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Sample records for photoactive protein nitrile

  1. Initial photoinduced dynamics of the photoactive yellow protein

    NARCIS (Netherlands)

    Larsen, D.S.; van Grondelle, R.

    2005-01-01

    The photoactive yellow protein (PYP) is the photoreceptor protein responsible for initiating the blue-light repellent response of the Halorhodospira halophila bacterium. Optical excitation of the intrinsic chromophore in PYP, p-coumaric acid, leads to the initiation of a photocycle that comprises

  2. Proline 68 enhances photoisomerization yield in photoactive yellow protein

    NARCIS (Netherlands)

    Rupenyan, A.B.; Vreede, J.; van Stokkum, I.H.M.; Hospes, M.; Kennis, J.T.M.; Hellingwerf, K.J.; Groot, M.L.

    2011-01-01

    In proteins and enzymes, the local environment of an active cofactor plays an important role in controlling the outcome of a functional reaction. In photoactive yellow protein (PYP), it ensures photoisomerization of the chromophore, a prerequisite for formation of a signaling state. PYP is the

  3. Proline 68 Enhances Photoisomerization Yield in Photoactive Yellow Protein

    NARCIS (Netherlands)

    Rupenyan, A.B.; Vreede, J.; van Stokkum, I.H.M.; Hospes, M.; Kennis, J.T.M.; Hellingwerf, K.J.; Groot, M.L.

    2011-01-01

    In proteins and enzymes, the local environment of an active cofactor plays an important role in controlling the outcome of a functional reaction. In photoactive yellow protein (PYP), it ensures photoisomerization of the chromophore, a prerequisite for formation of a signaling state. PYP is the

  4. Selective Incorporation of Nitrile-Based Infrared Probes into Proteins via Cysteine Alkylation

    Science.gov (United States)

    Jo, Hyunil; Culik, Robert M.; Korendovych, Ivan V.; DeGrado, William F.; Gai, Feng

    2010-01-01

    The nitrile stretching vibration is increasingly used as a sensitive infrared probe of local protein environments. However, site-specific incorporation of a nitrile moiety into proteins is difficult. Here we show that various aromatic nitriles can be easily incorporated into peptides and proteins via either thiol alkylation or arylation reaction. PMID:21077670

  5. Selective Incorporation of Nitrile-Based Infrared Probes into Proteins via Cysteine Alkylation

    OpenAIRE

    Jo, Hyunil; Culik, Robert M.; Korendovych, Ivan V.; DeGrado, William F.; Gai, Feng

    2010-01-01

    The nitrile stretching vibration is increasingly used as a sensitive infrared probe of local protein environments. However, site-specific incorporation of a nitrile moiety into proteins is difficult. Here we show that various aromatic nitriles can be easily incorporated into peptides and proteins via either thiol alkylation or arylation reaction.

  6. Incoherent manipulation of the photoactive yellow protein photocycle with dispersed pump-dump-probe spectroscopy.

    NARCIS (Netherlands)

    Larsen, D.S.; van Stokkum, I.H.M.; Vengris, M.; van der Horst, M.A.; de Weerd, F.; Hellingwerf, K.J.; van Grondelle, R.

    2004-01-01

    Photoactive yellow protein is the protein responsible for initiating the ``blue-light vision¿¿ of Halorhodospira halophila. The dynamical processes responsible for triggering the photoactive yellow protein photocycle have been disentangled with the use of a novel application of dispersed ultrafast

  7. Incoherent manipulation of the photoactive yellow protein photocycle with dispersed pump-dump-probe spectroscopy

    NARCIS (Netherlands)

    Larsen, D.S.; van Stokkum, I.H.M.; Vengris, M.; Horst, M.A.; de Weerd, F.L.; Hellingwerf, K.J.; van Grondelle, R.

    2004-01-01

    Photoactive yellow protein is the protein responsible for initiating the "blue-light vision" of Halorhodospira halophila. The dynamical processes responsible for triggering the photoactive yellow protein photocycle have been disentangled with the use of a novel application of dispersed ultrafast

  8. Contrasting the excited-state dynamics of the photoactive yellow protein chromophore: Protein versus solvent environments

    NARCIS (Netherlands)

    Vengris, M.; Horst, M.A.; Zgrablic, G.; van Stokkum, I.H.M.; Haacke, S.; Chergui, M.; Hellingwerf, K.J.; van Grondelle, R.; Larsen, D.S.

    2004-01-01

    Wavelength- and time-resolved fluorescence experiments have been performed on the photoactive yellow protein, the E46Q mutant, the hybrids of these proteins containing a nonisomerizing "locked" chromophore, and the native and locked chromophores in aqueous solution. The ultrafast dynamics of these

  9. Incoherent Manipulation of the Photoactive Yellow Protein Photocycle with Dispersed Pump-Dump-Probe Spectroscopy

    OpenAIRE

    Larsen, Delmar S.; van Stokkum, Ivo H. M.; Vengris, Mikas; van der Horst, Michael A.; de Weerd, Frank L.; Hellingwerf, Klaas J.; van Grondelle, Rienk

    2004-01-01

    Photoactive yellow protein is the protein responsible for initiating the ``blue-light vision¿¿ of Halorhodospira halophila. The dynamical processes responsible for triggering the photoactive yellow protein photocycle have been disentangled with the use of a novel application of dispersed ultrafast pump-dump-probe spectroscopy, where the photocycle can be started and interrupted with appropriately tuned and timed laser pulses. This ``incoherent¿¿ manipulation of the photocycle allows for the d...

  10. Gas phase absorption studies of photoactive yellow protein chromophore derivatives.

    Science.gov (United States)

    Rocha-Rinza, Toms; Christiansen, Ove; Rajput, Jyoti; Gopalan, Aravind; Rahbek, Dennis B; Andersen, Lars H; Bochenkova, Anastasia V; Granovsky, Alexander A; Bravaya, Ksenia B; Nemukhin, Alexander V; Christiansen, Kasper Lincke; Nielsen, Mogens Brøndsted

    2009-08-27

    Photoabsorption spectra of deprotonated trans p-coumaric acid and two of its methyl substituted derivatives have been studied in gas phase both experimentally and theoretically. We have focused on the spectroscopic effect of the location of the two possible deprotonation sites on the trans p-coumaric acid which originate to either a phenoxide or a carboxylate. Surprisingly, the three chromophores were found to have the same absorption maximum at 430 nm, in spite of having different deprotonation positions. However, the absorption of the chromophore in polar solution is substantially different for the distinct deprotonation locations. We also report on the time scales and pathways of relaxation after photoexcitation for the three photoactive yellow protein chromophore derivatives. As a result of these experiments, we could detect the phenoxide isomer within the deprotonated trans p-coumaric acid in gas phase; however, the occurrence of the carboxylate is uncertain. Several computational methods were used simultaneously to provide insights and assistance in the interpretation of our experimental results. The calculated excitation energies S(0)-S(1) are in good agreement with experiment for those systems having a negative charge on a phenoxide moiety. Although our augmented multiconfigurational quasidegenerate perturbation theory calculations agree with experiment in the description of the absorption spectrum of anions with a carboxylate functional group, there are some puzzling disagreements between experiment and some calculational methods in the description of these systems.

  11. On the involvement of single-bond rotation in the primary photochemistry of photoactive yellow protein

    NARCIS (Netherlands)

    Stahl, A.D.; Hospes, M.; Singhal, K.; van Stokkum, I.; van Grondelle, R.; Groot, M.L.; Hellingwerf, K.J.

    2011-01-01

    Prior experimental observations, as well as theoretical considerations, have led to the proposal that C4-C7 single-bond rotation may play an important role in the primary photochemistry of photoactive yellow protein (PYP). We therefore synthesized an analog of this protein's 4-hydroxy-cinnamic acid

  12. Initial steps of signal generation in photoactive yellow protein revealed with femtosecond mid-infrared spectroscopy

    NARCIS (Netherlands)

    Groot, M.L.; van Wilderen, L.; Larsen, D.S.; Horst, M.A.; van Stokkum, I.H.M.; Hellingwerf, K.J.; van Grondelle, R.

    2003-01-01

    Photoactive yellow protein (PYP) is a bacterial blue light sensor that induces Halorhodospira halophila to swim away from intense blue light. Light absorption by PYP's intrinsic chromophore, p-coumaric acid, leads to the initiation of a photocycle that comprises several distinct intermediates. Here

  13. Structural Evolution in Photoactive Yellow Protein Studied by Femtosecond Stimulated Raman Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yoshizawa M.

    2013-03-01

    Full Text Available Ultrafast structural evolution in photoactive yellow protein (PYP is studied by femtosecond stimulated Raman spectroscopy. A comparison between wild-type PYP and E46Q mutant reveals that the hydrogen-bonding network surrounding the chromophore of PYP is immediately rearranged in the electronic excited state.

  14. Is the photoactive yellow protein a UV-B/blue light photoreceptor?

    NARCIS (Netherlands)

    Carroll, E. C.; Hospes, M.; Valladares, C.; Hellingwerf, K.J.; Larsen, D.S.

    2011-01-01

    UV light below 300 nm is shown to generate the first photocycle intermediate in the blue light photoreceptor Photoactive Yellow Protein. Fluorescence and ultrafast transient absorption measurements indicate two excitation pathways: UV-B absorption by the chromophore and Fluorescence Resonant Energy

  15. Ultrafast dynamics of isolated model photoactive yellow protein chromophores: "Chemical perturbation theory" in the laboratory

    NARCIS (Netherlands)

    Vengris, M.; Larsen, D.S.; van der Horst, M.A.; Larsen, O.F.A.; Hellingwerf, K.J.; van Grondelle, R.

    2005-01-01

    Pump-probe and pump-dump probe experiments have been performed on several isolated model chromophores of the photoactive yellow protein (PYP). The observed transient absorption spectra are discussed in terms of the spectral signatures ascribed to solvation, excited-state twisting, and vibrational

  16. A short history of structure based research on the photocycle of photoactive yellow protein.

    Science.gov (United States)

    Schmidt, Marius

    2017-05-01

    The goals of time-resolved macromolecular crystallography are to extract the molecular structures of the reaction intermediates and the reaction dynamics from time-resolved X-ray data alone. To develop the techniques of time-resolved crystallography, biomolecules with special properties are required. The Photoactive Yellow Protein is the most sparkling of these.

  17. A short history of structure based research on the photocycle of photoactive yellow protein

    Directory of Open Access Journals (Sweden)

    Marius Schmidt

    2017-05-01

    Full Text Available The goals of time-resolved macromolecular crystallography are to extract the molecular structures of the reaction intermediates and the reaction dynamics from time-resolved X-ray data alone. To develop the techniques of time-resolved crystallography, biomolecules with special properties are required. The Photoactive Yellow Protein is the most sparkling of these.

  18. Nitrile-specifier Proteins Involved in Glucosinolate Hydrolysis in Arabidopsis thaliana*S⃞

    Science.gov (United States)

    Kissen, Ralph; Bones, Atle M.

    2009-01-01

    Glucosinolates are plant secondary metabolites present in Brassicaceae plants such as the model plant Arabidopsis thaliana. Intact glucosinolates are believed to be biologically inactive, whereas degradation products after hydrolysis have multiple roles in growth regulation and defense. The degradation of glucosinolates is catalyzed by thioglucosidases called myrosinases and leads by default to the formation of isothiocyanates. The interaction of a protein called epithiospecifier protein (ESP) with myrosinase diverts the reaction toward the production of epithionitriles or nitriles depending on the glucosinolate structure. Here we report the identification of a new group of nitrile-specifier proteins (AtNSPs) in A. thaliana able to generate nitriles in conjunction with myrosinase and a more detailed characterization of one member (AtNSP2). Recombinant AtNSP2 expressed in Escherichia coli was used to test its impact on the outcome of glucosinolate hydrolysis using a gas chromatography-mass spectrometry approach. AtNSP proteins share 30–45% sequence homology with A. thaliana ESP. Although AtESP and AtNSP proteins can switch myrosinase-catalyzed degradation of 2-propenylglucosinolate from isothiocyanate to nitrile, only AtESP generates the corresponding epithionitrile. Using the aromatic benzylglucosinolate, recombinant AtNSP2 is also able to direct product formation to the nitrile. Analysis of glucosinolate hydrolysis profiles of transgenic A. thaliana plants overexpressing AtNSP2 confirms its nitrile-specifier activity in planta. In silico expression analysis reveals distinctive expression patterns of AtNSPs, which supports a biological role for these proteins. In conclusion, we show that AtNSPs belonging to a new family of A. thaliana proteins structurally related to AtESP divert product formation from myrosinase-catalyzed glucosinolate hydrolysis and, thereby, likely affect the biological consequences of glucosinolate degradation. We discuss similarities and

  19. Correlating Nitrile IR Frequencies to Local Electrostatics Quantifies Noncovalent Interactions of Peptides and Proteins.

    Science.gov (United States)

    Deb, Pranab; Haldar, Tapas; Kashid, Somnath M; Banerjee, Subhrashis; Chakrabarty, Suman; Bagchi, Sayan

    2016-05-05

    Noncovalent interactions, in particular the hydrogen bonds and nonspecific long-range electrostatic interactions are fundamental to biomolecular functions. A molecular understanding of the local electrostatic environment, consistently for both specific (hydrogen-bonding) and nonspecific electrostatic (local polarity) interactions, is essential for a detailed understanding of these processes. Vibrational Stark Effect (VSE) has proven to be an extremely useful method to measure the local electric field using infrared spectroscopy of carbonyl and nitrile based probes. The nitrile chemical group would be an ideal choice because of its absorption in an infrared spectral window transparent to biomolecules, ease of site-specific incorporation into proteins, and common occurrence as a substituent in various drug molecules. However, the inability of VSE to describe the dependence of IR frequency on electric field for hydrogen-bonded nitriles to date has severely limited nitrile's utility to probe the noncovalent interactions. In this work, using infrared spectroscopy and atomistic molecular dynamics simulations, we have reported for the first time a linear correlation between nitrile frequencies and electric fields in a wide range of hydrogen-bonding environments that may bridge the existing gap between VSE and H-bonding interactions. We have demonstrated the robustness of this field-frequency correlation for both aromatic nitriles and sulfur-based nitriles in a wide range of molecules of varying size and compactness, including small molecules in complex solvation environments, an amino acid, disordered peptides, and structured proteins. This correlation, when coupled to VSE, can be used to quantify noncovalent interactions, specific or nonspecific, in a consistent manner.

  20. Small Molecule-Photoactive Yellow Protein Labeling Technology in Live Cell Imaging

    Directory of Open Access Journals (Sweden)

    Feng Gao

    2016-08-01

    Full Text Available Characterization of the chemical environment, movement, trafficking and interactions of proteins in live cells is essential to understanding their functions. Labeling protein with functional molecules is a widely used approach in protein research to elucidate the protein location and functions both in vitro and in live cells or in vivo. A peptide or a protein tag fused to the protein of interest and provides the opportunities for an attachment of small molecule probes or other fluorophore to image the dynamics of protein localization. Here we reviewed the recent development of no-wash small molecular probes for photoactive yellow protein (PYP-tag, by the means of utilizing a quenching mechanism based on the intramolecular interactions, or an environmental-sensitive fluorophore. Several fluorogenic probes have been developed, with fast labeling kinetics and cell permeability. This technology allows quick live-cell imaging of cell-surface and intracellular proteins without a wash-out procedure.

  1. Incoherent manipulation of the photoactive yellow protein photocycle with dispersed pump-dump-probe spectroscopy.

    Science.gov (United States)

    Larsen, Delmar S; van Stokkum, Ivo H M; Vengris, Mikas; van Der Horst, Michael A; de Weerd, Frank L; Hellingwerf, Klaas J; van Grondelle, Rienk

    2004-09-01

    Photoactive yellow protein is the protein responsible for initiating the "blue-light vision" of Halorhodospira halophila. The dynamical processes responsible for triggering the photoactive yellow protein photocycle have been disentangled with the use of a novel application of dispersed ultrafast pump-dump-probe spectroscopy, where the photocycle can be started and interrupted with appropriately tuned and timed laser pulses. This "incoherent" manipulation of the photocycle allows for the detailed spectroscopic investigation of the underlying photocycle dynamics and the construction of a fully self-consistent dynamical model. This model requires three kinetically distinct excited-state intermediates, two (ground-state) photocycle intermediates, I(0) and pR, and a ground-state intermediate through which the protein, after unsuccessful attempts at initiating the photocycle, returns to the equilibrium ground state. Also observed is a previously unknown two-photon ionization channel that generates a radical and an ejected electron into the protein environment. This second excitation pathway evolves simultaneously with the pathway containing the one-photon photocycle intermediates.

  2. Structural Determinats Underlying Photoprotection in the Photoactive Orange Carotenoid Protein of Cyanobacteria

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Adjele; Kinney, James N.; Zwart, Petrus H.; Punginelli, Claire; D' Haene, Sandrine; Perreau, Francois; Klein, Michael G.; Kirilovsky, Diana; Kerfeld, Cheryl

    2010-04-01

    The photoprotective processes of photosynthetic organisms involve the dissipation of excess absorbed light energy as heat. Photoprotection in cyanobacteria is mechanistically distinct from that in plants; it involves the Orange Carotenoid Protein (OCP), a water-soluble protein containing a single carotenoid. The OCP is a new member of the family of blue light photoactive proteins; blue-green light triggers the OCP-mediated photoprotective response. Here we report structural and functional characterization of the wildtype and two mutant forms of the OCP, from the model organism Synechocystis PCC6803. The structural analysis provides highresolution detail of the carotenoidprotein interactions that underlie the optical properties of the OCP, unique among carotenoid-proteins in binding a single pigment per polypeptide chain. Collectively, these data implicate several key amino acids in the function of the OCP and reveal that the photoconversion and photoprotective responses of the OCP to blue-green light can be decoupled.

  3. Locked chromophore analogs reveal that photoactive yellow protein regulates biofilm formation in the deep sea bacterium Idiomarina loihiensis

    NARCIS (Netherlands)

    van der Horst, M.A.; Stalcup, T.P.; Kaledhonkar, S.; Kumauchi, M.; Hara, M.; Xie, A.; Hellingwerf, K.J.; Hoff, W.D.

    2009-01-01

    Idiomarina loihiensis is a heterotrophic deep sea bacterium with no known photobiology. We show that light suppresses biofilm formation in this organism. The genome of I. loihiensis encodes a single photoreceptor protein: a homologue of photoactive yellow protein (PYP), a blue light receptor with

  4. Conversion of light-energy into molecular strain in the photocycle of the photoactive yellow protein.

    Science.gov (United States)

    Gamiz-Hernandez, Ana P; Kaila, Ville R I

    2016-01-28

    The Photoactive Yellow Protein (PYP) is a light-driven photoreceptor, responsible for the phototaxis of halophilic bacteria. Recently, a new short-lived intermediate (pR0) was characterized in the PYP photocycle using combined time-resolved X-ray crystallography and density functional theory calculations. The pR0 species was identified as a highly contorted cis-intermediate, which is stabilized by hydrogen bonds with protein residues. Here we show by hybrid quantum mechanics/classical mechanics (QM/MM) molecular dynamics simulations, and first-principles calculations of optical properties, that the optical shifts in the early steps of the PYP photocycle originate from the conversion of light energy into molecular strain, stored in the pR0 state, and its relaxation in subsequent reaction steps. Our calculations quantitatively reproduce experimental data, which enables us to identify molecular origins of the optical shifts. Our combined approach suggests that the short-lived pR0 intermediate stores ∼1/3 of the photon energy as molecular strain, thus providing the thermodynamic driving force for later conformational changes in the protein.

  5. Myeloperoxidase-mediated protein lysine oxidation generates 2-aminoadipic acid and lysine nitrile in vivo.

    Science.gov (United States)

    Lin, Hongqiao; Levison, Bruce S; Buffa, Jennifer A; Huang, Ying; Fu, Xiaoming; Wang, Zeneng; Gogonea, Valentin; DiDonato, Joseph A; Hazen, Stanley L

    2017-03-01

    Recent studies reveal 2-aminoadipic acid (2-AAA) is both elevated in subjects at risk for diabetes and mechanistically linked to glucose homeostasis. Prior studies also suggest enrichment of protein-bound 2-AAA as an oxidative post-translational modification of lysyl residues in tissues associated with degenerative diseases of aging. While in vitro studies suggest redox active transition metals or myeloperoxidase (MPO) generated hypochlorous acid (HOCl) may produce protein-bound 2-AAA, the mechanism(s) responsible for generation of 2-AAA during inflammatory diseases are unknown. In initial studies we observed that traditional acid- or base-catalyzed protein hydrolysis methods previously employed to measure tissue 2-AAA can artificially generate protein-bound 2-AAA from an alternative potential lysine oxidative product, lysine nitrile (LysCN). Using a validated protease-based digestion method coupled with stable isotope dilution LC/MS/MS, we now report protein bound 2-AAA and LysCN are both formed by hypochlorous acid (HOCl) and the MPO/H 2 O 2 /Cl - system of leukocytes. At low molar ratio of oxidant to target protein N ε -lysine moiety, 2-AAA is formed via an initial N ε -monochloramine intermediate, which ultimately produces the more stable 2-AAA end-product via sequential generation of transient imine and semialdehyde intermediates. At higher oxidant to target protein N ε -lysine amine ratios, protein-bound LysCN is formed via initial generation of a lysine N ε -dichloramine intermediate. In studies employing MPO knockout mice and an acute inflammation model, we show that both free and protein-bound 2-AAA, and in lower yield, protein-bound LysCN, are formed by MPO in vivo during inflammation. Finally, both 2-AAA and to lesser extent LysCN are shown to be enriched in human aortic atherosclerotic plaque, a tissue known to harbor multiple MPO-catalyzed protein oxidation products. Collectively, these results show that MPO-mediated oxidation of protein lysyl

  6. Characterization of recombinant nitrile-specifier proteins (NSPs) of Arabidopsis thaliana: dependency on Fe(II) ions and the effect of glucosinolate substrate and reaction conditions.

    Science.gov (United States)

    Kong, Xiang Yi; Kissen, Ralph; Bones, Atle M

    2012-12-01

    Glucosinolates are plant secondary metabolites that are part of a plant defence system against pathogens and pests, the myrosinase-glucosinolate system, in which glucosinolates get activated by enzymic degradation through thioglucoside glucohydrolases called myrosinases. Epithiospecifier protein (ESP) and nitrile-specifier proteins (NSPs) divert myrosinase-catalyzed hydrolysis of a given glucosinolate from the formation of isothiocyanate to that of epithionitrile and/or nitrile. As the biological activity of glucosinolate hydrolysis products varies considerably, a detailed characterization of these specifier proteins is of utmost importance to understand their biological role. Therefore, the Arabidopsis thaliana AtNSP1, AtNSP2 and AtNSP5 and a supposed ancestor protein AtNSP-like1 were expressed in Escherichia coli and the activity of the purified recombinant proteins was tested in vitro on three highly different glucosinolates and compared to that of purified AtESP. As previously reported, only AtESP showed epithiospecifier activity on 2-propenylglucosinolate. We further confirmed that purified AtNSP1, AtNSP2 and AtNSP5, but not the ancestor AtNSP-like1 protein, show nitrile-specifier activity on 2-propenylglucosinolate and benzylglucosinolate. We now show for the first time that in vitro AtNSP1, AtNSP2 and AtNSP5 are able to generate nitrile from indol-3-ylmethylglucosinolate. We also tested the effect of different Fe(II) ion concentrations on the nitrile-specifier activity of purified AtNSP1, AtNSP2 and AtNSP5 on 2-propenylglucosinolate and benzylglucosinolate. AtNSP-related nitrile production was highly dependent on the presence of Fe(II) ions in the reaction assay. In the absence of added Fe(II) ions nitriles were only detected when benzylglucosinolate was incubated with AtNSP1. While AtNSP1 also exhibited overall higher nitrile-specifier activity than AtNSP2 and AtNSP5 at a given Fe(II) ion concentration, the pattern of nitrile formation in relation to Fe

  7. Lack of negative charge in the E46Q mutant of photoactive yellow protein prevents partial unfolding of the blue shifted intermediate

    NARCIS (Netherlands)

    Derix, N.M.; Wechselberger, R.W.|info:eu-repo/dai/nl/304829005; van der Horst, M.A.; Hellingwerf, K.J.; Boelens, R.|info:eu-repo/dai/nl/070151407; Kaptein, R.|info:eu-repo/dai/nl/074334603; van Nuland, N.A.J.

    2003-01-01

    The long-lived light-induced intermediate (pB) of the E46Q mutant (glutamic acid is replaced by glutamine at position 46) of photoactive yellow protein (PYP) has been investigated by NMR spectroscopy. The ground state of this mutant is very similar to that of wild-type PYP (WT), whereas the pB

  8. Nitrile Probes of Electric Field Agree with Independently Measured Fields in Green Fluorescent Protein Even in the Presence of Hydrogen Bonding.

    Science.gov (United States)

    Slocum, Joshua D; Webb, Lauren J

    2016-05-25

    There is growing interest in using the nitrile vibrational oscillation as a site-specific probe of local environment to study dynamics, folding, and electrostatics in biological molecules such as proteins. Nitrile probes have been used extensively as reporters of electric field using vibrational Stark effect spectroscopy. However, the analysis of frequencies in terms of electric fields is potentially complicated by the large ground state dipole moment of the nitrile, which may irrevocably perturb the protein under investigation, and the ability of nitriles to accept hydrogen bonds, which causes frequency shifts that are not described by the Stark effect. The consequence of this is that vibrational spectroscopy of nitriles in biomolecules could be predominately sensitive to their local hydration status, not electrostatic environment, and have the potential to be particularly destabilizing to the protein. Here, we introduce green fluorescent protein (GFP) as a model system for addressing these concerns using biosynthetically incorporated p-cyanophenylalanine (pCNF) residues in the interior of GFP and measuring absorption energies of both the intrinsic GFP fluorophore and pCNF residues in response to a series of amino acid mutations. We show that observed changes in emission energy of GFP due to the mutations strongly correlate with changes in electric field experienced by both the nitrile probes and the intrinsic fluorophore. Additionally, we show that changes in electric field measured from the intrinsic fluorophore due to amino acid mutations are unperturbed by the addition of pCNF residues inserted nearby. Finally, we show that changes in electric field experienced by the vibrational probes trend monotonically with changes in field experienced by the native fluorophore even though the nitrile probe is engaged in moderate hydrogen bonding to nearby water molecules, indicated by the temperature dependence of the nitrile's absorption energy. Together these results

  9. Photoactive protochlorophyllide-enzyme complexes reconstituted with PORA, PORB and PORC proteins of A. thaliana: fluorescence and catalytic properties.

    Directory of Open Access Journals (Sweden)

    Michał Gabruk

    Full Text Available Photoactive Pchlide-POR-NADPH complexes were reconstituted using protochlorophyllide (Pchlide and recombinant light-dependent protochlorophyllide oxidoreductase (POR proteins, His₆-PORA, His₆-PORB and His₆-PORC, from Arabidopsis thaliana. We did not observe any differences in the kinetics of the protochlorophyllide photoreduction at room temperature among the PORA, PORB and PORC proteins. In contrast, the PORC protein showed lower yield of Chlide formation than PORA and PORB when preincubated in the dark for 30 min and then illuminated for a short time. The most significant observation was that reconstituted Pchlide-POR-NADPH complexes showed fluorescence maxima at 77 K similar to those observed for highly aggregated Pchlide-POR-NADPH complexes in prolamellar bodies (PLBs in vivo. Homology models of PORA, PORB and PORC of Arabidopsis thaliana were developed to compare predicted structures of POR isoforms. There were only slight structural differences, mainly in the organisation of helices and loops, but not in the shape of whole molecules. This is the first comparative analysis of all POR isoforms functioning at different stages of A. thaliana development.

  10. Photoactive assemblies of organic compounds and biomolecules: drug-protein supramolecular systems

    OpenAIRE

    Vayá Pérez, Ignacio; Lhiaubet-Vallet, Virginie Lyria; Jiménez Molero, María Consuelo; Miranda Alonso, Miguel Ángel

    2014-01-01

    [EN] The properties of singlet and triplet excited states are strongly medium-dependent. Hence, these species constitute valuable tools as reporters to probe compartmentalised microenvironments, including drug@protein supramolecular systems. In the present review, the attention is focused on the photophysical properties of the probe drugs (rather than those of the protein chromophores) using transport proteins (serum albumins and 1-acid glycoproteins) as hosts. Specifically, f...

  11. Photoactive assemblies of organic compounds and biomolecules: drug-protein supramolecular systems.

    Science.gov (United States)

    Vayá, Ignacio; Lhiaubet-Vallet, Virginie; Jiménez, M Consuelo; Miranda, Miguel A

    2014-06-21

    The properties of singlet and triplet excited states are strongly medium-dependent. Hence, these species constitute valuable tools as reporters to probe compartmentalised microenvironments, including drug@protein supramolecular systems. In the present review, the attention is focused on the photophysical properties of the probe drugs (rather than those of the protein chromophores) using transport proteins (serum albumins and α1-acid glycoproteins) as hosts. Specifically, fluorescence measurements allow investigation of the structural and dynamic properties of biomolecules or their complexes. Thus, the emission quantum yields and the decay kinetics of the drug singlet excited states provide key information to determine important parameters such as the stoichiometry of the complex, the binding constant, the relative degrees of occupancy of the different compartments, etc. Application of the FRET concept allows determination of donor-acceptor interchromophoric distances. In addition, anisotropy measurements can be related to the orientation of the drug within the binding sites, where the degrees of freedom for conformational relaxation are restricted. Transient absorption spectroscopy is also a potentially powerful tool to investigate the binding of drugs to proteins, where formation of encapsulated triplet excited states is favoured over other possible processes leading to ionic species (i.e. radical ions), and their photophysical properties are markedly sensitive to the microenvironment experienced within the protein binding sites. Even under aerobic conditions, the triplet lifetimes of protein-complexed drugs are remarkably long, which provides a broad dynamic range for identification of distinct triplet populations or for chiral discrimination. Specific applications of the laser flash photolysis technique include the determination of drug distribution among the bulk solution and the protein binding sites, competition of two types of proteins to bind a drug

  12. Nitrile Metabolizing Yeasts

    Science.gov (United States)

    Bhalla, Tek Chand; Sharma, Monica; Sharma, Nitya Nand

    Nitriles and amides are widely distributed in the biotic and abiotic components of our ecosystem. Nitrile form an important group of organic compounds which find their applications in the synthesis of a large number of compounds used as/in pharmaceutical, cosmetics, plastics, dyes, etc>. Nitriles are mainly hydro-lyzed to corresponding amide/acid in organic chemistry. Industrial and agricultural activities have also lead to release of nitriles and amides into the environment and some of them pose threat to human health. Biocatalysis and biotransformations are increasingly replacing chemical routes of synthesis in organic chemistry as a part of ‘green chemistry’. Nitrile metabolizing organisms or enzymes thus has assumed greater significance in all these years to convert nitriles to amides/ acids. The nitrile metabolizing enzymes are widely present in bacteria, fungi and yeasts. Yeasts metabolize nitriles through nitrilase and/or nitrile hydratase and amidase enzymes. Only few yeasts have been reported to possess aldoxime dehydratase. More than sixty nitrile metabolizing yeast strains have been hither to isolated from cyanide treatment bioreactor, fermented foods and soil. Most of the yeasts contain nitrile hydratase-amidase system for metabolizing nitriles. Transformations of nitriles to amides/acids have been carried out with free and immobilized yeast cells. The nitrilases of Torulopsis candida>and Exophiala oligosperma>R1 are enantioselec-tive and regiospecific respectively. Geotrichum>sp. JR1 grows in the presence of 2M acetonitrile and may have potential for application in bioremediation of nitrile contaminated soil/water. The nitrilase of E. oligosperma>R1 being active at low pH (3-6) has shown promise for the hydroxy acids. Immobilized yeast cells hydrolyze some additional nitriles in comparison to free cells. It is expected that more focus in future will be on purification, characterization, cloning, expression and immobilization of nitrile metabolizing

  13. Reactivity of nitriles

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    Reactivity of coordination nitriles in transition metal (Ru, Mo, W, Zr, Hf) complexes, namely: transformation of nitriles of the first coordination sphere into N-acyl-substituted amides, amidines, nitrile interaction; with water, alkalines, alcoholes, hydrogen, azide and cyanide ions is considered. Introduction of acetonitrile molecule to uranium (4)-carbon double bond is discussed

  14. Photoactive energetic materials

    Science.gov (United States)

    Chavez, David E.; Hanson, Susan Kloek; Scharff, Robert Jason; Veauthier, Jacqueline Marie; Myers, Thomas Winfield

    2018-02-27

    Energetic materials that are photoactive or believed to be photoactive may include a conventional explosive (e.g. PETN, nitroglycerine) derivatized with an energetic UV-absorbing and/or VIS-absorbing chromophore such as 1,2,4,5-tetrazine or 1,3,5-triazine. Absorption of laser light having a suitably chosen wavelength may result in photodissociation, decomposition, and explosive release of energy. These materials may be used as ligands to form complexes. Coordination compounds include such complexes with counterions. Some having the formula M(L).sub.n.sup.2+ were synthesized, wherein M is a transition metal and L is a ligand and n is 2 or 3. These may be photoactive upon exposure to a laser light beam having an appropriate wavelength of UV light, near-IR and/or visible light. Photoactive materials also include coordination compounds bearing non-energetic ligands; in this case, the counterion may be an oxidant such as perchlorate.

  15. Theoretical analysis of geometry and NMR isotope shift in hydrogen-bonding center of photoactive yellow protein by combination of multicomponent quantum mechanics and ONIOM scheme

    Energy Technology Data Exchange (ETDEWEB)

    Kanematsu, Yusuke; Tachikawa, Masanori [Quantum Chemistry Division, Yokohama City University, Seto 22-2, Kanazawa-ku, Yokohama 236-0027 (Japan)

    2014-11-14

    Multicomponent quantum mechanical (MC-QM) calculation has been extended with ONIOM (our own N-layered integrated molecular orbital + molecular mechanics) scheme [ONIOM(MC-QM:MM)] to take account of both the nuclear quantum effect and the surrounding environment effect. The authors have demonstrated the first implementation and application of ONIOM(MC-QM:MM) method for the analysis of the geometry and the isotope shift in hydrogen-bonding center of photoactive yellow protein. ONIOM(MC-QM:MM) calculation for a model with deprotonated Arg52 reproduced the elongation of O–H bond of Glu46 observed by neutron diffraction crystallography. Among the unique isotope shifts in different conditions, the model with protonated Arg52 with solvent effect reasonably provided the best agreement with the corresponding experimental values from liquid NMR measurement. Our results implied the availability of ONIOM(MC-QM:MM) to distinguish the local environment around hydrogen bonds in a biomolecule.

  16. Spectroscopic studies of model photo-receptors: validation of a nanosecond time-resolved micro-spectrophotometer design using photoactive yellow protein and α-phycoerythrocyanin.

    Science.gov (United States)

    Purwar, Namrta; Tenboer, Jason; Tripathi, Shailesh; Schmidt, Marius

    2013-09-13

    Time-resolved spectroscopic experiments have been performed with protein in solution and in crystalline form using a newly designed microspectrophotometer. The time-resolution of these experiments can be as good as two nanoseconds (ns), which is the minimal response time of the image intensifier used. With the current setup, the effective time-resolution is about seven ns, determined mainly by the pulse duration of the nanosecond laser. The amount of protein required is small, on the order of 100 nanograms. Bleaching, which is an undesirable effect common to photoreceptor proteins, is minimized by using a millisecond shutter to avoid extensive exposure to the probing light. We investigate two model photoreceptors, photoactive yellow protein (PYP), and α-phycoerythrocyanin (α-PEC), on different time scales and at different temperatures. Relaxation times obtained from kinetic time-series of difference absorption spectra collected from PYP are consistent with previous results. The comparison with these results validates the capability of this spectrophotometer to deliver high quality time-resolved absorption spectra.

  17. Irradiation of nitrile preforms

    International Nuclear Information System (INIS)

    Salame, M.; Steingiser, S.

    1982-01-01

    The process of forming containers from preforms of thermoplastic material comprising at least 20 weight percent of polymerized nitrile group containing monomer is claimed. The preforms are exposed to low dosage electron beam radiation and then, while at molding temperature, distended into containers in a mold. The radiaton causes polymerization of nitrile group containing monomers and the distending causes HCN generated during irradiation to be reduced in the thermoplastic material

  18. Optimization of photoactive protein Z for fast and efficient site-specific conjugation of native IgG.

    Science.gov (United States)

    Hui, James Z; Tsourkas, Andrew

    2014-09-17

    Antibody conjugates have been used in a variety of applications from immunoassays to drug conjugates. However, it is becoming increasingly clear that in order to maximize an antibody's antigen binding ability and to produce homogeneous antibody-conjugates, the conjugated molecule should be attached onto IgG site-specifically. We previously developed a facile method for the site-specific modification of full length, native IgGs by engineering a recombinant Protein Z that forms a covalent link to the Fc domain of IgG upon exposure to long wavelength UV light. To further improve the efficiency of Protein Z production and IgG conjugation, we constructed a panel of 13 different Protein Z variants with the UV-active amino acid benzoylphenylalanine (BPA) in different locations. By using this panel of Protein Z to cross-link a range of IgGs from different hosts, including human, mouse, and rat, we discovered two previously unknown Protein Z variants, L17BPA and K35BPA, that are capable of cross-linking many commonly used IgG isotypes with efficiencies ranging from 60% to 95% after only 1 h of UV exposure. When compared to existing site-specific methods, which often require cloning or enzymatic reactions, the Protein Z-based method described here, utilizing the L17BPA, K35BPA, and the previously described Q32BPA variants, represents a vastly more accessible and efficient approach that is compatible with nearly all native IgGs, thus making site-specific conjugation more accessible to the general research community.

  19. Insights into catalytic activity of industrial enzyme Co-nitrile hydratase. Docking studies of nitriles and amides.

    Science.gov (United States)

    Peplowski, Lukasz; Kubiak, Karina; Nowak, Wieslaw

    2007-07-01

    Nitrile hydratase (NHase) is an enzyme containing non-corrin Co3+ in the non-standard active site. NHases from Pseudonocardia thermophila JCM 3095 catalyse hydration of nitriles to corresponding amides. The efficiency of the enzyme is 100 times higher for aliphatic nitriles then aromatic ones. In order to understand better this selectivity dockings of a series of aliphatic and aromatic nitriles and related amides into a model protein based on an X-ray structure were performed. Substantial differences in binding modes were observed, showing better conformational freedom of aliphatic compounds. Distinct interactions with postranslationally modified cysteines present in the active site of the enzyme were observed. Modeling shows that water molecule activated by a metal ion may easily directly attack the docked acrylonitrile to transform this molecule into acryloamide. Thus docking studies provide support for one of the reaction mechanisms discussed in the literature.

  20. Photoactivity of Titanium Dioxide Foams

    Directory of Open Access Journals (Sweden)

    Maryam Jami

    2018-01-01

    Full Text Available TiO2 foams have been prepared by a simple mechanical stirring method. Short-chain amphiphilic molecules have been used to stabilize colloidal suspensions of TiO2 nanoparticles. TiO2 foams were characterized by X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, UV-vis absorption spectroscopy, and scanning electron microscopy (SEM. The photoassisted oxidation of NO in the gas phase according to ISO 22197-1 has been used to compare the photoactivity of the newly prepared TiO2 foams to that of the original powders. The results showed that the photoactivity is increased up to about 135%. Foam structures seem to be a good means of improving the photoactivity of semiconductor materials and can readily be used for applications such as air purification devices.

  1. Nitrile biotransformation by Aspergillus niger

    Czech Academy of Sciences Publication Activity Database

    Šnajdrová, Radka; Kristová, Veronika; Crestia, D.; Nikolaou, K.; Kuzma, Marek; Lemaire, M.; Gallienne, E.; Bolte, J.; Bezouška, K.; Křen, Vladimír; Martínková, Ludmila

    2004-01-01

    Roč. 29, - (2004), s. 227-232 ISSN 1381-1177 R&D Projects: GA MŠk OC D25.002; GA AV ČR IAA4020213 Institutional research plan: CEZ:AV0Z5020903 Keywords : aspergillus niger * nitrile-converting enzymes * nitrile hydratase Subject RIV: EE - Microbiology, Virology Impact factor: 1.547, year: 2004

  2. Preconditioning with subneurotoxic allyl nitrile: protection against allyl nitrile neurotoxicity.

    Science.gov (United States)

    Tanii, H; Higashi, T; Saijoh, K

    2010-02-01

    High-dose cruciferous allyl nitrile can induce behavioral abnormalities in rodents, while repeated exposure to allyl nitrile at subneurotoxic levels can increase phase 2 detoxification enzymes in many tissues, although the brain has not been investigated yet. In the present study, we examined the effect of 5 days repeated exposure to subneurotoxic allyl nitrile (0-400 micromol/kg/day) on the brain. Elevated glutathione S-transferase activity was recorded in the striatum, hippocampus, medulla oblongata plus pons, and cortex. Enhancement of quinone reductase activity was observed in the medulla oblongata plus pons, hippocampus, and cortex. In the medulla oblongata plus pons, elevated glutathione levels were recorded. Following repeated subneurotoxic allyl nitrile exposure (0-400 micromol/kg/day), mice were administered a high-dose allyl nitrile (1.2 mmol/kg) which alone led to appearance of behavioral abnormalities. Compared with the 0 micromol/kg/day group, animals in the 200 and 400 micromol/kg/day pre-treatment groups exhibited decreased behavioral abnormalities and elevated GABA-positive cell counts in the substantia nigra pars reticulata and the interpeduncular nucleus. These data suggest that repeated exposure to subneurotoxic levels of allyl nitrile can induce phase 2 enzymes in the brain, which together with induction in other tissues, may contribute to protection against allyl nitrile neurotoxicity. Copyright 2009 Elsevier Ltd. All rights reserved.

  3. Regiospecific decarboxylative allylation of nitriles

    Science.gov (United States)

    Recio, Antonio; Tunge, Jon A.

    2009-01-01

    Palladium-catalyzed decarboxylative α-allylation of nitriles readily occurs using Pd2(dba)3 and rac-BINAP. This catalyst mixture also allows the highly regiospecific α-allylation of nitriles in the presence of much more acidic α-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement. PMID:19921827

  4. Nitrile bonds as infrared probes of electrostatics in ribonuclease S.

    Science.gov (United States)

    Fafarman, Aaron T; Boxer, Steven G

    2010-10-28

    Three different nitrile-containing amino acids, p-cyanophenylalanine, m-cyanophenylalanine, and S-cyanohomocysteine, have been introduced near the active site of the semisynthetic enzyme ribonuclease S (RNase S) to serve as probes of electrostatic fields. Vibrational Stark spectra, measured directly on the probe-modified proteins, confirm the predominance of the linear Stark tuning rate in describing the sensitivity of the nitrile stretch to external electric fields, a necessary property for interpreting observed frequency shifts as a quantitative measure of local electric fields that can be compared with simulations. The X-ray structures of these nitrile-modified RNase variants and enzymatic assays demonstrate minimal perturbation to the structure and function, respectively, by the probes and provide a context for understanding the influence of the environment on the nitrile stretching frequency. We examine the ability of simulation techniques to recapitulate the spectroscopic properties of these nitriles as a means to directly test a computational electrostatic model for proteins, specifically that in the ubiquitous Amber-99 force field. Although qualitative agreement between theory and experiment is observed for the largest shifts, substantial discrepancies are observed in some cases, highlighting the ongoing need for experimental metrics to inform the development of theoretical models of electrostatic fields in proteins.

  5. Nitrile rubber and carboxylated nitrile rubber resistance to soybean biodiesel

    Directory of Open Access Journals (Sweden)

    Felipe Nunes Linhares

    2018-03-01

    Full Text Available Abstract Biodiesel has been considered a suitable substitute for petroleum diesel, but their chemical composition differs greatly. For this reason, biodiesel interacts differently than petroleum diesel with various materials, including rubbers. Therefore, the resistance of some elastomers should be thoroughly evaluated, specifically those which are commonly used in automotive industry. Nitrile rubber (NBR is widely used to produce vehicular parts that are constantly in contact with fuels. This paper aimed to assess the resistance of carboxylated nitrile rubber (XNBR with 28% of acrylonitrile content to soybean biodiesel in comparison with non-carboxylated nitrile rubber samples, with high and medium acrylonitrile content (33 and 45%. NBR with medium acrylonitrile content showed little resistance to biodiesel. However, carboxylated nitrile rubber even with low acrylonitrile content had similar performance to NBR with high acrylonitrile content.

  6. Antimalarial Activity of Azadipeptide Nitriles

    OpenAIRE

    Löser, Reik; Gut, Jiri; Rosenthal, Philip J.; Frizler, Maxim; Gütschow, Michael; Andrews, Katherine T.

    2009-01-01

    Azadipeptide nitriles – novel cysteine protease inhibitors – display structure-dependent antimalarial activity against both chloroquine-sensitive and chloroquine-resistant lines of cultured Plasmodium falciparum malaria parasites. Inhibition of parasite’s haemoglobin-degrading cysteine proteases was also investigated, revealing the azadipeptide nitriles as potent inhibitors of falcipain-2 and -3. A correlation between the cysteine protease-inhibiting activity and the antimalarial potential of...

  7. Allyl nitrile: Toxicity and health effects.

    Science.gov (United States)

    Tanii, Hideji

    2017-03-28

    Allyl nitrile (3-butenenitrile) occurs naturally in the environment, in particular, in cruciferous vegetables, indicating a possible daily intake of the compound. There is no report on actual health effects of allyl nitrile in humans, although it is possible that individuals in the environment are at a risk of exposure to allyl nitrile. However, little is known about its quantitative assessment for the environment and bioactivity in the body. This study provides a review of previous accumulated studies on allyl nitrile. Published literature on allyl nitrile was examined for findings on toxicity, metabolism, risk of various cancers, generation, intake estimates, and low-dose effects in the body. High doses of allyl nitrile produce toxicity characterized by behavioral abnormalities, which are considered to be produced by an active metabolite, 3,4-epoxybutyronitrile. Cruciferous vegetables have been shown to have a potential role in reducing various cancers. Hydrolysis of the glucosinolate sinigrin, rich in cruciferous vegetables, results in the generation of allyl nitrile. An intake of allyl nitrile is estimated at 0.12 μmol/kg body weight in Japan. Repeated exposure to low doses of allyl nitrile upregulates antioxidant/phase II enzymes in various tissues; this may contribute to a reduction in neurotoxicity and skin inflammation. These high and low doses are far more than the intake estimate. Allyl nitrile in the environment is a compound with diverse bioactivities in the body, characterized by inducing behavioral abnormalities at high doses and some antioxidant/phase II enzymes at low doses.

  8. Nitrile rubber and carboxylated nitrile rubber resistance to soybean biodiesel

    OpenAIRE

    Felipe Nunes Linhares; Cléverson Fernandes Senra Gabriel; Ana Maria Furtado de Sousa; Marcia Christina Amorim Moreira Leite; Cristina Russi Guimarães Furtado

    2018-01-01

    Abstract Biodiesel has been considered a suitable substitute for petroleum diesel, but their chemical composition differs greatly. For this reason, biodiesel interacts differently than petroleum diesel with various materials, including rubbers. Therefore, the resistance of some elastomers should be thoroughly evaluated, specifically those which are commonly used in automotive industry. Nitrile rubber (NBR) is widely used to produce vehicular parts that are constantly in contact with fuels. T...

  9. Interaction of nitriles with electrophilic reagents

    International Nuclear Information System (INIS)

    Gridnev, I.D.; Gridneva, N.A.

    1995-01-01

    Reactions of organic nitriles with various electrophiles, Lewis acids (BF 3 , BCl 3 , RuCl 2 , NbCl 5 , ReCl 4 , etc.) in particular, were analysed. Features of nitriles coordination with transition metals (Mo, Ru, Re, Pt, etc.) were considered. It is shown that numerous processes observed in these reactions exhibit rather similar features and are mainly controlled by the nucleophilic properties of a nitrile. REfs, 99, tabs. 8

  10. A high-throughput screening strategy for nitrile-hydrolyzing enzymes based on ferric hydroxamate spectrophotometry.

    Science.gov (United States)

    He, Yu-Cai; Ma, Cui-Luan; Xu, Jian-He; Zhou, Li

    2011-02-01

    Nitrile-hydrolyzing enzymes (nitrilase or nitrile hydratase/amidase) have been widely used in the pharmaceutical industry for the production of carboxylic acids and their derivatives, and it is important to build a method for screening for nitrile-hydrolyzing enzymes. In this paper, a simple, rapid, and high-throughput screening method based on the ferric hydroxamate spectrophotometry has been proposed. To validate the accuracy of this screening strategy, the nitrilases from Rhodococcus erythropolis CGMCC 1.2362 and Alcaligenes sp. ECU0401 were used for evaluating the method. As a result, the accuracy for assaying aliphatic and aromatic carboxylic acids was as high as the HPLC-based method. Therefore, the method may be potentially used in the selection of microorganisms or engineered proteins with nitrile-hydrolyzing enzymes.

  11. Iron-Catalyzed Dehydration of Aldoximes to Nitriles Requiring Neither Other Reagents Nor Nitrile Media.

    Science.gov (United States)

    Hyodo, Kengo; Kitagawa, Saki; Yamazaki, Masayuki; Uchida, Kingo

    2016-05-06

    The dehydration of aldoximes is an environmentally benign reaction affording the desired nitrile and water as a by-product. However, most of the reported catalytic dehydration reactions of aldoximes require a solvent containing nitrile to synthesize the corresponding nitrile compounds. Inspired by recent reports on the enzymatic synthesis under nitrile-free conditions, we here describe that a simple iron salt catalyzes the dehydration of aldoximes requiring neither other reagents nor nitrile media. Our method can be applied to the one-pot synthesis of nitiriles from aldehydes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Enantioselective biotransformations of nitriles in organic synthesis.

    Science.gov (United States)

    Wang, Mei-Xiang

    2015-03-17

    The hydration and hydrolysis of nitriles are valuable synthetic methods used to prepare carboxamides and carboxylic acids. However, chemical hydration and hydrolysis of nitriles involve harsh reaction conditions, have low selectivity, and generate large amounts of waste. Therefore, researchers have confined the scope of these reactions to simple nitrile substrates. However, biological transformations of nitriles are highly efficient, chemoselective, and environmentally benign, which has led synthetic organic chemists and biotechologists to study these reactions in detail over the last two decades. In nature, biological systems degrade nitriles via two distinct pathways: nitrilases catalyze the direct hydrolysis of nitriles to afford carboxylic acids with release of ammonia, and nitrile hydratases catalyze the conversion of nitriles into carboxamides, which then furnish carboxylic acids via hydrolysis in the presence of amidases. Researchers have subsequently developed biocatalytic methods into useful industrial processes for the manufacture of commodity chemicals, including acrylamide. Since the late 1990s, research by my group and others has led to enormous progress in the understanding and application of enantioselective biotransformations of nitriles in organic synthesis. In this Account, I summarize the important advances in enantioselective biotransformations of nitriles and amides, with a primary focus on research from my laboratory. I describe microbial whole-cell-catalyzed kinetic resolution of various functionalized nitriles, amino- and hydroxynitriles, and nitriles that contain small rings and the desymmetrization of prochiral and meso dinitriles and diamides. I also demonstrate how we can apply the biocatalytic protocol to synthesize natural products and bioactive compounds. These nitrile biotransformations offer an attractive and unique protocol for the enantioselective synthesis of polyfunctionalized organic compounds that are not readily obtainable by

  13. The genetic basis of constitutive and herbivore-induced ESP-independent nitrile formation in Arabidopsis.

    Science.gov (United States)

    Burow, Meike; Losansky, Anja; Müller, René; Plock, Antje; Kliebenstein, Daniel J; Wittstock, Ute

    2009-01-01

    Glucosinolates are a group of thioglucosides that are components of an activated chemical defense found in the Brassicales. Plant tissue damage results in hydrolysis of glucosinolates by endogenous thioglucosidases known as myrosinases. Spontaneous rearrangement of the aglucone yields reactive isothiocyanates that are toxic to many organisms. In the presence of specifier proteins, alternative products, namely epithionitriles, simple nitriles, and thiocyanates with different biological activities, are formed at the expense of isothiocyanates. Recently, simple nitriles were recognized to serve distinct functions in plant-insect interactions. Here, we show that simple nitrile formation in Arabidopsis (Arabidopsis thaliana) ecotype Columbia-0 rosette leaves increases in response to herbivory and that this increase is independent of the known epithiospecifier protein (ESP). We combined phylogenetic analysis, a screen of Arabidopsis mutants, recombinant protein characterization, and expression quantitative trait locus mapping to identify a gene encoding a nitrile-specifier protein (NSP) responsible for constitutive and herbivore-induced simple nitrile formation in Columbia-0 rosette leaves. AtNSP1 is one of five Arabidopsis ESP homologues that promote simple nitrile, but not epithionitrile or thiocyanate, formation. Four of these homologues possess one or two lectin-like jacalin domains, which share a common ancestry with the jacalin domains of the putative Arabidopsis myrosinase-binding proteins MBP1 and MBP2. A sixth ESP homologue lacked specifier activity and likely represents the ancestor of the gene family with a different biochemical function. By illuminating the genetic and biochemical bases of simple nitrile formation, our study provides new insights into the evolution of metabolic diversity in a complex plant defense system.

  14. Nitrile versus Latex for Glove Juice Sampling.

    Directory of Open Access Journals (Sweden)

    Timothy F Landers

    Full Text Available The objective of this study was to explore the utility of nitrile gloves as a replacement for latex surgical gloves in recovering bacteria from the hands. Two types of nitrile gloves were compared to latex gloves using the parallel streak method. Streaks of Klebsiella pneumoniae and Staphylococcus aureus were made on tryptic soy agar plates, and the zones of inhibition were measured around pieces of glove material placed on the plates. Latex gloves produced a mean zone of inhibition of 0.28 mm, compared to 0.002 mm for nitrile gloves (p<.001. While the parallel streak method is not intended as a quantitative estimate of antimicrobial properties, these results suggest that nitrile may be a viable alternative to latex in glove juice sampling methods, since nitrile avoids the risk of latex exposure.

  15. Differing mechanisms of simple nitrile formation on glucosinolate degradation in Lepidium sativum and Nasturtium officinale seeds.

    Science.gov (United States)

    Williams, David J; Critchley, Christa; Pun, Sharon; Chaliha, Mridusmita; O'Hare, Timothy J

    2009-01-01

    Glucosinolates are sulphur-containing glycosides found in brassicaceous plants that can be hydrolysed enzymatically by plant myrosinase or non-enzymatically to form primarily isothiocyanates and/or simple nitriles. From a human health perspective, isothiocyanates are quite important because they are major inducers of carcinogen-detoxifying enzymes. Two of the most potent inducers are benzyl isothiocyanate (BITC) present in garden cress (Lepidium sativum), and phenylethyl isothiocyanate (PEITC) present in watercress (Nasturtium officinale). Previous studies on these salad crops have indicated that significant amounts of simple nitriles are produced at the expense of the isothiocyanates. These studies also suggested that nitrile formation may occur by different pathways: (1) under the control of specifier protein in garden cress and (2) by an unspecified, non-enzymatic path in watercress. In an effort to understand more about the mechanisms involved in simple nitrile formation in these species, we analysed their seeds for specifier protein and myrosinase activities, endogenous iron content and glucosinolate degradation products after addition of different iron species, specific chelators and various heat treatments. We confirmed that simple nitrile formation was predominantly under specifier protein control (thiocyanate-forming protein) in garden cress seeds. Limited thermal degradation of the major glucosinolate, glucotropaeolin (benzyl glucosinolate), occurred when seed material was heated to >120 degrees C. In the watercress seeds, however, we show for the first time that gluconasturtiin (phenylethyl glucosinolate) undergoes a non-enzymatic, iron-dependent degradation to a simple nitrile. On heating the seeds to 120 degrees C or greater, thermal degradation of this heat-labile glucosinolate increased simple nitrile levels many fold.

  16. Nitrile versus Latex for Glove Juice Sampling.

    Science.gov (United States)

    Landers, Timothy F; Dent, Anthony

    2014-01-01

    The objective of this study was to explore the utility of nitrile gloves as a replacement for latex surgical gloves in recovering bacteria from the hands. Two types of nitrile gloves were compared to latex gloves using the parallel streak method. Streaks of Klebsiella pneumoniae and Staphylococcus aureus were made on tryptic soy agar plates, and the zones of inhibition were measured around pieces of glove material placed on the plates. Latex gloves produced a mean zone of inhibition of 0.28 mm, compared to 0.002 mm for nitrile gloves (pnitrile may be a viable alternative to latex in glove juice sampling methods, since nitrile avoids the risk of latex exposure.

  17. Enzyme-substrate binding landscapes in the process of nitrile biodegradation mediated by nitrile hydratase and amidase.

    Science.gov (United States)

    Zhang, Yu; Zeng, Zhuotong; Zeng, Guangming; Liu, Xuanming; Chen, Ming; Liu, Lifeng; Liu, Zhifeng; Xie, Gengxin

    2013-08-01

    The continuing discharge of nitriles in various industrial processes has caused serious environmental consequences of nitrile pollution. Microorganisms possess several nitrile-degrading pathways by direct interactions of nitriles with nitrile-degrading enzymes. However, these interactions are largely unknown and difficult to experimentally determine but important for interpretation of nitrile metabolisms and design of nitrile-degrading enzymes with better nitrile-converting activity. Here, we undertook a molecular modeling study of enzyme-substrate binding modes in the bi-enzyme pathway for degradation of nitrile to acid. Docking results showed that the top substrates having favorable interactions with nitrile hydratase from Rhodococcus erythropolis AJ270 (ReNHase), nitrile hydratase from Pseudonocardia thermophila JCM 3095 (PtNHase), and amidase from Rhodococcus sp. N-771 (RhAmidase) were benzonitrile, 3-cyanopyridine, and L-methioninamide, respectively. We further analyzed the interactional profiles of these top poses with corresponding enzymes, showing that specific residues within the enzyme's binding pockets formed diverse contacts with substrates. This information on binding landscapes and interactional profiles is of great importance for the design of nitrile-degrading enzyme mutants with better oxidation activity toward nitriles or amides in the process of pollutant treatments.

  18. Characterisation of nitrilase and nitrile hydratase biocatalytic systems

    CSIR Research Space (South Africa)

    Brady, D

    2004-03-01

    Full Text Available (Faber 1992; Vogel 1989; Weiner and Chaplin 2000). Other nitrile compounds Many nitrile substrates were available from the laboratory com- pound inventory. All other substrates were obtained from Acros or Sigma. Analytical methods A Chromolith... regioselectivity for converting aromatic nitriles to the corresponding acid, but was also capable of hydrolys- ing aliphatic nitriles (Cohen et al. 1990). This catalytic capacity of Rhodococcus Novo SP361 for a broad substrate range was also observed...

  19. The Genetic Basis of Constitutive and Herbivore-Induced ESP-Independent Nitrile Formation in Arabidopsis1[W][OA

    Science.gov (United States)

    Burow, Meike; Losansky, Anja; Müller, René; Plock, Antje; Kliebenstein, Daniel J.; Wittstock, Ute

    2009-01-01

    Glucosinolates are a group of thioglucosides that are components of an activated chemical defense found in the Brassicales. Plant tissue damage results in hydrolysis of glucosinolates by endogenous thioglucosidases known as myrosinases. Spontaneous rearrangement of the aglucone yields reactive isothiocyanates that are toxic to many organisms. In the presence of specifier proteins, alternative products, namely epithionitriles, simple nitriles, and thiocyanates with different biological activities, are formed at the expense of isothiocyanates. Recently, simple nitriles were recognized to serve distinct functions in plant-insect interactions. Here, we show that simple nitrile formation in Arabidopsis (Arabidopsis thaliana) ecotype Columbia-0 rosette leaves increases in response to herbivory and that this increase is independent of the known epithiospecifier protein (ESP). We combined phylogenetic analysis, a screen of Arabidopsis mutants, recombinant protein characterization, and expression quantitative trait locus mapping to identify a gene encoding a nitrile-specifier protein (NSP) responsible for constitutive and herbivore-induced simple nitrile formation in Columbia-0 rosette leaves. AtNSP1 is one of five Arabidopsis ESP homologues that promote simple nitrile, but not epithionitrile or thiocyanate, formation. Four of these homologues possess one or two lectin-like jacalin domains, which share a common ancestry with the jacalin domains of the putative Arabidopsis myrosinase-binding proteins MBP1 and MBP2. A sixth ESP homologue lacked specifier activity and likely represents the ancestor of the gene family with a different biochemical function. By illuminating the genetic and biochemical bases of simple nitrile formation, our study provides new insights into the evolution of metabolic diversity in a complex plant defense system. PMID:18987211

  20. 40 CFR 721.5350 - Substituted nitrile (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted nitrile (generic name... Substances § 721.5350 Substituted nitrile (generic name). (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted nitrile (PMN P-83...

  1. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino nitriles (generic). 721... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96...

  2. Expression control of nitrile hydratase and amidase genes in Rhodococcus erythropolis and substrate specificities of the enzymes.

    Science.gov (United States)

    Rucká, Lenka; Volkova, Olga; Pavlík, Adam; Kaplan, Ondřej; Kracík, Martin; Nešvera, Jan; Martínková, Ludmila; Pátek, Miroslav

    2014-06-01

    Bacterial amidases and nitrile hydratases can be used for the synthesis of various intermediates and products in the chemical and pharmaceutical industries and for the bioremediation of toxic pollutants. The aim of this study was to analyze the expression of the amidase and nitrile hydratase genes of Rhodococcus erythropolis and test the stereospecific nitrile hydratase and amidase activities on chiral cyanohydrins. The nucleotide sequences of the gene clusters containing the oxd (aldoxime dehydratase), ami (amidase), nha1, nha2 (subunits of the nitrile hydratase), nhr1, nhr2, nhr3 and nhr4 (putative regulatory proteins) genes of two R. erythropolis strains, A4 and CCM2595, were determined. All genes of both of the clusters are transcribed in the same direction. RT-PCR analysis, primer extension and promoter fusions with the gfp reporter gene showed that the ami, nha1 and nha2 genes of R. erythropolis A4 form an operon transcribed from the Pami promoter and an internal Pnha promoter. The activity of Pami was found to be weakly induced when the cells grew in the presence of acetonitrile, whereas the Pnha promoter was moderately induced by both the acetonitrile or acetamide used instead of the inorganic nitrogen source. However, R. erythropolis A4 cells showed no increase in amidase and nitrile hydratase activities in the presence of acetamide or acetonitrile in the medium. R. erythropolis A4 nitrile hydratase and amidase were found to be effective at hydrolysing cyanohydrins and 2-hydroxyamides, respectively.

  3. Making waves in a photoactive polymer film

    Science.gov (United States)

    Gelebart, Anne Helene; Jan Mulder, Dirk; Varga, Michael; Konya, Andrew; Vantomme, Ghislaine; Meijer, E. W.; Selinger, Robin L. B.; Broer, Dirk J.

    2017-06-01

    Oscillating materials that adapt their shapes in response to external stimuli are of interest for emerging applications in medicine and robotics. For example, liquid-crystal networks can be programmed to undergo stimulus-induced deformations in various geometries, including in response to light. Azobenzene molecules are often incorporated into liquid-crystal polymer films to make them photoresponsive; however, in most cases only the bending responses of these films have been studied, and relaxation after photo-isomerization is rather slow. Modifying the core or adding substituents to the azobenzene moiety can lead to marked changes in photophysical and photochemical properties, providing an opportunity to circumvent the use of a complex set-up that involves multiple light sources, lenses or mirrors. Here, by incorporating azobenzene derivatives with fast cis-to-trans thermal relaxation into liquid-crystal networks, we generate photoactive polymer films that exhibit continuous, directional, macroscopic mechanical waves under constant light illumination, with a feedback loop that is driven by self-shadowing. We explain the mechanism of wave generation using a theoretical model and numerical simulations, which show good qualitative agreement with our experiments. We also demonstrate the potential application of our photoactive films in light-driven locomotion and self-cleaning surfaces, and anticipate further applications in fields such as photomechanical energy harvesting and miniaturized transport.

  4. Reactions of acid bisphosphonodithioates with nitriles

    International Nuclear Information System (INIS)

    Kutyrev, G.A.; Korolev, O.S.; Yarkova, E.G.; Cherkasov, R.A.; Pudovik, A.N.

    1986-01-01

    The reactions of acid bisphosphonodithioates with aceto- and benzo-nitriles go with the intermediate formation of a 1:1 adduct, which breaks down into a thioamide and a cyclic trithiopyrophosphonate. The stability of the latter falls with the lengthening of the carbon chain in the original thiophosphorus reactant. A detailed analysis of IR and NMR spectra is given to confirm these results

  5. An update of nitrile photochemistry on Titan

    Science.gov (United States)

    Yung, Yuk L.

    1987-01-01

    Comparisons are undertaken between laboratory kinetics experiments and Voyager observations in order to shed light on possible chemical reaction pathways to the generation of cyanogen and dicyanoacetylene in Titan's upper atmosphere. The predicted concentrations of the simple nitrile compounds are found to be of a magnitude realistically corresponding to the Voyager observations.

  6. Synthetic Applications of Nitrile-Converting Enzymes

    Czech Academy of Sciences Publication Activity Database

    Martínková, Ludmila; Mylerová, Veronika

    2003-01-01

    Roč. 7, - (2003), s. 1279-1295 ISSN 1385-2728 R&D Projects: GA AV ČR IAA4020213 Institutional research plan: CEZ:AV0Z5020903 Keywords : nitrile * converting * enzymes Subject RIV: EE - Microbiology, Virology Impact factor: 2.521, year: 2003

  7. [Effects of nitriles and amides on the growth and the nitrile hydratase activity of the Rhodococcus sp. strain gt1].

    Science.gov (United States)

    Maksimov, A Iu; Kuznetsova, M V; Ovechkina, G V; Kozlov, S V; Maksimova, Iu G; Demakov, V A

    2003-01-01

    Effects of some nitriles and amides, as well as glucose and ammonium, on the growth and the nitrile hydratase (EC 4.2.1.84) activity of the Rhodococcus sp. strain gt1 isolated from soil were studied. The activity of nitrile hydratase mainly depended on carbon and nitrogen supply to cells. The activity of nitrile hydratase was high in the presence of glucose and ammonium at medium concentrations and decreased at concentrations of glucose more than 0.3%. Saturated unsubstituted aliphatic nitriles and amides were found to be a good source of nitrogen and carbon. However, the presence of nitriles and amides in the medium was not absolutely necessary for the expression of the activity of nitrile hydratase isolated from the Rhodococcus sp. strain gt1.

  8. Ribonuclease S dynamics measured using a nitrile label with 2D IR vibrational echo spectroscopy.

    Science.gov (United States)

    Bagchi, Sayan; Boxer, Steven G; Fayer, Michael D

    2012-04-05

    A nitrile-labeled amino acid, p-cyanophenylalanine, is introduced near the active site of the semisynthetic enzyme ribonuclease S to serve as a probe of protein dynamics and fluctuations. Ribonuclease S is the limited proteolysis product of subtilisin acting on ribonuclease A, and consists of a small fragment including amino acids 1-20, the S-peptide, and a larger fragment including residues 21-124, the S-protein. A series of two-dimensional vibrational echo experiments performed on the nitrile-labeled S-peptide and the RNase S are described. The time-dependent changes in the two-dimensional infrared vibrational echo line shapes are analyzed using the center line slope method to obtain the frequency-frequency correlation function (FFCF). The observations show that the nitrile probe in the S-peptide has dynamics that are similar to, but faster than, those of the single amino acid p-cyanophenylalanine in water. In contrast, the dynamics of the nitrile label when the peptide is bound to form ribonuclease S are dominated by homogeneous dephasing (motionally narrowed) contributions with only a small contribution from very fast inhomogeneous structural dynamics. The results provide insights into the nature of the structural dynamics of the ribonuclease S complex. The equilibrium dynamics of the nitrile labeled S-peptide and the ribonuclease S complex are also investigated by molecular dynamics simulations. The experimentally determined FFCFs are compared to the FFCFs obtained from the molecular dynamics simulations, thereby testing the capacity of simulations to determine the amplitudes and time scales of protein structural fluctuations on fast time scales under thermal equilibrium conditions.

  9. Photoactive devices including porphyrinoids with coordinating additives

    Science.gov (United States)

    Forrest, Stephen R; Zimmerman, Jeramy; Yu, Eric K; Thompson, Mark E; Trinh, Cong; Whited, Matthew; Diev, Vlacheslav

    2015-05-12

    Coordinating additives are included in porphyrinoid-based materials to promote intermolecular organization and improve one or more photoelectric characteristics of the materials. The coordinating additives are selected from fullerene compounds and organic compounds having free electron pairs. Combinations of different coordinating additives can be used to tailor the characteristic properties of such porphyrinoid-based materials, including porphyrin oligomers. Bidentate ligands are one type of coordinating additive that can form coordination bonds with a central metal ion of two different porphyrinoid compounds to promote porphyrinoid alignment and/or pi-stacking. The coordinating additives can shift the absorption spectrum of a photoactive material toward higher wavelengths, increase the external quantum efficiency of the material, or both.

  10. An Aeroplysinin-1 Specific Nitrile Hydratase Isolated from the Marine Sponge Aplysina cavernicola

    Directory of Open Access Journals (Sweden)

    Peter Proksch

    2013-08-01

    Full Text Available A nitrile hydratase (NHase that specifically accepts the nitrile aeroplysinin-1 (1 as a substrate and converts it into the dienone amide verongiaquinol (7 was isolated, partially purified and characterized from the Mediterranean sponge Aplysina cavernicola; although it is currently not known whether the enzyme is of sponge origin or produced by its symbiotic microorganisms. The formation of aeroplysinin-1 and of the corresponding dienone amide is part of the chemical defence system of A. cavernicola. The latter two compounds that show strong antibiotic activity originate from brominated isoxazoline alkaloids that are thought to protect the sponges from invasion of bacterial pathogens. The sponge was shown to contain at least two NHases as two excised protein bands from a non denaturating Blue Native gel showed nitrile hydratase activity, which was not observed for control samples. The enzymes were shown to be manganese dependent, although cobalt and nickel ions were also able to recover the activity of the nitrile hydratases. The temperature and pH optimum of the studied enzymes were found at 41 °C and pH 7.8. The enzymes showed high substrate specificity towards the physiological substrate aeroplysinin-1 (1 since none of the substrate analogues that were prepared either by partial or by total synthesis were converted in an in vitro assay. Moreover de-novo sequencing by mass spectrometry was employed to obtain information about the primary structure of the studied NHases, which did not reveal any homology to known NHases.

  11. Computational study on the inhibition mechanism of cruzain by nitrile-containing molecules.

    Science.gov (United States)

    Méndez-Lucio, Oscar; Romo-Mancillas, Antonio; Medina-Franco, José L; Castillo, Rafael

    2012-05-01

    Cysteine proteases from parasites as well as from mammals are promising drug targets for parasitic infections and systemic human diseases, respectively. Many reversible and irreversible inhibitors of this very large class of proteins have been designed. Among others, molecules with a nitrile moiety, which is a group that is susceptible to a nucleophilic attack by the enzyme, have been identified as good inhibitors. Although it is known that the nitrile group binds covalently to Cys25, there are no reports about the energetics involved in the mechanism of this process. Herein, density functional theory and quantum semi-empirical calculations were conducted in order to study the molecular recognition of cysteine proteases by nitrile-containing molecules. Results reported in this paper suggest an interaction that starts with a nucleophilic attack from the Cys25 to the inhibitor followed by a proton transfer from His162. Only one transition state was detected; however, we found the existence of an energy plateau in the potential energy surface. Based on the proposed mechanism, some structural features that could improve the biological activity of nitrile-containing molecules toward cysteine proteases are discussed. Copyright © 2012 Elsevier Inc. All rights reserved.

  12. Enzymatic degradation of aliphatic nitriles by Rhodococcus rhodochrous BX2, a versatile nitrile-degrading bacterium.

    Science.gov (United States)

    Fang, Shumei; An, Xuejiao; Liu, Hongyuan; Cheng, Yi; Hou, Ning; Feng, Lu; Huang, Xinning; Li, Chunyan

    2015-06-01

    Nitriles are common environmental pollutants, and their removal has attracted increasing attention. Microbial degradation is considered to be the most acceptable method for removal. In this work, we investigated the biodegradation of three aliphatic nitriles (acetonitrile, acrylonitrile and crotononitrile) by Rhodococcus rhodochrous BX2 and the expression of their corresponding metabolic enzymes. This organism can utilize all three aliphatic nitriles as sole carbon and nitrogen sources, resulting in the complete degradation of these compounds. The degradation kinetics were described using a first-order model. The degradation efficiency was ranked according to t1/2 as follows: acetonitrile>trans-crotononitrile>acrylonitrile>cis-crotononitrile. Only ammonia accumulated following the three nitriles degradation, while amides and carboxylic acids were transient and disappeared by the end of the assay. mRNA expression and enzyme activity indicated that the tested aliphatic nitriles were degraded via both the inducible NHase/amidase and the constitutive nitrilase pathways, with the former most likely preferred. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Characterisation of the nitrile biocatalytic activity of rhodococcus rhodochrous ATCC BAA-870

    CSIR Research Space (South Africa)

    Frederick, J

    2006-10-01

    Full Text Available rhodochrous ATCC BAA-870, was explored. The biocatalyst expressed a two enzyme system with sequential nitrile-converting activity: nitrile hydratase and amidase. This biocatalytic nitrile hydrolysis affords valuable applications in industry, including...

  14. Detection of Singlet Oxygen Formation inside Photoactive Biohybrid Composite Material

    Directory of Open Access Journals (Sweden)

    Kata Hajdu

    2017-12-01

    Full Text Available Photosynthetic reaction center proteins (RCs are the most efficient light energy converter systems in nature. The first steps of the primary charge separation in photosynthesis take place in these proteins. Due to their unique properties, combining RCs with nano-structures promising applications can be predicted in optoelectronic systems. In the present work RCs purified from Rhodobacter sphaeroides purple bacteria were immobilized on multiwalled carbon nanotubes (CNTs. Carboxyl—and amine-functionalised CNTs were used, so different binding procedures, physical sorption and chemical sorption as well, could be applied as immobilization techniques. Light-induced singlet oxygen production was measured in the prepared photoactive biocomposites in water-based suspension by histidine mediated chemical trapping. Carbon nanotubes were applied under different conditions in order to understand their role in the equilibration of singlet oxygen concentration in the suspension. CNTs acted as effective quenchers of 1O2 either by physical (resonance energy transfer or by chemical (oxidation reaction and their efficiency showed dependence on the diffusion distance of 1O2.

  15. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    The objective of this thesis is to report the development of a new, alternative process for the flexible production of nitrile compounds in continuous flow. Nitriles are an important class of compounds that find applications as solvents, chemical intermediates and pharmaceutical compounds......, alternative path to acetonitrile from ethanol via the oxidative dehydrogenation of ethylamine. The catalytic activity and product ratios of the batch and continuous flow reactions are compared and the effect of reaction conditions on the reaction is investigated. The effects of ammonia in the reaction...... dehydrogenation of ethylamine and post-reaction purging.Chapter 4 outlines the application of RuO2/Al2O3 catalysts to the oxidative dehydrogenation of benzylamine in air, utilizing a new reaction setup. Again, batch and continuous flow reactions are compared and the effects of reaction conditions, ammonia...

  16. Green proteorhodopsin reconstituted into nanoscale phospholipid bilayers (nanodiscs) as photoactive monomers.

    Science.gov (United States)

    Ranaghan, Matthew J; Schwall, Christine T; Alder, Nathan N; Birge, Robert R

    2011-11-16

    Over 4000 putative proteorhodopsins (PRs) have been identified throughout the oceans and seas of the Earth. The first of these eubacterial rhodopsins was discovered in 2000 and has expanded the family of microbial proton pumps to all three domains of life. With photophysical properties similar to those of bacteriorhodopsin, an archaeal proton pump, PRs are also generating interest for their potential use in various photonic applications. We perform here the first reconstitution of the minimal photoactive PR structure into nanoscale phospholipid bilayers (nanodiscs) to better understand how protein-protein and protein-lipid interactions influence the photophysical properties of PR. Spectral (steady-state and time-resolved UV-visible spectroscopy) and physical (size-exclusion chromatography and electron microscopy) characterization of these complexes confirms the preparation of a photoactive PR monomer within nanodiscs. Specifically, when embedded within a nanodisc, monomeric PR exhibits a titratable pK(a) (6.5-7.1) and photocycle lifetime (∼100-200 ms) that are comparable to the detergent-solubilized protein. These ndPRs also produce a photoactive blue-shifted absorbance, centered at 377 or 416 nm, that indicates that protein-protein interactions from a PR oligomer are required for a fast photocycle. Moreover, we demonstrate how these model membrane systems allow modulation of the PR photocycle by variation of the discoidal diameter (i.e., 10 or 12 nm), bilayer thickness (i.e., 23 or 26.5 Å), and degree of saturation of the lipid acyl chain. Nanodiscs also offer a highly stable environment of relevance to potential device applications.

  17. Copper-Mediated Reactions of Nitriles with Nitromethanes: Aza-Henry Reactions and Nitrile Hydrations.

    Science.gov (United States)

    Kuwabara, Jun; Sawada, Yoshiharu; Yoshimatsu, Mitsuhiro

    2018-02-16

    In this study, the first aza-Henry reaction of nitriles with nitromethane in a CuI/Cs 2 CO 3 /DBU system is described. The process was conveniently and directly used for the synthesis of β-aminonitroalkenes 2a-x and tolerated aryl-, alkyl-, hetaryl-, alkenyl-, and alkynylnitriles. The resulting aminonitroalkenes 2 could be successfully transformed to the corresponding 2-nitroacetophenones, 2-amino-1-halonitroalkenes, 2-alkylaminonitroalkenes, or 3-nitropyridines. In the presence of H 2 O, the aza-Henry reaction turned the reaction path to the nitrile hydration to exclusively yield the amides 3a-s.

  18. Photovoltaic device comprising compositionally graded intrinsic photoactive layer

    Science.gov (United States)

    Hoffbauer, Mark A; Williamson, Todd L

    2013-04-30

    Photovoltaic devices and methods of making photovoltaic devices comprising at least one compositionally graded photoactive layer, said method comprising providing a substrate; growing onto the substrate a uniform intrinsic photoactive layer having one surface disposed upon the substrate and an opposing second surface, said intrinsic photoactive layer consisting essentially of In.sub.1-xA.sub.xN,; wherein: i. 0.ltoreq.x.ltoreq.1; ii. A is gallium, aluminum, or combinations thereof; and iii. x is at least 0 on one surface of the intrinsic photoactive layer and is compositionally graded throughout the layer to reach a value of 1 or less on the opposing second surface of the layer; wherein said intrinsic photoactive layer is isothermally grown by means of energetic neutral atom beam lithography and epitaxy at a temperature of 600.degree. C. or less using neutral nitrogen atoms having a kinetic energy of from about 1.0 eV to about 5.0 eV, and wherein the intrinsic photoactive layer is grown at a rate of from about 5 nm/min to about 100 nm/min.

  19. Calculation of vibrational shifts of nitrile probes in the active site of ketosteroid isomerase upon ligand binding.

    Science.gov (United States)

    Layfield, Joshua P; Hammes-Schiffer, Sharon

    2013-01-16

    The vibrational Stark effect provides insight into the roles of hydrogen bonding, electrostatics, and conformational motions in enzyme catalysis. In a recent application of this approach to the enzyme ketosteroid isomerase (KSI), thiocyanate probes were introduced in site-specific positions throughout the active site. This paper implements a quantum mechanical/molecular mechanical (QM/MM) approach for calculating the vibrational shifts of nitrile (CN) probes in proteins. This methodology is shown to reproduce the experimentally measured vibrational shifts upon binding of the intermediate analogue equilinen to KSI for two different nitrile probe positions. Analysis of the molecular dynamics simulations provides atomistic insight into the roles that key residues play in determining the electrostatic environment and hydrogen-bonding interactions experienced by the nitrile probe. For the M116C-CN probe, equilinen binding reorients an active-site water molecule that is directly hydrogen-bonded to the nitrile probe, resulting in a more linear C≡N--H angle and increasing the CN frequency upon binding. For the F86C-CN probe, equilinen binding orients the Asp103 residue, decreasing the hydrogen-bonding distance between the Asp103 backbone and the nitrile probe and slightly increasing the CN frequency. This QM/MM methodology is applicable to a wide range of biological systems and has the potential to assist in the elucidation of the fundamental principles underlying enzyme catalysis.

  20. Nitrile group as infrared probe for the characterization of the conformation of bovine serum albumin solubilized in reverse micelles.

    Science.gov (United States)

    Xue, Luyan; Zou, Feixue; Zhao, Yin; Huang, Xirong; Qu, Yinbo

    2012-11-01

    Infrared spectroscopy is a powerful technique for structure characterization. For a protein hosted in a reversed micellar medium, the spectral features of the protein are always interfered by the IR absorption bands of the medium in addition to the congestion in their IR spectra. Fortunately, there is a transparent window in the 2500-2200 cm(-1) region. Incorporation of a vibrational probe with IR absorption frequencies in this region into proteins represents a promising strategy for the study of the conformation of a protein in a reverse micelle. In the present work, we incorporated 4-cyanobenzyl group (CN) into bovine serum albumin (BSA) via cysteine alkylation reactions under mild conditions. Circular dichroism spectroscopy showed that the CN modified BSA (CNBSA) could retain its conformation. When CNBSA was hosted in AOT reverse micelle, it was found that the nitrile group on BSA was sensitive to the conformational change of BSA induced by urea as an additive in the reverse micelle. The peak splitting of nitrile group was also observed when the size of AOT reverse micelle and the concentration of an electrolyte were varied. Obviously, the shift of the IR absorption peak and/or peak splitting of nitrile group on BSA are correlated with the change of BSA conformation in AOT reverse micelle. So we conclude that the nitrile infrared probe can be used to study protein conformation in a reverse micelle. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Photoactive glazed polymer-cement composite

    Science.gov (United States)

    Baltes, Liana; Patachia, Silvia; Tierean, Mircea; Ekincioglu, Ozgur; Ozkul, Hulusi M.

    2018-04-01

    Macro defect free cements (MDF), a kind of polymer-cement composites, are characterized by remarkably high mechanical properties. Their flexural strengths are 20-30 times higher than those of conventional cement pastes, nearly equal to that of an ordinary steel. The main drawback of MDF cements is their sensitivity to water. This paper presents a method to both diminish the negative impact of water on MDF cements mechanical properties and to enlarge their application by conferring photoactivity. These tasks were solved by glazing MDF cement with an ecological glaze containing nano-particles of TiO2. Efficiency of photocatalytic activity of this material was tested against methylene blue aqueous solution (4.4 mg/L). Influence of the photocatalyst concentration in the glaze paste and of the contact time on the photocatalysis process (efficiency and kinetic) was studied. The best obtained photocatalysis yield was of 97.35%, after 8 h of exposure to 254 nm UV radiation when used an MDF glazed with 10% TiO2 in the enamel paste. Surface of glazed material was characterized by optic microscopy, scratch test, SEM, XRD, and EDS. All these properties were correlated with the aesthetic aspect of the glazed surface aiming to propose using of this material for sustainable construction development.

  2. Biotransformation of nitriles to hydroxamic acids via a nitrile hydratase–amidase cascade reaction

    Czech Academy of Sciences Publication Activity Database

    Vejvoda, Vojtěch; Martínková, Ludmila; Veselá, Alicja Barbara; Kaplan, Ondřej; Lutz-Wahl, S.; Fischer, L.; Uhnáková, Bronislava

    2011-01-01

    Roč. 71, 1-2 (2011), s. 51-55 ISSN 1381-1177 R&D Projects: GA MŠk(CZ) LC06010; GA MŠk OC09046 Institutional research plan: CEZ:AV0Z50200510 Keywords : Nitrile hydratase * Rhodococcus erythropolis * Amidase Subject RIV: EE - Microbiology, Virology Impact factor: 2.735, year: 2011

  3. Theoretical studies of transition metal complexes with nitriles and isocyanides

    International Nuclear Information System (INIS)

    Kuznetsov, Maksim L

    2002-01-01

    Theoretical studies of transition metal complexes with nitriles and isocyanides are reviewed. The electronic structures and the nature of coordination bonds in these complexes are discussed. The correlation between the electronic structures of transition metal complexes with nitriles and isocyanides and their structural properties, spectroscopic characteristics, and reactivities are considered. The bibliography includes 121 references.

  4. Addition of HO-nucleophiles to free and coordinated nitriles

    International Nuclear Information System (INIS)

    Bokach, Nadejda A; Kukushkin, Vadim Yu

    2005-01-01

    The review surveys data on the addition of HO-nucleophiles (water, oximes, hydroxylamines, hydroxamic acids, alcohols) to nitriles. Main methods for C≡N bond activation in nucleophilic addition reactions are discussed. Particular attention is given to activation of nitriles through coordination to metal centres.

  5. The Application of Nitrile Hydratases in Organic Synthesis

    NARCIS (Netherlands)

    Van Pelt, S.

    2010-01-01

    Nitrile hydratases (NHases, E.C. 4.2.1.84) catalyse the transformation of nitriles into the corresponding amides and were first discovered 30 years ago in studies on the microbial degradation of toxic cyano-group-containing compounds. The use of NHases in synthetic chemistry is especially

  6. Manganese Catalyzed α-Olefination of Nitriles by Primary Alcohols.

    Science.gov (United States)

    Chakraborty, Subrata; Das, Uttam Kumar; Ben-David, Yehoshoa; Milstein, David

    2017-08-30

    Catalytic α-olefination of nitriles using primary alcohols, via dehydrogenative coupling of alcohols with nitriles, is presented. The reaction is catalyzed by a pincer complex of an earth-abundant metal (manganese), in the absence of any additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts.

  7. Borrelidin B: isolation, biological activity, and implications for nitrile biosynthesis.

    Science.gov (United States)

    Schulze, Christopher J; Bray, Walter M; Loganzo, Frank; Lam, My-Hanh; Szal, Teresa; Villalobos, Anabella; Koehn, Frank E; Linington, Roger G

    2014-11-26

    Borrelidin (1) is a nitrile-containing bacterially derived polyketide that is a potent inhibitor of bacterial and eukaryotic threonyl-tRNA synthetases. We now report the discovery of borrelidin B (2), a tetrahydro-borrelidin derivative containing an aminomethyl group in place of the nitrile functionality in borrelidin. The discovery of this new metabolite has implications for both the biosynthesis of the nitrile group and the bioactivity of the borrelidin compound class. Screening in the SToPS assay for tRNA synthetase inhibition revealed that the nitrile moiety is essential for activity, while profiling using our in-house image-based cytological profiling assay demonstrated that 2 retains biological activity by causing a mitotic stall, even in the absence of the nitrile motif.

  8. Molecular Design, Synthesis and Trypanocidal Activity of Dipeptidyl Nitriles as Cruzain Inhibitors

    Science.gov (United States)

    Avelar, Leandro A. A.; Camilo, Cristian D.; de Albuquerque, Sérgio; Fernandes, William B.; Gonçalez, Cristiana; Kenny, Peter W.; Leitão, Andrei; McKerrow, James H.; Montanari, Carlos A.; Orozco, Erika V. Meñaca; Ribeiro, Jean F. R.; Rocha, Josmar R.; Rosini, Fabiana; Saidel, Marta E.

    2015-01-01

    A series of compounds based on the dipeptidyl nitrile scaffold were synthesized and assayed for their inhibitory activity against the T. cruzi cysteine protease cruzain. Structure activity relationships (SARs) were established using three, eleven and twelve variations respectively at the P1, P2 and P3 positions. A K i value of 16 nM was observed for the most potent of these inhibitors which reflects a degree of non-additivity in the SAR. An X-ray crystal structure was determined for the ligand-protein complex for the structural prototype for the series. Twenty three inhibitors were also evaluated for their anti-trypanosomal effects and an EC50 value of 28 μM was observed for the most potent of these. Although there remains scope for further optimization, the knowledge gained from this study is also transferable to the design of cruzain inhibitors based on warheads other than nitrile as well as alternative scaffolds. PMID:26173110

  9. Field ion emission from tungsten wires covered with organic micro needles of benzyl nitrile

    International Nuclear Information System (INIS)

    Helal, A.I.; Zahran, N.F.

    1986-01-01

    Benzyl nitrile micro needles are grown on the surface of a 10 um tungsten wire. The activated wires are used as field anodes in field ionization source. The activation time using benzyl nitrile as an activator is much shorter than the corresponding time required for benzo nitrile activation. Field ionization mass spectra of benzo- and benzyl-nitriles are measured by the new emitters

  10. Structural Basis of Biological Nitrile Reduction*

    Science.gov (United States)

    Chikwana, Vimbai M.; Stec, Boguslaw; Lee, Bobby W. K.; de Crécy-Lagard, Valérie; Iwata-Reuyl, Dirk; Swairjo, Manal A.

    2012-01-01

    The enzyme QueF catalyzes the reduction of the nitrile group of 7-cyano-7-deazaguanine (preQ0) to 7-aminomethyl-7-deazaguanine (preQ1), the only nitrile reduction reaction known in biology. We describe here two crystal structures of Bacillus subtilis QueF, one of the wild-type enzyme in complex with the substrate preQ0, trapped as a covalent thioimide, a putative intermediate in the reaction, and the second of the C55A mutant in complex with the substrate preQ0 bound noncovalently. The QueF enzyme forms an asymmetric tunnel-fold homodecamer of two head-to-head facing pentameric subunits, harboring 10 active sites at the intersubunit interfaces. In both structures, a preQ0 molecule is bound at eight sites, and in the wild-type enzyme, it forms a thioimide covalent linkage to the catalytic residue Cys-55. Both structural and transient kinetic data show that preQ0 binding, not thioimide formation, induces a large conformational change in and closure of the active site. Based on these data, we propose a mechanism for the activation of the Cys-55 nucleophile and subsequent hydride transfer. PMID:22787148

  11. Realization of Intrinsically Stretchable Organic Solar Cells Enabled by Charge-Extraction Layer and Photoactive Material Engineering.

    Science.gov (United States)

    Hsieh, Yun-Ting; Chen, Jung-Yao; Fukuta, Seijiro; Lin, Po-Chen; Higashihara, Tomoya; Chueh, Chu-Chen; Chen, Wen-Chang

    2018-06-12

    The rapid development of wearable electronic devices has prompted a strong demand to develop stretchable organic solar cells (OSCs) to serve as the advanced powering systems. However, to realize an intrinsically stretchable OSC is challenging because it requires all the constituent layers to possess certain elastic properties. It thus necessitates a combined engineering of charge-transporting layers and photoactive materials. Herein, we first describe a stretchable electron-extraction layer using a blend of poly[(9,9-bis(3'-( N, N-dimethylamino)propyl)-2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene)] (PFN) and nitrile butadiene rubber (NBR, Nipol 1072). This hybrid PFN/NBR layer exhibits a much lower Derjaguin-Muller-Toporov modulus (0.45 GPa) than the value (1.25 GPa) of the pristine PFN and could withstand a high strain (60% strain) without showing any cracks. Moreover, besides enriching the stretchability of PFN, the terminal carboxyl groups of NBR can ionize PFN to promote its solution-processability in polar solvents and to ensure the interfacial dipole formation at the corresponding interface in the device, as evidenced by the Fourier transform infrared and ultraviolet photoelectron spectroscopy analyses. By further coupling the replacement of [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) with nonfullerene acceptors owing to better mechanical stretchability in the photoactive layer, OSCs with improved intrinsically stretchability and performance were demonstrated. An all-polymer OSC can exhibit a power conversion efficiency of 2.82% after 10% stretching, surpassing the PCBM-based device that can only withstand 5% strain.

  12. Cellulose nanocrystals reinforced foamed nitrile rubber nanocomposites.

    Science.gov (United States)

    Chen, Yukun; Zhang, Yuanbing; Xu, Chuanhui; Cao, Xiaodong

    2015-10-05

    Research on foamed nitrile rubber (NBR)/cellulose nanocrystals (CNs) nanocomposites is rarely found in the literatures. In this paper, CNs suspension and NBR latex was mixed to prepared the foamed NBR/CNs nanocomposites. We found that the CNs mainly located in the cell walls, effectively reinforcing the foamed NBR. The strong interaction between the CNs and NBR matrix restricted the mobility of NBR chains surrounding the CNs, hence increasing the crosslink density of the NBR matrix. CNs exhibited excellent reinforcement on the foamed NBR: a remarkable increase nearly 76% in the tensile strength of the foamed nanocomposites was achieved with a load of only 15 phr CNs. Enhanced mechanical properties make the foamed NBR/CNs nanocomposites a promising damping material for industrial applications with a potential to reduce the petroleum consumption. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Polybenzoxazole-filled nitrile butadiene rubber compositions

    Science.gov (United States)

    Gajiwala, Himansu M. (Inventor); Guillot, David G. (Inventor)

    2008-01-01

    An insulation composition that comprises at least one nitrile butadiene rubber (NBR) having an acrylonitrile content that ranges from approximately 26% by weight to approximately 35% by weight and polybenzoxazole (PBO) fibers. The NBR may be a copolymer of acrylonitrile and butadiene and may be present in the insulation composition in a range of from approximately 45% by weight to approximately 56% by weight of a total weight of the insulation composition. The PBO fibers may be present in a range of from approximately 3% by weight to approximately 10% by weight of a total weight of the insulation composition. A rocket motor including the insulation composition and a method of insulating a rocket motor are also disclosed.

  14. The Reduction of Nitriles to Aldehydes: Applications of Raney Nickel ...

    African Journals Online (AJOL)

    NJD

    The selective reduction of a nitrile to an aldehyde, especially when the substrate ..... prelude to reductive amination chemistry was thwarted by a rapid aldol ... and allowed the direct incorporation of the α-methylbenzylamine chiral auxiliary.

  15. Interactions of photoactive DNAs with terminal deoxynucleotidyl transferase: Identification of peptides in the DNA binding domain

    International Nuclear Information System (INIS)

    Farrar, Y.J.K.; Evans, R.K.; Beach, C.M.; Coleman, M.S.

    1991-01-01

    Terminal deoxynucleotidyl transferase (terminal transferase) was specifically modified in the DNA binding site by a photoactive DNA substrate (hetero-40-mer duplex containing eight 5-azido-dUMP residues at one 3' end). Under optimal photolabeling conditions, 27-40% of the DNA was covalently cross-linked to terminal transferase. The specificity of the DNA and protein interaction was demonstrated by protection of photolabeling at the DNA binding domain with natural DNA substrates. In order to recover high yields of modified peptides from limited amounts of starting material, protein modified with 32 P-labeled photoactive DNA and digested with trypsin was extracted 4 times with phenol followed by gel filtration chromatography. All peptides not cross-linked to DNA were extracted into the phenol phase while the photolyzed DNA and the covalently cross-linked peptides remained in the aqueous phase. The 32 P-containing peptide-DNA fraction was subjected to amino acid sequence analysis. Two sequences, Asp 221 -Lys 231 (peptide B8) and Cys 234 -Lys 249 (peptide B10), present in similar yield, were identified. Structure predictions placed the two peptides in an α-helical array of 39 angstrom which would accommodate a DNA helix span of 11 nucleotides. These peptides share sequence similarity with a region in DNA polymerase β that has been implicated in the binding of DNA template

  16. Green chemistry: highly selective biocatalytic hydrolysis of nitrile compounds

    CSIR Research Space (South Africa)

    Brady, D

    2006-09-01

    Full Text Available ambient temperatures and moderate pH, thereby reducing environmental impact, minimising the cost of equipment and improving reaction safety2. A further benefit is that biocatalysts can synthesise complex chemicals selectively3. This avoids... nitrile group in a dinitrile molecule permits the incorporation of the unreacted nitrile into the final product or further functionalisation, such as reduction to an amino group. Hence, these enzymes can be used to provide access to specific complex...

  17. Chiral lewis Acid catalysis in nitrile oxide cycloadditions.

    Science.gov (United States)

    Sibi, Mukund P; Itoh, Kennosuke; Jasperse, Craig P

    2004-05-05

    We describe examples of highly regio- and enantioselective nitrile oxide cycloadditions to unsaturated alkenes using substoichiometric amounts of a chiral Lewis acid. Pyrazolidinones proved to be effective achiral templates in the cycloadditions providing C-adducts typically in >30:1 selectivity and 80-99% ee. To avoid potential problems involving coordination of the Lewis acid by amine bases, we have devised a novel method for the generation of unstable nitrile oxides from hydroximinoyl chlorides using Amberlyst 21 as the base.

  18. Hydrolysis of nitriles by soil bacteria: variation with soil origin.

    Science.gov (United States)

    Rapheeha, O K L; Roux-van der Merwe, M P; Badenhorst, J; Chhiba, V; Bode, M L; Mathiba, K; Brady, D

    2017-03-01

    The aim of this study was to explore bacterial soil diversity for nitrile biocatalysts, in particular, those for hydrolysis of β-substituted nitriles, to the corresponding carboxamides and acids that may be incorporated into peptidomimetics. To achieve this, we needed to compare the efficiency of isolation methods and determine the influence of land use and geographical origin of the soil sample. Nitrile-utilizing bacteria were isolated from various soil environments across a 1000 km long transect of South Africa, including agricultural soil, a gold mine tailing dam and uncultivated soil. The substrate profile of these isolates was determined through element-limited growth studies on seven different aliphatic or aromatic nitriles. A subset of these organisms expressing broad substrate ranges was evaluated for their ability to hydrolyse β-substituted nitriles (3-amino-3-phenylpropionitrile and 3-hydroxy-4-phenoxybutyronitrile) and the active organisms were found to be Rhodococcus erythropolis from uncultivated soil and Rhodococcus rhodochrous from agricultural soils. The capacity for hydrolysis of β-substituted nitriles appears to reside almost exclusively in Rhodococci. Land use has a much greater effect on the biocatalysis substrate profile than geographical location. Enzymes are typically substrate specific in their catalytic reactions, and this means that a wide diversity of enzymes is required to provide a comprehensive biocatalysis toolbox. This paper shows that the microbial diversity of nitrile hydrolysis activity can be targeted according to land utilization. Nitrile biocatalysis is a green chemical method for the enzymatic production of amides and carboxylic acids that has industrial applications, such as in the synthesis of acrylamide and nicotinamide. The biocatalysts discovered in this study may be applied to the synthesis of peptidomimetics which are an important class of therapeutic compounds. © 2016 The Society for Applied Microbiology.

  19. Cycloaddition of nitrones to metal-activated nitriles and isocyanides

    International Nuclear Information System (INIS)

    Bokach, Nadejda A

    2010-01-01

    1,3-Dipolar cycloaddition reactions of nitrones to nitriles and isocyanides are considered. Attention is focused on metal-mediated processes and the role played by the nature of the metal centre and its oxidation state. The published data on the selectivity of metal-mediated cycloaddition of nitrones to nitriles and the new data on the cycloaddition of nitrones to coordinated isocyanide ligands are summarized and analyzed.

  20. The First Example of a Nitrile Hydratase Model Complex that Reversibly Binds Nitriles

    Science.gov (United States)

    Shearer, Jason; Jackson, Henry L.; Schweitzer, Dirk; Rittenberg, Durrell K.; Leavy, Tanya M.; Kaminsky, Werner; Scarrow, Robert C.; Kovacs, Julie A.

    2015-01-01

    Nitrile hydratase (NHase) is an iron-containing metalloenzyme that converts nitriles to amides. The mechanism by which this biochemical reaction occurs is unknown. One mechanism that has been proposed involves nucleophilic attack of an Fe-bound nitrile by water (or hydroxide). Reported herein is a five-coordinate model compound ([FeIII(S2Me2N3(Et,Pr))]+) containing Fe(III) in an environment resembling that of NHase, which reversibly binds a variety of nitriles, alcohols, amines, and thiocyanate. XAS shows that five-coordinate [FeIII(S2Me2N3(Et,Pr))]+ reacts with both methanol and acetonitrile to afford a six-coordinate solvent-bound complex. Competitive binding studies demonstrate that MeCN preferentially binds over ROH, suggesting that nitriles would be capable of displacing the H2O coordinated to the iron site of NHase. Thermodynamic parameters were determined for acetonitrile (ΔH = −6.2(±0.2) kcal/mol, ΔS = −29.4(±0.8) eu), benzonitrile (−4.2(±0.6) kcal/mol, ΔS = −18(±3) eu), and pyridine (ΔH = −8(±1) kcal/mol, ΔS = −41(±6) eu) binding to [FeIII(S2Me2N3(Et,Pr))]+ using variable-temperature electronic absorption spectroscopy. Ligand exchange kinetics were examined for acetonitrile, iso-propylnitrile, benzonitrile, and 4-tert-butylpyridine using 13C NMR line-broadening analysis, at a variety of temperatures. Activation parameters for ligand exchange were determined to be ΔH‡ = 7.1(±0.8) kcal/mol, ΔS‡ = −10(±1) eu (acetonitrile), ΔH‡ = 5.4(±0.6) kcal/mol, ΔS‡ = −17(±2) eu (iso-propionitrile), ΔH‡ = 4.9(±0.8) kcal/mol, ΔS‡ = −20(±3) eu (benzonitrile), and ΔH‡ = 4.7(±1.4) kcal/mol ΔS‡ = −18(±2) eu (4-tert-butylpyridine). The thermodynamic parameters for pyridine binding to a related complex, [FeIII(S2Me2N3(Pr,Pr))]+ (ΔH = −5.9(±0.8) kcal/mol, ΔS = −24(±3) eu), are also reported, as well as kinetic parameters for 4-tert-butylpyridine exchange (ΔH‡ = 3.1(±0.8) kcal/mol, ΔS‡)−25(±3) eu

  1. Biotransformation of nitriles to amides using soluble and immobilized nitrile hydratase from Rhodococcus erythropolis A4

    Czech Academy of Sciences Publication Activity Database

    Kubáč, David; Kaplan, Ondřej; Elišáková, Veronika; Pátek, Miroslav; Vejvoda, Vojtěch; Slámová, Kristýna; Tóthová, A.; Lemaire, M.; Gallienne, E.; Lutz-Wahl, S.; Fischer, L.; Kuzma, Marek; Pelantová, Helena; van Pelt, S.; Bolte, J.; Křen, Vladimír; Martínková, Ludmila

    2008-01-01

    Roč. 50, 2-4 (2008), s. 107-113 ISSN 1381-1177 R&D Projects: GA ČR GA203/05/2267; GA MŠk(CZ) LC06010; GA MŠk OC 171 Grant - others:XE(XE) ESF COST D25/0002/02; CZ(CZ) D10-CZ25/06-07; CZ(CZ) D-25 Institutional research plan: CEZ:AV0Z50200510 Keywords : rhodococcus erythropolis * nitrile hydratase * amidase Subject RIV: EE - Microbiology, Virology Impact factor: 2.015, year: 2008

  2. NSP-Dependent Simple Nitrile Formation Dominates upon Breakdown of Major Aliphatic Glucosinolates in Roots, Seeds, and Seedlings of Arabidopsis thaliana Columbia-0.

    Science.gov (United States)

    Wittstock, Ute; Meier, Kathrin; Dörr, Friederike; Ravindran, Beena M

    2016-01-01

    One of the best-studied plant defense systems, the glucosinolate-myrosinase system of the Brassicales, is composed of thioglucosides known as glucosinolates and their hydrolytic enzymes, the myrosinases. Tissue disruption brings these components together, and bioactive products are formed as a consequence of myrosinase-catalyzed glucosinolate hydrolysis. Among these products, isothiocyanates have attracted most interest as chemical plant defenses against herbivores and pathogens and health-promoting compounds in the human diet. Previous research has identified specifier proteins whose presence results in the formation of alternative product types, e.g., nitriles, at the expense of isothiocyanates. The biological roles of specifier proteins and alternative breakdown products are poorly understood. Here, we assessed glucosinolate breakdown product profiles obtained upon maceration of roots, seedlings and seeds of Arabidopsis thaliana Columbia-0. We identified simple nitriles as the predominant breakdown products of the major endogenous aliphatic glucosinolates in root, seed, and seedling homogenates. In agreement with this finding, genes encoding nitrile-specifier proteins (NSPs) are expressed in roots, seeds, and seedlings. Analysis of glucosinolate breakdown in mutants with T-DNA insertions in any of the five NSP genes demonstrated, that simple nitrile formation upon tissue disruption depended almost entirely on NSP2 in seeds and mainly on NSP1 in seedlings. In roots, about 70-80% of the nitrile-forming activity was due to NSP1 and NSP3 . Thus, glucosinolate breakdown product profiles are organ-specifically regulated in A. thaliana Col-0, and high proportions of simple nitriles are formed in some parts of the plant. This should be considered in future studies on biological roles of the glucosinolate-myrosinase system.

  3. NSP-dependent simple nitrile formation dominates upon breakdown of major aliphatic glucosinolates in roots, seeds, and seedlings of Arabidopsis thaliana Columbia-0

    Directory of Open Access Journals (Sweden)

    Ute Wittstock

    2016-12-01

    Full Text Available One of the best-studied plant defense systems, the glucosinolate-myrosinase system of the Brassicales, is composed of thioglucosides known as glucosinolates and their hydrolytic enzymes, the myrosinases. Tissue disruption brings these components together, and bioactive products are formed as a consequence of myrosinase-catalyzed glucosinolate hydrolysis. Among these products, isothiocyanates have attracted most interest as chemical plant defenses against herbivores and pathogens and health-promoting compounds in the human diet. Previous research has identified specifier proteins whose presence results in the formation of alternative product types, e.g. nitriles, at the expense of isothiocyanates. The biological roles of specifier proteins and alternative breakdown products are poorly understood. Here, we assessed glucosinolate breakdown product profiles obtained upon maceration of roots, seedlings and seeds of Arabidopsis thaliana Columbia-0. We identified simple nitriles as the predominant breakdown products of the major endogenous aliphatic glucosinolates in root, seed, and seedling homogenates. In agreement with this finding, genes encoding nitrile-specifier proteins (NSPs are expressed in roots, seeds, and seedlings. Analysis of glucosinolate breakdown in mutants with T-DNA insertions in any of the five NSP genes demonstrated, that simple nitrile formation upon tissue disruption depended almost entirely on NSP2 in seeds and mainly on NSP1 in seedlings. In roots, about 70-80 % of the nitrile-forming activity was due to NSP1 and NSP3. Thus, glucosinolate breakdown product profiles are organ-specifically regulated in A. thaliana Col 0, and high proportions of simple nitriles are formed in some parts of the plant. This should be considered in future studies on biological roles of the glucosinolate-myrosinase system.

  4. Supramolecular effects in dendritic systems containing photoactive groups

    Directory of Open Access Journals (Sweden)

    GIANLUCA CAMILLO AZZELLINI

    2000-03-01

    Full Text Available In this article are described dendritic structures containing photoactive groups at the surface or in the core. The observed supramolecular effects can be attributed to the nature of the photoactive group and their location in the dendritic architecture. The peripheric azobenzene groups in these dendrimeric compounds can be regarded as single residues that retain the spectroscopic and photochemical properties of free azobenzene moiety. The E and Z forms of higher generation dendrimer, functionalized with azobenzene groups, show different host ability towards eosin dye, suggesting the possibility of using such dendrimer in photocontrolled host-guest systems. The photophysical properties of many dendritic-bipyridine ruthenium complexes have been investigated. Particularly in aerated medium more intense emission and a longer excited-state lifetime are observed as compared to the parent unsubstituted bipyridine ruthenium complexes. These differences can be attributed to a shielding effect towards dioxygen quenching originated by the dendritic branches.

  5. Recent progress in photoactive organic field-effect transistors.

    Science.gov (United States)

    Wakayama, Yutaka; Hayakawa, Ryoma; Seo, Hoon-Seok

    2014-04-01

    Recent progress in photoactive organic field-effect transistors (OFETs) is reviewed. Photoactive OFETs are divided into light-emitting (LE) and light-receiving (LR) OFETs. In the first part, LE-OFETs are reviewed from the viewpoint of the evolution of device structures. Device performances have improved in the last decade with the evolution of device structures from single-layer unipolar to multi-layer ambipolar transistors. In the second part, various kinds of LR-OFETs are featured. These are categorized according to their functionalities: phototransistors, non-volatile optical memories, and photochromism-based transistors. For both, various device configurations are introduced: thin-film based transistors for practical applications, single-crystalline transistors to investigate fundamental physics, nanowires, multi-layers, and vertical transistors based on new concepts.

  6. Recent progress in photoactive organic field-effect transistors

    International Nuclear Information System (INIS)

    Wakayama, Yutaka; Hayakawa, Ryoma; Seo, Hoon-Seok

    2014-01-01

    Recent progress in photoactive organic field-effect transistors (OFETs) is reviewed. Photoactive OFETs are divided into light-emitting (LE) and light-receiving (LR) OFETs. In the first part, LE-OFETs are reviewed from the viewpoint of the evolution of device structures. Device performances have improved in the last decade with the evolution of device structures from single-layer unipolar to multi-layer ambipolar transistors. In the second part, various kinds of LR-OFETs are featured. These are categorized according to their functionalities: phototransistors, non-volatile optical memories, and photochromism-based transistors. For both, various device configurations are introduced: thin-film based transistors for practical applications, single-crystalline transistors to investigate fundamental physics, nanowires, multi-layers, and vertical transistors based on new concepts. (review)

  7. Nitrile functionalized halloysite nanotubes/poly(arylene ether nitrile) nanocomposites: Interface control, characterization, and improved properties

    International Nuclear Information System (INIS)

    Wan, Xinyi; Zhan, Yingqing; Zeng, Guangyong; He, Yi

    2017-01-01

    Highlights: • Novel nitrile functionalized HNTs were realized through the covalent bonding. • Then modified HNTs showed good dispersion and interfacial adhesion with PEN. • The modified HNTs exhibited excellent reinforcement effect on PEN. • The chemical crosslinking between HNTs and PEN further enhanced the performance of nanocomposites. - Abstract: To develop high-performance halloysite nanotube (HNT)-based nanocomposites, the two key issues need to be considered: precise interface control and the dispersal of HNTs. This study presents an efficient way to functionalize halloysite nanotubes with 3-aminophenoxy-phthalonitrile, followed by compounding with poly(arylene ether nitrile) (PEN), to prepare functional nanocomposite films. The surface functionalization of HNTs was characterized and confirmed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with neat PEN, the tensile strength and modulus of the resulting PEN nanocomposites with 3 wt% functionalized HNTs were found to increase by 25.7% and 20.7%, respectively. The good dispersion and high capacitance of the dielectric layer resulted in PEN/HNTs nancomposites with enhanced dielectric permittivity and relatively low dielectric loss. Moreover, the addition of functional HNTs greatly improved the thermal stability of PEN, which could be further enhanced through the chemical cross-linking reaction between the functional HNTs and the PEN matrix. This work provides a new path toward obtaining advanced polymer-based nanocomposites with functional properties.

  8. Nitrile functionalized halloysite nanotubes/poly(arylene ether nitrile) nanocomposites: Interface control, characterization, and improved properties

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Xinyi [School of Chemistry and Chemical Engineering, Southwest Petroleum University, 8 Xindu Avenue, Chengdu, Sichuan, 610500 (China); Zhan, Yingqing, E-mail: 201599010032@swpu.edu.cn [School of Chemistry and Chemical Engineering, Southwest Petroleum University, 8 Xindu Avenue, Chengdu, Sichuan, 610500 (China); Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, Southwest Petroleum University, Chengdu, Sichuan, China, 610500 (China); Zeng, Guangyong [School of Chemistry and Chemical Engineering, Southwest Petroleum University, 8 Xindu Avenue, Chengdu, Sichuan, 610500 (China); He, Yi, E-mail: heyi007@163.com [School of Chemistry and Chemical Engineering, Southwest Petroleum University, 8 Xindu Avenue, Chengdu, Sichuan, 610500 (China); Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, Southwest Petroleum University, Chengdu, Sichuan, China, 610500 (China); State Key Lab of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, 8Xindu Avenue, Chengdu, Sichuan, 610500 (China)

    2017-01-30

    Highlights: • Novel nitrile functionalized HNTs were realized through the covalent bonding. • Then modified HNTs showed good dispersion and interfacial adhesion with PEN. • The modified HNTs exhibited excellent reinforcement effect on PEN. • The chemical crosslinking between HNTs and PEN further enhanced the performance of nanocomposites. - Abstract: To develop high-performance halloysite nanotube (HNT)-based nanocomposites, the two key issues need to be considered: precise interface control and the dispersal of HNTs. This study presents an efficient way to functionalize halloysite nanotubes with 3-aminophenoxy-phthalonitrile, followed by compounding with poly(arylene ether nitrile) (PEN), to prepare functional nanocomposite films. The surface functionalization of HNTs was characterized and confirmed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with neat PEN, the tensile strength and modulus of the resulting PEN nanocomposites with 3 wt% functionalized HNTs were found to increase by 25.7% and 20.7%, respectively. The good dispersion and high capacitance of the dielectric layer resulted in PEN/HNTs nancomposites with enhanced dielectric permittivity and relatively low dielectric loss. Moreover, the addition of functional HNTs greatly improved the thermal stability of PEN, which could be further enhanced through the chemical cross-linking reaction between the functional HNTs and the PEN matrix. This work provides a new path toward obtaining advanced polymer-based nanocomposites with functional properties.

  9. Inverse electron-demand 1,3-dipolar cycloaddition of nitrile oxide with common nitriles leading to 3-functionalized 1,2,4-oxadiazoles.

    Science.gov (United States)

    Nishiwaki, Nagatoshi; Kobiro, Kazuya; Hirao, Shotaro; Sawayama, Jun; Saigo, Kazuhiko; Ise, Yumiko; Okajima, Yoshikazu; Ariga, Masahiro

    2011-10-07

    A carbamoyl-substituted nitrile oxide was generated upon treatment of easily available 2-methyl-4-nitro-3-isoxazolin-5(2H)-one with THF (not dried); the reaction proceeded efficiently even in the absence of any special reagents and reaction conditions. The nitrile oxide caused 1,3-dipolar cycloaddition with common aliphatic nitriles or electron-rich aromatic nitriles to afford 3-functionalized 1,2,4-oxadiazoles, which are expected to serve as precursors for the preparation of a variety of functional materials by the chemical transformation of the carbamoyl group. While conventional preparative methods for 1,2,4-oxadiazoles involve the cycloaddition of an electron-rich nitrile oxide with an electron-deficient nitrile or a nitrile activated by a Lewis acid, our method employs the complementary combination of an electron-rich nitrile and an electron-deficient nitrile oxide- the inverse electron-demand 1,3-cycloaddition. The DFT calculations using B3LYP 6-31G* supported the abovementioned inverse reactivity, and also suggested the presence of an accelerating effect by the carbamoyl group as a result of hydrogen bond formation with a dipolarophilic nitrile.

  10. Substrate and cofactor binding to nitrile reductase : A mass spectrometry based study

    NARCIS (Netherlands)

    Gjonaj, L.; Pinkse, M.W.H.; Fernandez Fueyo, E.; Hollmann, F.; Hanefeld, U.

    2016-01-01

    Nitrile reductases catalyse a two-step reduction of nitriles to amines. This requires the binding of two NADPH molecules during one catalytic cycle. For the nitrile reductase from E. coli (EcoNR) mass spectrometry studies of the catalytic mechanism were performed. EcoNR is dimeric and has no Rossman

  11. A Direct Comparison of Azide and Nitrile Vibrational Probes

    Science.gov (United States)

    Gai, Xin Sonia; Coutifaris, Basil A.; Brewer, Scott H.; Fenlon, Edward E.

    2011-01-01

    The synthesis of 2′-azido-5-cyano-2′-deoxyuridine, N3CNdU (1), from trityl-protected 2′-amino-2′-deoxyuridine was accomplished in four steps with a 12.5% overall yield. The IR absorption positions and profiles of the azide and nitrile group of N3CNdU were investigated in 14 different solvents and water/DMSO solvent mixtures. The azide probe was superior to the nitrile probe in terms of its extinction coefficient, which is 2–4 times larger. However, the nitrile IR absorbance profile is generally less complicated by accidental Fermi resonance. The IR frequencies of both probes undergo a substantial red shift upon going from water to aprotic solvents such as THF or DMSO. DFT calculations supported the hypothesis that the molecular origin of the higher observed frequency in water is primarily due to hydrogen bonds between the probes and water molecules. PMID:21336362

  12. Virus Capsids as Targeted Nanoscale Delivery Vessels of Photoactive Compounds for Site-Specific Photodynamic Therapy

    Science.gov (United States)

    Cohen, Brian A.

    The research presented in this work details the use of a viral capsid as an addressable delivery vessel of photoactive compounds for use in photodynamic therapy. Photodynamic therapy is a treatment that involves the interaction of light with a photosensitizing molecule to create singlet oxygen, a reactive oxygen species. Overproduction of singlet oxygen in cells can cause oxidative damage leading to cytotoxicity and eventually cell death. Challenges with the current generation of FDA-approved photosensitizers for photodynamic therapy primarily stem from their lack of tissue specificity. This work describes the packaging of photoactive cationic porphyrins inside the MS2 bacteriophage capsid, followed by external modification of the capsid with cancer cell-targeting G-quadruplex DNA aptamers to generate a tumor-specific photosensitizing agent. First, a cationic porphyrin is loaded into the capsids via nucleotide-driven packaging, a process that involves charge interaction between the porphyrin and the RNA inside the capsid. Results show that over 250 porphyrin molecules associate with the RNA within each MS2 capsid. Removal of RNA from the capsid severely inhibits the packaging of the cationic porphyrins. Porphyrin-virus constructs were then shown to photogenerate singlet oxygen, and cytotoxicity in non-targeted photodynamic treatment experiments. Next, each porphyrin-loaded capsid is externally modified with approximately 60 targeting DNA aptamers by employing a heterobifunctional crosslinking agent. The targeting aptamer is known to bind the protein nucleolin, a ubiquitous protein that is overexpressed on the cell surface by many cancer cell types. MCF-7 human breast carcinoma cells and MCF-10A human mammary epithelial cells were selected as an in vitro model for breast cancer and normal tissue, respectively. Fluorescently tagged virus-aptamer constructs are shown to selectively target MCF-7 cells versus MCF-10A cells. Finally, results are shown in which porphyrin

  13. Spectrometric Study of the Nitrile-Ketenimines Tautomerism

    International Nuclear Information System (INIS)

    Cisneros, H.S.; Laurella, S.; Ruiz, D.L.; Ponzinibbio, A.; Allegretti, P.E.; Furlong, J.J.P.

    2011-01-01

    Mass spectrometry is used to evaluate the occurrence of the nitrile-ketenimines tautomerism. Mass spectra of two differently substituted nitriles, ethyl-4,4-dicyano-3-methyl-3-butenoate and diethyl-2-cyano-3-methyl-2-pentenodiate are examined looking for common mass spectral behaviors. Ion fragmentation assignments for specific tautomers allow to predict the presence of the corresponding structures. Additionally, the mass spectrum and nuclear magnetic resonance spectra of ethyl-4,4-dicyano-2,2-diethyl-3-methyl-3-butenoate and that of the corresponding amination product support the occurrence of the ketenimines tautomer in the equilibrium

  14. Investigation of surface halide modification of nitrile butadiene rubber

    Science.gov (United States)

    Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

    2017-12-01

    The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

  15. Spectrometric Study of the Nitrile-Ketenimine Tautomerism

    Directory of Open Access Journals (Sweden)

    Hebe Saraví Cisneros

    2009-01-01

    Full Text Available Mass spectrometry is used to evaluate the occurrence of the nitrile-ketenimine tautomerism. Mass spectra of two differently substituted nitriles, ethyl-4,4-dicyano-3-methyl-3-butenoate and diethyl-2-cyano-3-methyl-2-pentenodiate are examined looking for common mass spectral behaviors. Ion fragmentation assignments for specific tautomers allow to predict the presence of the corresponding structures. Additionally, the mass spectrum and nuclear magnetic resonance spectra of ethyl-4,4-dicyano-2,2-diethyl-3-methyl-3-butenoate and that of the corresponding amination product support the occurrence of the ketenimine tautomer in the equilibrium.

  16. Reaction of nitriles intercalation in tantalum pentachloride complexes with amines

    International Nuclear Information System (INIS)

    Glushkova, M.A.; Chumaevskij, N.A.; Khmelevskaya, L.V.; Ershova, M.M.; Buslaev, Yu.A.

    1987-01-01

    Data on the study of aceto-, propio- and benzonitrile intercalation in TaCl 5 complexes with diethyl- and triethylamines in CCl 4 solution are discussed. Using the methods of IR and Raman spectroscopy it has been established that it is the nature of ligand, and not nitrile intercalated in the complex, that affects greatly the composition of final products. In contrast to acetonitrile, intercalation in the complex of propio- and benzonitriles is observed already at room temperature. On the basis of spectral data a supposition is made that carbon tetrachloride used as a solvent accelerates the reaction of nitrile intercalation and promotes their deprotonation in the presence of aprotonic amine

  17. Metal-ligand cooperative activation of nitriles by a ruthenium complex with a de-aromatized PNN pincer ligand

    NARCIS (Netherlands)

    Eijsink, Linda E; Perdriau, Sébastien C P; de Vries, Johannes G; Otten, Edwin

    2016-01-01

    The pincer complex (PNN)RuH(CO), with a de-aromatized pyridine in the ligand backbone, is shown to react with nitriles in a metal-ligand cooperative manner. This leads to the formation of a series of complexes with new Ru-N(nitrile) and C(ligand)-C(nitrile) bonds. The initial nitrile cycloaddition

  18. Kinetic effects of sulfur oxidation on catalytic nitrile hydration: nitrile hydratase insights from bioinspired ruthenium(II) complexes.

    Science.gov (United States)

    Kumar, Davinder; Nguyen, Tho N; Grapperhaus, Craig A

    2014-12-01

    Kinetic investigations inspired by the metalloenzyme nitrile hydratase were performed on a series of ruthenium(II) complexes to determine the effect of sulfur oxidation on catalytic nitrile hydration. The rate of benzonitrile hydration was quantified as a function of catalyst, nitrile, and water concentrations. Precatalysts L(n)RuPPh3 (n = 1-3; L(1) = 4,7-bis(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(2) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(3) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-sulfenato-propyl)-1-thia-4,7-diazacyclononane) were activated by substitution of triphenylphosphine with substrate in hot dimethylformamide solution. Rate measurements are consistent with a dynamic equilibrium between inactive aqua (L(n)Ru-OH2) and active nitrile (L(n)Ru-NCR) derivatives with K = 21 ± 1, 9 ± 0.9, and 23 ± 3 for L(1) to L(3), respectively. Subsequent hydration of the L(n)Ru-NCR intermediate yields the amide product with measured hydration rate constants (k's) of 0.37 ± 0.01, 0.82 ± 0.07, and 1.59 ± 0.12 M(-1) h(-1) for L(1) to L(3), respectively. Temperature dependent studies reveal that sulfur oxidation lowers the enthalpic barrier by 27 kJ/mol, but increases the entropic barrier by 65 J/(mol K). Density functional theory (DFT) calculations (B3LYP/LanL2DZ (Ru); 6-31G(d) (all other atoms)) support a nitrile bound catalytic cycle with lowering of the reaction barrier as a consequence of sulfur oxidation through enhanced nitrile binding and attack of the water nucleophile through a highly organized transition state.

  19. Photoactive dye-enhanced tissue ablation for endoscopic laser prostatectomy.

    Science.gov (United States)

    Ahn, Minwoo; Hau, Nguyen Trung; Van Phuc, Nguyen; Oh, Junghwan; Kang, Hyun Wook

    2014-11-01

    Laser light has been widely used as a surgical tool to treat benign prostate hyperplasia (BPH) over 20 years. Recently, application of high laser power up to 200 W was often reported to swiftly remove a large amount of prostatic tissue. The purpose of this study was to validate the feasibility of photoactive dye injection to enhance light absorption and eventually to facilitate tissue vaporization with low laser power. Chicken breast tissue was selected as a target tissue due to minimal optical absorption at the visible wavelength. Four biocompatible photoactive dyes, including amaranth (AR), black dye (BD), hemoglobin powder (HP), and endoscopic marker (EM), were selected and tested in vitro with a customized 532 nm laser system with radiant exposure ranging from 0.9 to 3.9 J/cm(2) . Light absorbance and ablation threshold were measured with UV-Vis spectrometer and Probit analysis, respectively, and compared to feature the function of the injected dyes. Ablation performance with dye-injection was evaluated in light of radiant exposure, dye concentration, and number of injection. Higher light absorption by injected dyes led to lower ablation threshold as well as more efficient tissue removal in the order of AR, BD, HP, and EM. Regardless of the injected dyes, ablation efficiency principally increased with radiant exposure, dye concentration, and number of injection. Among the dyes, AR created the highest ablation rate of 44.2 ± 0.2 µm/pulse due to higher absorbance and lower ablation threshold. High aspect ratios up to 7.1 ± 0.4 entailed saturation behavior in the tissue ablation injected with AR and BD, possibly resulting from plume shielding and increased scattering due to coagulation. Preliminary tests on canine prostate with a hydraulic injection system demonstrated that 80 W with dye injection yielded comparable ablation efficiency to 120 W with no injection, indicating 33% reduced laser power with almost equivalent performance. Due to

  20. Nitrile ylides: diastereoselective cycloadditions using chiral oxazolidinones without Lewis acid.

    Science.gov (United States)

    Sibi, Mukund P; Soeta, Takahiro; Jasperse, Craig P

    2009-12-03

    Lewis acid complexation is generally required for chiral-auxiliary-controlled stereoselectivity, and chiral Lewis acid catalysis is frequently optimal for introducing asymmetry. In this work, we show that nitrile ylide cycloadditions to electron-poor acceptors attached to chiral auxiliaries proceed in high yield and stereoselectivity in the absence of Lewis acids. In contrast, chiral Lewis acids are inferior in these cycloadditions.

  1. Hydrolysis of nitriles by soil bacteria: variation with soil origin

    CSIR Research Space (South Africa)

    Rapheeha, OKL

    2017-03-01

    Full Text Available . To achieve this, we needed to compare the efficiency of isolation methods and determine the influence of land use and geographical origin of the soil sample. Nitrile-utilizing bacteria were isolated from various soil environments across a 1000 km long...

  2. Positron annihilation studies on proton irradiated nitrile rubber

    International Nuclear Information System (INIS)

    Ravi Chandran, T.S.G.; Lobo, Blaise; Ranganath, M.R.; Gopal, S.; Sreeramalu, V.

    1996-01-01

    NBR (Nitrile Butadiene Rubber) was irradiated with 4 MeV proton beam from a variable energy cyclotron (VEC) at VEC Centre, Calcutta, to a flux of 10 16 ions/cm 2 , in a vacuum of 10 -9 Torr and was studied through positron lifetime measurements

  3. Deuterium labelling studies with unsaturated acids and nitriles

    International Nuclear Information System (INIS)

    Desai, U.V.; Mane, R.B.

    1986-01-01

    α-Deuteriated α,β-unsaturated acids have been prepared by Knoevenagel condensation of aldehydes with deuteriated malonic acid. The decarboxylation of α,β-unsaturated cyano acid with pyridine/D 2 O yields α- and γ-labelled nitriles. The deuterium incorporation is studied by pmr spectroscopy. (author). 8 refs

  4. 57Fe Moessbauer spectroscopic studies on photosensitive nitrile hydratase (NHase)

    International Nuclear Information System (INIS)

    Kobayashi, Yoshio; Odaka, Masafumi

    2001-01-01

    57 Fe Moessbauer spectroscopy is a very useful technique for elucidating the chemical properties and biological changes of Fe species located at the reaction centers in various biological systems. We have applied 57 Fe Moessbauer spectroscopy to study the mechanism of photoactivation and the structural change caused by light irradiation of nitrile hydratase (NHase). (author)

  5. Straightforward uranium-catalyzed dehydration of primary amides to nitriles

    International Nuclear Information System (INIS)

    Enthaler, Stephan

    2011-01-01

    The efficient uranium-catalyzed dehydration of a variety of primary amides, using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as a dehydration reagent, to the corresponding nitriles has been investigated. With this catalyst system, extraordinary catalyst activities and selectivities were feasible. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Study of glucoamylase immobilization in butadiene nitrile latex membrane

    International Nuclear Information System (INIS)

    Miller, E.

    1992-01-01

    Attempts have been undetaken to immobilize glucoamylaze by means of butadiene nitrile latex in the presence of a chemical initiator and 60 Co γ-radiation. The activity, stability of conjugates in the membrane and permeability of oxygen in these membranes were determined. (author) 14 refs.; 5 figs

  7. Degradation of nitrile rubber fuel hose by biodiesel use

    International Nuclear Information System (INIS)

    Coronado, Marcos; Montero, Gisela; Valdez, Benjamín; Stoytcheva, Margarita; Eliezer, Amir; García, Conrado; Campbell, Héctor; Pérez, Armando

    2014-01-01

    Nowadays biodiesel is becoming an increasingly important and popular fuel, obtained from renewable sources, and contributes to pollutant emissions reduction and decreasing fossil fuels dependence. However, its easier oxidation and faster degradation in comparison to diesel led to compatibility problems between biodiesel and various metallic and polymeric materials contacted. Therefore, the objective of this work is to investigate the effect of different mixtures diesel–biodiesel (fuel type B5, B10, B20) used in Baja California, Mexico on the resistance of nitrile rubber fuel hoses at temperatures of 25 °C and 70 °C applying gravimetric tests, tensile strength measurements and scanning electron microscopy analysis. The factors affecting the material mass change were identified using an experimental design analysis. It was found that the fuel temperature did not conduct to significant mass loss of nitrile rubber fuel hose, while biodiesel concentration affected the properties of the elastomer, causing the phenomenon of swelling. The exposure of hoses to fuel with increasing concentrations of biodiesel led to tensile strength decrease. - Highlights: • The biodiesel oxidation led to problems with polymeric materials. • The degradation of a nitrile rubber fuel hose in biodiesel blends was assessed. • The nitrile rubber showed greater affinity for biodiesel than diesel. • The elastomer swelled, cracked and lost its mechanical properties by biodiesel. • SEM analysis confirmed surface morphology changes in higher biodiesel blends

  8. Mechanistic study on exchange between labeled cyanide and nitriles

    International Nuclear Information System (INIS)

    Hussain, Munir; Chaney, J.E.; Digenis, G.A.; Layton, W.J.

    1985-01-01

    The potential of a clean, rapid exchange between the nitrile function of mandelonitrile and cyanide was examined for the preparation of labeled mandelonitrile which could be subsequently rapidly reduced with borane to labeled phenylethanolamine (PEOH). The mandelonitrile exchange (CN-CN) was studied using [ 13 C]-NaCN with crown ethers in THF, monitoring the results with 13 C-NMR. A large increase in the intensity of the signal due to [ 13 C]-nitrile was observed. The exchange was also carried out using [ 14 C]-NaCN, and the exchanged nitrile was reduced to [ 14 C]-PEOH. The chemical yield for the reduction of [ 14 C]-mandelonitrile to [ 14 C]-PEOH was 60% and the overall radio-chemical yield of the cyanide-exchange and borane reduction (based on [ 14 C]-NaCN used) was 20%. Mechanisms are proposed which were found to be consistent with results of cyanide exchange of appropriately selected nitriles. (author)

  9. Selective oxidation of alcohols using photoactive VO@g-C3N4.

    Science.gov (United States)

    A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated activity of the catalyst could be attributed to photoactive graphitic carbon nitrides surface.

  10. Evaluation of genotoxicity of nitrile fragrance ingredients using in vitro and in vivo assays.

    Science.gov (United States)

    Bhatia, S P; Politano, V T; Api, A M

    2013-09-01

    Genotoxicity studies were conducted on a group of 8 fragrance ingredients that belong to the nitrile family. These nitriles are widely used in consumer products however there is very limited data in the literature regarding the genotoxicity of these nitriles. The 8 nitriles were assessed for genotoxicity using an Ames test, in vitro chromosome aberration test or in vitro micronucleus test. The positive results observed in the in vitro tests were further investigated using an in vivo micronucleus test. The results from these different tests were compared and these 8 nitriles are not considered to be genotoxic. Dodecanitrile and 2,2,3-trimethylcyclopent-3-enylacetonitrile were negative in the in vitro chromosome aberration test and in vitro micronucleus test, respectively. While citronellyl nitrile, 3-methyl-5-phenylpentanenitrile, cinnamyl nitrile, and 3-methyl-5-phenylpent-2-enenitrile revealed positive results in the in vitro tests, but confirmatory in vivo tests determined these nitriles to be negative in the in vivo micronucleus assay. The remaining two nitriles (benzonitrile and α-cyclohexylidene benzeneacetonitrile) were negative in the in vivo micronucleus test. This study aims to evaluate the genotoxicity potential of these nitriles as well as enrich the literature with genotoxicity data on fragrance ingredients. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Nitrile functionalized halloysite nanotubes/poly(arylene ether nitrile) nanocomposites: Interface control, characterization, and improved properties

    Science.gov (United States)

    Wan, Xinyi; Zhan, Yingqing; Zeng, Guangyong; He, Yi

    2017-01-01

    To develop high-performance halloysite nanotube (HNT)-based nanocomposites, the two key issues need to be considered: precise interface control and the dispersal of HNTs. This study presents an efficient way to functionalize halloysite nanotubes with 3-aminophenoxy-phthalonitrile, followed by compounding with poly(arylene ether nitrile) (PEN), to prepare functional nanocomposite films. The surface functionalization of HNTs was characterized and confirmed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with neat PEN, the tensile strength and modulus of the resulting PEN nanocomposites with 3 wt% functionalized HNTs were found to increase by 25.7% and 20.7%, respectively. The good dispersion and high capacitance of the dielectric layer resulted in PEN/HNTs nancomposites with enhanced dielectric permittivity and relatively low dielectric loss. Moreover, the addition of functional HNTs greatly improved the thermal stability of PEN, which could be further enhanced through the chemical cross-linking reaction between the functional HNTs and the PEN matrix. This work provides a new path toward obtaining advanced polymer-based nanocomposites with functional properties.

  12. Expansion of ribosomally produced natural products: a nitrile hydratase- and Nif11-related precursor family

    Directory of Open Access Journals (Sweden)

    Mitchell Douglas A

    2010-05-01

    Full Text Available Abstract Background A new family of natural products has been described in which cysteine, serine and threonine from ribosomally-produced peptides are converted to thiazoles, oxazoles and methyloxazoles, respectively. These metabolites and their biosynthetic gene clusters are now referred to as thiazole/oxazole-modified microcins (TOMM. As exemplified by microcin B17 and streptolysin S, TOMM precursors contain an N-terminal leader sequence and C-terminal core peptide. The leader sequence contains binding sites for the posttranslational modifying enzymes which subsequently act upon the core peptide. TOMM peptides are small and highly variable, frequently missed by gene-finders and occasionally situated far from the thiazole/oxazole forming genes. Thus, locating a substrate for a particular TOMM pathway can be a challenging endeavor. Results Examination of candidate TOMM precursors has revealed a subclass with an uncharacteristically long leader sequence closely related to the enzyme nitrile hydratase. Members of this nitrile hydratase leader peptide (NHLP family lack the metal-binding residues required for catalysis. Instead, NHLP sequences display the classic Gly-Gly cleavage motif and have C-terminal regions rich in heterocyclizable residues. The NHLP family exhibits a correlated species distribution and local clustering with an ABC transport system. This study also provides evidence that a separate family, annotated as Nif11 nitrogen-fixing proteins, can serve as natural product precursors (N11P, but not always of the TOMM variety. Indeed, a number of cyanobacterial genomes show extensive N11P paralogous expansion, such as Nostoc, Prochlorococcus and Cyanothece, which replace the TOMM cluster with lanthionine biosynthetic machinery. Conclusions This study has united numerous TOMM gene clusters with their cognate substrates. These results suggest that two large protein families, the nitrile hydratases and Nif11, have been retailored for

  13. Permeation of aromatic solvent mixtures through nitrile protective gloves.

    Science.gov (United States)

    Chao, Keh-Ping; Hsu, Ya-Ping; Chen, Su-Yi

    2008-05-30

    The permeation of binary and ternary mixtures of benzene, toluene, ethyl benzene and p-xylene through nitrile gloves were investigated using the ASTM F739 test cell. The more slowly permeating component of a mixture was accelerated to have a shorter breakthrough time than its pure form. The larger differences in solubility parameter between a solvent mixture and glove resulted in a lower permeation rate. Solubility parameter theory provides a potential approach to interpret the changes of permeation properties for BTEX mixtures through nitrile gloves. Using a one-dimensional diffusion model based on Fick's law, the permeation concentrations of ASTM F739 experiments were appropriately simulated by the estimated diffusion coefficient and solubility. This study will be a fundamental work for the risk assessment of the potential dermal exposure of workers wearing protective gloves.

  14. Comparison of the effect of using latex and nitrile gloves hand dexterity among Iranian population

    Directory of Open Access Journals (Sweden)

    T. Allahyari

    2014-02-01

    .Conclusion: Considering that there was no significant difference in the score of both fine finger and gross hand dexterity while using nitrile gloves as compared to the control condition (without gloves, means that use of nitrile gloves has no adverse effect on hand dexterity therefore, using nitrile gloves is recommended as a alternative for the latex gloves, considering the additional advantage of no allergic reaction in this gloves.

  15. Group 4 metallocene complexes with pendant nitrile groups

    Czech Academy of Sciences Publication Activity Database

    Pinkas, Jiří; Gyepes, R.; Kubišta, Jiří; Horáček, Michal; Lamač, Martin

    2011-01-01

    Roč. 696, 11-12 (2011), s. 2364-2372 ISSN 0022-328X R&D Projects: GA ČR GPP207/10/P200; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : metallocene * group 4 elements * nitrile Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.384, year: 2011

  16. Synthesis and microbial transformation of Beta-amino nitriles

    Czech Academy of Sciences Publication Activity Database

    Winkler, M.; Martínková, Ludmila; Knall, A. C.; Krahulec, S.; Klempier, N.

    2005-01-01

    Roč. 61, - (2005), s. 4249-4260 ISSN 0040-4020 R&D Projects: GA ČR GA203/05/2267; GA MŠk OC D25.001 Grant - others:COST D25/0002/02 Institutional research plan: CEZ:AV0Z50200510 Keywords : microbial nitrile hydrolysis * enantioselectivity Subject RIV: EE - Microbiology, Virology Impact factor: 2.610, year: 2005

  17. Selection and screening for enzymes of nitrile metabolism

    Czech Academy of Sciences Publication Activity Database

    Martínková, Ludmila; Vejvoda, Vojtěch; Křen, Vladimír

    2008-01-01

    Roč. 133, č. 3 (2008), s. 318-326 ISSN 0168-1656 R&D Projects: GA AV ČR IAA500200708; GA ČR GA203/05/2267; GA MŠk(CZ) LC06010; GA MŠk OC 171 Institutional research plan: CEZ:AV0Z50200510 Keywords : nitrilase * nitrile hydratase * amidase Subject RIV: CE - Biochemistry Impact factor: 2.748, year: 2008

  18. Photoactive dye enhanced tissue ablation for endoscopic laser prostatectomy

    Science.gov (United States)

    Ahn, Minwoo; Nguyen, Trung Hau; Nguyen, Van Phuc; Oh, Junghwan; Kang, Hyun Wook

    2015-02-01

    Laser light has been widely used as a surgical tool to treat benign prostate hyperplasia with high laser power. The purpose of this study was to validate the feasibility of photoactive dye injection to enhance light absorption and eventually to facilitate tissue ablation with low laser power. The experiment was implemented on chicken breast due to minimal optical absorption Amaranth (AR), black dye (BD), hemoglobin powder (HP), and endoscopic marker (EM), were selected and tested in vitro with a customized 532-nm laser system with radiant exposure ranging from 0.9 to 3.9 J/cm2. Light absorbance and ablation threshold were measured with UV-VIS spectrometer and Probit analysis, respectively, and compared to feature the function of the injected dyes. Ablation performance with dye-injection was evaluated in light of radiant exposure, dye concentration, and number of injection. Higher light absorption by injected dyes led to lower ablation threshold as well as more efficient tissue removal in the order of AR, BD, HP, and EM. Regardless of the injected dyes, ablation efficiency principally increased with input parameter. Among the dyes, AR created the highest ablation rate of 44.2+/-0.2 μm/pulse due to higher absorbance and lower ablation threshold. Preliminary tests on canine prostate with a hydraulic injection system demonstrated that 80 W with dye injection yielded comparable ablation efficiency to 120 W with no injection, indicating 33 % reduced laser power with almost equivalent performance. In-depth comprehension on photoactive dye-enhanced tissue ablation can help accomplish efficient and safe laser treatment for BPH with low power application.

  19. "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles.

    Science.gov (United States)

    Jagadeesh, Rajenahally V; Junge, Henrik; Beller, Matthias

    2015-01-01

    Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2 O3 )-based catalysts applying molecular oxygen. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Nitrile anion cyclization with epoxysilanes followed by Brook rearrangement/ring-opening of cyclopropane nitriles/alkylation.

    Science.gov (United States)

    Okugawa, Seigo; Masu, Hyuma; Yamaguchi, Kentaro; Takeda, Kei

    2005-12-09

    [reactions: see text] The reaction of delta-silyl-gamma,delta-epoxypentanenitrile derivatives 9-12 with a base and an alkylating agent affords (Z)-delta-siloxy-gamma,delta-unsaturated pentanenitrile derivatives via a tandem process that involves the formation of a cyclopropane derivative by epoxy nitrile cyclization followed by Brook rearrangement and an anion-induced cleavage of the cyclopropane ring. Exclusive formation of a (Z)-derivative from trans-epoxides is explained by the reaction pathway that involves a backside displacement of the epoxide by the alpha-nitrile carbanion and the O-Si bond formation followed by concerted processes involving Brook rearrangement and the anti-mode of eliminative ring fission of the cyclopropane from the rotamer 19. The fact that (E)-isomers are exclusively obtained from cis-epoxides and alpha-cyclopropyl-alpha-silylcarbinol derivative 26 provides experimental support for the proposed pathway.

  1. Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

    Science.gov (United States)

    Liu, Yan-Yun; Yang, Xu-Heng; Song, Ren-Jie; Luo, Shenglian; Li, Jin-Heng

    2017-04-01

    Difunctionalization of alkenes has become a powerful tool for quickly increasing molecular complexity in synthesis. Despite significant progress in the area of alkene difunctionalization involving the incorporation of a nitrogen atom across the C-C double bonds, approaches for the direct 1,2-carboamination of alkenes to produce linear N-containing molecules are scarce and remain a formidable challenge. Here we describe a radical-mediated oxidative intermolecular 1,2-alkylamination of alkenes with alkyl nitriles and amines involving C(sp3)-H oxidative functionalization catalysed by a combination of Ag2CO3 with iron Lewis acids. This three-component alkene 1,2-alkylamination method is initiated by the C(sp3)-H oxidative radical functionalization, which enables one-step formation of two new chemical bonds, a C-C bond and a C-N bond, to selectively produce γ-amino alkyl nitriles.

  2. Nitriles at Silica Interfaces Resemble Supported Lipid Bilayers.

    Science.gov (United States)

    Berne, Bruce J; Fourkas, John T; Walker, Robert A; Weeks, John D

    2016-09-20

    Nitriles are important solvents not just for bulk reactions but also for interfacial processes such as separations, heterogeneous catalysis, and electrochemistry. Although nitriles have a polar end and a lipophilic end, the cyano group is not hydrophilic enough for these substances to be thought of as prototypical amphiphiles. This picture is now changing, as research is revealing that at a silica surface nitriles can organize into structures that, in many ways, resemble lipid bilayers. This unexpected organization may be a key component of unique interfacial behavior of nitriles that make them the solvents of choice for so many applications. The first hints of this lipid-bilayer-like (LBL) organization of nitriles at silica interfaces came from optical Kerr effect (OKE) experiments on liquid acetonitrile confined in the pores of sol-gel glasses. The orientational dynamics revealed by OKE spectroscopy suggested that the confined liquid is composed of a relatively immobile sublayer of molecules that accept hydrogen bonds from the surface silanol groups and an interdigitated, antiparallel layer that is capable of exchanging into the centers of the pores. This picture of acetonitrile has been borne out by molecular dynamics simulations and vibrational sum-frequency generation (VSFG) experiments. Remarkably, these simulations further indicate that the LBL organization is repeated with increasing disorder at least 20 Å into the liquid from a flat silica surface. Simulations and VSFG and OKE experiments indicate that extending the alkyl chain to an ethyl group leads to the formation of even more tightly packed LBL organization featuring entangled alkyl tails. When the alkyl portion of the molecule is a bulky t-butyl group, packing constraints prevent well-ordered LBL organization of the liquid. In each case, the surface-induced organization of the liquid is reflected in its interfacial dynamics. Acetonitrile/water mixtures are favored solvent systems for separations

  3. Nitrile-assisted oxidation over oxidative-annulation: Pd-catalyzed α,β-dehydrogenation of α-cinnamyl β-keto nitriles.

    Science.gov (United States)

    Nallagonda, Rajender; Reddy, Reddy Rajasekhar; Ghorai, Prasanta

    2017-09-13

    A palladium-catalyzed oxidation reaction is disclosed where the nitrile functionality on the substrate simply changes the course of the reaction. Our previous finding showed that using the Pd(ii)-catalyst in the presence of benzoquinone as an oxidant, 2-cinnamyl-1,3-dicarbonyls provides functionalized furans via oxidative cyclization. When a nitrile group is replaced with one of the carbonyl functionalities of the same substrate, the oxidative cyclization was completely suppressed; instead, the oxidation at the α,β-position occurred to provide α,β,γ,δ-diene containing β-keto nitriles.

  4. Selective Oxidation of Alcohols Using Photoactive VO@g‑C3N4

    Data.gov (United States)

    U.S. Environmental Protection Agency — A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated...

  5. Synthesis of positron labeled photoactive compounds: 18F labeled aryl azides for positron labeling of biochemical molecules

    International Nuclear Information System (INIS)

    Hashizume, Kazunari; Hashimoto, Naota; Miyake, Yoshihiro

    1995-01-01

    The authors have prepared various [ 18 F] fluorine labeled aryl azides as a novel photoactive compounds suitable for positron labeling of biochemical molecules. The introduction of fluorine substituents to aryl azides can be expected to have dramatic effects on their nature and reactivity toward photolysis. Positron labeled reagents for labeling proteins or peptides have recently attracted considerable attention due to their wide applicability in biochemistry and positron emission tomography (PET). Various labeled azide compounds are often used in biochemistry for radiolabeling biological molecules by photolysis, but there have been no reports on the preparation or use of fluorine-18 labeled azides. The authors now report a novel synthesis of 18 F-labeled aryl azides which will have wide application in the biochemistry and nuclear medicine as a means for 18 F-fluorine labeling for proteins, peptides, and nucleic acids. 2 tabs

  6. Selective and reactive hydration of nitriles to amides in water using silver nanoparticles stabilized by organic ligands

    International Nuclear Information System (INIS)

    Kawai, Koji; Kawakami, Hayato; Narushima, Takashi; Yonezawa, Tetsu

    2015-01-01

    Water-dispersible silver nanoparticles stabilized by silver–carbon covalent bonds were prepared. They exhibited high catalytic activities for the selective hydration of nitriles to amides in water. The activation of a nitrile group by the functional groups of the substrates and the hydrophobic layer on the nanoparticles influenced the catalyzed reaction were confirmed. Alkyl nitriles could also be selectively hydrated

  7. Synthesis of Quinolines through Three-Component Cascade Annulation of Aryl Diazonium Salts, Nitriles, and Alkynes.

    Science.gov (United States)

    Wang, Hao; Xu, Qian; Shen, Sheng; Yu, Shouyun

    2017-01-06

    An efficient and rapid synthesis of multiply substituted quinolines is described. This method is enabled by a three-component cascade annulation of readily available aryl diazonium salts, nitriles, and alkynes. This reaction is catalyst- and additive-free. Various aryl diazonium salts, nitriles, and alkynes can participate in this transformation, and the yields are up to 83%.

  8. Triphenylphosphine dibromide: A useful reagent for conversion of aldoximes into nitriles

    Directory of Open Access Journals (Sweden)

    Fatemeh Darvish

    2015-11-01

    Full Text Available A simple and convenient method for the synthesis of nitriles by dehydration of aldoximes has been developed using triphenylphosphine dibromide in acetonitrile at room temperature. A variety of aromatic and heteroaromatic aldoximes are converted into the corresponding nitriles in high yields.

  9. Reactions of nitriles with iodonium salt of bis(1,2-dicarbollyl)cobalt

    International Nuclear Information System (INIS)

    Knyazev, S.P.; Kirin, V.N.; Chernyshev, E.A.

    1996-01-01

    Interaction of nitriles with iodonium salt bis(1,2-dicarbollyl)cobalt, resulting in the 8,8'-disubstituted derivatives, is studied. Interaction of nitrile group with iodonium fragment is accompanied by B-I bond discontinuity and by formation of B-N bond with subsequent formation of amino alcohol, which regroups into amide. 3 refs

  10. Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

    Science.gov (United States)

    Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

  11. Synthesis of Nitriles via Palladium-Catalyzed Water Shuffling from Amides to Acetonitrile

    OpenAIRE

    Zhang, Wandi; Haskins, Christopher W.; Yang, Yang; Dai, Mingji

    2014-01-01

    Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

  12. Synthesis of nitriles via palladium-catalyzed water shuffling from amides to acetonitrile.

    Science.gov (United States)

    Zhang, Wandi; Haskins, Christopher W; Yang, Yang; Dai, Mingji

    2014-12-07

    Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

  13. Cysteine protease inhibition by nitrile-based inhibitors: a computational study

    Science.gov (United States)

    Quesne, Matthew G.; Ward, Richard A.; de Visser, Sam P.

    2013-01-01

    Cysteine protease enzymes are important for human physiology and catalyze key protein degradation pathways. These enzymes react via a nucleophilic reaction mechanism that involves a cysteine residue and the proton of a proximal histidine. Particularly efficient inhibitors of these enzymes are nitrile-based, however, the details of the catalytic reaction mechanism currently are poorly understood. To gain further insight into the inhibition of these molecules, we have performed a combined density functional theory and quantum mechanics/molecular mechanics study on the reaction of a nitrile-based inhibitor with the enzyme active site amino acids. We show here that small perturbations to the inhibitor structure can have dramatic effects on the catalysis and inhibition processes. Thus, we investigated a range of inhibitor templates and show that specific structural changes reduce the inhibitory efficiency by several orders of magnitude. Moreover, as the reaction takes place on a polar surface, we find strong differences between the DFT and QM/MM calculated energetics. In particular, the DFT model led to dramatic distortions from the starting structure and the convergence to a structure that would not fit the enzyme active site. In the subsequent QM/MM study we investigated the use of mechanical vs. electronic embedding on the kinetics, thermodynamics and geometries along the reaction mechanism. We find minor effects on the kinetics of the reaction but large geometric and thermodynamics differences as a result of inclusion of electronic embedding corrections. The work here highlights the importance of model choice in the investigation of this biochemical reaction mechanism. PMID:24790966

  14. C- and N-Metalated Nitriles: The Relationship between Structure and Selectivity.

    Science.gov (United States)

    Yang, Xun; Fleming, Fraser F

    2017-10-17

    Metalated nitriles are exceptional nucleophiles capable of forging highly hindered stereocenters in cases where enolates are unreactive. The excellent nucleophilicity emanates from the powerful inductive stabilization of adjacent negative charge by the nitrile, which has a miniscule steric demand. Inductive stabilization is the key to understanding the reactivity of metalated nitriles because this permits a continuum of structures that range from N-metalated ketenimines to nitrile anions. Solution and solid-state analyses reveal two different metal coordination sites, the formally anionic carbon and the nitrile nitrogen, with the site of metalation depending intimately on the solvent, counterion, temperature, and ligands. The most commonly encountered structures, C- and N-metalated nitriles, have either sp 3 or sp 2 hybridization at the nucleophilic carbon, which essentially translates into two distinct organometallic species with similar but nonidentical stereoselectivity, regioselectivity, and reactivity preferences. The hybridization differences are particularly important in S N i displacements of cyclic nitriles because the orbital orientations create very precise trajectories that control the cyclization selectivity. Harnessing the orbital differences between C- and N-metalated nitriles allows selective cyclization to afford nitrile-containing cis- or trans-hydrindanes, decalins, or bicyclo[5.4.0]undecanes. Similar orbital constraints favor preferential S N i displacements with allylic electrophiles on sp 3 centers over sp 2 centers. The strategy permits stereoselective displacements on secondary centers to set contiguous tertiary and quaternary stereocenters or even contiguous vicinal quaternary centers. Stereoselective alkylations of acyclic nitriles are inherently more challenging because of the difficulty in creating steric differentiation in a dynamic system with rotatable bonds. However, judicious substituent placement of vicinal dimethyl groups and a

  15. Lactic acid bacteria convert glucosinolates to nitriles efficiently yet differently from enterobacteriaceae.

    Science.gov (United States)

    Mullaney, Jane A; Kelly, William J; McGhie, Tony K; Ansell, Juliet; Heyes, Julian A

    2013-03-27

    Glucosinolates from the genus Brassica can be converted into bioactive compounds known to induce phase II enzymes, which may decrease the risk of cancers. Conversion via hydrolysis is usually by the brassica enzyme myrosinase, which can be inactivated by cooking or storage. We examined the potential of three beneficial bacteria, Lactobacillus plantarum KW30, Lactococcus lactis subsp. lactis KF147, and Escherichia coli Nissle 1917, and known myrosinase-producer Enterobacter cloacae to catalyze the conversion of glucosinolates in broccoli extract. Enterobacteriaceae consumed on average 65% glucoiberin and 78% glucoraphanin, transforming them into glucoiberverin and glucoerucin, respectively, and small amounts of iberverin nitrile and erucin nitrile. The lactic acid bacteria did not accumulate reduced glucosinolates, consuming all at 30-33% and transforming these into iberverin nitrile, erucin nitrile, sulforaphane nitrile, and further unidentified metabolites. Adding beneficial bacteria to a glucosinolate-rich diet may increase glucosinolate transformation, thereby increasing host exposure to bioactives.

  16. An investigation of nitrile transforming enzymes in the chemo-enzymatic synthesis of the taxol sidechain.

    Science.gov (United States)

    Wilding, Birgit; Veselá, Alicja B; Perry, Justin J B; Black, Gary W; Zhang, Meng; Martínková, Ludmila; Klempier, Norbert

    2015-07-28

    Paclitaxel (taxol) is an antimicrotubule agent widely used in the treatment of cancer. Taxol is prepared in a semisynthetic route by coupling the N-benzoyl-(2R,3S)-3-phenylisoserine sidechain to the baccatin III core structure. Precursors of the taxol sidechain have previously been prepared in chemoenzymatic approaches using acylases, lipases, and reductases, mostly featuring the enantioselective, enzymatic step early in the reaction pathway. Here, nitrile hydrolysing enzymes, namely nitrile hydratases and nitrilases, are investigated for the enzymatic hydrolysis of two different sidechain precursors. Both sidechain precursors, an openchain α-hydroxy-β-amino nitrile and a cyanodihydrooxazole, are suitable for coupling to baccatin III directly after the enzymatic step. An extensive set of nitrilases and nitrile hydratases was screened towards their activity and selectivity in the hydrolysis of two taxol sidechain precursors and their epimers. A number of nitrilases and nitrile hydratases converted both sidechain precursors and their epimers.

  17. Nitrile-converting enzymes: an eco-friendly tool for industrial biocatalysis.

    Science.gov (United States)

    Ramteke, Pramod W; Maurice, Navodita G; Joseph, Babu; Wadher, Bharat J

    2013-01-01

    Nitriles are organic compounds bearing a − C ≡ N group; they are frequently known to occur naturally in both fauna and flora and are also synthesized chemically. They have wide applicability in the fields of medicine, industry, and environmental monitoring. However, the majority of nitrile compounds are considered to be lethal, mutagenic, and carcinogenic in nature and are known to cause potential health problems such as nausea, bronchial irritation, respiratory distress, convulsions, coma, and skeletal deformities in humans. Nitrile-converting enzymes, which are extracted from microorganisms, are commonly termed nitrilases and have drawn the attention of researchers all over the world to combat the toxicity of nitrile compounds. The present review focuses on the utility of nitrile-converting enzymes, sources, classification, structure, properties, and applications, as well as the future perspective on nitrilases. © 2013 International Union of Biochemistry and Molecular Biology, Inc.

  18. Study of radiation induced structural changes in nitrile rubber

    International Nuclear Information System (INIS)

    Cardona, F.; Hill, D.J.T.; Pomery, P.J.; Whittaker, A.K.

    1996-01-01

    Full text: Copolymers of butadiene (BD) and acrylonitrile (AN) (NBR rubber), have become important commercial material. NBR rubbers are part of a larger classification of products often referred to as special-purpose rubbers. Oil resistance is the most important property of nitrile rubbers, and refer to the ability of the vulcanised product to retain its original physical properties such as modulus, tensile strength, abrasion resistance and dimensions, while in contact with oils and fuels. Despite these reported advantages very few studies have been conducted on the radiation yields and structural changes in nitrile rubbers during exposure to high energy radiation. In this study we are investigating the stability against gamma and UV radiation, to different doses in vacuum, of butadiene, acrylonitrile and NBR copolymers with different composition ratio BD/AN. The mechanism of radiation induced structural changes is being investigated using experimental techniques such as ESR, NMR (Solid-state), FT-IR, RAMAN and UV spectroscopy. Also is being investigated the effect of irradiation on the mechanical properties of stressed and unstressed samples by TGA, DSC, DMA, Instron and Creep Test measurements. So far the main effect have been a marked radiation-induced loss of unsaturation in the butadiene units, cis to trans isomerization and formation of crosslink structures (intermolecular and intramolecular). One of the main challenges in the studies of NBR polymers is to observe directly the crosslinks produces by the radiation induced chemical reactions. IR spectroscopy is unsuitable because of the low molar absorbity of the peaks related to intermolecular crosslinking and the overlapping of the peaks (1630-1670 cm-1) related to intramolecular crosslinking (cyclization), with conjugated and nonconjugated (-C=C-; -C=N-) double bonds. A. K. Whittaker has shown that crosslink structures in PBD can be detected and measured directly using solid-state 13 C NMR. This technique

  19. Nitrile crosslinked polyphenyl-quinoxaline/graphite fiber composites

    Science.gov (United States)

    Alston, W. B.

    1976-01-01

    Studies were performed to reduce the 600 F thermoplasticity of polyphenylquinoxaline (PPQ) matrix resins by introducing crosslinking by the reaction of terminal nitrile groups. Seven solvents and solvent mixtures were studied as the crosslinking catalysts and used to fabricate crosslinked PPQ/HMS graphite fiber composites. The room temperature and 600 F composite mechanical properties after short time and prolonged 600 F air exposure and the 600 F composite weight loss were determined and compared to those properties of high molecular weight, linear PPQ/HMS graphite fiber composites.

  20. Centimetre-scale electron diffusion in photoactive organic heterostructures

    Science.gov (United States)

    Burlingame, Quinn; Coburn, Caleb; Che, Xiaozhou; Panda, Anurag; Qu, Yue; Forrest, Stephen R.

    2018-02-01

    The unique properties of organic semiconductors, such as flexibility and lightness, are increasingly important for information displays, lighting and energy generation. But organics suffer from both static and dynamic disorder, and this can lead to variable-range carrier hopping, which results in notoriously poor electrical properties, with low electron and hole mobilities and correspondingly short charge-diffusion lengths of less than a micrometre. Here we demonstrate a photoactive (light-responsive) organic heterostructure comprising a thin fullerene channel sandwiched between an electron-blocking layer and a blended donor:C70 fullerene heterojunction that generates charges by dissociating excitons. Centimetre-scale diffusion of electrons is observed in the fullerene channel, and this can be fitted with a simple electron diffusion model. Our experiments enable the direct measurement of charge diffusivity in organic semiconductors, which is as high as 0.83 ± 0.07 square centimetres per second in a C60 channel at room temperature. The high diffusivity of the fullerene combined with the extraordinarily long charge-recombination time yields diffusion lengths of more than 3.5 centimetres, orders of magnitude larger than expected for an organic system.

  1. Multiphoton manipulations of enzymatic photoactivity in aspartate aminotransferase.

    Science.gov (United States)

    Hill, Melissa P; Freer, Lucy H; Vang, Mai C; Carroll, Elizabeth C; Larsen, Delmar S

    2011-04-21

    The aspartate aminotransferase (AAT) enzyme utilizes the chromophoric pyridoxal 5'-phosphate (PLP) cofactor to facilitate the transamination of amino acids. Recently, we demonstrated that, upon exposure to blue light, PLP forms a reactive triplet state that rapidly (in microseconds) generates the high-energy quinonoid intermediate when bound to PLP-dependent enzymes [J. Am. Chem. Soc.2010, 132 (47), 16953-16961]. This increases the net catalytic activity (k(cat)) of AAT, since formation of the quinonoid is partially rate limiting via the thermally activated enzymatic pathway. The magnitude of observed photoenhancement initially scales linearly with pump fluence; however when a critical threshold is exceeded, the photoactivity saturates and is even suppressed at greater excitation fluences. The photodynamic mechanisms associated with this suppression behavior are characterized with the use of ultrafast multipulse pump-dump-probe and pump-repump-probe transient absorption techniques in combination with complementary two-color, steady-state excitation assays. Via multistate kinetic modeling of the transient ultrafast data and the steady-state assay data, the nonmonotonic incident power dependence of the photoactivty in AAT is decomposed into contributions from high-intensity dumping of the excited singlet state and repumping of the excited triplet state with induces the repopulation of the ground state via rapid intersystem crossing in the higher-lying triplet electronic manifold.

  2. The Diatom Staurosirella pinnata for Photoactive Material Production.

    Directory of Open Access Journals (Sweden)

    Roberta De Angelis

    Full Text Available A native isolate of the colonial benthic diatom Staurosirella pinnata was cultivated for biosilica production. The silicified cell walls (frustules were used as a source of homogeneous and structurally predictable porous biosilica for dye trapping and random laser applications. This was coupled with the extraction of lipids from biomass showing potential to fabricate photoactive composite materials sustainably. The strain was selected for its ease of growth in culture and harvesting. Biosilica and lipids were obtained at the end of growth in indoor photobioreactors. Frustules were structurally characterized microscopically and their chemistry analyzed with Fourier Transform Infrared Spectroscopy. Frustule capacity of binding laser dyes was evaluated on a set of frustules/Rhodamine B (Rho B solutions and with respect to silicon dioxide and diatomite by Fluorescence Spectroscopy demonstrating a high affinity for the organic dye. The effect of dye trapping property in conveying Rho B emission to frustules, with enhancement of scattering events, was analyzed on Rho B doped polyacrylamide gels filled or not with frustules. Amplified spontaneous emission was recorded at increasing pump power indicating the onset of a random laser effect in frustule filled gels at lower power threshold compared to unfilled matrices.

  3. The Diatom Staurosirella pinnata for Photoactive Material Production

    Science.gov (United States)

    Prosposito, Paolo; Casalboni, Mauro; Lamastra, Francesca Romana; Nanni, Francesca; Congestri, Roberta

    2016-01-01

    A native isolate of the colonial benthic diatom Staurosirella pinnata was cultivated for biosilica production. The silicified cell walls (frustules) were used as a source of homogeneous and structurally predictable porous biosilica for dye trapping and random laser applications. This was coupled with the extraction of lipids from biomass showing potential to fabricate photoactive composite materials sustainably. The strain was selected for its ease of growth in culture and harvesting. Biosilica and lipids were obtained at the end of growth in indoor photobioreactors. Frustules were structurally characterized microscopically and their chemistry analyzed with Fourier Transform Infrared Spectroscopy. Frustule capacity of binding laser dyes was evaluated on a set of frustules/Rhodamine B (Rho B) solutions and with respect to silicon dioxide and diatomite by Fluorescence Spectroscopy demonstrating a high affinity for the organic dye. The effect of dye trapping property in conveying Rho B emission to frustules, with enhancement of scattering events, was analyzed on Rho B doped polyacrylamide gels filled or not with frustules. Amplified spontaneous emission was recorded at increasing pump power indicating the onset of a random laser effect in frustule filled gels at lower power threshold compared to unfilled matrices. PMID:27828985

  4. [Applications of nitrile converting enzymes in the production of fine chemicals].

    Science.gov (United States)

    Zheng, Yuguo; Xue, Yaping; Liu, Zhiqiang; Zheng, Renchao; Shen, Yinchu

    2009-12-01

    Nitriles are an important type of synthetic intermediates in the production of fine chemicals because of their easy preparations and versatile transformations. The traditional chemical conversion of nitriles to carboxylic acids and amides is feasible but it requires relatively harsh conditions of heat, acid or alkali. Nitrile converting enzymes (nitrilase, nitrile hydratase and amidase) which are used as biocatalyst for the production of fine chemicals have attracted substantial interest because of their ability to convert readily available nitriles into the corresponding higher value amides or acids under mild conditions with excellent chemo-, regio- and stereo-selectivities. Many nitrile converting enzymes have been explored and widely used for the production of fine chemicals. In this paper, various examples of biocatalytic synthesis of pharmaceuticals and their intermediates, agrochemicals and their intermediates, food and feed additives, and other fine chemicals are presented. In the near future, an increasing number of novel nitrile converting enzymes will be screened and their potential in the production of useful fine chemicals will be further exploited.

  5. Cytotoxic and genotoxic potential of food-borne nitriles in a liver in vitro model

    Science.gov (United States)

    Kupke, Franziska; Herz, Corinna; Hanschen, Franziska S.; Platz, Stefanie; Odongo, Grace A.; Helmig, Simone; Bartolomé Rodríguez, María M.; Schreiner, Monika; Rohn, Sascha; Lamy, Evelyn

    2016-01-01

    Isothiocyanates are the most intensively studied breakdown products of glucosinolates from Brassica plants and well recognized for their pleiotropic effects against cancer but also for their genotoxic potential. However, knowledge about the bioactivity of glucosinolate-borne nitriles in foods is very poor. As determined by GC-MS, broccoli glucosinolates mainly degrade to nitriles as breakdown products. The cytotoxicity of nitriles in human HepG2 cells and primary murine hepatocytes was marginal as compared to isothiocyanates. Toxicity of nitriles was not enhanced in CYP2E1-overexpressing HepG2 cells. In contrast, the genotoxic potential of nitriles was found to be comparable to isothiocyanates. DNA damage was persistent over a certain time period and CYP2E1-overexpression further increased the genotoxic potential of the nitriles. Based on actual in vitro data, no indications are given that food-borne nitriles could be relevant for cancer prevention, but could pose a certain genotoxic risk under conditions relevant for food consumption. PMID:27883018

  6. Comparing the level of dexterity offered by latex and nitrile SafeSkin gloves.

    Science.gov (United States)

    Sawyer, Jo; Bennett, Allan

    2006-04-01

    An increase in the occurrence of latex allergy has been concurrent with the increasing use of latex gloves by laboratory and healthcare workers. In recent years nitrile gloves have been used to replace latex gloves to prevent latex allergy. Nitrile gloves offer a comparable level of protection against chemical and biological agents and are more puncture resistant. However, if manual dexterity is compromised by nitrile gloves to a greater degree than latex then this may increase the risk of sharps injuries. The Purdue pegboard test, which measures both gross and fine finger dexterity, was used to test the dexterity levels of two glove types used at HPA CEPR; Kimberly-Clark SafeSkin nitrile and latex laboratory gloves. There was a statistically significant 8.6% increase in fine finger dexterity provided by latex compared with nitrile SafeSkin laboratory gloves but no difference in gross dexterity between the glove types. There was no significant relationship between glove dexterity and age or gender. The selection of glove size was influenced by the digit length of participants. Moreover, those with longer, thinner fingers appeared to have an advantage when using nitrile SafeSkin gloves. The level of dexterity provided by latex and nitrile SafeSkin gloves for tasks on a gross dexterity level are comparable and health workers will benefit from the non-allergenic properties of nitrile. For tasks requiring fine finger dexterity nitrile SafeSkin gloves may impede dexterity. Despite this, the degree of restriction appears to have a negligible impact on safety in this study when compared with the risk of latex sensitization and subsequent allergy. In addition to glove material, working practices must also take into account glove size, fit, grip and thickness, as these factors can all influence dexterity.

  7. Electron beam modification and crosslinking: Influence of nitrile and carboxyl contents and level of unsaturation on structure and properties of nitrile rubber

    International Nuclear Information System (INIS)

    Vijayabaskar, V.; Tikku, V.K.; Bhowmick, Anil K.

    2006-01-01

    The structural changes of nitrile rubber with varying nitrile contents, hydrogenated nitrile rubber and carboxylated nitrile rubber in the presence and absence of a polyfunctional monomer, namely trimethylolpropane triacrylate, at different doses of electron beam irradiation, were investigated with the help of FTIR spectroscopy (in the attenuated total reflectance mode), dynamic mechanical thermal analysis and sol-gel analysis. Solid-state NMR with gated high power decoupling technique was used to understand the mechanism of crosslinking of the irradiated samples. The allylic radicals generated in the butadiene chains react to form intermolecular crosslinkages. There was a significant decrease in the concentration of olefinic groups for the nitrile rubber on irradiation. This was also affirmed by the increase in the carbon resonances due to C-C linkages from the NMR technique, indicating more crosslinkages. The spectroscopic crosslink densities were determined and the results were compared with the swelling measurements. The variation in the crosslink clustering for rubbers with different acrylonitrile contents was explained using the NMR technique. The increase in crosslinking was also revealed by the increase in the percent gel content and dynamic storage moduli with radiation doses. The lifetime of spurs formed and the critical dose, an important criterion for overlapping of spurs, were determined for both the grafted and the ungrafted nitrile rubbers of different grades and compared using a mathematical model. The ratio of scissioning to crosslinking for nitrile rubber was determined using Charlesby-Pinner equation. The mechanical properties had also been studied for both the modified and the unmodified systems

  8. Compatibilization efficiency of carboxylated nitrile rubber and epoxy pre-polymer in nitrile/acrylic rubber blends

    Directory of Open Access Journals (Sweden)

    Micheli L. Celestin

    2013-01-01

    Full Text Available An investigation has been made of the effects from a compatibilizer, viz. carboxylated nitrile rubber (XNBR, on several properties of nitrile rubber (NBR and acrylic rubber (ACM blends, including curing characteristics, mechanical, dynamic mechanical and dielectric properties. The presence of XNBR until 10 phr resulted in an improvement of the ultimate tensile properties, especially elongation at break. The mechanical properties associated to the volume fraction of rubber in the network (Vr and torque values suggest the co-vulcanization phenomenon imparted by the compatibilization. The oil resistance of NBR/ACM (50:50 wt. (% blends (compatibilized and non compatibilized was similar to that observed for pure ACM and significantly higher than NBR. The addition of small amounts of epoxy pre-polymer in combination with XNBR resulted in an additional improvement of the tensile properties. The dynamic mechanical and dielectric properties of the blends were also investigated. The loss modulus values of the compatibilized blends were significantly lower indicating an increase of the elastic characteristics. All blends presented two dielectric relaxation peaks confirming the heterogeneity of the compatibilized blends

  9. Nitrile hydratase of Rhodococcus erythropolis: characterization of the enzyme and the use of whole cells for biotransformation of nitriles.

    Science.gov (United States)

    Kamble, Ashwini L; Banoth, Linga; Meena, Vachan Singh; Singh, Amit; Chisti, Yusuf; Banerjee, U C

    2013-08-01

    The intracellular cobalt-type nitrile hydratase was purified from the bacterium Rhodococcuserythropolis. The pure enzyme consisted of two subunits of 29 and 30 kDa. The molecular weight of the native enzyme was estimated to be 65 kDa. At 25 °C the enzyme had a half-life of 25 h. The Michaelis-Menten constants K m and v max for the enzyme were 0.624 mM and 5.12 μmol/min/mg, respectively, using 3-cyanopyridine as the substrate. The enzyme-containing freely-suspended bacterial cells and the cells immobilized within alginate beads were evaluated for converting the various nitriles to amides. In a packed bed reactor, alginate beads (2 % alginate; 3 mm bead diameter) containing 200 mg/mL of cells, achieved a conversion of >90 % for benzonitrile and 4-cyanopyridine in 38 h (25 °C, pH 7.0) at a feed substrate concentration of 100 mM. The beads could be reused for up to six reaction cycles.

  10. Integrity of Disposable Nitrile Exam Gloves Exposed to Simulated Movement

    Science.gov (United States)

    Phalen, Robert N.; Wong, Weng Kee

    2011-01-01

    Every year, millions of health care, first responder, and industry workers are exposed to chemical and biological hazards. Disposable nitrile gloves are a common choice as both a chemical and physical barrier to these hazards, especially as an alternative to natural latex gloves. However, glove selection is complicated by the availability of several types or formulations of nitrile gloves, such as low-modulus, medical-grade, low-filler, and cleanroom products. This study evaluated the influence of simulated movement on the physical integrity (i.e., holes) of different nitrile exam glove brands and types. Thirty glove products were evaluated out-of-box and after exposure to simulated whole-glove movement for 2 hr. In lieu of the traditional 1-L water-leak test, a modified water-leak test, standardized to detect a 0.15 ± 0.05 mm hole in different regions of the glove, was developed. A specialized air inflation method simulated bidirectional stretching and whole-glove movement. A worst-case scenario with maximum stretching was evaluated. On average, movement did not have a significant effect on glove integrity (chi-square; p=0.068). The average effect was less than 1% between no movement (1.5%) and movement (2.1%) exposures. However, there was significant variability in glove integrity between different glove types (p ≤ 0.05). Cleanroom gloves, on average, had the highest percentage of leaks, and 50% failed the water-leak test. Low-modulus and medical-grade gloves had the lowest percentages of leaks, and no products failed the water-leak test. Variability in polymer formulation was suspected to account for the observed discrepancies, as well as the inability of the traditional 1-L water-leak test to detect holes in finger/thumb regions. Unexpectedly, greater than 80% of the glove defects were observed in the finger and thumb regions. It is recommended that existing water-leak tests be re-evaluated and standardized to account for product variability. PMID:21476169

  11. Self-subunit swapping occurs in another gene type of cobalt nitrile hydratase.

    Directory of Open Access Journals (Sweden)

    Yi Liu

    Full Text Available Self-subunit swapping is one of the post-translational maturation of the cobalt-containing nitrile hydratase (Co-NHase family of enzymes. All of these NHases possess a gene organization of , which allows the activator protein to easily form a mediatory complex with the α-subunit of the NHase after translation. Here, we discovered that the incorporation of cobalt into another type of Co-NHase, with a gene organization of , was also dependent on self-subunit swapping. We successfully isolated a recombinant NHase activator protein (P14K of Pseudomonas putida NRRL-18668 by adding a Strep-tag N-terminal to the P14K gene. P14K was found to form a complex [α(StrepP14K(2] with the α-subunit of the NHase. The incorporation of cobalt into the NHase of P. putida was confirmed to be dependent on the α-subunit substitution between the cobalt-containing α(StrepP14K(2 and the cobalt-free NHase. Cobalt was inserted into cobalt-free α(StrepP14K(2 but not into cobalt-free NHase, suggesting that P14K functions not only as a self-subunit swapping chaperone but also as a metallochaperone. In addition, NHase from P. putida was also expressed by a mutant gene that was designed with a order. Our findings expand the general features of self-subunit swapping maturation.

  12. The enhanced photoactivity of nanosized Bi2WO6 catalyst for the degradation of 4-chlorophenol

    International Nuclear Information System (INIS)

    Fu Hongbo; Yao Wenqing; Zhang Liwu; Zhu Yongfa

    2008-01-01

    Nanosized Bi 2 WO 6 catalyst exhibited the enhanced photoactivity for the degradation of 4-chlorophenol (4-CP) under visible irradiation compared to the sample prepared by high-temperature solid reaction. The photoactivity of the catalyst was sensitive to pH variation of the suspension. Nanosized Bi 2 WO 6 catalyst showed the highest activity at pH 7.2. The photodegradation of 4-CP by nanosized Bi 2 WO 6 catalyst followed a pseudo-first-order reaction. After three recycling runs for the photodegradation of 4-CP, the activity of the catalyst did not show any significant loss, suggesting that the catalyst was stable under visible irradiation

  13. Laboratory investigation of nitrile ices of Titan's stratospheric clouds

    Science.gov (United States)

    Nna Mvondo, D.; Anderson, C. M.; McLain, J. L.; Samuelson, R. E.

    2017-09-01

    Titan's mid to lower stratosphere contains complex cloud systems of numerous organic ice particles comprised of both hydrocarbon and nitrile compounds. Most of these stratospheric ice clouds form as a result of vapor condensation formation processes. However, there are additional ice emission features such as dicyanoacetylene (C4N2) and the 220 cm-1 ice emission feature (the "Haystack") that are difficult to explain since there are no observed vapor emission features associated with these ices. In our laboratory, using a high-vacuum chamber coupled to a FTIR spectrometer, we are engaged in a dedicated investigation of Titan's stratospheric ices to interpret and constrain Cassini Composite InfraRed Spectrometer (CIRS) far-IR data. We will present laboratory transmittance spectra obtained for propionitrile (CH3CH2CN), cyanogen (C2N2) and hydrogen cyanide (HCN) ices, as well as various combinations of their mixtures, to better understand the cloud chemistry occurring in Titan's stratosphere.

  14. Carboxylated nitrile butadiene rubber/hybrid filler composites

    Directory of Open Access Journals (Sweden)

    Ahmad Mousa

    2012-08-01

    Full Text Available The surface properties of the OSW and NLS are measured with the dynamic contact-angle technique. The x-ray photoelectron spectroscopy (XPS of the OSW reveals that the OSW possesses various reactive functional groups namely hydroxyl groups (OH. Hybrid filler from NLS and OSW were incorporated into carboxylated nitrile rubber (XNBR to produce XNBR hybrid composites. The reaction of OH groups from the OSW with COOH of the XNBR is checked by attenuated total reflectance spectra (ATR-IR of the composites. The degree of curing ΔM (maximum torque-minimum torque as a function of hybrid filler as derived from moving die rheometer (MDR is reported. The stress-strain behavior of the hybrid composites as well as the dynamic mechanical thermal analysis (DMTA is studied. Bonding quality and dispersion of the hybrid filler with and in XNBR are examined using scanning-transmission electron microscopy (STEM in SEM.

  15. Nucleophilic addition of nitriles to secondary terpene alcohols

    International Nuclear Information System (INIS)

    Kozlov, N.G.; Popova, L.A.; Nesterov, G.V.

    1987-01-01

    The addition of nitriles of varying nucleophilicity to isocamphanol and exo-1,5,5-trimethyl-bicyclo[2.2.1]heptan-2-ol (isofenchol) was investigated. The authors examined the effect of the reaction conditions on the yield and structure of the target products of the reaction: N-substituted amides. As a result of the study, it was shown that in the reaction with chloroacetonitrile, propionitrile, methoxypropionitrile, isovaleronitrile, and phenylacetonitrile under the conditions of the Ritter reaction, isocamphanol is transformed into the corresponding substituted exo-N-acyl-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylamines, as in the reaction with aceto- and benzonitriles, due to 2,6-hydride displacement accompanied by Wagner-Meerwein rearrangement. The structures of these amides were demonstrated by PMR spectroscopy

  16. Tetraoxane-pyrimidine nitrile hybrids as dual stage antimalarials.

    Science.gov (United States)

    Oliveira, Rudi; Guedes, Rita C; Meireles, Patrícia; Albuquerque, Inês S; Gonçalves, Lídia M; Pires, Elisabete; Bronze, Maria Rosário; Gut, Jiri; Rosenthal, Philip J; Prudêncio, Miguel; Moreira, Rui; O'Neill, Paul M; Lopes, Francisca

    2014-06-12

    The use of artemisinin or other endoperoxides in combination with other drugs is a strategy to prevent development of resistant strains of Plasmodium parasites. Our previous work demonstrated that hybrid compounds, comprising endoperoxides and vinyl sulfones, were capable of high activity profiles comparable to artemisinin and chloroquine while acting through two distinct mechanisms of action: oxidative stress and falcipain inhibition. In this study, we adapted this approach to a novel class of falcipain inhibitors: peptidomimetic pyrimidine nitriles. Pyrimidine tetraoxane hybrids displayed potent nanomolar activity against three strains of Plasmodium falciparum and falcipain-2, combined with low cytotoxicity. In vivo, a decrease in parasitemia and an increase in survival of mice infected with Plasmodium berghei was observed when compared to control. All tested compounds combined good blood stage activity with significant effects on liver stage parasitemia, a most welcome feature for any new class of antimalarial drug.

  17. Nitrilases in nitrile biocatalysis: recent progress and forthcoming research

    Directory of Open Access Journals (Sweden)

    Gong Jin-Song

    2012-10-01

    Full Text Available Abstract Over the past decades, nitrilases have drawn considerable attention because of their application in nitrile degradation as prominent biocatalysts. Nitrilases are derived from bacteria, filamentous fungi, yeasts, and plants. In-depth investigations on their natural sources function mechanisms, enzyme structure, screening pathways, and biocatalytic properties have been conducted. Moreover, the immobilization, purification, gene cloning and modifications of nitrilase have been dwelt upon. Some nitrilases are used commercially as biofactories for carboxylic acids production, waste treatment, and surface modification. This critical review summarizes the current status of nitrilase research, and discusses a number of challenges and significant attempts in its further development. Nitrilase is a significant and promising biocatalyst for catalytic applications.

  18. Nitrilases in nitrile biocatalysis: recent progress and forthcoming research

    Science.gov (United States)

    2012-01-01

    Over the past decades, nitrilases have drawn considerable attention because of their application in nitrile degradation as prominent biocatalysts. Nitrilases are derived from bacteria, filamentous fungi, yeasts, and plants. In-depth investigations on their natural sources function mechanisms, enzyme structure, screening pathways, and biocatalytic properties have been conducted. Moreover, the immobilization, purification, gene cloning and modifications of nitrilase have been dwelt upon. Some nitrilases are used commercially as biofactories for carboxylic acids production, waste treatment, and surface modification. This critical review summarizes the current status of nitrilase research, and discusses a number of challenges and significant attempts in its further development. Nitrilase is a significant and promising biocatalyst for catalytic applications. PMID:23106943

  19. Macromolecular surface design: photopatterning of functional stable nitrile oxides.

    Science.gov (United States)

    Altintas, Ozcan; Glassner, Mathias; Rodriguez-Emmenegger, Cesar; Welle, Alexander; Trouillet, Vanessa; Barner-Kowollik, Christopher

    2015-05-04

    The efficient trapping of photogenerated thioaldehydes with functional shelf-stable nitrile oxides in a 1,3-dipolar cycloaddition is a novel and versatile photochemical strategy for polymer end-group functionalization and surface modification under mild and equimolar conditions. The modular ligation in solution was followed in detail by electrospray ionization mass spectrometry (ESI-MS). X-ray photoelectron spectroscopy (XPS) was employed to analyze the functionalized surfaces, whereas time-of-flight secondary-ion mass spectrometry (ToF-SIMS) confirmed the spatial control of the surface functionalization using a micropatterned shadow mask. Polymer brushes were grown from the surface in a spatially confined regime by surface-initiated atom transfer radical polymerization (SI-ATRP) as confirmed by TOF-SIMS, XPS as well as ellipsometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Energy Storage of Polyarylene Ether Nitriles at High Temperature

    Science.gov (United States)

    Tang, Xiaohe; You, Yong; Mao, Hua; Li, Kui; Wei, Renbo; Liu, Xiaobo

    2018-03-01

    Polyarylene ether nitrile (PEN) was synthesized and used as film capacitors for energy storage at high temperature. Scanning electron microscopy observation indicated that the films of PEN have pinholes at nanoscales which restricted the energy storage properties of the material. The pinhole shadowing effect through which the energy storage properties of PEN were effectively improved to be 2.3 J/cm3 was observed by using the overlapped film of PEN. The high glass transition temperature (T g) of PEN was as high as 216 °C and PEN film showed stable dielectric constant, breakdown strength and energy storage density before the T g. The PEN films will be a potential candidate as high performance electronic storage materials used at high temperature.

  1. A bioavailable cathepsin S nitrile inhibitor abrogates tumor development.

    Science.gov (United States)

    Wilkinson, Richard D A; Young, Andrew; Burden, Roberta E; Williams, Rich; Scott, Christopher J

    2016-04-21

    Cathepsin S has been implicated in a variety of malignancies with genetic ablation studies demonstrating a key role in tumor invasion and neo-angiogenesis. Thus, the application of cathepsin S inhibitors may have clinical utility in the treatment of cancer. In this investigation, we applied a cell-permeable dipeptidyl nitrile inhibitor of cathepsin S, originally developed to target cathepsin S in inflammatory diseases, in both in vitro and in vivo tumor models. Validation of cathepsin S selectivity was carried out by assaying fluorogenic substrate turnover using recombinant cathepsin protease. Complete kinetic analysis was carried out and true K i values calculated. Abrogation of tumour invasion using murine MC38 and human MCF7 cell lines were carried out in vitro using a transwell migration assay. Effect on endothelial tube formation was evaluated using primary HUVEC cells. The effect of inhibitor in vivo on MC38 and MCF7 tumor progression was evaluated using cells propagated in C57BL/6 and BALB/c mice respectively. Subsequent immunohistochemical staining of proliferation (Ki67) and apoptosis (TUNEL) was carried out on MCF7 tumors. We confirmed that this inhibitor was able to selectively target cathepsin S over family members K, V, L and B. The inhibitor also significantly reduced MC38 and MCF7 cell invasion and furthermore, significantly reduced HUVEC endothelial tubule formation in vitro. In vivo analysis revealed that the compound could significantly reduce tumor volume in murine MC38 syngeneic and MCF7 xenograft models. Immunohistochemical analysis of MCF7 tumors revealed cathepsin S inhibitor treatment significantly reduced proliferation and increased apoptosis. In summary, these results highlight the characterisation of this nitrile cathepsin S inhibitor using in vitro and in vivo tumor models, presenting a compound which may be used to further dissect the role of cathepsin S in cancer progression and may hold therapeutic potential.

  2. Chemical Resistance of Disposable Nitrile Gloves Exposed to Simulated Movement

    Science.gov (United States)

    Phalen, Robert N.; Wong, Weng Kee

    2012-01-01

    Large discrepancies between laboratory permeation testing and field exposures have been reported, with indications that hand movement could account for a portion of these differences. This study evaluated the influence of simulated movement on chemical permeation of 30 different disposable nitrile glove products. Products were investigated out-of-box and with exposure to simulated whole-glove movement. Permeation testing was conducted using ethanol as a surrogate test chemical. A previously designed pneumatic system was used to simulate hand movement. No movement and movement tests were matched-paired to control for environmental conditions, as were statistical analyses. Permeation data were collected for a 30-min exposure period or until a breakthrough time (BT) and steady-state permeation rate (SSPR) could be determined. A third parameter, area under the curve at 30 min (AUC-30), was used to estimate potential worker exposure. With movement, a significant decrease in BT (p ≤ 0.05), ranging from 6–33%, was observed for 28 products. The average decrease in BT was 18% (p ≤ 0.001). With movement, a significant increase in SSPR (p ≤ 0.05), ranging from 1–78%, was observed with 25 products. The average increase in SSPR was 18% (p ≤ 0.001). Significant increases in AUC-30 (p ≤ 0.05), ranging from 23–277%, were also observed for all products where it could be calculated. On average, there was a 58% increase (p ≤ 0.001). The overall effect of movement on permeation through disposable nitrile gloves was significant. Simulated movement significantly shortened the BT, increased the SSPR, and increased the cumulative 30-min exposure up to three times. Product variability also accounted for large differences, up to 40 times, in permeation and cumulative exposure. Glove selection must take these factors into account. It cannot be assumed that all products will perform in a similar manner. PMID:23009187

  3. Regio- and stereochemistry of 1,3-dipolar cycloaddition of nitrile oxides to alkenes

    International Nuclear Information System (INIS)

    Litvinovskaya, Raisa P; Khripach, Vladimir A

    2001-01-01

    The published data on the chemistry of intermolecular 1,3-dipolar cycloaddition of nitrile oxides to different types of alkene derivatives are systematised. Various aspects of stereo- and regiochemistry of this reaction are considered. The bibliography includes 182 references.

  4. Biotransformation of nitriles by Rhodococcus equi A4 immobilized in LentiKats

    Czech Academy of Sciences Publication Activity Database

    Kubáč, David; Čejková, A.; Masák, J.; Jirků, V.; Lemaire, M.; Gallienne, E.; Bolte, J.; Stloukal, R.; Martínková, Ludmila

    2006-01-01

    Roč. 39, - (2006), s. 59-61 ISSN 1381-1177 R&D Projects: GA ČR GA203/05/2267; GA MŠk OC D25.001; GA AV ČR IAA4020213 Institutional research plan: CEZ:AV0Z50200510 Keywords : nitrile hydratase * amidase * nitriles Subject RIV: EE - Microbiology, Virology Impact factor: 2.149, year: 2006

  5. Changes in chemical permeation of disposable latex, nitrile, and vinyl gloves exposed to simulated movement.

    Science.gov (United States)

    Phalen, Robert N; Le, Thi; Wong, Weng Kee

    2014-01-01

    Glove movement can affect chemical permeation of organic compounds through polymer glove products. However, conflicting reports make it difficult to compare the effects of movement on chemical permeation through commonly available glove types. The aim of this study was to evaluate the effect of movement on chemical permeation of an organic solvent through disposable latex, nitrile, and vinyl gloves. Simulated whole-glove permeation testing was conducted using ethyl alcohol and a previously designed permeation test system. With exposure to movement, a significant decrease (p ≤ 0.001) in breakthrough time (BT) was observed for the latex (-23%) and nitrile gloves (-31%). With exposure to movement, only the nitrile glove exhibited a significant increase (p ≤ 0.001) in steady-state permeation rate (+47%) and cumulative permeation at 30 min (+111%). Even though the nitrile glove provided optimum chemical resistance against ethyl alcohol, it was most affected by movement. With exposure to movement, the latex glove was an equivalent option for overall worker protection, because it was less affected by movement and the permeation rate was lower than that of the nitrile glove. In contrast, the vinyl glove was the least affected by movement, but did not provide adequate chemical resistance to ethyl alcohol in comparison with the nitrile and latex gloves. Glove selection should take movement and polymer type into account. Some glove polymer types are less affected by movement, most notably the latex glove in this test. With nitrile gloves, at least a factor of three should be used when attempting to assign a protection factor when repetitive hand motions are anticipated. Ultimately, the latex gloves outperformed nitrile and vinyl in these tests, which evaluated the effect of movement on chemical permeation. Future research should aim to resolve some of the observed discrepancies in test results with latex and vinyl gloves.

  6. Vapour pressures and enthalpies of vapourization of a series of the linear aliphatic nitriles

    International Nuclear Information System (INIS)

    Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Koutek, Bohumir; Doubsky, Jan

    2005-01-01

    Vapour pressures and the molar enthalpies of vapourization ΔlgHm-bar of the linear aliphatic nitriles C 7 -C 17 have been determined by the transpiration method. Kovat's indices of these compounds were measured by capillary gas-chromatography. A linear correlation of enthalpies of vapourization ΔlgHm-bar at T=298.15 K of the nitriles studied with the Kovats indices has been found

  7. Ferrous and ferric ions-based high-throughput screening strategy for nitrile hydratase and amidase.

    Science.gov (United States)

    Lin, Zhi-Jian; Zheng, Ren-Chao; Lei, Li-Hua; Zheng, Yu-Guo; Shen, Yin-Chu

    2011-06-01

    Rapid and direct screening of nitrile-converting enzymes is of great importance in the development of industrial biocatalytic process for pharmaceuticals and fine chemicals. In this paper, a combination of ferrous and ferric ions was used to establish a novel colorimetric screening method for nitrile hydratase and amidase with α-amino nitriles and α-amino amides as substrates, respectively. Ferrous and ferric ions reacted sequentially with the cyanide dissociated spontaneously from α-amino nitrile solution, forming a characteristic deep blue precipitate. They were also sensitive to weak basicity due to the presence of amino amide, resulting in a yellow precipitate. When amino amide was further hydrolyzed to amino acid, it gave a light yellow solution. Mechanisms of color changes were further proposed. Using this method, two isolates with nitrile hydratase activity towards 2-amino-2,3-dimethyl butyronitrile, one strain capable of hydrating 2-amino-4-(hydroxymethyl phosphiny) butyronitrile and another microbe exhibiting amidase activity against 2-amino-4-methylsulfanyl butyrlamide were obtained from soil samples and culture collections of our laboratory. Versatility of this method enabled it the first direct and inexpensive high-throughput screening system for both nitrile hydratase and amidase. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. Photoactive thin film semiconducting iron pyrite prepared by sulfurization of iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Smestad, G.; Ennaoui, A.; Fiechter, S.; Tributsch, H.; Hofmann, W.K.; Birkholz, M. (Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Solare Energetik Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Materialforschung); Kautek, W. (Bundesanstalt fuer Materialforschung und -pruefung, Berlin (Germany, F.R.))

    1990-03-01

    Photoactive iron pyrite (FeS{sub 2}) thin film layers have been synthesized by a simple method involving the reaction of Fe{sub 3}O{sub 4} or Fe{sub 2}O{sub 3} with elemental sulfur. The films were formed on a variety of different substrate materials by converting or sulfurizing iron oxide layers. The subsequent sulfur treatment of the oxide layers consisted of exposure of the films to gaseous sulfur in open or closed ampules at 350degC for 0.5-2 h. The morphology, composition and photoactivity of the films produced were checked using X-ray diffraction, X-ray photoelectron spectroscopy (ESCA), optical absorption, steady state and transient photoconductivity. The best films showed good crystallinity and purity with concurrent photoconductivity and photoelectrochemical response. The ability of this technique to produce photoactive material can be explained by interpretation of the Gibbs ternary phase diagram for the Fe-O-S system, and may be related to the production of photoactive pyrite in nature. A discussion is made as to the future improvement of the solar cell response by proper optimization of geometric and configurational properties. (orig.).

  9. Synthesis of new, UV-photoactive dansyl derivatives for flow cytometric studies on bile acid uptake.

    Science.gov (United States)

    Rohacova, Jana; Marin, M Luisa; Martínez-Romero, Alicia; O'Connor, José-Enrique; Gomez-Lechon, M Jose; Donato, M Teresa; Castell, Jose V; Miranda, Miguel A

    2009-12-07

    Four new fluorescent derivatives of cholic acid have been synthesized; they incorporate a dansyl moiety at 3alpha-, 3beta-, 7alpha- or 7beta- positions. These cholic acid analogs are UV photoactive and also exhibit green fluorescence. In addition, they have been demonstrated to be suitable for studying the kinetics of bile acid transport by flow cytometry.

  10. Application of photoactive electrospun nanofiber materials with immobilized meso-tetraphenylporphyrin for parabens photodegradation

    Czech Academy of Sciences Publication Activity Database

    Gmurek, M.; Bizukojc, M.; Mosinger, Jiří; Ledakowicz, S.

    2015-01-01

    Roč. 240, FEB (2015), s. 160-167 ISSN 0920-5861 Institutional support: RVO:61388980 Keywords : Esters of p-hydroxybenzoic acid * Langmuir-Hinshelwood model * Heterogeneous photosensitized oxidation * Molecular singlet oxygen * Photoactive materials Subject RIV: CA - Inorganic Chemistry Impact factor: 4.312, year: 2015

  11. Activity Enhancement Based on the Chemical Equilibrium of Multiple-Subunit Nitrile Hydratase from Bordetella petrii.

    Science.gov (United States)

    Liu, Yi; Liu, Ping; Lin, Lu; Zhao, Yueqin; Zhong, Wenjuan; Wu, Lunjie; Zhou, Zhemin; Sun, Weifeng

    2016-09-01

    The maturation mechanism of nitrile hydratase (NHase) of Pseudomonas putida NRRL-18668 was discovered and named as "self-subunit swapping." Since the NHase of Bordetella petrii DSM 12804 is similar to that of P. putida, the NHase maturation of B. petrii is proposed to be the same as that of P. putida. However, there is no further information on the application of NHase according to these findings. We successfully rapidly purified NHase and its activator through affinity his tag, and found that the cell extracts of NHase possessed multiple types of protein ingredients including α, β, α2β2, and α(P14K)2 who were in a state of chemical equilibrium. Furthermore, the activity was significantly enhanced through adding extra α(P14K)2 to the cell extracts of NHase according to the chemical equilibrium. Our findings are useful for the activity enhancement of multiple-subunit enzyme and for the first time significantly increased the NHase activity according to the chemical equilibrium.

  12. Role of CYP2E1-mediated metabolism in the acute and vestibular toxicities of nineteen nitriles in the mouse.

    Science.gov (United States)

    Saldaña-Ruíz, Sandra; Soler-Martín, Carla; Llorens, Jordi

    2012-01-25

    Allylnitrile, cis-crotononitrile, and 3,3'-iminodipropionitrile are known to cause vestibular toxicity in rodents, and evidence is available indicating that cis-2-pentenenitrile shares this effect. We evaluated nineteen nitriles for vestibular toxicity in wild type (129S1) and CYP2E1-null mice, including all the above, several neurotoxic nitriles, and structurally similar nitriles. A new acute toxicity test protocol was developed to facilitate evaluation of the vestibular toxicity by a specific behavioral test battery at doses up to sub-lethal levels while using a limited number of animals. A mean number of 8.5±0.3 animals per nitrile, strain and sex was necessary to obtain evidence of vestibular toxicity and optionally an estimation of the lethal dose. For several but not all nitriles, lethal doses significantly increased in CYP2E1-null mice. The protocol revealed the vestibular toxicity of five nitriles, including previously identified ototoxic compounds and one nitrile (trans-crotononitrile) known to have a different profile of neurotoxic effects in the rat. In all five cases, both sexes were affected and no decrease in susceptibility was apparent in CYP2E1-null mice respect to 129S1 mice. Fourteen nitriles caused no vestibular toxicity, including six nitriles tested in CYP2E1-null mice at doses significantly larger than the maximal doses that can be tested in wild type animals. We conclude that only a subset of low molecular weight nitriles is toxic to the vestibular system, that species-dependent differences exist in this vestibular toxicity, and that CYP2E1-mediated metabolism is not involved in this effect of nitriles although it has a role in the acute lethality of some of these compounds. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  13. [Identification of migrants from nitrile-butadiene rubber gloves].

    Science.gov (United States)

    Mutsuga, Motoh; Kawamura, Yoko; Wakui, Chiseko; Maitani, Tamio

    2003-04-01

    Polyvinyl chloride gloves containing di(2-ethylhexyl) phthalate are restricted for food contact use. In their place, disposable gloves made from nitrile-butadiene rubber (NBR) are used in contact with foodstuffs. Some unknown substances were found to migrate into n-heptane from NBR gloves. By GC/MS, HR-MS and NMR, their chemical structures were confirmed to be 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (used as a plasticizer), 4,4'-butylidenedi(6-tert-butyl-m-cresol), a mixture of styrenated phenols consisting of 2-(alpha-methylbenzyl)phenol, 4-(alpha-methylbenzyl)phenol, 2,6-di(alpha-methylbenzyl)phenol, 2,4-di(alpha-methylbenzyl)phenol and 2,4,6-tri(alpha-methylbenzyl)phenol (used as antioxidants), and 2,4-di-tert-butylphenol, which seems to a degradation product of antioxidant. Migration levels of these compounds were 1.68 micrograms/cm2 of 2,4-di-tert-butylphenol, 2.80 micrograms/cm2 of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 46.08 micrograms/cm2 of styrenated phenols and 4.22 micrograms/cm2 of 4,4'-butylidenedi(6-tert-butyl-m-cresol) into n-heptane, respectively. The content of total styrenated phenols was 6,900 micrograms/g in NBR gloves.

  14. Reinforcement of nitrile rubber by in situ formed zinc disorbate

    Directory of Open Access Journals (Sweden)

    2010-09-01

    Full Text Available Zinc disorbate (ZDS was in situ formed by the reaction between sorbic acid (SA and zinc oxide (ZnO in nitrile rubber (NBR. The effects of SA amount on the curing characteristics, crosslink density and mechanical properties of peroxide- cured NBR were studied. The results showed that ZDS was generated mainly during the rubber vulcanization, rather than the open mill compounding phase. The results from the crosslink density determinations showed that the formation of ZDS significantly increased the ionic bond content in the vulcanizates. In addition, the formation of ZDS greatly enhanced the mechanical properties of NBR vulcanizates. The modulus, tensile strength, tear strength and hardness were found to be increased with the loading of ZDS. Preheating the compounds before compression moulding was beneficial to the formation of ZDS, and consequently the increases in mechanical properties. At 40 parts per hundred rubber (phr of SA and 16 phr ZnO, five to six folds of tensile strength and tear strength of the neat NBR vulcanizate were achieved. Transmission electron microscopy (TEM results confirmed the nano-dispersion structure of the polymerized ZDS in the NBR matrix.

  15. A molecular study of gas solubility in nitrile rubber

    Science.gov (United States)

    Khawaja, Musab; Mostofi, Arash; Sutton, Adrian

    2015-03-01

    One of the most important uses of elastomers in the oil industry is for seals to encase and protect sensitive monitoring equipment from contamination by gases and liquids at the high pressures and temperatures in the well. Failure of such seals sometimes occurs on decompression when they are returned to the surface. The conditions in the well lead to gases being absorbed by Nitrile rubber (NBR) seals. NBR exhibits a strong permselectivity towards CO2 compared to other gases; something attributed experimentally to the enhanced solubility of CO2. In this study an explanation is sought at the molecular level for this phenomenon. A series of molecular mechanics calculations are performed to compute solubilities of different gases in NBR. The effect of acrylonitrile content on their solubilities is studied for the first time by simulation, and we discuss the important issue of convergence with respect to the sampling of different elastomer configurations. It is observed that the presence of cyano groups has a marked impact on the solubility of CO2 and an explanation is offered.

  16. Molecular Simulation of Gas Solubility in Nitrile Butadiene Rubber.

    Science.gov (United States)

    Khawaja, M; Sutton, A P; Mostofi, A A

    2017-01-12

    Molecular simulation is used to compute the solubility of small gases in nitrile butadiene rubber (NBR) with a Widom particle-insertion technique biased by local free volume. The convergence of the method is examined as a function of the number of snapshots upon which the insertions are performed and the number of insertions per snapshot and is compared to the convergence of the unbiased Widom insertion technique. The effect of varying the definition of local free volume is also investigated. The acrylonitrile content of the polymer is altered to examine its influence on the solubility of helium, CO 2 , and H 2 O, and the solubilities of polar gases are found to be enhanced relative to those of nonpolar gases, in qualitative agreement with experiment. To probe this phenomenon further, the solubilities are decomposed into contributions from the neighborhoods of different atoms, using a Voronoi cell construction, and a strong bias is found for CO 2 and H 2 O in particular to be situated near nitrogen sites in the elastomer. Temperature is shown to suppress the solubility of CO 2 and H 2 O but to increase that of helium. Increasing pressure is found to suppress the solubility of all gases but at different rates, according to a balance between their molecular sizes and electrostatic interactions with the polymer. These results are relevant to the use of NBR seals at elevated temperatures and pressures, such as in oil and gas wells.

  17. High performance light-colored nitrile-butadiene rubber nanocomposites.

    Science.gov (United States)

    Lei, Yanda; Guo, Baochun; Chen, Feng; Zhu, Lixin; Zhou, Wenyou; Jia, Demin

    2011-12-01

    High mechanical performance nitrile-butadiene rubber (NBR) with light color was fabricated by the method of in situ formation of zinc disorbate (ZDS) or magnesium disorbate (MDS). The in situ formed ZDS and its polymerization via internal mixing was confirmed by X-ray diffaraction. The mechanical properties, ageing resistance, morphology and the dynamic mechanical analysis were fully studied. It was found that with increasing loading of metallic disorbate both the curing rate and the ionic crosslink density was largely increased. The modulus, tensile strength and tear strength were largely increased. With a comparison between internal mixing and opening mixing, the mechanical performance for the former one was obviously better than the latter one. The high performance was ascribed to the finely dispersion nano domains with irregular shape and obscure interfacial structures. Except for the NBR vulcanizate with a high loading of MDS, the others' ageing resistance with incorporation of these two metallic disorbate was found to be good. Dynamic mechanical analysis (DMA) showed that, with increasing loading of metallic disorbate, the highly increased storage modulus above -20 degrees C, the up-shifted glass transition temperature (Tg) and the reduced mechanical loss were ascribed to strengthened interfacial interactions.

  18. Nitrile-synthesizing enzyme: Screening, purification and characterization.

    Science.gov (United States)

    Kumano, Takuto; Suzuki, Takahisa; Shimizu, Sakayu; Kobayashi, Michihiko

    2016-09-12

    Cyanide is known as a toxic compound for almost all living organisms. We have searched for cyanide-resistant bacteria from the soil and stock culture collection of our laboratory, and have found the existence of a lot of microorganisms grown on culture media containing 10 mM potassium cyanide. Almost all of these cyanide-resistant bacteria were found to show β-cyano-L-alanine (β-CNAla) synthetic activity. β-CNAla synthase is known to catalyze nitrile synthesis: the formation of β-CNAla from potassium cyanide and O-acetyl-L-serine or L-cysteine. We found that some microorganisms were able to detoxify cyanide using O-methyl-DL-serine, O-phospho-L-serine and β-chloro-DL-alanine. In addition, we purified β-CNAla synthase from Pseudomonas ovalis No. 111 in nine steps, and characterized the purified enzyme. This enzyme has a molecular mass of 60,000 and appears to consist of two identical subunits. The purified enzyme exhibits a maximum activity at pH 8.5-9.0 at an optimal temperature of 40-50°C. The enzyme is specific for O-acetyl-L-serine and β-chloro-DL-alanine. The Km value for O-acetyl-L-serine is 10.0 mM and Vmax value is 3.57 μmol/min/mg.

  19. Reactions of diiron m-aminocarbyne complexes containing nitrile ligands

    Directory of Open Access Journals (Sweden)

    Busetto Luigi

    2003-01-01

    Full Text Available The acetonitrile ligand in the mu-aminocarbyne complexes [Fe2{mu-CN(MeR}(mu-CO(CO(NCMe(Cp2][SO 3CF3] (R = Me, 2a, CH2Ph, 2b, Xyl, 2c (Xyl = 2,6-Me2C6H3 is readily displaced by halides and cyanide anions affording the corresponding neutral species [Fe2{mu-CN(MeR}(mu-CO(CO(X(Cp2 ] (X = Br, I, CN. Complexes 2 undergo deprotonation and rearrangement of the coordinated MeCN upon treatment with organolithium reagents. Trimethylacetonitrile, that does not contain acidic alpha hydrogens has been used in place of MeCN to form the complexes [Fe2{mu-CN(MeR}(mu-CO(CO(NCCMe3 (Cp2][SO3CF3] (7a-c. Attempts to replace the nitrile ligand in 3 with carbon nucleophiles (by reaction with RLi failed, resulting in decomposition products. However the reaction of 7c with LiCºCTol (Tol = C6H4Me, followed by treatment with HSO3CF3, yielded the imino complex [Fe2{mu-CN(MeXyl}(mu-CO(CO {N(HC(CºCC6H4Me-4CMe3}(Cp 2][SO3CF3 ] (8, obtained via acetilyde addition at the coordinated NCCMe3.

  20. Nitrile-functionalized tertiary amines as highly efficient and reversible SO2 absorbents

    International Nuclear Information System (INIS)

    Hong, Sung Yun; Kim, Heehwan; Kim, Young Jin; Jeong, Junkyo; Cheong, Minserk; Lee, Hyunjoo; Kim, Hoon Sik; Lee, Je Seung

    2014-01-01

    Highlights: • Nitrile-functionalized tertiary amines physically and reversibly absorb SO 2 . • Tertiary alkanolamines chemically and irreversibly absorb SO 2 through OH group. • SO 2 absorption modes were studied by spectroscopy and computational calculations. -- Abstract: Three different types of nitrile-functionalized amines, including 3-(N,N-diethylamino)propionitrile (DEAPN), 3-(N,N-dibutylamino)propionitrile (DBAPN), and N-methyl-N,N-dipropionitrile amine (MADPN) were synthesized, and their SO 2 absorption performances were evaluated and compared with those of hydroxy-functionalized amines such as N,N-diethyl-N-ethanol amine (DEEA), N,N-dibutyl-N-ethanol amine (DBEA), and N-methyl-N,N-diethanol amine (MDEA). Absorption–desorption cycle experiments clearly demonstrate that the nitrile-functionalized amines are more efficient than the hydroxy-functionalized amines in terms of absorption rate and regenerability. Computational calculations with DBEA and DBAPN revealed that DBEA bearing a hydroxyethyl group chemically interacts with SO 2 through oxygen atom, forming an ionic compound with a covalently bound -OSO 2 − group. On the contrary, DBAPN bearing a nitrile group physically interacts with SO 2 through the nitrogen and the hydrogen atoms of the two methylene groups adjacent to the amino and nitrile functionalities

  1. Active Site Mapping of Human Cathepsin F with Dipeptide Nitrile Inhibitors.

    Science.gov (United States)

    Schmitz, Janina; Furtmann, Norbert; Ponert, Moritz; Frizler, Maxim; Löser, Reik; Bartz, Ulrike; Bajorath, Jürgen; Gütschow, Michael

    2015-08-01

    Cleavage of the invariant chain is the key event in the trafficking pathway of major histocompatibility complex class II. Cathepsin S is the major processing enzyme of the invariant chain, but cathepsin F acts in macrophages as its functional synergist which is as potent as cathepsin S in invariant chain cleavage. Dedicated low-molecular-weight inhibitors for cathepsin F have not yet been developed. An active site mapping with 52 dipeptide nitriles, reacting as covalent-reversible inhibitors, was performed to draw structure-activity relationships for the non-primed binding region of human cathepsin F. In a stepwise process, new compounds with optimized fragment combinations were designed and synthesized. These dipeptide nitriles were evaluated on human cysteine cathepsins F, B, L, K and S. Compounds 10 (N-(4-phenylbenzoyl)-leucylglycine nitrile) and 12 (N-(4-phenylbenzoyl)leucylmethionine nitrile) were found to be potent inhibitors of human cathepsin F, with Ki values nitriles from our study, a 3D activity landscape was generated to visualize structure-activity relationships for this series of cathepsin F inhibitors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Nitrile-functionalized tertiary amines as highly efficient and reversible SO{sub 2} absorbents

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Sung Yun; Kim, Heehwan; Kim, Young Jin; Jeong, Junkyo; Cheong, Minserk [Department of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-701 (Korea, Republic of); Lee, Hyunjoo [Clean Energy Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Kim, Hoon Sik, E-mail: khs2004@khu.ac.kr [Department of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-701 (Korea, Republic of); Lee, Je Seung, E-mail: leejs70@khu.ac.kr [Department of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-701 (Korea, Republic of)

    2014-01-15

    Highlights: • Nitrile-functionalized tertiary amines physically and reversibly absorb SO{sub 2}. • Tertiary alkanolamines chemically and irreversibly absorb SO{sub 2} through OH group. • SO{sub 2} absorption modes were studied by spectroscopy and computational calculations. -- Abstract: Three different types of nitrile-functionalized amines, including 3-(N,N-diethylamino)propionitrile (DEAPN), 3-(N,N-dibutylamino)propionitrile (DBAPN), and N-methyl-N,N-dipropionitrile amine (MADPN) were synthesized, and their SO{sub 2} absorption performances were evaluated and compared with those of hydroxy-functionalized amines such as N,N-diethyl-N-ethanol amine (DEEA), N,N-dibutyl-N-ethanol amine (DBEA), and N-methyl-N,N-diethanol amine (MDEA). Absorption–desorption cycle experiments clearly demonstrate that the nitrile-functionalized amines are more efficient than the hydroxy-functionalized amines in terms of absorption rate and regenerability. Computational calculations with DBEA and DBAPN revealed that DBEA bearing a hydroxyethyl group chemically interacts with SO{sub 2} through oxygen atom, forming an ionic compound with a covalently bound -OSO{sub 2}{sup −} group. On the contrary, DBAPN bearing a nitrile group physically interacts with SO{sub 2} through the nitrogen and the hydrogen atoms of the two methylene groups adjacent to the amino and nitrile functionalities.

  3. Magnetic Fe@g‑C3N4: A Photoactive Catalyst for the Hydrogenation of Alkenes and Alkynes

    Data.gov (United States)

    U.S. Environmental Protection Agency — A photoactive catalyst, Fe@g-C3N4, has been developed for the hydrogenation of alkenes and alkynes using hydrazine hydrate as a source of hydrogen. The magnetically...

  4. Reactivity of the geminal phosphinoborane tBu2PCH2BPh2 towards alkynes, nitriles, and nitrilium triflates

    NARCIS (Netherlands)

    Habraken, E.R.M.; Mens, L.C.; Nieger, M.; Lutz, M.; Ehlers, A.W.; Slootweg, J.C.

    2017-01-01

    The reactivity of the geminal phosphinoborane tBu2PCH2BPh2 towards terminal alkynes, nitriles and nitrilium salts is investigated. Terminal alkynes react via C–H bond splitting (deprotonation) resulting in the formation of phosphonium borates. In contrast, both nitriles and nitrilium salts undergo

  5. Substituent effects on mono-substituted and poly-substituted nitriles; Efeitos dos substituintes em nitrilas mono- e polissubstituidas

    Energy Technology Data Exchange (ETDEWEB)

    Sofia, Raquel C.R.; Carneiro, Paulo I.B.; Rittner, Roberto [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica; Fabi, Marino T [Rhodia S.A., Sao Paulo, SP (Brazil)

    1992-12-31

    This work studies various mono substituted aliphatic nitriles, Y C H{sub 2} (Y=H, F, Cl, Br, I, OMe, S Me, SEt{sub 2}, Me and Ph), and some reference nitriles (Y=Et, n-Pr, n-Bu, n-Am, n-Hex and n-Hept) 12 refs., 3 tabs.

  6. Density functional theory and quantum mechanics/molecular mechanics study of cysteine protease inhibition by nitrile-based inhibitors.

    Directory of Open Access Journals (Sweden)

    Sam P De Visser

    2013-12-01

    Full Text Available Cysteine protease enzymes are important for human physiology and catalyze key protein degradation pathways. These enzymes react via a nucleophilic reaction mechanism that involves a cysteine residue and the proton of a proximal histidine. Particularly efficient inhibitors of these enzymes are nitrile-based, however, the details of the catalytic reaction mechanism currently are poorly understood. To gain further insight into the inhibition of these molecules, we have performed a combined density functional theory and quantum mechanics/molecular mechanics study on the reaction of a nitrile-based inhibitor with the enzyme active site amino acids. We show here that small perturbations to the inhibitor structure can have dramatic effects on the catalysis and inhibition processes. Thus, we investigated a range of inhibitor templates and show that specific structural changes reduce the inhibitory efficiency by several orders of magnitude. Moreover, as the reaction takes place on a polar surface, we find strong differences between the DFT and QM/MM calculated energetics. In particular, the DFT model led to dramatic distortions from the starting structure and the convergence to a structure that would not fit the enzyme active site. In the subsequent QM/MM study we investigated the use of mechanical versus electronic embedding on the kinetics, thermodynamics and geometries along the reaction mechanism. We find minor effects on the kinetics of the reaction but large geometric and thermodynamics differences as a result of inclusion of electronic embedding corrections. The work here highlights the importance of model choice in the investigation of this biochemical reaction mechanism.

  7. Inkjet printable-photoactive all inorganic perovskite films with long effective photocarrier lifetimes

    Science.gov (United States)

    Ilie, C. C.; Guzman, F.; Swanson, B. L.; Evans, I. R.; Costa, P. S.; Teeter, J. D.; Shekhirev, M.; Benker, N.; Sikich, S.; Enders, A.; Dowben, P. A.; Sinitskii, A.; Yost, A. J.

    2018-05-01

    Photoactive perovskite quantum dot films, deposited via an inkjet printer, have been characterized by x-ray diffraction and x-ray photoelectron spectroscopy. The crystal structure and bonding environment are consistent with CsPbBr3 perovskite quantum dots. The current–voltage (I–V) and capacitance–voltage (C–V) transport measurements indicate that the photo-carrier drift lifetime can exceed 1 ms for some printed perovskite films. This far exceeds the dark drift carrier lifetime, which is below 50 ns. The printed films show a photocarrier density 109 greater than the dark carrier density, making these printed films ideal candidates for application in photodetectors. The successful printing of photoactive-perovskite quantum dot films of CsPbBr3, indicates that the rapid prototyping of various perovskite inks and multilayers is realizable.

  8. Biotransformation of benzonitrile herbicides via the nitrile hydratase-amidase pathway in rhodococci.

    Science.gov (United States)

    Veselá, Alicja B; Pelantová, Helena; Sulc, Miroslav; Macková, Martina; Lovecká, Petra; Thimová, Markéta; Pasquarelli, Fabrizia; Pičmanová, Martina; Pátek, Miroslav; Bhalla, Tek Chand; Martínková, Ludmila

    2012-12-01

    The aim of this work was to determine the ability of rhodococci to transform 3,5-dichloro-4-hydroxybenzonitrile (chloroxynil), 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil), 3,5-diiodo-4-hydroxybenzonitrile (ioxynil) and 2,6-dichlorobenzonitrile (dichlobenil); to identify the products and determine their acute toxicities. Rhodococcus erythropolis A4 and Rhodococcus rhodochrous PA-34 converted benzonitrile herbicides into amides, but only the former strain was able to hydrolyze 2,6-dichlorobenzamide into 2,6-dichlorobenzoic acid, and produced also more of the carboxylic acids from the other herbicides compared to strain PA-34. Transformation of nitriles into amides decreased acute toxicities for chloroxynil and dichlobenil, but increased them for bromoxynil and ioxynil. The amides inhibited root growth in Lactuca sativa less than the nitriles but more than the acids. The conversion of the nitrile group may be the first step in the mineralization of benzonitrile herbicides but cannot be itself considered to be a detoxification.

  9. [Transformation of 2- and 4-cyanopyridines by free and immobilized cells of nitrile-hydrolyzing bacteria].

    Science.gov (United States)

    Maksimova, Iu G; Vasil'ev, D M; Ovechkina, G V; Maksimov, A Iu; Demakov, V A

    2013-01-01

    The transformation dynamics of 2- and 4-cyanopyridines by cells suspended and adsorbed on inorganic carriers has been studied in the Rhodococcus ruber gt 1 strain possessing nitrile hydratase activity and the Pseudomonas fluorescens C2 strain containing nitrilase. It was shown that both nitrile hydratase and nitrilase activities of immobilized cells against 2-cyanopyridine were 1.5-4 times lower compared to 4-cyanopyridine and 1.6-2 times lower than the activities of free cells against 2-cyanpopyridine. The possibility of obtaining isonicotinic acid during the combined conversion of 4-cyanopyridine by a mixed suspension of R. ruber gt 1 cells with a high level of nitrile hydratase activity and R. erythropolis 11-2 cells with a pronounced activity of amidase has been shown. Immobilization of Rhodococcus cells on raw coal and Pseudomonas cells on china clay was shown to yield a heterogeneous biocatalyst for the efficient transformation of cyanopyridines into respective amides and carbonic acids.

  10. Real-time PCR detection of aldoxime dehydratase genes in nitrile-degrading microorganisms.

    Science.gov (United States)

    Dooley-Cullinane, Tríona Marie; O'Reilly, Catherine; Coffey, Lee

    2017-02-01

    Aldoxime dehydratase catalyses the conversion of aldoximes to their corresponding nitriles. Utilization of the aldoxime-nitrile metabolising enzyme pathway can facilitate the move towards a greener chemistry. In this work, a real-time PCR assay was developed for the detection of aldoxime dehydratase genes in aldoxime/nitrile metabolising microorganisms which have been purified from environmental sources. A conventional PCR assay was also designed allowing gene confirmation via sequencing. Aldoxime dehydratase genes were identified in 30 microorganisms across 11 genera including some not previously shown to harbour the gene. The assay displayed a limit of detection of 1 pg/μL DNA or 7 CFU/reaction. This real-time PCR assay should prove valuable in the high-throughput screening of micro-organisms for novel aldoxime dehydratase genes towards pharmaceutical and industrial applications.

  11. Model fire tests on polyphosphazene rubber and polyvinyl chloride (PVC)/nitrile rubber foams

    Science.gov (United States)

    Widenor, W. M.

    1978-01-01

    A video tape record of model room fire tests was shown, comparing polyphosphazene (P-N) rubber and polyvinyl chloride (PVC)/nitrile rubber closed-cell foams as interior finish thermal insulation under conditions directly translatable to an actual fire situation. Flashover did not occur with the P-N foam and only moderate amounts of low density smoke were formed, whereas with the PVC/nitrile foam, flashover occurred quickly and large volumes of high density smoke were emitted. The P-N foam was produced in a pilot plant under carefully controlled conditions. The PVC/nitrile foam was a commercial product. A major phase of the overall program involved fire tests on P-N open-cell foam cushioning.

  12. Mass spectrometric analysis of EPO IEF-PAGE interfering substances in nitrile examination gloves.

    Science.gov (United States)

    Reichel, Christian

    2012-10-01

    Direct detection of doping with recombinant erythropoietins (rhEPO) is accomplished by isoelectric focusing (IEF) or sodium dodecylsulfate (SDS) polyacrylamide gel electrophoresis (PAGE). In a recent publication, Lasne et al. (Electrophoresis 2011, 32, 1444) showed that improper use of nitrile examination gloves during sample collection, sample preparation, and IEF-PAGE may lead to distorted or absent EPO IEF-profiles. In order to clarify which substances are responsible for this observation, a mass spectrometric study on water extractable compounds found in nitrile gloves was performed. Several substance classes were shown to be present, among them polyethylene glycols (PEG), anionic and nonionic surfactants, as well as alcohol ethoxylates and plasticizers. It could be demonstrated that alkylbenzenesulfonates, the main category of detectable anionic detergents, and among them sodium dodecylbenzenesulfonate (SDBS) and its homologs, are the prime reason for the interference of nitrile gloves with EPO IEF-PAGE. Copyright © 2012 John Wiley & Sons, Ltd.

  13. VACUUM ULTRAVIOLET PHOTOABSORPTION SPECTRA OF NITRILE ICES FOR THEIR IDENTIFICATION ON PLUTO

    International Nuclear Information System (INIS)

    Sivaraman, B.; Pavithraa, S.; Lo, J.-I.; Cheng, B.-M.; Sekhar, B. N. Raja; Hill, H.; Mason, N. J.

    2016-01-01

    Icy bodies, such as Pluto, are known to harbor simple and complex molecules. The recent New Horizons flyby of Pluto has revealed a complex surface composed of bright and dark ice surfaces, indicating a rich chemistry based on nitrogen (N 2 ), methane (CH 4 ), and carbon monoxide (CO). Nitrile (CN) containing molecules such as acetonitrile (CH 3 CN), propionitrile (CH 3 CH 2 CN), butyronitrile (CH 3 CH 2 CH 2 CN), and isobutyronitrile ((CH 3 ) 2 CHCN) are some of the nitrile molecules that are known to be synthesized by radiative processing of such simple ices. Through the provision of a spectral atlas for such compounds we propose that such nitriles may be identified from the ALICE payload on board New Horizons .

  14. Ruthenium Tris(2-pyridylmethyl)amine as an Effective Photocaging Group for Nitriles

    Science.gov (United States)

    2015-01-01

    Ruthenium(II) tris(2-pyridylmethyl)amine (TPA) is an effective caging group for nitriles that provides high levels of control over the enzyme activity with light. Two caged nitriles were prepared, [Ru(TPA)(MeCN)2](PF6)2 (1) and [Ru(TPA)(3)2](PF6)2 (2), where 3 is the cathepsin K inhibitor Cbz-Leu-NHCH2CN, and characterized by various spectroscopic techniques and mass spectrometry. Both 1 and 2 show the release of a single nitrile within 20 min of irradiation with 365 nm light. Complex 2 acts as a potent, photoactivated inhibitor of human cathepsin K. IC50 values were determined for 2 and 3. Enzyme inhibition for 2 was enhanced by a factor of 89 upon exposure to light, with IC50 values of 63 nM (light) and 5.6 μM (dark). PMID:24661182

  15. One-pot Synthesis of Soluble Nanoscale CIGS Photoactive Functional Materials

    Directory of Open Access Journals (Sweden)

    Yan Aixia

    2007-01-01

    Full Text Available Abstract Promising alternatives for solar energy utilization are thin film technologies involving various new materials. This contribution describes an easy and inexpensive synthetic method that can be used to prepare soluble nanoscale triphenyl phosphine-coordinated CIGS (TPP-CIGS photoactive functional materials. This complex is stable in the solid state under the irradiation of the ambient light, but its solution becomes a little bit unstable under the illumination of the low intensity laser.

  16. Preliminary study towards photoactivity enhancement using a biocompatible titanium dioxide/carbon nanotubes composite

    Energy Technology Data Exchange (ETDEWEB)

    Cendrowski, Krzysztof, E-mail: kcendrowski@zut.edu.pl [West Pomeranian University of Technology Szczecin, Centre of Knowledge Based Nanomaterials and Technologies, Institute of Chemical and Environment Engineering, Pulaskiego 10, Szczecin 70-322 (Poland); Jedrzejczak, Malgorzata [West Pomeranian University of Technology Szczecin, Faculty of Biotechnology and Animal Science, Laboratory of Molecular Cytogenetic, Dr Judyma 10, Szczecin 71-460 (Poland); Peruzynska, Magdalena [Department of Experimental and Clinical Pharmacology, Pomeranian Medical University, al. Powstancow Wielkopolskich 72, Szczecin 70-111 (Poland); Dybus, Andrzej [West Pomeranian University of Technology Szczecin, Faculty of Biotechnology and Animal Science, Laboratory of Molecular Cytogenetic, Dr Judyma 10, Szczecin 71-460 (Poland); Drozdzik, Marek [Department of Experimental and Clinical Pharmacology, Pomeranian Medical University, al. Powstancow Wielkopolskich 72, Szczecin 70-111 (Poland); Mijowska, Ewa [West Pomeranian University of Technology Szczecin, Centre of Knowledge Based Nanomaterials and Technologies, Institute of Chemical and Environment Engineering, Pulaskiego 10, Szczecin 70-322 (Poland)

    2014-08-25

    Graphical abstract: Scheme demonstrating the experimental steps toward the formation of titania/multiwalled carbon nanotubes (TiO{sub 2}-MWCNTs) from multiwalled carbon nanotubes (MWCNT). - Highlights: • Easy and efficient method of impregnation carbon nanotubes with titania. • High photoactivity. • Correlation between the interaction of carbon nanotubes with titania on the photocatalytic properties. • High biocompatibility of the nanotubes. - Abstract: Recent research is focused on the enhancement in photoactivity of titanium dioxide/carbon nanotubes through formation of novel nanocomposites that exhibit a high specific surface area, remarkable electron transfer and biocompatibility. Here, we explore a new synthesis route in the system composed of nanocrystalline titanium dioxide supported on external walls and inner space of multiwalled carbon nanotubes (MWCNT). The advantages of this method are: its simplicity, direct fusion of titanium dioxide particles on the carbon material, and formation of chemical bond Ti–O–C between TiO{sub 2} and MWCNT. Photocatalytic performance of this system has been compared to a commercial catalyst (Degussa P25) in a model reaction of phenol decomposition in/under UV light. The efficiency of the process increased by the factor of 2.5 when the TiO{sub 2}–MWCNT photocatalyst was utilized. Further, the photoactive nanocomposite was analysed towards its biocompatibility in order to establish a safe dose of the catalyst. Its influence on the cells viability was studied on mouse fibroblasts and human liver tissue cells, in the range from 0 to 100 μg/mL. This has revealed that the composite in concentrations up to 25 μg/mL exerted low toxicity, which allowed for finding a compromise between the highest safe dose and acceptable photoactivity of the catalyst.

  17. Preliminary study towards photoactivity enhancement using a biocompatible titanium dioxide/carbon nanotubes composite

    International Nuclear Information System (INIS)

    Cendrowski, Krzysztof; Jedrzejczak, Malgorzata; Peruzynska, Magdalena; Dybus, Andrzej; Drozdzik, Marek; Mijowska, Ewa

    2014-01-01

    Graphical abstract: Scheme demonstrating the experimental steps toward the formation of titania/multiwalled carbon nanotubes (TiO 2 -MWCNTs) from multiwalled carbon nanotubes (MWCNT). - Highlights: • Easy and efficient method of impregnation carbon nanotubes with titania. • High photoactivity. • Correlation between the interaction of carbon nanotubes with titania on the photocatalytic properties. • High biocompatibility of the nanotubes. - Abstract: Recent research is focused on the enhancement in photoactivity of titanium dioxide/carbon nanotubes through formation of novel nanocomposites that exhibit a high specific surface area, remarkable electron transfer and biocompatibility. Here, we explore a new synthesis route in the system composed of nanocrystalline titanium dioxide supported on external walls and inner space of multiwalled carbon nanotubes (MWCNT). The advantages of this method are: its simplicity, direct fusion of titanium dioxide particles on the carbon material, and formation of chemical bond Ti–O–C between TiO 2 and MWCNT. Photocatalytic performance of this system has been compared to a commercial catalyst (Degussa P25) in a model reaction of phenol decomposition in/under UV light. The efficiency of the process increased by the factor of 2.5 when the TiO 2 –MWCNT photocatalyst was utilized. Further, the photoactive nanocomposite was analysed towards its biocompatibility in order to establish a safe dose of the catalyst. Its influence on the cells viability was studied on mouse fibroblasts and human liver tissue cells, in the range from 0 to 100 μg/mL. This has revealed that the composite in concentrations up to 25 μg/mL exerted low toxicity, which allowed for finding a compromise between the highest safe dose and acceptable photoactivity of the catalyst

  18. High photoactive and visible-light responsive graphene/titanate nanotubes photocatalysts: preparation and characterization.

    Science.gov (United States)

    Qianqian, Zhai; Tang, Bo; Guoxin, Hu

    2011-12-30

    A series of graphene/titanate nanotubes (TNTs) photocatalysts using graphene and nanoscale TiO(2) or P25 as original materials were fabricated by hydrothermal method. Both low hydrothermal temperature and proper amount of graphene are propitious to better photoactivity. The photocatalytic activities of these nanocomposites far exceed that of P25, pure TNTs and reported TiO(2)-based nanocomposites for the degradation of Rhodamine-B under visible-light irradiation. These prepared photocatalysts were characterized by TEM, XRD, XPS, BET, FTIR and UV-vis diffuse reflection spectra, and the results indicate that the outstanding photoactivities in visible-light region result from sensitization effect of graphene rather than impurity level in the band gap of TNTs. Furthermore, large BET surface areas of these photocatalysts (almost 10 times larger than that of previously reported graphene/TiO(2) nanoparticles) evidently enhance their absorption abilities and photocatalytic performances (the rate constants of degrading Rhodamine-B are at least 5 times higher than that of previously reported photocatalysts). These photocatalysts show good stability, and their photoactivities do not obviously decrease after four times of repeated uses. A detailed photocatalytic mechanism is suggested, as well. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Alkylation of nitriles with gaseous carbenium ions. The ritter reaction in the dilute gas state

    International Nuclear Information System (INIS)

    Cacace, F.; Ciranni, G.; Giacomello, P.

    1982-01-01

    Radiolytically formed carbenium ions, such as sec-C 3 H 7 + , sec-C 4 H 9 + , and t-C 4 H 9 + , react in the gas phase with model aliphatic and aromatic nitriles yielding the corresponding nitrilium ions. The latter undergo efficient condensation with water that eventually leads to the formation of the corresponding N-alkylamides. The mechanism is analogous to the Ritter reaction in solution. The reactivity and selectivity of the gas-phase electrophilic attack on nitriles has been deduced from competition experiments under conditions that largely exclude the effects of solvation, ion pairing, etc., which complicate the interpretation of solution-chemistry measurements. 1 table

  20. Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles.

    Science.gov (United States)

    Lambert, Kyle M; Bobbitt, James M; Eldirany, Sherif A; Kissane, Liam E; Sheridan, Rose K; Stempel, Zachary D; Sternberg, Francis H; Bailey, William F

    2016-04-04

    Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98% isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Mechanistic insights into the oxidative dehydrogenation of amines to nitriles in continuous flow

    DEFF Research Database (Denmark)

    Corker, Emily C.; Ruiz-Martínez, Javier; Riisager, Anders

    2015-01-01

    The oxidative dehydrogenation of various aliphatic amines to their corresponding nitrile compounds using RuO2/Al2O3 catalysts in air was successfully applied to a continuous flow reaction. Conversions of amines (up to >99%) and yields of nitriles (up to 77%) varied depending on reaction conditions...... and the amine utilised. The presence of water was found to be important for the activity and stability of the RuO2/Al2O3 catalyst. The Hammett relationship and in situ infrared spectroscopy were applied to divulge details about the catalytic mechanism of the oxidative dehydrogenation of amines over RuO2/Al2O3...

  2. Pengaruh Penggunaan Nitril Butadiene Rubber Dan Pale Crepe Pada Pembuatan Sol Karet Untuk Sepatu Pengaman

    OpenAIRE

    Yuniari, Arum

    2010-01-01

    Rubber sole for safety shoes was different on physical specification with general sole, especially on abrasion resistance and oil resistance. The objective of the study was to determine the effect of nitril butadiene rubber and pale crepe on physical properties of vulcanized rubber sole for safety shoes. Rubber sole for safety shoes was produced by blending pale crepe and nitril butadiene rubber with ratio of : 50/50; 60/40; 70/30 and 80/20 phr, respectively. Carbon black as filler was also v...

  3. Pengaruh penggunaan nitril butadiene rubber dan pale crepe pada pembuatan sol karet untuk sepatu pengaman

    OpenAIRE

    Arum Yuniari

    2010-01-01

    Abstract Rubber sole for safety shoes was different on physical specification with general sole, especially on abrasion resistance and oil resistance. The objective of the study was to determine the effect of nitril butadiene rubber and pale crepe on physical properties of vulcanized rubber sole for safety shoes. Rubber sole for safety shoes was produced by blending pale crepe and nitril butadiene rubber with ratio of : 50/50; 60/40; 70/30 and 80/20 phr, respectively. Carbon black as fill...

  4. Tetra­kis(aceto­nitrile)copper(I) hydrogen oxalate–oxalic acid–aceto­nitrile (1/0.5/0.5)

    Science.gov (United States)

    Royappa, A. Timothy; Stepherson, Jacob R.; Vu, Oliver D.; Royappa, Andrew D.; Stern, Charlotte L.; Müller, Peter

    2013-01-01

    In the title compound, [Cu(CH3CN)4](C2HO4)·0.5C2H2O4·0.5CH3CN, the CuI ion is coordinated by the N atoms of four aceto­nitrile ligands in a slightly distorted tetra­hedral environment. The oxalic acid mol­ecule lies across an inversion center. The aceto­nitrile solvent mol­ecule is disordered across an inversion center and was refined with half occupancy. In the crystal, the hydrogen oxalate anions and oxalic acid mol­ecules are linked via O—H⋯O hydrogen bonds, forming chains along [010]. PMID:24098175

  5. Morphological Control of the Photoactive Layer in Bulk Heterojunction Organic Solar Cells

    KAUST Repository

    Su, Yisong

    2011-07-23

    For its inherent advantages, such as lightweight, low cost, flexibility, and opportunity to cover large surface areas, organic solar cells have attracted more and more attention in both academia and industry. However, the efficiency of organic solar cell is still much lower than silicon solar cells, but steadily rising as it now stands above 8%. The architecture of bulk heterojunction solar cells can improve the performance of organic solar cell a lot, but these improvements are highly dependent on the morphology of photoactive layer. Therefore, by controlling the morphology of photoactive layer, most commonly composed of a P3HT donor polymer and PCBM small molecule, the performance of organic solar cells could be optimized. The use of solvent additives in the solution formulation is particularly interesting, because it is a low cost method of controlling the phase separation of the photoactive layer and possibly removing the need for subsequent thermal and solvent vapor annealing. However, the role of the solvent additive remains not well understood and much debate remains on the mechanisms by which it impacts phase separation. In the first part of this thesis, we investigate the role of the solvent additive on the individual components (solvent, donor and acceptor) of the solution and the photoactive layer both in the bulk solution, during solution-processing and in the post-processing solid state of the film. In the second part of this thesis, we investigate the role of the additive on the blended solution state and resulting thin film phase separation. Finally, we propose a new method of controlling phase separation based on the insight into the role of the solvent additive. In the first part, we used an additive [octandiethiol (OT)] in the solvent to help the aggregation of P3HT in the solution. From the UV-vis experiments, the crystallinity of P3HT in the solutions increased while it decreased in thin films with steady increase of additive concentration. This

  6. Biotransformation of benzonitrile herbicides via the nitrile hydratase-amidase pathway in rhodococci

    Czech Academy of Sciences Publication Activity Database

    Veselá, Alicja Barbara; Pelantová, Helena; Šulc, Miroslav; Macková, M.; Lovecká, P.; Thimová, P.; Pasquarelli, F.; Pičmanová, Martina; Pátek, Miroslav; Bhalla, T. C.; Martínková, Ludmila

    2012-01-01

    Roč. 39, č. 12 (2012), s. 1811-1819 ISSN 1367-5435 R&D Projects: GA MŠk OC09046; GA ČR(CZ) GAP504/11/0394; GA ČR GD305/09/H008 Keywords : Nitrile hydratase * Amidase * Benzonitrile herbicides Subject RIV: EE - Microbiology, Virology Impact factor: 2.321, year: 2012

  7. An entry to a chiral dihydropyrazole scaffold: enantioselective [3 + 2] cycloaddition of nitrile imines.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Jasperse, Craig P

    2005-06-15

    We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

  8. Nitriles form mixed-coligand complexes with 99mTc-HYNIC-Peptide

    International Nuclear Information System (INIS)

    Liu Guozheng; Wescott, Charles; Sato, Aaron; Wang Yi; Liu Ning; Zhang Yumin; Rusckowski, Mary; Hnatowich, Donald J.

    2002-01-01

    Using a 12-amino acid peptide conjugated with HYNIC as a model, we investigated nitriles as possible coligands for labeling with 99m Tc. After the preparation of the 99m Tc labeled HYNIC-peptide using tricine as coligand, the addition of acetonitile was found by reverse phase HPLC to block further coligand exchange with ethylenediamine diacetic acid (EDDA) at room temperature. The addition of this nitrile changed the pharmacokinetics of the 99m Tc labeled peptide in normal mice towards faster clearance and significant differences in accumulation in most tissues sampled. By replacing acetonitrile with cyanoacetate, a nitrile not present in the HPLC eluant, it was possible to show the existence of a new, more hydrophilic, species by reverse phase HPLC. We conclude that nitriles can act as coligands for HYNIC-conjugated peptides labeled with 99m Tc and tricine. Furthermore, the presence of acetonitrile during Sep-Pak or HPLC purification may inadvertently generate a mixed tricine/acetonitile coligand 99m Tc-HYNIC-peptide complex

  9. Capture of an elusive nitrile ylide as an intermediate in isoxazole-oxazole photoisomerization.

    Science.gov (United States)

    Nunes, Cláudio M; Reva, Igor; Fausto, Rui

    2013-11-01

    The unimolecular photochemistry of 3,5-dimethylisoxazole (1) induced by a narrow-band tunable UV laser was studied using low-temperature matrix isolation coupled with infrared spectroscopy. Monomers of 1 were isolated in argon matrices at 15 K and characterized spectroscopically. Irradiation of matrix-isolated 1 at λ = 222 nm (near its absorption maximum) led to the corresponding 2H-azirine 3 and ketenimine 6 as primary photoproducts and also to nitrile ylide 4 and 2,5-dimethyloxazole (5). The photoproducts were identified (i) by comparison with infrared spectra of authentic matrix-isolated samples of 3 and 5 and (ii) using additional irradiations at longer wavelengths (where 1 does not react) which induce selective photoisomerizations of 4 and 6. In particular, irradiation with λ = 340 nm led to the unequivocal identification of the nitrile ylide anti-4, which was transformed into oxazole 5. The details of the 1,5-electrocyclization of the carbonyl nitrile ylide 4 and its structural nature (propargyl-like versus allene-like geometry) were also characterized using theoretical calculations. Thus, the elusive carbonyl nitrile ylide 4 was captured and characterized for the first time as an intermediate in the isoxazole-oxazole photoisomerization.

  10. A Single Enzyme Transforms a Carboxylic Acid into a Nitrile through an Amide Intermediate.

    Science.gov (United States)

    Nelp, Micah T; Bandarian, Vahe

    2015-09-01

    The biosynthesis of nitriles is known to occur through specialized pathways involving multiple enzymes; however, in bacterial and archeal biosynthesis of 7-deazapurines, a single enzyme, ToyM, catalyzes the conversion of the carboxylic acid containing 7-carboxy-7-deazaguanine (CDG) into its corresponding nitrile, 7-cyano-7-deazaguanine (preQ0 ). The mechanism of this unusual direct transformation was shown to proceed via the adenylation of CDG, which activates it to form the newly discovered amide intermediate 7-amido-7-deazaguanine (ADG). This is subsequently dehydrated to form the nitrile in a process that consumes a second equivalent of ATP. The authentic amide intermediate is shown to be chemically and kinetically competent. The ability of ToyM to activate two different substrates, an acid and an amide, accounts for this unprecedented one-enzyme catalysis of nitrile synthesis, and the differential rates of these two half reactions suggest that this catalytic ability is derived from an amide synthetase that gained a new function. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Nitrile-functionalized tertiary amines as highly efficient and reversible SO2 absorbents.

    Science.gov (United States)

    Hong, Sung Yun; Kim, Heehwan; Kim, Young Jin; Jeong, Junkyo; Cheong, Minserk; Lee, Hyunjoo; Kim, Hoon Sik; Lee, Je Seung

    2014-01-15

    Three different types of nitrile-functionalized amines, including 3-(N,N-diethylamino)propionitrile (DEAPN), 3-(N,N-dibutylamino)propionitrile (DBAPN), and N-methyl-N,N-dipropionitrile amine (MADPN) were synthesized, and their SO2 absorption performances were evaluated and compared with those of hydroxy-functionalized amines such as N,N-diethyl-N-ethanol amine (DEEA), N,N-dibutyl-N-ethanol amine (DBEA), and N-methyl-N,N-diethanol amine (MDEA). Absorption-desorption cycle experiments clearly demonstrate that the nitrile-functionalized amines are more efficient than the hydroxy-functionalized amines in terms of absorption rate and regenerability. Computational calculations with DBEA and DBAPN revealed that DBEA bearing a hydroxyethyl group chemically interacts with SO2 through oxygen atom, forming an ionic compound with a covalently bound OSO2(-) group. On the contrary, DBAPN bearing a nitrile group physically interacts with SO2 through the nitrogen and the hydrogen atoms of the two methylene groups adjacent to the amino and nitrile functionalities. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Unexpected nitrile formation in bio-based mesoporous materials (Starbons®).

    Science.gov (United States)

    Attard, Jennifer; Milescu, Roxana; Budarin, Vitaliy; Matharu, Avtar S; Clark, James H

    2018-01-16

    The bio-based mesoporous materials made from polysaccharides, Starbons® can be modified by two different routes to give high levels of N-content, unexpectedly including significant quantities of nitrile groups which can improve the materials performance in applications including metal capture.

  13. Selective biotransformation of substituted alicyclic nitriles by Rhodococcus equi A4

    Czech Academy of Sciences Publication Activity Database

    Martínková, Ludmila; Klempier, N.; Preiml, M.; Ovesná, Mária; Kuzma, Marek; Mylerová, Veronika; Křen, Vladimír

    2002-01-01

    Roč. 80, - (2002), s. 724-727 ISSN 0008-4042 R&D Projects: GA ČR GA524/00/1275; GA AV ČR IAA4020802 Keywords : nitrile hydratase * substituted cyclohexanecarbonitriles * cyclopentanecarbonitriles Subject RIV: EE - Microbiology, Virology Impact factor: 1.260, year: 2002

  14. Optimization of triazine nitriles as rhodesain inhibitors: structure-activity relationships, bioisosteric imidazopyridine nitriles, and X-ray crystal structure analysis with human cathepsin L.

    Science.gov (United States)

    Ehmke, Veronika; Winkler, Edwin; Banner, David W; Haap, Wolfgang; Schweizer, W Bernd; Rottmann, Matthias; Kaiser, Marcel; Freymond, Céline; Schirmeister, Tanja; Diederich, François

    2013-06-01

    The cysteine protease rhodesain of Trypanosoma brucei parasites causing African sleeping sickness has emerged as a target for the development of new drug candidates. Based on a triazine nitrile moiety as electrophilic headgroup, optimization studies on the substituents for the S1, S2, and S3 pockets of the enzyme were performed using structure-based design and resulted in inhibitors with inhibition constants in the single-digit nanomolar range. Comprehensive structure-activity relationships clarified the binding preferences of the individual pockets of the active site. The S1 pocket tolerates various substituents with a preference for flexible and basic side chains. Variation of the S2 substituent led to high-affinity ligands with inhibition constants down to 2 nM for compounds bearing cyclohexyl substituents. Systematic investigations on the S3 pocket revealed its potential to achieve high activities with aromatic vectors that undergo stacking interactions with the planar peptide backbone forming part of the pocket. X-ray crystal structure analysis with the structurally related enzyme human cathepsin L confirmed the binding mode of the triazine ligand series as proposed by molecular modeling. Sub-micromolar inhibition of the proliferation of cultured parasites was achieved for ligands decorated with the best substituents identified through the optimization cycles. In cell-based assays, the introduction of a basic side chain on the inhibitors resulted in a 35-fold increase in antitrypanosomal activity. Finally, bioisosteric imidazopyridine nitriles were studied in order to prevent off-target effects with unselective nucleophiles by decreasing the inherent electrophilicity of the triazine nitrile headgroup. Using this ligand, the stabilization by intramolecular hydrogen bonding of the thioimidate intermediate, formed upon attack of the catalytic cysteine residue, compensates for the lower reactivity of the headgroup. The imidazopyridine nitrile ligand showed

  15. Hydrogenation of nitriles on a well-characterized nickel surface: From surface science studies to liquid phase catalytic activity measurements

    Energy Technology Data Exchange (ETDEWEB)

    Gardin, Denis Emmanuel [Univ. of California, Berkeley, CA (United States)

    1993-12-01

    Nitrile hydrogenation is the most commonly used method for preparing diverse amines. This thesis is aimed at the mechanism and factors affecting the performance of Ni-based catalysts in nitrile hydrogenations. Surface science techniques are used to study bonding of nitriles and amines to a Ni(111) surface and to identify surface intermediates. Liquid-phase hydrogenations of cyclohexene and 1-hexene on a Pt foil were carried out successfully. Finally, knowledge about the surface structure, surface chemical bond, dynamics of surface atoms (diffusion, growth), and reactivity of metal surfaces from solid-gas interface studies, is discussed.

  16. Biocatalytic Synthesis of Nitriles through Dehydration of Aldoximes: The Substrate Scope of Aldoxime Dehydratases.

    Science.gov (United States)

    Betke, Tobias; Higuchi, Jun; Rommelmann, Philipp; Oike, Keiko; Nomura, Taiji; Kato, Yasuo; Asano, Yasuhisa; Gröger, Harald

    2018-04-16

    Nitriles, which are mostly needed and produced by the chemical industry, play a major role in various industry segments, ranging from high-volume, low-price sectors, such as polymers, to low-volume, high-price sectors, such as chiral pharma drugs. A common industrial technology for nitrile production is ammoxidation as a gas-phase reaction at high temperature. Further popular approaches are substitution or addition reactions with hydrogen cyanide or derivatives thereof. A major drawback, however, is the very high toxicity of cyanide. Recently, as a synthetic alternative, a novel enzymatic approach towards nitriles has been developed with aldoxime dehydratases, which are capable of converting an aldoxime in one step through dehydration into nitriles. Because the aldoxime substrates are easily accessible, this route is of high interest for synthetic purposes. However, whenever a novel method is developed for organic synthesis, it raises the question of substrate scope as one of the key criteria for application as a "synthetic platform technology". Thus, the scope of this review is to give an overview of the current state of the substrate scope of this enzymatic method for synthesizing nitriles with aldoxime dehydratases. As a recently emerging enzyme class, a range of substrates has already been studied so far, comprising nonchiral and chiral aldoximes. This enzyme class of aldoxime dehydratases shows a broad substrate tolerance and accepts aliphatic and aromatic aldoximes, as well as arylaliphatic aldoximes. Furthermore, aldoximes with a stereogenic center are also recognized and high enantioselectivities are found for 2-arylpropylaldoximes, in particular. It is further noteworthy that the enantiopreference depends on the E and Z isomers. Thus, opposite enantiomers are accessible from the same racemic aldehyde and the same enzyme. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Copper-catalyzed one-pot synthesis of 1,2,4-triazoles from nitriles and hydroxylamine.

    Science.gov (United States)

    Xu, Hao; Ma, Shuang; Xu, Yuanqing; Bian, Longxiang; Ding, Tao; Fang, Xiaomin; Zhang, Wenkai; Ren, Yanrong

    2015-02-06

    A simple and efficient copper-catalyzed one-pot synthesis of substituted 1,2,4-triazoles through reactions of two nitriles with hydroxylamine has been developed. The protocol uses simple and readily available nitriles and hydroxylamine hydrochloride as the starting materials and inexpensive Cu(OAc)2 as the catalyst, and the corresponding 1,2,4-triazole derivatives are obtained in moderate to good yields. The reactions include sequential intermolecular addition of hydroxylamine to one nitrile to provide amidoxime, copper-catalyzed treatment of the amidoxime with another nitrile, and intramolecular dehydration/cyclization. This finding provides a new and useful strategy for synthesis of 1,2,4-triazole derivatives.

  18. 1,3-Dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues

    International Nuclear Information System (INIS)

    Kotyatkina, Anna I; Zhabinsky, Vladimir N; Khripach, Vladimir A

    2001-01-01

    The published data on the use of 1,3-dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues are systematised and reviewed. The bibliography includes 145 references.

  19. Nitrile-converting enzymes as a tool to improve biocatalysis in organic synthesis: recent insights and promises.

    Science.gov (United States)

    Gong, Jin-Song; Shi, Jin-Song; Lu, Zhen-Ming; Li, Heng; Zhou, Zhe-Min; Xu, Zheng-Hong

    2017-02-01

    Nitrile-converting enzymes, including nitrilase and nitrile hydratase (NHase), have received increasing attention from researchers of industrial biocatalysis because of their critical role as a tool in organic synthesis of carboxylic acids and amides from nitriles. To date, these bioconversion approaches are considered as one of the most potential industrial processes using resting cells or purified enzymes as catalysts for production of food additives, pharmaceutical, and agrochemical precursors. This review focuses on the distribution and catalytic mechanism research of nitrile-converting enzymes in recent years. Molecular biology aspects to improve the biocatalytic performance of microbial nitrilase and NHase are demonstrated. The process developments of microbial nitrilase and NHase for organic synthesis are also discussed.

  20. Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: scope, limitations, and mechanistic studies.

    Science.gov (United States)

    Skillinghaug, Bobo; Sköld, Christian; Rydfjord, Jonas; Svensson, Fredrik; Behrends, Malte; Sävmarker, Jonas; Sjöberg, Per J R; Larhed, Mats

    2014-12-19

    A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle.

  1. Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding: The effect of acrylonitrile content and hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Likozar, Blaz, E-mail: blaz.likozar@fkkt.uni-lj.si [Polymer Competence Center Leoben GmbH, Montanuniversitaet Leoben, Roseggerstrasse 12, A-8700 Leoben (Austria); Major, Zoltan, E-mail: zoltan.major@jku.at [Polymer Competence Center Leoben GmbH, Montanuniversitaet Leoben, Roseggerstrasse 12, A-8700 Leoben (Austria)

    2010-11-01

    The purpose of this work was to prepare nanocomposites by mixing multi-walled carbon nanotubes (MWCNT) with nitrile and hydrogenated nitrile elastomers (NBR and HNBR). Utilization of transmission electronic microscopy (TEM), scanning electron microscopy (SEM), and small- and wide-angle X-ray scattering techniques (SAXS and WAXS) for advanced morphology observation of conducting filler-reinforced nitrile and hydrogenated nitrile rubber composites is reported. Principal results were increases in hardness (maximally 97 Shore, type A), elastic modulus (maximally 981 MPa), tensile strength (maximally 27.7 MPa), elongation at break (maximally 216%), cross-link density (maximally 7.94 x 10{sup 28} m{sup -3}), density (maximally 1.16 g cm{sup -3}), and tear strength (11.2 kN m{sup -1}), which were clearly visible at particular acrylonitrile contents both for unhydrogenated and hydrogenated polymers due to enhanced distribution of carbon nanotubes (CNT) and their aggregated particles in the applied rubber matrix. Conclusion was that multi-walled carbon nanotubes improved the performance of nitrile and hydrogenated nitrile rubber nanocomposites prepared by melt compounding.

  2. Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding: The effect of acrylonitrile content and hydrogenation

    Science.gov (United States)

    Likozar, Blaž; Major, Zoltan

    2010-11-01

    The purpose of this work was to prepare nanocomposites by mixing multi-walled carbon nanotubes (MWCNT) with nitrile and hydrogenated nitrile elastomers (NBR and HNBR). Utilization of transmission electronic microscopy (TEM), scanning electron microscopy (SEM), and small- and wide-angle X-ray scattering techniques (SAXS and WAXS) for advanced morphology observation of conducting filler-reinforced nitrile and hydrogenated nitrile rubber composites is reported. Principal results were increases in hardness (maximally 97 Shore, type A), elastic modulus (maximally 981 MPa), tensile strength (maximally 27.7 MPa), elongation at break (maximally 216%), cross-link density (maximally 7.94 × 1028 m-3), density (maximally 1.16 g cm-3), and tear strength (11.2 kN m-1), which were clearly visible at particular acrylonitrile contents both for unhydrogenated and hydrogenated polymers due to enhanced distribution of carbon nanotubes (CNT) and their aggregated particles in the applied rubber matrix. Conclusion was that multi-walled carbon nanotubes improved the performance of nitrile and hydrogenated nitrile rubber nanocomposites prepared by melt compounding.

  3. Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding: The effect of acrylonitrile content and hydrogenation

    International Nuclear Information System (INIS)

    Likozar, Blaz; Major, Zoltan

    2010-01-01

    The purpose of this work was to prepare nanocomposites by mixing multi-walled carbon nanotubes (MWCNT) with nitrile and hydrogenated nitrile elastomers (NBR and HNBR). Utilization of transmission electronic microscopy (TEM), scanning electron microscopy (SEM), and small- and wide-angle X-ray scattering techniques (SAXS and WAXS) for advanced morphology observation of conducting filler-reinforced nitrile and hydrogenated nitrile rubber composites is reported. Principal results were increases in hardness (maximally 97 Shore, type A), elastic modulus (maximally 981 MPa), tensile strength (maximally 27.7 MPa), elongation at break (maximally 216%), cross-link density (maximally 7.94 x 10 28 m -3 ), density (maximally 1.16 g cm -3 ), and tear strength (11.2 kN m -1 ), which were clearly visible at particular acrylonitrile contents both for unhydrogenated and hydrogenated polymers due to enhanced distribution of carbon nanotubes (CNT) and their aggregated particles in the applied rubber matrix. Conclusion was that multi-walled carbon nanotubes improved the performance of nitrile and hydrogenated nitrile rubber nanocomposites prepared by melt compounding.

  4. a Look at Nitrile Chemistry in SGR B2(N) Using the Combined Power of the GBT and the VLA

    Science.gov (United States)

    Steber, Amanda; Zaleski, Daniel P.; Seifert, Nathan A.; Neill, Justin; Muckle, Matt; Pate, Brooks; Corby, Joanna F.; Remijan, Anthony

    2014-06-01

    Nitriles form the most prolific family of molecules known in the ISM, and laboratory work shows that radical-driven chemistry can account for the formation of a diverse set of nitrile and imine molecules. Broadband reaction screening of nitrile chemistry in a pulsed discharge nozzle coupled to a chirped-pulse Fourier transform rotational spectrometer has enabled detections of several new interstellar species including E- and Z-ethanimine and E-cyanomethanimine. The detections were made by direct comparisons of laboratory broadband rotational spectra with the Robert C. Byrd Green Bank Telescope (GBT) PRebiotic Interstellar MOlecule Survery (PRIMOS) survey towards Sgr B2(N), the most chemically complex interstellar region known. In order to probe nitrile chemistry in Sgr B2, we targeted low energy rotational transitions in the 18-21 GHz range of several nitriles with the Karl G. Jansky Very Large Array (VLA) at ˜1 arcsecond resolution. The data indicate that most nitriles and nitrile derivatives are co-spatial with shell shaped continuum features thought to be expanding ionization fronts. The CH2CN radical and imine species in particular are NOT associated with the hot core known as the "Large Molecule Heimat", where most large organic molecules are thought to reside. This result suggests radical driven nitrile chemistry may be promoted by near-UV radiation in moderate density regions of molecular clouds, and the data will be useful for evaluating possible formation mechanisms. R.A. Loomis et al. Ap. J. L., 765, (L9), 2013. D.P. Zaleski et al. Ap. J. L., 765, (L10), 2013.

  5. Simultaneous determination of sulphoraphane and sulphoraphane nitrile in Brassica vegetables using ultra-performance liquid chromatography with tandem mass spectrometry.

    Science.gov (United States)

    Alvarez-Jubete, Laura; Smyth, Thomas J; Valverde, Juan; Rai, Dilip K; Barry-Ryan, Catherine

    2014-01-01

    Several analytical methods exist for the determination of sulphoraphane or sulphoraphane nitrile from biological matrices and plant extracts. However, no UPLC-MS/MS method exists for the simultaneous detection of both. To develop and validate an UPLC-MS/MS method for the simultaneous analysis of sulphoraphane and sulphoraphane nitrile from Brassica oleracea L. ssp. italica This method was developed utilising an Acquity BEH C8 column with gradient elution combined with tandem mass spectrometry, using positive electrospray ionisation in multiple reaction monitoring mode. The retention times for sulphoraphane and sulphoraphane nitrile were 0.4 and 0.6 min respectively, and total run time was 3 min. The method was validated for linearity, sensitivity, precision, accuracy, matrix effects and recovery. The method was employed to determine glucoraphanin hydrolysis products in broccoli and the predominant product was found to vary depending on the variety tested. It was also applied to the accurate determination of sulphoraphane and sulphoraphane nitrile in broccoli samples hydrolysed under different conditions. It was observed that the formation of sulphoraphane and sulphoraphane nitrile was influenced by the temperature of the reaction. The validated UPLC-MS/MS method for simultaneous detection of sulphoraphane and sulphoraphane nitrile was shown to be applicable to broccoli plants and is expected to be applicable to other cruciferous sources. Copyright © 2013 John Wiley & Sons, Ltd.

  6. Understanding the adsorptive and photoactivity properties of Ag-graphene oxide nanocomposites.

    Science.gov (United States)

    Martínez-Orozco, R D; Rosu, H C; Lee, Soo-Wohn; Rodríguez-González, V

    2013-12-15

    Nanocomposites of graphene oxide (GO) and silver nanoparticles (AgNPs) were synthetized using a practical photochemical silver functionalization. Their photocatalytic activities were evaluated with two dyes, Rhodamine B and Indigo Carmine, under visible-light irradiation. The prepared nanocomposites were characterized by HRTEM, FESEM, XRD, Raman, FTIR and UV-vis absorption spectroscopy. These nanocomposites present new defect domains of sp(3) type in combination with several graphitic functional groups that act as nucleation sites for anchoring AgNPs, while the sp(2)-sp(3) edge defects domains of GO generate the photoactivity. Furthermore, their photocatalytic performances are governed by their large adsorption capacity, and strong interaction with dye chromophores. A comprehensive photocatalytic way underlying the importance of adsorption is suggested to explain the low visible-light responsive photoactivity of the AgNPs-GO nanocomposites and the possible binding-site saturation. Then, the usage of H2SO4 allows the production of ionic species and helps to confirm the strong adsorption of both dyes. The ability to synthesize AgNPs-GO nanocomposites with extensive adsorptive capacity is certainly of interest for the efficient removal of hazardous materials. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Thermal Annealing Effect on Poly(3-hexylthiophene: Fullerene:Copper-Phthalocyanine Ternary Photoactive Layer

    Directory of Open Access Journals (Sweden)

    H. Derouiche

    2013-01-01

    Full Text Available We have fabricated poly(3-hexylthiophene (P3HT/copper phthalocyanine (CuPc/fullerene (C60 ternary blend films. This photoactive layer is sandwiched between an indium tin oxide (ITO/poly(3,4-ethylenedioxythiophene:poly(styrene sulfonate (PEDOT/PSS photoanode and a bathocuproine (BCP/aluminium photocathode. The thin films have been characterized by atomic force microscope (AFM and ultraviolet/visible spectroscopy in order to study the influence of P3HT doping on the morphological and optical properties of the photoactive layer. We have also compared the characteristics of three different organic solar cells: ITO/PEDOT:PSS/CuPc0.5:C600.5/BCP/Al and ITO/PEDOT:PSS/P3HT0.3:CuPc0.3:C600.4/BCP/Al with and without annealing. Both structures show good photovoltaic behaviour. Indeed, the incorporation of P3HT into CuPc:C60 thin film improves all the photovoltaic characteristics. We have also seen that thermal annealing significantly improves the optical absorption ability and stabilizes the organic solar cells making it more robust to chemical degradation.

  8. Size-controlled soft-template synthesis of carbon nanodots toward versatile photoactive materials.

    Science.gov (United States)

    Kwon, Woosung; Lee, Gyeongjin; Do, Sungan; Joo, Taiha; Rhee, Shi-Woo

    2014-02-12

    Size-controlled soft-template synthesis of carbon nanodots (CNDs) as novel photoactive materials is reported. The size of the CNDs can be controlled by regulating the amount of an emulsifier. As the size increases, the CNDs exhibit blue-shifted photoluminescence (PL) or so-called an inverse PL shift. Using time-correlated single photon counting, ultraviolet photoelectron spectroscopy, and low-temperature PL measurements, it is revealed that the CNDs are composed of sp² clusters with certain energy gaps and their oleylamine ligands act as auxochromes to reduce the energy gaps. This insight can provide a plausible explanation on the origin of the inverse PL shift which has been debatable over a past decade. To explore the potential of the CNDs as photoactive materials, several prototypes of CND-based optoelectronic devices, including multicolored light-emitting diodes and air-stable organic solar cells, are demonstrated. This study could shed light on future applications of the CNDs and further expedite the development of other related fields. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. TiO_2/WO_3 photoactive bilayers in the UV-Vis light region

    International Nuclear Information System (INIS)

    Vasilaki, E.; Vernardou, D.; Kenanakis, G.; Katsarakis, N.; Vamvakaki, M.

    2017-01-01

    In this work, photoactive bilayered films consisting of anatase TiO_2 and monoclinic WO_3 were synthesized by a sol-gel route. Titanium isopropoxide and tungsten hexachloride were used as metal precursors and deposition was achieved by spin-coating on Corning glass substrates. The samples were characterized by X-ray diffraction, photoluminescence, UV-Vis, and Raman spectroscopy, as well as field emission scanning electron microscopy. The prepared immobilized catalysts were tested for their photocatalytic performance by the decolorization of methylene blue in aqueous matrices, under UV-Vis light irradiation. The annealing process influenced the crystallinity of the bilayered films, while the concentration of the tungsten precursor solution and the position of the tungsten trioxide layer further affected their photocatalytic performance. In particular, the photocatalytic performance of the bilayered films was optimized at a concentration of 0.1 M of the WO_3 precursor solution, when deposited as an overlying layer on TiO_2 by two annealing steps (∝76% methylene blue decolorization in 300 min of irradiation versus ∝59% in the case of a bare TiO_2 film). In general, the coupled layer catalysts exhibited superior photoactivity compared to that of bare TiO_2 films with WO_3 acting as an electron trap, resulting, therefore, in a more efficient electron-hole separation and inhibiting their recombination. (orig.)

  10. Photoactive TiO2 Films Formation by Drain Coating for Endosulfan Degradation

    Directory of Open Access Journals (Sweden)

    Natalia Tapia-Orozco

    2013-01-01

    Full Text Available Heterogeneous photocatalysis is an advanced oxidation process in which a photoactive catalyst, such as TiO2, is attached to a support to produce free radical species known as reactive oxygen species (ROS that can be used to break down toxic organic compounds. In this study, the draining time, annealing temperature, and draining/annealing cycles for TiO2 films grown by the drain coating method were evaluated using a 23 factorial experimental design to determine the photoactivity of the films via endosulfan degradation. The TiO2 films prepared with a large number of draining/annealing cycles at high temperatures enhanced (P>0.05 endosulfan degradation and superoxide radical generation after 30 minutes of illumination with UV light. We demonstrated a negative correlation (R2=0.69; P>0.01 between endosulfan degradation and superoxide radical generation. The endosulfan degradation rates were the highest at 30 minutes with the F6 film. In addition, films prepared using conditions F1, F4, and F8 underwent an adsorption/desorption process. The kinetic reaction constants, Kapp (min−1, were 0.0101, 0.0080, 0.0055, 0.0048, and 0.0035 for F6, F2, F5, F3, and F1, respectively. The endosulfan metabolites alcohol, ether, and lactone were detected and quantified at varying levels in all photocatalytic assays.

  11. An Efficient Synthesis of Nitriles from Aldoximes Using Diethyl Phosphorocyanidate under Mild Conditions

    International Nuclear Information System (INIS)

    Lee, Kieseung; An, Hyeonseong; Hwang, Chanyeon

    2012-01-01

    Nitriles are valuable intermediates in organic synthesis not only because they serve as the appropriate precursors to various functional groups, but also because they are widely used as the key intermediates for pharmaceuticals, agrochemicals and various N-heterocyclic compounds. The cyano group itself is also frequently found in many biologically important molecules. Therefore, a variety of synthetic routes to nitriles from diverse chemical precursors have been developed. Among these routes, nitrile synthesis from aldoximes using an appropriate dehydrating agent has been a general and clean method. For this purpose, numerous reagents such as chlorosulfonyl isocyanate, di-2-pyridyl sulfite, Burgess reagent, [RuCl 2 (p-cymene)] 2 /MS, 4A, BOP, Pd(OAc) 2 /PPh 3 , Cu(OAc) 2 /ultrasound have been developed. These reagents, however, may have limitations in some respects such as harsh reaction conditions, use of expensive or less readily available reagents, low yields, and lack of generality. Therefore, there is still a need to develop mild and general method for this conversion. Diethyl phosphorocyanidate (DEPC) was initially introduced as an efficient peptide coupling reagent, and has been utilized for useful organic reactions. Previously, we reported that 2-chloro-1-methylpyridinium iodide is an efficient and mild reagent for the dehydration of aldoximes to nitriles under mild conditions. In continuation of our interest in developing mild method for the conversion of aldoximes to nitriles, we herein wish to report the first application of DEPC to the efficient synthesis of nitriles from aldoximes under mild conditions (Scheme 1). In order to obtain the information regarding the optimum reaction conditions, 4-pyridine aldoxime (1a) was reacted with DEPC without base, and in presence of various base in CH 2 Cl 2 at rt for a prolonged reaction time (20 h) (Table 1). CH 2 CI 2 was chosen as reaction medium in this reaction due to the good solubility for both 1 and 3 in CH

  12. An Efficient Synthesis of Nitriles from Aldoximes Using Diethyl Phosphorocyanidate under Mild Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kieseung; An, Hyeonseong; Hwang, Chanyeon [Woosuk Univ.,Wanju (Korea, Republic of)

    2012-10-15

    Nitriles are valuable intermediates in organic synthesis not only because they serve as the appropriate precursors to various functional groups, but also because they are widely used as the key intermediates for pharmaceuticals, agrochemicals and various N-heterocyclic compounds. The cyano group itself is also frequently found in many biologically important molecules. Therefore, a variety of synthetic routes to nitriles from diverse chemical precursors have been developed. Among these routes, nitrile synthesis from aldoximes using an appropriate dehydrating agent has been a general and clean method. For this purpose, numerous reagents such as chlorosulfonyl isocyanate, di-2-pyridyl sulfite, Burgess reagent, [RuCl{sub 2}(p-cymene)]{sub 2}/MS, 4A, BOP, Pd(OAc){sub 2}/PPh{sub 3}, Cu(OAc){sub 2}/ultrasound have been developed. These reagents, however, may have limitations in some respects such as harsh reaction conditions, use of expensive or less readily available reagents, low yields, and lack of generality. Therefore, there is still a need to develop mild and general method for this conversion. Diethyl phosphorocyanidate (DEPC) was initially introduced as an efficient peptide coupling reagent, and has been utilized for useful organic reactions. Previously, we reported that 2-chloro-1-methylpyridinium iodide is an efficient and mild reagent for the dehydration of aldoximes to nitriles under mild conditions. In continuation of our interest in developing mild method for the conversion of aldoximes to nitriles, we herein wish to report the first application of DEPC to the efficient synthesis of nitriles from aldoximes under mild conditions (Scheme 1). In order to obtain the information regarding the optimum reaction conditions, 4-pyridine aldoxime (1a) was reacted with DEPC without base, and in presence of various base in CH{sub 2}Cl{sub 2} at rt for a prolonged reaction time (20 h) (Table 1). CH{sub 2}CI{sub 2} was chosen as reaction medium in this reaction due to the

  13. Photoisomerization and Photoionization of the photoactive yellow protein chromophore in solution.

    NARCIS (Netherlands)

    Larsen, D.S.; Vengris, M.; van Stokkum, I.H.M.; van der Horst, M.A.; de Weerd, F.; Hellingwerf, K.J.; van Grondelle, R.

    2004-01-01

    Dispersed pump-dump-probe spectroscopy has the ability to characterize and identify the underlying ultrafast dynamical processes in complicated chemical and biological systems. This technique builds on traditional pump-probe techniques by exploring both ground- and excited-state dynamics and

  14. Nitrile-synthesizing enzyme: Gene cloning, overexpression and application for the production of useful compounds.

    Science.gov (United States)

    Kumano, Takuto; Takizawa, Yuko; Shimizu, Sakayu; Kobayashi, Michihiko

    2016-09-12

    One of the nitrile-synthesizing enzymes, β-cyano-L-alanine synthase, catalyzes β-cyano-L-alanine (β-CNAla) from potassium cyanide and O-acetyl-L-serine or L-cysteine. We have identified this enzyme from Pseudomonas ovalis No. 111. In this study, we cloned the β-CNAla synthase gene and expressed it in Escherichia coli and Rhodococcus rhodochrous. Furthermore, we carried out co-expression of β-CNAla synthase with nitrilase or nitrile hydratases in order to synthesize aspartic acid and asparagine from KCN and O-acetyl-L-serine. This strategy can be used for the synthesis of labeled amino acids by using a carbon-labeled KCN as a substrate, resulting in an application for positron emission tomography.

  15. [3 + 2]-Cycloadditions of nitrile ylides after photoactivation of vinyl azides under flow conditions

    Directory of Open Access Journals (Sweden)

    Stephan Cludius-Brandt

    2013-08-01

    Full Text Available The photodenitrogenation of vinyl azides to 2H-azirines by using a photoflow reactor is reported and compared with thermal formation of 2H-azirines. Photochemically, the ring of the 2H-azirines was opened to yield the nitrile ylides, which underwent a [3 + 2]-cycloaddition with 1,3-dipolarophiles. When diisopropyl azodicarboxylate serves as the dipolarophile, 1,3,4-triazoles become directly accessible starting from the corresponding vinyl azide.

  16. Wear testing and finite element analysis of nitrile rubber (NBR) hand pump seals

    OpenAIRE

    Alkadhimi, Fadel

    2015-01-01

    The use of Nitrile Butadiene Rubber NBR as seal in machines has increased in recent years. NBR is considered as the standard material for sealing and NBR owes its many applications to a range of special mechanical properties. However, the non-linear mechanical properties and incompressible behaviour of NBR make the analysis of NBR very difficult. The literature review highlighted the fact that the most common technical cause of hand pump failures was the wear of the piston seals. The contact ...

  17. NMR studies on 1,3-dipolar cycloaddition of nitrile oxides to norbornenes

    International Nuclear Information System (INIS)

    Gucma, Mirosław; Gołębiewski, W. Marek; Krawczyk, Maria

    2013-01-01

    The 1,3-dipolar cycloaddition reaction of nitrile oxides to norbornenes substituted with an acrylate-derived moiety was examined. Only adducts to norbornene system were formed with a good exo selectivity and complete site-selectivity. Structures of the products were elucidated by an extensive application of electrospray ionization-mass spectrometry (ESI-MS) and 2D 1 H and 13 C nuclear magnetic resonance (NMR). (author)

  18. [Risk assessment and risk control for occupational exposure to chemical toxicants from an isophorone nitrile device].

    Science.gov (United States)

    Wang, Dejun; Fu, Xiaokuan; Kong, Fanling; Sui, Shaofeng; Jiang, Yuanyuan; Du, Yinglin; Zhou, Jingyang

    2014-06-01

    Risk assessment and risk control for occupational exposure to chemical toxicants were performed on an isophorone nitrile device with an annual production of 5,000 tons, based on improved Singaporean semi-quantitative risk assessment method, with consideration of actual situation in China and in the present project. With the use of engineering analysis and identification of occupational hazards in the improved Singaporean semi-quantitative risk assessment method, hazard rating (HR) and risk assessment were performed on chemical toxicants from an isophorone nitrile device with an annual production of 5,000 tons. The chemical toxicants in the isophorone nitrile device were mainly isophorone, hydrocyanic acid, methanol, phosphoric acid, sodium hydroxide, and sodium cyanide; the HR values were mild hazard (2), extreme hazard (5), mild hazard (2), mild hazard (2), moderate hazard (3), and extreme hazard (5), respectively, and the corresponding exposure rating (ER) values were 2.09, 2.72, 2.76, 1.68, 2.0, and 1.59, respectively. The risk of chemical toxicants in this project was assessed according to the formula Risk = [HR×ER](1/2). Hydrocyanic acid was determined as high risk, sodium hydroxide and sodium cyanide as medium risk, and isophorone, methanol, and phosphoric acid as low risk. Priority in handling of risks was determined by risk rating. The table of risk control measure was established for pre-assessment of occupational hazards. With risk assessment in this study, we concluded that the isophorone nitrile device with 5,000 ton annual production was a high-occupational hazard device. This device is a project of extreme occupational hazard. The improved Singaporean semi-quantitative risk assessment method is a scientific and applicable method, and is especially suitable for pre-evaluation of on-site project with no analogy.

  19. NMR studies on 1,3-dipolar cycloaddition of nitrile oxides to norbornenes

    Energy Technology Data Exchange (ETDEWEB)

    Gucma, Miroslaw; Golebiewski, W. Marek; Krawczyk, Maria, E-mail: golebiewski@ipo.waw.pl [Institute of Industrial Organic Chemistry, Warsaw (Poland)

    2013-05-15

    The 1,3-dipolar cycloaddition reaction of nitrile oxides to norbornenes substituted with an acrylate-derived moiety was examined. Only adducts to norbornene system were formed with a good exo selectivity and complete site-selectivity. Structures of the products were elucidated by an extensive application of electrospray ionization-mass spectrometry (ESI-MS) and 2D {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR). (author)

  20. Real-time PCR detection of Fe-type nitrile hydratase genes from environmental isolates suggests horizontal gene transfer between multiple genera.

    Science.gov (United States)

    Coffey, Lee; Owens, Erica; Tambling, Karen; O'Neill, David; O'Connor, Laura; O'Reilly, Catherine

    2010-11-01

    Nitriles are widespread in the environment as a result of biological and industrial activity. Nitrile hydratases catalyse the hydration of nitriles to the corresponding amide and are often associated with amidases, which catalyze the conversion of amides to the corresponding acids. Nitrile hydratases have potential as biocatalysts in bioremediation and biotransformation applications, and several successful examples demonstrate the advantages. In this work a real-time PCR assay was designed for the detection of Fe-type nitrile hydratase genes from environmental isolates purified from nitrile-enriched soils and seaweeds. Specific PCR primers were also designed for amplification and sequencing of the genes. Identical or highly homologous nitrile hydratase genes were detected from isolates of numerous genera from geographically diverse sites, as were numerous novel genes. The genes were also detected from isolates of genera not previously reported to harbour nitrile hydratases. The results provide further evidence that many bacteria have acquired the genes via horizontal gene transfer. The real-time PCR assay should prove useful in searching for nitrile hydratases that could have novel substrate specificities and therefore potential in industrial applications.

  1. Infrared Spectra and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

    Science.gov (United States)

    Anderson, Carrie; Ferrante, Robert F.; Moore, W. James; Hudson, Reggie; Moore, Marla H.

    2011-01-01

    Spectra and optical constants of nitrile ices known or suspected to be in Titan?s atmosphere have been determined from 2.0 to 333.3 microns (approx.5000 to 30/cm). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan?s winter pole. Ices studied were: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C2H5CN, propionitrile; and HC3N, cyanoacetylene. Optical constants were calculated, using Kramers-Kronig analysis, for each nitrile ice?s spectrum measured at a variety of temperatures, in both the amorphous- and crystalline phases. Spectra were also measured for many of the nitriles after quenching at the annealing temperature and compared with those of annealed ices. For each of these molecules we also measured the real component, n, of the refractive index for amorphous and crystalline phases at 670 nm. Several examples of the information contained in these new data sets and their usefulness in modeling Titan?s observed features will be presented (e.g., the broad emission feature at 160/cm; Anderson and Samuelson, 2011).

  2. Particle emission rates during electrostatic spray deposition of TiO2 nanoparticle-based photoactive coating

    DEFF Research Database (Denmark)

    Koivisto, Antti J.; Jensen, Alexander C. Ø.; Kling, Kirsten I.

    2017-01-01

    Here, we studied the particle release rate during Electrostatic spray deposition of anatase-(TiO2)-based photoactive coating onto tiles and wallpaper using a commercially available electrostatic spray device. Spraying was performed in a 20.3m3 test chamber while measuring concentrations of 5.6nm ...

  3. Photoactive Blends of Poly(para-phenylenevinylene) (PPV) with Methanofullerenes from a Novel Precursor : Photophysics and Device Performance

    NARCIS (Netherlands)

    Brabec, C.J.; Cravino, A.; Zerza, G.; Sariciftci, N.S.; Kiebooms, R.; Vanderzande, D.; Hummelen, J.C.

    2001-01-01

    Homogeneous blends of a processable methanofullerene, [6,6]-phenyl C61-butyric acid methyl ester (PCBM), with poly(para-phenylenevinylene) (PPV) synthesized using a novel nonionic precursor route were produced. These photoactive blends have been investigated by excited-state spectroscopy and by

  4. Magnetic Fe@g-C3N4: A Photoactive Catalyst for the Hydrogenation of Alkenes and Alkynes

    Science.gov (United States)

    A photoactive catalyst, Fe@g-C3N4, has been developed for the hydrogenation of alkenes and alkynes using hydrazine hydrate as a source of hydrogen. The magnetically separable Fe@g-C3N4 eliminates the use of high pressure hydrogenation and the reaction can be accomplished using vi...

  5. Bonding of human meniscal and articular cartilage with photoactive 1,8-naphthalimide dyes

    Science.gov (United States)

    Judy, Millard M.; Nosir, Hany R.; Jackson, Robert W.; Matthews, James Lester; Lewis, David E.; Utecht, Ronald E.; Yuan, Dongwu

    1996-05-01

    This study focused on meniscal cartilage repair by using the laser-activated photoactive 1,8- naphthalimide dye N,N'-bis-{6-[2-(2-(2- aminoethoxy)ethoxy)ethoxyethyl]amino-1H-benz (de)isoquinolin-1,3(2H)-dion-2- yl}-1,11-diamino-3,6,9-trioxaundecane. Harvested cadaveric human menisci were debrided and carved into strips 1 mm thick, 10 mm long, and 3 mm wide. Each strip was divided into two flaps, the surface painted with photoactive dye, the painted surfaces overlapped, the sample wrapped in Saran film, and the composite sandwiched between two glass slides at a pressure of approximately 3 kg/cm2. The sample then was transilluminated by argon ion laser light of 457.9-nm wavelength at a power density of 200 mW/cm2 with exposure times up to 5 h (3902 J/cm2 energy density). Essentially, the same procedures were performed for human femoral articular cartilage samples. Control experiments were conducted with laser irradiation alone and with dye alone. All the specimens were stored in isotonic saline solution for 2 h after irradiation to ensure hydration. The bond shear-strength was then tested and samples prepared for optical and electron transmission microscopy. Shear strength values of up to 1.8 kg/cm2 for meniscal tissues and 1.2 kg/cm2 for articular cartilaginous tissues were obtained for exposures of 3902 J/cm2. Shear strength values of approximately 0.9 kg/cm2 and 0.4 kg/cm2, respectively, for meniscus and cartilage were obtained with 459 J/cm2 exposure. Dye- and light-only controls exhibited 0 kg/cm2 shear strength values. Microscopy revealed close contact at the bonded surface in the laser-activated, dye-treated-specimens. This study shows that the laser-activated photoactive dyes have the capability of athermally bonding the meniscal and articular cartilage surfaces.

  6. Studies on nitrile rubber degradation in zinc bromide completion fluid and its prevention by surface fluorination

    Science.gov (United States)

    Vega-Cantu, Yadira Itzel

    Poly(acrylonitrile-co-butadiene) or nitrile-butadiene rubber (NBR) is frequently used as an O-ring material in the oil extraction industry due to its excellent chemical properties and resistance to oil. However, degradation of NBR gaskets is known to occur during the well completion and oil extraction process where packers are exposed to completion fluids such as ZnBr2 brine. Under these conditions NBR exhibits accelerated chemical degradation resulting in embrittlement and cracking. Samples of NBR, poly(acrylonitrile) (PAN) and poly(butadiene) (PB) have been exposed to ZnBr2 based completion fluid, and analyzed by ATR and diffuse reflectance IR. Analysis shows the ZnBr2 based completion fluid promotes hydrolysis of the nitrile group to form amides and carboxylic groups. Analysis also shows that carbon-carbon double bonds in NBR are unaffected after short exposure to zinc bromide based completion fluid, but are quickly hydrolyzed in acidic bromide mixtures. Although fluoropolymers have excellent chemical resistance, their strength is less than nitrile rubber and replacing the usual gasket materials with fluoroelastomers is expensive. However, a fluoropolymer surface on a nitrile elastomer can provide the needed chemical resistance while retaining their strength. In this study, we have shown that this can be achieved by direct fluorination, a rather easy and inexpensive process. Samples of NBR O-rings have been fluorinated by exposure to F2 and F2/HF mixtures at various temperatures. Fluorination with F 2 produces the desired fluoropolymer layer; however, fluorination by F2/HF mixtures gave a smoother fluorinated layer at lower temperatures and shorter times. Fluorinated samples were exposed to ZnBr2 drilling fluid and solvents. Elemental analysis shows that the fluorinated layer eliminates ZnBr2 diffusion into the NBR polymeric matrix. It was also found that surface fluorination significantly retards the loss of mechanical properties such as elasticity, tensile

  7. Chemical Engineering of Photoactivity in Heterometallic Titanium-Organic Frameworks by Metal Doping.

    Science.gov (United States)

    Castells-Gil, Javier; Padial, Natalia M; Almora-Barrios, Neyvis; Albero, Josep; Ruiz-Salvador, A Rabdel; González-Platas, Javier; García, Hermenegildo; Martí-Gastaldo, Carlos

    2018-06-06

    We report a new family of titanium-organic frameworks that enlarges the limited number of crystalline, porous materials available for this metal. They are chemically robust and can be prepared as single crystals at multi-gram scale from multiple precursors. Their heterometallic structure enables engineering of their photoactivity by metal doping rather than by linker functionalization. Compared to other methodologies based on the post-synthetic metallation of MOFs, our approach is well-fitted for controlling the positioning of dopants at an atomic level to gain more precise control over the band-gap and electronic properties of the porous solid. Changes in the band-gap are also rationalized with computational modelling and experimentally confirmed by photocatalytic H 2 production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Temperature dependences of photoconductivity of CdHgTe crystals with photoactive inclusions

    International Nuclear Information System (INIS)

    Vlasenko, A.I.; Vlasenko, Z.K.

    1999-01-01

    Temperature dependences of life time τ and spectral characteristics of photoconductivity for Cd x Hg 1-x Te crystals (x = 0.2) with photoactive inclusions are investigated. It is shown that the N-type character of effective lifetime temperature dependences in nonhomogeneous crystals, in particular, its sharp temperature activation in the region of transition from the impurity to the intrinsic conductivity is determined by not the Shockley-Read mechanism, but by the interband impact mechanism with changing effective geometrical sizes of recombination active regions under temperature increase. Within the frames of this model the smoothing of the non-monotone character of the photoconductivity spectral characteristics in the region of fundamental absorption under the heating is explained. The calculation results that are in qualitative agreement with the experimental data are presented [ru

  9. Potential Impacts from Using Photoactive Roads as AN Air Quality Mitigation Strategy

    Science.gov (United States)

    Toro, C.; Jobson, B. T.; Shen, S.; Chung, S. H.; Haselbach, L.

    2013-12-01

    Mobile sources are major contributors to photochemical air pollution in urban areas. It has been proposed that the use of TiO2 coated roadways ('photoactive roads') could be an effective approach to reduce mobile source emissions by oxidizing NOx and VOC emissions at the roadway surface. However, studies have shown that formation of HONO and aldehydes can occur from some TiO2 treated surfaces during the photocatalytic oxidation of NOx and VOC, respectively. By changing the NOx-to-VOC ratio and generating photolabile HOx radical precursors, photoactive roads may enhance ozone formation rates in urban areas. In this work we present results that quantify NOx and VOC loss rates onto TiO2 treated asphalt and concrete samples, as well as HONO and aldehydes yields that result from the photocatalytic process. The treatment used a commercially available product. These objectives are relevant considering that the quantification of pollutant loss rates and yields of byproducts have not been determined for asphalt and that in the US more than 90% of the roadway surface is made of this material. Surface reaction probabilities (γ) and byproduct yields were determined using a CSTR photochemical chamber under varying conditions of water vapor and UV-A light intensity. Our results indicate that asphalt surfaces have a significantly higher molar yield of HONO compared to concrete surfaces with similar TiO2 loading. Concrete surfaces have reaction probabilities with NO one order of magnitude higher than asphalt samples. Fresh asphalt samples showed negligible photocatalytic activity, presumably due to absorption of TiO2 into the bitumen substrate. Laboratory-prepared asphalt samples with a higher degree of exposed aggregates showed increased HONO molar yields when compared to real-road asphalt samples, whose HONO molar yield was ~1%. Preliminary results for aldehydes formation showed similar molar yields between aged asphalt and concrete, even though aged asphalt samples had twice

  10. The Influence of Cr3+ on TiO2 Crystal Growth and Photoactivity Properties

    Science.gov (United States)

    Wahyuningsih, S.; Hidayatika, W. N.; Sari, P. L.; Sari, P. P.; Hidayat, R.; Munawaroh, H.; Ramelan, A. H.

    2018-03-01

    The photocatalyst technology is an integrated combination of photochemical processes and catalysis in order to carry out a chemical transformation reaction. One of the semiconductor materials that have good photocatalytic activity is TiO2 anatase. This study aim to determine the effect of the Cr3+ addition on the growth of TiO2 rutile crystal and the increasing of TiO2 photoactivity. Diffractogram X-Ray of the samples showed that the synthesized TiO2 at 400 °C has been produced 100% TiO2 anatase. Synthesis of TiO2 doped Cr3+ composite was using wet impregnation method. The TiO2 doped Cr3+ composites have beed grown by annealed at a temperature of 300, 400, 500, 600 and 700 °C, respectively Annealing process have capabled to gain to the TiO2 doped Cr3+ nanocomposite. The result product annealed at 500 °C only appear anatase phase due to the Cr3+ addition influence that was able to suppress the growth of rutile. Identification of TiO2 doped Cr3+ composite using Fourier Transform Infra-Red (FT-IR) showed O-Cr vibration at 2283.72 cm-1. The TiO2 doped Cr3+ photoactivity was studied to degrade Rhodamin B. The best result on photodegradation of Rhodamin B was performed by using TiO2 doped Cr3+ composite which was annealed at 700 °C i.e. 74.71%.

  11. Degradation of blending vulcanized natural rubber and nitril rubber (NR/NBR) by dimethyl ether through variation of elastomer ratio

    Science.gov (United States)

    Saputra, A. H.; Juneva, S.; Sari, T. I.; Cifriadi, A.

    2018-04-01

    Dimethyl ether can cause degradation of the rubber material seal in some applications. In order to use of natural rubber in industry, research about a blending of natural rubber (NR) and nitrile rubber (NBR) to produce rubber to meet the standard seal material application were conducted. This study will observe the degradation mechanisms that occur in the blending natural rubber and nitrile rubber (NR/NBR) by dimethyl ether. Nitrile rubber types used in this study is medium quality nitrile rubber with 33% of acrylonitrile content (NBR33). The observed parameters are percent change in mass, mechanical properties and surface morphology. This study is limited to see the effect of variation vulcanized blending ratio (NR/NBR33) against to swelling. The increase of nitrile rubber (NBR33) ratio of blending rubber vulcanized can reduce the tensile strength and elongation. The best elastomer variation was obtained after comparing with the standard feasibility material of seal is rubber vulcanized blending (NR/NBR33) with ratio 40:60 NR: NBR.

  12. Unexpected catalytic reactions of silyl-protected enol diazoacetates with nitrile oxides that form 5-arylaminofuran-2(3H)-one-4-carboxylates.

    Science.gov (United States)

    Xu, Xinfang; Shabashov, Dmitry; Zavalij, Peter Y; Doyle, Michael P

    2012-02-03

    Silyl-protected enol diazoacetates undergo dirhodium(II)-catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. © 2012 American Chemical Society

  13. Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile-ketenimine equilibria.

    Science.gov (United States)

    Giussi, Juan M; Gastaca, Belen; Albesa, Alberto; Cortizo, M Susana; Allegretti, Patricia E

    2011-02-01

    The study of tautomerics equilibria is really important because the reactivity of each compound with tautomeric capacity can be determined from the proportion of each tautomer. In the present work the tautomeric equilibria in some γ,δ-unsaturated β-hydroxynitriles and γ,δ-unsaturated β-ketonitriles were studied. The first family of compounds presents two possible theoretical tautomers, nitrile and ketenimine, while the second one presents four possible theoretical tautomers, keto-nitrile, enol (E and Z)-nitrile and keto-ketenimine. The equilibrium in gas phase was studied by gas chromatography-mass spectrometry (GC-MS). Tautomerization enthalpies were calculated by this methodology, and results were compared with those obtained by density functional theory (DFT) calculations, observing a good agreement between them. Nitrile tautomers were favored within the first family of compounds, while keto-nitrile tautomers were favored in the second family. Copyright © 2010 Elsevier B.V. All rights reserved.

  14. Review of organic nitrile incineration at the Toxic Substances Control Act Incinerator

    International Nuclear Information System (INIS)

    1997-10-01

    Lockheed Martin Energy Systems, Inc. (LMES) operates the East Tennessee Technology Park (ETTP), formerly called the Oak Ridge K-25 Site, where uranium was enriched under contract with the US Department of Energy (DOE). Currently, ETTP missions include environmental management, waste management (WM), and the development of new technologies. As part of its WM mission, ETTP operates the TSCA (Toxic Substances Control Act) Incinerator (TSCAI) for treatment of hazardous waste and polychlorinated biphenyls (PCBs) contaminated with low-level radioactivity. Beginning in the autumn of 1995, employees from diverse ETTP buildings and departments reported experiencing headaches, fatigue, depression, muscle aches, sleeplessness, and muscle tremors. These symptoms were judged by a physician in the ETTP Health Services Department to be consistent with chronic exposures to hydrogen cyanide (HCN). The National Institute for Occupational Safety and Health (NIOSH) was called in to perform a health hazard evaluation to ascertain whether the employees' illnesses were in fact caused by occupational exposure to HCN. The NIOSH evaluation found no patterns for employees' reported symptoms with respect to work location or department. NIOSH also conducted a comprehensive air sampling study, which did not detect airborne cyanides at the ETTP. Employees, however, expressed concerns that the burning of nitrile-bearing wastes at the TSCAI might have produced HCN as a combustion product. Therefore, LMES and DOE established a multidisciplinary team (TSCAI Technical Review Team) to make a more detailed review of the possibility that combustion of nitrile-bearing wastes at the TSCAI might have either released nitriles or created HCN as a product of incomplete combustion (PIC)

  15. Mechanical, thermal and friction properties of rice bran carbon/nitrile rubber composites: Influence of particle size and loading

    International Nuclear Information System (INIS)

    Li, Mei-Chun; Zhang, Yinhang; Cho, Ur Ryong

    2014-01-01

    Highlights: • A novel rice bran carbon (RBC) is used to reinforce nitrile rubber. • We study the effect of RBC particle size on the performances of nitrile rubber. • We study the effect of RBC loading on the performances of nitrile rubber. • The addition of RBC improves the mechanical properties of nitrile rubber. • The addition of RBC improves the anti-skid properties of nitrile rubber. - Abstract: Four types of rice bran carbon (RBC) with different particle sizes were compounded with nitrile rubber (NBR) in a laboratory size two-roll miller. The obtained RBC/NBR composites were characterized using Field Emission Scanning Electron Microscopy (FE-SEM) and tensile tests. Experimental results showed the RBC with lowest particle size exhibited best dispersion state and superior reinforcement ability. Then, we investigated the influence of RBC loading on the morphology, vulcanization characteristics, mechanical, thermal and friction properties of NBR composites. Experimental results indicated that the incorporation of RBC resulted in higher torque values, longer curing time, but shorter scorch time. The addition of RBC remarkably improved the mechanical properties of NBR composites. However, when the RBC loading exceeded 60 phr, the improvement in the tensile strength was not significant due to the poor dispersion state and weak interfacial bonding between RBC and NBR matrix, which were confirmed by Mooney–Rivlin stress–strain curves and FE-SEM observations. The thermal stabilities of RBC/NBR composites were largely improved as the loading of RBC increased. Friction tests revealed that under a certain concentration, the presence of RBC increased the static friction coefficient of NBR composites, suggesting the anti-skid role of RBC in the NBR composites. The overall results demonstrated that RBC could act as ideal filler for NBR composites providing both economic and environmental advantages

  16. Carbohydrates as efficient catalysts for the hydration of α-amino nitriles.

    Science.gov (United States)

    Chitale, Sampada; Derasp, Joshua S; Hussain, Bashir; Tanveer, Kashif; Beauchemin, André M

    2016-11-01

    Directed hydration of α-amino nitriles was achieved under mild conditions using simple carbohydrates as catalysts exploiting temporary intramolecularity. A broadly applicable procedure using both formaldehyde and NaOH as catalysts efficiently hydrated a variety of primary and secondary susbtrates, and allowed the hydration of enantiopure substrates to proceed without racemization. This work also provides a rare comparison of the catalytic activity of carbohydrates, and shows that the simple aldehydes at the basis of chemical evolution are efficient organocatalysts mimicking the function of hydratase enzymes. Optimal catalytic efficiency was observed with destabilized aldehydes, and with difficult substrates only simple carbohydrates such as formaldehyde and glycolaldehyde proved reliable.

  17. New strategy and easy fabrication of solid-state supercapacitor based on polypyrrole and nitrile rubber.

    Science.gov (United States)

    Lee, Sangyool; Lee, Youngkwan; Cho, Mi-Suk; Nam, Jae-Do

    2008-09-01

    Solid state redox supercapacitors were fabricated using a solid polymer electrolyte, nitrile butadiene rubber (NBR)-KCI and chemically deposited polypyrrole (PPy) as the conducting polymer electrodes on both surfaces of a NBR film. The optimal conditions for the preparation of the PPy/NBR electrode were confirmed as functions of the uptake of pyrrole monomer into the NBR matrix as well as the immersion time in an oxidant solution. The morphology of the PPy-NBR-KCI capacitor was observed using scanning electron microscopy. The performance of the capacitors was characterized using a galvanostatic charge-discharge technique.

  18. Spin trapping of cyanoalkyl radicals in the liquid phase γ radiolysis of nitriles

    International Nuclear Information System (INIS)

    Mao, S.W.; Kevan, L.

    1976-01-01

    The following radicals have been identified in the liquid phase γ radiolysis of several nitriles by spin trapping with phenyl tert-butyl nitrone: CH 2 CN in acetonitrile, H and CH 3 CHCN(question) in propionitrile, CH(CN) 2 in malononitrile, and H, CN, and CH 2 CH 2 CN in succinonitrile. γ proton splittings are observed for the CH 2 CN and CH(CH) 2 spin adducts. The results are discussed in comparison with solid phase radiolysis data and with alkyl radical spin adduct splittings

  19. Positron annihilation analysis of epoxy/hydroxyl terminated butyl nitrile rubber (EP/HTBN) system

    International Nuclear Information System (INIS)

    Zeng Minfeng; Chen Ning; Ji Genzhong; Sun Xudong; Zhao Rener; Xiao Huiquan; Qi Chenze; Wang Baoyi

    2007-01-01

    The free volume properties of epoxy/hydroxyl terminated butyl nitrile rubber (EP/HTBN) have been studied by means of positron annihilation technique. The toughness effect is found to be correlated with the content of HTBN and the free volume properties of the EP/HTBN interfaces. When the content of HTBN component is 5%, the free volume size in the interface is close to that of EP, and the toughness effect is strong. But with further addition of HTBN, holes with big size free volume are formed in the interface, and the toughness effect is limited. (authors)

  20. Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

    International Nuclear Information System (INIS)

    Negron-Mendoza, A.; Draganic, Z.D.; Navarro-Gonzalez, R.; Graganic, I.G.

    1983-01-01

    A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH 4 CN, CH 3 CN, and C 2 H 4 CN, that had received multikilogray doses of 60 Co γ radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond

  1. A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration.

    Science.gov (United States)

    Geri, Jacob B; Szymczak, Nathaniel K

    2015-10-14

    A new bifunctional pincer ligand framework bearing pendent proton-responsive hydroxyl groups was prepared and metalated with Ru(II) and subsequently isolated in four discrete protonation states. Stoichiometric reactions with H2 and HBPin showed facile E-H (E = H or BPin) activation across a Ru(II)-O bond, providing access to unusual Ru-H species with strong interactions with neighboring proton and boron atoms. These complexes were found to promote the catalytic hydroboration of ketones and nitriles under mild conditions, and the activity was highly dependent on the ligand's protonation state. Mechanistic experiments revealed a crucial role of the pendent hydroxyl groups for catalytic activity.

  2. Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.

    Science.gov (United States)

    Kim, Jinho; Stahl, Shannon S

    2013-07-05

    An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- t Bu 2 bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N -oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.

  3. Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature

    OpenAIRE

    Kim, Jinho; Stahl, Shannon S.

    2013-01-01

    An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst...

  4. Improvement of Some Physical Properties of Loaded Nitrile Rubber Vulcanized by Ionizing Radiation

    International Nuclear Information System (INIS)

    Abdel-Aziz, M.M.; Basfar, A.A.; Mofti, S.

    2000-01-01

    The effect of four-selected polyfunctional compounds namely, tri methylacrylic ester, trimethylol propane trimethacrylate, zinc diacrylate and modified pentaerthritol triacrylate, as crosslinking agents, on the mechanical properties of radiation vulcanized nitrile rubber was studied. The effect of incorporation of either HAF-carbon black or fumed silica, as filler and reinforcing agents, on its mechanical properties was also studied. The co agent namely, tri methylacrylic ester, was found to produce a set of optimum mechanical properties, i.e. moderate crosslink density, good tensile strength and elasticity at low irradiation doses, i.e.40 kGy

  5. Hydrolysis of Ibuprofen Nitrile and Ibuprofen Amide and Deracemisation of Ibuprofen Using Nocardia corallina B-276

    OpenAIRE

    Myrna Solís-Oba; Norberto Manjarrez; Aida Solís; Ricardo Lievano; Herminia Inés Pérez

    2012-01-01

    A novel application of whole cells of Nocardia corallina B-276 for the deracemisation of ibuprofen is reported. This microorganism successfully hydrolysed ibuprofen nitrile to ibuprofen amide, and ibuprofen amide to ibuprofen, using a suspension of cells in a potassium phosphate buffer solution (0.1 M, pH = 7.0). These results can be explained by the presence of NHase and amidase enzymes, but the reactions are not enantioselective and low ee values were obtained. However, (R)-ibuprofen was is...

  6. Synthesis of β-phenylchalcogeno-α, β-unsaturated esters, ketones and nitriles using microwave and solvent-free conditions

    International Nuclear Information System (INIS)

    Lenardao, Eder J.; Silva, Marcio S.; Mendes, Samuel R.; Azambuja, Francisco de; Jacob, Raquel G.; Perin, Gelson; Santos, Paulo Cesar Silva dos

    2007-01-01

    A simple, clean and efficient solvent-free protocol was developed for hydrochalcogenation of alkynes containing a Michael acceptor (ester, ketone and nitrile) with phenylchalcogenolate anions generated in situ from the respective diphenyl dichalcogenide (Se, Te, S), using alumina supported sodium borohydride. This efficient and improved method is general and furnishes the respective (Z)-β-phenylchalcogeno-α,β-unsaturated esters, ketones and nitriles, in good yield and higher selectivity, compared with those that use organic solvent and inert atmosphere. The use of microwave (MW) irradiation facilitates the procedure and accelerates the reaction. (author)

  7. Research and application of fuzzy subtractive clustering model on tensile strength of radiation vulcanization for nitrile-butadiene rubber

    International Nuclear Information System (INIS)

    Zuo Duwen; Wang Hong; Zhu Nankang

    2010-01-01

    By use of fuzzy subtractive clustering model, the relationship between tensile strength of radiation vulcanization of NBRL (Nitrile-butadiene rubber latex) and irradiation parameters have been investigated. The correlation coefficient was calculated to be 0.8222 in the comparison of experimental data to the predicted data. It was obvious that fuzzy model identification method is not only high precision with small computation, but also easy to be used. It can directly supply the evolution of tensile strength of NBR by fuzzy modeling method in radiation vulcanization process for nitrile-butadiene rubber. (authors)

  8. Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.

    Science.gov (United States)

    Wang, Teng; Jiao, Ning

    2014-04-15

    Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our

  9. Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

    International Nuclear Information System (INIS)

    Sharanin, Yu A; Goncharenko, M P; Litvinov, Victor P

    1998-01-01

    Published data on the methods for synthesis of carbo- and heterocyclic compounds based on reactions of α,β-unsaturated nitriles with carbonyl compounds and activated phenols are surveyed. It is demonstrated that all these reactions occur via nucleophilic addition of the carbanion generated from a carbonyl compound to the double bond of an unsaturated nitrile (the Michael reaction). The main routes of transformation of the adducts into carbo- and heterocyclic compounds are considered. The methods for regioselective preparation of fused 4H-pyrans or 1,4-dihydropyridines by varying conditions of cyclisation of Michael adducts are discussed. The bibliography includes 249 references.

  10. Magnetic Fe@g??C3N4: A Photoactive Catalyst for the Hydrogenation of Alkenes and Alkynes

    Science.gov (United States)

    A photoactive catalyst, Fe@g-C3N4, has been developed for the hydrogenation of alkenes and alkynes using hydrazine hydrate as a source of hydrogen. The magnetically separable Fe@g-C3N4 eliminates the use of high pressure hydrogenation, and the reaction can be accomplished using visible light without the need for external sources of energy.This dataset is associated with the following publication:Baig, N., S. Verma, R. Varma , and M. Nadagouda. Magnetic Fe@g-C3N4: A Photoactive Catalyst for the Hydrogenation of Alkenes and Alkynes. ACS Sustainable Chemistry & Engineering. American Chemical Society, Washington, DC, USA, 4(3): 1661-1664, (2016).

  11. Photoactive layer-by-layer films of cellulose phosphate and titanium dioxide containing phosphotungstic acid

    Energy Technology Data Exchange (ETDEWEB)

    Ullah, Sajjad [Instituto de Química de São Carlos, Universidade de São Paulo, PO Box 780, São Carlos, São Paulo 13564-970 (Brazil); Acuña, José Javier Sáez [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo Andre, Sao Paulo, 09210-170 (Brazil); Pasa, André Avelino [Surface and Thin Film Laboratory, Physics Department, Federal University of Santa Catarina, PO Box 476, Florianópolis, SC 88040-900 (Brazil); Bilmes, Sara A. [Universidad de Buenos Aires, Facultad Ciencias Exactas y Naturales, Instituto de Química Física de los Materiales, Medio Ambiente y Energía – INQUIMAE, Ciudad Universitaria, Pab. 2, Buenos Aires C1428EHA (Argentina); Vela, Maria Elena; Benitez, Guillermo [Laboratorio de Nanoscopías y Fisicoquímica de Superficies, Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata – CONICET, diagonal 113 esquina 64. C.C.16.Suc.4, 1900 La Plata (Argentina); Rodrigues-Filho, Ubirajara Pereira, E-mail: uprf@iqsc.usp.br [Instituto de Química de São Carlos, Universidade de São Paulo, PO Box 780, São Carlos, São Paulo 13564-970 (Brazil)

    2013-07-15

    A versatile layer-by-layer (LbL) procedure for the preparation of highly dispersed, adherent and porous multilayer films of TiO{sub 2} nanoparticles (NPs) and phosphotungstic acid (HPW) on a variety of substrates at room temperature was developed based on the use of cellulose phosphate (CP) as an efficient and non-conventional polyelectrolyte. UV/vis absorption spectroscopy confirmed the linear and regular growth of the films with the number of immersion cycles and a strong adsorption ability of CP towards TiO{sub 2} NPs. FTIR spectroscopy showed that HPW binds to the surface of TiO{sub 2} through the oxygen atom at the corner of the Keggin structure. XPS results showed that the interaction between TiO{sub 2} and CP is through Ti–O–P linkage. A model is proposed for the TiO{sub 2}–HPW interaction based on XPS and FTIR results. FEG/SEM study of the surface morphology revealed a porous film structure with a homogenous distribution of the TiO{sub 2} NPs induced by CP. HRTEM studies showed that the resulting composite films consist of crystalline anatase and rutile phases and poly-nano-crystalline HPW with a semi-crystalline TiO{sub 2}–HPW interface. These CP/TiO{sub 2} and CP/TiO{sub 2}/HPW LbL films showed good photoactivity against both saturated and unsaturated species, for instance, stearic acid (SA), crystal violet (CV) and methylene blue (MB) under UV irradiation. The CP/HPW films formed on bacterial cellulose (BC) showed good photochromic response which is enhanced in presence of TiO{sub 2} due to an interfacial electron transfer from TiO{sub 2} to HPW. This simple and environmentally safe method can be used to form coatings on a variety of surfaces with photoactive TiO{sub 2} and TiO{sub 2}/HPW films.

  12. [Ti8Zr2O12(COO16] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Shuai Yuan

    2017-11-01

    Full Text Available Metal–organic frameworks (MOFs based on Ti-oxo clusters (Ti-MOFs represent a naturally self-assembled superlattice of TiO2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti8Zr2O12­(COO16] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti8Zr2O12­(COO16] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.

  13. [Ti8Zr2O12(COO)16] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal-Organic Frameworks.

    Science.gov (United States)

    Yuan, Shuai; Qin, Jun-Sheng; Xu, Hai-Qun; Su, Jie; Rossi, Daniel; Chen, Yuanping; Zhang, Liangliang; Lollar, Christina; Wang, Qi; Jiang, Hai-Long; Son, Dong Hee; Xu, Hongyi; Huang, Zhehao; Zou, Xiaodong; Zhou, Hong-Cai

    2018-01-24

    Metal-organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO 2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti 8 Zr 2 O 12 (COO) 16 ] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti 8 Zr 2 O 12 (COO) 16 ] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.

  14. Photoactive layered nanocomposites obtained by direct transferring of anodic TiO{sub 2} nanotubes to commodity thermoplastics

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, Ruy, E-mail: ruy.sanzgonzalez@cnr.it [CNR-IMM, Via Santa Sofia 64, I-95123 Catania (Italy); Buccheri, Maria Antonietta; Zimbone, Massimo; Scuderi, Viviana; Amiard, Guillaume; Impellizzeri, Giuliana [CNR-IMM, Via Santa Sofia 64, I-95123 Catania (Italy); Romano, Lucia [CNR-IMM, Via Santa Sofia 64, I-95123 Catania (Italy); Department of Physics, University of Catania, Via Santa Sofia 64, I-95123 Catania (Italy); Privitera, Vittorio [CNR-IMM, Via Santa Sofia 64, I-95123 Catania (Italy)

    2017-03-31

    Highlights: • Rapid and scalable synthesis of flexible photoactive layered nanocomposites is presented. • The nanocomposites show similar photonic efficiencies to TiO{sub 2} nanotubes and commercial products. • The nanocomposites exhibit antibacterial properties under 1 mW cm{sup −2} UVA. • The synthesis process is solvent-free and reduces the amount of raw materials. - Abstract: TiO{sub 2} nanotubes demonstrated to be a versatile nanostructure for biomaterials, clean energy and water remediation applications. However, the cost of titanium and the poor mechanical properties of the nanotubes hinder their adoption at large scale. This work presents a straightforward and scalable method for transferring photoactive anodic TiO{sub 2} nanotubes from titanium foils to commodity thermoplastic polymers, polypropylene, polyethylene terephthalate, polycarbonate, and polymethylmetacrylate, allowing the reusing of the remaining titanium. The obtained flexible nanocomposites reach a maximum photonic efficiencies of 0.038% (ISO-10678:2010) representing the 93% of photonic efficiency of TiO{sub 2} nanotubes on titanium. In addition, the nanocomposites and TiO{sub 2} nanotubes on titanium present similar antibacterial properties under 1 mW cm{sup −2} UV-A, 60% of Escherichia coli survival after 1 h of exposition. The final objective of this work is to point out main concepts and key parameters for a low-cost fabrication of a photoactive nanocomposite material.

  15. An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

    Science.gov (United States)

    Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

    2014-10-28

    The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

  16. Pengaruh penggunaan nitril butadiene rubber dan pale crepe pada pembuatan sol karet untuk sepatu pengaman

    Directory of Open Access Journals (Sweden)

    Arum Yuniari

    2010-06-01

    Full Text Available Abstract Rubber sole for safety shoes was different on physical specification with general sole, especially on abrasion resistance and oil resistance. The objective of the study was to determine the effect of nitril butadiene rubber and pale crepe on physical properties of vulcanized rubber sole for safety shoes. Rubber sole for safety shoes was produced by blending pale crepe and nitril butadiene rubber with ratio of : 50/50; 60/40; 70/30 and 80/20 phr, respectively. Carbon black as filler was also variated with, 40 ; 50 and 60 phr. Compounding processing used two roll mill machine and vulcanized rubber sole was by using pressed use hydraulic press machine. The results showed that vulcanized rubber sole for safety shoes with good quality consist of pale crepe and NBR 80/20 phr and carbon black 40 phr, which was characterized by tensile strength 16.81 N/mm2, tear strength 11.68 N/mm, density 1.12 g/cm3, abrasion resistance 58.51 mm3, hardness 71.60 shore A, resistance to cut growth 30.000 times was 1.15 mm and oil resistance 65.44%, respectively. The quality parameters was complied with standard quality of SNI 0111 : 2009, for safety shoes from leather and vulcanized rubber sole that fulfill oil reistance parameter.

  17. INFRARED SPECTRA AND OPTICAL CONSTANTS OF NITRILE ICES RELEVANT TO TITAN's ATMOSPHERE

    International Nuclear Information System (INIS)

    Moore, Marla H.; Hudson, Reggie; Ferrante, Robert F.; James Moore, W.

    2010-01-01

    Spectra and optical constants of nitrile ices known or suspected to be in Titan's atmosphere are presented from 2.0 to 333.3 μm (∼5000-30 cm -1 ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied are: HCN, hydrogen cyanide; C 2 N 2 , cyanogen; CH 3 CN, acetonitrile; C 2 H 5 CN, propionitrile; and HC 3 N, cyanoacetylene. For each of these molecules, we also report new cryogenic measurements of the real refractive index, n, determined in both the amorphous and crystalline phases at 670 nm. These new values have been incorporated into our optical constant calculations. Spectra were measured and optical constants were calculated for each nitrile at a variety of temperatures, including, but not limited to, 20, 35, 50, 75, 95, and 110 K, in both the amorphous phase and the crystalline phase. This laboratory effort used a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference was used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryostat. Optical constants, real (n) and imaginary (k) refractive indices, were determined using Kramers-Kronig analysis. Our calculation reproduces the complete spectrum, including all interference effects.

  18. Nitrile-hydrolyzing enzyme from Meyerozyma guilliermondii and its potential in biosynthesis of 3-hydroxypropionic acid.

    Science.gov (United States)

    Zhang, Qiang; Gong, Jin-Song; Dong, Ting-Ting; Liu, Ting-Ting; Li, Heng; Dou, Wen-Fang; Lu, Zhen-Ming; Shi, Jin-Song; Xu, Zheng-Hong

    2017-06-01

    3-Hydroxypropionic acid (3-HP) is an important platform chemical in organic synthesis. Traditionally, 3-HP was produced by chemical methods and fermentation process. In this work, a novel enzymatic method was developed for green synthesis of 3-HP. A yeast strain harboring nitrile-hydrolyzing enzyme was newly isolated from environmental samples using 3-hydroxypropionitrile (3-HPN) as the sole nitrogen source. It was identified to be Meyerozyma guilliermondii CGMCC12935 by sequencing of the 18S ribosomal DNA and internal transcribed spacer, together with analysis of the morphology characteristics. The catalytic properties of M. guilliermondii CGMCC12935 resting cells were determined, and the optimum activity was achieved at 55 °C and pH 7.5. The enzyme showed broad substrate specificity towards nitriles, especially 3-HPN, aminoacetonitrile and 3-cyanopyridine. The presence of Ag + , Pb 2+ and excess substrate inhibited the enzyme activity, whereas 5% (v/v) ethyl acetate had a positive effect on the enzyme activity. M. guilliermondii CGMCC12935 resting cells by addition of 3% glucose could thoroughly hydrolyze 500 mM 3-HPN into 3-HP within 100 h and the maximal accumulative production of 3-HP reached 216.33 mM, which was over twofolds than the control group with no additional glucose. And this work would lay the foundation for biological production of 3-HP in industry.

  19. Permeability test and fuzzy orthogonal analysis of hydrogenated nitrile O-ring

    Directory of Open Access Journals (Sweden)

    Qin Hu

    2015-03-01

    Full Text Available In the high temperature, high pressure and high corrosive environment of the oil and gas drilling downhole, the weatherability of rubber sealing material has a great influence on the production safety. In order to study the important degree of every key environmental factor in downhole influencing the sealing performance of rubber sealing material, a new device of simulating downhole environment is designed to test the permeability of O-ring. The sample is hydrogenated nitrile O-ring and orthogonal experiment method is used to do nine tests by getting three levels from temperature, pressure and CO2 volume fraction. Test adopts fuzzy orthogonal method to analyze the main effects and the interaction between two factors, taking tensile strength, diameter variety rate and pH value of indicator as evaluation index. The results show that: the environmental factor influencing the sealing performance of hydrogenated nitrile O-ring from high to low by turns is temperature, pressure and CO2 volume fraction, while the interaction between temperature and pressure is the most significant. It provides a new way to study the influence of downhole complex environment on the performance of rubber sealing material. Moreover, the results have important reference value to further study the failure mechanism of rubber sealing ring in many environmental factors and the rational use in engineering.

  20. Surfactant-free synthesis of hierarchical niobic acid microflowers assembled from ultrathin nanosheets with efficient photoactivities

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Wenhao [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); Pan, Feng, E-mail: phypf2012@163.com [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); Wang, Yanyan [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); Xiao, Shuning [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); International Joint Lab on Resource Chemistry SHNU-NUS-PU, Department of Chemistry, Shanghai Normal University, Shanghai 200234 (China); Wu, Kai [Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); BNLMS, SKLSCUSS, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 (China); Xu, Guo Qin [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); National University of Singapore (Suzhou) Research Institute, 377 Lin Quan Street, Suzhou Industrial Park, Jiangsu Prov., 215123 (China); and others

    2017-01-15

    Highlights: • 3D hierarchical niobic acid microflower was synthesized by a surfactant-free method. • The microflower was composed of ultrathin nanosheets with ∼5 nm thickness. • The microflower showed high photoactivity owing to the 3D structural features. • This microflower was converted to Nb{sub 2}O{sub 5} without significant structural alteration. • Nb{sub 2}O{sub 5} nanoneedles can also be obtained by adjusting the pH value during synthesis. - Abstract: Hierarchical niobic acid (Nb{sub 2}O{sub 5}·nH{sub 2}O) microflowers are synthesized by a surfactant-free hydrothermal approach. The three-dimensional microflowers are assembled from two-dimensional ultrathin nanosheets with thickness of ∼5 nm. Using rhodamine B as a probe, the Nb{sub 2}O{sub 5}·nH{sub 2}O microflowers exhibit high photocatalytic activity under UV light irradiation. Furthermore, the Nb{sub 2}O{sub 5}·nH{sub 2}O microflowers are easily converted to niobium pentoxide without significant structural alteration.

  1. Effect of urea on the photoactivity of titania powder prepared by sol-gel method

    International Nuclear Information System (INIS)

    Cheng Ping; Deng Changsheng; Gu Mingyuan; Dai Xiaming

    2008-01-01

    The synthesis of nanocrystalline titania powders from the hydrolysis of Ti(OBu n ) 4 in the presence of urea was investigated. DRS results showed that a redshift occurred in the absorption edge of titania with increasing the content of urea. XRD results indicated that urea showed a retarding effect on the transformation of titania from anatase to rutile. Moreover, the addition of urea resulted in a higher Brunauer-Emmett-Teller (BET) surface area as well as a larger average pore size of TiO 2 nanoparticles. The average pore size of urea/TiO 2 gels calcined at 500 deg. C increased with the increase of urea content, while the specific surface area increased with the amount of urea to reach a maximum at 10% and then decreased with further increase of the amount of urea. The maximal specific surface area of 64.4 m 2 g -1 was obtained for 10% urea/TiO 2 gels calcined at 500 deg. C, which showed an average particle size of 15 nm and pore size distribution in the range of mesopores centered at 5.8 nm. The photocatalytic experiments exhibited that titania nanoparticles prepared in the presence of urea could effectively photodegrade methyl orange under visible light irradiation due to the redshift of the absorption edge. The maximum photoactivity was achieved when the content of urea was 10%, which was attributed to the higher specific surface area

  2. Nitridation of one-dimensional tungsten oxide nanostructures: Changes in structure and photoactivity

    KAUST Repository

    Varga, Tamás

    2017-10-12

    In the search for stable, visible light active photoelectrodes, hydrothermally synthesized tungsten oxide nanowires were modified via nitrogen incorporation into their structure. To this end, nanowires were heat-treated in ammonia/nitrogen atmosphere at different temperatures. This procedure caused transitions in their structure that were investigated along with the photoelectrochemical properties of the samples. Results were subsequently compared to the reference samples treated in inert nitrogen atmosphere. Morphological changes and structural transitions were followed by transmission and scanning electron microscopy and X-ray diffraction. Bandgap energies were determined from the UV–vis spectra of the materials, while photoelectrochemical properties were tested by linear sweep photovoltammetry and electrochemical impedance spectroscopy. Pristine tungsten oxide nanowires were first transformed into tungsten oxynitride and then tungsten nitride during high-temperature calcination in ammonia atmosphere. Electron microscopic investigation revealed that, along with phase transition, the initial fibrous morphology gradually converted into nanosheets. Simultaneously, bandgap energies significantly decreased in the calcination process, too. Photoelectrochemical measurements demonstrated that photoactivity in the treated samples was not improved by the decrease of the bandgap. This behavior might be explained with the deterioration of charge carrier transport properties of the materials due to the increased number of structural defects (acting as trap states), and current ongoing work aims to verify this notion.

  3. The Influence of NiO Addition in TiO2 Structure and Its Photoactivity

    Science.gov (United States)

    Wahyuningsih, S.; Ramelan, A. H.; Purwanti, P. D.; Munawaroh, H.; Ichsan, S.; Kristiawan, Y. R.

    2018-03-01

    The synthesis of TiO2 together with the TiO2-NiO composite using various annealing temperatures has been studied. The synthesis of TiO2 was performed by sol gel method using Titanium Tetra Isopropoxide (TTIP) precursor, whereas the synthesis of TiO2-NiO composite was done by wet impregnation method using NiNO3.6H2O precursor. This study aims to determine the influence of NiO addition in its structure and photoactivity. The diffraction of synthesized TiO2 at 400 °C temperature shows anatase TiO2 peak at 2θ = 25.35 °. The addition of NiO dopant to the synthesis of TiO2 process is carried out by annealing at 300 °C, 400 °C, 500 °C, 600 °C, and 700 °C, respectively. The TiO2-NiO composite has been prepared and shows the diffraction peak of NiO at 2θ=43° about 33.08 to 36.68%. The optimum result of Rhodamine B photodegradation with TiO2 was 43.15%, while the optimum result of Rhodamine B degradation with TiO2-NiO composite was 92.85%.

  4. Electrochemical synthesis of photoactive In/sub 2/Se/sub 3/ thin films

    Energy Technology Data Exchange (ETDEWEB)

    Herrero, J; Ortega, J

    1987-12-01

    In/sub 2/Se/sub 3/ thin films were grown by alternate electrodeposition of selenium and indium from separate baths onto titanium substrates with subsequent thermal annealing. The influence of annealing temperature on the properties of the obtained films was examined. The results of X-ray diffraction patterns led to the conclusion that films were ..beta..-phase when the temperature ranged between 300 and 500/sup 0/C. At 600/sup 0/C the thin film loses Se and the ratio Se/In decreases. Only photoanodic response, n-type thin films, was observed when the samples were tested in a photoelectrochemical cell with a sulfite/sulfate redox couple. Values of the photocurrent on the spectra response were increased when the annealing temperature was also increased, showing the best photocurrent values at 500/sup 0/C, and the films that were annealed at 600/sup 0/C showed no photoactivity. Spectral responses after chemical etching of the samples showed a significant increase of the photocurrent. Application of Gaertner-Butler's model to the interface semiconductor-electrolyte makes it possible to obtain the semiconductor energy gap, on samples heated at 500/sup 0/C, corresponding to a direct allowed band transition.

  5. Photoactivity of N-doped ZnO nanoparticles in oxidative and reductive reactions

    Science.gov (United States)

    Oliveira, Jéssica A.; Nogueira, André E.; Gonçalves, Maria C. P.; Paris, Elaine C.; Ribeiro, Caue; Poirier, Gael Y.; Giraldi, Tania R.

    2018-03-01

    N-doped ZnO is a prospective material for photocatalytic reactions. However, only oxidative paths are well investigated in the literature. This paper describes a comparative study about ZnO and ZnO:N potential for oxidative and reductive reactions, probed by rhodamine B dye photodegradation and CO2 photoreduction. The materials were prepared by the polymeric precursor method, using urea as a nitrogen source, and different heat treatments were used to observe their effects on surface decontamination, crystallinity, particle sizes and shapes, and photocatalytic performance. ZnO and ZnO:N presented a wurtzite crystalline structure and nanometric-scale particles. Samples submitted to higher temperatures showed lower specific surface areas, but higher crystallinity and lower contents of species adsorbed on their surfaces. On the other hand, the photocatalysts annealed in shorter times presented smaller crystallite sizes and lower crystallinity. These factors influenced the photoactivity in both conditions, i.e., oxidation and reduction reactions, under the ultraviolet and visible light, indicating that structural factors influenced the adequate charge separation and consequent photocatalytic activity since the as-synthesized samples were versatile photocatalysts in both redox reactions.

  6. Anti-Inflammatory and Antioxidant Effects of Repeated Exposure to Cruciferous Allyl Nitrile in Sensitizer-Induced Ear Edema in Mice.

    Science.gov (United States)

    Tanii, Hideji; Sugitani, Kayo; Saijoh, Kiyofumi

    2016-02-29

    Skin sensitizers induce allergic reactions through the induction of reactive oxygen species. Allyl nitrile from cruciferous vegetables has been reported to induce antioxidants and phase II detoxification enzymes in various tissues. We assessed the effects of repeated exposure to allyl nitrile on sensitizer-induced allergic reactions. Mice were dosed with allyl nitrile (0-200 µmol/kg), and then received a dermal application of 1 of 3 sensitizers on the left ear or 1 of 2 vehicles on the right ear. Quantitative assessment of edema was carried out by measuring the difference in weight between the portions taken from the right and left ears. We tested enzymes (superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), and thiobarbituric acid reactive substances (TBARS) in ears. Repeated exposure to allyl nitrile reduced edemas induced by glutaraldehyde and by 2, 4-dinitrochlorobenzene (DNCB), but not by formaldehyde. The repeated exposure decreased levels of TBARS, a marker of oxidative stress, induced by glutaraldehyde and by DNCB, but not by formaldehyde. Allyl nitrile elevated SOD levels for the 3 sensitizers, and CAT levels for formaldehyde and DNCB. Allyl nitrile also increased GPx levels for formaldehyde and DNCB, but not for glutaraldehyde. The reduced edemas were associated with changes in oxidative stress levels and antioxidant enzymes. Repeated exposure to allyl nitrile reduced allergic reactions induced by glutaraldehyde and by DNCB, but not by formaldehyde. This reduction was associated with changes in ROS levels and antioxidant enzyme activities.

  7. Herbivore-induced poplar cytochrome P450 enzymes of the CYP71 family convert aldoximes to nitriles which repel a generalist caterpillar.

    Science.gov (United States)

    Irmisch, Sandra; Clavijo McCormick, Andrea; Günther, Jan; Schmidt, Axel; Boeckler, Gerhard Andreas; Gershenzon, Jonathan; Unsicker, Sybille B; Köllner, Tobias G

    2014-12-01

    Numerous plant species emit volatile nitriles upon herbivory, but the biosynthesis as well as the relevance of these nitrogenous compounds in plant-insect interactions remains unknown. Populus trichocarpa has been shown to produce a complex blend of nitrogenous volatiles, including aldoximes and nitriles, after herbivore attack. The aldoximes were previously reported to be derived from amino acids by the action of cytochrome P450 enzymes of the CYP79 family. Here we show that nitriles are derived from aldoximes by another type of P450 enzyme in P. trichocarpa. First, feeding of deuterium-labeled phenylacetaldoxime to poplar leaves resulted in incorporation of the label into benzyl cyanide, demonstrating that poplar volatile nitriles are derived from aldoximes. Then two P450 enzymes, CYP71B40v3 and CYP71B41v2, were characterized that produce aliphatic and aromatic nitriles from their respective aldoxime precursors. Both possess typical P450 sequence motifs but do not require added NADPH or cytochrome P450 reductase for catalysis. Since both enzymes are expressed after feeding by gypsy moth caterpillars, they are likely to be involved in herbivore-induced volatile nitrile emission in P. trichocarpa. Olfactometer experiments showed that these volatile nitriles have a strong repellent activity against gypsy moth caterpillars, suggesting they play a role in induced direct defense against poplar herbivores. © 2014 The Authors The Plant Journal © 2014 John Wiley & Sons Ltd.

  8. Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

    Science.gov (United States)

    Hudson, R. L.; Moore, M. H.

    2004-12-01

    Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH 3CN, CH 3CH 2CN, CH 2CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH 3) 2CHCN and (CH 3) 3CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH 3CN, CH 3CH 2CN, and (CH 3) 2CHCN also formed ketenimines. In the presence of H 2O, no isonitriles were detected but rather the cyanate ion (OCN -) was seen in all cases. Although isonitriles, ketenimines, and OCN - were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.

  9. Formation and nitrile hydrogenation performance of Ru nanoparticles on a K-doped Al2O3 surface.

    Science.gov (United States)

    Muratsugu, Satoshi; Kityakarn, Sutasinee; Wang, Fei; Ishiguro, Nozomu; Kamachi, Takashi; Yoshizawa, Kazunari; Sekizawa, Oki; Uruga, Tomoya; Tada, Mizuki

    2015-10-14

    Decarbonylation-promoted Ru nanoparticle formation from Ru3(CO)12 on a basic K-doped Al2O3 surface was investigated by in situ FT-IR and in situ XAFS. Supported Ru3(CO)12 clusters on K-doped Al2O3 were converted stepwise to Ru nanoparticles, which catalyzed the selective hydrogenation of nitriles to the corresponding primary amines via initial decarbonylation, the nucleation of the Ru cluster core, and the growth of metallic Ru nanoparticles on the surface. As a result, small Ru nanoparticles, with an average diameter of less than 2 nm, were formed on the support and acted as efficient catalysts for nitrile hydrogenation at 343 K under hydrogen at atmospheric pressure. The structure and catalytic performance of Ru catalysts depended strongly on the type of oxide support, and the K-doped Al2O3 support acted as a good oxide for the selective nitrile hydrogenation without basic additives like ammonia. The activation of nitriles on the modelled Ru catalyst was also investigated by DFT calculations, and the adsorption structure of a nitrene-like intermediate, which was favourable for high primary amine selectivity, was the most stable structure on Ru compared with other intermediate structures.

  10. The anomalous substituent effect of the ethyl group in the 13 C NMR and IR data of some aliphatic nitriles

    International Nuclear Information System (INIS)

    Garcia, Janaina C.; Barbarini, Jose E.; Rittner, Roberto; Rocco, Silvana A.; Tormena, Claudio F.

    1999-01-01

    This work reports a full assignment of 13 C and 1 H chemical shifts for some aliphatic nitriles from acetonitrile to octanonitrile and the observed shieldings for the carbon cyano group are correlated with the ν CN and with the electronic and steric parameters

  11. Biotransformation of 3-substituted methyl (R,S)-4-cyanobutanoates with nitrile- and amide-converting biocatalysts

    Czech Academy of Sciences Publication Activity Database

    Martínková, Ludmila; Klempier, N.; Bardakji, J.; Kandelbauer, A.; Ovesná, M.; Podařilová, T.; Kuzma, Marek; Přepechalová, Irena; Griengl, G.; Křen, Vladimír

    2001-01-01

    Roč. 14, - (2001), s. 95-99 ISSN 1381-1177 R&D Projects: GA AV ČR IAA4020802 Institutional research plan: CEZ:AV0Z5020903 Keywords : Rhodococcus equi * nitrile hydratase * amidase Subject RIV: EE - Microbiology, Virology Impact factor: 1.408, year: 2001

  12. Solvation structure determination of nickel(II) ion in six nitriles using extended X-ray absorption fine structure spectroscopy

    International Nuclear Information System (INIS)

    Inada, Yasuhiro; Funahashi, Shigenobu

    1997-01-01

    The solvation structures of the nickel(II) ion in six nitriles have been determined using X-ray absorption fine structure spectroscopy. The coordination number and the Ni-N bond length are 6 and 206.9 ± 0.6 pm in acetonitrile, 5.9 ± 0.2 and 206.9 ± 0.6 pm in propionitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in butyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in isobutyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in valeronitrile, and 6.0 ± 0.2 and 206.5 ± 0.7 pm in benzonitrile, respectively. The structure parameters around the nickel(II) ion in all the nitriles are not affected by the bulkiness of the nitrile molecules. On the basis of the obtained structure parameters, we have discussed the structural characteristics around the nickel(II) ion with nitrogen and oxygen donor solvents and the reaction mechanisms for nitrile exchange on the nickel(II) ion. (author)

  13. High-yield continuous production of nicotinic acid via nitrile hydratase–amidase cascade reactions using cascade CSMRs

    Czech Academy of Sciences Publication Activity Database

    Cantarella, L.; Gallifuoco, A.; Malandra, A.; Martínková, Ludmila; Spera, A.; Cantarella, M.

    2011-01-01

    Roč. 48, 4-5 (2011), 345-350 ISSN 0141-0229 R&D Projects: GA MŠk OC09046 Institutional research plan: CEZ:AV0Z50200510 Keywords : Nitrile hydratase-amidase cascade system * 3-Cyanopyridine bioconversion * Nicotinic acid Subject RIV: EE - Microbiology, Virology Impact factor: 2.367, year: 2011

  14. D-π-A Compounds with Tunable Intramolecular Charge Transfer Achieved by Incorporation of Butenolide Nitriles as Acceptor Moieties

    DEFF Research Database (Denmark)

    Moreno-Yruela, Carlos; Garín, Javier; Orduna, Jesús

    2015-01-01

    Chromophores where a polyenic spacer separates a 4H-pyranylidene or benzothiazolylidene donor and three different butenolide nitriles have been synthesized and characterized. The role of 2(5H)-furanones as acceptor units on the polarization and the second-order nonlinear (NLO) properties has been...

  15. Expression control of nitrile hydratase and amidase genes in Rhodococcus erythropolis and substrate specificities of the enzymes

    Czech Academy of Sciences Publication Activity Database

    Rucká, Lenka; Volkova, Olga; Pavlík, Adam; Kaplan, Ondřej; Kracík, M.; Nešvera, Jan; Martínková, Ludmila; Pátek, Miroslav

    2014-01-01

    Roč. 105, č. 6 (2014), s. 1179-1190 ISSN 0003-6072 R&D Projects: GA MŠk(CZ) LC06010; GA ČR(CZ) GAP504/11/0394 Institutional support: RVO:61388971 Keywords : Rhodococcus erythropolis * Amidase * Nitrile hydratase Subject RIV: EE - Microbiology, Virology Impact factor: 1.806, year: 2014

  16. A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

    Science.gov (United States)

    One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

  17. Synthesis of benzimidazoles by potassium tert-butoxide-promoted intermolecular cyclization reaction of 2-iodoanilines with nitriles.

    Science.gov (United States)

    Xiang, Shi-Kai; Tan, Wen; Zhang, Dong-Xue; Tian, Xian-Li; Feng, Chun; Wang, Bi-Qin; Zhao, Ke-Qing; Hu, Ping; Yang, Hua

    2013-11-14

    The synthesis of benzimidazoles by intermolecular cyclization reaction of 2-iodoanilines with nitriles has been developed. These reactions proceeded without the aid of any transition metals or ligands and just using KOBu(t) as the base. A variety of substituted benzimidazole derivatives can be synthesized by the approach.

  18. Unraveling the reaction mechanism on nitrile hydration catalyzed by [Pd(OH2)4]2+: insights from theory.

    Science.gov (United States)

    Tílvez, Elkin; Menéndez, María I; López, Ramón

    2013-07-01

    Density functional theory methodologies combined with continuum and discrete-continuum descriptions of solvent effects were used to investigate the [Pd(OH2)4](2+)-catalyzed acrylonitrile hydration to yield acrylamide. According to our results, the intramolecular hydroxide attack mechanism and the external addition mechanism of a water molecule with rate-determining Gibbs energy barriers in water solution of 27.6 and 28.3 kcal/mol, respectively, are the most favored. The experimental kinetic constants of the hydration started by hydroxide, k(OH), and water, k(H2O), attacks for the cis-[Pd(en)(OH2)2](2+)-catalyzed dichloroacetonitrile hydration rendered Gibbs energy barriers whose energy difference, 0.7 kcal/mol, is the same as that obtained in the present study. Our investigation reveals the nonexistence of the internal attack of a water ligand for Pd-catalyzed nitrile hydration. At the low pHs used experimentally, the equilibrium between [Pd(OH2)3(nitrile)](2+) and [Pd(OH2)2(OH)(nitrile)](+) is completely displaced to [Pd(OH2)3(nitrile)](2+). Experimental studies in these conditions stated that water acts as a nucleophile, but they could not distinguish whether it was a water ligand, an external water molecule, or a combination of both possibilities. Our theoretical explorations clearly indicate that the external water mechanism becomes the only operative one at low pHs. On the basis of this mechanistic proposal it is also possible to ascribe an (1)H NMR signal experimentally detected to the presence of a unidentate iminol intermediate and to explain the influence of nitrile concentration reported experimentally for nitriles other than acrylonitrile in the presence of aqua-Pd(II) complexes. Therefore, our theoretical point of view on the mechanism of nitrile hydration catalyzed by aqua-Pd(II) complexes can shed light on these relevant processes at a molecular level as well as afford valuable information that can help in designing new catalysts in milder and more

  19. Au nanostructure-decorated TiO2 nanowires exhibiting photoactivity across entire UV-visible region for photoelectrochemical water splitting.

    Science.gov (United States)

    Pu, Ying-Chih; Wang, Gongming; Chang, Kao-Der; Ling, Yichuan; Lin, Yin-Kai; Fitzmorris, Bob C; Liu, Chia-Ming; Lu, Xihong; Tong, Yexiang; Zhang, Jin Z; Hsu, Yung-Jung; Li, Yat

    2013-08-14

    Here we demonstrate that the photoactivity of Au-decorated TiO2 electrodes for photoelectrochemical water oxidation can be effectively enhanced in the entire UV-visible region from 300 to 800 nm by manipulating the shape of the decorated Au nanostructures. The samples were prepared by carefully depositing Au nanoparticles (NPs), Au nanorods (NRs), and a mixture of Au NPs and NRs on the surface of TiO2 nanowire arrays. As compared with bare TiO2, Au NP-decorated TiO2 nanowire electrodes exhibited significantly enhanced photoactivity in both the UV and visible regions. For Au NR-decorated TiO2 electrodes, the photoactivity enhancement was, however, observed in the visible region only, with the largest photocurrent generation achieved at 710 nm. Significantly, TiO2 nanowires deposited with a mixture of Au NPs and NRs showed enhanced photoactivity in the entire UV-visible region. Monochromatic incident photon-to-electron conversion efficiency measurements indicated that excitation of surface plasmon resonance of Au is responsible for the enhanced photoactivity of Au nanostructure-decorated TiO2 nanowires. Photovoltage experiment showed that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was attributable to the effective surface passivation of Au NPs. Furthermore, 3D finite-difference time domain simulation was performed to investigate the electrical field amplification at the interface between Au nanostructures and TiO2 upon SPR excitation. The results suggested that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was partially due to the increased optical absorption of TiO2 associated with SPR electrical field amplification. The current study could provide a new paradigm for designing plasmonic metal/semiconductor composite systems to effectively harvest the entire UV-visible light for solar fuel production.

  20. Steric congestion at, and proximity to, a ferrous center leads to hydration of α-nitrile substituents forming coordinated carboxamides.

    Science.gov (United States)

    Thallaj, Nasser K; Orain, Pierre-Yves; Thibon, Aurore; Sandroni, Martina; Welter, Richard; Mandon, Dominique

    2014-08-04

    The question of the conversion of nitrile groups into amides (nitrile hydration) by action of water in mild and eco-compatible conditions and in the presence of iron is addressed in this article. We come back to the only known example of hydration of a nitrile function into carboxamide by a ferrous [Fe(II)] center in particularly mild conditions and very efficiently and demonstrate that these unusual conditions result from the occurrence of steric stress at the reaction site and formation of a more stable end product. Two bis(cyano-substituted) (tris 2-pyridyl methyl amine) ligands have been prepared, and the structures of the corresponding FeCl2 complexes are reported, both in the solid state and in solution. These two ligands only differ by the position of the nitrile group on the tripod in the α and β position, respectively, with respect to the pyridine nitrogen. In any case, intramolecular coordination is impossible. Upon action of water, the nitrile groups are hydrated however only if they are located in the α position. The fact that the β-substituted β-(NC)2TPAFeCl2 complex is not water sensitive suggests that the reaction proceeds in an intramolecular way at the vicinity of the metal center. In the bis α-substituted α-(NC)2TPAFeCl2 complex, both functions are converted in a very clean fashion, pointing out that this complex exhibits ligand flexibility and is not deactivated after the first hydration. At a preparative scale, this reaction allows the one-pot conversion of the bis(cyano-substituted) tripod into a bis(amido-substituted) one in particularly mild conditions with a very good yield. Additionally, the XRD structure of a ferric compound in which the two carboxamido ligands are bound to the metal in a seven-coordinate environment is reported.

  1. Highly efficient polymer solar cells with printed photoactive layer: rational process transfer from spin-coating

    KAUST Repository

    Zhao, Kui

    2016-09-05

    Scalable and continuous roll-to-roll manufacturing is at the heart of the promise of low-cost and high throughput manufacturing of solution-processed photovoltaics. Yet, to date the vast majority of champion organic solar cells reported in the literature rely on spin-coating of the photoactive bulk heterojunction (BHJ) layer, with the performance of printed solar cells lagging behind in most instances. Here, we investigate the performance gap between polymer solar cells prepared by spin-coating and blade-coating the BHJ layer for the important class of modern polymers exhibiting no long range crystalline order. We find that thickness parity does not always yield performance parity even when using identical formulations. Significant differences in the drying kinetics between the processes are found to be responsible for BHJ nanomorphology differences. We propose an approach which benchmarks the film drying kinetics and associated BHJ nanomorphology development against those of the champion laboratory devices prepared by spin-coating the BHJ layer by adjusting the process temperature. If the optimization requires the solution concentration to be changed, then it is crucial to maintain the additive-to-solute volume ratio. Emulating the drying kinetics of spin-coating is also shown to help achieve morphological and performance parities. We put this approach to the test and demonstrate printed PTB7:PC71BM polymer solar cells with efficiency of 9% and 6.5% PCEs on glass and flexible PET substrates, respectively. We further demonstrate performance parity for two other popular donor polymer systems exhibiting rigid backbones and absence of a long range crystalline order, achieving a PCE of 9.7%, the highest efficiency reported to date for a blade coated organic solar cell. The rational process transfer illustrated in this study should help the broader and successful adoption of scalable printing methods for these material systems.

  2. Characteristics of the excited states of Nitrofurantoin, an anti-inflammatory and photoactive nitrofuran derivative

    Energy Technology Data Exchange (ETDEWEB)

    Parra, Gustavo G., E-mail: gugparra@gmail.com [Departamento de Física, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes 3900, Ribeirão Preto, SP (Brazil); Ferreira, Lucimara P.; Codognato, Débora C.K. [Departamento de Física, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes 3900, Ribeirão Preto, SP (Brazil); Cavalheiro, Carla C.S. [Departamento de Físico-Química, Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador São-Carlense 400, São Carlos, SP (Brazil); Borissevitch, Iouri [Departamento de Física, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes 3900, Ribeirão Preto, SP (Brazil); Instituto de Física, Universidade Federal de Goiás, 74001-970 Goiânia, GO (Brazil)

    2017-05-15

    Spectral characteristics of bio and photoactive nitrofuran derivative drug [N-(5-nitro-2-furfurylidene)−1-aminohydantoin], (Nitrofurantoin, NFT) were investigated using optical absorption and fluorescence spectroscopies, both in “steady-state” and time resolved forms. The irradiation of the NFT in the UV region in aqueous solution induces the fluorescence with quantum yield Φ{sub fl}≈0.03% and lifetime τ{sub fl}≈1 ns with these values being practically independent of the NFT protonation state. The NFT transient absorption spectrum and lifetime (τ{sub T}) depend on the NFT protonation state with τ{sub T} being 0.04 μs for mono-protonated NFT state, 0.22 μs for its non-protonated one, and with quantum yield, Φ{sub T} ≈ 0.0001% which is practically independent of its protonation state. The quenching of this transient by molecular oxygen accompanied by simultaneous singlet oxygen formation ({sup 1}O{sub 2}) allows associate this specie with the NFT molecules in the triplet state being the efficiency of this process dependent of NFT protonation state, η{sub pH10}≈0.53 and η{sub pH2.5}≈0.07. The extremely low quantum yields, Φ{sub fl} and Φ{sub T}, and short τ{sub fl} and τ{sub T} are, probably, associated with alternative ways of the dissipation of the NFT excited state energy: the NFT photoisomerization and NO{sup •} photorelease. The synergic action of two highly reactive species such as {sup 1}O{sub 2} and NO{sup •} in biological medium is extremely valuable for applications in photochemotherapy, thus making NFT a potential candidate for further studies in vitro and in vivo.

  3. Single-molecule conductance with nitrile and amino contacts with Ag or Cu electrodes

    International Nuclear Information System (INIS)

    Li, Dong-Fang; Mao, Jin-Chuan; Chen, De-Li; Chen, Fang; Ze-Wen, Hong; Zhou, Xiao-Yi; Wang, Ya-Hao; Zhou, Xiao-Shun; Niu, Zhen-Jiang; Maisonhaute, Emmanuel

    2015-01-01

    The single-molecule conductance of 1,4-dicyanobenzene (DCB), 1,4-benzenediamine (BDA) and 4,4'-biphenyldicarbonitrile (BPDC) with Ag and/or Cu electrodes is measured by electrochemical jump-to-contact STM-break junction. All single-molecule junctions present three sets of conductance values revealing different contact geometries. We observe that the single-molecule conductance of Ag-BDA-Ag junction is larger that of Ag-DCB-Ag junction, and DCB with Ag contacts are more conductive than that with Cu ones. This is related to a different electronic coupling between the molecules and the electrodes. Tunneling decay constants of 1.70 and 1.68 per phenyl group were found for Ag and Cu electrodes, respectively. The present study therefore shows that nitrile and amino groups can also be used as effective anchors for other metals than gold

  4. Investigation on thermal oxidative aging of nitrile rubber (NBR) O-rings under compression stress

    Science.gov (United States)

    Liu, X. R.; Zhang, W. F.; Lou, W. T.; Huang, Y. X.; Dai, W.

    2017-11-01

    The degradation behaviors of nitrile rubber O-rings exposure to air under compression were investigated at three elevated temperatures. The physical and mechanical properties of the aging samples before and after exposure at selected time were studied by measuring weight loss, tensile strength and elongation at break. The Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and fracture morphology were used to reveal the microstructural changes of the aging samples. The results indicate that the weight decreased with exposure time and temperature. Based on the results of the crosslinking density, the crosslinking predominates during the most of aging process. The significant changes in tensile strength and elongation at break also indicate the severe degradation in air. The fracture morphology results show that the fracture surface after 64 days of exposure to air turns rough and present defects. The ATR-FTIR results demonstrate that the hydroxyl groups were formed for the samples aged in air.

  5. Prediction of the lifetime of nitrile-butadiene rubber by FT-IR.

    Science.gov (United States)

    Kawashima, Tetsuya; Ogawa, Toshio

    2005-12-01

    A quantitative measurement method with FT-IR was proposed for a thermal degradation analysis of nitrile-butadiene rubber (NBR). An NBR film was prepared as a model sample on a barium fluoride (BaF2) crystal plate, which was subjected to a heat treatment. The absorbances of various functional groups were measured directly by FT-IR after thermal degradation at high temperatures. By measuring the absorbances, it was possible to readily determine quantitatively each of the functional groups after the degradation of NBR. By assuming that the NBR lifetime was the point at which the absorbance of a carbon-carbon double bond reaches 45% of that prior to thermal treatment, a method for predicting the lifetime of NBR heated below 150 degrees C was proposed, by using an Arrhenius plot of the heating time versus heating temperature.

  6. Optimization of mechanical performance of oxidative nano-particle electrode nitrile butadiene rubber conducting polymer actuator.

    Science.gov (United States)

    Kim, Baek-Chul; Park, S J; Cho, M S; Lee, Y; Nam, J D; Choi, H R; Koo, J C

    2009-12-01

    Present work delivers a systematical evaluation of actuation efficiency of a nano-particle electrode conducting polymer actuator fabricated based on Nitrile Butadiene Rubber (NBR). Attempts are made for maximizing mechanical functionality of the nano-particle electrode conducting polymer actuator that can be driven in the air. As the conducting polymer polypyrrole of the actuator is to be fabricated through a chemical oxidation polymerization process that may impose certain limitations on both electrical and mechanical functionality of the actuator, a coordinated study for optimization process of the actuator is necessary for maximizing its performance. In this article actuation behaviors of the nano-particle electrode polypyrrole conducting polymer is studied and an optimization process for the mechanical performance maximization is performed.

  7. Correlation between free-volume parameters and physical properties of polyethylene-nitrile rubber blend

    Science.gov (United States)

    Gomaa, E.; Mostafa, N.; Mohsen, M.; Mohammed, M.

    2004-10-01

    Positron annihilation lifetime spectroscopy (PALS) was used to study the immiscibility of a polar nitrile rubber (NBR) that had been blended with pure and waste, low- and high-density polyethylene (PE). The effect of the weight percent of the rubber added to the PE was also investigated. It was found that a complicated variation (positive and negative) in both free-volume parameters (τ3 and I 3) from the values of the initial polymers forms an immiscible blend. These results are supported by a significant broadening in the free-volume hole size distributions. This has been interpreted in terms of interfacial spaces created between the boundaries of the two phases. Furthermore, a correlation was established between the free-volume parameters (τ3 and I 3) and the electrical and mechanical properties of the before mentioned polymer blends as a function of the weight percent of waste PE.

  8. Synthesis and characterization of semi-crystalline polyarylene ether nitrile with AIEE feature

    Science.gov (United States)

    Wang, Pan; Li, Kui; Jia, Kun; Liu, Xiaobo

    2017-12-01

    An AIEgen 1, 2-di (4-hydroxyphenyl)-1, 2-diphenylethene (TPE-2OH) was introduced into the back bone of semi-crystalline poly arylene ether nitriles (PEN). The fluorescence spectra results indicated that the derived polymer displayed a typical aggregation-induced emission enhancement (AIEE) active with an emitting peak at ∼470 nm. Then the AIEE active PEN was prepared into films through casting method and realised strong fluorescence emission and excellent mechanics properties. Besides, the crystal AIEE active polymer shows sphere micro-morphology along with a strong blue emission. These findings will open a door for further research on the high performance semi-crystalline PEN at flexible display technology and optical sensors.

  9. Anti-trypanosomal activity of non-peptidic nitrile-based cysteine protease inhibitors.

    Science.gov (United States)

    Burtoloso, Antonio C B; de Albuquerque, Sérgio; Furber, Mark; Gomes, Juliana C; Gonçalez, Cristiana; Kenny, Peter W; Leitão, Andrei; Montanari, Carlos A; Quilles, José Carlos; Ribeiro, Jean F R; Rocha, Josmar R

    2017-02-01

    The cysteine protease cruzipain is considered to be a validated target for therapeutic intervention in the treatment of Chagas disease. Anti-trypanosomal activity against the CL Brener strain of T. cruzi was observed in the 0.1 μM to 1 μM range for three nitrile-based cysteine protease inhibitors based on two scaffolds known to be associated with cathepsin K inhibition. The two compounds showing the greatest potency against the trypanosome were characterized by EC50 values (0.12 μM and 0.25 μM) that were an order of magnitude lower than the corresponding Ki values measured against cruzain, a recombinant form of cruzipain, in an enzyme inhibition assay. This implies that the anti-trypanosomal activity of these two compounds may not be explained only by the inhibition of the cruzain enzyme, thereby triggering a putative polypharmacological profile towards cysteine proteases.

  10. A Nitrile Glucoside and Biflavones from the Leaves of Campylospermum excavatum (Ochnaceae).

    Science.gov (United States)

    Njock, Gaétan Bayiha Ba; Grougnet, Raphaël; Efstathiou, Antonia; Smirlis, Despina; Genta-Jouve, Grégory; Michel, Sylvie; Mbing, Joséphine Ngo; Kritsanida, Marina

    2017-11-01

    The study of the MeOH extract of the leaves of Campylospermum excavatum led to the isolation of a nitrile glucoside, named campyloside C (1) and an original derivative of ochnaflavone, 7-O-methylochnaflavone (2), along with three known biflavonoids, amentoflavone, sequoiaflavone, and sotetsuflavone (3 - 5). The linkage site of the sub-units of 2 was confirmed by chemical correlation, after semi-synthesis of a trimethoxylated derivative of ochnaflavone (2a). The structures of these compounds as well as their relative and absolute configurations were assigned by 1D- and 2D-NMR experiments, HR-ESI-MS and Electronic Circular Dichroism (ECD) calculations. A low-pass J filter HMBC experiment was performed in order to define the configuration of the double bond of 1. All of the biflavonoids were evaluated against protozoan parasites. Amentoflavone moderately inhibited the promastigote form of Leishmania infantum. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

  11. Sensitivity of core-level spectroscopy to electrostatic environments of nitrile groups: An ab initio study

    Directory of Open Access Journals (Sweden)

    Abid Hussain

    2017-09-01

    Full Text Available Ab initio quantum chemistry calculations have been performed to probe the influence of hydrogen bonding on the electronic structure of hydrogen cyanide (HCN. Our calculations determine the origin of nitrogen-specific Raman spectral features from resonant inelastic X-ray scattering occurring in the presence of a water molecule and an electric dipole field. The similarity of the two interactions in altering the electronic structure of the nitrogen atom differs only in the covalent contributions from the water molecule. The CN stretching mode as a structural probe was also investigated to study the electronic origin of the anomalous frequency shift of the nitrile group when subjected to hydrogen bonding and an electrostatic dipole field. The major changes in the electronic structure of HCN are electrostatic in nature and originate from dipole-dipole interactions. The relative shifts of the CN stretching frequency are in good agreement with those experimentally observed.

  12. Investigation of friction in rectangular Nitrile-Butadiene Rubber (NBR) hydraulic rod seals for defence applications

    Energy Technology Data Exchange (ETDEWEB)

    Bhaumik, Shankar; Guruprasad, S.; Bhandari, P. [R and DE , Dighi (India); Kumaraswamy, A. [Defence Institute of Advanced Technology, Girinagar (India)

    2015-11-15

    Contact based FE simulations have been carried out to estimate the contact pressure distribution at seal/rod interface at sealed oil pressures of 10, 20 and 30 MPa and constant rod velocity of 0.12 m/s. Oil film thickness at the interface was then computed analytically at various combinations of oil pressures and rod velocities. Seal contact pressure and oil film thickness data along with surface roughness, intermolecular interaction between seal/rod interfaces has been perused to estimate the friction in Nitrile-Butadiene Rubber (NBR) rectangular hydraulic rod seals using theoretical models such as Inverse hydrodynamic lubrication (IHL), Greenwood-Williamson (GW) and Wassink's models. The friction at seal/rod interface was also measured experimentally using a specially designed test rig. The comparison of theoretical and experimental data revealed that, friction computed from GW and Wassink's models had good agreement with the experimental results.

  13. Nitrile versus isonitrile adsorption at interstellar grain surfaces. II. Carbonaceous aromatic surfaces

    Science.gov (United States)

    Bertin, M.; Doronin, M.; Michaut, X.; Philippe, L.; Markovits, A.; Fillion, J.-H.; Pauzat, F.; Ellinger, Y.; Guillemin, J.-C.

    2017-12-01

    Context. Almost 20% of the 200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims: In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods: The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results: The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.

  14. Theoretical study of the nucleophilic addition of oximes to the nitrile complexes trans-/cis-[ReCl4(NCCH3)2

    International Nuclear Information System (INIS)

    Klestova-Nadeeva, E. A.; Kuznetsov, M. L.; Dement'ev, A. I.

    2005-01-01

    The reaction of nucleophilic addition of oximes (HON=CRR 1 ) to organic nitriles coordinated in the rhenium complexes trans-/cis-[ReCl 4 (NCCH 3 ) 2 ] was theoretically studied by the Hartree-Fock and density functional theory (B3LYP) methods. The reaction mechanism involves (I) the initial change of the oxime conformation; (II) the formation of the orientation complex with the coordinated nitrile molecule, which transforms into a four-membered transition state; (III) the formation of the addition product in a less stable conformation; and (IV) the formation of the ultimate addition product. The calculations make it possible to interpret the activation of nitriles in terms of the activated complex theory as a result of stabilization of the transition state in going from the free to the coordinated nitrile [ru

  15. Graphene nanoplatelet doping of P3HT:PCBM photoactive layer of bulk heterojunction organic solar cells for enhancing performance

    Science.gov (United States)

    Aïssa, Brahim; Nedil, Mourad; Kroeger, Jens; Ali, Adnan; Isaifan, Rima J.; Essehli, Rachid; Mahmoud, Khaled A.

    2018-03-01

    Hybrid organic photovoltaic (OPV) cells based on conjugated polymer photoactive materials are promising candidates for flexible, high-performance and low-cost energy sources owing to their inexpensive materials, cost-effective processing and ease of fabrication by simple solution processes. However, the modest PV performance obtained to date—in particular the low power conversion efficiency (PCE)—has impeded the large scale deployment of OPV cells. The low PCE in OPV solar cells is mainly attributed to the low carrier mobility, which is closely correlated to the transport diffusion length of the charge carriers within the photoactive layers. The 2D graphene material could be an excellent candidate for assisting charge transport improvement in the active layer of OPV cells, due to its huge carrier mobility, thermal and chemical stability, and its compatibility with the solution process. In this work, we report on the improvement of the optoelectronic properties and photovoltaic performance of graphene nanoplatelet (GNP)-doped P3HT:PCBM photoactive blended layers, integrated into a bulk heterojunction (BHJ) organic-photovoltaic-based device, using PEDOT:PSS on an ITO/glass substrate. First, the light absorption capacity was observed to increase with respect to the GNP content, while the photoluminescence showed clear quenching, indicating electron transfer between the graphene sheets and the polymeric matrix. Then, the incorporation of GNP into the BHJ active layer resulted in enhanced PV performance with respect to the reference cell, and the best PV performance was obtained with 3 wt.% of GNP loading, with an open-circuit voltage of 1.24 V, a short-circuit current density value of 6.18 mA cm-2, a fill factor of 47.12%, and a power conversion efficiency of about 3.61%. We believe that the obtained results contribute to the development of organic photovoltaic devices and to the understanding of the impact of sp2-bonded carbon therein.

  16. Comparing the photophysics of the two forms of the Orange Carotenoid Protein using 2D electronic spectroscopy

    Directory of Open Access Journals (Sweden)

    Mathies R.A.

    2013-03-01

    Full Text Available Broadband two-dimensional electronic spectroscopy is applied to investigate the photophysics of the photoactive orange carotenoid protein, which is involved in nonphotochemical quenching in cyanobacteria. Differences in dynamics between the light and dark forms arise from the different structure of the carotenoid in the protein pocket, with consequences for the biological role of the two forms.

  17. Simple approach to detection and estimation of photoactivity of silver particles on graphene oxide in aqueous-organic dispersion

    Science.gov (United States)

    Vlasov, D. V.; Vlasova, T. D.; Apresyan, L. A.; Krasovskiy, V. I.; Feofanov, I. N.; Kazaryan, M. A.

    2015-12-01

    The effect of sediment flotation was observed in dispersion of graphene oxide flakes with Ag-particles deposited thereon in the aqueous-organic (containing dimethylformamide) under the visible light action, with subsequent stabilization of the dispersion, which does not occur in the absence of Ag-particles. The main reason for this laser light induced movement of sediment graphene oxide flakes may be associated with the appearance of small bubbles. The further development of this approach seem to be able to estimate the of graphene flakes photoactivity with different activating particles.

  18. Nitrile imines and nitrile ylides: rearrangements of benzonitrile N-methylimine and benzonitrile dimethylmethylide to azabutadienes, carbodiimides, and ketenimines. Chemical activation in thermolysis of azirenes, tetrazoles, oxazolones, isoxazolones, and oxadiazolones.

    Science.gov (United States)

    Bégué, Didier; Dargelos, Alain; Berstermann, Hans M; Netsch, Klaus P; Bednarek, Pawel; Wentrup, Curt

    2014-02-07

    Flash vacuum thermolysis (FVT) of 1-methyl-5-phenyltetrazole (5b), 2-methyl-5-phenyltetrazole (1b), and 3-methyl-5-phenyl-1,3,4-oxadiazol-2(3H)-one (3b) affords the nitrile imine (2b), which rearranges in part to N-methyl-N'-phenylcarbodiimide (7b). Another part of 2b undergoes a 1,4-H shift to the diazabutadiene (13). 13 undergoes two chemically activated decompositions, to benzonitrile and CH2═NH and to styrene and N2. FVT of 2,2-dimethyl-4-phenyl-oxazol-5(2H)-one (16) at 400 °C yields 3-methyl-1-phenyl-2-azabutadiene (18) in high yield. In contrast, FVT of 3,3-dimethyl-2-phenyl-1-azirene (21) at 600 °C or 4,4-dimethyl-3-phenyl-isoxazolone (20) at 600 °C affords only a low yield of azabutadiene (18) due to chemically activated decomposition of 18 to styrene and acetonitrile. There are two reaction paths from azirene (21): one (path a) leading to nitrile ylide (17) and the major products styrene and acetonitrile and the other (path b) leading to the vinylnitrene (22) and ketenimine (23). The nitrile ylide PhC(-)═N(+)═C(CH3)2 (17) is implicated as the immediate precursor of azabutadiene (18). FVT of either 3-phenylisoxazol-5(4H)one (25) or 2-phenylazirene (26) at 600 °C affords N-phenylketenimine (28). The nitrile ylide PhC(-)═N(+)═CH2 (30) is postulated as a reversibly formed intermediate. N-Phenylketenimine (28) undergoes chemically activated free radical rearrangement to benzyl cyanide. The mechanistic interpretations are supported by calculations of the energies of key intermediates and transition states.

  19. Highly regio- and diastereoselective, acidic clay supported intramolecular nitrile oxide-alkene cycloaddition on D-ribose derived nitriles: an efficient synthetic route to isoxazoline fused five and six membered carbocycles.

    Science.gov (United States)

    Panda, Amarendra; Das, Sulagna; Pal, Shantanu

    2014-10-29

    An efficient synthetic route to isoxazoline fused carbocycles from carbohydrate scaffolds that comprise of free hydroxyl group(s) is described with high regio- and stereoselectivity. Montmorillonite K-10/chloramine T oxidation and in situ intramolecular nitrile oxide-alkene cycloaddition (INOC) of D-ribose derived oximes have been developed for the diversity oriented synthesis of isoxazoline fused five and six membered carbocycles. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. β-Isocyanoalanine as an IR probe: comparison of vibrational dynamics between isonitrile and nitrile-derivatized IR probes.

    Science.gov (United States)

    Maj, Michał; Ahn, Changwoo; Kossowska, Dorota; Park, Kwanghee; Kwak, Kyungwon; Han, Hogyu; Cho, Minhaeng

    2015-05-07

    An infrared (IR) probe based on isonitrile (NC)-derivatized alanine 1 was synthesized and the vibrational properties of its NC stretching mode were investigated using FTIR and femtosecond IR pump-probe spectroscopy. It is found that the NC stretching mode is very sensitive to the hydrogen-bonding ability of solvent molecules. Moreover, its transition dipole strength is larger than that of nitrile (CN) in nitrile-derivatized IR probe 2. The vibrational lifetime of the NC stretching mode is found to be 5.5 ± 0.2 ps in both D2O and DMF solvents, which is several times longer than that of the azido (N3) stretching mode in azido-derivatized IR probe 3. Altogether these properties suggest that the NC group can be a very promising sensing moiety of IR probes for studying the solvation structure and dynamics of biomolecules.

  1. Crystallization and preliminary X-ray characterization of the nitrile reductase QueF: a queuosine-biosynthesis enzyme

    International Nuclear Information System (INIS)

    Swairjo, Manal A.; Reddy, Robert R.; Lee, Bobby; Van Lanen, Steven G.; Brown, Shannon; Crécy-Lagard, Valérie de; Iwata-Reuyl, Dirk; Schimmel, Paul

    2005-01-01

    Structural informatics and modelling correctly predicted that substrate was required to obtain diffracting crystals of the first characterized nitrile oxidoreductase: the homododecameric QueF. QueF (MW = 19.4 kDa) is a recently characterized nitrile oxidoreductase which catalyzes the NADPH-dependent reduction of 7-cyano-7-deazaguanine (preQ 0 ) to 7-aminomethyl-7-deazaguanine, a late step in the biosynthesis of the modified tRNA nucleoside queuosine. Initial crystals of homododecameric Bacillus subtilis QueF diffracted poorly to 8.0 Å. A three-dimensional model based on homology with the tunnel-fold enzyme GTP cyclohydrolase I suggested catalysis at intersubunit interfaces and a potential role for substrate binding in quaternary structure stabilization. Guided by this insight, a second crystal form was grown that was strictly dependent on the presence of preQ 0 . This crystal form diffracted to 2.25 Å resolution

  2. Preparation and characterization of electrospun poly(phthalazinone ether nitrile ketone) membrane with novel thermally stable properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gang; Zhang, Hao; Qian, Bingqing [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Wang, Jinyan, E-mail: wangjinyan@dlut.edu.cn [Department of Polymer Science and Materials, Dalian University of Technology, Dalian 116024 (China); Jian, Xigao [Department of Polymer Science and Materials, Dalian University of Technology, Dalian 116024 (China); Qiu, Jieshan, E-mail: jqiu@dlut.edu.cn [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

    2015-10-01

    Highlights: • Poly (phthalazinone ether nitrile ketone) (PPENK) was used to successfully prepare nanofiber membranes by electrospinning. • Electrospun membrane exhibits a good thermostability. • Electrospun membrane. - Abstract: Electrospun nanofibrous membranes have several applications because of their excellent properties, such as high porosity, small fiber diameter, and large surface area. However, high-temperature resistant electrospun membranes remain a challenge because of the absence of precursors that offer spinnability, scalability, and superior thermal stability. In this study, poly(phthalazinone ether nitrile ketone) (PPENK) was used to successfully prepare nanofiber membranes by electrospinning. Electrospun PPENK membranes were characterized by scanning electron microscopy, differential scanning calorimetry, Fourier transform infrared spectroscopy, and tensile stress–strain tests. Results indicated that the prepared electrospun membranes had a very high glass transition temperature, superior chemical resistance, and excellent mechanical strength. These desirable properties broaden their potential application in membranes and treatment of various hot fluid streams without strict temperature control.

  3. Rational Design of Zirconium-doped Titania Photocatalysts with Synergistic Brønsted Acidity and Photoactivity.

    Science.gov (United States)

    Ma, Runyuan; Wang, Liang; Zhang, Bingsen; Yi, Xianfeng; Zheng, Anmin; Deng, Feng; Yan, Xuhua; Pan, Shuxiang; Wei, Xiao; Wang, Kai-Xue; Su, Dang Sheng; Xiao, Feng-Shou

    2016-10-06

    The preparation of photocatalysts with high activities under visible-light illumination is challenging. We report the rational design and construction of a zirconium-doped anatase catalyst (S-Zr-TiO 2 ) with Brønsted acidity and photoactivity as an efficient catalyst for the degradation of phenol under visible light. Electron microscopy images demonstrate that the zirconium sites are uniformly distributed on the sub-10 nm anatase crystals. UV-visible spectrometry indicates that the S-Zr-TiO 2 is a visible-light-responsive catalyst with narrower band gap than conventional anatase. Pyridine-adsorption infrared and acetone-adsorption 13 C NMR spectra confirm the presence of Brønsted acidic sites on the S-Zr-TiO 2 sample. Interestingly, the S-Zr-TiO 2 catalyst exhibits high catalytic activity in the degradation of phenol under visible-light illumination, owing to a synergistic effect of the Brønsted acidity and photoactivity. Importantly, the S-Zr-TiO 2 shows good recyclability. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Non-destructive lateral mapping of the thickness of the photoactive layer in polymer-based solar cells

    DEFF Research Database (Denmark)

    Sylvester-Hvid, Kristian O.; Tromholt, Thomas; Jørgensen, Mikkel

    2013-01-01

    Non-destructive lateral mapping of the thickness of the photoactive layer in poly(3-hexyl-thiophene) : 1-(3-methoxy-carbonyl)propyl-1-phenyl-(6,6)C61 (P3HT : PCBM) solar cells is demonstrated. The method employs a spatially resolved (XY) recording of ultraviolet-visible spectra in reflection...... geometry at normal incidence, using a dense raster defined by a circular probe spot of 800-µm diameter. The evaluation of the thickness of the photoactive layer at each raster point employs an algorithm-driven comparison of the measured absorption spectrum with spectral features, as compiled from......-coated float glass substrates. After this, two application examples for solar cells processed either by spin coating or slot die coating of the P3HT : PCBM layer follow. The spin-coated solar cells have glass as the substrate with the P3HT : PCBM spun at different spinning speeds. The slot die-coated solar...

  5. TiO{sub 2}/WO{sub 3} photoactive bilayers in the UV-Vis light region

    Energy Technology Data Exchange (ETDEWEB)

    Vasilaki, E. [University of Crete, Department of Chemistry, Heraklion, Crete (Greece); Technological Educational Institute of Crete, Center of Materials Technology and Photonics, School of Engineering, Heraklion, Crete (Greece); Vernardou, D. [Technological Educational Institute of Crete, Center of Materials Technology and Photonics, School of Engineering, Heraklion, Crete (Greece); Kenanakis, G.; Katsarakis, N. [Technological Educational Institute of Crete, Center of Materials Technology and Photonics, School of Engineering, Heraklion, Crete (Greece); Foundation for Research and Technology-Hellas, Institute of Electronic Structure and Laser, Vassilika Vouton, P.O. Box 1385, Heraklion, Crete (Greece); Vamvakaki, M. [Foundation for Research and Technology-Hellas, Institute of Electronic Structure and Laser, Vassilika Vouton, P.O. Box 1385, Heraklion, Crete (Greece); University of Crete, Department of Materials Science and Technology, Heraklion, Crete (Greece)

    2017-04-15

    In this work, photoactive bilayered films consisting of anatase TiO{sub 2} and monoclinic WO{sub 3} were synthesized by a sol-gel route. Titanium isopropoxide and tungsten hexachloride were used as metal precursors and deposition was achieved by spin-coating on Corning glass substrates. The samples were characterized by X-ray diffraction, photoluminescence, UV-Vis, and Raman spectroscopy, as well as field emission scanning electron microscopy. The prepared immobilized catalysts were tested for their photocatalytic performance by the decolorization of methylene blue in aqueous matrices, under UV-Vis light irradiation. The annealing process influenced the crystallinity of the bilayered films, while the concentration of the tungsten precursor solution and the position of the tungsten trioxide layer further affected their photocatalytic performance. In particular, the photocatalytic performance of the bilayered films was optimized at a concentration of 0.1 M of the WO{sub 3} precursor solution, when deposited as an overlying layer on TiO{sub 2} by two annealing steps (∝76% methylene blue decolorization in 300 min of irradiation versus ∝59% in the case of a bare TiO{sub 2} film). In general, the coupled layer catalysts exhibited superior photoactivity compared to that of bare TiO{sub 2} films with WO{sub 3} acting as an electron trap, resulting, therefore, in a more efficient electron-hole separation and inhibiting their recombination. (orig.)

  6. 1,3-Dipolar cycloadditions of ethoxycarbonyl-nitrile benzylimine and synthesis of ß-amino acids. Synthesis and reactions of ethyl 2-chloro-2-ethoxyacetate and 2-chloro-2-ethoxyacetylchloride

    DEFF Research Database (Denmark)

    Bach, K.K.; El-Seedi, H.R.; Jensen, H.M.

    1994-01-01

    The principles of 1,2-cyano-hydroxylation of olefins were applied to the preparation of 1,2-cyano-amines. The dipole component of this cycloaddition was nitrile imines, which formed pyrazolines with olefins. Ring cleavage was accomplished by thermolysis of 3-carboxypyrazolines, which gave 1,2-cyano-amines...... were carried out with the allylic ester - nitrile oxide and allylic ester - nitrile imine systems....

  7. Dramatic inversion of charge polarity in diketopyrrolopyrrole-based organic field-effect transistors via a simple nitrile group substitution.

    Science.gov (United States)

    Yun, Hui-Jun; Kang, Seok-Ju; Xu, Yong; Kim, Seul Ong; Kim, Yun-Hi; Noh, Yong-Young; Kwon, Soon-Ki

    2014-11-19

    A record-breaking high electron mobility of 7.0 cm(2) V(-1) s(-1) for n-channel polymer OFETs is reported. By the incorporation of only one nitrile group as an electron-withdrawing function in the vinyl linkage of the DPP-based copolymer, a dramatic inversion of majority charge-carriers from holes to electrons is achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Remote Stereoinductive Intramolecular Nitrile Oxide Cycloaddition: Asymmetric Total Synthesis and Structure Revision of (-)-11β-Hydroxycurvularin.

    Science.gov (United States)

    Choe, Hyeonjeong; Pham, Thuy Trang; Lee, Joo Yun; Latif, Muhammad; Park, Haeil; Kang, Young Kee; Lee, Jongkook

    2016-03-18

    The first total synthesis and structure revision of (-)-11β-hydroxycurvularin (1b), a macrolide possessing a β-hydroxyketone moiety, were accomplished. The β-hydroxyketone moiety in this natural product was introduced by cleavage of the N-O bond in an isoxazoline ring that was formed diastereoselectively in a 1,5-remote stereocontrolled fashion by employing intramolecular nitrile oxide cycloaddition.

  9. Chiral Cu(II-catalyzed enantioselective β-borylation of α,β-unsaturated nitriles in water

    Directory of Open Access Journals (Sweden)

    Lei Zhu

    2015-10-01

    Full Text Available The promising performance of copper(II complexes was demonstrated for asymmetric boron conjugate addition to α,β-unsaturated nitriles in water. The catalyst system, which consisted of Cu(OAc2 and a chiral 2,2′-bipyridine ligand, enabled β-borylation and chiral induction in water. Subsequent protonation, which was accelerated in aqueous medium, led to high activity of this asymmetric catalysis. Both solid and liquid substrates were suitable despite being insoluble in water.

  10. Photoactive Nitric Oxide Delivery Systems based on Metal Nitrosyl-Biomaterial Composites

    Science.gov (United States)

    Heilman, Brandon James

    Gaseous NO has been recognized as a potent antibiotic even against highly drug-resistant pathogens such as methicillin-resistant Staphylococcus aureus (MRSA) in both animal and human studies. However, difficulties in the delivery of the toxic (and reactive) gas demands innovative techniques to deliver NO in a controlled manner to malignant sites throughout the body. Metal nitrosyls reported by our group have demonstrated rapid NO release under the complete control of visible and NIR light. Careful incorporation of these photoactive nitrosyls into polymer matrices has afforded a set of nitrosyl-polymer composites in order to localize the NO-donors at a targeted site, ensure reliable NO release kinetics in vivo, and prevent potentially cytotoxic interactions of the metal nitrosyl or its reaction-products with the treatment site. The work presented in this thesis was pursued to derive clinically relevant NO-delivery systems and demonstrate their utility for the treatment of infection. In chapter 2, an NO-releasing polyurethane film (PUX-NO) is described with dispersed xerogel particles containing up to 3 mol% of [Mn(PaPy 3)(NO)](ClO4) entrapped in a silica matrix and swelled with excess moisture. The polyurethane based xerogel-nitrosyl (PUX-NO) films demonstrated rapid NO photorelease upon illumination with low-power visible light which was sufficient to eradicate clinically relevant loads (105 CFU mL-1 ) of several gram-positive and gram-negative pathogenic bacteria, including a strain of methicillin-resistant of S. aureus. The results of this study suggest that PUX-NO films are suitable for use as a NO-releasing occlusive film for the treatment of skin and soft-tissue infections or chronic, non-healing wounds. Since the NO-release rate from the films can be modulated by simple adjustment of the intensity of the light source, the films could be used to first clear the microbial burden from the wound site using high fluxes of NO, and then, provide a moderate

  11. Sulfonated poly(fluorenyl ether ketone nitrile) electrolyte membrane with high proton conductivity and low water uptake

    Energy Technology Data Exchange (ETDEWEB)

    Tian, S.H.; Wang, S.J.; Xiao, M.; Meng, Y.Z. [State Key Laboratory of Optoelectronic Materials and Technologies/Institute of Optoelectronic and Functional Composite Materials, Sun Yat-sen University, Guangzhou 510275 (China); Shu, D. [School of Chemistry and Environmental, South China Normal University, Guangzhou 510006 (China)

    2010-01-01

    High molecular weight sulfonated poly(fluorenyl ether ketone nitrile)s with different equivalent weight (EW) from 681 to 369 g mequiv.{sup -1} are synthesized by the nucleophilic substitution polycondensation of various amounts of sulfonated difluorobenzophenone (SDFBP) and 2,6-difluorobenzonitrile (DFBN) with bisphenol fluorene (BPF). The synthesized copolymers are characterized by {sup 1}H NMR, FT-IR, TGA, and DSC techniques. The membranes cast from the corresponding copolymers exhibit superior thermal stability, good oxidative stability and high proton conductivity, but low water uptake due to the strong nitrile dipole interchain interactions that combine to limit swelling. Among all the membranes, the membrane with EW of 441 g mequiv.{sup -1} shows optimum properties of both high proton conductivity of 41.9 mS cm{sup -1} and low water uptake of 42.6%. Accordingly, That membrane is fabricated into a membrane electrode assembly (MEA) and evaluated in a single proton exchange membrane fuel cell (PEMFC). The experimental results indicate its similar cell performance as that of Nafion {sup registered} 117 at 70 C, but much better cell performance at higher temperatures. At the potential of 0.6 V, the current density of fuel cell using the prepared membrane and Nafion {sup registered} 117 is 0.46 and 0.25 A cm{sup -2}, respectively. The highest current density of the former reaches as high as 1.25 A cm{sup -2}. (author)

  12. Light Activation of a Cysteine Protease Inhibitor: Caging of a Peptidomimetic Nitrile with RuII(bpy)2

    Science.gov (United States)

    Respondek, Tomasz; Garner, Robert N.; Herroon, Mackenzie K.; Podgorski, Izabela; Turro, Claudia; Kodanko, Jeremy J.

    2013-01-01

    A novel method for caging protease inhibitors is described. The complex [RuII(bpy)2(1)2](PF6)2 (2) was prepared from the nitrile-based peptidomimetic inhibitor Ac-Phe-NHCH2CN (1). 1H NMR, UV-vis and IR spectroscopic and mass spectrometric data confirm that two equiv of inhibitor 1 bind to RuII through the nitrile functional group. Complex 2 shows excellent stability in aqueous solution in the dark and fast release of 1 upon irradiation with visible light. Due to binding to the RuII center, the nitriles of complex 2 are caged, and 2 does not act as a potent enzyme inhibitor. However, when 2 is irradiated, it releases 1 that inhibits the cysteine proteases papain and cathepsins B, K and L, up to two times more potently than 1 alone. Ratios for IC50 values for 2 range from 6:1 to 33:1 under dark vs. light conditions, against isolated enzymes and in human cell lysates, confirming a high level of photoinduced enzyme inhibition is obtained with this method. PMID:21973207

  13. Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru − N ≡ C interface

    International Nuclear Information System (INIS)

    Zhang, Fengqi; Huang, Lin; Zou, Jiasui; Yan, Jinwu; Zhu, Jiaying; Kang, Xiongwu; Chen, Shaowei

    2017-01-01

    Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru−N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å 2 . Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm −1 upon adsorption on the nanoparticle surfaces, as confirmed by 15 N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal−organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

  14. Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

    Science.gov (United States)

    Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

    2012-01-14

    Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

  15. Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru − N ≡ C interface

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fengqi; Huang, Lin; Zou, Jiasui [South China University of Technology, New Energy Research Institute, School of Environment and Energy, Guangzhou Higher Education Mega Centre (China); Yan, Jinwu; Zhu, Jiaying [South China University of Technology, School of Bioscience and Bioengineering, Guangzhou Higher Education Mega Centre (China); Kang, Xiongwu, E-mail: esxkang@scut.edu.cn; Chen, Shaowei, E-mail: shaowei@ucsc.edu [South China University of Technology, New Energy Research Institute, School of Environment and Energy, Guangzhou Higher Education Mega Centre (China)

    2017-03-15

    Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru−N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å{sup 2}. Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm{sup −1} upon adsorption on the nanoparticle surfaces, as confirmed by {sup 15}N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal−organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

  16. Preliminary Study on Effect of Chemical Composition Alteration on Elastic Recovery and Stress Recovery of Nitrile Gloves

    Directory of Open Access Journals (Sweden)

    Tan Kai Yang

    2018-01-01

    Full Text Available Nitrile gloves are widely used in the medical and automobile field due to its superiority in hypo-allergic component and chemical resistance over natural latex gloves. However, poor elastic recovery of nitrile glove to compressive force also creates an aesthetic issue for customers with high levels of wrinkling after removing from glove box. This paper demonstrates the preliminary study on the varies chemical composition such as crosslinking agents, sulphur and zinc oxide, the accelerator agent added during curing process, and the rubber filler Titanium Dioxide, on the elastic recovery and stress relaxation in nitrile gloves manufacturing. These chemical were studied at different concentration level comparing the high and low level versus the normal production range. Due to the inconsistency in the analysis technique on the surface imaging, the elastic recovery result was unable to be quantified and was not conclusive at this point. The cross linking agents, sulphur and zinc oxide, and the accelerator agent, played a significant role in the mechanical strength of the gloves. Increment of these chemicals result in higher tensile strength, but a reduction in the elasticity of the materials in which causes a lesser elongation at break percentage for the gloves. Both cross-linkers demonstrate different behaviour where higher sulphur content, provide higher stress relaxation (SR% yet zinc oxide shows otherwise.

  17. The Effect of Donor and Nonfullerene Acceptor Inhomogeneous Distribution within the Photoactive Layer on the Performance of Polymer Solar Cells with Different Device Structures

    Directory of Open Access Journals (Sweden)

    Yaping Wang

    2017-11-01

    Full Text Available Due to the inhomogeneous distribution of donor and acceptor materials within the photoactive layer of bulk heterojunction organic solar cells (OSCs, proper selection of a conventional or an inverted device structure is crucial for effective exciton dissociation and charge transportation. Herein, we investigate the donor and acceptor distribution within the non-fullerene photoactive layer based on PBDTTT-ET:IEICO by time-of-flight secondary-ion mass spectroscopy (TOF-SIMS and scanning Kelvin probe microscopy (SKPM, indicating that more IEICO enriches on the surface of the photoactive layer while PBDTTT-ET distributes homogeneously within the photoactive layer. To further understand the effect of the inhomogeneous component distribution on the photovoltaic performance, both conventional and inverted OSCs were fabricated. As a result, the conventional device shows a power conversion efficiency (PCE of 8.83% which is 41% higher than that of inverted one (6.26%. Eventually, we employed nickel oxide (NiOx instead of PEDOT:PSS as anode buffer layer to further enhance the stability and PCE of OSCs with conventional structure, and a promising PCE of 9.12% is achieved.

  18. Identification of semicarbazones, thiosemicarbazones and triazine nitriles as inhibitors of Leishmania mexicana cysteine protease CPB.

    Directory of Open Access Journals (Sweden)

    Jörg Schröder

    Full Text Available Cysteine proteases of the papain superfamily are present in nearly all eukaryotes. They play pivotal roles in the biology of parasites and inhibition of cysteine proteases is emerging as an important strategy to combat parasitic diseases such as sleeping sickness, Chagas' disease and leishmaniasis. Homology modeling of the mature Leishmania mexicana cysteine protease CPB2.8 suggested that it differs significantly from bovine cathepsin B and thus could be a good drug target. High throughput screening of a compound library against this enzyme and bovine cathepsin B in a counter assay identified four novel inhibitors, containing the warhead-types semicarbazone, thiosemicarbazone and triazine nitrile, that can be used as leads for antiparasite drug design. Covalent docking experiments confirmed the SARs of these lead compounds in an effort to understand the structural elements required for specific inhibition of CPB2.8. This study has provided starting points for the design of selective and highly potent inhibitors of L. mexicana cysteine protease CPB that may also have useful efficacy against other important cysteine proteases.

  19. Ionic elastomers based on carboxylated nitrile rubber (XNBR and magnesium aluminum layered double hydroxide (hydrotalcite

    Directory of Open Access Journals (Sweden)

    A. Laskowska

    2014-06-01

    Full Text Available The presence of carboxyl groups in carboxylated nitrile butadiene rubber (XNBR allows it to be cured with different agents. This study considers the effect of crosslinking of XNBR by magnesium aluminum layered double hydroxide (MgAl-LDH, known also as hydrotalcite (HT, on rheometric, mechano-dynamical and barrier properties. Results of XNBR/HT composites containing various HT loadings without conventional curatives are compared with XNBR compound crosslinked with commonly used zinc oxide. Hydrotalcite acts as an effective crosslinking agent for XNBR, as is particularly evident from rheometric and Fourier transform infrared spectroscopy (FTIR studies. The existence of ionic crosslinks was also detected by dynamic mechanical analysis (DMA of the resulting composites. DMA studies revealed that the XNBR/HT composites exhibited two transitions – one occurring at low temperature is associated to the Tg of elastomer and the second at high temperature corresponds to the ionic transition temperature Ti. Simultaneous application of HT as a curing agent and a filler may deliver not only environmentally friendly, zinc oxide-free rubber product but also ionic elastomer composite with excellent mechanical, barrier and transparent properties.

  20. Sound Absorption Properties Of Single-Hole Hollow Polyester Fiber Reinforced Hydrogenated Carboxyl Nitrile Rubber Composites

    Directory of Open Access Journals (Sweden)

    Jie Hong

    2017-09-01

    Full Text Available A series of single-hole hollow polyester fiber (SHHPF reinforced hydrogenated carboxyl nitrile rubber (HXNBR composites were fabricated. In this study, the sound absorption property of the HXNBR/SHHPF composite was tested in an impedance tube, the composite morphology was characterized by scanning electron microscope (SEM, and the tensile mechanical property was measured by strength tester. The results demonstrated that a remarkable change in sound absorption can be observed by increasing the SHHPF content from 0% to 40%. In the composite with 40% SHHPF in 1 mm thickness, the sound absorption coefficient reached 0.671 at 2,500 Hz; the effective bandwidth was 1,800-2,500 Hz for sound absorption coefficient larger than 0.2. But the sound absorption property of the composite deteriorated when the SHHPF content increased to 50% in 1 mm thickness. While with 20% SHHPF proportion, the sound absorption property was improved by increasing the thickness of composites from 1 to 5 mm. Compared with the pure HXNBR of the same thickness, the tensile mechanical property of the composite improved significantly by increasing the SHHPF proportion. As a lightweight composite with excellent sound absorption property, the HXNBR/SHHPF composite has potential practical application value in the fields of engineering.

  1. Influence Of Gamma Irradiation On Mechanical And Thermal Properties Of Waste Polyethylene / Nitrile Butadiene Rubber Blend

    International Nuclear Information System (INIS)

    Aly, R.O.

    2012-01-01

    Gamma irradiation radical-radical interaction crosslinking of elastomers and thermoplastic is a special type of crosslinking technique that has gained importance over conventional chemical crosslinking method as process is fast, pollution free and simple. In this study, a blend polymer, based on waste polyethylene and nitrile butadiene rubber, has been irradiated with gamma rays then mechanically and thermally investigated at varying NBR content. FTIR and SEM techniques were used in addition to the swelling behaviour by toluene solvent to emphasize the blend formation. The mechanical properties like tensile strength, elongation at break and modulus at different elongations were studied and compared with those of non-irradiated ones. A relatively low radiation dose was found effective in improving the level of mechanical properties. Differential scanning calorimeter and thermogravimetric analysis were used to study the thermal characteristics of the irradiated polymer. Enhancement in thermal stability has been observed for higher NBR containing blends and via radiation-induced crosslinking up to ≅ 50 kGy

  2. Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide

    Directory of Open Access Journals (Sweden)

    Rui Zhong

    2018-05-01

    Full Text Available Graphene oxide (GO, modified with anti-aging agent p-phenylenediamine (PPD, was added into nitrile rubber (NBR in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR, Raman, and X-ray diffraction (XRD. Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA show an increased storage modulus (G’ and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG and differential scanning calorimetry (DSC. Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn–Wall–Ozawa (FWO equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO–PPD. In addition, mechanical properties (tensile strength and elongation at break of both before and after aged NBR/GO–PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

  3. Effect of Graphene Oxide on Anti-aging Property of Nitrile Butadiene Rubber

    Directory of Open Access Journals (Sweden)

    ZHANG Lin

    2017-03-01

    Full Text Available The blends with higher damping performance was prepared based on nitrile butadiene rubber(NBR with addition of graphene oxide(GO and modified graphene oxide(MGO prepared by improved Hammer method. Meanwhile, the damping property and the anti-aging property of the blends were investigated by DMA, AFM, SEM and so forth. The results show that after the addition of the GO and MGO, the tangent of loss angle(tanδ increases and also the anti-aging property is improved. When adding less amount of GO in the matrix, the anti-aging property is better; when adding MGO in the matrix, the amount of addition is not obviously related with the anti-aging property of the blends. The dispersion of GO and MGO has positive correlation with its anti-aging property. By microscopic analysis, the main reason for the decrease of anti-aging property of the blends is the agglomeration of the GO. The interface effect formed by the addition of MGO and GO is the main reason for its high damping property and anti-aging property.

  4. Swelling and tribological properties of melt-mixed fluoroelastomer/nitrile rubber blends under crude oil

    Science.gov (United States)

    Tagelsir, Yasin; Li, San-Xi; Lv, Xiaoren; Wang, Shijie; Wang, Song; Osman, Zeinab

    2018-01-01

    The melt-mixed fluoroelastomer (FKM)/ nitrile rubber (NBR) blends of (90/10, 80/20, 70/30, 60/40 and 50/50) ratios with same hardness were prepared, and their swelling and tribological properties under crude oil were investigated for the purpose of developing high performance cost-effective elastomers meeting requirement of oil extraction progressive cavity pump stator. Differential scanning calorimetry confirmed compatible blend system for all blends. Field emission scanning electron microscopy (FE-SEM) showed co-continuous morphology of 200-400 nm phase size for all blends, expect FKM/NBR (90/10) which exhibited partially continuous phase morphology of 100-250 nm phase size. The results of swelling and linear wear tests under crude oil indicated that swelling percentage, coefficient of friction and specific wear rate of FKM/NBR blends were much better than NBR, with FKM/NBR (90/10 and 80/20) showing swelling percentage and specific wear rate very close to FKM. Attenuated total reflectance-Fourier transform infrared spectroscopy disclosed that fracture of macromolecular chains was the main mechanochemical effect of unswollen and swollen worn surfaces, in addition to oxygenated degradation detected with increasing NBR ratio in the blends. The fracture of macromolecular chains resulted in slight fatigue wear mechanism, which was also confirmed by FE-SEM of the worn surfaces.

  5. Predicting the solubility of gases in Nitrile Butadiene Rubber in extreme conditions using molecular simulation

    Science.gov (United States)

    Khawaja, Musab; Molinari, Nicola; Sutton, Adrian; Mostofi, Arash

    In the oil and gas industry, elastomer seals play an important role in protecting sensitive monitoring equipment from contamination by gases - a problem that is exacerbated by the high pressures and temperatures found down-hole. The ability to predict and prevent such permeative failure has proved elusive to-date. Nitrile butadiene rubber (NBR) is a common choice of elastomer for seals due to its resistance to heat and fuels. In the conditions found in the well it readily absorbs small molecular weight gases. How this behaviour changes quantitatively for different gases as a function of temperature and pressure is not well-understood. In this work a series of fully atomistic simulations are performed to understand the effect of extreme conditions on gas solubility in NBR. Widom particle insertion is used to compute solubilities. The importance of sampling and allowing structural relaxation upon compression are highlighted, and qualitatively reasonable trends reproduced. Finally, while at STP it has previously been shown that the solubility of CO2 is higher than that of He in NBR, we observe that under the right circumstances it is possible to reverse this trend.

  6. Advanced Booster Composite Case/Polybenzimidazole Nitrile Butadiene Rubber Insulation Development

    Science.gov (United States)

    Gentz, Steve; Taylor, Robert; Nettles, Mindy

    2015-01-01

    The NASA Engineering and Safety Center (NESC) was requested to examine processing sensitivities (e.g., cure temperature control/variance, debonds, density variations) of polybenzimidazole nitrile butadiene rubber (PBI-NBR) insulation, case fiber, and resin systems and to evaluate nondestructive evaluation (NDE) and damage tolerance methods/models required to support human-rated composite motor cases. The proposed use of composite motor cases in Blocks IA and II was expected to increase performance capability through optimizing operating pressure and increasing propellant mass fraction. This assessment was to support the evaluation of risk reduction for large booster component development/fabrication, NDE of low mass-to-strength ratio material structures, and solid booster propellant formulation as requested in the Space Launch System NASA Research Announcement for Advanced Booster Engineering Demonstration and/or Risk Reduction. Composite case materials and high-energy propellants represent an enabling capability in the Agency's ability to provide affordable, high-performing advanced booster concepts. The NESC team was requested to provide an assessment of co- and multiple-cure processing of composite case and PBI-NBR insulation materials and evaluation of high-energy propellant formulations.

  7. Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide.

    Science.gov (United States)

    Zhong, Rui; Zhang, Zhao; Zhao, Hongguo; He, Xianru; Wang, Xin; Zhang, Rui

    2018-05-30

    Graphene oxide (GO), modified with anti-aging agent p -phenylenediamine (PPD), was added into nitrile rubber (NBR) in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR), Raman, and X-ray diffraction (XRD). Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA) show an increased storage modulus (G') and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn⁻Wall⁻Ozawa (FWO) equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO⁻PPD. In addition, mechanical properties (tensile strength and elongation at break) of both before and after aged NBR/GO⁻PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

  8. Natural rubber/nitrile butadiene rubber/hindered phenol composites with high-damping properties

    Directory of Open Access Journals (Sweden)

    Xiuying Zhao

    2015-10-01

    Full Text Available New natural rubber (NR/nitrile butadiene rubber (NBR/hindered phenol (AO-80 composites with high-damping properties were prepared in this study. The morphological, structural, and mechanical properties were characterized by atomic force microscopy (AFM, polarized Fourier transform infrared spectrometer (FTIR, dynamic mechanical thermal analyzer (DMTA, and a tensile tester. Each composite consisted of two phases: the NR phase and the NBR/AO-80 phase. There was partial compatibility between the NR phase and the NBR/AO-80 phase, and the NR/NBR/AO-80 (50/50/20 composite exhibited a co-continuous morphology. Strain-induced crystallization occurred in the NR phase at strains higher than 200%, and strain-induced orientation appeared in the NBR/AO-80 phase with the increase of strain from 100% to 500%. The composites had a special stress–strain behavior and mechanical properties because of the simultaneous strain-induced orientation and strain-induced crystallization. In the working temperature range of a seismic isolation bearing, the composites (especially the NR/NBR/AO-80 (50/50/20 composite presented a high loss factor, high area of loss peak (TA, and high hysteresis energy. Therefore, the NR/NBR/AO-80 rubber composites are expected to have important application as a high-performance damping material for rubber bearing.

  9. Tribological properties and morphology of bimodal elastomeric nitrile butadiene rubber networks

    International Nuclear Information System (INIS)

    Guo, Yin; Wang, Jiaxu; Li, Kang; Ding, Xingwu

    2013-01-01

    Highlights: • Bimodal elastomeric NBR as a new material was developed. • The structure of bimodal elastomeric NBR networks was determined. • The relationship between structure and mechanical properties was investigated. • The tribological properties and mechanisms of bimodal NBR were analyzed. • The benefits of bimodal NBR in the field of tribology were discussed. - Abstract: Bimodal nitrile butadiene rubber (NBR) was examined in this study. The molecular structure was determined by dynamic mechanical analysis and transmission electron microscopy. The relationship between the structure and the mechanical properties related to elastomeric tribological properties was investigated. The properties and the mechanisms of friction and wear of bimodal elastomeric NBR networks were also analyzed. The lubricating characteristics of bimodal NBR networks were revealed based on the mechanisms of friction and wear. Results show that bimodal NBR networks are similar to bimodal polydimethylsiloxane networks. The form and density of the network structure can be controlled from elastomeric networks to thermosetting resin networks. The mechanical properties of bimodal NBR networks, such as elasticity, elongation at break, fatigue characteristic, tensile strength, elastic modulus, and thermal stability can be precisely controlled following the variation in network structure. The friction, wear, and lubrication of bimodal NBR networks can be clearly described according to the principles of tribology. Common elastomers cannot simultaneously reduce friction and wear because of the different mechanisms of friction and wear; however, bimodal elastomer networks can efficiently address this problem

  10. Could nitrile derivatives of turnip (Brassica rapa) glucosinolates be hepato- or cholangiotoxic in cattle?

    Science.gov (United States)

    Collett, Mark G; Stegelmeier, Bryan L; Tapper, Brian A

    2014-07-30

    Turnip (Brassica rapa ssp. rapa) and rape (Brassica napus ssp. biennis) and other brassica forage crops are regarded as "safe" feed for cattle during late summer and fall in the North Island of New Zealand when high Pithomyces chartarum spore counts in pastures frequently lead to sporidesmin toxicity (facial eczema). Sporadic acute severe cases of turnip photosensitization in dairy cows characteristically exhibit high γ-glutamyl transferase and glutamate dehydrogenase serum enzyme activities that mimic those seen in facial eczema. The two diseases can, however, be distinguished by histopathology of the liver, where lesions, in particular those affecting small bile ducts, differ. To date, the hepato-/cholangiotoxic phytochemical causing liver damage in turnip photosensitization in cattle is unknown. Of the hydrolysis products of the various glucosinolate secondary compounds found in high concentrations in turnip and rape, work has shown that nitriles and epithionitriles can be hepatotoxic (and nephro- or pancreatotoxic) in rats. These derivatives include β-hydroxy-thiiranepropanenitrile and 3-hydroxy-4-pentenenitrile from progoitrin; thiiranepropanenitrile and 4-pentenenitrile from gluconapin; thiiranebutanenitrile and 5-hexenenitrile from glucobrassicanapin; phenyl-3-propanenitrile from gluconasturtiin; and indole-3-acetonitrile from glucobrassicin. This perspective explores the possibility of the preferential formation of such derivatives, especially the epithionitriles, in acidic conditions in the bovine rumen, followed by absorption, hepatotoxicity, and secondary photosensitization.

  11. Nifurtimox Activation by Trypanosomal Type I Nitroreductases Generates Cytotoxic Nitrile Metabolites*

    Science.gov (United States)

    Hall, Belinda S.; Bot, Christopher; Wilkinson, Shane R.

    2011-01-01

    The prodrug nifurtimox has been used for more than 40 years to treat Chagas disease and forms part of a recently approved combinational therapy that targets West African trypanosomiasis. Despite this, its mode of action is poorly understood. Detection of reactive oxygen and nitrogen intermediates in nifurtimox-treated extracts led to the proposal that this drug induces oxidative stress in the target cell. Here, we outline an alternative mechanism involving reductive activation by a eukaryotic type I nitroreductase. Several enzymes proposed to metabolize nifurtimox, including prostaglandin F2α synthase and cytochrome P450 reductase, were overexpressed in bloodstream-form Trypanosoma brucei. Only cells with elevated levels of the nitroreductase displayed altered susceptibility to this nitrofuran, implying a key role in drug action. Reduction of nifurtimox by this enzyme was shown to be insensitive to oxygen and yields a product characterized by LC/MS as an unsaturated open-chain nitrile. This metabolite was shown to inhibit both parasite and mammalian cell growth at equivalent concentrations, in marked contrast to the parental prodrug. These experiments indicate that the basis for the selectivity of nifurtimox against T. brucei lies in the expression of a parasite-encoded type I nitroreductase. PMID:21345801

  12. Permeation of limonene through disposable nitrile gloves using a dextrous robot hand.

    Science.gov (United States)

    Banaee, Sean; S Que Hee, Shane

    2017-03-28

    The purpose of this study was to investigate the permeation of the low-volatile solvent limonene through different disposable, unlined, unsupported, nitrile exam whole gloves (blue, purple, sterling, and lavender, from Kimberly-Clark). This study utilized a moving and static dextrous robot hand as part of a novel dynamic permeation system that allowed sampling at specific times. Quantitation of limonene in samples was based on capillary gas chromatography-mass spectrometry and the internal standard method (4-bromophenol). The average post-permeation thicknesses (before reconditioning) for all gloves for both the moving and static hand were more than 10% of the pre-permeation ones (P≤0.05), although this was not so on reconditioning. The standardized breakthrough times and steady-state permeation periods were similar for the blue, purple, and sterling gloves. Both methods had similar sensitivity. The lavender glove showed a higher permeation rate (0.490±0.031 μg/cm 2 /min) for the moving robotic hand compared to the non-moving hand (P≤0.05), this being ascribed to a thickness threshold. Permeation parameters for the static and dynamic robot hand models indicate that both methods have similar sensitivity in detecting the analyte during permeation and the blue, purple, and sterling gloves behave similarly during the permeation process whether moving or non-moving.

  13. Synthesis of new α-amino nitriles with insecticidal action on Aedes aegypti (Diptera: Culicidae

    Directory of Open Access Journals (Sweden)

    Andrés G. Rueda

    2018-04-01

    Full Text Available Aedes aegypti is the principal vector of arboviral pathogens that may cause diseases as dengue fever, chikungunya and zika. The harmful environmental effects of commercial pesticides coalesced with the development of insecticide-resistant populations encourage the discovery and generation of new alternative products as a tool to reduce the incidence of vector-borne diseases. In this work, through the classic three component Strecker reaction of commercial benzaldehydes, cyclic secondary amines and KCN, a new series of nine α-amino nitriles, girgensohnine analogs, has been synthetized and screened for larvicide and adulticide properties against A. aegypti, one of the dominant vectors of dengue, chikungunya and zika in tropical and subtropical areas all over the world. Molecules 3 and 4 were identified as potential larvicidal agents with LC50 values of 50.55 and 69.59 ppm, respectively. Molecule 3 showed 100% of mortality after 2 h of treatment when a concentration of 30 ppm in adulticidal assays was evaluated. Additionally, in order to elucidate the mode of action of these molecules, their acetylcholinesterase (AChE inhibitory properties were evaluated using the Ellman assay. It was found that the molecules possess a weak AChE inhibitory activity with IC50 values between 148.80 and 259.40 μM, indicating that AChE could not be a principal target for insecticide activity. Keywords: Arthropod-borne diseases, Girgensohnine analogs, Strecker reaction, Insecticidal activity, Vector control

  14. Effect of Nanoclay on Mechanical Properties and Ablation Behavior of a Nitrile-Based Heat Insulator

    Directory of Open Access Journals (Sweden)

    Fatemeh Arabgol

    2013-02-01

    Full Text Available Thermal insulation of rocket motor chamber is one of the most important functions of elastomeric ablative material. Combustion of solid rocket motor propellant produces turbulent media containing gases with a velocity more than 1000 m/s, temperature and pressure more than 3000°C and 10 MPa, respectively,which destroys all metallic alloys. Elastomeric nanocomposite heat insulators are more attractive subjects in comparison to their non-elastomeric counterparts, due to their excellent thermal stresses and larger deformation bearing capacity. Nitrile rubber with high thermal properties is a proper candidate in such applications. Development in ablation performance of these heat shields is considered as an important challenge nowadays. A few works have been recently carried out using organoclay to enhancethe ablation and mechanical properties of heat insulators. In this work, an elastomeric heat insulator with superior ablative and mechanical properties was presented using nanotechnology. The results showed that an elastomeric nanocomposite heat insulator containing 15 wt% organoclay exhibits superior characteristics compared to its composite counterpart such as: 46% more tensile strength, 60% more elongationat-break, 1.7 times higher modulus (at 100% strain, 62% higher “insulating index number” and 36% lower mass ablation and erosion rates under a standard test with a heat flux of 2500 kW/m2 for 15 s.

  15. Permeation of limonene through disposable nitrile gloves using a dextrous robot hand

    Science.gov (United States)

    Banaee, Sean; S Que Hee, Shane

    2017-01-01

    Objectives: The purpose of this study was to investigate the permeation of the low-volatile solvent limonene through different disposable, unlined, unsupported, nitrile exam whole gloves (blue, purple, sterling, and lavender, from Kimberly-Clark). Methods: This study utilized a moving and static dextrous robot hand as part of a novel dynamic permeation system that allowed sampling at specific times. Quantitation of limonene in samples was based on capillary gas chromatography-mass spectrometry and the internal standard method (4-bromophenol). Results: The average post-permeation thicknesses (before reconditioning) for all gloves for both the moving and static hand were more than 10% of the pre-permeation ones (P≤0.05), although this was not so on reconditioning. The standardized breakthrough times and steady-state permeation periods were similar for the blue, purple, and sterling gloves. Both methods had similar sensitivity. The lavender glove showed a higher permeation rate (0.490±0.031 μg/cm2/min) for the moving robotic hand compared to the non-moving hand (P≤0.05), this being ascribed to a thickness threshold. Conclusions: Permeation parameters for the static and dynamic robot hand models indicate that both methods have similar sensitivity in detecting the analyte during permeation and the blue, purple, and sterling gloves behave similarly during the permeation process whether moving or non-moving. PMID:28111415

  16. P3HT:PCBM Incorporated with Silicon Nanoparticles as Photoactive Layer in Efficient Organic Photovoltaic Devices

    Directory of Open Access Journals (Sweden)

    Shang-Chou Chang

    2013-01-01

    Full Text Available Silicon nanoparticles doped poly(3-hexylthiophene and [6,6]-phenyl C61-butyric acid methyl ester blends (P3HT:PCBM: Si NP have been produced as the photoactive layer of organic photovoltaic devices (OPVs. The silicon nanoparticles’ size is between 80 and 100 nm checked by transmission electron microscope (TEM. The 0.35 wt% Si NP doping OPVs exhibit higher power conversion efficiency (PCE than other OPVs. The PCE of the OPVs increases from 3.01% to 3.38% mainly due to increasing short-circuit current density from 8.38 to 9.48 mA/cm2, while the open-circuit voltage remains the same. The Si NP can provide extra exciton separation and electron pathways in hybrid solar cells.

  17. Effect of nitrogen doping on wetting and photoactive properties of laser processed zinc oxide-graphene oxide nanocomposite layers

    Energy Technology Data Exchange (ETDEWEB)

    György, E., E-mail: egyorgy@icmab.es [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Barcelona (CSIC-ICMAB), Campus UAB, 08193 Bellaterra (Spain); National Institute for Lasers, Plasma and Radiation Physics, P. O. Box MG 36, 76900 Bucharest V (Romania); Pérez del Pino, A. [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Barcelona (CSIC-ICMAB), Campus UAB, 08193 Bellaterra (Spain); Logofatu, C. [National Institute for Materials Physics, P. O. Box MG. 7, 77125 Bucharest (Romania); Duta, A.; Isac, L. [Transilvania University of Brasov, Research Centre for Renewable Energy Systems and Recycling, Eroilor 29, 500036, Brasov (Romania)

    2014-07-14

    Zinc oxide-graphene oxide nanocomposite layers were submitted to laser irradiation in air or controlled nitrogen atmosphere using a frequency quadrupled Nd:YAG (λ = 266 nm, τ{sub FWHM} ≅ 3 ns, ν = 10 Hz) laser source. The experiments were performed in air at atmospheric pressure or in nitrogen at a pressure of 2 × 10{sup 4} Pa. The effect of the irradiation conditions, incident laser fluence value, and number of subsequent laser pulses on the surface morphology of the composite material was systematically investigated. The obtained results reveal that nitrogen incorporation improves significantly the wetting and photoactive properties of the laser processed layers. The kinetics of water contact angle variation when the samples are submitted to laser irradiation in nitrogen are faster than that of the samples irradiated in air, the surfaces becoming super-hydrophilic under UV light irradiation.

  18. Enhancement in light harvesting ability of photoactive layer P3HT: PCBM using CuO nanoparticles

    Science.gov (United States)

    Tiwari, D. C.; Dwivedi, Shailendra Kumar; Dipak, Pukhrambam; Chandel, Tarun

    2018-05-01

    In this paper, we have synthesized CuO nanoparticles via precipitation method and incorporated CuO nanoparticles in the P3HT-poly (3-hexyl) thiophene: PCBM-[6, 6]-phenyl-C61-butyric acid methyl ester heterogeneous blend. The ratio of P3HT to CuO in the blend was varied, while maintaining the fixed ratio of PCBM. The UV-visible absorption spectra of P3HT: PCBM photoactive layer containing different weight percentages of CuO nanoparticles showed a clear enhancement in the photo absorption of the active layer. The absorption band starts from 310 nm to 750 nm for P3HT: CuO (NPs):PCBM (0.5:0.5:1). This shows that incorporation of CuO nanoparticles leads to larger absorption band. In addition, the X-ray diffraction (XRD) shows improvement in P3HT crystallinity and the better formation of CuO nanostructures.

  19. Direct in situ activation of Ag0 nanoparticles in synthesis of Ag/TiO2 and its photoactivity

    International Nuclear Information System (INIS)

    Jaafar, N.F.; Jalil, A.A.; Triwahyono, S.; Efendi, J.; Mukti, R.R.; Jusoh, R.; Jusoh, N.W.C.; Karim, A.H.; Salleh, N.F.M.; Suendo, V.

    2015-01-01

    Graphical abstract: - Highlights: • Ag 0 loaded on TiO 2 was prepared by a direct in situ electrochemical method. • 5 wt% Ag–TiO 2 demonstrated the best photocatalytic degradation of 2-CP. • Isomorphous substitution of Ag with Ti occurred to form Ti−O−Ag bonds. • Ag 0 and oxygen vacancies trapped electrons to enhance e–H + separation. • Substitution of Ag in the TiO 2 structure decreased the number of oxygen vacancies. - Abstract: Metallic Ag nanoparticles (Ag 0 ) were successfully activated using a direct in situ electrochemical method before being supported on TiO 2 . Catalytic testing showed that 5 wt% Ag–TiO 2 gave the highest photodegradation (94%) of 50 mg L −1 2-chlorophenol (2-CP) at pH 5 using 0.375 g L −1 catalyst within 6 h, while under similar conditions, 1 wt% and 10 wt% Ag–TiO 2 only gave 75% and 78% degradation, respectively. Characterization results illustrated that the photoactivity was affected by the amount of Ag 0 and oxygen vacancies which act as an electrons trap to enhance the electron–hole separation. While, the Ag−O−Ti bonds formation reduced the photoactivity. The degradation followed a pseudo-first order Langmuir–Hinshelwood model where adsorption was the controlling step. Study on the effect of scavengers showed that the hole (H + ) and hydroxyl radical (OH·) play important roles in the photodegradation. The regenerated photocatalyst was still stable after five cycling runs

  20. Enhanced the hydrophobic surface and the photo-activity of TiO2-SiO2 composites

    Science.gov (United States)

    Wahyuni, S.; Prasetya, A. T.

    2017-02-01

    The aim of this research is to develop nanomaterials for coating applications. This research studied the effect of various TiO2-SiO2 composites in acrylic paint to enhance the hydrophobic properties of the substrate. Titanium dioxide containing silica in the range 20-35 mol% has been synthesized using sol-gel route. The XRD’s spectra show that increasing SiO2 content in the composite, decreasing its crystalline properties but increasing the surface area. TiO2-SiO2 composite was dispersed in acrylic paint in 2% composition by weight. The largest contact angle was 70, which produced by the substrate coated with TS-35-modified acrylic paint. This study also investigated the enhanced photo-activity of TiO2-SiO2 modified with poly-aniline. The XRD spectra show that the treatment does not change the crystal structure of TiO2. The photo-activity of the composite was evaluated by degradation of Rhodamine-B with visible light. The best performance of the degradation process was handled by the composite treated with 0.1mL anilines per gram of TiO2-SiO2 composite (TSP-A). On the other side, the contact angle 70 has not shown an excellent hydrophobic activity. However, the AFM spectra showed that nanoroughness has started to form on the surface of acrylic paint modified with TiO2-SiO2 than acrylic alone.

  1. Controlled Deposition and Performance Optimization of Perovskite Solar Cells Using Ultrasonic Spray-Coating of Photoactive Layers.

    Science.gov (United States)

    Chang, Wei-Chieh; Lan, Ding-Hung; Lee, Kun-Mu; Wang, Xiao-Feng; Liu, Cheng-Liang

    2017-04-10

    This study investigated a new film-deposition technique, ultrasonic spray-coating, for use in the production of a photoactive layer of perovskite solar cells. Stable atomization and facile fabrication of perovskite thin films by ultrasonic spray-coating were achieved in a one-step method through manipulating the ink formulation (e.g., solution concentration, precursor composition, and mixing solvent ratio) and the drying kinetics (e.g., post-annealing temperature). The performance of the perovskite solar cells was mainly influenced by the intrinsic film morphology and crystalline orientation of the deposited perovskite layer. By suitable optimization of the spreading and drying conditions of the ink, ultrasonic spray-coated perovskite photovoltaic devices were obtained with a maximum power conversion efficiency of 11.30 %, a fill factor of 73.6 %, a short-circuit current of 19.7 mA cm -1 , and an open-circuit voltage of 0.78 V, respectively. Notably, the average power efficiency reached above 10 %, attributed to the large flower-like perovskite crystal with orientation along the (1 1 2)/(2 0 0) and (2 2 4)/(4 0 0) directions. Thus, the ultrasonic spray-coating method for perovskite photoactive layers, combining advantages of good photovoltaic performance results and benefits from cost and processing, has the potential for large-scale commercial production. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Aging-Resistant Functionalized LDH⁻SAS/Nitrile-Butadiene Rubber Composites: Preparation and Study of Aging Kinetics/Anti-Aging Mechanism.

    Science.gov (United States)

    Li, Tianxiang; Shi, Zhengren; He, Xianru; Jiang, Ping; Lu, Xiaobin; Zhang, Rui; Wang, Xin

    2018-05-18

    With the aim of improving the anti-aging properties of nitrile-butadiene rubber (NBR), a functional organic filler, namely LDH⁻SAS, prepared by intercalating 4-amino-benzenesulfonic acid monosodium salt (SAS) into layered double hydroxides (LDHs) through anion exchange, was added to nitrile-butadiene rubber (NBR), giving the NBR/LDH⁻SAS composites. Successful preparation of LDH⁻SAS was confirmed by XRD, TGA and FTIR. LDH⁻SAS was well dispersed in the NBR matrix, owing to its strong interaction with the nitrile group of NBR. The obtained NBR/LDH⁻SAS composites exhibited excellent thermo-oxidative aging resistance as shown by TGA-DSC. Further investigation by ATR-FTIR indicated that SAS can capture the radical groups, even during the aging process, which largely accounts for the improved aging resistance.

  3. Aging-Resistant Functionalized LDH–SAS/Nitrile-Butadiene Rubber Composites: Preparation and Study of Aging Kinetics/Anti-Aging Mechanism

    Science.gov (United States)

    Li, Tianxiang; Shi, Zhengren; He, Xianru; Jiang, Ping; Lu, Xiaobin; Zhang, Rui

    2018-01-01

    With the aim of improving the anti-aging properties of nitrile-butadiene rubber (NBR), a functional organic filler, namely LDH–SAS, prepared by intercalating 4-amino-benzenesulfonic acid monosodium salt (SAS) into layered double hydroxides (LDHs) through anion exchange, was added to nitrile-butadiene rubber (NBR), giving the NBR/LDH–SAS composites. Successful preparation of LDH–SAS was confirmed by XRD, TGA and FTIR. LDH–SAS was well dispersed in the NBR matrix, owing to its strong interaction with the nitrile group of NBR. The obtained NBR/LDH–SAS composites exhibited excellent thermo-oxidative aging resistance as shown by TGA-DSC. Further investigation by ATR-FTIR indicated that SAS can capture the radical groups, even during the aging process, which largely accounts for the improved aging resistance. PMID:29783656

  4. Cloning, purification, crystallization and preliminary X-ray diffraction analysis of nitrile hydratase from the themophilic Bacillus smithii SC-J05-1

    International Nuclear Information System (INIS)

    Hourai, Shinji; Ishii, Takeshi; Miki, Misao; Takashima, Yoshiki; Mitsuda, Satoshi; Yanagi, Kazunori

    2005-01-01

    The nitrile hydratase from the themophilic B. smithii SC-J05-1 (Bs NHase) has been purified, cloned and crystallized. Nitrile hydratase (NHase) converts nitriles to the corresponding amides and is recognized as having important industrial applications. Purification, cloning, crystallization and initial crystallographic studies of the NHase from Bacillus smithii SC-J05-1 (Bs NHase) were conducted to analyze the activity, specificity and thermal stability of this hydrolytic enzyme. Bs NHase was purified to homogeneity from microbial cells of B. smithii SC-J05-1 and the nucleotide sequences of both the α- and β-subunits were determined. Purified Bs NHase was used for crystallization and several crystal forms were obtained by the vapour-diffusion method. Microseeding and the addition of magnesium ions were essential components to obtain crystals suitable for X-ray diffraction analysis

  5. Do clinical examination gloves provide adequate electrical insulation for safe hands-on defibrillation? I: Resistive properties of nitrile gloves.

    Science.gov (United States)

    Deakin, Charles D; Lee-Shrewsbury, Victoria; Hogg, Kitwani; Petley, Graham W

    2013-07-01

    Uninterrupted chest compressions are a key factor in determining resuscitation success. Interruptions to chest compression are often associated with defibrillation, particularly the need to stand clear from the patient during defibrillation. It has been suggested that clinical examination gloves may provide adequate electrical resistance to enable safe hands-on defibrillation in order to minimise interruptions. We therefore examined whether commonly used nitrile clinical examination gloves provide adequate resistance to current flow to enable safe hands-on defibrillation. Clinical examination gloves (Kimberly Clark KC300 Sterling nitrile) worn by members of hospital cardiac arrest teams were collected immediately following termination of resuscitation. To determine the level of protection afforded by visually intact gloves, electrical resistance across the glove was measured by applying a DC voltage across the glove and measuring subsequent resistance. Forty new unused gloves (control) were compared with 28 clinical (non-CPR) gloves and 128 clinical (CPR) gloves. One glove in each group had a visible tear and was excluded from analysis. Control gloves had a minimum resistance of 120 kΩ (median 190 kΩ) compared with 60 kΩ in clinical gloves (both CPR (median 140 kΩ) and non-CPR groups (median 160 kΩ)). Nitrile clinical examination gloves do not provide adequate electrical insulation for the rescuer to safely undertake 'hands-on' defibrillation and when exposed to the physical forces of external chest compression, even greater resistive degradation occurs. Further work is required to identify gloves suitable for safe use for 'hands-on' defibrillation. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  6. Reduced systemic toxicity and preserved vestibular toxicity following co-treatment with nitriles and CYP2E1 inhibitors: a mouse model for hair cell loss.

    Science.gov (United States)

    Saldaña-Ruíz, Sandra; Boadas-Vaello, Pere; Sedó-Cabezón, Lara; Llorens, Jordi

    2013-10-01

    Several nitriles, including allylnitrile and cis-crotononitrile, have been shown to be ototoxic and cause hair cell degeneration in the auditory and vestibular sensory epithelia of mice. However, these nitriles can also be lethal due in large part to the microsomal metabolic release of cyanide, which is mostly dependent on the activity of the 2E1 isoform of the cytochrome P450 (CYP2E1). In this study, we co-administered mice with a nitrile and, to reduce their lethal effects, a selective CYP2E1 inhibitor: diallylsulfide (DAS) or trans-1,2-dichloroethylene (TDCE). Both in female 129S1/SvImJ (129S1) mice co-treated with DAS and cis-crotononitrile and in male RjOrl:Swiss/CD-1 (Swiss) mice co-treated with TDCE and allylnitrile, the nitrile caused a dose-dependent loss of vestibular function, as assessed by a specific behavioral test battery, and of hair cells, as assessed by hair bundle counts using scanning electron microscopy. In the experiments, the CYP2E1 inhibitors provided significant protection against the lethal effects of the nitriles and did not diminish the vestibular toxicity as assessed by behavioral effects in comparison to animals receiving no inhibitor. Additional experiments using a single dose of allylnitrile demonstrated that TDCE does not cause hair cell loss on its own and does not modify the vestibular toxicity of the nitrile in either male or female 129S1 mice. In all the experiments, high vestibular dysfunction scores in the behavioral test battery predicted extensive to complete loss of hair cells in the utricles. This provides a means of selecting animals for subsequent studies of vestibular hair cell regeneration or replacement.

  7. Cure and mechanical properties of carboxylated nitrile rubber (XNBR) vulcanized by alkaline earth metal compounds

    Science.gov (United States)

    Tulyapitak, Tulyapong

    Compounds of carboxylated nitrile rubber (XNBR) with alkaline metal oxides and hydroxide were prepared, and their cure and mechanical properties were investigated. Magnesium oxide (MgO) with different specific surface areas (45, 65, and 140 m2/g) was used. Increased specific surface area and concentration of MgO resulted in higher cure rate. Optimum stiffness, tensile strength, and ultimate strain required an equimolar amount of acidity and MgO. The effect of specific surface area on tensile properties was not significant. Crosslink density of XNBR-MgO vulcanizates increased with increased amounts of MgO. ATR-IR spectroscopy showed that neutralization occurs in two steps: (1) During mixing and storage, MgO reacts with carboxyl groups (RCOOH) to give RCOOMgOH. (2) Upon curing, these react bimolecularly to form RCOOMgOOCR and Mg(OH)2. Dynamic mechanical thermal analysis revealed an ionic transition at higher temperature, in addition to the glass transition. The ionic transition shifts to higher temperature with increasing MgO concentration. Like MgO-XNBR systems, cure rates of XNBR-calcium hydroxide (Ca(OH)2) and XNBR-barium oxide (BaO) compounds increased with increased content of curing agents. Curing by these two agents resulted in ionic crosslinks. To ensure optimum tensile properties, equimolar amounts of carboxyl groups and curing agents were required. Dynamic mechanical analysis revealed the ionic transition in these two systems. It shifted to higher temperature with increased amounts of curing agents. In contrast to MgO, Ca(OH)2, and BaO, calcium oxide (CaO) gave results similar to those for thermally cured samples. No ionic transition was observed in XNBR-CaO systems. Tensile strength of XNBR depended on the strength of ionic crosslinks, which was dependent on the size of the alkaline metal ions.

  8. Stereoselective synthesis of the Halaven C14-C26 fragment from D-quinic acid: crystallization-induced diastereoselective transformation of an α-methyl nitrile.

    Science.gov (United States)

    Belanger, Francis; Chase, Charles E; Endo, Atsushi; Fang, Francis G; Li, Jing; Mathieu, Steven R; Wilcoxen, Annie Z; Zhang, Huiming

    2015-04-20

    Crystallization-induced diastereoselective transformation (CIDT) of an α-methyl nitrile completes an entirely non-chromatographic synthesis of the halichondrin B C14-C26 stereochemical array. The requisite α-methyl nitrile substrate is derived from D-quinic acid through a series of substrate-controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14-C26 fragment were derived from the single chiral source D-quinic acid. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. In situ generation of nitrilium from nitrile ylide and the subsequent Mumm rearrangement: copper-catalyzed synthesis of unsymmetrical diacylglycine esters.

    Science.gov (United States)

    Chen, Jijun; Shao, Ying; Ma, Liang; Ma, Meihua; Wan, Xiaobing

    2016-12-07

    A novel in situ generation of nitrilium from a nitrile ylide and the subsequent Mumm rearrangement of carboxylic acid, nitrile, and diazo compounds gave various unsymmetrical diacylglycine esters in moderate to high yields. This copper-catalyzed cascade reaction enables one-pot generation of two C-N bonds, one C[double bond, length as m-dash]O bond, and one C-H bond, with nitrogen as the only byproduct. The reaction has a broad functional-group tolerance, is rapid, easily scales up to the 100 mmol scale, and is insensitive to air and moisture.

  10. Reactions of 1,3-dioxacycloalkanes and their 2-arsena, 2-bora, 2-germa, 2-sila, and 2-thia analogs with nitriles

    International Nuclear Information System (INIS)

    Kuznetsov, V.V.

    2005-01-01

    New reactions of five-, six-, and seven-membered 1,3-dioxacycloalkanes and their 2-arsena, 2-bora, 2-germa, 2-sila, and 2-thia analogs with nitriles giving rise to 1,3-oxazacycloalkanes and then to amino alcohols are surveyed. The reactions under consideration, including the reactions of boronic and boric acid esters with nitriles, supplement the known chemical transformations of 1,3-dioxacycloalkanes and their 2-hetero atomic analogs and provide a wide scope for the synthesis of diverse functional derivatives on their basis [ru

  11. An efficient one-pot three-component synthesis of α-amino nitriles via Strecker reaction catalysed by bismuth(III nitrate

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2016-09-01

    Full Text Available A convenient and efficient one-pot method for the synthesis of a variety of α-amino nitriles from aldehydes, amines and trimethylsilyl cyanide (TMSCN in the presence of a catalytic amount of Bi(NO33 at room temperature in acetonitrile (MeCN is described. The significant features of this method are simple work-up procedure, inexpensive and non-toxic catalyst, shorter reaction times and excellent product yields. The catalyst Bi(NO33 can be reused. The reusability of the catalyst has been studied for the synthesis of various amino nitriles.

  12. Coherent Protein Dynamics Explored at FELIX

    CERN Document Server

    Austin, Robert

    2004-01-01

    We have discovered that there exists a very narrow (less than 0.02 microns) wide resonance in the amide I band of myoglobin and photoactive yellow protein that can be driven to greater than 30% saturation using very narrow linewidth pump-probe spectroscopy at FELIX. The extraordinary narrowness of this transition and the extraordinary ease of saturation inplies that this band is highly anharmonic and decoupled from the other oscillators in the amide I band. We will present detailed measurments on this discovery and implications for energy flow in proteins.

  13. Inhibition of enterovirus 71 replication by an α-hydroxy-nitrile derivative NK-1.9k.

    Science.gov (United States)

    Wang, Yaxin; Cao, Lin; Zhai, Yangyang; Ma, Jiaming; Nie, Quandeng; Li, Ting; Yin, Zheng; Sun, Yuna; Shang, Luqing

    2017-05-01

    Enterovirus 71 (EV71) is one of the major etiological agents of human hand-foot-and-mouth disease (HFMD) worldwide. EV71 infection in young children and people with immunodeficiency causes severe symptoms with a high fatality rates. However, there is still no approved drugs to treat such infections. Based on our previous report of a peptide-aldehyde anti-EV71 protease, we present here a highly specific α-hydroxy-nitrile derivative NK-1.9k, which inhibited the proliferation of multiple EV71 strains and coxsackievirus A16 (CVA16) in various cells with EC 50 of 37.0 nM with low cytotoxicity (CC 50  > 200 μM). The hydroxy-nitrile covalent warhead conferred NK-1.9k high potency and selectivity to interact with the cysteine residue of the active site of the viral protease. We also documented the resistance to NK-1.9k with a N69S mutation in EV71 3C pro . The combination of NK-1.9k and EV71 polymerase or entry inhibitors produced strong synergistic antiviral effects. Collectively, our findings suggest our compounds can potentially be developed as drugs for the treatment of HFMD. Copyright © 2017. Published by Elsevier B.V.

  14. Nitrile functionalized silyl ether with dissolved LiTFSI as new electrolyte solvent for lithium-ion batteries

    International Nuclear Information System (INIS)

    Pohl, Benjamin; Grünebaum, Mariano; Drews, Mathias; Passerini, Stefano; Winter, Martin; Wiemhöfer, Hans‑Dieter

    2015-01-01

    Highlights: • A new electrolyte based on a nitrile-silyl ether solvent and LiTFSI as lithium salt was successfully tested. • This electrolyte shows higher ionic conductivities as compared to earlier published silicon based solvents. • Due to the absence of ether groups, the electrochemical stability is extended to 5.4 V vs. Li/Li + . • With LiTFSI, the electrolyte can be cycled up to 4.15 V vs. Li/Li + without causing anodic aluminum dissolution. - Abstract: 3-((Trimethylsilyl) oxy) propionitrile is introduced as non-volatile solvent for lithium-ion battery electrolytes using LiTFSI as lithium salt. The thermal and chemical stability of the electrolytes offer an enhanced safety as compared to conventional volatile carbonate electrolytes. In cell tests, the investigated LiTFSI nitrile silyl ether electrolyte shows compatibility with LiFePO 4 , LiNi 0.33 Mn 0.33 Co 0.33 O 2 and graphite active materials.

  15. Prebiotic synthesis of 2-deoxy-d-ribose from interstellar building blocks promoted by amino esters or amino nitriles.

    Science.gov (United States)

    Steer, Andrew M; Bia, Nicolas; Smith, David K; Clarke, Paul A

    2017-09-25

    Understanding the prebiotic genesis of 2-deoxy-d-ribose, which forms the backbone of DNA, is of crucial importance to unravelling the origins of life, yet remains open to debate. Here we demonstrate that 20 mol% of proteinogenic amino esters promote the selective formation of 2-deoxy-d-ribose over 2-deoxy-d-threopentose in combined yields of ≥4%. We also demonstrate the first aldol reaction promoted by prebiotically-relevant proteinogenic amino nitriles (20 mol%) for the enantioselective synthesis of d-glyceraldehyde with 6% ee, and its subsequent conversion into 2-deoxy-d-ribose in yields of ≥ 5%. Finally, we explore the combination of these two steps in a one-pot process using 20 mol% of an amino ester or amino nitrile promoter. It is hence demonstrated that three interstellar starting materials, when mixed together with an appropriate promoter, can directly lead to the formation of a mixture of higher carbohydrates, including 2-deoxy-d-ribose.

  16. Highly porous ZnS microspheres for superior photoactivity after Au and Pt deposition and thermal treatment

    Energy Technology Data Exchange (ETDEWEB)

    Singla, Shilpa; Pal, Bonamali, E-mail: bpal@thapar.edu

    2013-11-15

    Graphical abstract: Highly porous ZnS microsphere of size 2–5 μm having large surface area ca. 173.14 m{sup 2} g{sup −1} exhibits superior photocatalytic activity for the oxidation of 4-nitrophenol under UV light irradiation. The rate of photooxidation has been significantly improved by Au and Pt deposition and after sintering, respectively, due to rapid electron acceptance by metal from photoexcited ZnS and growth of crystalline ZnS phase. - Highlights: • Photoactive ZnS microsphere of size 2–5 μm was prepared by hydrothermal route. • Highly porous cubic spherical ZnS crystals possess a large surface area, 173 m{sup 2} g{sup −1}. • 1 wt% Au and Pt photodeposition highly quenched the photoluminescence at 437 nm. • Sintering and metal loading notably improve the photooxidation rate of 4-nitrophenol. • Pt co-catalyst always exhibits superior photoactivity of ZnS microsphere than Au. - Abstract: This work highlights the enhanced photocatalytic activity of porous ZnS microspheres after Au and Pt deposition and heat treatment at 500 °C for 2 h. Microporous ZnS particles of size 2–5 μm with large surface area 173.14 m{sup 2} g{sup −1} and pore volume 0.0212 cm{sup 3} g{sup −1} were prepared by refluxing under an alkaline medium. Photoluminescence of ZnS at 437 nm attributed to sulfur or zinc vacancies were quenched to 30% and 49%, respectively, after 1 wt% Au and Pt loading. SEM images revealed that each ZnS microparticle consist of several smaller ZnS spheres of size 2.13 nm as calculated by Scherrer's equation. The rate of photooxidation of 4-nitrophenol (10 μM) under UV (125 W Hg arc–10.4 mW/cm{sup 2}) irradiation has been significantly improved by Au and Pt deposition followed by sintering due to better electron capturing capacity of deposited metals and growth of crystalline ZnS phase with less surface defects.

  17. Photodynamics of BLUF domain proteins: a new class of the biological blue-light photoreceptors

    OpenAIRE

    Zirak Yousefabadi, Peyman

    2008-01-01

    BLUF domains are light sensors of many microorganisms. They are present in the multi-domain proteins e.g. AppA from the phototrophic proteobacterium Rhodobacter sphaeroides, YcgF from Escherichia coli, PAC (photoactive adenylyl cyclase) from the unicellular flagellate Euglena gracilis and single domain proteins e.g. BlrB from Rhodobacter sphaeroides, Slr1694 from cyanobacterium Synechocystis sp.PCC6803, and Tll0078 of the thermophilic unicellular cyanobacterium Thermosynechococcus elongates B...

  18. Incorporating an Electrode Modification Layer with a Vertical Phase Separated Photoactive Layer for Efficient and Stable Inverted Nonfullerene Polymer Solar Cells.

    Science.gov (United States)

    Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Li, Jinyan; Bai, Yiming; Wang, Fuzhi; Bian, Xingming; Hayat, Tasawar; Alsaedi, Ahmed; Tan, Zhan'ao

    2017-12-20

    For bulk heterojunction polymer solar cells (PSCs), the donors and acceptors featuring specific phase separation and concentration distribution within the electron donor/acceptor blends crucially affect the exciton dissociation and charge transportation. Herein, efficient and stable nonfullerene inverted PSCs incorporating a phase separated photoactive layer and a titanium chelate electrode modification layer are demonstrated. Water contact angle (WCA), scanning kelvin probe microscopy (SKPM), and atomic force microscopy (AFM) techniques are implemented to characterize the morphology of photoactive layers. Compared with the control conventional device, the short-circuit current density (J sc ) is enhanced from 14.74 to 17.45 mAcm -2 . The power conversion efficiency (PCE) for the inverted PSCs with a titanium (diisopropoxide)-bis-(2,4-pentanedionate) (TIPD) layer increases from 9.67% to 11.69% benefiting from the declined exciton recombination and fairly enhanced charge transportation. Furthermore, the nonencapsulated inverted device with a TIPD layer demonstrates the best long-term stability, 85% of initial PCE remaining and an almost undecayed open-circuit voltage (V oc ) after 1440 h. Our results reveal that the titanium chelate is an excellent electrode modification layer to incorporate with a vertical phase separated photoactive layer for producing high-efficiency and high-stability inverted nonfullerene PSCs.

  19. Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

    Energy Technology Data Exchange (ETDEWEB)

    Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.; Achterberg, R. K.; Molter, E. M.; Palmer, M. Y.; Charnley, S. B.; Lindberg, J. E.; Mumma, M. J. [NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States); Teanby, N. A. [School of Earth Sciences, University of Bristol, Wills Memorial Building, Queen’s Road, Bristol, BS8 1RJ (United Kingdom); Kisiel, Z. [Institute of Physics, Polish Academy of Sciences, Al. Lotnikøw 32/46, 02-668 Warszawa (Poland); Irwin, P. G. J., E-mail: martin.cordiner@nasa.gov [Atmospheric, Oceanic and Planetary Physics, Clarendon Laboratory, University of Oxford, Parks Road, Oxford, OX1 3PU (United Kingdom)

    2017-11-01

    Vinyl cyanide (C{sub 2}H{sub 3}CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C{sub 2}H{sub 3}CN on Titan by Palmer et al. with the detection of three new C{sub 2}H{sub 3}CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C{sub 2}H{sub 3}CN on Titan. We present simultaneous observations of C{sub 2}H{sub 5}CN, HC{sub 3}N, and CH{sub 3}CN emission, and obtain the first (tentative) detection of C{sub 3}H{sub 8} (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC{sub 3}N and C{sub 2}H{sub 5}CN, which are theorized to be short-lived in Titan’s atmosphere, C{sub 2}H{sub 3}CN is most abundant over the southern (winter) pole, whereas the longer-lived CH{sub 3}CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C{sub 2}H{sub 3}CN and C{sub 2}H{sub 5}CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C{sub 2}H{sub 3}CN is found to be 3.03 ± 0.29 ppb, with a C{sub 2}H{sub 5}CN/C{sub 2}H{sub 3}CN abundance ratio of 2.43 ± 0.26. Our HC{sub 3}N and CH{sub 3}CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.

  20. Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

    Science.gov (United States)

    Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.; Achterberg, R. K.; Molter, E. M.; Teanby, N. A.; Palmer, M. Y.; Charnley, S. B.; Lindberg, J. E.; Kisiel, Z.; Mumma, M. J.; Irwin, P. G. J.

    2017-11-01

    Vinyl cyanide (C2H3CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C2H3CN on Titan by Palmer et al. with the detection of three new C2H3CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C2H3CN on Titan. We present simultaneous observations of C2H5CN, HC3N, and CH3CN emission, and obtain the first (tentative) detection of C3H8 (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC3N and C2H5CN, which are theorized to be short-lived in Titan’s atmosphere, C2H3CN is most abundant over the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C2H3CN and C2H5CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C2H3CN is found to be 3.03 ± 0.29 ppb, with a C2H5CN/C2H3CN abundance ratio of 2.43 ± 0.26. Our HC3N and CH3CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.

  1. Desenvolvimento de látices nitrílicos carboxilados Development of carboxylated nitrile latices

    Directory of Open Access Journals (Sweden)

    Ana Luzia O. Macedo

    2008-03-01

    Full Text Available É apresentando um estudo sobre o desenvolvimento de um processo de polimerização em emulsão de acrilonitrila, butadieno e ácido carboxílico, em escala piloto. O objetivo desse estudo é a produção de látex nitrílico carboxilado com alto teor de sólidos diretamente no processo de polimerização, sem a necessidade de etapas pós-reação de concentração. Foi estudado o efeito da temperatura, do tipo e quantidade de emulsificante, do tipo e quantidade de iniciador, do tipo de agitador e da velocidade de agitação e das etapas de adição incremental. Para isso, foram realizadas 32 reações, das quais somente 7 chegaram ao alvo de teor de sólidos desejado (50%. Os látices obtidos foram caracterizados quanto ao seu teor de sólidos, tamanho e distribuição de tamanhos das partículas, e por espectroscopia na região do infravermelho para determinação da composição monomérica. Foram obtidos látices com até 57% de sólidos totais. O tamanho médio de partícula variou de 130 a 230 nm.An emulsion polymerization process of acrylonitrile, butadiene and carboxylic acid was studied, in a pilot plant, for producing carboxylated nitrile latices with high solids content directly from the polymerization process, without the need of post-reaction steps of concentration. The effect of temperature, type and amount of emulsifier, type and amount of initiator, type of stirring system, stirring speed and incremental additions for producing high solid latices was studied. To attain this goal, 32 polymerization reactions were carried out, but only 7 attained the target for total solids (50%. The solids content, the average particle size and its distribution and the monomer composition were determined. A latex containing up to 57% of total solids was obtained. The average particle size ranged from 130 to 230 nm.

  2. Effect of physicochemical parameters on nitrile-hydrolyzing potentials of newly isolated nitrilase of Fusarium oxysporum f. sp. lycopercisi ED-3.

    Science.gov (United States)

    Bura Gohain, Manorama; Talukdar, Shruti; Talukdar, Madhumita; Yadav, Archana; Gogoi, Binod Kumar; Bora, Tarun Chandra; Kiran, Shashi; Gulati, Arvind

    2015-01-01

    In recent years, nitrilases from fungus have received increasing attention, and most of the studies are performed on nitrilases of bacterial origin. Frequently used methods are based on analytical methods such as high-performance liquid chromatography, liquid chromatography-mass spectrometry, and gas chromatography; therefore, an efficient, user friendly, and rapid method has been developed to screen nitrilase enzyme based on the principle of color change of a pH indicator. Phenol red amended with the minimal medium appears light yellow at neutral pH, which changes into pink with the formation of ammonia, indicating nitrilase activity in the reaction medium. A highly potent strain ED-3 identified as Fusarium oxysporum f. sp. lycopercisi (specific activity 17.5 µmol/Min/mg dcw) was isolated using this method. The nitrilase activity of F. oxysporum f. sp. lycopercisi ED-3 strain showed wide substrate specificity toward aliphatic nitriles, aromatic nitriles, and orthosubstituted heterocyclic nitriles. 4-Aminobenzonitrile was found to be a superior substrate among all the nitriles used in this study. This nitrilase was active within pH 5-10 and temperature ranging from 25 to 60 °C with optimal at pH 7.0 and temperature at 50 °C. The nitrilase activity was enhanced to several folds through optimization of culture and biotransformation conditions from 1,121 to 1,941 µmol/Min. © 2014 International Union of Biochemistry and Molecular Biology, Inc.

  3. Compositional analysis of nitrile terminated poly(propylene imine) dendrimers by high-performance liquid chromatography combined with electrospray mass spectrometry

    NARCIS (Netherlands)

    van der Wal, S; Mengerink, Y; Brackman, JC; de Brabander, EMM; Jeronimus-Stratingh, CM; Bruins, AP

    1998-01-01

    Separation methods for nitrile terminated poly(propylene imine) dendrimers were developed to monitor and optimize their large scale production. Detailed analyses of defects within a dendrimer generation were performed by HPLC at alkaline pH (sodium hydroxide) on a polymer-based column or at neutral

  4. Application of continuous stirred membrane reactor to 3-cyanopyridine bioconversion using the nitrile hydratase–amidase cascade system of Microbacterium imperiale CBS 498-74

    Czech Academy of Sciences Publication Activity Database

    Cantarella, L.; Gallifuoco, A.; Malandra, A.; Martínková, Ludmila; Pasquarelli, F.; Spera, A.; Cantarella, M.

    2010-01-01

    Roč. 47, č. 3 (2010), s. 64-70 ISSN 0141-0229 R&D Projects: GA MŠk OC09046 Institutional research plan: CEZ:AV0Z50200510 Keywords : Nitrile hydratase-amidase cascade system * 3-Cyanopyridine bioconversion * Nicotinamide Subject RIV: EE - Microbiology, Virology Impact factor: 2.287, year: 2010

  5. Bio-Inspired Nitrile Hydration by Peptidic Ligands Based on L-Cysteine, L-Methionine or L-Penicillamine and Pyridine-2,6-dicarboxylic Acid

    Directory of Open Access Journals (Sweden)

    Cillian Byrne

    2014-12-01

    Full Text Available Nitrile hydratase (NHase, EC 4.2.1.84 is a metalloenzyme which catalyses the conversion of nitriles to amides. The high efficiency and broad substrate range of NHase have led to the successful application of this enzyme as a biocatalyst in the industrial syntheses of acrylamide and nicotinamide and in the bioremediation of nitrile waste. Crystal structures of both cobalt(III- and iron(III-dependent NHases reveal an unusual metal binding motif made up from six sequential amino acids and comprising two amide nitrogens from the peptide backbone and three cysteine-derived sulfur ligands, each at a different oxidation state (thiolate, sulfenate and sulfinate. Based on the active site geometry revealed by these crystal structures, we have designed a series of small-molecule ligands which integrate essential features of the NHase metal binding motif into a readily accessible peptide environment. We report the synthesis of ligands based on a pyridine-2,6-dicarboxylic acid scaffold and L-cysteine, L-S-methylcysteine, L-methionine or L-penicillamine. These ligands have been combined with cobalt(III and iron(III and tested as catalysts for biomimetic nitrile hydration. The highest levels of activity are observed with the L-penicillamine ligand which, in combination with cobalt(III, converts acetonitrile to acetamide at 1.25 turnovers and benzonitrile to benzamide at 1.20 turnovers.

  6. Nitrile Hydration by Thiolate–and Alkoxide–Ligated Co-NHase Analogues. Isolation of Co(III)-Amidate and Co(III)–Iminol Intermediates

    Science.gov (United States)

    Swartz, Rodney D.; Coggins, Michael K.; Kaminsky, Werner; Kovacs, Julie A.

    2011-01-01

    Nitrile hydratases (NHases) are thiolate–ligated Fe(III)- or Co(III)-containing enzymes, which convert nitriles to the corresponding amide under mild conditions. Proposed NHase mechanisms involve M(III)–NCR, M(III)–OH, M(III)–iminol and M(III)–amide intermediates. Spectroscopic and kinetic data support the involvement of a M(III)–NCR intermediate. A H–bonding network facilitates this enzymatic reaction. There have been no reported crystallographically characterized examples of these key intermediates. Herein we describe two biomimetic Co(III)–NHase analogues that hydrate MeCN. Four key crystallographically characterized NHase intermediate anaologues, [CoIII(SMe2N4(tren))(MeCN)]2+ (1), [CoIII(SMe2N4(tren))(OH)]+ (3), [CoIII(SMe2N4(tren))(NHC(O)CH3)]+ (2), and [CoIII(OMe2N4(tren))(NHC(OH)CH3)]2+ (5) are described. Iminol–bound 5 represents the first example of a Co(III)-iminol compound in any ligand environment. Kinetic parameters (k1(298 K)= 2.98(5) M−1s−1, ΔH‡ = 12.65(3) kcal/mol, ΔS‡ = −14(7) e.u.) for nitrile hydration by 1 are reported, and the activation energy Ea= 13.2 kcal/mol is compared with that (Ea= 5.5 kcal/mol) of the NHase enzyme. A mechanism involving initial exchange of the bound MeCN for OH− is ruled out by the fact that nitrile exchange from 1 (kex(300 K)= 7.3(1) x10−3 s−1) is two orders of magnitude slower than nitrile hydration, and that hydroxide bound 3 does not promote nitrile hydration. Reactivity of an analogue that incorporates an alkoxide as a mimic of the highly conserved NHase serine residue shows that this moiety facilitates nitrile hydration under milder conditions. Hydrogen-bonding to the alkoxide stabilizes a Co(III)-iminol intermediate. Comparison of the thiolate versus alkoxide intermediate structures shows that C≡N bond activation and C=O bond formation proceed further along the reaction coordinate when a thiolate is incorporated into the coordination sphere. PMID:21351789

  7. Nitrile hydration by thiolate- and alkoxide-ligated Co-NHase analogues. Isolation of Co(III)-amidate and Co(III)-iminol intermediates.

    Science.gov (United States)

    Swartz, Rodney D; Coggins, Michael K; Kaminsky, Werner; Kovacs, Julie A

    2011-03-23

    Nitrile hydratases (NHases) are thiolate-ligated Fe(III)- or Co(III)-containing enzymes, which convert nitriles to the corresponding amide under mild conditions. Proposed NHase mechanisms involve M(III)-NCR, M(III)-OH, M(III)-iminol, and M(III)-amide intermediates. There have been no reported crystallographically characterized examples of these key intermediates. Spectroscopic and kinetic data support the involvement of a M(III)-NCR intermediate. A H-bonding network facilitates this enzymatic reaction. Herein we describe two biomimetic Co(III)-NHase analogues that hydrate MeCN, and four crystallographically characterized NHase intermediate analogues, [Co(III)(S(Me2)N(4)(tren))(MeCN)](2+) (1), [Co(III)(S(Me2)N(4)(tren))(OH)](+) (3), [Co(III)(S(Me2)N(4)(tren))(NHC(O)CH(3))](+) (2), and [Co(III)(O(Me2)N(4)(tren))(NHC(OH)CH(3))](2+) (5). Iminol-bound 5 represents the first example of a Co(III)-iminol compound in any ligand environment. Kinetic parameters (k(1)(298 K) = 2.98(5) M(-1) s(-1), ΔH(‡) = 12.65(3) kcal/mol, ΔS(‡) = -14(7) e.u.) for nitrile hydration by 1 are reported, and the activation energy E(a) = 13.2 kcal/mol is compared with that (E(a) = 5.5 kcal/mol) of the NHase enzyme. A mechanism involving initial exchange of the bound MeCN for OH- is ruled out by the fact that nitrile exchange from 1 (k(ex)(300 K) = 7.3(1) × 10(-3) s(-1)) is 2 orders of magnitude slower than nitrile hydration, and that hydroxide bound 3 does not promote nitrile hydration. Reactivity of an analogue that incorporates an alkoxide as a mimic of the highly conserved NHase serine residue shows that this moiety facilitates nitrile hydration under milder conditions. Hydrogen-bonding to the alkoxide stabilizes a Co(III)-iminol intermediate. Comparison of the thiolate versus alkoxide intermediate structures shows that C≡N bond activation and C═O bond formation proceed further along the reaction coordinate when a thiolate is incorporated into the coordination sphere.

  8. Enhanced photoactivity from single-crystalline SrTaO2N nanoplates synthesized by topotactic nitridation

    International Nuclear Information System (INIS)

    Fu, Jie; Skrabalak, Sara E.

    2017-01-01

    There are few methods yielding oxynitride crystals with defined shape, yet shape-controlled crystals often give enhanced photoactivity. Herein, single-crystalline SrTaO 2 N nanoplates and polyhedra are achieved selectively. Central to these synthetic advances is the crystallization pathways used, in which single-crystalline SrTaO 2 N nanoplates form by topotactic nitridation of aerosol-prepared Sr 2 Ta 2 O 7 nanoplates and SrTaO 2 N polyhedra form by flux-assisted nitridation of the nanoplates. Evaluation of these materials for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) showed improved performance for the SrTaO 2 N nanoplates, with a record apparent quantum efficiency (AQE) of 6.1 % for OER compared to the polyhedra (AQE: 1.6 %) and SrTaO 2 N polycrystals (AQE: 0.6 %). The enhanced performance from the nanoplates arises from their morphology and lower defect density. These results highlight the importance of developing new synthetic routes to high quality oxynitrides. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Enhanced Photoactivity from Single-Crystalline SrTaO2 N Nanoplates Synthesized by Topotactic Nitridation.

    Science.gov (United States)

    Fu, Jie; Skrabalak, Sara E

    2017-11-06

    There are few methods yielding oxynitride crystals with defined shape, yet shape-controlled crystals often give enhanced photoactivity. Herein, single-crystalline SrTaO 2 N nanoplates and polyhedra are achieved selectively. Central to these synthetic advances is the crystallization pathways used, in which single-crystalline SrTaO 2 N nanoplates form by topotactic nitridation of aerosol-prepared Sr 2 Ta 2 O 7 nanoplates and SrTaO 2 N polyhedra form by flux-assisted nitridation of the nanoplates. Evaluation of these materials for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) showed improved performance for the SrTaO 2 N nanoplates, with a record apparent quantum efficiency (AQE) of 6.1 % for OER compared to the polyhedra (AQE: 1.6 %) and SrTaO 2 N polycrystals (AQE: 0.6 %). The enhanced performance from the nanoplates arises from their morphology and lower defect density. These results highlight the importance of developing new synthetic routes to high quality oxynitrides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks.

    Science.gov (United States)

    Carmona, Francisco J; Rojas, Sara; Sánchez, Purificación; Jeremias, Hélia; Marques, Ana R; Romão, Carlos C; Choquesillo-Lazarte, Duane; Navarro, Jorge A R; Maldonado, Carmen R; Barea, Elisa

    2016-07-05

    The encapsulation of the photoactive, nontoxic, water-soluble, and air-stable cationic CORM [Mn(tacn)(CO)3]Br (tacn = 1,4,7-triazacyclononane) in different inorganic porous matrixes, namely, the metalorganic framework bio-MOF-1, (NH2(CH3)2)2[Zn8(adeninate)4(BPDC)6]·8DMF·11H2O (BPDC = 4,4'-biphenyldicarboxylate), and the functionalized mesoporous silicas MCM-41-SO3H and SBA-15-SO3H, is achieved by a cation exchange strategy. The CO release from these loaded materials, under simulated physiological conditions, is triggered by visible light. The results show that the silica matrixes, which are unaltered under physiological conditions, slow the kinetics of CO release, allowing a more controlled CO supply. In contrast, bio-MOF-1 instability leads to the complete leaching of the CORM. Nevertheless, the degradation of the MOF matrix gives rise to an enhanced CO release rate, which is related to the presence of free adenine in the solution.

  11. Charge carrier transport and collection enhancement of copper indium diselenide photoactive nanoparticle-ink by laser crystallization

    Energy Technology Data Exchange (ETDEWEB)

    Nian, Qiong; Cheng, Gary J., E-mail: gjcheng@purdue.edu [Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47906 (United States); School of Industrial Engineering, Purdue University, West Lafayette, Indiana 47906 (United States); Zhang, Martin Y. [School of Industrial Engineering, Purdue University, West Lafayette, Indiana 47906 (United States); Wang, Yuefeng [Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47906 (United States); School of Materials Engineering, Purdue University, West Lafayette, Indiana 47906 (United States); Das, Suprem R.; Bhat, Venkataprasad S. [Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47906 (United States); Huang, Fuqiang [Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 200050 (China)

    2014-09-15

    There has been increasing needs for cost-effective and high performance thin film deposition techniques for photovoltaics. Among all deposition techniques, roll-to-roll printing of nanomaterials has been a promising method. However, the printed thin film contains many internal imperfections, which reduce the charge-collection performance. Here, direct pulse laser crystallization (DPLC) of photoactive nanoparticles-inks is studied to meet this challenge. In this study, copper indium selenite (CIS) nanoparticle-inks is applied as an example. Enhanced crystallinity, densified structure in the thin film is resulted after DLPC under optimal conditions. It is found that the decreased film internal imperfections after DPLC results in reducing scattering and multi-trapping effects. Both of them contribute to better charge-collection performance of CIS absorber material by increasing extended state mobility and carrier lifetime, when carrier transport and kinetics are coupled. Charge carrier transport was characterized after DPLC, showing mobility increased by 2 orders of magnitude. Photocurrent under AM1.5 illumination was measured and shown 10 times enhancement of integrated power density after DPLC, which may lead to higher efficiency in photo-electric energy conversion.

  12. Probing the structural dependency of photoinduced properties of colloidal quantum dots using metal-oxide photo-active substrates

    International Nuclear Information System (INIS)

    Patty, Kira; Campbell, Quinn; Hamilton, Nathan; West, Robert G.; Sadeghi, Seyed M.; Mao, Chuanbin

    2014-01-01

    We used photoactive substrates consisting of about 1 nm coating of a metal oxide on glass substrates to investigate the impact of the structures of colloidal quantum dots on their photophysical and photochemical properties. We showed during irradiation these substrates can interact uniquely with such quantum dots, inducing distinct forms of photo-induced processes when they have different cores, shells, or ligands. In particular, our results showed that for certain types of core-shell quantum dot structures an ultrathin layer of a metal oxide can reduce suppression of quantum efficiency of the quantum dots happening when they undergo extensive photo-oxidation. This suggests the possibility of shrinking the sizes of quantum dots without significant enhancement of their non-radiative decay rates. We show that such quantum dots are not influenced significantly by Coulomb blockade or photoionization, while those without a shell can undergo a large amount of photo-induced fluorescence enhancement via such blockade when they are in touch with the metal oxide.

  13. A novel photoactive and three-dimensional stainless steel anode dramatically enhances the current density of bioelectrochemical systems.

    Science.gov (United States)

    Feng, Huajun; Tang, Chenyi; Wang, Qing; Liang, Yuxiang; Shen, Dongsheng; Guo, Kun; He, Qiaoqiao; Jayaprada, Thilini; Zhou, Yuyang; Chen, Ting; Ying, Xianbin; Wang, Meizhen

    2018-04-01

    This study reports a high-performance 3D stainless-steel photoanode (3D SS photoanode) for bioelectrochemical systems (BESs). The 3D SS photoanode consists of 3D carbon-coated SS felt bioactive side and a flat α-Fe 2 O 3 -coated SS plate photoactive side. Without light illumination, the electrode reached a current density of 26.2 ± 1.9 A m -2 , which was already one of the highest current densities reported thus far. Under illumination, the current density of the electrode was further increased to 46.5 ± 2.9 A m -2 . The mechanism of the photo-enhanced current production can be attributed to the reduced charge-transfer resistance between electrode surface and the biofilm with illumination. It was also found that long-term light illumination can enhance the biofilm formation on the 3D SS photoanode. These findings demonstrate that using the synergistic effect of photocatalysis and microbial electrocatalysis is an efficient way to boost the current production of the existing high-performance 3D anodes for BESs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. FT-Raman and FTIR spectra of photoactive aminobenzazole derivatives in the solid state: A combined experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Alves, Rodrigo Martins [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil); Rodembusch, Fabiano Severo [Universidade Federal do Rio Grande do Sul, Grupo de Pesquisa em Fotoquímica Orgânica Aplicada, Av. Bento Gonçalves 9500, CEP 91501-970 Porto Alegre, RS (Brazil); Habis, Charles [Northern Virginia Community College, Manassas, VA (United States); Moreira, Eduardo Ceretta, E-mail: eduardomoreira@unipampa.edu.br [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil)

    2014-12-15

    This study reports the experimental investigation of two photoactive aminobenzazole derivatives in the solid state by FT-Raman and Infrared Spectroscopies (FTIR) and its comparison with theoretical models. The optimized molecular structure, vibrational frequencies, and corresponding vibrational assignments of these compounds have been investigated experimentally and theoretically using Spanish Initiative for Electronic Simulations with Thousands of Atoms (SIESTA) and Gaussian03 Software Package. The FT-Raman and FTIR spectra were acquired with high resolution and emission frequencies identified by simulating the vibrational modes. The most intense peak observed in the FT-Raman spectra is the in-plane deformation vibrational of O–H bond that could be related to the vibrational region responsible for the stabilization of the enol conformer in the ground state which undergoes ESIPT to form a keto tautomer in the excited state. Additionally, the position of the amino group played an important role on the vibrational characteristics of the studied compounds. Also, the simulations proved to be a good approach in undertaking the FTIR and FT-Raman experiments. The use of graphic correlations helps us to determine the method and basis that best fit the experimental results. - Highlights: • Structural and vibrational properties of two aminobenzazoles were reported. • Comparison between experimental techniques and theoretical models. • The position of the amino group played an important role on the vibrational characteristics of the studied compounds.

  15. Particle emission rates during electrostatic spray deposition of TiO2 nanoparticle-based photoactive coating.

    Science.gov (United States)

    Koivisto, Antti J; Jensen, Alexander C Ø; Kling, Kirsten I; Kling, Jens; Budtz, Hans Christian; Koponen, Ismo K; Tuinman, Ilse; Hussein, Tareq; Jensen, Keld A; Nørgaard, Asger; Levin, Marcus

    2018-01-05

    Here, we studied the particle release rate during Electrostatic spray deposition of anatase-(TiO 2 )-based photoactive coating onto tiles and wallpaper using a commercially available electrostatic spray device. Spraying was performed in a 20.3m 3 test chamber while measuring concentrations of 5.6nm to 31μm-size particles and volatile organic compounds (VOC), as well as particle deposition onto room surfaces and on the spray gun user hand. The particle emission and deposition rates were quantified using aerosol mass balance modelling. The geometric mean particle number emission rate was 1.9×10 10 s -1 and the mean mass emission rate was 381μgs -1 . The respirable mass emission-rate was 65% lower than observed for the entire measured size-range. The mass emission rates were linearly scalable (±ca. 20%) to the process duration. The particle deposition rates were up to 15h -1 for deposited particles consisted of mainly TiO 2 , TiO 2 mixed with Cl and/or Ag, TiO 2 particles coated with carbon, and Ag particles with size ranging from 60nm to ca. 5μm. As expected, no significant VOC emissions were observed as a result of spraying. Finally, we provide recommendations for exposure model parameterization. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

  16. Enhanced photoactivity from single-crystalline SrTaO{sub 2}N nanoplates synthesized by topotactic nitridation

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Jie; Skrabalak, Sara E. [Department of Chemistry, Indiana University, Bloomington, IN (United States)

    2017-11-06

    There are few methods yielding oxynitride crystals with defined shape, yet shape-controlled crystals often give enhanced photoactivity. Herein, single-crystalline SrTaO{sub 2}N nanoplates and polyhedra are achieved selectively. Central to these synthetic advances is the crystallization pathways used, in which single-crystalline SrTaO{sub 2}N nanoplates form by topotactic nitridation of aerosol-prepared Sr{sub 2}Ta{sub 2}O{sub 7} nanoplates and SrTaO{sub 2}N polyhedra form by flux-assisted nitridation of the nanoplates. Evaluation of these materials for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) showed improved performance for the SrTaO{sub 2}N nanoplates, with a record apparent quantum efficiency (AQE) of 6.1 % for OER compared to the polyhedra (AQE: 1.6 %) and SrTaO{sub 2}N polycrystals (AQE: 0.6 %). The enhanced performance from the nanoplates arises from their morphology and lower defect density. These results highlight the importance of developing new synthetic routes to high quality oxynitrides. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Effect of growth media on cell envelope composition and nitrile hydratase stability in Rhodococcus rhodochrous strain DAP 96253.

    Science.gov (United States)

    Tucker, Trudy-Ann; Crow, Sidney A; Pierce, George E

    2012-11-01

    Rhodococcus is an important industrial microorganism that possesses diverse metabolic capabilities; it also has a cell envelope, composed of an outer layer of mycolic acids and glycolipids. Selected Rhodococcus species when induced are capable of transforming nitriles to the corresponding amide by the enzyme nitrile hydratase (NHase), and subsequently to the corresponding acid via an amidase. This nitrile biochemistry has generated interest in using the rhodococci as biocatalysts. It was hypothesized that altering sugars in the growth medium might impact cell envelope components and have effects on NHase. When the primary carbon source in growth media was changed from glucose to fructose, maltose, or maltodextrin, the NHase activity increased. Cells grown in the presence of maltose and maltodextrin showed the highest activities against propionitrile, 197 and 202 units/mg cdw, respectively. Stability of NHase was also affected as cells grown in the presence of maltose and maltodextrin retained more NHase activity at 55 °C (45 and 23 %, respectively) than cells grown in the presence of glucose or fructose (19 and 10 %, respectively). Supplementation of trehalose in the growth media resulted in increased NHase stability at 55 °C, as cells grown in the presence of glucose retained 40 % NHase activity as opposed to 19 % without the presence of trehalose. Changes in cell envelope components, such mycolic acids and glycolipids, were evaluated by high-performance liquid chromatography (HPLC) and thin-layer chromatography (TLC), respectively. Changing sugars and the addition of inducing components for NHase, such as cobalt and urea in growth media, resulted in changes in mycolic acid profiles. Mycolic acid content increased 5 times when cobalt and urea were added to media with glucose. Glycolipids levels were also affected by the changes in sugars and addition of inducing components. This research demonstrates that carbohydrate selection impacts NHase activity and

  18. Enzyme-semiconductor interactions: Routes from fundamental aspects to photoactive devices

    Energy Technology Data Exchange (ETDEWEB)

    Lewerenz, H.J. [Division of Solar Energy, Hahn-Meitner-Institut GmbH, Berlin (Germany)

    2008-09-15

    Scanning tunnelling microscopy (STM) experiments at protein-semiconductor systems are analyzed using concepts from applied semiconductor physics such as Fermi level pinning and MIS (metal-insulator-semiconductor) junction electronics. Routes for immobilization of enzymes (proteins) on nanostructured surfaces of MoTe{sub 2} and Si are outlined using so-called DLVO and non-DLVO interaction forces. An overview of the catalytic activity of the imaged enzymes, reverse transcriptases of the retroviruses HIV 1 and AMV (avian myeloblastosis virus), is given including their tertiary structural properties which is revealed also in the STM and tapping mode AFM images. For the interpretation of STM images, a resonant charge transfer mechanism is invoked, based on the potential dependence of the image contrast and the energy band structure of MoTe{sub 2} near the valence band maximum. First analyses of the charge transport from the semiconductor to the STM tip at negative bias of MoTe{sub 2} suggest that the observed uninhibited conductivity in the constant current experiments results from solvation-assisted release of electrons from traps that exist along the polypeptide chains and that charge transport occurs at the circumference of the enzymes where biological water is present. Therefore, charge injection into catalytically active enzymes such as hydrogenase or water oxidase of photosystem I and II with subsequent charge transport to the active sites appears difficult to realize. Possibilities of radiation-less long-distance energy transfer based on the Foerster mechanism, its multichromic extension and on Dexter exciton hopping are considered for catalytically active hybrid inorganic/organic absorber-enzyme structures. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Nanocomposites of nitrile (NBR) rubber with multi-walled carbon nanotubes

    Science.gov (United States)

    Warasitthinon, Nuthathai

    Nanotechnology offers the promise of creating new materials with enhanced performance. There are different kinds of fillers used in rubber nanocomposites, such as carbon black, silica, carbon fibers, and organoclays. Carbon nanotube reinforced elastomers have potential for improved rubber properties in aggressive environments. The first chapter is an introduction to the literature. The second chapter investigated the incorporation of multi-walled carbon nanotubes (MWCNTs) into rubber matrix for potential use in high temperature applications. The vulcanization kinetics of acrylonitrile butadiene rubber (NBR) reinforced with multi-walled carbon nanotubes was investigated. The vulcanized NBR rubber with different loading percentages of MWCNTs was also compared to NBR reinforced with carbon black N330. The optimum curing time at 170°C (T90) was found to decrease with increasing content of MWCNTs. Increased filler loading of both carbon black and MWCNTs gave higher modulus and strength. The MWCNTs filled materials gave better retention of modulus and tensile strength at high temperatures, but lower strength as compared to the carbon black filled samples. In the third chapter, carbon black (CB, 50phr) content in nitrile rubber (NBR) nanocomposites was partially replaced by multi-walled carbon nanotubes (MWCNTs). NBR/CB/CNTs nanocomposites with varying ratio of CB/CNTs (50/0 phr to 40/10 phr) were formulated via the melt-mixing method using an internal mixer. The reinforcing effect of single filler (CB) and mixture of fillers (CB and CNTs) on the properties of NBR nanocomposites was investigated. The cure kinetics and bound rubber content were analyzed using rheometry and solvent swelling method. In addition, mechanical behavior at both room temperature and high temperature (350°F/ 121°C) were examined. The scorch time and curing time values showed that there was no significant effect on the curing behavior of NBR nanocomposites after the partial replacement of CB with

  20. Preparation and Sound Absorption Properties of a Barium Titanate/Nitrile Butadiene Rubber–Polyurethane Foam Composite with Multilayered Structure

    Science.gov (United States)

    Jiang, Xueliang; Yang, Zhen; Wang, Zhijie; Zhang, Fuqing; You, Feng

    2018-01-01

    Barium titanate/nitrile butadiene rubber (BT/NBR) and polyurethane (PU) foam were combined to prepare a sound-absorbing material with an alternating multilayered structure. The effects of the cell size of PU foam and the alternating unit number on the sound absorption property of the material were investigated. The results show that the sound absorption efficiency at a low frequency increased when decreasing the cell size of PU foam layer. With the increasing of the alternating unit number, the material shows the sound absorption effect in a wider bandwidth of frequency. The BT/NBR-PU foam composites with alternating multilayered structure have an excellent sound absorption property at low frequency due to the organic combination of airflow resistivity, resonance absorption, and interface dissipation. PMID:29565321

  1. Preparation and Sound Absorption Properties of a Barium Titanate/Nitrile Butadiene Rubber–Polyurethane Foam Composite with Multilayered Structure

    Directory of Open Access Journals (Sweden)

    Xueliang Jiang

    2018-03-01

    Full Text Available Barium titanate/nitrile butadiene rubber (BT/NBR and polyurethane (PU foam were combined to prepare a sound-absorbing material with an alternating multilayered structure. The effects of the cell size of PU foam and the alternating unit number on the sound absorption property of the material were investigated. The results show that the sound absorption efficiency at a low frequency increased when decreasing the cell size of PU foam layer. With the increasing of the alternating unit number, the material shows the sound absorption effect in a wider bandwidth of frequency. The BT/NBR-PU foam composites with alternating multilayered structure have an excellent sound absorption property at low frequency due to the organic combination of airflow resistivity, resonance absorption, and interface dissipation.

  2. Preparation and Sound Absorption Properties of a Barium Titanate/Nitrile Butadiene Rubber-Polyurethane Foam Composite with Multilayered Structure.

    Science.gov (United States)

    Jiang, Xueliang; Yang, Zhen; Wang, Zhijie; Zhang, Fuqing; You, Feng; Yao, Chu

    2018-03-22

    Barium titanate/nitrile butadiene rubber (BT/NBR) and polyurethane (PU) foam were combined to prepare a sound-absorbing material with an alternating multilayered structure. The effects of the cell size of PU foam and the alternating unit number on the sound absorption property of the material were investigated. The results show that the sound absorption efficiency at a low frequency increased when decreasing the cell size of PU foam layer. With the increasing of the alternating unit number, the material shows the sound absorption effect in a wider bandwidth of frequency. The BT/NBR-PU foam composites with alternating multilayered structure have an excellent sound absorption property at low frequency due to the organic combination of airflow resistivity, resonance absorption, and interface dissipation.

  3. Reinforcement of Multiwalled Carbon Nanotube in Nitrile Rubber: In Comparison with Carbon Black, Conductive Carbon Black, and Precipitated Silica

    Directory of Open Access Journals (Sweden)

    Atip Boonbumrung

    2016-01-01

    Full Text Available The properties of nitrile rubber (NBR reinforced by multiwalled carbon nanotube (MWCNT, conductive carbon black (CCB, carbon black (CB, and precipitated silica (PSi were investigated via viscoelastic behavior, bound rubber content, electrical properties, cross-link density, and mechanical properties. The filler content was varied from 0 to 15 phr. MWCNT shows the greatest magnitude of reinforcement considered in terms of tensile strength, modulus, hardness, and abrasion resistance followed by CCB, CB, and PSi. The MWCNT filled system also exhibits extremely high levels of filler network and trapped rubber even at relatively low loading (5 phr leading to high electrical properties and poor dynamic mechanical properties. Although CCB possesses the highest specific surface area, it gives lower level of filler network than MWCNT and also gives the highest elongation at break among all fillers. Both CB and PSi show comparable degree of reinforcement which is considerably lower than CCB and MWCNT.

  4. CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds

    International Nuclear Information System (INIS)

    Yu, Chao

    2017-01-01

    Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu 36 Ni 64 NPs are the best catalyst for both AB methanolysis (TOF = 49.1 mol H2 mol CuNi -1 min -1 and E a = 24.4 kJ/mol) and hydrogenation reactions (conversion yield >97%). In conclusion, the G-CuNi represents a unique noble-metal-free catalyst for hydrogenation reactions in a green environment without using pure hydrogen.

  5. Two-Dimensional Infrared Study of Vibrational Coupling between Azide and Nitrile Reporters in a RNA Nucleoside.

    Science.gov (United States)

    Schmitz, Andrew J; Hogle, David G; Gai, Xin Sonia; Fenlon, Edward E; Brewer, Scott H; Tucker, Matthew J

    2016-09-08

    The vibrations in the azide, N3, asymmetric stretching region and nitrile, CN, symmetric stretching region of 2'-azido-5-cyano-2'-deoxyuridine (N3CNdU) are examined by two-dimensional infrared (2D IR) spectroscopy. At earlier waiting times, the 2D IR spectrum shows the presence of both vibrational transitions along the diagonal and off-diagonal cross peaks indicating vibrational coupling. The coupling strength is determined from the off-diagonal anharmonicity to be 66 cm(-1) for the intramolecular distance of ∼7.9 Å, based on a structural map generated for this model system. In addition, the frequency-frequency correlation decay is detected, monitoring the solvent dynamics around each individual probe position. Overall, these vibrational reporters can be utilized in tandem to simultaneously track global structural information and fast structural fluctuations.

  6. Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

    Science.gov (United States)

    Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

    2000-12-01

    Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

  7. Isothiocyanates, Nitriles, and Epithionitriles from Glucosinolates Are Affected by Genotype and Developmental Stage in Brassica oleracea Varieties.

    Science.gov (United States)

    Hanschen, Franziska S; Schreiner, Monika

    2017-01-01

    Vegetables of the Brassica oleracea group, such as broccoli, cauliflower, and cabbage, play an important role for glucosinolate consumption in the human diet. Upon maceration of the vegetable tissue, glucosinolates are degraded enzymatically to form volatile isothiocyanates, nitriles, and epithionitriles. However, only the uptake of isothiocyanates is linked to the cancer-preventive effects. Thus, it is of great interest to evaluate especially the isothiocyanate formation. Here, we studied the formation of glucosinolates and their respective hydrolysis products in sprouts and fully developed vegetable heads of different genotypes of the five B. oleracea varieties: broccoli, cauliflower as well as white, red, and savoy cabbages. Further, the effect of ontogeny (developmental stages) during the head development on the formation of glucosinolates and their respective hydrolysis products was evaluated at three different developmental stages (mini, fully developed, and over-mature head). Broccoli and red cabbage were mainly rich in 4-(methylsulfinyl)butyl glucosinolate (glucoraphanin), whereas cauliflower, savoy cabbage and white cabbage contained mainly 2-propenyl (sinigrin) and 3-(methylsulfinyl)propyl glucosinolate (glucoiberin). Upon hydrolysis, epithionitriles or nitriles were often observed to be the main hydrolysis products, with 1-cyano-2,3-epithiopropane being most abundant with up to 5.7 μmol/g fresh weight in white cabbage sprouts. Notably, sprouts often contained more than 10 times more glucosinolates or their hydrolysis products compared to fully developed vegetables. Moreover, during head development, both glucosinolate concentrations as well as hydrolysis product concentrations changed and mini heads contained the highest isothiocyanate concentrations. Thus, from a cancer-preventive point of view, consumption of mini heads of the B. oleracea varieties is recommended.

  8. Photocatalytic deposition of Ag nanoparticles on TiO2: Metal precursor effect on the structural and photoactivity properties

    Directory of Open Access Journals (Sweden)

    E. Albiter

    2015-09-01

    Full Text Available A series of 1 wt.% Ag–TiO2 photocatalysts were obtained by photodeposition using different organic (acetylacetonate, Ag-A and inorganic (nitrate, Ag-N, and perchlorate, Ag-C silver precursors in order to determinate the influence of the silver precursor on final properties of the photocatalysts. The resulting photocatalytic materials were characterized by different techniques (UV–Vis DRS, TEM/HRTEM and XPS and their photocatalytic activity was evaluated in the degradation of rhodamine B (used as model pollutant in aqueous solution under simulated solar light. The photocatalytic reduction of Ag species to Ag0 on TiO2 was higher with silver nitrate as precursor compared to acetylacetonate or perchlorate. All the Ag-modified TiO2 photocatalysts exhibited a surface plasmon resonance effect in the visible region (400–530 nm indicating different metal particle sizes depending on the Ag precursor used in their synthesis. A higher photocatalytic activity was obtained with all the Ag/TiO2 samples compared with non-modified TiO2. The descending order of photocatalytic activity was as follows: Ag-A/TiO2 ≈ Ag-N/TiO2 > Ag-C/TiO2 > TiO2-P25. The enhanced photoactivity was attributed to the presence of different amounts Ag0 nanoparticles homogeneously distributed on Ag2O and TiO2, trapping the photogenerated electrons and avoiding charge recombination.

  9. The Synthesis and Photophysical Characterization of Porphyrin Photoactive Materials for Use as Sensitizers in Organic Photovoltaics and Photodynamic Therapy

    Science.gov (United States)

    Marin, Dawn Marie

    Solar energy conversion and photodynamic therapy (PDT) are very different applications. However, both utilize very similar photoactive molecules called porphyrins. Porphyrins are structural analogs of chlorophyll and also function as prosthetic groups in some biological enzymes. Understanding the structure/function relationship of these molecules is crucial for enhancing the energy generation efficiency of molecular solar cells and improving chemotherapeutic activity in PDT. In this dissertation, two approaches were applied with the goal of increasing the efficiency of molecular semiconductors for these applications: the heavy atom effect and donor-acceptor molecules. We enhanced the efficiency of triplet excited state formation and singlet oxygen generation for porphyrin sensitizers using the heavy atom effect. The heavy atom effect induces spin-orbit coupling to promote intersystem crossing into the triplet state. In this study, a carbomethoxyphenyl substituent was replaced with either a bromophenyl or an iodophenyl substituent on 5,10,15,20-tetrakis(4-carbomethoxyphenyl)porphyrin. The longer lifetimes obtained from the increase in the triplet excited state allow for longer exciton diffusion lengths and lower recombination rates in photovoltaics. Also, the enhanced intersystem crossing is beneficial for photodynamic therapy because it increases singlet oxygen generation, which destroys tumor cells. Optimizing photovoltaic performance and PDT efficacy can also be accomplished with donor-acceptor molecules because they have extended electronic pi bond delocalization across the molecule, which causes the molecule to absorb longer wavelengths of light. Donor-acceptor molecules should produce photovoltaic devices that absorb more of the solar spectrum and produce sensitizers that absorb wavelengths of light that can penetrate through tissues. Donor-acceptor molecules were synthesized using 5,15-bis(4-carbomethoxyphenyl)porphyrin as the acceptor and thiazolo[5,4-d

  10. Multifunctional theranostic Pluronic mixed micelles improve targeted photoactivity of Verteporfin in cancer cells

    Energy Technology Data Exchange (ETDEWEB)

    Silva Pellosi, Diogo [Laboratory of Phobiology and photomdicine, Department of Chemistry (FFCLRP), University of São Paulo, Av. dos Bandeirantes 3900, 14040-901, Vila Monte Alegre, Ribeirão Preto (Brazil); Calori, Italo Rodrigo [Research Nucleus of Photodynamic Therapy, Department of Chemistry, State University of Maringá, Av. Colombo 5790, 97020-900 Maringá (Brazil); Barcelos de Paula, Leonardo [Laboratory of Phobiology and photomdicine, Department of Chemistry (FFCLRP), University of São Paulo, Av. dos Bandeirantes 3900, 14040-901, Vila Monte Alegre, Ribeirão Preto (Brazil); Hioka, Noboru [Research Nucleus of Photodynamic Therapy, Department of Chemistry, State University of Maringá, Av. Colombo 5790, 97020-900 Maringá (Brazil); Quaglia, Fabiana [Laboratory of Drug Delivery, Department of Pharmacy, University of Napoli Federico II, Via Domenico Montesanto 49, 80131 Napoli (Italy); Tedesco, Antonio Claudio, E-mail: atedesco@usp.br [Laboratory of Phobiology and photomdicine, Department of Chemistry (FFCLRP), University of São Paulo, Av. dos Bandeirantes 3900, 14040-901, Vila Monte Alegre, Ribeirão Preto (Brazil)

    2017-02-01

    Nanotechnology development provides new strategies to treat cancer by integration of different treatment modalities in a single multifunctional nanoparticle. In this scenario, we applied the multifunctional Pluronic P123/F127 mixed micelles for Verteporfin-mediated photodynamic therapy in PC3 and MCF-7 cancer cells. Micelles functionalization aimed the targeted delivery by the insertion of biotin moiety on micelle surface and fluorescence image-based through rhodamine-B dye conjugation in the polymer chains. Multifunctional Pluronics formed spherical nanoparticulated micelles that efficiently encapsulated the photosensitizer Verteporfin maintaining its favorable photophysical properties. Lyophilized formulations were stable at least for 6 months and readily reconstituted in aqueous media. The multifunctional micelles were stable in protein-rich media due to the dual Pluronic mixed micelles characteristic: high drug loading capacity provided by its micellar core and high kinetic stability due its biocompatible shell. Biotin surface functionalized micelles showed higher internalization rates due biotin-mediated endocytosis, as demonstrated by competitive cellular uptake studies. Rhodamine B-tagged micelles allowed monitoring cellular uptake and intracellular distribution of the formulations. Confocal microscopy studies demonstrated a larger intracellular distribution of the formulation and photosensitizer, which could drive Verteporfin to act on multiple cell sites. Formulations were not toxic in the dark condition, but showed high Verteporfin-induced phototoxicity against both cancer cell lines at low drug and light doses. These results point Verteporfin-loaded multifunctional micelles as a promising tool to further developments in photodynamic therapy of cancer. - Highlights: • We optimized the theranostic mixed micelles – verteporfin formulations. • Multifunctional Pluronic micelles formed nano-sized spherical nanoparticles. • Biotin surface conjugation

  11. Synthesis and biological properties of 5-azido-2'-deoxyuridine 5'-triphosphate, a photoactive nucleotide suitable for making light-sensitive DNA

    International Nuclear Information System (INIS)

    Evans, R.K.; Haley, B.E.

    1987-01-01

    A photoactive nucleotide analogue of dUTP, 5-azido-2'-deoxyuridine 5'-triphosphate (5-N 3 dUTP), was synthesized from dUMP in five steps. The key reaction in the synthesis of 5-N 3 dUTP is the nitration of dUMP in 98% yield in 5 min at 25 0 C using an excess of nitrosonium tetrafluoroborate in anhydrous dimethylformamide. Reduction of the resulting 5-nitro compound with zinc and 20 mM HCl gave 5-aminodeoxyuridine monophosphate (5-NH 2 dUMP). Diazotization of 5-NH 2 dUMP with HNO 2 followed by the addition NaN 3 to the acidic diazonium salt solution gave a photoactive nucleotide derivative in 80-90% yield. The monophosphate product was identified as 5-N 3 dUMP by proton NMR, UV, IR, and chromatographic analysis as well as by the mode of synthesis and its photosensitivity. After formation of 5-N 3 dUTP through a chemical coupling of pyrophosphate to 5-N 3 dUMP, the triphosphate form of the nucleotide was found to support DNA synthesis by Escherichia coli DNA polymerase I at a rate indistinguishable from that supported by dTTP. When UMP was used as the starting compound, 5-N 3 UTP was formed in an analogous fashion with similar yields and produced a photoactive nucleotide which is a substrate for E. coli RNA polymerase. To prepare [γ- 32 P]-5-N 3 dUTP for use as an active-site-directed photoaffinity labeling reagent, a simple method of preparing γ- 32 P-labeled pyrimidine nucleotides was developed. [γ- 32 P]-5-N 3 dUTP is an effective photoaffinity labeling reagent for DNA polymerase I and was found to bind to the active site with a 2-fold higher affinity than dTTP. The photoactivity of 5-N 3 dUMP is stable to extremes of pH, and [γ- 32 P]-5-N 3 dUTP was an effective photolabeling reagent even in the presence of 10 mM dithiothreitol

  12. New small molecule inhibitors of histone methyl transferase DOT1L with a nitrile as a non-traditional replacement for heavy halogen atoms.

    Science.gov (United States)

    Spurr, Sophie S; Bayle, Elliott D; Yu, Wenyu; Li, Fengling; Tempel, Wolfram; Vedadi, Masoud; Schapira, Matthieu; Fish, Paul V

    2016-09-15

    A number of new nucleoside derivatives are disclosed as inhibitors of DOT1L activity. SARs established that DOT1L inhibition could be achieved through incorporation of polar groups and small heterocycles at the 5-position (5, 6, 12) or by the application of alternative nitrogenous bases (18). Based on these results, CN-SAH (19) was identified as a potent and selective inhibitor of DOT1L activity where the polar 5-nitrile group was shown by crystallography to bind in the hydrophobic pocket of DOT1L. In addition, we show that a polar nitrile group can be used as a non-traditional replacement for heavy halogen atoms. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Highly Selective Separation of Carbon Dioxide from Nitrogen and Methane by Nitrile/Glycol-Difunctionalized Ionic Liquids in Supported Ionic Liquid Membranes (SILMs)

    OpenAIRE

    Hojniak, Sandra D.; Silverwood, Ian P.; Laeeq Khan, Asim; Vankelecom, Ivo F.J.; Dehaen, Wim; Kazarian, Sergei G.; Binnemans, Koen

    2014-01-01

    Novel difunctionalized ionic liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic liquid membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature liquidity of the pyrrolidinium and imidazolium ILs, t...

  14. Synthetic Studies on Bioactive Natural Polyketides: Intramolecular Nitrile Oxide-Olefin Cycloaddition Approach for Construction of a Macrolactone Skeleton of Macrosphelide B

    Directory of Open Access Journals (Sweden)

    Seung-Mann Paek

    2011-06-01

    Full Text Available Studies on the synthesis of macrosphelide B via an intramolecular nitrile oxide-olefin cycloaddition (INOC is described. In particular, an asymmetric INOC approach using phase transfer catalysts seems to be a potentially efficient and versatile procedure for the construction of the macrolactone skeleton of macrosphelide B in terms of facial selectivity. Our preliminary and unprecedented stereoselective procedure is anticipated to be usefully applied through further studies for the synthesis of the macrosphelide family.

  15. Actinide gas-phase chemistry: Reactions of An+ and AnO+ [An = Th, U, Np, Pu, Am] with nitriles and butylamine

    International Nuclear Information System (INIS)

    Gibson, J.K.

    1999-01-01

    Laser ablation with prompt reaction and detection was applied to study gas-phase reactions of actinide ions, An + and AnO + [An = Th, U, Pu, Np, Am], with nitriles and butylamine; Tb and Tm were included for comparison. Particular emphasis was on Np and Am as this is the region of the An series where a transition to Ln-like character is manifested. A goal was to assess the role of the coordinating N: site on actinide ion-molecule interactions. The results for the nitriles were generally reminiscent of those for reactions with alkenes and the inert character of Pu + and Am + with regard to dehydrogenation, despite adduct formation, indicated that Csingle bondH activation requires two non-5f electrons to produce a Csingle bondAn + single bondH complex. With the butyronitriles and valeronitrile, Am + produced AmC 2 H 4 + , possibly via an ion/dipole interaction. Most MO + exhibited only adduct formation with the nitriles although ThO + was distinctively reactive, consistent with a description of Th as a quasi-d-block element. Both Np + and Tb + were substantially effective at dehydrogenating butylamine and Am + exhibited a lesser degree of reactivity. Reactions of the MO + , TbO + , NpO + , and AmO + with butylamine revealed a dramatic effect of oxoligation: AmO + was at least as reactive as TbO + and NpO + . It is postulated that the MO + reactions proceeded via a multicentered intermediate without insertion into a C-H bond. Bis-complexes were produced with nitriles and butylamine, attesting to strong complexation with the :N functionality. An ancillary discovery was Am 2 ± An dimers/clusters should elucidate the nature of actinide intermetallic bonding, including the role of 5f electrons

  16. Design, synthesis and crystallographic analysis of nitrile-based broad-spectrum peptidomimetic inhibitors for coronavirus 3C-like proteases.

    Science.gov (United States)

    Chuck, Chi-Pang; Chen, Chao; Ke, Zhihai; Wan, David Chi-Cheong; Chow, Hak-Fun; Wong, Kam-Bo

    2013-01-01

    Coronaviral infection is associated with up to 5% of respiratory tract diseases. The 3C-like protease (3CL(pro)) of coronaviruses is required for proteolytic processing of polyproteins and viral replication, and is a promising target for the development of drugs against coronaviral infection. We designed and synthesized four nitrile-based peptidomimetic inhibitors with different N-terminal protective groups and different peptide length, and examined their inhibitory effect on the in-vitro enzymatic activity of 3CL(pro) of severe-acute-respiratory-syndrome-coronavirus. The IC(50) values of the inhibitors were in the range of 4.6-49 μM, demonstrating that the nitrile warhead can effectively inactivate the 3CL(pro) autocleavage process. The best inhibitor, Cbz-AVLQ-CN with an N-terminal carbobenzyloxy group, was ~10x more potent than the other inhibitors tested. Crystal structures of the enzyme-inhibitor complexes showed that the nitrile warhead inhibits 3CL(pro) by forming a covalent bond with the catalytic Cys145 residue, while the AVLQ peptide forms a number of favourable interactions with the S1-S4 substrate-binding pockets. We have further showed that the peptidomimetic inhibitor, Cbz-AVLQ-CN, has broad-spectrum inhibition against 3CL(pro) from human coronavirus strains 229E, NL63, OC43, HKU1, and infectious bronchitis virus, with IC(50) values ranging from 1.3 to 3.7 μM, but no detectable inhibition against caspase-3. In summary, we have shown that the nitrile-based peptidomimetic inhibitors are effective against 3CL(pro), and they inhibit 3CL(pro) from a broad range of coronaviruses. Our results provide further insights into the future design of drugs that could serve as a first line defence against coronaviral infection. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  17. Melamine-Schiff base/manganese complex with denritic structure: An efficient catalyst for oxidation of alcohols and one-pot synthesis of nitriles.

    Science.gov (United States)

    Kazemnejadi, Milad; Nikookar, Mahsa; Mohammadi, Mohammad; Shakeri, Alireza; Esmaeilpour, Mohsen

    2018-05-18

    Efficient and selective oxidation of alcohol to the corresponding carbonyl and/or nitrile was carried out by a new water-soluble melamine-based dendritic Mn(III) complex (Melamine-Mn (III)-Schiff base complex) in the presence of 2,4,6-trichloro-1,3,5-triazine (TCT) and O 2 at room temperature. Also, the oxidation of amine to the corresponding nitrile with high selectivity and conversion was performed at room temperature using the current method and high amounts of turnover frequencies (TOFs) were obtained for reactions. This system was also applicable for direct preparation of oxime through oxidation of alcohol. The catalyst was characterized by Fourier-transform infrared (FTIR), ultraviolet-visible (UV-Vis), thermogravimetric analysis (TGA), energy-dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), CHN and inductively coupled plasma (ICP) analyses. Also, oxidation/reduction behavior of the catalyst was studied by cyclic voltammetry (CV). Moreover, chemoselectivity of the catalyst was discussed with various combinations. The water-soluble catalyst could be recycled from the reaction mixture and reused for several times with a very low losing in efficiency. The recovered catalyst was also investigated with various analyses. Finally, gram scale preparation of nitrile was evaluated by present method. Copyright © 2018 Elsevier Inc. All rights reserved.

  18. Preparation and dual microwave-absorption properties of carboxylic poly(arylene ether nitrile)/Fe3O4 hybrid microspheres

    International Nuclear Information System (INIS)

    Ma Zhen; Meng Fanbin; Zhao Rui; Zhan Yingqing; Zhong Jiachun; Liu Xiaobo

    2012-01-01

    The carboxylic poly(arylene ether nitrile)/Fe 3 O 4 hybrid microspheres were prepared via solvothermal method. The carboxylic poly(arylene ether nitrile) (PEN-COOH) was introduced into the Fe 3 O 4 microspheres by chemisorption with mass content up to 15% as defined by infrared spectra and thermal gravimetric analysis. The hybrid sphere is of hierarchical polymer–inorganic microstructure as observed by transmission electron microscopy. The microwave-absorption of the sample owns a shifting peak and a special immobilized peak with the variation of absorber thickness from 3 to 5 mm. Maximum microwave-absorption of the product is capable of over −30 dB in the range of 10–12 GHz. By proposed equivalent filter circuit model, the immobilized peak was attributed to the ordered nanostructure where the Fe 3 O 4 nanocrystals were isolated by PEN-COOH. The product has the potential to be applied as microwave absorber with high microwave-absorption, good dispersibility and robust polymer–inorganic interfacial adherence. - Highlights: ► We prepared poly(arylene ether nitrile)/Fe 3 O 4 hybrid microspheres with hierarchical polymer–inorganic nanostructure. ► A shifting and an immobilized microwave absorbing peaks were observed on the sample. ► Possible mechanism was proposed on the basis of electromagnetic data.

  19. Effect of multiple alcohol-based hand rub applications on the tensile properties of thirteen brands of medical exam nitrile and latex gloves.

    Science.gov (United States)

    Gao, Pengfei; Horvatin, Matthew; Niezgoda, George; Weible, Robyn; Shaffer, Ronald

    2016-12-01

    Current CDC guidance for the disinfection of gloved hands during the doffing of personal protective equipment (PPE) following the care of a patient with Ebola recommends for multiple applications of alcohol-based hand rub (ABHR) on medical exam gloves. To evaluate possible effects of ABHR applications on glove integrity, thirteen brands of nitrile and latex medical exam gloves from five manufacturers and two different ABHRs were included in this study. A pair of gloves were worn by a test operator and the outside surfaces of the gloves were separately treated with an ABHR for 1-6 applications. Tensile strength and ultimate elongation of the gloves without any ABHR treatments (control gloves) and gloves after 1-6 ABHR applications were measured based on the ASTM D412 standard method. In general, tensile strength decreased with each ABHR application. ABHRs had more effect on the tensile strength of the tested nitrile than latex gloves, while ethanol-based ABHR (EBHR) resulted in lesser changes in tensile strength compared to isopropanol-based ABHR (IBHR). The results show that multiple EBHR applications on the latex gloves and some of the nitrile gloves tested should be safe for Ebola PPE doffing based on the CDC guidance. Appropriate hospital staff practice using ABHR treatment and doffing gloves is recommended to become more familiar with changes in glove properties.

  20. Palladium-catalyzed meta-selective C-H bond activation with a nitrile-containing template: computational study on mechanism and origins of selectivity.

    Science.gov (United States)

    Yang, Yun-Fang; Cheng, Gui-Juan; Liu, Peng; Leow, Dasheng; Sun, Tian-Yu; Chen, Ping; Zhang, Xinhao; Yu, Jin-Quan; Wu, Yun-Dong; Houk, K N

    2014-01-08

    Density functional theory investigations have elucidated the mechanism and origins of meta-regioselectivity of Pd(II)-catalyzed C-H olefinations of toluene derivatives that employ a nitrile-containing template. The reaction proceeds through four major steps: C-H activation, alkene insertion, β-hydride elimination, and reductive elimination. The C-H activation step, which proceeds via a concerted metalation-deprotonation (CMD) pathway, is found to be the rate- and regioselectivity-determining step. For the crucial C-H activation, four possible active catalytic species-monomeric Pd(OAc)2, dimeric Pd2(OAc)4, heterodimeric PdAg(OAc)3, and trimeric Pd3(OAc)6-have been investigated. The computations indicated that the C-H activation with the nitrile-containing template occurs via a Pd-Ag heterodimeric transition state. The nitrile directing group coordinates with Ag while the Pd is placed adjacent to the meta-C-H bond in the transition state, leading to the observed high meta-selectivity. The Pd2(OAc)4 dimeric mechanism also leads to the meta-C-H activation product but with higher activation energies than the Pd-Ag heterodimeric mechanism. The Pd monomeric and trimeric mechanisms require much higher activation free energies and are predicted to give ortho products. Structural and distortion energy analysis of the transition states revealed significant effects of distortions of the template on mechanism and regioselectivity, which provided hints for further developments of new templates.

  1. Ligand-controlled reactivity, selectivity, and mechanism of cationic ruthenium-catalyzed hydrosilylations of alkynes, ketones, and nitriles: a theoretical study.

    Science.gov (United States)

    Yang, Yun-Fang; Chung, Lung Wa; Zhang, Xinhao; Houk, K N; Wu, Yun-Dong

    2014-09-19

    Density functional theory calculations with the M06 functional have been performed on the reactivity, selectivity, and mechanism of hydrosilylations of alkynes, ketones, and nitriles catalyzed by cationic ruthenium complexes [CpRu(L)(MeCN)2](+), with L = P(i)Pr3 or MeCN. The hydrosilylation of alkynes with L = P(i)Pr3 involves an initial silyl migration mechanism to generate the anti-Markovnikov product, in contrast to the Markovnikov product obtained with L = MeCN. The bulky phosphine ligand directs the silyl group to migrate to Cβ of the alkyne. This explains the anti-Markovnikov selectivity of the catalyst with L = P(i)Pr3. By contrast, the silane additions to either ketone or nitrile proceed through an ionic SN2-Si outer-sphere mechanism, in which the substrate attacks the Si center. The P(i)Pr3 ligand facilitates the activation of the Si-H bond to furnish a η(2)-silane complex, whereas a η(1)-silane complex is formed for the MeCN ligand. This property of the phosphine ligand enables the catalytic hydrosilylation of ketones and nitriles in addition to that of alkynes.

  2. Protein Electrochemistry: Questions and Answers.

    Science.gov (United States)

    Fourmond, V; Léger, C

    This chapter presents the fundamentals of electrochemistry in the context of protein electrochemistry. We discuss redox proteins and enzymes that are not photoactive. Of course, the principles described herein also apply to photobioelectrochemistry, as discussed in later chapters of this book. Depending on which experiment is considered, electron transfer between proteins and electrodes can be either direct or mediated, and achieved in a variety of configurations: with the protein and/or the mediator free to diffuse in solution, immobilized in a thick, hydrated film, or adsorbed as a sub-monolayer on the electrode. The experiments can be performed with the goal to study the protein or to use it. Here emphasis is on mechanistic studies, which are easier in the configuration where the protein is adsorbed and electron transfer is direct, but we also explain the interpretation of signals obtained when diffusion processes affect the response.This chapter is organized as a series of responses to questions. Questions 1-5 are related to the basics of electrochemistry: what does "potential" or "current" mean, what does an electrochemical set-up look like? Questions 6-9 are related to the distinction between adsorbed and diffusive redox species. The answers to questions 10-13 explain the interpretation of slow and fast scan voltammetry with redox proteins. Questions 14-19 deal with catalytic electrochemistry, when the protein studied is actually an enzyme. Questions 20, 21 and 22 are general.

  3. Enhancement of Power Efficiency and Stability of P3HT-Based Organic Solar Cells under Elevated Operating-Temperatures by Using a Nanocomposite Photoactive Layer

    Directory of Open Access Journals (Sweden)

    Tran Thi Thao

    2015-01-01

    Full Text Available With the aim to find out an enhanced operating-temperature range for photovoltaic device parameters, two types of the photoactive layer were prepared: poly(3-hexylthiophene (P3HT and P3HT+nc-TiO2 (PTC thin films. The enhancement obtained for the photoelectrical conversion efficiency of the composite based OSCs is attributed to the presence of nanoheterojunctions of TiO2/P3HT. For the temperature range of 30–70°C, the decrease of the open-circuit potential was compensated by an increase of the fill factor; and the increase in the short-circuit current resulted in an overall increase of the energy conversion efficiency. At elevated temperatures of 60–80°C the efficiency of the P3HT- and PTC-based cells reached a maximum value of 1.6% and 2.1%, respectively. Over this temperature range the efficiency of P3HT-based OSC decreased strongly to zero, whereas for the PTC cells it maintained a value as large as 1.2% at the temperature range of 110–140°C. The improved thermal stability of the composite-based device was attributed to the lowered thermal expansion coefficient of the nanocomposite photoactive layer.

  4. Photoactive curcumin-derived dyes with surface anchoring moieties used in ZnO nanoparticle-based dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Ganesh, T.; Kim, Jong Hoon; Yoon, Seog Joon; Kil, Byung-Ho; Maldar, N.N.; Han, Jin Wook; Han, Sung-Hwan

    2010-01-01

    Photoactive, eco-friendly and high molar extinction coefficient, curcumin-derived dyes (BCMoxo and BCtCM) have been explored in ZnO nanoparticles (NPs)-based dye-sensitized solar cells (DSSCs). The boron complex curcumin dyes modified with di-carboxylic anchor groups (BCtCM) provided surface attachment with a strong UV-vis region absorption than the dye molecule without anchor groups (BCMoxo). Photoanodes primed with poly-dispersive ZnO NPs (∼80-50 nm) specifically devised for these dyes and optimized for the critical thickness, sensitization time and concentration using a solvent-free ionic electrolyte so as to get current density as high as 1.66 mA/cm 2 under 80 mW/cm 2 irradiation. Therefore, a successful conversion of visible light into electricity by using these curcumin-derived dyes (natural derived photoactive molecules) as photosensitizer in DSSCs would be a great interest in future studies for enhancing further conversion efficiencies.

  5. Photoactive curcumin-derived dyes with surface anchoring moieties used in ZnO nanoparticle-based dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Ganesh, T.; Kim, Jong Hoon; Yoon, Seog Joon; Kil, Byung-Ho; Maldar, N.N. [Inorganic Nano-Materials Laboratory, Department of Chemistry, Hanyang University, Sung-Dong-Ku, Haengdang-dong 17, Seoul (Korea, Republic of); Han, Jin Wook, E-mail: jwhan@hanyang.ac.kr [Inorganic Nano-Materials Laboratory, Department of Chemistry, Hanyang University, Sung-Dong-Ku, Haengdang-dong 17, Seoul (Korea, Republic of); Han, Sung-Hwan, E-mail: shhan@hanyang.ac.kr [Inorganic Nano-Materials Laboratory, Department of Chemistry, Hanyang University, Sung-Dong-Ku, Haengdang-dong 17, Seoul (Korea, Republic of)

    2010-09-01

    Photoactive, eco-friendly and high molar extinction coefficient, curcumin-derived dyes (BCMoxo and BCtCM) have been explored in ZnO nanoparticles (NPs)-based dye-sensitized solar cells (DSSCs). The boron complex curcumin dyes modified with di-carboxylic anchor groups (BCtCM) provided surface attachment with a strong UV-vis region absorption than the dye molecule without anchor groups (BCMoxo). Photoanodes primed with poly-dispersive ZnO NPs ({approx}80-50 nm) specifically devised for these dyes and optimized for the critical thickness, sensitization time and concentration using a solvent-free ionic electrolyte so as to get current density as high as 1.66 mA/cm{sup 2} under 80 mW/cm{sup 2} irradiation. Therefore, a successful conversion of visible light into electricity by using these curcumin-derived dyes (natural derived photoactive molecules) as photosensitizer in DSSCs would be a great interest in future studies for enhancing further conversion efficiencies.

  6. Ultrathin TiO2 layer coated-CdS spheres core-shell nanocomposite with enhanced visible-light photoactivity.

    Science.gov (United States)

    Chen, Zhang; Xu, Yi-Jun

    2013-12-26

    Development of various strategies for controllable fabrication of core-shell nanocomposites (CSNs) with highly active photocatalytic performance has been attracting ever-increasing research attention. In particular, control of the ultrathin layer TiO2 shell in constructing CSNs in an aqueous phase is a significant but technologically challenging issue. Here, this paper demonstrates the interface assembly synthesis of CdS nanospheres@TiO2 core-shell photocatalyst via the electrostatic interaction of negatively charged water-stable titania precursor with positively charged CdS nanospheres (CdS NSPs), followed by the formation of the ultrathin-layer TiO2 shell through a facile refluxing process in aqueous phase. The as-formed CdS NSPs@TiO2 core-shell nanohybrid exhibits a high visible-light-driven photoactivity for selective transformation and reduction of heavy metal ions. The ultrathin TiO2 layer coated on CdS NSPs results in excellent light transmission property, enhanced adsorption capacity, and improved transfer of charge carriers and lifespan of photoinduced electron-hole pairs, which would prominently contribute to the significant photoactivity enhancement. It is anticipated that this facile aqueous-phase synthesis strategy could be extended to design a variety of more efficient CSN photocatalysts with controllable morphology toward target applications in diverse photoredox processes.

  7. ITO electrode/photoactive layer interface engineering for efficient inverted polymer solar cells based on P3HT and PCBM using a solution-processed titanium chelate

    International Nuclear Information System (INIS)

    Zhang Wenqing; Zheng Hua; Tan Zhan'ao; Qian Deping; Li Liangjie; Xu Qi; Li Shusheng; Li Yongfang

    2012-01-01

    We report efficient inverted polymer solar cells (PSCs) based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) using alcohol-soluble titanium (diisopropoxide) bis (2,4-pentanedionate) (TIPD) as an electron selective layer between the indium tin oxide (ITO) electrode and the photoactive layer. The thermally annealed TIPD layer is highly transparent in the visible range and shows effective electron collection ability. By optimizing the electron-collecting layer, the photoactive layer and the hole-collecting layer, the power conversion efficiency (PCE) of the inverted device with the structure ITO/TIPD/P3HT : PCBM/MoO 3 /Ag reaches 4.10% under the illumination of AM1.5G, 100 mW cm -2 , which is among the highest values for inverted PSCs based on P3HT : PCBM. The PCE of the inverted device is improved in comparison with the conventional device (3.77%) under the same experimental conditions. (paper)

  8. The rearrangements of naphthylnitrenes: UV/Vis and IR spectra of azirines, cyclic ketenimines, and cyclic nitrile ylides.

    Science.gov (United States)

    Maltsev, Alexander; Bally, Thomas; Tsao, Meng-Lin; Platz, Matthew S; Kuhn, Arvid; Vosswinkel, Michael; Wentrup, Curt

    2004-01-14

    Ar matrix photolysis of 1- and 2-naphthyl azides 3 and 4 at 313 nm initially affords the singlet naphthyl nitrenes, (1)()1 and (1)()2. Relaxation to the corresponding lower energy, persistent triplet nitrenes (3)()1 and (3)()2 competes with cyclization to the azirines 15 and 18, which can also be formed photochemically from the triplet nitrenes. On prolonged irradiation, the azirines can be converted to the seven-membered cyclic ketenimines 10 and 13, respectively, as described earlier by Dunkin and Thomson. However, instead of the o-quinoid ketenimines 16 and 19, which are the expected primary ring-opening products of azirines 15 and 18, respectively, we observed their novel bond-shift isomers 17 and 20, which may be formally regarded as cyclic nitrile ylides. The existence of such ylidic heterocumulenes has been predicted previously, but this work provides the first experimental observation of such species. The factors which are responsible for the special stability of the ylidic species 17 and 20 are discussed.

  9. The improvement of the mechanical properties of PMMA denture base by Al2O3 particles with nitrile rubber

    Science.gov (United States)

    Alhareb, Ahmed Omran; Akil, Hazizan Md; Ahmad, Zainal Arifin

    2017-07-01

    Poly methyl methacrylate (PMMA) is mostly used for fabrication of denture base by heat-curing technique. Therefore, the purpose of this study is to investigate the effect of Al2O3 filler as toughening particles together with nitrile butadiene rubber (NBR) particles as impact modifier were used to reinforce PMMA denture base materials on the impact strength (IS) and fracture toughness (KIC). PMMA powder was mixed with liquid methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent. The powder components are PMMA, benzoyl peroxide, NBR (5, 7.5 and 10 wt%), and Al2O3 filler (5 wt%) treated by silane. The liquid components are 90% of methyl methacrylate and 10 % ethylene glycol dimethacryate. FTIR analyses confirmed that the Al2O3 filler was successfully treated with silane as coupling agent. The morphology of fracture surfaces was characterized using field emission scanning electron microscopy (FESEM). The results shown that IS and KIC improved significantly when using treated the Al2O3 filler. IS has increased to 56% (8.26 KJ/m2) and 73% (2.77 MPa.m1/2) for KIC when treated Al2O3 filler compared to unreinforced PMMA matrix. Statistical analyses of data results were significantly improved (PNBR with treated Al2O3 filler compared to other the compositions.

  10. Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

    Energy Technology Data Exchange (ETDEWEB)

    Agrawal, Neha, E-mail: neha87bhu@gmail.com [Defence Material Store Research Development and Establishment (DMSRDE), DRDO, GT Road, Kanpur 208013, U.P (India); Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra (India); Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Mukhopadhyay, K.; Prasad, N. E. [Defence Material Store Research Development and Establishment (DMSRDE), DRDO, GT Road, Kanpur 208013, U.P (India); Gandhi, M. N.; Bhattacharyya, A. R. [Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra (India)

    2016-05-06

    Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS{sub 2}) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS{sub 2} and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS{sub 2} and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

  11. Isolation and identification of some unknown substances in disposable nitrile-butadiene rubber gloves used for food handling.

    Science.gov (United States)

    Mutsuga, M; Wakui, C; Kawamura, Y; Maitani, T

    2002-11-01

    In Japan, disposable gloves made from nitrile-butadiene rubber (NBR) are frequently used in contact with foods. In a previous paper, we investigated substances migrating from various gloves made of polyvinyl chloride, polyethylene, natural rubber and NBR. Zinc di-n-butyldithiocarbamate (ZDBC), diethyldithiocarbamate (ZDEC) used as vulcanization accelerators, di(2-ethylhexyl)phthalate (DEHP) used as a plasticizer and many unknown compounds that migrated from NBR gloves into n-heptane were detected by GC/MS. In this paper, six unknown compounds were obtained from one kind of NBR glove by n-hexane extraction and each was isolated by silica gel chromatography. From the results of NMR and mass spectral analysis of the six unknown compounds, their structures are proposed as 1,4-dione-2,5-bis(1,1-dimethylpropyl)cyclohexadiene (1), 2-(1,1-dimethylethyl)-4-(1,1,3,3-tetra methylbutyl)phenol (2), 2,6-bis(1,1-dimethylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (3), 2,4-bis(1,1,3,3-tetramethylbutyl)phenol (4), 2-(1,1-dimethylethyl)4,6-bis(1,1,3,3-tetramethylbutyl)phenol (5) and 2,4,6-tris(1,1,3,3-tetramethylbutyl)phenol (6). Compound 1 was observed in five of the seven kinds of NBR gloves, and compounds 2-4 and 6, which are not listed in Chemical Abstract (CA), were present in four kinds of gloves.

  12. Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

    International Nuclear Information System (INIS)

    Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Mukhopadhyay, K.; Prasad, N. E.; Gandhi, M. N.; Bhattacharyya, A. R.

    2016-01-01

    Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS_2) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS_2 and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS_2 and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

  13. Influence of gamma irradiation on mechanical and thermal properties of waste polyethylene/nitrile butadiene rubber blend

    Directory of Open Access Journals (Sweden)

    Raouf O. Aly

    2016-11-01

    Full Text Available Gamma irradiation radical–radical interaction crosslinking of elastomers and thermoplastic is a special type of crosslinking technique that has gained importance over conventional chemical crosslinking method as process is fast, pollution free, and simple. In this work a blend polymer, based on waste polyethylene and nitrile butadiene rubber, has been irradiated with gamma-rays, mechanically and thermally investigated at varying NBR content. FTIR and SEM techniques were used in addition to the swelling behavior to emphasize the blend formation. Mechanical properties like tensile strength, elongation at break and modulus at different elongations were studied and compared with those of unirradiated ones. A relatively low-radiation dose was found effective in improving the level of mechanical properties. Differential scanning calorimeter and thermogravimetric analysis were used to study the thermal characteristics of the irradiated polymer. Enhancement in thermal stability has been observed for higher NBR containing blends and via radiation-induced crosslinking up to ≈50 kGy.

  14. Endocrine disruptive effects of chemicals eluted from nitrile-butadiene rubber gloves using reporter gene assay systems.

    Science.gov (United States)

    Satoh, Kanako; Nonaka, Ryouichi; Ohyama, Ken-ichi; Nagai, Fumiko; Ogata, Akio; Iida, Mitsuru

    2008-03-01

    Disposable gloves made of nitrile-butadiene rubber (NBR) are used for contact with foodstuffs rather than polyvinyl chloride gloves containing di(2-ethylhexyl)phthalate (DEHP), because endocrine-disruptive effects are suspected for phthalate diesters including DEHP. However, 4,4'-butylidenebis(6-t-butyl-m-cresol) (BBBC), 2,4-di-t-butylphenol, and 2,2,4-trimetyl-1,3-pentanediol diisobutyrate can be eluted from NBR gloves, and possibly also detected in food. In this study, we examined the endocrine-disrupting effects of these chemicals via androgen receptor (AR) and estrogen receptor (ER)-mediated pathways using stably transfected reporter gene cell lines expressing AR (AR-EcoScreen system) and ER (MVLN cells), respectively. We also examined the binding activities of these chemicals to AR and ER. The IC50 value of BBBC for antagonistic androgen was in the range of 10(-6)M. The strength of inhibition was about 5 times that of a known androgen antagonist, 1,1'-(2,2-dichloroethylidene)bis[4-chlorobenzene] (p,p'-DDE), and similar to that of bisphenol A. The IC50 value of BBBC for antagonistic estrogen was in the range of 10(-6)M. These results suggest that BBBC and its structural homologue, 4,4'-thiobis(6-t-butyl-m-cresol) are androgen and estrogen antagonists. It is therefore necessary to study these chemicals in vivo, and clarify their effect on the endocrine system.

  15. Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

    Science.gov (United States)

    Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Gandhi, M. N.; Bhattacharyya, A. R.; Mukhopadhyay, K.; Prasad, N. E.

    2016-05-01

    Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS2) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS2 and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS2 and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

  16. Enhancement of thermo-stability and product tolerance of Pseudomonas putida nitrile hydratase by fusing with self-assembling peptide.

    Science.gov (United States)

    Liu, Yi; Cui, Wenjing; Liu, Zhongmei; Cui, Youtian; Xia, Yuanyuan; Kobayashi, Michihiko; Zhou, Zhemin

    2014-09-01

    Self-assembling amphipathic peptides (SAPs) are the peptides that can spontaneously assemble into ordered nanostructures. It has been reported that the attachment of SAPs to the N- or C-terminus of an enzyme can benefit the thermo-stability of the enzyme. Here, we discovered that the thermo-stability and product tolerance of nitrile hydratase (NHase) were enhanced by fusing with two of the SAPs (EAK16 and ELK16). When the ELK16 was fused to the N-terminus of β-subunit, the resultant NHase (SAP-NHase-2) became an active inclusion body; EAK16 fused NHase in the N-terminus of β-subunit (SAP-NHase-1) and ELK16 fused NHase in the C-terminus of β-subunit (SAP-NHase-10) did not affect NHase solubility. Compared with the deactivation of the wild-type NHase after 30 min incubation at 50°C, SAP-NHase-1, SAP-NHase-2 and SAP-NHase-10 retained 45%, 30% and 50% activity; after treatment in the buffer containing 10% acrylamide, the wild-type retained 30% activity, while SAP-NHase-1, SAP-NHase-2 and SAP-NHase-10 retained 52%, 42% and 55% activity. These SAP-NHases with enhanced thermo-stability and product tolerance would be helpful for further industrial applications of the NHase. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  17. Transport properties of carboxylated nitrile butadiene rubber (XNBR)-nanoclay composites; a promising material for protective gloves in occupational exposures.

    Science.gov (United States)

    Mirzaei Aliabadi, Mostafa; Naderi, Ghasem; Shahtaheri, Seyed Jamaleddin; Forushani, Abbas Rahimi; Mohammadfam, Iraj; Jahangiri, Mehdi

    2014-02-28

    This study was conducted in response to one of the research needs of National Institute for Occupational Safety and Health (NIOSH), i.e. the application of nanomaterials and nanotechnology in the field of occupational safety and health. In order to fill this important knowledge gap, the equilibrium solubility and diffusion of carbon tetrachloride and ethyl acetate through carboxylated nitrile butadiene rubber (XNBR)-clay nanocomposite, as a promising new material for chemical protective gloves (or barrier against the transport of organic solvent contaminant), were examined by swelling procedure. Near Fickian diffusion was observed for XNBR based nanocomposites containing different amounts of nanoclay. Decontamination potential is a key factor in development of a new material for reusable chemical protective gloves applications, specifically for routine or highly toxic exposures. A thermal decontamination regime for nanocomposite was developed for the first time. Then, successive cycles of exposure/decontamination for nanocomposite were performed to the maximum 10 cycles for the first time. This result confirms that the two selected solvents cannot deteriorate the rubber-nanoclay interaction and, therefore, such gloves can be reusable after decontamination.

  18. Visible light photoactivity of TiO{sub 2} loaded with monometallic (Au or Pt) and bimetallic (Au/Pt) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gołąbiewska, Anna, E-mail: annagolabiewska@o2.pl [Department of Chemical Technology, Gdansk University of Technology, 80-233 Gdańsk (Poland); Lisowski, Wojciech [Mazovia Center for Surface Analysis, Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw (Poland); Jarek, Marcin; Nowaczyk, Grzegorz [NanoBioMedical Center, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Zielińska-Jurek, Anna; Zaleska, Adriana [Department of Chemical Technology, Gdansk University of Technology, 80-233 Gdańsk (Poland)

    2014-10-30

    Graphical abstract: - Highlights: • Au/Pt nanoparticles enhanced TiO{sub 2} photocatalytic activity under visible irradiation. • Higher photoactivity of Au/Pt-TiO{sub 2} resulted from smaller Au/Pt particles. • Intermetallic state of AuPt favors charge transfer between the metals. • TiO{sub 2} obtained by TIP hydrolysis seems to be best matrix for Au/Pt-TiO{sub 2}. - Abstract: TiO{sub 2} modified with monometallic (Au or Pt) and bimetallic (Au/Pt) nanoparticles have been prepared using a water-in-oil microemulsion system (water/AOT/cyclohexane) followed by calcination step. The effect of metal ratio, reducing agent type (NaBH{sub 4} or N{sub 2}H{sub 4}), TiO{sub 2} matrix type (P-25, ST-01, TiO-5, TiO{sub 2} nanotubes or TiO{sub 2} obtained by TIP hydrolysis) as well as calcination temperature (from 350 to 650 °C) were systematically investigated. Obtained photocatalysts were characterized by UV–vis diffuse-reflectance spectroscopy (DRS), BET surface area measurements, scanning transmission microscopy (STEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity under visible light (λ > 420 nm) has been estimated in phenol degradation reaction in aqueous phase. The results showed that phenol degradation rate under visible light in the presence of TiO{sub 2} loaded with Au/Pt nanoparticles differed from 0.7 to 2.2 μmol dm{sup −3} min{sup −1} for samples prepared using different reducing agent. Sodium borohydride (NaBH{sub 4}) favors formation of smaller Au/Pt nanoparticles and higher amount gold in Au/Pt is in the form of electronegative species (Au{sup δ−}) resulted in higher photoactivity. TiO{sub 2} obtained by TIP hydrolysis in microemulsion system seems to be the best support for Au/Pt nanoparticles from all among investigated matrix. It was also observed that enhancement of calcination temperature from 450 to 650 °C resulted in rapid drop of Au/Pt-TiO{sub 2} photoactivity under visible light

  19. Inhibitor mechanisms in the S1 binding site of the dopamine transporter defined by multi-site molecular tethering of photoactive cocaine analogs.

    Science.gov (United States)

    Krout, Danielle; Pramod, Akula Bala; Dahal, Rejwi Acharya; Tomlinson, Michael J; Sharma, Babita; Foster, James D; Zou, Mu-Fa; Boatang, Comfort; Newman, Amy Hauck; Lever, John R; Vaughan, Roxanne A; Henry, L Keith

    2017-10-15

    Dopamine transporter (DAT) blockers like cocaine and many other abused and therapeutic drugs bind and stabilize an inactive form of the transporter inhibiting reuptake of extracellular dopamine (DA). The resulting increases in DA lead to the ability of these drugs to induce psychomotor alterations and addiction, but paradoxical findings in animal models indicate that not all DAT antagonists induce cocaine-like behavioral outcomes. How this occurs is not known, but one possibility is that uptake inhibitors may bind at multiple locations or in different poses to stabilize distinct conformational transporter states associated with differential neurochemical endpoints. Understanding the molecular mechanisms governing the pharmacological inhibition of DAT is therefore key for understanding the requisite interactions for behavioral modulation and addiction. Previously, we leveraged complementary computational docking, mutagenesis, peptide mapping, and substituted cysteine accessibility strategies to identify the specific adduction site and binding pose for the crosslinkable, photoactive cocaine analog, RTI 82, which contains a photoactive azide attached at the 2β position of the tropane pharmacophore. Here, we utilize similar methodology with a different cocaine analog N-[4-(4-azido-3-I-iodophenyl)-butyl]-2-carbomethoxy-3-(4-chlorophenyl)tropane, MFZ 2-24, where the photoactive azide is attached to the tropane nitrogen. In contrast to RTI 82, which crosslinked into residue Phe319 of transmembrane domain (TM) 6, our findings show that MFZ 2-24 adducts to Leu80 in TM1 with modeling and biochemical data indicating that MFZ 2-24, like RTI 82, occupies the central S1 binding pocket with the (+)-charged tropane ring nitrogen coordinating with the (-)-charged carboxyl side chain of Asp79. The superimposition of the tropane ring in the three-dimensional binding poses of these two distinct ligands provides strong experimental evidence for cocaine binding to DAT in the S1 site

  20. A novel photo-active Cd:1,4-benzene dicarboxylate metal organic framework templated using [Ru(ii)(2,2'-bipyridine)3]2+: synthesis and photophysics of RWLC-5.

    Science.gov (United States)

    Larsen, Randy W; Mayers, Jacob M; Wojtas, Lukasz

    2017-09-26

    The development of photoactive porous materials is of significant importance for applications ranging from sustainable energy to pharmaceutical development and catalysis. A particularly attractive class of photo-active materials is the metal-organic framework (MOF)-based platform in which the photo-active elements are components of the framework itself or photo-active guests encapsulated within the MOF cavities. It has now been demonstrated that the photo-active [Ru(2,2'-bipyridine) 3 ] 2+ (RuBpy) complex can template the formation of MOFs with varying three dimensional structures. Here we report the synthesis and structural and photo-physical characterization of a new RuBpy-templated MOF composed of Cd 2+ ions with 1,4-benzenedicarboxylate ligands (RWLC-5) that contains crystallographically resolved RuBpy complexes. The new material displays a biphasic emission decay (130 ns and 1180 ns, T = 20 °C) and a bathochromically shifted emission maximum, relative to RuBpy in solution (603 nm for RuBpy in ethanol vs. 630 nm for RWLC-5). The emission lifetimes also do not display temperature-dependent decays which are characteristic of RuBpy type complexes as well as other RuBpy templated MOFs. The lack of temperature dependence is consistent with the complete deactivation of the 3 LF state of the encapsulated RuBpy complex due to a constrained environment. The fast phase decay is attributed to a water molecule hydrogen bonded to a bipyridine ligand associated with ∼38% of the encapsulated RuBpy complexes resulting in the nonradiative deactivation of the 3 MLCT state.

  1. A comparative study on the performance of hybrid solar cells containing ZnSTe QDs in hole transporting layer and photoactive layer

    Energy Technology Data Exchange (ETDEWEB)

    Najeeb, Mansoor Ani [Qatar University, Center for Advanced Materials (CAM) (Qatar); Abdullah, Shahino Mah; Aziz, Fakhra [University of Malaya, Low Dimensional Materials Research Centre (LDMRC), Department of Physics, Faculty of Science (Malaysia); Ahmad, Zubair, E-mail: zubairtarar@qu.edu.qa; Shakoor, R. A. [Qatar University, Center for Advanced Materials (CAM) (Qatar); Mohamed, A. M. A. [Suez University, Department of Metallurgical and Materials Engineering, Faculty of Petroleum and Mining Engineering (Egypt); Khalil, Uzma [University of Peshawar, Department of Electronics, Jinnah College for Women (Pakistan); Swelm, Wageh; Al-Ghamdi, Ahmed A. [King Abdulaziz University, Department of Physics, Faculty of Science (Saudi Arabia); Sulaiman, Khaulah [University of Malaya, Low Dimensional Materials Research Centre (LDMRC), Department of Physics, Faculty of Science (Malaysia)

    2016-12-15

    In this paper, ZnSTe quantum dots-based hybrid solar cells (HSC) with two different device architectures have been investigated. The improved performance of the poly(3-hexylthiophene) (P3HT) and [6,6]phenyl C{sub 71} butyric acid methyl ester (PC{sub 71}BM)-based bulk heterojunction (BHJ) solar cells by the incorporation of ZnSTe quantum dots (QDs) with an average size of 2.96 nm in PEDOT:PSS layer and active layer that have been demonstrated. Although the efficiency of both types of devices is almost the same, a close comparison reveals different reasons behind their improved performance. The device prepared with QDs in the HTL has shown reduced series resistance, increased shunt resistance, and improved mobility. On the other hand, QDs in the photoactive layer demonstrates increased photo-generation leading to improved efficiency.

  2. Fabrication and photoactivity of ionic liquid-TiO2 structures for efficient visible-light-induced photocatalytic decomposition of organic pollutants in aqueous phase.

    Science.gov (United States)

    Gołąbiewska, Anna; Paszkiewicz-Gawron, Marta; Sadzińska, Aleksandra; Lisowski, Wojciech; Grabowska, Ewelina; Zaleska-Medynska, Adriana; Łuczak, Justyna

    2018-01-01

    To investigate the effect of the ionic liquid (IL) chain length on the surface properties and photoactivity of TiO 2 , a series of TiO 2 microspheres have been synthesized via a solvothermal method assisted by 1-methyl-3-octadecylimidazolium chloride ([ODMIM][Cl]) and 1-methyl-3-tetradecylimidazolium chloride ([TDMIM][Cl]). All as-prepared samples were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), scanning transmission microscopy (STEM) and the Brunauer-Emmett-Teller (BET) surface area method, whereas the photocatalytic activity was evaluated by the degradation of phenol in aqueous solution under visible light irradiation (λ > 420 nm). The highest photoefficiency (four times higher than pristine TiO 2 ) was observed for the TiO 2 sample obtained in the presence of [TDMIM][Cl] for a IL to TiO 2 precursor molar ratio of 1:3. It was revealed that interactions between the ions of the ionic liquid and the surface of the growing titanium dioxide spheres results in a red-shift of absorption edge for the IL-TiO 2 semiconductors. In this regard, the direct increase of the photoactivity of IL-TiO 2 in comparison to pristine TiO 2 was observed. The active species trapping experiments indicated that O 2 •- is the main active species, created at the surface of the IL-TiO 2 material under visible-light illumination, and is responsible for the effective phenol degradation.

  3. Direct in situ activation of Ag{sup 0} nanoparticles in synthesis of Ag/TiO{sub 2} and its photoactivity

    Energy Technology Data Exchange (ETDEWEB)

    Jaafar, N.F. [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Jalil, A.A., E-mail: aishah@cheme.utm.my [Institute of Hydrogen Economy, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Department of Chemical Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Triwahyono, S. [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Ibnu Sina Institute for Fundamental Science Studies, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Efendi, J. [Department of Chemistry, Universitas Negeri Padang, Jl. Prof. Hamka, Air Tawar, Padang, West Sumatera (Indonesia); Mukti, R.R. [Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jl Ganesha No. 10, Bandung 40132 (Indonesia); Jusoh, R.; Jusoh, N.W.C. [Department of Chemical Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Karim, A.H. [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Salleh, N.F.M. [Department of Chemical Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Suendo, V. [Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jl Ganesha No. 10, Bandung 40132 (Indonesia)

    2015-05-30

    Graphical abstract: - Highlights: • Ag{sup 0} loaded on TiO{sub 2} was prepared by a direct in situ electrochemical method. • 5 wt% Ag–TiO{sub 2} demonstrated the best photocatalytic degradation of 2-CP. • Isomorphous substitution of Ag with Ti occurred to form Ti−O−Ag bonds. • Ag{sup 0} and oxygen vacancies trapped electrons to enhance e–H{sup +} separation. • Substitution of Ag in the TiO{sub 2} structure decreased the number of oxygen vacancies. - Abstract: Metallic Ag nanoparticles (Ag{sup 0}) were successfully activated using a direct in situ electrochemical method before being supported on TiO{sub 2}. Catalytic testing showed that 5 wt% Ag–TiO{sub 2} gave the highest photodegradation (94%) of 50 mg L{sup −1} 2-chlorophenol (2-CP) at pH 5 using 0.375 g L{sup −1} catalyst within 6 h, while under similar conditions, 1 wt% and 10 wt% Ag–TiO{sub 2} only gave 75% and 78% degradation, respectively. Characterization results illustrated that the photoactivity was affected by the amount of Ag{sup 0} and oxygen vacancies which act as an electrons trap to enhance the electron–hole separation. While, the Ag−O−Ti bonds formation reduced the photoactivity. The degradation followed a pseudo-first order Langmuir–Hinshelwood model where adsorption was the controlling step. Study on the effect of scavengers showed that the hole (H{sup +}) and hydroxyl radical (OH·) play important roles in the photodegradation. The regenerated photocatalyst was still stable after five cycling runs.

  4. The influence of alizarin and fluorescein on the photoactivity of Ni, Pt and Ru-doped TiO2 layers

    International Nuclear Information System (INIS)

    Rosu, Marcela-Corina; Suciu, Ramona-Crina; Lazar, Mihaela D.; Bratu, I.

    2013-01-01

    Highlights: ► The Ni, Pt, Ru-doped TiO 2 materials and sensitized with alizarin and fluorescein dyes were prepared by wet chemical route. ► The samples were characterized by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N 2 physisorption measurements. ► A combined influence of the dopants and dyes was observed, leading to a beneficial effect to TiO 2 photoactivity. -- Abstract: The doping with different metal ions and sensitization with organic compounds are two well known methods used to improve the photoactivity of TiO 2 . In this respect, the metallic ions-doped TiO 2 samples were prepared by embedding Ni, Pt and Ru ions into TiO 2 crystalline network and then, each sample was sensitized with alizarin and fluorescein dyes. The qualitative evaluation of prepared TiO 2 -based materials was made by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N 2 physisorption measurements. The optoelectronic properties investigated by UV–vis spectroscopy show that the optical response of Ni-doped TiO 2 layer shifts to visible. The X-ray spectra do not show peaks of nickel, platinum and ruthenium oxide crystals or pure metals. The FT/IR spectra proved the presence of dye molecules adsorbed on titania nanoparticles surface. These results demonstrated that the studied dopants and dyes have potential to promote modified TiO 2 -based materials as good candidates to be used in photolectrocatalytic processes

  5. The influence of alizarin and fluorescein on the photoactivity of Ni, Pt and Ru-doped TiO{sub 2} layers

    Energy Technology Data Exchange (ETDEWEB)

    Rosu, Marcela-Corina, E-mail: marcela.rosu@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Street, 400293, Cluj-Napoca (Romania); Suciu, Ramona-Crina; Lazar, Mihaela D.; Bratu, I. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Street, 400293, Cluj-Napoca (Romania)

    2013-04-20

    Highlights: ► The Ni, Pt, Ru-doped TiO{sub 2} materials and sensitized with alizarin and fluorescein dyes were prepared by wet chemical route. ► The samples were characterized by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N{sub 2} physisorption measurements. ► A combined influence of the dopants and dyes was observed, leading to a beneficial effect to TiO{sub 2} photoactivity. -- Abstract: The doping with different metal ions and sensitization with organic compounds are two well known methods used to improve the photoactivity of TiO{sub 2}. In this respect, the metallic ions-doped TiO{sub 2} samples were prepared by embedding Ni, Pt and Ru ions into TiO{sub 2} crystalline network and then, each sample was sensitized with alizarin and fluorescein dyes. The qualitative evaluation of prepared TiO{sub 2}-based materials was made by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N{sub 2} physisorption measurements. The optoelectronic properties investigated by UV–vis spectroscopy show that the optical response of Ni-doped TiO{sub 2} layer shifts to visible. The X-ray spectra do not show peaks of nickel, platinum and ruthenium oxide crystals or pure metals. The FT/IR spectra proved the presence of dye molecules adsorbed on titania nanoparticles surface. These results demonstrated that the studied dopants and dyes have potential to promote modified TiO{sub 2}-based materials as good candidates to be used in photolectrocatalytic processes.

  6. On the interactions of nitriles and fluoro-substituted pyridines with silicon tetrafluoride: Computations and thin film IR spectroscopy

    Science.gov (United States)

    Hora, Nicholas J.; Wahl, Benjamin M.; Soares, Camilla; Lara, Skylee A.; Lanska, John R.; Phillips, James A.

    2018-04-01

    The nature of the interactions between silicon tetrafluoride and series of nitrogen bases, including nitriles (RCN, with R > CH3), pyridine, and various fluoro-substituted pyridines, has been investigated via quantum-chemical computations, low-temperature IR spectroscopy, and bulk reactivity experiments. Using (primarily) M06 with the 6-311+G(2df,2pd) basis set, we obtained equilibrium structures, binding energies, harmonic frequencies, and N-Si potentials in the gas-phase and in bulk dielectric media for an extensive series of 1:1 molecular complexes, including: C6H5CH2CN-SiF4, CH3CH2CN-SiF4, (CH3)3CCN-SiF4, C5H5N-SiF4, 4-FC5H4N-SiF4, 3,5-C5F2H3N-SiF4, 2,6-C5F2H3N-SiF4 and 3,4,5-C5F3H2N-SiF4. In addition, for the analogous 2:1 complexes of pyridine and 3,5-difluororpyridine, we obtained equilibrium structures, binding energies, and harmonic frequencies. The N-Si distances in the 1:1 nitrile complexes are fairly long, ranging from 2.84 Å to 2.88 Å, and the binding energies range from 4.0 to 4.2 kcal/mol (16.7-17.6 kJ/mol). Also, computations predict extremely anharmonic N-Si potentials, for which the inner portions of the curve are preferentially stabilized in dielectric media, which predict an enhancement of these interactions in condensed-phases. However, we see no evidence of bulk reactivity between C6H5CH2CN, CH3CH2CN, or (CH3)3CCN and SiF4, nor any significant interaction between (CH3)3CCN and SiF4 in low temperature IR spectra of solid, (CH3)3CCN/SiF4 thin films. Conversely, the interactions in four of the five 1:1, pyridine-SiF4 complexes are generally stronger; binding energies range from 5.7 to 9.6 kcal/mol (23.8-40.2 kJ/mol), and correspondingly the N-Si distances are relatively short (2.12-2.25 Å). The exception is 2,6-C5F2H3N-SiF4, for which the binding energy is only 3.6 kcal/mol (15.1 kJ/mol), and the N-Si distance is quite long (3.12 Å). In addition, both pyridine and 3,5-difluororpyridine were found to form stable reaction products with SiF4

  7. Highly selective separation of carbon dioxide from nitrogen and methane by nitrile/glycol-difunctionalized ionic liquids in supported ionic liquid membranes (SILMs).

    Science.gov (United States)

    Hojniak, Sandra D; Silverwood, Ian P; Khan, Asim Laeeq; Vankelecom, Ivo F J; Dehaen, Wim; Kazarian, Sergei G; Binnemans, Koen

    2014-07-03

    Novel difunctionalized ionic liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic liquid membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the considerably reduced permeances of N2 and CH4, most likely due to the ability of the -CN group to reject the nonpolar contaminant gases. Apart from the CO2 solubility, IL-CO2 interactions and IL swelling were studied with the in situ ATR-FTIR spectroscopy. Different strengths of the IL-CO2 interactions were found to be the major difference between the two classes of ILs. The difunctionalized ILs interacted stronger with CO2 than the glycol-functionalized ILs, as manifested in the smaller bandwidths of the bending mode band of CO2 for the latter.

  8. Understanding interpenetrating-polymer-network-like porous nitrile butadiene rubber hybrids by their long-period miscibility

    International Nuclear Information System (INIS)

    Zhang, Jihua; Wang, Lifeng; Zhao, Yunfeng

    2013-01-01

    Highlights: • Hydrogen bonds are introduced into NBR to develop its IPN-like porous hybrids. • NBR is partly miscible with AO-60. • AO-60 possesses the viscoelastic behavior resembling that of polymers. • Phase separation aggravates and AO-60 crystallizes in the durations. • The porous hybrids may have potential damping applications. - Abstract: In this article, tetrakis [methylene-3-(3, 5-di-tert-butyl-4-hydroxy phenyl) propionyloxy] methane (AO-60) with hydrogen bonds was designed to interpenetrate into the chemical crosslinking bonds of nitrile butadiene rubber (NBR) and then porous materials were prepared. Scanning electron microscopy (SEM), atomic force microscopy (AFM) images and dynamic mechanical analyses (DMA) demonstrate that NBR is partly miscible with AO-60 which induces the micro-pores and interpenetrating-polymer-network (IPN)-like phase morphology in the hybrids. The wide double tan δ peak in DMA curve displays that AO-60 possesses similar viscoelastic behaviors to polymers which come from supramolecular interactions between polar groups of NBR chains and hydroxyl (OH) groups of AO-60. To further understand the supramolecular abilities of AO-60 in the rubber, the long-period observations for their miscibility are conducted. With the increase of durations, the hydrogen bond network from AO-60 is weakened. The phase separation between AO-60 and NBR is aggravated and even extremely few AO-60 crystallizes which develops multi-scale porous morphology in the hybrids. It is believed that these findings can serve as a guide for the designs of the IPN-like hybrids with small molecule substances and their applications of damping materials

  9. Investigation of Ageing Behaviour of Nitrile-Butadiene Rubber with Added Graphene in an Accelerated Thermal Ageing Environment

    Directory of Open Access Journals (Sweden)

    Fei-Zhou Li

    2018-01-01

    Full Text Available In this paper, the thermal ageing of nitrile-butadiene rubber (NBR reinforced with different graphene (GE concentrations has been investigated. NBR and NBR-GE composites were exposed to an accelerated thermal ageing environment produced by an air-circulating oven for seven days. The mechanical properties, chemical changes, and thermal stability of ageing samples and neat samples were evaluated. The results showed that the surface damage of NBR was severe and inhomogeneous, and the degree of ageing was most serious on the edge region of the voids, but NBR-GE composites were changed slightly before and after ageing. The tensile strength increased with the increase of GE concentration, up to a maximum value, and decreased with further increases in GE concentration. The GE embedded crosslinked network limited the segment movement of chains in the stretch direction and played a role in the composites properties, and the GE sheets (contained the functional groups of −OH, −C=O and C=C after ageing. This behaviour may indicate greater interface adhesion between the GE and NBR. In addition, results obtained by thermogravimetric analysis (TGA indicated that the thermal stability of NBR significantly changed with accelerated thermal ageing environment, but with addition of a certain amount of GE to NBR, the thermal stability of NBR could be improved. The NBR/GE composites exhibited good comprehensive performance with a mass fraction of GE of 10 %. Before and after the thermal ageing, the failure mechanism of NBR-GE composites appeared intergranular and ductile fracture, respectively.

  10. Blends of nitrile butadiene rubber/poly (vinyl chloride: The use of maleated anhydride castor oil based plasticizer

    Directory of Open Access Journals (Sweden)

    Indiah Ratna Dewi

    2016-06-01

    Full Text Available Recently, much attention has been focused on research to replace petroleum-based plasticizers, with biodegradable materials, such as biopolymer which offers competitive mechanical properties. In this study, castor oil was modified with maleic anhydride (MAH to produce bioplasticizer named maleated anhydride castor oil (MACO, and used in nitrile butadiene rubber (NBR/poly vinyl chloride (PVC blend. The effect of MACO on its cure characteristics and mechanical properties of NBR/PVC blend has been determined. The reactions were carried out at different castor oil (CO/xylene ratios, i.e. 1:0 and 1:1 by weight, and fixed CO/MAH ratio, 1:3 by mole. DOP, CO, and MACO were added into each NBR/PVC blend according to the formula. It was found that the viscosity and safe process level of NBR/PVC blend is similar from all plasticizer, however, MACO (1:0 showed the highest cure rate index (CRI. MACO-based plasticizer gave a higher value of the mechanical properties of the NBR/PVC blend as compared to DOP based plasticizer. MACO (1:1 based plasticizer showed a rather significance performance compared to another type of plasticizers both before and after aging. The value of hardness, elongation at break, tensile strength, and tear strength were 96 Shore A, 155.91 %, 19.15 MPa, and 74.47 MPa, respectively. From this result, NBR/PVC blends based on MACO plasticizer can potentially replace the DOP, and therefore, making the rubber blends eco-friendly.

  11. Effect of magnetic and thermal properties of iron oxide nanoparticles (IONs) in nitrile butadiene rubber (NBR) latex

    Science.gov (United States)

    Ong, Hun Tiar; Julkapli, Nurhidayatullaili Muhd; Hamid, Sharifah Bee Abd; Boondamnoen, O.; Tai, Mun Foong

    2015-12-01

    Nitrile butadiene rubber (NBR) gloves are one of the most important personal protective equipments but they are possible to tear off and contaminate food or pharmaceutical and healthcare products during manufacturing and packaging process. High tendency of torn glove remaining in food or products due to white or light flesh-coloured glove is not easy to be detected by naked eyes. In this paper, iron oxide nanoparticles (IONs) selected as additive for NBR to improve its detectability by mean of magnetic properties. IONs synthesized via precipitation method and compounded with NBR latex before casting on petri dish. The properties of IONs were investigated by X-ray Diffractometry (XRD), Transmission Electron Microscope (TEM), Raman Spectroscopy and Vibrating Sample Magnetometer (VSM). Meanwhile NBR/IONs composites were studied by Thermogravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Vibrating Sample Magnetometer (VSM). It observed that, synthesized IONs shows of 25.28 nm crystallite with 25.86 nm semipherical (changed as) shape. Meanwhile, Magnetite and maghemite phase are found in range of 670 cm-1 and 700 cm-1 respectively, which it contributes magnetization saturation of 73.96 emu/g at 10,000 G by VSM. Thermal stability and magnetic properties were increased with incorporating IONs into NBR latex up to 20 phr. NBR/IONs 5 phr has the optimum thermal stability, lowest glass transition temperature (-14.83 °C) and acceptable range of magnetization saturation (3.83 emu/g at 10,000 G) to form NBR gloves with magnetic detectability.

  12. Probing α-relaxation with nuclear magnetic resonance echo decay and relaxation: a study on nitrile butadiene rubber.

    Science.gov (United States)

    Sturniolo, Simone; Pieruccini, Marco; Corti, Maurizio; Rigamonti, Attilio

    2013-01-01

    One dimensional (1)H NMR measurements have been performed to probe slow molecular motions in nitrile butadiene rubber (NBR) around its calorimetric glass transition temperature Tg. The purpose is to show how software aided data analysis can extract meaningful dynamical data from these measurements. Spin-lattice relaxation time, free induction decay (FID) and magic sandwich echo (MSE) measurements have been carried out at different values of the static field, as a function of temperature. It has been evidenced how the efficiency of the MSE signal in reconstructing the original FID exhibits a sudden minimum at a given temperature, with a slight dependence from the measuring frequency. Computer simulations performed with the software SPINEVOLUTION have shown that the minimum in the efficiency reconstruction of the MSE signal corresponds to the average motional frequency taking a value around the inter-proton coupling. The FID signals have been fitted with a truncated form of a newly derived exact correlation function for the transverse magnetization of a dipolar interacting spin pair, which allows one to avoid the restriction of the stationary and Gaussian approximations. A direct estimate of the conformational dynamics on approaching the Tg is obtained, and the results are in agreement with the analysis performed via the MSE reconstruction efficiency. The occurrence of a wide distribution of correlation frequencies for the chains motion, with a Vogel-Fulcher type temperature dependence, is addressed. A route for a fruitful study of the dynamics accompanying the glass transition by a variety of NMR measurements is thus proposed. Copyright © 2013 Elsevier Inc. All rights reserved.

  13. One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

    Directory of Open Access Journals (Sweden)

    Roman Yu. Peshkov

    2016-07-01

    Full Text Available A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents.

  14. Reactions of uranium (III) and (IV) compounds with ketones, nitriles and acid chlorides. Towards a use of uranium complexes in organic synthesis

    International Nuclear Information System (INIS)

    Adam, Raymond

    1993-01-01

    In this research thesis, the author shows that various organic molecules can be interestingly transformed into uranium complexes with degrees of oxidation of +3 or +4. In a first part, the author describes reactions of carbonyl compounds with the UCl 4 -Na(Hg) reducing system. Then, he addresses reductions of ketones, nitriles and acid chlorides by a uranium (III) complex: Cp 3 U(THF). The third part reports a detailed study of the reduction of ketones by U(BH 4 ) 4 [fr

  15. Enhancement of Compatibility between Ultrahigh-Molecular-Weight Polyethylene Particles and Butadiene.Nitrile Rubber Matrix with Nanoscale Ceramic Particles and Characterization of Evolving Layer

    International Nuclear Information System (INIS)

    Shadrinov, Nikolay V.; Sokolova, Marina D.; Cho, Jinho; Okhlopkova, A. A.; Lee, Jungkeun; Jeong, Daeyong

    2013-01-01

    This article examines the modification of surface properties of ultrahigh-molecular-weight polyethylene (UHMWPE) with nanoscale ceramic particles to fabricate an improved composite with butadiene.nitrile rubber (BNR). Adhesion force data showed that ceramic zeolite particles on the surface of UHMWPE modulated the surface state of the polymer and increased its compatibility with BNR. Atomic force microscopy phase images showed that UHMWPE made up the microphase around the zeolite particles and formed the evolving layer with a complex interface. The complex interface resulted in improvements in the mechanical properties of the composite, especially its low-temperature resistance coefficients, thereby improving its performance in low-temperature applications

  16. Studies of bio-mimetic medium of ionic and non-ionic micelles by a simple charge transfer fluorescence probe N,N-dimethylaminonapthyl-(acrylo)-nitrile

    Science.gov (United States)

    Samanta, Anuva; Paul, Bijan Kumar; Guchhait, N.

    2011-05-01

    In this report we have studied micellization process of anionic, cationic and non-ionic surfactants using N,N-dimethylaminonapthyl-(acrylo)-nitrile (DMANAN) as an external fluorescence probe. Micropolarity, microviscosity, critical micellar concentration of these micelles based on steady state absorption and fluorescence and time resolved emission spectroscopy of the probe DMANAN show that the molecule resides in the micelle-water interface for ionic micelles and in the core for the non-ionic micelle. The effect of variation of pH of the micellar solution as well as fluorescence quenching measurements of DMANAN provide further support for the location of the probe in the micelles.

  17. Formation of nitrile species on Ag nanostructures supported on a-Al2O3: a new corrosion route for silver exposed to the atmosphere

    Science.gov (United States)

    Peláez, R. J.; Espinós, J. P.; Afonso, C. N.

    2017-04-01

    The aging of supported Ag nanostructures upon storage in ambient conditions (air and room temperature) for 20 months has been studied. The samples are produced on glass substrates by pulsed laser deposition (PLD); first a 15 nm thick buffer layer of amorphous aluminum oxide (a-Al2O3) is deposited, followed by PLD of Ag. The amount of deposited Ag ranges from that leading to a discontinuous layer up to an almost-percolated layer with a thickness of oxidized faster, the smaller the amount of Ag. The corrosion leads to the formation of nitrile species due to the reaction between NO x species from the atmosphere adsorbed at the surface of Ag, and hydrocarbons adsorbed in defects at the surface of the a-Al2O3 layer during the deposition of the Ag nanostructures by PLD that migrate to the surface of the metal with time. The nitrile formation thus results in the main oxidation mechanism and inhibits almost completely the formation of sulphate/sulphide. Finally, the optical changes upon aging offer an easy-to-use tool for following the aging process. They are dominated by an enhanced absorption in the UV side of the spectrum and a blue-shift of the surface plasmon resonance that are, respectively, related to the formation of a dielectric overlayer on the Ag nanostructure and changes in the dimensions/features of the nanostructures, both due to the oxidation process.

  18. Adhesion of nitrile rubber to UV-assisted surface chemical modified PET fabric, part II: Interfacial characterization of MDI grafted PET

    Science.gov (United States)

    Razavizadeh, Mahmoud; Jamshidi, Masoud

    2016-08-01

    Fiber to rubber adhesion is an important subject in rubber industry. It is well known that surface treatment (i.e. physical, mechanical and chemical) is an effective method to improve interfacial bonding of fibers and/or fabrics to rubbers. UV irradiation is an effective method which has been used to increase fabric-rubber interfacial interactions. In this research UV assisted chemical modification of PET fabrics was used to increase PET to nitrile rubber (NBR) adhesion. Nitrile rubber is a perfect selection as fuel and oil resistant rubber. However it has weak bonding to PET fabric. For this purpose PET fabric was carboxylated under UV irradiation and then methylenediphenyl diisocyanate (MDI) was grafted on carboxylated PET. The chemical composition of the fabric before and after surface treatment was investigated by X-ray photoelectron spectroscopy (XPS). The sectional morphology of the experimental PET fibers and the interface between rubber compound and PET fabric was studied using scanning electron microscope (SEM). The morphology and structure of the product were analyzed by an energy dispersive X-ray spectrometer (EDX). FTIR-ATR and H NMR analysis were used to assess surface modifications on the PET irradiated fabrics.

  19. Catalytic Mechanism of Nitrile Hydratase Proposed by Time-resolved X-ray Crystallography Using a Novel Substrate, tert-Butylisonitrile*S⃞

    Science.gov (United States)

    Hashimoto, Koichi; Suzuki, Hiroyuki; Taniguchi, Kayoko; Noguchi, Takumi; Yohda, Masafumi; Odaka, Masafumi

    2008-01-01

    Nitrile hydratases (NHases) have an unusual iron or cobalt catalytic center with two oxidized cysteine ligands, cysteine-sulfinic acid and cysteine-sulfenic acid, catalyzing the hydration of nitriles to amides. Recently, we found that the NHase of Rhodococcus erythropolis N771 exhibited an additional catalytic activity, converting tert-butylisonitrile (tBuNC) to tert-butylamine. Taking advantage of the slow reactivity of tBuNC and the photoreactivity of nitrosylated NHase, we present the first structural evidence for the catalytic mechanism of NHase with time-resolved x-ray crystallography. By monitoring the reaction with attenuated total reflectance-Fourier transform infrared spectroscopy, the product from the isonitrile carbon was identified as a CO molecule. Crystals of nitrosylated inactive NHase were soaked with tBuNC. The catalytic reaction was initiated by photo-induced denitrosylation and stopped by flash cooling. tBuNC was first trapped at the hydrophobic pocket above the iron center and then coordinated to the iron ion at 120 min. At 440 min, the electron density of tBuNC was significantly altered, and a new electron density was observed near the isonitrile carbon as well as the sulfenate oxygen of αCys114. These results demonstrate that the substrate was coordinated to the iron and then attacked by a solvent molecule activated by αCys114-SOH. PMID:18948265

  20. THE DISSOCIATIVE RECOMBINATION OF PROTONATED ACRYLONITRILE, CH2CHCNH+, WITH IMPLICATIONS FOR THE NITRILE CHEMISTRY IN DARK MOLECULAR CLOUDS AND THE UPPER ATMOSPHERE OF TITAN

    International Nuclear Information System (INIS)

    Vigren, E.; Hamberg, M.; Zhaunerchyk, V.; Kaminska, M.; Thomas, R. D.; Larsson, M.; Geppert, W. D.; Millar, T. J.; Walsh, C.

    2009-01-01

    Measurements on the dissociative recombination (DR) of protonated acrylonitrile, CH 2 CHCNH + , have been performed at the heavy ion storage ring CRYRING located in the Manne Siegbahn Laboratory in Stockholm, Sweden. It has been found that at ∼2 meV relative kinetic energy about 50% of the DR events involve only ruptures of X-H bonds (where X = C or N) while the rest leads to the production of a pair of fragments each containing two heavy atoms (alongside H and/or H 2 ). The absolute DR cross section has been investigated for relative kinetic energies ranging from ∼1 meV to 1 eV. The thermal rate coefficient has been determined to follow the expression k(T) = 1.78 x 10 -6 (T/300) - 0.80 cm 3 s -1 for electron temperatures ranging from ∼10 to 1000 K. Gas-phase models of the nitrile chemistry in the dark molecular cloud TMC-1 have been run and results are compared with observations. Also, implications of the present results for the nitrile chemistry of Titan's upper atmosphere are discussed.

  1. μ-Hexa-thio-metadiphosphato-bis-[(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6) O)rubidium] aceto-nitrile disolvate.

    Science.gov (United States)

    Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

    2013-12-01

    The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto-nitrile solvent mol-ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb(+) ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6](2-) moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6](2-) anion. The hexa-thio-metadiphosphate anion is built up from two tetra-hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto-nitrile solvent mol-ecules stacked along [010].

  2. Nitrile/Buna N Material Failure Assessment for an O-Ring used on the Gaseous Hydrogen Flow Control Valve (FCV) of the Space Shuttle Main Engine

    Science.gov (United States)

    Wingard, Doug

    2006-01-01

    After the rollout of Space Shuttle Discovery in April 2005 in preparation for return-to-flight, there was a failure of the Orbiter (OV-103) helium signature leak test in the gaseous hydrogen (GH2) system. Leakage was attributed to the Flow Control Valve (FCV) in Main Engine 3. The FCV determined to be the source of the leak for OV-103 is designated as LV-58. The nitrile/Buna N rubber O-ring seal was removed from LV-58, and failure analysis indicated radial cracks providing leak paths in one quadrant. Cracks were eventually found in 6 of 9 FCV O-rings among the three Shuttle Orbiters, though none were as severe as those for LV-58, OV-103. Testing by EM10 at MSFC on all 9 FCV O- rings included: laser dimensional, Shore A hardness and properties from a dynamic mechanical analyzer (DMA) and an Instron tensile machine. The following test data was obtained on the cracked quadrant of the LV-58, OV-103 O-ring: (1) the estimated compression set was only 9.5%, compared to none for the rest of the O-ring; (2) Shore A hardness for the O.D. was higher by almost 4 durometer points than for the rest of the O-ring; and (3) DMA data showed that the storage/elastic modulus E was almost 25% lower than for the rest of the O-ring. Of the 8 FCV O-rings tested on an Instron, 4 yielded tensile strengths that were below the MIL spec requirement of 1350 psi-a likely influence of rubber cracking. Comparisons were made between values of modulus determined by DNA (elastic) and Instron (Young s). Each nitrile/Buna N O-ring used in the FCV conforms to the MIL-P-25732C specification. A number of such O-rings taken from shelf storage at MSFC and Kennedy Space Center (KSC) were used to generate a reference curve of DMA glass transition temperature (Tg) vs. shelf storage time ranging from 8 to 26 years. A similar reference curve of TGA onset temperature (of rubber weight loss) vs. shelf storage time was also generated. The DMA and TGA data for the used FCV O-rings were compared to the reference

  3. Variability in surface infrared reflectance of thirteen nitrile rubber gloves at key wavelengths for analysis of captan.

    Science.gov (United States)

    Phalen, R N; Que Hee, Shane S

    2007-02-01

    The aim of this study was to investigate the surface variability of 13 powder-free, unlined, and unsupported nitrile rubber gloves using attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectrophotometry at key wavelengths for analysis of captan contamination. The within-glove, within-lot, and between-lot variability was measured at 740, 1124, 1252, and 1735 cm(-1), the characteristic captan reflectance minima wavelengths. Three glove brands were assessed after conditioning overnight at relative humidity (RH) values ranging from 2 +/- 1 to 87 +/- 4% and temperatures ranging from -8.6 +/- 0.7 to 59.2 +/- 0.9 degrees C. For all gloves, 1735 cm(-1) provided the lowest background absorbance and greatest potential sensitivity for captan analysis on the outer glove surface: absorbances ranged from 0.0074 +/- 0.0005 (Microflex) to 0.0195 +/- 0.0024 (SafeSkin); average within-glove coefficients of variation (CV) ranged from 2.7% (Best, range 0.9-5.3%) to 10% (SafeSkin, 1.2-17%); within-glove CVs greater than 10% were for one brand (SafeSkin); within-lot CVs ranged from 2.8% (Best N-Dex) to 28% (SafeSkin Blue); and between-lot variation was statistically significant (p < or = 0.05) for all but two SafeSkin lots. The RH had variable effects dependent on wavelength, being minimal at 1735, 1252, and 1124 cm(-1) and highest at 3430 cm(-1) (O-H stretch region). There was no significant effect of temperature conditioning. Substantial within-glove, within-lot, and between-lot variability was observed. Thus, surface analysis using ATR-FT-IR must treat glove brands and lots as different. ATR-FT-IR proved to be a useful real-time analytical tool for measuring glove variability, detecting surface humidity effects, and choosing selective and sensitive wavelengths for analysis of nonvolatile surface contaminants.

  4. Effect of magnetic and thermal properties of iron oxide nanoparticles (IONs) in nitrile butadiene rubber (NBR) latex

    International Nuclear Information System (INIS)

    Ong, Hun Tiar; Julkapli, Nurhidayatullaili Muhd; Hamid, Sharifah Bee Abd; Boondamnoen, O.; Tai, Mun Foong

    2015-01-01

    Nitrile butadiene rubber (NBR) gloves are one of the most important personal protective equipments but they are possible to tear off and contaminate food or pharmaceutical and healthcare products during manufacturing and packaging process. High tendency of torn glove remaining in food or products due to white or light flesh-coloured glove is not easy to be detected by naked eyes. In this paper, iron oxide nanoparticles (IONs) selected as additive for NBR to improve its detectability by mean of magnetic properties. IONs synthesized via precipitation method and compounded with NBR latex before casting on petri dish. The properties of IONs were investigated by X-ray Diffractometry (XRD), Transmission Electron Microscope (TEM), Raman Spectroscopy and Vibrating Sample Magnetometer (VSM). Meanwhile NBR/IONs composites were studied by Thermogravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Vibrating Sample Magnetometer (VSM). It observed that, synthesized IONs shows of 25.28 nm crystallite with 25.86 nm semipherical (changed as) shape. Meanwhile, Magnetite and maghemite phase are found in range of 670 cm −1 and 700 cm −1 respectively, which it contributes magnetization saturation of 73.96 emu/g at 10,000 G by VSM. Thermal stability and magnetic properties were increased with incorporating IONs into NBR latex up to 20 phr. NBR/IONs 5 phr has the optimum thermal stability, lowest glass transition temperature (−14.83 °C) and acceptable range of magnetization saturation (3.83 emu/g at 10,000 G) to form NBR gloves with magnetic detectability. - Highlights: • We synthesized IONs with high magnetization saturation (M s ). • High M s of IONs were incorporated into NBR latex in order to induce magnetic properties in the NBR composite. • Introduction of IONs into NBR latex would improve thermal properties. • The produced NBR/IONs 5 phr composite exceeded the minimum magnetic moment sensor of the detector. • They have high potential for the

  5. Effect of magnetic and thermal properties of iron oxide nanoparticles (IONs) in nitrile butadiene rubber (NBR) latex

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Hun Tiar; Julkapli, Nurhidayatullaili Muhd; Hamid, Sharifah Bee Abd, E-mail: sharifahbee@um.edu.my; Boondamnoen, O.; Tai, Mun Foong

    2015-12-01

    Nitrile butadiene rubber (NBR) gloves are one of the most important personal protective equipments but they are possible to tear off and contaminate food or pharmaceutical and healthcare products during manufacturing and packaging process. High tendency of torn glove remaining in food or products due to white or light flesh-coloured glove is not easy to be detected by naked eyes. In this paper, iron oxide nanoparticles (IONs) selected as additive for NBR to improve its detectability by mean of magnetic properties. IONs synthesized via precipitation method and compounded with NBR latex before casting on petri dish. The properties of IONs were investigated by X-ray Diffractometry (XRD), Transmission Electron Microscope (TEM), Raman Spectroscopy and Vibrating Sample Magnetometer (VSM). Meanwhile NBR/IONs composites were studied by Thermogravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Vibrating Sample Magnetometer (VSM). It observed that, synthesized IONs shows of 25.28 nm crystallite with 25.86 nm semipherical (changed as) shape. Meanwhile, Magnetite and maghemite phase are found in range of 670 cm{sup −1} and 700 cm{sup −1} respectively, which it contributes magnetization saturation of 73.96 emu/g at 10,000 G by VSM. Thermal stability and magnetic properties were increased with incorporating IONs into NBR latex up to 20 phr. NBR/IONs 5 phr has the optimum thermal stability, lowest glass transition temperature (−14.83 °C) and acceptable range of magnetization saturation (3.83 emu/g at 10,000 G) to form NBR gloves with magnetic detectability. - Highlights: • We synthesized IONs with high magnetization saturation (M{sub s}). • High M{sub s} of IONs were incorporated into NBR latex in order to induce magnetic properties in the NBR composite. • Introduction of IONs into NBR latex would improve thermal properties. • The produced NBR/IONs 5 phr composite exceeded the minimum magnetic moment sensor of the detector. • They have high

  6. Boosting the Visible-Light Photoactivity of BiOCl/BiVO4/N-GQD Ternary Heterojunctions Based on Internal Z-Scheme Charge Transfer of N-GQDs: Simultaneous Band Gap Narrowing and Carrier Lifetime Prolonging.

    Science.gov (United States)

    Zhu, Mingyue; Liu, Qian; Chen, Wei; Yin, Yuanyuan; Ge, Lan; Li, Henan; Wang, Kun

    2017-11-08

    The efficient separation of photogenerated electron-hole pairs in photoactive materials is highly desired, allowing their transfer to specific sites for undergoing redox reaction in various applications. The construction of ternary heterojunctions is a practical strategy to enhance the migration of photogenerated electron that realizes the synergistic effect of multicomponents rather than the simple overlay of single component. Here, we demonstrate an available way to fabricate new BiOCl/BiVO 4 /nitrogen-doped graphene quantum dot (N-GQD) ternary heterojunctions that exhibit higher efficiency in charge separation than any binary heterojunction or pure material under visible-light irradiation. UV-vis diffuse reflectance spectroscopy demonstrated that the proposed BiOCl/BiVO 4 /N-GQD ternary heterojunctions possess the narrower band gap energy. More importantly, the ternary heterojunctions reveal the prolonged lifetime of photogenerated charges and enhanced the separation efficiency of photogenerated electron-hole pairs, which may be ascribed to sensitization based on an internal Z-scheme charge transfer at the interface of N-GQDs with oxygen functional groups. Furthermore, we examine the photoactive performance of proposed ternary heterojunctions in aqueous solution by using the photodegradation of bisphenol A as a model system and BiOCl/BiVO 4 /N-GQD ternary heterojunctions also display a dramatically enhanced photodegradation rate. The proposed charge separation and transfer process of BiOCl/BiVO 4 /N-GQD ternary heterojunctions for the enhanced photoactivity were deduced by electrochemical measurements, photoluminescence, and electron spin resonance. The results demonstrate that a Z-scheme charge process was formed between BiOCl/BiVO 4 binary heterojunctions and N-GQDs, leading to an efficient charge carrier separation and strong photocatalytic ability. Notably, this work may assist in a better understanding of the role of N-GQDs in kinds of heterojunctions

  7. Fabrication of Ce/N co-doped TiO{sub 2}/diatomite granule catalyst and its improved visible-light-driven photoactivity

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yan; Liu, Kuiren, E-mail: liukr@smm.neu.edu.cn

    2017-02-15

    Highlights: • Ce/N co-doped TiO{sub 2}/diatomite granule (CNTD-G) was prepared via sol-gel method. • The optimal doping amount of Ce was determined. • The effects of impurity ions on photodegradation process were studied. • The intermediates generated during photodegradation process were deduced. • The mechanism of photodegradation process was proposed. - Abstract: Eliminating antibiotic remnants in aquatic environment has become one of the hottest topics among current research works. Thus, we prepared Ce, N co-doped TiO{sub 2}/diatomite granule (CNTD-G) catalyst to provide a new method. As one typical antibiotics, oxytetracycline (OTC) was selected as the target pollutant to be degradated under visible light irradiation. The carrier diatomite helped the spread of TiO{sub 2} nanoparticles onto its surface, and inhibited their agglomeration. The synergy of Ce and N dopants highly improved the visible-light-driven photoactivity of TiO{sub 2}. The optimal doping amount and degradation conditions were determined. Besides, the effects of impurity ions were also investigated, including cations: Ca{sup 2+}, Mg{sup 2+}; or anions: NO{sub 3}{sup −}, SO{sub 4}{sup 2−} and PO{sub 4}{sup 3−}. The intermediates generated during degradation process were studied, and the mechanism of the photodegradation process was proposed. CNTD-G could be easily collected from the reactor, and showed excellent recyclability.

  8. A new photoactive Ru(II)tris(2,2'-bipyridine) templated Zn(II) benzene-1,4-dicarboxylate metal organic framework: structure and photophysical properties.

    Science.gov (United States)

    Whittington, Christi L; Wojtas, Lukasz; Gao, Wen-Yang; Ma, Shengqian; Larsen, Randy W

    2015-03-28

    It has now been demonstrated that Ru(ii)tris(2,2'-bipyridine) (RuBpy) can be utilized to template the formation of new metal organic framework (MOF) materials containing crystallographically resolved RuBpy clusters with unique photophysical properties. Two such materials, RWLC-1 and RWLC-2, have now been reported from our laboratory and are composed of RuBpy encapsulated in MOFs composed of Zn(ii) ions and 1,3,5-tris(4-carboxyphenyl)benzene ligands (C. L. Whittington, L. Wojtas and R. W. Larsen, Inorg. Chem., 2014, 53, 160-166). Here, a third RuBpy templated photoactive MOF is described (RWLC-3) that is derived from the reaction between Zn(ii) ions and 1,4-dicarboxybenzene in the presence of RuBpy. Single Crystal X-ray diffraction studies determined the position of RuBpy cations within the crystal lattice. The RWLC-3 structure is described as a 2-fold interpenetrated pillared honeycomb network (bnb) containing crystallographically resolved RuBpy clusters. The two bnb networks are weakly interconnected. The encapsulated RuBpy exhibits two emission decay lifetimes (τ-fast = 120 ns, τ-slow = 453 ns) and a bathochromic shift in the steady state emission spectrum relative to RuBpy in ethanol.

  9. Photoactivity enhancement of the Cd{sub x}Zn{sub 1−x}S nanoparticles by immobilizing on the graphene under visible light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jian, E-mail: wangjian@sxicc.ac.cn [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taoyuan South Road 27, Taiyuan 030001, Shanxi (China); University of Chinese Academy of Sciences, Beijing 100039 (China); Yang, Pengju [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taoyuan South Road 27, Taiyuan 030001, Shanxi (China); University of Chinese Academy of Sciences, Beijing 100039 (China); Zhao, Jianghong [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taoyuan South Road 27, Taiyuan 030001, Shanxi (China); Zhu, Zhenping, E-mail: zpzhu@sxicc.ac.cn [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taoyuan South Road 27, Taiyuan 030001, Shanxi (China)

    2013-10-01

    The photocatalytic activity of semiconductor is strongly dependent on the efficient separation of photogenerated electron–hole pairs. In the present work, the graphene-immobilized Cd{sub x}Zn{sub 1−x}S nanoparticles with a uniform and small diameter have been prepared by one-step solvothermal route. After dispersing Cd{sub x}Zn{sub 1−x}S on the graphene surface well, the composites of Cd{sub x}Zn{sub 1−x}S and graphenes show better photocatalytic activity than pure Cd{sub x}Zn{sub 1−x}S nanoparticles. And the issue of photocorrosion, a disadvantage of Cd{sub x}Zn{sub 1−x}S photocatalysts, has also been solved partly. The mechanisms on enhancement of photocatalytic activity were further investigated. Under visible light irradiation, photogenerated electrons of Cd{sub x}Zn{sub 1−x}S can be transferred into the graphene, and the electron and hole was effectively separated, leading to the photoactivity enhancement.

  10. Fabrication of Ce/N co-doped TiO_2/diatomite granule catalyst and its improved visible-light-driven photoactivity

    International Nuclear Information System (INIS)

    Chen, Yan; Liu, Kuiren

    2017-01-01

    Highlights: • Ce/N co-doped TiO_2/diatomite granule (CNTD-G) was prepared via sol-gel method. • The optimal doping amount of Ce was determined. • The effects of impurity ions on photodegradation process were studied. • The intermediates generated during photodegradation process were deduced. • The mechanism of photodegradation process was proposed. - Abstract: Eliminating antibiotic remnants in aquatic environment has become one of the hottest topics among current research works. Thus, we prepared Ce, N co-doped TiO_2/diatomite granule (CNTD-G) catalyst to provide a new method. As one typical antibiotics, oxytetracycline (OTC) was selected as the target pollutant to be degradated under visible light irradiation. The carrier diatomite helped the spread of TiO_2 nanoparticles onto its surface, and inhibited their agglomeration. The synergy of Ce and N dopants highly improved the visible-light-driven photoactivity of TiO_2. The optimal doping amount and degradation conditions were determined. Besides, the effects of impurity ions were also investigated, including cations: Ca"2"+, Mg"2"+; or anions: NO_3"−, SO_4"2"− and PO_4"3"−. The intermediates generated during degradation process were studied, and the mechanism of the photodegradation process was proposed. CNTD-G could be easily collected from the reactor, and showed excellent recyclability.

  11. Fabrication of Ce/N co-doped TiO2/diatomite granule catalyst and its improved visible-light-driven photoactivity.

    Science.gov (United States)

    Chen, Yan; Liu, Kuiren

    2017-02-15

    Eliminating antibiotic remnants in aquatic environment has become one of the hottest topics among current research works. Thus, we prepared Ce, N co-doped TiO 2 /diatomite granule (CNTD-G) catalyst to provide a new method. As one typical antibiotics, oxytetracycline (OTC) was selected as the target pollutant to be degradated under visible light irradiation. The carrier diatomite helped the spread of TiO 2 nanoparticles onto its surface, and inhibited their agglomeration. The synergy of Ce and N dopants highly improved the visible-light-driven photoactivity of TiO 2 . The optimal doping amount and degradation conditions were determined. Besides, the effects of impurity ions were also investigated, including cations: Ca 2+ , Mg 2+ ; or anions: NO 3 - , SO 4 2- and PO 4 3- . The intermediates generated during degradation process were studied, and the mechanism of the photodegradation process was proposed. CNTD-G could be easily collected from the reactor, and showed excellent recyclability. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Nitrile rubber - based nanocomposites prepared by melt mixing: effect of the mixing parameters on mechanical, dynamic-mechanical and creep behavior

    Directory of Open Access Journals (Sweden)

    Bluma G. Soares

    2010-01-01

    Full Text Available Nanocomposites constituted by nitrile rubber matrix and Cloisite 15A (OC15A as the organoclay were prepared by melt blending and cured with the m-phenylene-bis-maleimide (BMI/dicumyl peroxide (DCP system. The effect of mixing parameters on the clay dispersion was evaluated, including mixing temperature and time, and rotor speed of the internal mixer. The organoclay effectively accelerated the vulcanization reaction of NBR, which was attributed to the presence of the alkylammonium salt as the intercalant. All nanocomposites displayed improved tensile properties indicating a good reinforcing action of the clay. Also, the creep compliance was substantially reduced with the incorporation of the clay. X-ray diffraction studies showed the presence of intercalated and deintercalated clay population. The mixing parameters did not have an important effect on clay dispersion and properties of NBR-clay nanocomposites, except for the creep behavior.

  13. Facile Synthesis of N-Tosyl Aza-Baylis-Hillman Adducts of Acrylamide via a Pd-Catalyzed Hydration of Nitrile to Amide

    International Nuclear Information System (INIS)

    Kim, Eun Sun; Kim, Yu Mi; Kim, Jae Nyoung

    2010-01-01

    We developed an efficient palladium-catalyzed two-step protocol for the synthesis of N-tosyl aza-Baylis-Hillman adducts of acrylamide. The method involved the preparation of the corresponding Baylis-Hillman adducts of acrylonitrile and the following Pd-catalyzed hydration of nitrile with acetaldoxime. The Baylis-Hillman reaction, which involves the coupling of activated vinyl compounds with electrophiles under the catalytic influence of a tertiary amine, gives rise to adducts, so called Baylis-Hillman adducts, with a new stereocenter and has proven to be a very useful carbon-carbon bond-forming method in the synthesis of highly functionalized molecules. As the activated vinyl compounds, various compounds have been used in the Baylis-Hillman reaction including acrylates, acrylonitrile, vinyl ketones, vinyl sulfones and acrylamides. However, among the activated vinyl compounds acrylamide has not been used much for the synthesis of the corresponding Baylis-Hillman adducts due to its sluggish reactivity

  14. Hydrophil diaphragms on the basis of perfluorated copolymers FEP and polyacryl nitrile: Manufacture by radiation- initiated grafting and their use for pervaporation

    International Nuclear Information System (INIS)

    Scholz, H.

    1986-01-01

    The radiation-initiated grafting copolymerisation of hydrophil monomers to FEP, a copolymer of tetrafluorethene and hexafluorpropene and to polyacryl nitrile (PAN) was examined in this dissertation. The grafted products were used as diaphragms for the separation of water-ethanol mixtures by pervaporation. Water was separated through the diaphragm from the mixture in the pervaporation experiments. It was shown how the mechanical properties of the basic polymer affect the interaction between basic polymer and grafted polymer and how the grafting conditions affect the diaphragm properties. By grafting acrylic acid on to the basic polymers FEP and PAN, very good results were achieved for the water-ethanol separation, if the diaphragms were used in the K form. The selectivity of PAN-g-acrylic acid-K for water reached values of α > 1000. (orig./RB) [de

  15. Adhesion of nitrile rubber to UV-assisted surface chemical modified PET fabric, part II: Interfacial characterization of MDI grafted PET

    Energy Technology Data Exchange (ETDEWEB)

    Razavizadeh, Mahmoud; Jamshidi, Masoud, E-mail: mjamshidi@iust.ac.ir

    2016-08-30

    Highlights: • In this research UV-irradiated PET fabric was chemically modified. • The fabric at first carboxylated under UV irradiation using glutaric anhydride, then it was grafted using isocyanate (i.e. MDI). • The surface of the fabric was characterized before and after each treating satge. • The composite samples were prepared and tested for T-Peel test. The surfaces of the fabrics were surface characterized to understand. - Abstract: Fiber to rubber adhesion is an important subject in rubber industry. It is well known that surface treatment (i.e. physical, mechanical and chemical) is an effective method to improve interfacial bonding of fibers and/or fabrics to rubbers. UV irradiation is an effective method which has been used to increase fabric-rubber interfacial interactions. In this research UV assisted chemical modification of PET fabrics was used to increase PET to nitrile rubber (NBR) adhesion. Nitrile rubber is a perfect selection as fuel and oil resistant rubber. However it has weak bonding to PET fabric. For this purpose PET fabric was carboxylated under UV irradiation and then methylenediphenyl diisocyanate (MDI) was grafted on carboxylated PET. The chemical composition of the fabric before and after surface treatment was investigated by X-ray photoelectron spectroscopy (XPS). The sectional morphology of the experimental PET fibers and the interface between rubber compound and PET fabric was studied using scanning electron microscope (SEM). The morphology and structure of the product were analyzed by an energy dispersive X-ray spectrometer (EDX). FTIR-ATR and H NMR analysis were used to assess surface modifications on the PET irradiated fabrics.

  16. Adhesion of nitrile rubber (NBR) to polyethylene terephthalate (PET) fabric. Part 1: PET surface modification by methylenediphenyl di-isocyanate (MDI)

    International Nuclear Information System (INIS)

    Razavizadeh, Mahmoud; Jamshidi, Masoud

    2016-01-01

    Graphical abstract: - Highlights: • Glutaric anhydride peroxide (GAP) was grafted on PET surface by UV irradiation method. Then MDI was attached to GAP on PET surface. • The fabric was vulcanized by nitrile rubber. • Peet test was performed after each stage of surface modification. • Curing temperature was increased and the tests were repeated. • Effect of MDI coating on PET without carboxylation was evaluated. Effect of vulcanizing temperature on this product was also studied. - Abstract: Fiber to rubber adhesion is an important subject in rubber composite industry. It is well known that surface physical, mechanical and chemical treatments are effective methods to improve interfacial bonding. Ultra violet (UV) light irradiation is an efficient method which is used to increase interfacial interactions. In this research UV assisted chemical modification of PET fabric was used to increase its bonding to nitrile rubber (NBR). NBR is perfect selection to produce fuel and oil resistant rubber parts but it has weak bonding to fabrics. For this purpose at first, the PET fabric was carboxylated under UV irradiation and then methylenediphenyl diisocyanate (MDI) was reacted and grafted to carboxylated PET. T-peel test was used to evaluate PET fabric to NBR bonding strength. Attenuated total reflectance-Fourier transform infrared spectroscopy (FTIR-AT) was used to assess surface modifications of the PET fabrics. The chemical composition of the PET surfaces before and after carboxylation and MDI grafting was investigated by X-ray photoelectron spectroscopy (XPS). It was found that at vulcanizing temperature of 150 °C, carboxylation in contrary to MDI grafting, improved considerably PET to NBR adhesion. Finally effect of curing temperature on PET to NBR bonding strength was determined. It was found that increasing vulcanizing temperature to 170 °C caused considerable improvement (about 134%) in bonding strength.

  17. Adhesion of nitrile rubber to UV-assisted surface chemical modified PET fabric, part II: Interfacial characterization of MDI grafted PET

    International Nuclear Information System (INIS)

    Razavizadeh, Mahmoud; Jamshidi, Masoud

    2016-01-01

    Highlights: • In this research UV-irradiated PET fabric was chemically modified. • The fabric at first carboxylated under UV irradiation using glutaric anhydride, then it was grafted using isocyanate (i.e. MDI). • The surface of the fabric was characterized before and after each treating satge. • The composite samples were prepared and tested for T-Peel test. The surfaces of the fabrics were surface characterized to understand. - Abstract: Fiber to rubber adhesion is an important subject in rubber industry. It is well known that surface treatment (i.e. physical, mechanical and chemical) is an effective method to improve interfacial bonding of fibers and/or fabrics to rubbers. UV irradiation is an effective method which has been used to increase fabric-rubber interfacial interactions. In this research UV assisted chemical modification of PET fabrics was used to increase PET to nitrile rubber (NBR) adhesion. Nitrile rubber is a perfect selection as fuel and oil resistant rubber. However it has weak bonding to PET fabric. For this purpose PET fabric was carboxylated under UV irradiation and then methylenediphenyl diisocyanate (MDI) was grafted on carboxylated PET. The chemical composition of the fabric before and after surface treatment was investigated by X-ray photoelectron spectroscopy (XPS). The sectional morphology of the experimental PET fibers and the interface between rubber compound and PET fabric was studied using scanning electron microscope (SEM). The morphology and structure of the product were analyzed by an energy dispersive X-ray spectrometer (EDX). FTIR-ATR and H NMR analysis were used to assess surface modifications on the PET irradiated fabrics.

  18. Synthesis, structural characterization and evaluation of floating B-N codoped TiO{sub 2}/expanded perlite composites with enhanced visible light photoactivity

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xin; Wang, Wei; Wang, Xuejiang, E-mail: wangxj@tongji.edu.cn; Zhang, Jing; Zhao, Jianfu; Gu, Zaoli; Zhou, Lijie

    2015-09-15

    Graphical abstract: - Highlights: • We added expanded perlite as a floating carrier to immobilize B-N codoped TiO{sub 2}. • The photo-reaction occurred on the surface of water and easily utilized the solar energy and O{sub 2} to make photodegradation efficiently. • The composites combined the adsorptivity of expanded perlite and photoactivity of B-N-TiO{sub 2}. • The floating photocatalysts give a simple way to recycle, which is important to the application of photocatalysis technology. - Abstract: Floating photocatalysts of boron-nitrogen codoped TiO{sub 2} grafted on expanded perlite (B-N-TiO{sub 2}/EP) were prepared by a facile sol–gel method. The catalysts were characterized by N{sub 2} adsorption–desorption (BET), scanning electron microscope (SEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and UV–vis diffuse reflectance spectroscopy (UV–vis–DRS). The results revealed that the physicochemical properties of the photocatalysts, such as BET surface area, porosity and pore size could be controlled by adjusting the calcination temperature and EP dosage. XRD patterns were mainly influenced by calcination temperature and the transformation of anatase to rutile occurred at 650 °C. Uniform TiO{sub 2} loading, higher surface area and absorption in visible light region were obtained for B-N-TiO{sub 2}/EP calcined at 550 °C with 3.0 g EP addition. Moreover, photocatalytic activity for RhB destruction under visible light irradiation was slightly influenced by TiO{sub 2} loading in the range of 1–3 g EP dosage. BNTEP550 showed the highest photocatalytic activity indicating to be a promising photocatalyst employed to remediate contaminated waters using solar irradiation.

  19. One-pot, facile fabrication of a Ag3PO4-based ternary Z-scheme photocatalyst with excellent visible-light photoactivity and anti-photocorrosion performance

    Science.gov (United States)

    Xie, Mingyuan; Zhang, Tailiang

    2018-04-01

    Ag3PO4 can-not be widely used as an efficient photocatalyst in practical applications because of its susceptibility to photocorrosion. In this study, a novel, ternary Z-scheme photocatalytic system containing graphene oxide (GO), Ag3PO4 and SnS2 was fabricated by a one-pot, mild, in-situ precipitation method successfully. Using Rhodamine B (RhB) as the target of elimination, GO/Ag3PO4/SnS2 exhibited outstanding photocatalytic and anti-photocorrosion properties compared with those of Ag3PO4, Ag3PO4/SnS2 and GO/Ag3PO4. RhB was thoroughly degraded over the optimized GO/Ag3PO4/SnS2 nanocomposite after only 15 min under visible-light irradiation; this result is approximately 2.14, 3.33 and 5.83 times faster than that of GO/Ag3PO4, Ag3PO4/SnS2 and Ag3PO4, respectively. After three reuses, the photocatalytic activity of the ternary composite slightly decreased but remained 2.36, 4.08 and 12.70 times higher than those of the reused GO/Ag3PO4, Ag3PO4/SnS2 and Ag3PO4, respectively. In this system, the efficient separation and migration of the photoinduced current carriers in Ag3PO4 was realized through a double Z-scheme electron-transfer mechanism in which the GO nanosheets acted as the photocatalyst and electron mediator, thereby enhancing the photoactivity and stability of Ag3PO4. The present study provides a new perspective for enhancing photocatalytic and anti-photocorrosion performances in perishable photocatalysts for organic sewage and other environmental contamination treatments.

  20. Direct formation of new, phase-stable, and photoactive anatase-type Ti1-2XNbXScXO2 solid solution nanoparticles by hydrothermal method

    International Nuclear Information System (INIS)

    Hirano, Masanori; Ito, Takaharu

    2008-01-01

    A new anatase phase of photoactive Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) solid solutions was directly formed as nanoparticles from precursor solutions of TiOSO 4 , NbCl 5 , and Sc(NO 3 ) 3 under mild hydrothermal conditions at 180 deg. C for 5 h using the hydrolysis of urea. With the increase of the content of niobium and scandium from X = 0 to 0.2, the lattice parameters a 0 and c 0 , the crystallite size, and the optical band gap of anatase gradually increased. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The anatase-type Ti 1-2X Nb X Sc X O 2 (X = 0.05) showed approximately two times and three times as high photocatalytic activity as those of the hydrothermal anatase-type pure TiO 2 and commercially available reference pure TiO 2 (ST-01), respectively. The anatase phase of Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) existed stably up to 900 deg. C during heat treatment in air. New rutile-type Ti 1-2X Nb X Sc X O 2 solid solutions are formed through the phase transformation. The starting temperature of anatase-to-rutile phase transformation for Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) solid solutions was delayed but its completing temperature was accelerated