K; Puri, Sunil K; Sharon, Ashoke; Maulik, Prakas R; Chaturvedi, Vinita

    2015-10-16

    New, highly stable tricyclic antitubercular ozonides 9 and 10 derived from artemisinin are reported in 39 and 9% yields, respectively. The ozonide groups of 9 and 10 were found to be stable under strong basic and acidic conditions. The absolute configuration of ozonides 9 was confirmed by X-ray crystallography. Ozonide 10 shows promising antitubercular activity against M. tuberculosis H37Ra and M. tuberculosis H37Rv with MIC values of 0.39 and 3.12 μg/mL, respectively. PMID:26430796

  15. Bioavailability of Plant-Derived Antioxidants

    PubMed Central

    Abourashed, Ehab A.

    2013-01-01

    Natural products with antioxidant properties have been extensively utilized in the pharmaceutical and food industry and have also been very popular as health-promoting herbal products. This review provides a summary of the literature published around the first decade of the 21st century regarding the oral bioavailability of carotenoids, polyphenols and sulfur compounds as the three major classes of plant-derived antioxidants. The reviewed original research includes more than 40 compounds belonging to the above mentioned classes of natural antioxidants. In addition, related reviews published during the same period have been cited. A brief introduction to general bioavailability-related definitions, procedures and considerations is also included. PMID:26784467

  16. Deriving the unit hydrograph by root selection

    NASA Astrophysics Data System (ADS)

    Turner, J. E.; Dooge, J. C. I.; Bree, T.

    1989-09-01

    De Laine's method of deriving the unit hydrograph from the common roots of polynomials corresponding to different storms is used as a basis for proposing a new procedure in which the unit hydrograph roots can be selected from among the polynomial roots for the runoff of a single storm. The selection is made on the basis that the complex unit hydrograph roots form a characteristic "skew circle" pattern when plotted on an Argand diagram. The application of the procedure to field data is illustrated for both a single-peaked and a double-peaked event.

  17. Cationically polymerizable monomers derived from renewable sources

    SciTech Connect

    Crivello, J.V.

    1992-10-01

    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year's research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  18. Exact cosmological solutions with nonminimal derivative coupling

    SciTech Connect

    Sushkov, Sergey V.

    2009-11-15

    We consider a gravitational theory of a scalar field {phi} with nonminimal derivative coupling to curvature. The coupling terms have the form {kappa}{sub 1}R{phi}{sub ,{mu}}{phi}{sup ,{mu}} and {kappa}{sub 2}R{sub {mu}}{sub {nu}}{phi}{sup ,{mu}}{phi}{sup ,{nu}}, where {kappa}{sub 1} and {kappa}{sub 2} are coupling parameters with dimensions of length squared. In general, field equations of the theory contain third derivatives of g{sub {mu}}{sub {nu}} and {phi}. However, in the case -2{kappa}{sub 1}={kappa}{sub 2}{identical_to}{kappa}, the derivative coupling term reads {kappa}G{sub {mu}}{sub {nu}}{phi}{sup ,{mu}}{phi}{sup ,{nu}} and the order of corresponding field equations is reduced up to second one. Assuming -2{kappa}{sub 1}={kappa}{sub 2}, we study the spatially-flat Friedman-Robertson-Walker model with a scale factor a(t) and find new exact cosmological solutions. It is shown that properties of the model at early stages crucially depend on the sign of {kappa}. For negative {kappa}, the model has an initial cosmological singularity, i.e., a(t){approx}(t-t{sub i}){sup 2/3} in the limit t{yields}t{sub i}; and for positive {kappa}, the Universe at early stages has the quasi-de Sitter behavior, i.e., a(t){approx}e{sup Ht} in the limit t{yields}-{infinity}, where H=(3{radical}({kappa})){sup -1}. The corresponding scalar field {phi} is exponentially growing at t{yields}-{infinity}, i.e., {phi}(t){approx}e{sup -t/{radical}}{sup ({kappa})}. At late stages, the Universe evolution does not depend on {kappa} at all; namely, for any {kappa} one has a(t){approx}t{sup 1/3} at t{yields}{infinity}. Summarizing, we conclude that a cosmological model with nonminimal derivative coupling of the form {kappa}G{sub {mu}}{sub {nu}}{phi}{sup ,{mu}}{phi}{sup ,{nu}} is able to explain in a unique manner both a quasi-de Sitter phase and an exit from it without any fine-tuned potential.

  19. Arctic seabirds transport marine-derived contaminants.

    PubMed

    Blais, Jules M; Kimpe, Lynda E; McMahon, Dominique; Keatley, Bronwyn E; Mallory, Mark L; Douglas, Marianne S V; Smol, John P

    2005-07-15

    Long-range atmospheric transport of pollutants is generally assumed to be the main vector for arctic contamination, because local pollution sources are rare. We show that arctic seabirds, which occupy high trophic levels in marine food webs, are the dominant vectors for the transport of marine-derived contaminants to coastal ponds. The sediments of ponds most affected by seabirds had 60 times higher DDT, 25 times higher mercury, and 10 times higher hexachlorobenzene concentrations than nearby control sites. Bird guano greatly stimulates biological productivity in these extreme environments but also serves as a major source of industrial and agricultural pollutants in these remote ecosystems. PMID:16020729

  20. Eight new bibenzyl derivatives from Dendrobium candidum.

    PubMed

    Li, Yan; Wang, Chun-Lan; Zhao, Hai-Jun; Guo, Shun-Xing

    2014-01-01

    Eight bibenzyl derivatives, namely dendrocandins J-Q (1-8), were isolated from the stems of Dendrobium candidum. Their structures were elucidated by 1D and 2D NMR experiments and mass spectrometry. Compounds 1-8 were examined for antioxidant activity by 1,1-diphenyl-2-picrylhydrazyl free radical scavenging assay, and the IC50 values were 36.8, 70.2, 45.0, 60.5, 87.6, 50.4, 22.3, and 30.3 μM, respectively. PMID:25355458