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Sample records for non-racemic sulfinyl imines

  1. Reversal of diastereofacial selectivity in hydride reductions of N-tert-butanesulfinyl imines.

    Science.gov (United States)

    Colyer, John T; Andersen, Neil G; Tedrow, Jason S; Soukup, Troy S; Faul, Margaret M

    2006-09-01

    A variety of N-tert-butanesulfinyl imines were reduced with NaBH4 in THF containing 2% water to provide the corresponding secondary sulfinamides in high yield and diastereoselectivity. By using the same sulfinyl imine starting materials and changing the reductant to L-Selectride, the stereoselectivity could be efficiently reversed to afford the opposite product diastereomer in high yield and selectivity.

  2. Remote stereocontrol by sulfinyl groups: reduction of delta-ketosulfoxides.

    Science.gov (United States)

    García Ruano, José L; Fernández-Ibáñez, M Angeles; Maestro, M Carmen; Rodríguez-Fernández, M Mercedes

    2005-03-04

    The reduction of delta-ketosulfoxides constitutes the first evidence of the efficiency of the sulfinyl group to control the stereoselectivity of 1,5-asymmetric induction processes. The use of DIBAL/Yb(OTf)3 or L-Selectride as the reducing agents provides delta-hydroxysulfoxides with the opposite configuration at the hydroxylic carbon in a highly stereoselective way.

  3. Preparation of 35S-labelled albendazole sulfinyl (ABZO)

    International Nuclear Information System (INIS)

    Zhang Lufang; Wu Yuanfang; Yang Zhiming

    1992-01-01

    Albendazole is an important insecticide and albendazole sulfinyl (ABZO) is the effective component. In order to investigate its absorption, distribution and excretion in vivo, 35 S-labelled tracer was necessary for experiment. 35 S-labelled intermediate was made by isotopic exchange. The radiochemical yield was over 90%. After purification by TLC, the radiochemical purity of the 35 S-ABZO determined by PC and electrophoresis was over 95%

  4. Anionic PPV polymerization from the sulfinyl precursor route : Block copolymer formation from sequential addition of monomers

    NARCIS (Netherlands)

    Cosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas

    2013-01-01

    The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to

  5. NON-RACEMIC AMINO ACID PRODUCTION BY ULTRAVIOLET IRRADIATION OF ACHIRAL INTERSTELLAR ICE ANALOGS WITH CIRCULARLY POLARIZED LIGHT

    International Nuclear Information System (INIS)

    De Marcellus, Pierre; Nuevo, Michel; Danger, Gregoire; Deboffle, Dominique; Le Sergeant d'Hendecourt, Louis; Meinert, Cornelia; Filippi, Jean-Jacques; Meierhenrich, Uwe J.; Nahon, Laurent

    2011-01-01

    The delivery of organic matter to the primitive Earth via comets and meteorites has long been hypothesized to be an important source for prebiotic compounds such as amino acids or their chemical precursors that contributed to the development of prebiotic chemistry leading, on Earth, to the emergence of life. Photochemistry of inter/circumstellar ices around protostellar objects is a potential process leading to complex organic species, although difficult to establish from limited infrared observations only. Here we report the first abiotic cosmic ice simulation experiments that produce species with enantiomeric excesses (e.e.'s). Circularly polarized ultraviolet light (UV-CPL) from a synchrotron source induces asymmetric photochemistry on initially achiral inter/circumstellar ice analogs. Enantioselective multidimensional gas chromatography measurements show significant e.e.'s of up to 1.34% for ( 13 C)-alanine, for which the signs and absolute values are related to the helicity and number of CPL photons per deposited molecule. This result, directly comparable with some L excesses measured in meteorites, supports a scenario in which exogenous delivery of organics displaying a slight L excess, produced in an extraterrestrial environment by an asymmetric astrophysical process, is at the origin of biomolecular asymmetry on Earth. As a consequence, a fraction of the meteoritic organic material consisting of non-racemic compounds may well have been formed outside the solar system. Finally, following this hypothesis, we support the idea that the protosolar nebula has indeed been formed in a region of massive star formation, regions where UV-CPL of the same helicity is actually observed over large spatial areas.

  6. Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters

    DEFF Research Database (Denmark)

    Nguyen, Ngoc-Lan Thi; Vo, Hong-Thom; Duus, Fritz

    2017-01-01

    The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylim......The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3...

  7. Formation of enamines by alkylation of imines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1966-01-01

    cf. CA 64, 12473c. With ice-cooling, 1 equiv. alkylating agent was added to one equiv. of the imine in 1M soln. in a solvent in the presence of NaH to give both N- and C-alkylated products. The following summarizes the date (imine, solvent, alkylating agent, % unreacted imine, % N-alkylated product,

  8. Preparation of poly (imine imine ketone) s microshells

    International Nuclear Information System (INIS)

    Cui Yi; Luo Xuan; Fan Yongheng; Zhang Lin; Liu Lei; Lin Runxiong

    2010-01-01

    Large diameter (0.6 ∼ 2.0 mm) microshells of poly (imine imine ketone) s (PIIKs) were prepared by micro-liquid technique and double-layer latex technique. A double T-channel droplet generator was designed and developed for the fabrication of PIIKs microshells of controlled size continuously. Manipulative conditions of the diameter and thickness of shells were studied, and the effect of density mismatch on shell quality was discussed. Phase separation during the preparation process affects the morphology of shells. Spinodal phase separation tends to occur at the outer surface of the shells, while binodal phase separation at the inner surface. The diameters of PIIKs shells were measured, 88% of which vary in ± 5% of the average diameter. The sphericity is better than 99%. (authors)

  9. Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters

    Directory of Open Access Journals (Sweden)

    Ngoc-Lan Thi Nguyen

    2017-09-01

    Full Text Available The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylimidazolium chloride and aluminum chloride were found to be the most efficient and recyclable reaction framework. Ultrasound sonication appeared to be the most useful and green activation method to afford the sulfoxides in yields better than or equivalent to those obtained under the longer-lasting conventional stirring conditions.

  10. Imine-based [2]catenanes in water.

    Science.gov (United States)

    Caprice, Kenji; Pupier, Marion; Kruve, Anneli; Schalley, Christoph A; Cougnon, Fabien B L

    2018-02-07

    We report the efficient condensation of imine-based macrocycles from dialdehyde A and aliphatic diamines B n in pure water. Within the libraries, we identified a family of homologous amphiphilic [2]catenanes, whose self-assembly is primarily driven by the hydrophobic effect. The length and odd-even character of the diamine alkyl linker dictate both the yield and the conformation of the [2]catenanes, whose particular thermodynamic stability further shifts the overall equilibrium in favour of imine condensation. These findings highlight the role played by solvophobic effects in the self-assembly of complex architectures.

  11. The alkylation of imine anions formation of enamines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The ambident anions derived from imines were alkylated using a variety of solvents and alkylating agents. Under reactive conditions enamines (N-alkylation) are formed as the main products instead of the usually obsd. homologous imines (C-alkylation). The influence of the type of imine, solvent, and

  12. Chemoselective organocatalytic aerobic oxidation of primary amines to secondary imines.

    Science.gov (United States)

    Wendlandt, Alison E; Stahl, Shannon S

    2012-06-01

    Biomimetic aerobic oxidation of primary benzylic amines has been achieved by using a quinone catalyst. Excellent selectivity is observed for primary, unbranched benzylic amines relative to secondary/tertiary amines, branched benzylic amines, and aliphatic amines. The exquisite selectivity for benzylic amines enables oxidative self-sorting within dynamic mixtures of amines and imines to afford high yields of cross-coupled imine products.

  13. Enhanced reactivities toward amines by introducing an imine arm to the pincer ligand: Direct coupling of two amines to form an imine without oxidant

    KAUST Repository

    He, Lipeng

    2012-07-23

    Dehydrogenative homocoupling of primary alcohols to form esters and coupling of amines to form imines was accomplished using a class of novel pincer ruthenium complexes. The reactivities of the ruthenium pincer complexes for the direct coupling of amines to form imines were enhanced by introducing an imine arm to the pincer ligand. Selective oxidation of benzylamines to imines was achieved using aniline derivatives as the substrate and solvent. © 2012 American Chemical Society.

  14. Enhanced reactivities toward amines by introducing an imine arm to the pincer ligand: Direct coupling of two amines to form an imine without oxidant

    KAUST Repository

    He, Lipeng; Chen, Tao; Gong, Dirong; Lai, Zhiping; Huang, Kuo-Wei

    2012-01-01

    Dehydrogenative homocoupling of primary alcohols to form esters and coupling of amines to form imines was accomplished using a class of novel pincer ruthenium complexes. The reactivities of the ruthenium pincer complexes for the direct coupling of amines to form imines were enhanced by introducing an imine arm to the pincer ligand. Selective oxidation of benzylamines to imines was achieved using aniline derivatives as the substrate and solvent. © 2012 American Chemical Society.

  15. Hydride, hydrogen, proton, and electron affinities of imines and their reaction intermediates in acetonitrile and construction of thermodynamic characteristic graphs (TCGs) of imines as a "molecule ID card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Liu, Qiao-Yun; Chen, Qiang; Mei, Lian-Rui

    2010-02-05

    A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C=N pi-bond in the imines were estimated. The polarity of the C=N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.

  16. Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

    KAUST Repository

    Hamzaoui, Bilel

    2016-02-15

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

  17. Asymmetric and symmetric bolaform supra-amphiphiles: formation of imine bond influenced by aggregation.

    Science.gov (United States)

    Wang, Guangtong; Wu, Guanglu; Wang, Zhiqiang; Zhang, Xi

    2014-02-18

    A series of bolaform supra-amphilphiles with different symmetries were fabricated through dynamic benzoic imine bond formation. The pH dependence of imine formations of these supra-amphiphiles were characterazied. We found that the extent of the imine formation of these supra-amphiphies were different. The supra-amphiphiles with a poorer symmetry always exhibited a lower imine formation at a given pH. Therefore, the varied extent of imine bond formation indicate the different aggregations of these supra-amphilphiles, which are controlled by the molecular symmetry of the supra-amphiphiles.

  18. Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Basset, Jean-Marie

    2016-01-01

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

  19. Enhanced Ionic Conductivity of Poly(Ethylene Imine) Phosphate

    DEFF Research Database (Denmark)

    Senadeera, G.K.R.; Careem, M.A.; Skaarup, Steen

    1996-01-01

    The conductivity of mixtures of phosphoric acid with poly(ethylene imine) has been studied, and it was found that the conductivity of such mixtures with high acid content can be enhanced by the addition of highly dispersed silica (fumed silica). At the same time, silica addition increases the sti...

  20. o-Naphthoquinone-Catalyzed Aerobic Oxidation of Amines to (Ket)imines: A Modular Catalyst Approach.

    Science.gov (United States)

    Goriya, Yogesh; Kim, Hun Young; Oh, Kyungsoo

    2016-10-07

    A modular aerobic oxidation of amines to imines has been achieved using an ortho-naphthoquinone (o-NQ) catalyst. The cooperative catalyst system of o-NQ and Cu(OAc) 2 enabled the formation of homocoupled imines from benzylamines, while the presence of TFA helped the formation of cross-coupled imines in excellent yields. The current mild aerobic oxidation protocol could also be applied to the oxidation of secondary amines to imines or ketimines with the help of cocatalyst, Ag 2 CO 3 , with excellent yields.

  1. Occurrence of cyclic imines in European commercial seafood and consumers risk assessment

    DEFF Research Database (Denmark)

    Rambla-Alegre, Maria; Miles, Christopher O.; de la Iglesia, Pablo

    2018-01-01

    Cyclic imines constitute a quite recently discovered group of marine biotoxins that act on neural receptors and that bioaccumulate in seafood. They are grouped together due to the imino group functioning as their common pharmacore, responsible for acute neurotoxicity in mice. Cyclic imines (CIs...... countries (Italy, Portugal, Slovenia, Spain, Ireland, Norway, The Netherlands and Denmark) were obtained over 2 years. Emerging cyclic imine concentrations in all the samples were analysed on a LC-3200QTRAP and LC-HRMS QExactive mass spectrometer. In shellfish, two CIs, pinnatoxin G (PnTX-G) and 13...

  2. Stereoselective Reduction of Imines with Trichlorosilane Using Solid-Supported Chiral Picolinamides

    Directory of Open Access Journals (Sweden)

    Sílvia D. Fernandes

    2016-09-01

    Full Text Available The stereoselective reduction of imines with trichlorosilane catalyzed by chiral Lewis bases is a well-established procedure for the synthesis of enantio-enriched amines. Five supported cinchona-based picolinamides have been prepared and their activity tested in a model reaction. The comparison of different supporting materials revealed that polystyrene gave better results than silica in terms of stereoselectivity. The applicability of the solid-supported catalyst of choice to the reduction of different imines was also demonstrated. Additionally, for the first time, a catalytic reactor containing a polymer-immobilized chiral picolinamide has been employed for the stereoselective reduction of imines with trichlorosilane under continuous flow conditions.

  3. Semi-catalytic reduction of secondary amides to imines and aldehydes.

    Science.gov (United States)

    Lee, Sun-Hwa; Nikonov, Georgii I

    2014-06-21

    Secondary amides can be reduced by silane HSiMe2Ph into imines and aldehydes by a two-stage process involving prior conversion of amides into iminoyl chlorides followed by catalytic reduction mediated by the ruthenium complex [Cp(i-Pr3P)Ru(NCCH3)2]PF6 (1). Alkyl and aryl amides bearing halogen, ketone, and ester groups were converted with moderate to good yields under mild reaction conditions to the corresponding imines and aldehydes. This procedure does not work for substrates bearing the nitro-group and fails for heteroaromatic amides. In the case of cyano substituted amides, the cyano group is reduced to imine.

  4. α,β-Unsaturated imines via Ru-catalyzed coupling of allylic alcohols and amines.

    Science.gov (United States)

    Rigoli, Jared W; Moyer, Sara A; Pearce, Simon D; Schomaker, Jennifer M

    2012-03-07

    A convenient synthesis of α,β-unsaturated imines requiring only an allylic alcohol, an amine and a Ru catalyst has been developed. The use of large excesses of oxidant and the purification of sensitive intermediates can be avoided.

  5. Thermal, structural and electrochemical properties of new aliphatic-aromatic imine with piperazine moieties blended with titanium dioxide

    Science.gov (United States)

    Różycka, Anna; Fryń, Patryk; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Dąbczyński, Paweł; Rysz, Jakub; Pociecha, Damian; Hreniak, Agnieszka; Marzec, Monika

    2018-02-01

    A new piperazine imine, (7E)-N-((4-((E)-(4-hexadecylphenylimino)methyl)piperazin-1-yl)methylene)-4-dodecylbenzenamine, has been synthesized by the condensation of 1,4-piperazinedicarboxaldehyde with 4-hexadecylaniline. The imine was characterized by cyclic voltammetry, Fourier transform middle-infrared absorption spectroscopy and X-ray diffraction. Thermal properties of imine was analyzed by differential scanning calorimetry method during first and second heating scan at 10 and 20 °C/min. Texture of imine was investigated by polarized optical microscopy and atomic force microscopy. Furthermore, imine was blended with titanium dioxide in anatase form and fully characterized by the same methods. Piperazine imine and its mixture with titanium dioxide exhibited only a transition from crystal to isotropic state. Imine exhibits two-step reduction wave attributed to one-electron transfer in each step as was found by cyclic voltammetry. Both titanium dioxide and poly(3-hexylthiophene) change the electrochemical properties of piperazine imine, however, in different ways. Studied imine blended with titanium dioxide exhibited higher value of energy band gap than pure piperazine imine and lower Eg than pure poly(3-hexylthiophene).

  6. Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

    Science.gov (United States)

    Zhao, Qingyang; Wen, Jialin; Tan, Renchang; Huang, Kexuan; Metola, Pedro; Wang, Rui; Anslyn, Eric V; Zhang, Xumu

    2014-08-04

    Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Identification of quinone imine containing glutathione conjugates of diclofenac in rat bile.

    Science.gov (United States)

    Waldon, Daniel J; Teffera, Yohannes; Colletti, Adria E; Liu, Jingzhou; Zurcher, Danielle; Copeland, Katrina W; Zhao, Zhiyang

    2010-12-20

    High-resolution accurate MS with an LTQ-Orbitrap was used to identify quinone imine metabolites derived from the 5-hydroxy (5-OH) and 4 prime-hydroxy (4'-OH) glutathione conjugates of diclofenac in rat bile. The initial quinone imine metabolites formed by oxidation of diclofenac have been postulated to be reactive intermediates potentially involved in diclofenac-mediated hepatotoxicity; while these metabolites could be formed using in vitro systems, they have never been detected in vivo. This report describes the identification of secondary quinone imine metabolites derived from 5-OH and 4'-OH diclofenac glutathione conjugates in rat bile. To verify the proposed structures, the diclofenac quinone imine GSH conjugate standards were prepared synthetically and enzymatically. The novel metabolite peaks displayed the identical retention times, accurate mass MS/MS spectra, and the fragmentation patterns as the corresponding authentic standards. The formation of these secondary quinone metabolites occurs only under conditions where bile salt homeostasis was experimentally altered. Standard practice in biliary excretion experiments using bile duct-cannulated rats includes infusion of taurocholic acid and/or other bile acids to replace those lost due to continuous collection of bile; for this experiment, the rats received no replacement bile acid infusion. High-resolution accurate mass spectrometry data and comparison with chemically and enzymatically prepared quinone imines of diclofenac glutathione conjugates support the identification of these metabolites. A mechanism for the formation of these reactive quinone imine containing glutathione conjugates of diclofenac is proposed.

  8. Visible Light Induced Green Transformation of Primary Amines to Imines Using a Silicate Supported Anatase Photocatalyst

    Directory of Open Access Journals (Sweden)

    Sifani Zavahir

    2015-01-01

    Full Text Available Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary amines, presumably owing to the high reactivity of generated imines of primary amines that are easily dehydrogenated to nitriles. Herein, we report the oxidative coupling of a series of primary benzylic amines into corresponding imines with dioxygen as the benign oxidant over composite catalysts of TiO2 (anatase-silicate under visible light irradiation of λ > 460 nm. Visible light response of this system is believed to be as a result of high population of defects and contacts between silicate and anatase crystals in the composite and the strong interaction between benzylic amine and the catalyst. It is found that tuning the intensity and wavelength of the light irradiation and the reaction temperature can remarkably enhance the reaction activity. Water can also act as a green medium for the reaction with an excellent selectivity. This report contributes to the use of readily synthesized, environmentally benign, TiO2 based composite photocatalyst and solar energy to realize the transformation of primary amines to imine compounds.

  9. Visible light induced green transformation of primary amines to imines using a silicate supported anatase photocatalyst.

    Science.gov (United States)

    Zavahir, Sifani; Zhu, Huaiyong

    2015-01-26

    Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary amines, presumably owing to the high reactivity of generated imines of primary amines that are easily dehydrogenated to nitriles. Herein, we report the oxidative coupling of a series of primary benzylic amines into corresponding imines with dioxygen as the benign oxidant over composite catalysts of TiO2 (anatase)-silicate under visible light irradiation of λ > 460 nm. Visible light response of this system is believed to be as a result of high population of defects and contacts between silicate and anatase crystals in the composite and the strong interaction between benzylic amine and the catalyst. It is found that tuning the intensity and wavelength of the light irradiation and the reaction temperature can remarkably enhance the reaction activity. Water can also act as a green medium for the reaction with an excellent selectivity. This report contributes to the use of readily synthesized, environmentally benign, TiO2 based composite photocatalyst and solar energy to realize the transformation of primary amines to imine compounds.

  10. Synthesis, Characterisation and DFT Calculations of Azo-Imine Dyes

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    Sevil Özkınalı

    2017-11-01

    Full Text Available In this study, azo dyes containing an imine group were synthesised by coupling p-hydroxybenzylidene aniline with the diazonium salts of p-toluidine, 4-aminophenol, aniline, p-chloroaniline, p-fluoroaniline, and p-nitroaniline. The compounds were characterised by melting point, elemental, UV-Vis and IR analyses as well as 1H-NMR and 13C-NMR spectroscopies. Moreover, the experimental data were supplemented with density functional theory (DFT calculations. The experimental data on FT-IR and UV–Vis spectra of the compounds were compared with theoretical results. The DFT calculations were performed to obtain the ground state geometries of the compounds using the B3LYP hybrid functional level with 6-311++g(2d,2p basis set. Frontier molecular orbital energies, band gap energies and some chemical reactivity parameters, such as chemical hardness and electronegativity, were calculated and compared with experimental values. A significant correlation was observed between the dipole moment and polarities of the solvents and the absorption wavelength of the compounds.

  11. ASSOCIATION OF BRANCHED POLYETHYLENE IMINE WITH SURFACTANTS IN AQUEOUS SOLUTION

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    Ismael C. Bellettini

    2015-07-01

    Full Text Available Three polymer-surfactant systems comprised of branched polyethylene imine (PEI with an anionic surfactant (sodium dodecylsulfate; SDS, a cationic surfactant (tetradecyltrimethylammonium bromide; TTAB, and a zwitterionic surfactant (N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; SB3-14 were studied based on the properties of surface tension, pyrene fluorescence emission, dynamic light scattering, pH, and zeta potential measurements. The critical aggregation concentration (cac and polymer saturation point (psp were determined for all three systems. The effect of these surfactants on the physico-chemical characteristics (diameter and surface charge of the complexes formed was determined. Polymer-surfactant interactions occurred in all of the systems studied, with the strongest interactions, electrostatic in nature, occurring in the SDS-PEI system. After the neutralization of the polymer charges with the addition of the surfactant, the hydrophobic effect started to control the interlacing of the polymer chains. For the PEI-TTAB system, a very dense film was formed at surfactant concentrations above 2.0 mmol L-1. In this case, the bromide counter-ion interacted with both the positively-charged PEI and the head of the surfactant, which is responsible for the formation of double layer coordination complexes. For the system composed of PEI and the zwitterionic surfactant, less cooperative associations occurred in comparison with the other systems.

  12. Thermally Stable Heterocyclic Imines as New Potential Nonlinear Optical Materials

    Science.gov (United States)

    Nesterov, Volodymyr V.; Antipin, Mikhail Y.; Nesterov, Vladimir N.; Moore, Craig E.; Cardelino, Beatriz H.; Timofeeva, Tatiana V.

    2004-01-01

    In the course of a search for new thermostable acentric nonlinear optical crystalline materials, several heterocyclic imine derivatives were designed, with the general structure D-pi-A(D'). Introduction of a donor amino group (D') into the acceptor moiety was expected to bring H-bonds into their crystal structures, and so to elevate their melting points and assist in an acentric molecular packing. Six heterocycle-containing compounds of this type were prepared, single crystals were grown for five of them, and these crystals were characterized by X-ray analysis. A significant melting temperature elevation was found for all of the synthesized compounds. Three of the compounds were also found to crystallize in acentric space groups. One of the acentric compounds is built as a three-dimensional H-bonded molecular network. In the other two compounds, with very similar molecular structure, the molecules form one-dimensional H-bonded head-to-head associates (chains). These chains are parallel in two different crystallographic directions and form very unusual interpenetrating chain patterns in an acentric crystal. Two of the compounds crystallized with centrosymmetric molecular packing.

  13. Syntheses of Azo-Imine Derivatives from Vanillin as an Acid Base Indicator

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    Bambang Purwono

    2013-05-01

    Full Text Available Preparations of azo, imine and azo-imine derivatives from vanillin as an indicator of acid-base titration have been carried out. The azo derivative of 4-hydroxy-3-methoxy-5-(phenylazobenzaldehyde 2 was produced by diazotitation reaction of vanillin in 37.04% yield. The azo product was then refluxed with aniline in ethanol to yield azo-imine derivatives, 2-methoxy-6-(phenylazo-4-((phenyliminomethylphenol 1 in 82.21% yield. The imine derivative, 2-methoxy-4-((phenyliminomethyl-phenol 3 was obtained by refluxing of vanillin and aniline mixture in ethanol solvent and produced 82.17% yield. The imine product was then reacted with benzenediazonium chloride salt. However, the products indicated hydrolyzed product of 4-hydroxy-3-methoxy-5-(phenylazobenzaldehyde 2 in 22.15% yield. The 2-methoxy-4-((phenyliminomethylphenol 2 could be used as an indicator for titration of NaOH by H2C2O4 with maximum concentration of H2C2O4 0.1 M while the target compound 1 could be used as titration indicator for titration of NaOH with H2C2O4 with same result using phenolphthalein indicator.

  14. Highly selective formation of imines catalyzed by silver nanoparticles supported on alumina

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Poreddy, Raju; Engelbrekt, Christian

    2014-01-01

    The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al2O3 was studied. The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines. The reactions were performed under mild conditions......-2 in the gas phase. The use of an efficient and selective Ag catalyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reaction protocol for imine synthesis. (C) 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B...... and afforded the imines in high yield (up to 99%) without any byproducts other than H2O. The highest activity was obtained over 5 wt% Ag/Al2O3 in toluene with air as oxidant. The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the production of H...

  15. An Efficient Synthesis of Substituted Quinolines via Indium(III) Chloride Catalyzed Reaction of Imines with Alkynes

    International Nuclear Information System (INIS)

    Zhu, Mei; Fu, Weijun; Xun, Chen; Zou, Guanglong

    2012-01-01

    An efficient synthetic method for the preparation of quinolines through indium(III) chloride-catalyzed tandem addition-cyclization-oxidation reactions of imines with alkynes was developed. The processes can provide a diverse range of quinoline derivatives in good yields from simple imines and alkynes

  16. Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

    Science.gov (United States)

    Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

    2015-04-07

    The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. RuO4-mediated oxidation of secondary amines 2. imines as main reaction intermediates

    Directory of Open Access Journals (Sweden)

    Florea Cristina A.

    2017-01-01

    Full Text Available Oxidation by RuO4 (generated in situ from RuO2 and NaIO4 of secondary amines such as Bn–NH–CH2R (1; R=H, Me gave complex reaction mixtures, but mainly amides. In the presence of cyanide, the leading products were α-aminonitriles. Comparison of the oxidation products of 1 with those from the corresponding imines PhCH=N–CH2R and Bn–N=CH–R showed that formation of the indicated imines is the first main step in the oxidation of 1. A detailed mechanism is proposed.

  18. Thermally Induced Denitrogenative Annulation for the Synthesis of Dihydroquinolinimines and Chroman-4-imines.

    Science.gov (United States)

    Chou, Chih-Hung; Chen, Ying-Yu; Rajagopal, Basker; Tu, Hsiu-Chung; Chen, Kuan-Lin; Wang, Sheng-Fu; Liang, Chien-Fu; Tyan, Yu-Chang; Lin, Po-Chiao

    2016-03-04

    A rapid growth in synthetic methods for the preparation of diverse organic molecules using N-sulfonyl-1,2,3-triazoles is of great interest in organic synthesis. Transition metals are generally used to activate the α-imino diazo intermediates. Metal-free methods have not been studied in detail, but can be a good complement to transition metal catalysis in the mild reaction conditions. We herein report a novel method for the preparation of 2,3-dihydroquinolin-4-imine and chroman-4-imine analogs from their corresponding N-sulfonyl-1,2,3-triazoles in the absence of metal catalysts. To achieve intramolecular annulation, the introduction of an electron-donating group is required at the meta position of N-sulfonyl-1,2,3-triazole methyl anilines. The inclusion of tailored substituents on the aniline moieties and nitrogen atoms enhances the nucleophilicity of the phenyl π-electrons, thus allowing them to undergo a Friedel-Crafts-type reaction with the highly electrophilic ketenimines. This metal-free method was carefully optimized to generate a variety of dihydroquinolin-4-imines and chroman-4-imines in moderate-to-good yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

    Directory of Open Access Journals (Sweden)

    Pégot Bruce

    2006-09-01

    Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.

  20. Copper(II)-catalyzed exo and enantioselective cycloadditions of azomethine imines.

    Science.gov (United States)

    Sibi, Mukund P; Rane, Digamber; Stanley, Levi M; Soeta, Takahiro

    2008-07-17

    A strategy for exo and enantioselective 1,3-dipolar cycloaddition of azomethine imines to 2-acryloyl-3-pyrazolidinone is described. The corresponding cycloadducts are isolated with high diastereoselectivities (up to >96:4 exo/endo) and enantioselectivities (up to 98% ee).

  1. 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.

  2. In(OTf)3 catalyzed allylation reaction of imines with tetraallyltin

    Institute of Scientific and Technical Information of China (English)

    Xiao Ning Wei; Ling Yan Liu; Bing Wang; Wei Xing Chang; Jing Li

    2009-01-01

    In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol (allyl)4Sn/In(OTf)3 for simple imines was developed.

  3. Functionalized Poly(propylene imine) Dendrimers as Novel Phase Transfer Catalyst in Supercritical Cabon Dioxide

    NARCIS (Netherlands)

    Goetheer, E.L.V.; Baars, M.W.P.L.; Broeke, van den L.J.P.; Meijer, E.W.; Keurentjes, J.T.F.

    2000-01-01

    Perfluoro-functionalized poly(propylene imine) dendrimers have been used as reactive extractants for anionic species and as phase transfer catalysts for two types of reactions. Different generations of dendrimers have been used for applications in carbon dioxide. First, the reactive extraction of

  4. The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

    Science.gov (United States)

    Hepburn, Hamish B; Lam, Hon Wai

    2014-10-20

    Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Rh(III)-catalyzed olefination of N-sulfonyl imines: synthesis of ortho-olefinated benzaldehydes.

    Science.gov (United States)

    Zhang, Tao; Wu, Lamei; Li, Xingwei

    2013-12-20

    Rh(III)-catalyzed olefination of N-sulfonyl imines using acrylates and styrenes has been achieved for the synthesis of ortho-olefinated benaldehydes. This reaction proceeds via a chelation assisted C-H olefination/in situ hydrolysis process.

  6. Profuse and Selective Growth in vitro of Rat Spinal Axons on a Micro-Patterned Poly (ethylene imine) Grid

    National Research Council Canada - National Science Library

    Mouveroux, J

    2001-01-01

    To distribute neurites (axons) along a surface and to guide them towards specific point targets we cultured spinal cord explants on coverslips printed with a micro-patterned grid of poly (ethylene imine) (PEI) lanes...

  7. Docking, synthesis and bioassay studies of imine derivatives as potential inhibitors for dengue NS2B/ NS3 serine protease

    Directory of Open Access Journals (Sweden)

    Neni Frimayanti

    2017-11-01

    Full Text Available Objective: To search imine derivatives as new active agents against dengue type 2 NS2B/NS3 using molecular docking, since there is no effective vaccine against flaviviral infections. Methods: In this research, molecular docking was performed for a series of imine derivatives and the information obtained from the docking studies was used to explore the binding modes of these imine derivatives with dengue type 2 NS2B/NS3 serine protease. A set of imine were synthesized and bioassay study of the inhibitory activities of these compounds was then performed. Results: The results indicated that MY8 and MY4 have the ability to inhibit DEN2 NS2B/NS3 proteolytic activity. Conclusions: These two compounds were chosen as the reference for the next stage in drug design as new inhibitor agents against NS2B/NS3.

  8. An efficient protocol for the synthesis of highly sensitive indole imines utilizing green chemistry: optimization of reaction conditions.

    Science.gov (United States)

    Nisar, Bushra; Rubab, Syeda Laila; Raza, Abdul Rauf; Tariq, Sobia; Sultan, Ayesha; Tahir, Muhammad Nawaz

    2018-04-11

    Novel and highly sensitive indole-based imines have been synthesized. Their synthesis has been compared employing a variety of protocols. Ultimately, a convenient, economical and high yielding set of conditions employing green chemistry have been designed for their synthesis.

  9. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    Science.gov (United States)

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. N-Aryl-oxazolidin-2-imine Muscle Selective Androgen Receptor Modulators Enhance Potency through Pharmacophore Reorientation

    Energy Technology Data Exchange (ETDEWEB)

    Nirschl, Alexandra A.; Zou, Yan; Krystek, Jr., Stanley R.; Sutton, James C.; Simpkins, Ligaya M.; Lupisella, John A.; Kuhns, Joyce E.; Seethala, Ramakrishna; Golla, Rajasree; Sleph, Paul G.; Beehler, Blake C.; Grover, Gary J.; Egan, Donald; Fura, Aberra; Vyas, Viral P.; Li, Yi-Xin; Sack, John S.; Kish, Kevin F.; An, Yongmi; Bryson, James A.; Gougoutas, Jack Z.; DiMarco, John; Zahler, Robert; Ostrowski, Jacek; Hamann, Lawrence G.; (BMS)

    2010-11-09

    A novel selective androgen receptor modulator (SARM) scaffold was discovered as a byproduct obtained during synthesis of our earlier series of imidazolidin-2-ones. The resulting oxazolidin-2-imines are among the most potent SARMs known, with many analogues exhibiting sub-nM in vitro potency in binding and functional assays. Despite the potential for hydrolytic instability at gut pH, compounds of the present class showed good oral bioavailability and were highly active in a standard rodent pharmacological model.

  11. Electron induced conformational changes of an imine-based molecular switch on a Au(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Lotze, Christian; Henningsen, Nils; Franke, Katharina; Schulze, Gunnar; Pascual, Jose Ignacio [Inst. f. Experimentalphysik, Freie Universitaet Berlin (Germany); Luo, Ying; Haag, Rainer [Inst. f. Organische Chemie, Freie Universitaet Berlin (Germany)

    2009-07-01

    Azobenzene-based molecules exhibit a cis-trans configurational photoisomerisation in solution. Recently, the adsorption properties of azobenzene derivatives have been investigated on different metal surfaces in order to explore the possible changes in the film properties induced by external stimuli. In azobenzene, the diazo-bridge is a key group for the isomerization process. Its interaction with a metal surface is dominated through the N lone-pair electrons, which reduces the efficiency of the conformational change. In order to reduce the molecule-surface interaction, we explore an alternative molecular architecture by substituting the diazo-bridge (-N=N-) of azobenzene by an imine-group (-N=CH-). We have investigated the imine-based compound para-carboxyl-di-benzene-imine (PCI) adsorbed on a Au(111) surface. The carboxylic terminations mediates the formation of strongly bonded molecular dimers, which align in ordered rows preferentially following the fcc regions of the Au(111) herringbone reconstruction. Low temperature scanning tunneling microscopy was used to induce conformational changes between trans and cis state of individual molecules in a molecular monolayer.

  12. EVALUATION OF ANTIOXIDANT ACTIVITY OF SOME IMINES DERIVATIVES OF L-ARGININE.

    Science.gov (United States)

    Iacob, Andreea-Teodora; Drăgan, Maria; Constantin, Sandra; Lupaşcu, Florentina; Confederat, Luminiţa; Buron, F; Routier, S; Profire, Lenuţa

    2016-01-01

    L-Arginine is an a-amino acid which plays important roles in different diseases or processes, such as Alzheimer disease, inflammatory process, healing and tissue regeneration and it also could be useful as an anti-atherosclerotic agent. Considering the large amount of studies on the beneficial effects of different antioxidants, this paper is focused on the evaluation of the antioxidant potential of some imine derivatives, synthesized by the authors and described in a previous article. The evaluation of the antioxidant power was performed using phosphomolydenum-reducing antioxidant power (PRAP) and ferric reducing antioxidant power (FRAP) assays, tests described in the literature and which are used with some minor modifications. It was found that most of the imine derivatives are more active than the L-Arginine in the PPAP and FRAP assays. The most active derivative was the compound obtained by condensation of L-arginine with 2,3-dihydroxybenzaldehyde (2k) and 2-nitrobenzaldehyde (2g). Following the described protocol, some imine derivatives of L-arginine were evaluated in terms of antioxidant potential using in vitro methods. The most favorable influence was obtained by the aromatic substitution with nitro and hydroxyl, the corresponding derivatives being the most active derivatives compared to L-arginine.

  13. Electronic structure and UV spectra of N-arylthio-1,4-benzoquinone imines

    International Nuclear Information System (INIS)

    Pirozhenko, V.V.; Boldeskul, I.E.; Kolesnikov, V.T.; Vid, L.V.; Kuz'menko, L.O.

    1986-01-01

    The electronic structure of N-arylthio-1,4-benzoquinone imines (II) was studied by quantum-chemical methods (CNDO/2). It was shown that the special characteristics of the reactivity of the compounds in reaction with chlorine compared with sulfenylketimines R 2 C=N-S-Ar not containing a quinonoid ring may be due to the different nature of the lowest unoccupied molecular orbitals (LUMO). The UV spectra of compounds (II) were investigated. In the visible region the spectra of all the compounds contain strong absorption (R 1 = R 2 = R 3 = R 4 = R 5 = H, λ/sub m/ = 433 nm, epsilon/sub m/ = 2.12 x 10 4 liters/mole x cm), due to intramolecular charge transfer from the sulfur atom to the quinonoid fragment of the molecule. It was established that there is a linear relation between the energy of the transition and the σ + constants of the substituents in the aryl fragment. The assignment of the transitions was confirmed by calculations of the UV spectra of N-arylthio-1,4-benzoquinone imines by the PPP method. Comparison of the UV spectra of these compounds with the UV spectra of N-arylsulfonyl-1,4-benzoquinone imines makes it possible to conclude that the sulfur atom of the SO 2 group, unlike the divalent sulfur atom, is not capable of transmitting the electronic effects of the substituents from one part of the molecule to the other

  14. Electric-field triggered controlled release of bioactive volatiles from imine-based liquid crystalline phases.

    Science.gov (United States)

    Herrmann, Andreas; Giuseppone, Nicolas; Lehn, Jean-Marie

    2009-01-01

    Application of an electric field to liquid crystalline film forming imines with negative dielectric anisotropy, such as N-(4-methoxybenzylidene)-4-butylaniline (MBBA, 1), results in the expulsion of compounds that do not participate in the formation of the liquid crystalline phase. Furthermore, amines and aromatic aldehydes undergo component exchange with the imine by generating constitutional dynamic libraries. The strength of the electric field and the duration of its application to the liquid crystalline film influence the release rate of the expelled compounds and, at the same time, modulate the equilibration of the dynamic libraries. The controlled release of volatile organic molecules with different chemical functionalities from the film was quantified by dynamic headspace analysis. In all cases, higher headspace concentrations were detected in the presence of an electric field. These results point to the possibility of using imine-based liquid crystalline films to build devices for the controlled release of a broad variety of bioactive volatiles as a direct response to an external electric signal.

  15. Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes.

    Science.gov (United States)

    Kovaříček, Petr; Lehn, Jean-Marie

    2012-06-06

    The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in-place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of

  16. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir

    2017-04-06

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  17. Harvesting Covert Networks: The Case Study of the iMiner Database

    DEFF Research Database (Denmark)

    Memon, Nasrullah; Wiil, Uffe Kock; Alhajj, Reda

    2011-01-01

    was incorporated in the iMiner prototype tool, which makes use of investigative data mining techniques to analyse data. This paper will present the developed framework along with the form and structure of the terrorist data in the database. Selected cases will be referenced to highlight the effectiveness of the i...... collected by intelligence agencies and government organisations is inaccessible to researchers. To counter the information scarcity, we designed and built a database of terrorist-related data and information by harvesting such data from publicly available authenticated websites. The database...

  18. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir; Merle, Nicolas; Minenkov, Yury; De Mallmann, Aimery; Samantaray, Manoja; Le Qué mé ner, Fré dé ric; Szeto, Kai C.; Abou-Hamad, Edy; Cavallo, Luigi; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  19. Synthesis and biology of cyclic imine toxins, an emerging class of potent, globally distributed marine toxins.

    Science.gov (United States)

    Stivala, Craig E; Benoit, Evelyne; Aráoz, Rómulo; Servent, Denis; Novikov, Alexei; Molgó, Jordi; Zakarian, Armen

    2015-03-01

    From a small group of exotic compounds isolated only two decades ago, Cyclic Imine (CI) toxins have become a major class of marine toxins with global distribution. Their distinct chemical structure, biological mechanism of action, and intricate chemistry ensures that CI toxins will continue to be the subject of fascinating fundamental studies in the broad fields of chemistry, chemical biology, and toxicology. The worldwide occurrence of potent CI toxins in marine environments, their accumulation in shellfish, and chemical stability are important considerations in assessing risk factors for human health. This review article aims to provide an account of chemistry, biology, and toxicology of CI toxins from their discovery to the present day.

  20. Synthesis and reactions of imines of α,β-ethylenic silicon-containing aldehydes with complex metal hydrides

    International Nuclear Information System (INIS)

    Surnin, V.A.; Stadnichuk, M.D.

    1986-01-01

    Imines of 3-trimethylsilyl-2-propenal or its hydrocarbon analog are reduced chemoselectively at the C=N double bond by sodium borohydride. The direction of lithium aluminum hydride reduction of these imines is not influenced by the nature of the element attached to the C=C bond silicon versus carbon, but rather is determined by the nature of the radical group attached to the nitrogen atom; N-arylimines undergo addition with lithium aluminum hydride at the C=N bond exclusively, whereas for N-alkylimines the addition reactions occur either partially or in full in the 1,4-position, depending on the reaction conditions, to give imines of saturated aldehydes after demetallation

  1. Synthesis and characterization of two new TiO2-containing benzothiazole-based imine composites for organic device applications.

    Science.gov (United States)

    Różycka, Anna; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Pociecha, Damian; Malinowski, Marek; Fryń, Patryk; Hreniak, Agnieszka; Rysz, Jakub; Dąbczyński, Paweł; Marzec, Monika

    2018-01-01

    The effect of the presence of titanium dioxide in two new imines, ( E , E )-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[ d ][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and ( E )- N -[(benzo[ d ][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO 2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol-gel method) exhibited a surface area of 59.5 m 2 /g according to Brunauer-Emmett-Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett-Joyner-Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m 3 /g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Col hk ). The imine:TiO 2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO-LUMO energy levels compared to pure TiO 2 . This implies that TiO 2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO 2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO 2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO 2 surface with SP1 and SP2 were observed. The imine:TiO 2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications.

  2. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

  3. Synthesis and characterization of two new TiO2-containing benzothiazole-based imine composites for organic device applications

    Science.gov (United States)

    Różycka, Anna; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Pociecha, Damian; Malinowski, Marek; Fryń, Patryk; Hreniak, Agnieszka; Rysz, Jakub; Dąbczyński, Paweł

    2018-01-01

    The effect of the presence of titanium dioxide in two new imines, (E,E)-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[d][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and (E)-N-[(benzo[d][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol–gel method) exhibited a surface area of 59.5 m2/g according to Brunauer–Emmett–Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett–Joyner–Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m3/g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Colhk). The imine:TiO2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO–LUMO energy levels compared to pure TiO2. This implies that TiO2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO2 surface with SP1 and SP2 were observed. The imine:TiO2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications. PMID:29600135

  4. Nanomechanical properties of hydroxyapatite (HAP) with DAB dendrimers (poly-propylene imine) coatings onto titanium surfaces

    International Nuclear Information System (INIS)

    Charitidis, Costas A.; Skarmoutsou, Amalia; Tsetsekou, Athena; Brasinika, Despina; Tsiourvas, Dimitris

    2013-01-01

    Highlights: ► The synthesis of hydroxyapatite (HAP) nanoparticles in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB). ► The nanomechanical properties of different HAP-DAB coatings onto titanium surfaces. ► Wear resistance and adhesion properties of the synthesized coatings quantified by nanoindentation data analysis. -- Abstract: Coatings of hydroxyapatite (HAP) nanorods onto titanium surfaces were synthesized with the aim to improve coatings’ mechanical properties and adhesion to the substrate. The coatings are consisting of HAP nanorods synthesized in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB) bearing 32 amine end groups employing varying calcium: dendrimer ratios and varying hydrothermal treatments. The quality, surface morphology and structure of the coatings were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy dispersive microanalysis. Wear resistance and adhesion properties of the coatings onto titanium substrates were studied through nanoindentation analysis. The experimental conditions, namely the calcium: dendrimer molar ratio and the hydrothermal treatment temperature were carefully selected; thus, it was possible to produce coatings of high hardness and elastic modulus values (ranging between 1–4.5 GPa and 40–150 GPa, respectively) and/or high wear resistance and plastic deformation values

  5. A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

    Energy Technology Data Exchange (ETDEWEB)

    Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of); Park Soo Youl [Interface Chemistry and Engineering Research Team, Korea Research Institute of Chemical Technology, Daejon (Korea, Republic of)

    2016-12-15

    Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory.

  6. A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

    International Nuclear Information System (INIS)

    Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi; Park Soo Youl

    2016-01-01

    Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory

  7. Polyethylene imine modified hydrochar adsorption for chromium (VI) and nickel (II) removal from aqueous solution.

    Science.gov (United States)

    Shi, Yuanji; Zhang, Tao; Ren, Hongqiang; Kruse, Andrea; Cui, Ruofan

    2018-01-01

    An adsorbent hydrochar was synthesized from corn cobs and modified with polyethylene imine (PEI). The hydrochars before and after modification were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis. FTIR and XPS revealed that the PEI was grafted onto the hydrochar via ether and imine bonds formed with glutaraldehyde. The maximum adsorption capacities for Cr(VI) (33.663mg/g) and Ni(II) (29.059mg/g) on the modified hydrochars were 365% and 43.7% higher, respectively, than those on the unmodified hydrochar. A pseudo-second-order model described the adsorption of Ni(II) and Cr(VI) on all the adsorbents. The adsorption of Cr(VI) was endothermic, spontaneous, increased disorder, and obeyed the Langmuir model. By contrast, the adsorption of Ni(II) was exothermic, spontaneous, decreased disorder, and obeyed the Freundlich model. XPS confirmed that the adsorption sites and mechanisms for Ni(II) and Cr(VI) on the modified hydrochars were different. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Nanomechanical properties of hydroxyapatite (HAP) with DAB dendrimers (poly-propylene imine) coatings onto titanium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Charitidis, Costas A., E-mail: charitidis@chemeng.ntua.gr [School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Skarmoutsou, Amalia [School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Tsetsekou, Athena; Brasinika, Despina [School of Mining Engineering and Metallurgy, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Tsiourvas, Dimitris [National Centre for Scientific Research “Demokritos”, Institute of Physical Chemistry, Agia Paraskevi, 15310 Athens (Greece)

    2013-04-20

    Highlights: ► The synthesis of hydroxyapatite (HAP) nanoparticles in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB). ► The nanomechanical properties of different HAP-DAB coatings onto titanium surfaces. ► Wear resistance and adhesion properties of the synthesized coatings quantified by nanoindentation data analysis. -- Abstract: Coatings of hydroxyapatite (HAP) nanorods onto titanium surfaces were synthesized with the aim to improve coatings’ mechanical properties and adhesion to the substrate. The coatings are consisting of HAP nanorods synthesized in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB) bearing 32 amine end groups employing varying calcium: dendrimer ratios and varying hydrothermal treatments. The quality, surface morphology and structure of the coatings were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy dispersive microanalysis. Wear resistance and adhesion properties of the coatings onto titanium substrates were studied through nanoindentation analysis. The experimental conditions, namely the calcium: dendrimer molar ratio and the hydrothermal treatment temperature were carefully selected; thus, it was possible to produce coatings of high hardness and elastic modulus values (ranging between 1–4.5 GPa and 40–150 GPa, respectively) and/or high wear resistance and plastic deformation values.

  9. A Highly Stable Microporous Covalent Imine Network Adsorbent for Natural Gas Upgrading and Flue Gas CO2 Capture

    KAUST Repository

    Das, Swapan Kumar; Wang, Xinbo; Ostwal, Mayur; Lai, Zhiping

    2016-01-01

    The feasible capture and separation of CO2 and N2 from CH4 is an important task for natural gas upgrading and the control of greenhouse gas emissions. Here, we studied the microporous covalent imine networks (CIN) material prepared through Schiff

  10. Synthesis of N-substituted a,a-difluoro-b-aminophosphonates by addition of diethyl lithiodifluoromethylphosphonate to imines

    Czech Academy of Sciences Publication Activity Database

    Cherkupally, Prabhakar; Beier, Petr

    2012-01-01

    Roč. 141, Sep (2012), s. 76-82 ISSN 0022-1139 R&D Projects: GA ČR GP203/08/P310 Institutional support: RVO:61388963 Keywords : nucleophilic addition * difluorophosphonate * aminophosphonate * imines Subject RIV: CC - Organic Chemistry Impact factor: 1.939, year: 2012

  11. Effect of aluminum alkyls on a homogeneous and silica-supported phenoxy-imine titanium catalyst for ethylene trimerization

    NARCIS (Netherlands)

    Karbach, Fabian F.; Severn, John R.; Duchateau, Robbert

    A phenoxy-imine titanium catalyst (FI-catalyst) for selective ethylene trimerization was immobilized on methyl aluminoxane (MAO) pretreated silica and its activity and selectivity was compared with that of the corresponding homogeneous catalyst system. The homogeneous and heterogeneous ethylene

  12. Hydrogenation of imines catalysed by ruthenium(II) complexes based on lutidine-derived CNC pincer ligands.

    Science.gov (United States)

    Hernández-Juárez, Martín; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

    2013-01-14

    The preparation of new Ru(II) complexes incorporating fac-coordinated lutidine-derived CNC ligands is reported. These derivatives are selectively deprotonated by (t)BuOK at one of the methylene arms of the pincer, leading to catalytically active species in the hydrogenation of imines.

  13. Azeotropic Preparation of a "C"-Phenyl "N"-Aryl Imine: An Introductory Undergraduate Organic Chemistry Laboratory Experiment

    Science.gov (United States)

    Silverberg, Lee J.; Coyle, David J.; Cannon, Kevin C.; Mathers, Robert T.; Richards, Jeffrey A.; Tierney, John

    2016-01-01

    Imines are important in biological chemistry and as intermediates in organic synthesis. An experiment for introductory undergraduate organic chemistry is presented in which benzaldehyde was condensed with "p"-methoxyaniline in toluene to give 4-methoxy-"N"-(phenylmethylene)benzenamine. Water was removed by azeotropic…

  14. Multivalent contrast agents based on Gd-DTPA-terminated poly (propylene imine) dendrimers for Magnetic Resonance Imaging

    NARCIS (Netherlands)

    Langereis, S.; Lussanet, de Q.G; Genderen, van M.H.P.; Backes, W.H.; Meijer, E.W.

    2004-01-01

    A convenient methodol. has been developed for the synthesis of gadolinium-diethylenetriaminepentaacetic acid (Gd-DTPA)-terminated poly(propylene imine) dendrimers as contrast agents for magnetic resonance imaging (MRI). In our strategy, isocyanate-activated, tert-butyl-protected DTPA analogs were

  15. Poly(Propylene Imine Dendrimers and Amoxicillin as Dual-Action Antibacterial Agents

    Directory of Open Access Journals (Sweden)

    Natalia Wrońska

    2015-10-01

    Full Text Available Besides acting as antimicrobial compounds, dendrimers can be considered as agents that improve the therapeutic effectiveness of existing antibiotics. In this work we present a new approach to using amoxicillin (AMX against reference strains of common Gram-negative pathogens, alone and in combination with poly(propylene imine (PPI dendrimers, or derivatives thereof, in which 100% of the available hydrogen atoms are substituted with maltose (PPI 100%malG3. The concentrations of dendrimers used remained in the range non-toxic to eukaryotic cells. The results indicate that PPI dendrimers significantly enhance the antibacterial effect of amoxicillin alone, allowing antibiotic doses to be reduced. It is important to reduce doses of amoxicillin because its widespread use in medicine could lead to the development of bacterial resistance and environmental pollution. This is the first report on the combined antibacterial activity of PPI surface-modified maltose dendrimers and amoxicillin.

  16. Interactive transport of guanidinylated poly(propylene imine)-based dendrimers through liposomal and cellular membranes.

    Science.gov (United States)

    Tsogas, Ioannis; Sideratou, Zili; Tsiourvas, Dimitris; Theodossiou, Theodossis A; Paleos, Constantinos M

    2007-10-15

    The ability of guanidinylated poly(propylene imine) dendrimers to translocate across lipid bilayers was assessed by employing either a model phosphate-bearing liposomal membrane system or A549 human lung carcinoma cells. Two dendrimer generations, differing in the number of surface guanidinium groups, were employed, while surface acetylation or the use of spacers affected the binding of the guanidinium group to the phosphate moiety and finally the transport efficiency. Following adhesion of dendrimers with liposomes, fusion or transport occurred. Transport through the liposomal bilayer was observed at low guanidinium/phosphate molar ratios, and was enhanced when the bilayer was in the liquid-crystalline phase. For effective transport through the liposomal membrane, an optimum balance between the binding strength and the degree of hydrophobicity of the guanidinylated dendrimer is required. In experiments performed in vitro with cells, efficient penetration and internalization in subcellular organelles and cytosol was observed.

  17. Total synthesis of fluoxetine and duloxetine through an in situ imine formation/borylation/transimination and reduction approach.

    Science.gov (United States)

    Calow, Adam D J; Fernández, Elena; Whiting, Andrew

    2014-08-28

    We report efficient, catalytic, asymmetric total syntheses of both (R)-fluoxetine and (S)-duloxetine from α,β-unsaturated aldehydes conducting five sequential one-pot steps (imine formation/copper mediated β-borylation/transimination/reduction/oxidation) followed by the specific ether group formation which deliver the desired products (R)-fluoxetine in 45% yield (96% ee) and (S)-duloxetine in 47% yield (94% ee).

  18. Convergent Synthesis of Piperidines by the Union of Conjugated Alkynes with Imines: A Unique Regioselective Bond Construction for Heterocycle Synthesis

    Science.gov (United States)

    Chen, Ming Z.; Micalizio, Glenn C.

    2009-01-01

    A two-step process is described for the union of aromatic imines, conjugated alkynes and aldehydes that results in a stereoselective synthesis of highly substituted piperidines. This synthetic process has been made possible by defining a unique regioselective functionalization of conjugated alkynes that establishes a suitably functionalized substrate for subsequent heterocycle-forming cationic annulation. Given the flexibility of the coupling process, heterocycles can be accessed through a process that establishes up to four stereogenic centers and four fused rings. PMID:19817447

  19. Rhodium(III)-catalyzed three-component reaction of imines, alkynes, and aldehydes through C-H activation.

    Science.gov (United States)

    Huang, Ji-Rong; Song, Qiang; Zhu, Yu-Qin; Qin, Liu; Qian, Zhi-Yong; Dong, Lin

    2014-12-15

    An efficient rhodium(III)-catalyzed tandem three-component reaction of imines, alkynes and aldehydes through CH activation has been developed. High stereo- and regioselectivity, as well as good yields were obtained in most cases. The simple and atom-economical approach offers a broad scope of substrates, providing polycyclic skeletons with potential biological properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

    Science.gov (United States)

    Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

    2009-10-15

    A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

  1. Mesomorphic Behavior of Symmetrical and Unsymmetrical Azomethines with Two Imine Groups

    Directory of Open Access Journals (Sweden)

    Patrice Rannou

    2009-02-01

    Full Text Available Seven symmetrical azomethines with two imine groups (HC=N were synthesized by condensation of the benzene-1,4-dicarboxaldehydewith five amines (first group: A1-A5 and of the 2,5-thiophenedicarboxaldehyde with two amines (second group: AT1-AT2. Additionally, two unsymmetrical azomethines were obtained by a two step condensation of benzene-1,4-dicarboxaldehydewith pyren-1-amine(1st step (abbreviated hereinafter as AP1 and then AP1 was reacted with4-dodecylaniline or 4-hexadecylaniline (2nd step (third group: AP1A-AP1B. Liquid crystalline properties of the azomethines were studied by differential scanning calorimetry (DSC, polarizing optical microscopy (POM and UV-vis spectroscopy in the function of temperature [UV-vis(T]. The Wide-Angle X-ray Diffraction (WAXD technique was used to probe the structural properties of the azomethines. Mesomorphic behavior was observed for symmetrical and unsymmetrical azomethines, obtained from the benzene-1,4-dicarboxaldehyde and symmetrical ones prepared from 2,5-thiophenedicarboxaldehyde and different amineshaving aliphatic chains. Based on the POM and DSC measurements the following mesophases were detected: nematic, smectic A, smectic C, smectic F (I, smectic G (J.

  2. Synthesis of Chromane Derivatives via Indium-mediated Intramolecular Allenylation and Allylation to Imines

    International Nuclear Information System (INIS)

    Kang, Han Young; Yu, Yeon Kwon

    2004-01-01

    The results of preparing chromans by intramolecular allylation are shown in Table 2. The results indicated that the indium-mediated allylation was not as efficient as the allenylation. About 10-20% decrease in yields was observed. As mentioned above, in each case only a single isomer was observed, and the stereochemistry of the product was determined as cis by analysis of 1 H NMR and NOE spectra. There are, however, still some limitations in these transformations. Especially, in the case of allylation mixtures of cis and trans isomers are always produced in about 2 : 1 ratio (cis/trans). The ratio was not improved under the various reaction conditions we attempted. Since the indium-mediated addition to carbonyl groups has been successful, it occurred to us that it would be worthwhile to test the addition to carbon-nitrogen double bonds, that is, imine groups. We wish to report here the results of the investigations on allylation and allenylation to C=N bond to provide the chromane structures. The whole transformations

  3. On the mechanism of imine elimination from Fischer tungsten carbene complexes

    Directory of Open Access Journals (Sweden)

    Philipp Veit

    2016-06-01

    Full Text Available (Aminoferrocenyl(ferrocenylcarbene(pentacarbonyltungsten(0 (CO5W=C(NHFcFc (W(CO5(E-2 is synthesized by nucleophilic substitution of the ethoxy group of (CO5W=C(OEtFc (M(CO5(1Et by ferrocenyl amide Fc-NH– (Fc = ferrocenyl. W(CO5(E-2 thermally and photochemically eliminates bulky E-1,2-diferrocenylimine (E-3 via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E-3 are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO5(E-2 decays thermally in a first-order rate-law with a Gibbs free energy of activation of ΔG‡298K = 112 kJ mol−1. Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent densitiy functional theory [(TD-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II intermediates cis(N,H-W(CO4(H(Z-15 and cis(C,H-W(CO4(H(Z-15.

  4. d-Fructose-Decorated Poly(ethylene imine) for Human Breast Cancer Cell Targeting.

    Science.gov (United States)

    Englert, Christoph; Pröhl, Michael; Czaplewska, Justyna A; Fritzsche, Carolin; Preußger, Elisabeth; Schubert, Ulrich S; Traeger, Anja; Gottschaldt, Michael

    2017-08-01

    The high affinity of GLUT5 transporter for d-fructose in breast cancer cells has been discussed intensely. In this contribution, high molar mass linear poly(ethylene imine) (LPEI) is functionalized with d-fructose moieties to combine the selectivity for the GLUT5 transporter with the delivery potential of PEI for genetic material. The four-step synthesis of a thiol-group bearing d-fructose enables the decoration of a cationic polymer backbone with d-fructose via thiol-ene photoaddition. The functionalization of LPEI is confirmed by 2D NMR techniques, elemental analysis, and size exclusion chromatography. Importantly, a d-fructose decoration of 16% renders the polymers water-soluble and eliminates the cytotoxicity of PEI in noncancer L929 cells, accompanied by a reduced unspecific cellular uptake of the genetic material. In contrast, the cytotoxicity as well as the cell specific uptake is increased for triple negative MDA-MB-231 breast cancer cells. Therefore, the introduction of d-fructose shows superior potential for cell targeting, which can be assumed to be GLUT5 dependent. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Syntheses of poly(phenoxy-imine)s anchored with carboxyl group: Characterization and photovoltaic studies

    Science.gov (United States)

    Kaya, İsmet; Ayten, Bahar; Şenol, Dilek

    2018-04-01

    A serious of pyridine based Schiff bases (M1, M2, and M3) were synthesized via condensation reaction of 4-aminosalicyclic acid with 2-pyridinecarboxaldehyde, 3-pyridine carboxyaldehyde and 4-pyridinecarboxaldehyde, respectively. The transformation of Schiff bases into their poly(phenoxy-imine) species (P1, P2, P3) was obtained using oxidative polycondensation (OP) by NaOCl as the oxidant in alkaline medium at 70 °C. The structures of the synthesized compounds were characterized by solubility test, FT-IR, UV-Vis and NMR techniques. Thermal data were obtained by TG-DTA and DSC techniques. Photoluminescence (PL) properties of the synthesized materials were examined in organic solvent. Fluorescence measurements were carried out in various concentrated solutions to determine the optimum concentrations and PL intensities. P3 could be used in light-emitting diodes due to its multicolor (white, blue, green and yellow) light-emitting property. The efficiency (η) of a solar cell of P1, P2 and P3 were determined by single channel Potentiostat/Galvanostat with electrochemical impedance spectroscopy. The order of conductivities was found to be as P3>P2>P1 as a result of iodine doping. The best performing photovoltaic cell with Isc (mA cm-2), Voc (V), FF, and η (%) as -0.642, 0.399, 0.461 and -0.118 was obtained for P3.

  6. Arabidopsis and Maize RidA Proteins Preempt Reactive Enamine/Imine Damage to Branched-Chain Amino Acid Biosynthesis in Plastids[C][W][OPEN

    Science.gov (United States)

    Niehaus, Thomas D.; Nguyen, Thuy N.D.; Gidda, Satinder K.; ElBadawi-Sidhu, Mona; Lambrecht, Jennifer A.; McCarty, Donald R.; Downs, Diana M.; Cooper, Arthur J.L.; Fiehn, Oliver; Mullen, Robert T.; Hanson, Andrew D.

    2014-01-01

    RidA (for Reactive Intermediate Deaminase A) proteins are ubiquitous, yet their function in eukaryotes is unclear. It is known that deleting Salmonella enterica ridA causes Ser sensitivity and that S. enterica RidA and its homologs from other organisms hydrolyze the enamine/imine intermediates that Thr dehydratase forms from Ser or Thr. In S. enterica, the Ser-derived enamine/imine inactivates a branched-chain aminotransferase; RidA prevents this damage. Arabidopsis thaliana and maize (Zea mays) have a RidA homolog that is predicted to be plastidial. Expression of either homolog complemented the Ser sensitivity of the S. enterica ridA mutant. The purified proteins hydrolyzed the enamines/imines formed by Thr dehydratase from Ser or Thr and protected the Arabidopsis plastidial branched-chain aminotransferase BCAT3 from inactivation by the Ser-derived enamine/imine. In vitro chloroplast import assays and in vivo localization of green fluorescent protein fusions showed that Arabidopsis RidA and Thr dehydratase are chloroplast targeted. Disrupting Arabidopsis RidA reduced root growth and raised the root and shoot levels of the branched-chain amino acid biosynthesis intermediate 2-oxobutanoate; Ser treatment exacerbated these effects in roots. Supplying Ile reversed the root growth defect. These results indicate that plastidial RidA proteins can preempt damage to BCAT3 and Ile biosynthesis by hydrolyzing the Ser-derived enamine/imine product of Thr dehydratase. PMID:25070638

  7. Intracellular siRNA delivery dynamics of integrin-targeted, PEGylated chitosan-poly(ethylene imine) hybrid nanoparticles

    DEFF Research Database (Denmark)

    Ragelle, Héloïse; Colombo, Stefano; Pourcelle, Vincent

    2015-01-01

    chitosan-poly(ethylene imine) hybrid nanoparticles. The amount of intracellular siRNA delivered by αvβ3-targeted versus non-targeted nanoparticles was quantified in the human non-small cell lung carcinoma cell line H1299 expressing enhanced green fluorescent protein (EGFP) using a stem-loop reverse...... that these nanoparticles might end up in late endosomes or lysosomes without releasing their cargo to the cell cytoplasm. Thus, the silencing efficiency of the chitosan-based nanoparticles is strongly dependent on the uptake and the intracellular trafficking in H1299 EGFP cells, which is critical information towards...

  8. Enantioselective Synthesis of α-Mercapto-β-amino Esters via Rh(II)/Chiral Phosphoric Acid-Cocatalyzed Three-Component Reaction of Diazo Compounds, Thiols, and Imines.

    Science.gov (United States)

    Xiao, Guolan; Ma, Chaoqun; Xing, Dong; Hu, Wenhao

    2016-12-02

    An enantioselective method for the synthesis of α-mercapto-β-amino esters has been developed via a rhodium(II)/chiral phosphoric acid-cocatalyzed three-component reaction of diazo compounds, thiols, and imines. This transformation is proposed to proceed through enantioselective trapping of the sulfonium ylide intermediate generated in situ from the diazo compound and thiol by the phosphoric acid-activated imine. With this method, a series of α-mercapto-β-amino esters were obtained in good yields with moderate to good stereoselectivities.

  9. Oxidative N-Heterocyclic Carbene-Catalyzed γ-Carbon Addition of Enals to Imines: Mechanistic Studies and Access to Antimicrobial Compounds.

    Science.gov (United States)

    Zheng, Peng-Cheng; Cheng, Jiajia; Su, Shihu; Jin, Zhichao; Wang, Yu-Huang; Yang, Song; Jin, Lin-Hong; Song, Bao-An; Chi, Yonggui Robin

    2015-07-06

    The reaction mechanism of the γ-carbon addition of enal to imine under oxidative N-heterocyclic carbene catalysis is studied experimentally. The oxidation, γ-carbon deprotonation, and nucleophilic addition of γ-carbon to imine were found to be facile steps. The results of our study also provide highly enantioselective access to tricyclic sulfonyl amides that exhibit interesting antimicrobial activities against X. oryzae, a bacterium that causes bacterial disease in rice growing. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Solid-phase receptor-based assay for the detection of cyclic imines by chemiluminescence, fluorescence, or colorimetry.

    Science.gov (United States)

    Rodríguez, Laura P; Vilariño, Natalia; Molgó, Jordi; Aráoz, Rómulo; Antelo, Alvaro; Vieytes, Mercedes R; Botana, Luis M

    2011-08-01

    The spirolides and gymnodimines are marine phycotoxins included in the group of cyclic imines. The toxicity of these compounds to humans is still unknown, although their toxicity by intraperitoneal injection in rodents is very high. A receptor-based method was developed using the competition of the 13-desmethyl spirolide C with biotin-labeled α-bungarotoxin for binding to nicotinic acetylcholine receptors and the immobilization of the α-bungarotoxin-receptor complex on streptavidin-coated surfaces. The quantification of the immobilized receptor can be achieved using a specific antibody. Finally, after the addition of a secondary antibody labeled with horseradish peroxidase, three alternative substrates of this enzyme generate a chemiluminescent, fluorescent, or colorimetric signal. The assay performs well in shellfish extracts and the detection range is 5-150 nM of 13-desmethyl spirolide C in shellfish extracts, which is at least 5 times more sensitive than the existing fluorescence polarization assay. This assay can also detect gymnodimine, although with 10 times lower sensitivity than the spirolide. The detection of cyclic imines with microplate assays would be useful for screening purposes in order to reduce the number of samples to be processed by bioassays or analytical methods.

  11. Unusual Conformational Aspects of Some Novel Chiral Non-Racemic Pyridinyl-2-phosphonates

    NARCIS (Netherlands)

    Dros, A.C.; Zijlstra, R.W.J.; Duijnen, P.Th. van; Spek, A.L.; Kooijman, H.; Kellogg, R.M.

    1998-01-01

    Reaction of pyridinyl-2-phosphonyl dichloride (6) with 1-phenyl-2,2-dimethylpropane-1,3-diol (9) leads to the two epimeric 2-oxo-2-(2-pyridinyl)-4-phenyl-5,5-dimethyl-1,3,2-dioxaphosphorinanes (10a,b). These can be separated and the stereochemistry assigned on the basis of 31P NMR spectroscopy. For

  12. Isotopic evidence for extraterrestrial non- racemic amino acids in the Murchison meteorite

    Science.gov (United States)

    Engel, M. H.; Macko, S. A.

    1997-09-01

    Many amino acids contain an asymmetric centre, occurring as laevorotatory, L, or dextrorotatory, D, compounds. It is generally assumed that abiotic synthesis of amino acids on the early Earth resulted in racemic mixtures (L- and D-enantiomers in equal abundance). But the origin of life required, owing to conformational constraints, the almost exclusive selection of either L- or D-enantiomers, and the question of why living systems on the Earth consist of L-enantiomers rather than D-enantiomers is unresolved. A substantial fraction of the organic compounds on the early Earth may have been derived from comet and meteorite impacts. It has been reported previously that amino acids in the Murchison meteorite exhibit an excess of L-enantiomers, raising the possibility that a similar excess was present in the initial inventory of organic compounds on the Earth. The stable carbon isotope compositions of individual amino acids in Murchison support an extraterrestrial origin-rather than a terrestrial overprint of biological amino acids-although reservations have persisted (see, for example, ref. 9). Here we show that individual amino-acid enantiomers from Murchison are enriched in 15N relative to their terrestrial counterparts, so confirming an extraterrestrial source for an L-enantiomer excess in the Solar System that may predate the origin of life on the Earth.

  13. Pyridine group assisted addition of diazo-compounds to imines in the 3-CC reaction of 2-aminopyridines, aldehydes, and diazo-compounds.

    Science.gov (United States)

    Gulevich, Anton V; Helan, Victoria; Wink, Donald J; Gevorgyan, Vladimir

    2013-02-15

    A novel three-component coupling (3-CC) reaction of 2-aminoazines, aromatic aldehydes, and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles as well as β-amino acid derivatives.

  14. 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

  15. In situ generation of N-Boc-protected alkenyl imines: controlling the E/Z geometry of alkenyl moieties in the Mukaiyama-Mannich reaction.

    Science.gov (United States)

    Bai, Jian-Fei; Sasagawa, Hajime; Yurino, Taiga; Kano, Taichi; Maruoka, Keiji

    2017-07-18

    Readily available Boc-protected Z-alkenyl aminals could be used as Z-alkenyl and E-alkenyl imine precursors under acidic conditions. In the Mukaiyama-Mannich reaction of Z-alkenyl Boc-aminals, the E/Z geometry of the products was controlled by the catalyst used. The present method was also applied to asymmetric Mukaiyama-Mannich reactions.

  16. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Ahmad Dar

    2012-06-01

    Full Text Available The present work is intended to determine the catalytic activity of Mixed Oxide supported gold for aerobic oxidative dehydrogenation of amines to imines using Ceria as a main constituent of the each support. The model catalysts Au/CeO2:TiO2 Au/CeO2:SiO2, Au/CeO2:ZrO2 and Au/CeO2:Al2Os were prepared by deposition co-precipitation method and deposition of gold was determined by EDEX analysis. The supported nano-gold catalyzes the dehydrogenation of secondary amines to imines without loss of activity. On recycling good amount of product yield is obtained. Oxidation of secondary amines to imines is carried at 100˚C and almost 90 % conversion was obtained with >99% selectivity. © 2012 BCREC UNDIP. All rights reservedReceived: 26th December 2011; Revised: 7th June 2012; Accepted: 13rd June 2012[How to Cite: B.A. Dar, M. Sharma, B. Singh. (2012. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen. Bulletin of Chemical Reaction Engineering & Catalysis, 7(1: 79-84.  doi:10.9767/bcrec.7.1.1257.79-84][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1257.79-84 ] | View in 

  17. Photocatalytic organic transformation by layered double hydroxides: highly efficient and selective oxidation of primary aromatic amines to their imines under ambient aerobic conditions.

    Science.gov (United States)

    Yang, Xiu-Jie; Chen, Bin; Li, Xu-Bing; Zheng, Li-Qiang; Wu, Li-Zhu; Tung, Chen-Ho

    2014-06-25

    We report the first application of layered double hydroxide as a photocatalyst in the transformation of primary aromatic amines to their corresponding imines with high efficiency and selectivity by using oxygen in an air atmosphere as a terminal oxidant under light irradiation.

  18. Reactions of Cp2MCl2 (M=Ti or Zr with Imine-Oxime Ligands. Formation of Metallacycles

    Directory of Open Access Journals (Sweden)

    C. Tripathi

    2005-07-01

    Full Text Available The reactions of bis(cyclopentadienyltitanium(IV/zirconium(IV dichloridewith a series of imine-oxime ligands (LH2, derived by condensing benzil-α-monoxime and2-phenylenediamine, 4-phenylenediamine, 4-methyl-2-phenylenediamine, 2,6-diamino-pyridine, have been studied in anhydrous tetrahydrofuran in the presence of base andmetallocycles of the [Cp2M(L] (M=Ti or Zr type have been isolated. Tentative structureshave been proposed for the products based on elemental analysis, electrical conductance andspectral (electronic, IR and 1H-NMR data. Proton NMR spectra indicate that on the NMRtime scale there is rapid rotation of the cyclopentadienyl ring around the metal-ring axis at25oC. Studies were conducted to assess the growth inhibiting potential of the complexessynthesized and the ligands against various bacterial strains.

  19. Morphological mutations induced by gamma rays, ethylene imine and N-nitroso-N-ethyl urea in lentil (Lens culinaris medik.)

    International Nuclear Information System (INIS)

    Solanki, I.S.; Sharma, B.

    2003-01-01

    Dry and healthy seeds of a large seeded lentil cv, 'Precoz Selection', were treated with three doses each of gamma rays, ethylene imine (EI) and N-nitroso-N-ethyl urea (NEU). Based on the frequency of morphological mutations, the mutagens were arranged in the order: NEU > EI >. Gamma rays and dose-dependent relationship was observed in the case of gamma rays (5 kR 1 damage groups induced morphological mutations in the order: HH > HL > LH > LL. The morphological mutations included changes for growth habit, foliage, plant height and maturity and flowering behaviour. A mild relative mutagenic specificity and differences in mutability of genes for different traits were observed, In general the spectrum of morphological mutations was not influenced by the groups of M 1 damage, except that some mutation types occurred more frequently, than others in certain groups. (author)

  20. Pyridine Group-Assisted Addition of Diazo-Compounds to Imines in the 3-CC Reaction of 2-Aminopyridines, Aldehydes, and Diazo-Compounds

    Science.gov (United States)

    Gulevich, Anton V.; Helan, Victoria; Wink, Donald J.

    2013-01-01

    A novel three-component (3-CC) coupling reaction of 2-aminoazines, aromatic aldehydes and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles, as well as to β-amino acid derivatives. PMID:23373731

  1. Syn-Selective Synthesis of β-Branched α-Amino Acids by Alkylation of Glycine-Derived Imines with Secondary Sulfonates.

    Science.gov (United States)

    Lou, Sha; McKenna, Grace M; Tymonko, Steven A; Ramirez, Antonio; Benkovics, Tamas; Conlon, David A; González-Bobes, Francisco

    2015-10-16

    A syn-selective synthesis of β-branched α-amino acids has been developed based on the alkylation of glycine imine esters with secondary sulfonates. The potassium counterion for the enolate, the solvent, and the leaving group on the electrophile were key levers to maximize the diasteroselectivity of the alkylation. The optimized conditions enabled a straightforward preparation of a number of β-branched α-amino acids that can be challenging to obtain.

  2. A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

    Science.gov (United States)

    Largeron, Martine; Fleury, Maurice-Bernard

    2015-02-23

    The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Influence of Endo- and Exocyclic Heteroatoms on Stabilities and 1,3-Dipolar Cycloaddition Reactivities of Mesoionic Azomethine Ylides and Imines.

    Science.gov (United States)

    Champagne, Pier Alexandre; Houk, K N

    2017-10-20

    The geometries, stabilities, and 1,3-dipolar cycloaddition reactivities of 24 mesoionic azomethine ylides and imines were investigated using density functional theory calculations at the M06-2X/6-311+G-(d,p)/M06-2X/6-31G-(d) level. The computed structures highlight how the commonly used "aromatic" resonance form should be replaced by two more accurate resonance structures. Stabilities of the dipoles were assessed by various homodesmotic schemes and are consistent with these compounds being nonaromatic. The activation free energies with ethylene or acetylene range from 11.8 to 36.6 kcal/mol. Within each dipole type, the predicted cycloaddition reactivities correlate with the reaction energies and the resonance stabilization energies provided by the various substituents. Endocyclic (X) heteroatoms increase the reactivity of the 1,3-dipoles in the order of O > NH ≅ S, whereas exocyclic (Y) substituents increase it in the order of CH 2 > NH > O > S. Distortion/interaction analysis indicated that the difference in reactivity between differently substituted 1,3-dipoles is driven by distortion, whereas the difference between azomethine ylides and imines is related to lower interaction energies of imines with the dipolarophiles.

  4. Poly(vinyl-alcohol)/poly(ethylene-glycol)/poly(ethylene-imine) blend membranes - structure and CO2 facilitated transport

    International Nuclear Information System (INIS)

    Ben Hamouda, S.; Quang, Trong Nguyen; Langevin, D.; Sadok, Roudeslic

    2010-01-01

    Poly(vinyl-alcohol) (PVA)/poly(ethylene-imine) (PEI)/poly(ethylene-glycol) (PEG) blend membranes were prepared by solution casting followed by solvent evaporation. The effects of the blend polymer composition on the membrane structure and CO 2 /N 2 permeation characteristics were investigated. IR spectroscopy evidenced strong hydrogen bonding interactions between amorphous PVA and PEI, and weaker interactions between PVA and PEG. DSC studies showed that PVA crystallization was partially inhibited by the interactions between amorphous PVA and PEI blend, in which PEG separated into nodules. The CO 2 permeability decreased with an increase in CO 2 partial pressure in feed gas, while the N 2 permeability remained constant. This result indicated that only CO 2 was transported by the facilitated transport mechanism. The CO 2 and N 2 permeabilities increased monotonically with the PEI content in the blend membranes, whereas the ideal selectivity of CO 2 to N 2 transport showed a maximum. When CO 2 is humidified, its permeability through the blend membranes is much higher than that of dry CO 2 , but the change in permeability due to the presence of humidity is reversible. (authors)

  5. Photometric Characterization of the Reductive Amination Scope of the Imine Reductases from Streptomyces tsukubaensis and Streptomyces ipomoeae.

    Science.gov (United States)

    Matzel, Philipp; Krautschick, Lukas; Höhne, Matthias

    2017-10-18

    Imine reductases (IREDs) have emerged as promising enzymes for the asymmetric synthesis of secondary and tertiary amines starting from carbonyl substrates. Screening the substrate specificity of the reductive amination reaction is usually performed by time-consuming GC analytics. We found two highly active IREDs in our enzyme collection, IR-20 from Streptomyces tsukubaensis and IR-Sip from Streptomyces ipomoeae, that allowed a comprehensive substrate screening with a photometric NADPH assay. We screened 39 carbonyl substrates combined with 17 amines as nucleophiles. Activity data from 663 combinations provided a clear picture about substrate specificity and capabilities in the reductive amination of these enzymes. Besides aliphatic aldehydes, the IREDs accepted various cyclic (C 4 -C 8 ) and acyclic ketones, preferentially with methylamine. IR-Sip also accepted a range of primary and secondary amines as nucleophiles. In biocatalytic reactions, IR-Sip converted (R)-3-methylcyclohexanone with dimethylamine or pyrrolidine with high diastereoselectivity (>94-96 % de). The nucleophile acceptor spectrum depended on the carbonyl substrate employed. The conversion of well-accepted substrates could also be detected if crude lysates were employed as the enzyme source. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effect of the shell on the transport properties of poly(glycerol) and Poly(ethylene imine) nanoparticles

    International Nuclear Information System (INIS)

    Adeli, M.; Haag, R.; Zarnegar, Z.

    2007-01-01

    Dendritic core-shell architectures containing poly (glycerol) and poly (ethylene imine) cores and poly(lactide) shell (PG-PLA and PEI-PLA respectively) were synthesized. Analogous of these core-shell architectures containing the same cores but poly (L-lactide) shell (PG-PLLA and PEI-PLLA, respectively) were also synthesized. In this work PG and PEI were used as macroinitiator for ring opening polymerization of the lactid and L-lactide monomers. Different molar ratios of monomer to end functional groups of PG ([LA]/[OH]) and PEI ([LA]/[NHn] (n = 1 or 2)) were used to prepare the core-shell architectures with different shell thickness. These core-shell architectures were able to encapsulate and transport the small guest molecules. Their transport capacity (TC) depended on the type and thickness of the shells. TC of core-shell architectures containing PLLA shell was higher than that for their analogs containing PLA shell. The diameter of core-shell architectures was between 20-80 nm. The rate of release of guest molecules from chloroform solution of nanocarriers to water phase was investigated and it depended on the type of the core, shell and solvent

  7. Gold nanoparticles capped with benzalkonium chloride and poly (ethylene imine) for enhanced loading and skin permeability of 5-fluorouracil.

    Science.gov (United States)

    Safwat, Mohamed A; Soliman, Ghareb M; Sayed, Douaa; Attia, Mohamed A

    2017-11-01

    To enhance 5-fluorouracil (5-FU) permeability through the skin by loading onto gold nanoparticles (GNPs) capped with two cationic ligands, benzalkonium chloride (BC) or poly (ethylene imine) (PEI). Whereas 5-FU has excellent efficacy against many cancers, its poor permeability through biological membranes and several adverse effects limit its clinical benefits. BC and PEI were selected to stabilize GNPs and to load 5-FU through ionic interactions. 5-FU/BC-GNPs and 5-FU/PEI-GNPs were prepared at different 5-FU/ligand molar ratios and different pH values and were evaluated using different techniques. GNPs stability was tested as a function of salt concentration and storage time. 5-FU release from BC- and PEI-GNPs was evaluated as a function of solution pH. Ex vivo permeability studies of different 5-FU preparations were carried out using mice skin. 5-FU-loaded GNPs size and surface charge were dependent on the 5-FU/ligand molar ratios. 5-FU entrapment efficiency and loading capacity were dependent on the used ligand, 5-FU/ligand molar ratio and solution pH. Maximum drug entrapment efficiency of 59.0 ± 1.7% and 46.0 ± 1.1% were obtained for 5-FU/BC-GNPs and 5-FU/PEI-GNPs, respectively. 5-FU-loaded GNPs had good stability against salinity and after storage for 4 months at room temperature and at 4 °C. In vitro 5-FU release was pH- and ligand-dependent where slower release was observed at higher pH and for 5-FU/BC-GNPs. 5-FU permeability through mice skin was significantly higher for drug-loaded GNPs compared with drug-ligand complex or drug aqueous solution. Based on these results, BC- and PEI-GNPs might find applications as effective topical delivery systems of 5-FU.

  8. Ionic Conductivity and Potential Application for Fuel Cell of a Modified Imine-Based Covalent Organic Framework.

    Science.gov (United States)

    Montoro, Carmen; Rodríguez-San-Miguel, David; Polo, Eduardo; Escudero-Cid, Ricardo; Ruiz-González, Maria Luisa; Navarro, Jorge A R; Ocón, Pilar; Zamora, Félix

    2017-07-26

    We present the novel potential application of imine-based covalent organic frameworks (COFs), formed by the direct Schiff reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde building blocks in m-cresol or acetic acid, named RT-COF-1 or RT-COF-1Ac/RT-COF-1AcB. The post-synthetic treatment of RT-COF-1 with LiCl leads to the formation of LiCl@RT-COF-1. The ionic conductivity of this series of polyimine COFs has been characterized at variable temperature and humidity, using electrochemical impedance spectroscopy. LiCl@RT-COF-1 exhibits a conductivity value of 6.45 × 10 -3 S cm -1 (at 313 K and 100% relative humidity) which is among the highest values so far reported in proton conduction for COFs. The mechanism of conduction has been determined using 1 H and 7 Li solid-state nuclear magnetic resonance spectroscopy. Interestingly, these materials, in the presence of controlled amounts of acetic acid and under pressure, show a remarkable processability that gives rise to quasi-transparent and flexible films showing in-plane structural order as confirmed by X-ray crystallography. Finally, we prove that these films are useful for the construction of proton exchange membrane fuel cells (PEMFC) reaching values up to 12.95 mW cm -2 and 53.1 mA cm -2 for maximum power and current density at 323 K, respectively.

  9. Synthesis and characterization of poly(propylene imine)-dendrimer-grafted gold nanoparticles as nanocarriers of doxorubicin.

    Science.gov (United States)

    Golshan, Marzieh; Salami-Kalajahi, Mehdi; Mirshekarpour, Mina; Roghani-Mamaqani, Hossein; Mohammadi, Maryam

    2017-07-01

    The aim of current work is synthesis 4th-generation-poly(propylene imine) (PPI)-dendrimer modified gold nanoparticles (Au-G4A) as nanocarriers for doxorubicin (DOX) and studying in vitro drug release kinetics from nanocarriers into different media. Accordingly, AuNPs were synthesized by reduction of chloroauric acid (HAuCl 4 ) aqueous solution with trisodium citrate and modified with cysteamine to obtain amine-functionalized (Au-NH 2 ) nanoparticles. Au-NH 2 nanoparticles were used as multifunctional cores and participated in Michael addition of acrylonitrile and reduction process by lithium aluminum hydride (LAH) to synthesize Au-G4A nanoparticles. Also, peripheral primary amine groups of Au-G4A were conjugated with folic acid (FA) (Au-G4F) to study the bioconjugation effect on drug release behavior of nanostructures. Ultraviolet spectroscopy (UV-vis), atomic force microscopy (AFM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and thermal gravimetric analysis (TGA) were used to approve the synthesis of different nanostructures. Finally, Au-G4A and Au-G4F samples were loaded with DOX and exposed to environments with different pH values to examine the release properties of nanostructures. Also, drug release kinetics was investigated by fitting of experimental data with different release models. As a result, synthesized dendritic structures showed Higuchi and Korsmeyer-Peppas models release behavior due to better solubility of drug in release media with respect to dendrimer cavities and drug release through polymeric matrix respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. A Highly Stable Microporous Covalent Imine Network Adsorbent for Natural Gas Upgrading and Flue Gas CO2 Capture

    KAUST Repository

    Das, Swapan Kumar

    2016-06-06

    The feasible capture and separation of CO2 and N2 from CH4 is an important task for natural gas upgrading and the control of greenhouse gas emissions. Here, we studied the microporous covalent imine networks (CIN) material prepared through Schiff base condensation and exhibited superior chemical robustness under both acidic and basic conditions and high thermal stability. The material possesses a relatively uniform nanoparticle size of approximately 70 to 100 nm. This network featured permanent porosity with a high surface area (722 m2g-1) and micropores. A single-component gas adsorption study showed enhanced CO2 and CH4 uptakes of 3.32 mmol/g and 1.14 mmol/g, respectively, at 273 K and 1 bar, coupled with high separation selectivities for CO2/CH4, CH4/N2, and CO2/N2 of 23, 11.8 and 211, respectively. The enriched Lewis basicity in the porous skeletons favours the interaction of quadrupolar CO2 and polarizable CH4, resulting in enhanced CH4 and CO2 uptake and high CH4/N2, CO2/CH4 and CO2/N2 selectivities. Breakthrough experiments showed high CO2/CH4, CH4/N2 and CO2/N2 selectivities of 7.29, 40 and 125, respectively, at 298 K and 1 bar. High heats of adsorption for CH4 and CO2 (QstCH4; 32.61 kJ mol-1 and QstCO2; 42.42 kJ mol-1) provide the ultimate validation for the high selectivity. To the best of our knowledge, such a versatile adsorbent material that displays both enhanced uptake and selectivity for a variety of binary gas mixtures, including CO2/ CH4, CO2/N2 and CH4/N2, has not been extensively explored.

  11. Synthesis of 3-acetyl-N-aryl-4-diethylaminoselenet-2(2H)-imines from 4-diethylamino-3-butyn-2-one and aryl isoselenocyanates

    OpenAIRE

    Atanassov, Plamen K; Linden, Anthony; Heimgartner, Heinz

    2004-01-01

    The reaction of aryl isoselenocyanates (1a-d) with 4-diethylamino-3-butyn-2-one (6) in refluxing tetrahydrofuran afforded N-arylselenet-2(2H)-imines (7) in moderate yields. The structure of the stable 4-bromophenyl derivative (7b) has been established by X-Ray crystallography. A stepwise cycloaddition via an intermediate zwitterion (A/A¢) is proposed as the reaction mechanism. In boiling tetrahydrofuran, the selenetimines (7) are in equilibrium with ketenimines (B), which were intercepted by ...

  12. Quantum-chemical evaluation of the lability of π-electronic systems in N-benzoyl derivatives of phosphorus and sulfur imines

    International Nuclear Information System (INIS)

    Egorov, Yu.P.; Pen'kovskii, V.V.; Boldeskul, I.E.

    1986-01-01

    The charges on atoms, the bond indices, their components, and the energies of the highest occupied π orbitals of four N-benzoyl derivatives of phosphorus and sulfur imines have been calculated by the CNDO/2 method in an spd basis. According to the results obtained, the π system of a bridging sulfur-nitrogen group is more labile than a phosphorus-nitrogen group, in agreement with the experimental evaluations of the transmission of the electronic effects of substituents in these systems. An interpretation of this lability has been given

  13. EMR searching of quantum behavior of magnetic γ-Fe2O3 nanoparticles encapsulated into poly(propylene imine dendrimer

    Directory of Open Access Journals (Sweden)

    Vorobeva V.E., Domracheva N.E., Gruzdev M.S.

    2016-12-01

    Full Text Available The superparamagnetic γ-Fe2O3 nanoparticles (average diameter of 2.5 nm encapsulated in poly(propylene imine dendrimer have been investigated by electron magnetic resonance (EMR. EMR measurements have been recorded in perpendicular and parallel configurations in the wide temperature range (4.2-300 K. It has been shown that the model based on the spin value S = 30, corresponding to the total magnetic moment of the nanoparticle, can be used to interpret the experimental results and the proof of the quantum behavior of γ-Fe2O3 nanoparticles.

  14. In vivo targeted gene delivery to peripheral neurons mediated by neurotropic poly(ethylene imine-based nanoparticles

    Directory of Open Access Journals (Sweden)

    Lopes CDF

    2016-06-01

    Full Text Available Cátia DF Lopes,1–3,* Hugo Oliveira,1,* Inês Estevão,1 Liliana Raquel Pires,1 Ana Paula Pêgo1,2,4,5 1INEB – Instituto de Engenharia Biomédica, Universidade do Porto (UPorto, Porto, Portugal; 2i3S – Instituto de Investigação e Inovação em Saúde, NanoBiomaterials for Targeted Therapies Group, UPorto, Porto, Portugal; 3FMUP – Faculdade de Medicina da Universidade do Porto, Porto, Portugal; 4ICBAS – Instituto de Ciências Biomédicas Abel Salazar, UPorto, Porto, Portugal; 5FEUP – Faculdade de Engenharia da Universidade do Porto, Porto, Portugal *These authors contributed equally to this work Abstract: A major challenge in neuronal gene therapy is to achieve safe, efficient, and minimally invasive transgene delivery to neurons. In this study, we report the use of a nonviral neurotropic poly(ethylene imine-based nanoparticle that is capable of mediating neuron-specific transfection upon a subcutaneous injection. Nanoparticles were targeted to peripheral neurons by using the nontoxic carboxylic fragment of tetanus toxin (HC, which, besides being neurotropic, is capable of being retrogradely transported from neuron terminals to the cell bodies. Nontargeted particles and naked plasmid DNA were used as control. Five days after treatment by subcutaneous injection in the footpad of Wistar rats, it was observed that 56% and 64% of L4 and L5 dorsal root ganglia neurons, respectively, were expressing the reporter protein. The delivery mediated by HC-functionalized nanoparticles spatially limited the transgene expression, in comparison with the controls. Histological examination revealed no significant adverse effects in the use of the proposed delivery system. These findings demonstrate the feasibility and safety of the developed neurotropic nanoparticles for the minimally invasive delivery of genes to the peripheral nervous system, opening new avenues for the application of gene therapy strategies in the treatment of peripheral

  15. Diastereo- and regioselective addition of thioamide dianions to imines and aziridines: synthesis of N-thioacyl-1,2-diamines and N-thioacyl-1,3-diamines.

    Science.gov (United States)

    Shibahara, Fumitoshi; Kobayashi, Shun-ichiro; Maruyama, Toshifumi; Murai, Toshiaki

    2013-01-02

    Addition reactions of thioamide dianions that were derived from N-arylmethyl thioamides to imines and aziridines were carried out. The reactions of imines gave the addition products of N-thioacyl-1,2-diamines in a highly diastereoselective manner in good-to-excellent yields. The diastereomeric purity of these N-thioacyl-1,2-diamines could be enriched by simple recrystallization. The reduction of N-thioacyl-1,2-diamines with LiAlH(4) gave their corresponding 1,2-diamines in moderate-to-good yields with retention of their stereochemistry. The oxidative-desulfurization/cyclization of an N-thioacyl-1,2-diamine in CuCl(2)/O(2) and I(2)/pyridine systems gave the cyclized product in moderate yield and the trans isomer was obtained as the sole product. On the other hand, a similar cyclization reaction with antiformin (aq. NaClO) as an oxidant gave the cis isomer as the major product. The reactions of N-tosylaziridines gave the addition products of N-thioacyl-1,3-diamines with low diastereoselectivity but high regioselectivity and in good-to-excellent yields. The use of AlMe(3) as an additive improved the efficiency and regioselectivity of the reaction. The stereochemistry of the obtained products was determined by X-ray diffraction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Poly-Cross-Linked PEI Through Aromatically Conjugated Imine Linkages as a New Class of pH-Responsive Nucleic Acids Packing Cationic Polymers

    Science.gov (United States)

    Chen, Shun; Jin, Tuo

    2016-01-01

    Cationic polyimines polymerized through aromatically conjugated bis-imine linkages and intra-molecular cross-linking were found to be a new class of effective transfection materials for their flexibility in structural optimization, responsiveness to intracellular environment, the ability to facilitate endosome escape and cytosol release of the nucleic acids, as well as self-metabolism. When three phthalaldehydes of different substitution positions were used to polymerize highly branched low-molecular weight polyethylenimine (PEI 1.8K), the product through ortho-phthalimines (named PPOP) showed significantly higher transfection activity than its two tere- and iso-analogs (named PPTP and PPIP). Physicochemical characterization confirmed the similarity of three polyimines in pH-responded degradability, buffer capacity, as well as the size and Zeta potential of the polyplexes formed from the polymers. A mechanistic speculation may be that the ortho-positioned bis-imine linkage of PPOP may only lead to the straight trans-configuration due to steric hindrance, resulting in larger loops of intra-polymer cross-linking and more flexible backbone. PMID:26869931

  17. Structural, kinetic, and docking studies of artificial imine reductases based on biotin-streptavidin technology: an induced lock-and-key hypothesis.

    Science.gov (United States)

    Robles, Victor Muñoz; Dürrenberger, Marc; Heinisch, Tillmann; Lledós, Agustí; Schirmer, Tilman; Ward, Thomas R; Maréchal, Jean-Didier

    2014-11-05

    An artificial imine reductase results upon incorporation of a biotinylated Cp*Ir moiety (Cp* = C5Me5(-)) within homotetrameric streptavidin (Sav) (referred to as Cp*Ir(Biot-p-L)Cl] ⊂ Sav). Mutation of S112 reveals a marked effect of the Ir/streptavidin ratio on both the saturation kinetics as well as the enantioselectivity for the production of salsolidine. For [Cp*Ir(Biot-p-L)Cl] ⊂ S112A Sav, both the reaction rate and the selectivity (up to 96% ee (R)-salsolidine, kcat 14-4 min(-1) vs [Ir], KM 65-370 mM) decrease upon fully saturating all biotin binding sites (the ee varying between 96% ee and 45% ee R). In contrast, for [Cp*Ir(Biot-p-L)Cl] ⊂ S112K Sav, both the rate and the selectivity remain nearly constant upon varying the Ir/streptavidin ratio [up to 78% ee (S)-salsolidine, kcat 2.6 min(-1), KM 95 mM]. X-ray analysis complemented with docking studies highlight a marked preference of the S112A and S112K Sav mutants for the SIr and RIr enantiomeric forms of the cofactor, respectively. Combining both docking and saturation kinetic studies led to the formulation of an enantioselection mechanism relying on an "induced lock-and-key" hypothesis: the host protein dictates the configuration of the biotinylated Ir-cofactor which, in turn, by and large determines the enantioselectivity of the imine reductase.

  18. The polymerisation of oligo(ethylene glycol methyl ether) methacrylate from a multifunctional poly(ethylene imine) derived amide : a stabiliser for the synthesis and dispersion of magnetite nanoparticles

    NARCIS (Netherlands)

    Kleine, A.; Altan, C.L.; Yarar, U.E.; Sommerdijk, N.A.J.M.; Bucak, S.; Holder, S.J.

    2014-01-01

    A facile synthetic route to poly(ethylene imine)-graft-poly(oligo(ethylene glycol methyl ether)) (PEI-graft-POEGMA) functionalised superparamagnetic magnetite nanoparticles is described. The polymerisation of OEGMA from a model molecular amide demonstrated the feasibility of POEGMA synthesis under

  19. Enhanced visible-light photocatalytic activity for selective oxidation of amines into imines over TiO{sub 2}(B)/anatase mixed-phase nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Jun [Institute of Applied Chemistry, Henan Polytechnic University, Jiaozuo 454003 (China); State Key Laboratory Cultivation Base for Gas Geology and Gas Control, School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003 (China); Yang, Juan, E-mail: yangjuanhpu@yahoo.com [Institute of Applied Chemistry, Henan Polytechnic University, Jiaozuo 454003 (China); Wang, Xiaohan; Zhang, Lei; Li, Yingjie [Institute of Applied Chemistry, Henan Polytechnic University, Jiaozuo 454003 (China)

    2015-09-15

    Graphical abstract: Visible-light photocatalytic activities for selective oxidation of amines into imines are greatly affected by the crystal structure of TiO{sub 2} catalysts and mixed-phase TiO{sub 2}(B)/anatase possess higher photoactivity because of the moderate adsorption ability and efficient charge separation. - Highlights: • Visible-light photocatalytic oxidation of amines to imines is studied over different TiO{sub 2}. • Photocatalytic activities are greatly affected by the crystal structure of TiO{sub 2} nanowires. • Mixed-phase TiO{sub 2}(B)/anatase exhibits higher catalytic activity than single-phase TiO{sub 2}. • Enhanced activity is ascribed to efficient adsorption ability and interfacial charge separation. • Photoinduced charge transfer mechanism on TiO{sub 2}(B)/anatase catalysts is also proposed. - Abstract: Wirelike catalysts of mixed-phase TiO{sub 2}(B)/anatase TiO{sub 2}, bare anatase TiO{sub 2} and TiO{sub 2}(B) are synthesized via calcining precursor hydrogen titanate obtained from hydrothermal process at different temperatures between 450 and 700 °C. Under visible light irradiation, mixed-phase TiO{sub 2}(B)/anatase TiO{sub 2} catalysts exhibit enhanced photocatalytic activity in comparison with pure TiO{sub 2}(B) and anatase TiO{sub 2} toward selective oxidation of benzylamines into imines and the highest photocatalytic activity is achieved by TW-550 sample consisting of 65% TiO{sub 2}(B) and 35% anatase. The difference in photocatalytic activities of TiO{sub 2} samples can be attributed to the different adsorption abilities resulted from their crystal structures and interfacial charge separation driven by surface-phase junctions between TiO{sub 2}(B) and anatase TiO{sub 2}. Moreover, the photoinduced charge transfer mechanism of surface complex is also proposed over mixed-phase TiO{sub 2}(B)/anatase TiO{sub 2} catalysts. Advantages of this photocatalytic system include efficient utilization of solar light, general suitability to

  20. Enhanced visible-light photocatalytic activity for selective oxidation of amines into imines over TiO2(B)/anatase mixed-phase nanowires

    International Nuclear Information System (INIS)

    Dai, Jun; Yang, Juan; Wang, Xiaohan; Zhang, Lei; Li, Yingjie

    2015-01-01

    Graphical abstract: Visible-light photocatalytic activities for selective oxidation of amines into imines are greatly affected by the crystal structure of TiO 2 catalysts and mixed-phase TiO 2 (B)/anatase possess higher photoactivity because of the moderate adsorption ability and efficient charge separation. - Highlights: • Visible-light photocatalytic oxidation of amines to imines is studied over different TiO 2 . • Photocatalytic activities are greatly affected by the crystal structure of TiO 2 nanowires. • Mixed-phase TiO 2 (B)/anatase exhibits higher catalytic activity than single-phase TiO 2 . • Enhanced activity is ascribed to efficient adsorption ability and interfacial charge separation. • Photoinduced charge transfer mechanism on TiO 2 (B)/anatase catalysts is also proposed. - Abstract: Wirelike catalysts of mixed-phase TiO 2 (B)/anatase TiO 2 , bare anatase TiO 2 and TiO 2 (B) are synthesized via calcining precursor hydrogen titanate obtained from hydrothermal process at different temperatures between 450 and 700 °C. Under visible light irradiation, mixed-phase TiO 2 (B)/anatase TiO 2 catalysts exhibit enhanced photocatalytic activity in comparison with pure TiO 2 (B) and anatase TiO 2 toward selective oxidation of benzylamines into imines and the highest photocatalytic activity is achieved by TW-550 sample consisting of 65% TiO 2 (B) and 35% anatase. The difference in photocatalytic activities of TiO 2 samples can be attributed to the different adsorption abilities resulted from their crystal structures and interfacial charge separation driven by surface-phase junctions between TiO 2 (B) and anatase TiO 2 . Moreover, the photoinduced charge transfer mechanism of surface complex is also proposed over mixed-phase TiO 2 (B)/anatase TiO 2 catalysts. Advantages of this photocatalytic system include efficient utilization of solar light, general suitability to amines, reusability and facile separation of nanowires catalysts

  1. Highly selective probe based on imine linkage for Zn{sup 2+} and HSO{sub 3}{sup −} in mixed aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Kamaljot; Chaudhary, Savita; Singh, Sukhjinder; Mehta, S.K., E-mail: skmehta@pu.ac.in

    2015-04-15

    A simple salicylaldehyde derived Schiff base N, N′- bis (p-chloro salicylidene)-1, 2- ethylenediamine (L) was synthesized and characterized. The receptor demonstrates simultaneous dual channel chromogenic and fluorogenic signaling towards HSO{sub 3}{sup −} and Zn{sup 2+} in mixed aqueous media. Solvatochromism was employed systematically for modulating its optoelectronic properties. The probe was successfully assessed to monitor HSO{sub 3}{sup −} detection via UV–vis spectroscopy. DFT calculations and {sup 1}H NMR spectroscopy further support the results based on shifting of equilibrium. Moreover, the sensor showed large fluorescence enhancement with blue-shift of 48 nm after addition of Zn{sup 2+}. The probe exhibits high selectivity over other competitive ions with high detection limit of 6.54×10{sup −5} M and 3.21×10{sup −6} M for HSO{sub 3}{sup −} and Zn{sup 2+}, respectively. Importantly, this is one of the rare reports in which Schiff base was utilized for the fabrication of chromogenic or fluorogenic sensor using solvent effect for multianalyte detection. - Highlights: • Easy synthesis of highly selective and sensitive Salicylideneaniline moiety. • Solvatochromism induced tautomerism between the enol-imine and keto-amine forms. • Computational studies revealing the effect of solvent on stability of NH form. • Discriminative detection of HSO{sub 3}{sup −} and Zn{sup 2+} by different spectroscopic techniques. • Optical feedbacks as absorption transitions with HSO{sub 3}{sup −} on bisulphite adduct formation. • Fluorescence enhancement for Zn{sup 2+} based on imine binding mechanism.

  2. Internal catalysis in imine formation from acetone and acetone-d6 and conformationally constrained derivatives of N,N-dimethyl-1,3-propanediamine

    International Nuclear Information System (INIS)

    Hine, J.; Li, W.S.

    1975-01-01

    The kinetics of the reactions of 3-exo-dimethylaminomethyl-2-endo-norbornanamine (1), cis-2-(dimethylaminomethyl)cyclohexylamine (2), and 3-endo-dimethylaminomethyl-2-endo-norbornanamine (3) with acetone, and of these three diamines, neopentylamine, and 2-endo-norbornanamine with acetone-d 6 to give imines were studied at 35 0 and various pH's by use of hydroxylamine to capture the imines as they are formed. Acetone-d 6 was more reactive than acetone in the reactions with hydroxylamine alone as well as in the reactions with each of the diamines; the average k/sup D//k/sup H/ was 1.2. The rate constants for the monoprotonated diamines were so large relative to those for the unprotonated diamines that reliable values for the latter could not be obtained. The dominant reaction mechanism appears to be a reversible formation of the carbinolamine derived from the tertiary-protonated form of the monoprotonated diamine followed by rate-controlling internal acid-catalyzed formation of the iminium ion. The rate constants are compared with those obtained as a by-product of deuterium exchange studies of reactions of 1, 2, 3, and five other monoprotonated diamines by the same mechanism. The comparisons show that structural features that destabilize conformations in which the two amino groups are far apart may decrease the reactivity by relative stabilization []of a cyclic hydrogen-bonded form of the monoprotonated diamine as well as increasing the reactivity by relative stabilization of the transition state. Freezing the H 2 N--C--C--CH 2 NMe 2 dihedral angle of 1,3-diamines at values near 0, 60, and 120 0 does not give large differences in reactivity. Comparison of the rate constants for reactions of unprotonated neopentylamine and 2-endo-norbornanamine with those obtained previously for amines of the type XCH 2 CH 2 NH 2 gives no evidence for steric hindrance. (auth)

  3. Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral β-amino acids.

    Science.gov (United States)

    Cantú-Reyes, Margarita; Alvarado-Beltrán, Isabel; Ballinas-Indilí, Ricardo; Álvarez-Toledano, Cecilio; Hernández-Rodríguez, Marcos

    2017-09-20

    We report a one-pot synthesis of chiral β 2,2,3 -amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure β-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

  4. A systematic theoretical study of the electronic structures of porphyrin dimers: DFT and TD-DFT calculations on diporphyrins linked by ethane, ethene, ethyne, imine, and azo bridges.

    Science.gov (United States)

    Rintoul, Llew; Harper, Shannon R; Arnold, Dennis P

    2013-11-21

    Theoretical calculations of the geometries, electronic structures and electronic absorption spectra of a series of covalently-linked porphyrin dimers are reported. The diporphyrins comprise 5,10,15-triphenylporphyrinatozinc(II) (ZnTriPP) units linked through the meso carbons by two-atom bridges, namely 1,2-ethanediyl (1), trans-1,2-ethenediyl (2), ethynediyl (3), 1,2-iminomethenediyl (4), and transdiazenediyl (5). The structures were optimised in toluene solvent by Density Functional Theory (DFT), using the integral equation formalism variant of the polarizable continuum model. The calculations were performed using the B3LYP functional and the 6-31G(d,p) basis set. The complete molecules were modelled, with no substitution of smaller groups on the periphery. In parallel, the compounds 2–5 were prepared by known or novel synthetic routes, to enable comparisons of experimental electronic absorption spectra with those calculated using time dependent-DFT at the same level of theory. As the ethane dimer 1 is not yet synthetically accessible, the model monomer meso-2-phenylethylZnTriPP was used for comparisons with the theoretical predictions. The results form a self-consistent set, enabling for the first time legitimate comparisons of the electronic structures of the series, especially regarding the degree to which the porphyrin p-systems interact by conjugation across the bridges. The theoretical calculations of the electronic transitions match the observed spectra in toluene to a remarkable degree, especially with respect to the peak maximum of the Q band, which represents to a large degree the energy of the HOMO–LUMO transition. The imine 4 is intrinsically polar due to the asymmetric bridge, and the HOMO is located almost exclusively on the ZnTriPP unit attached to the nitrogen of the imine, and the LUMO on the C-attached ring. Thus the Q-band transition is mapped as a comprehensive charge-transfer from the former ring to the latter. This may have consequences

  5. Structural and electrochemical studies of TiO2 complexes with (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivative bases towards organic devices.

    Science.gov (United States)

    Rozycka, Anna; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Hreniak, Agnieszka; Marzec, Monika

    2018-06-12

    Three (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (-HC[double bond, length as m-dash]CH-) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (SAI1 and SAI2) and -5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about -3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO-LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500-1700 cm-1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C[double bond, length as m-dash]N)-TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm-2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes.

  6. The Amelioration of N-Acetyl-p-Benzoquinone Imine Toxicity by Ginsenoside Rg3: The Role of Nrf2-Mediated Detoxification and Mrp1/Mrp3 Transports

    Directory of Open Access Journals (Sweden)

    Sang Il Gum

    2013-01-01

    Full Text Available Previously, we found that Korean red ginseng suppressed acetaminophen (APAP-induced hepatotoxicity via alteration of its metabolic profile involving GSTA2 induction and that ginsenoside Rg3 was a major component of this gene induction. In the present study, therefore, we assessed the protective effect of Rg3 against N-acetyl-p-benzoquinone imine (NAPQI, a toxic metabolic intermediate of APAP. Excess NAPQI resulted in GSH depletion with increases in the ALT and AST activities in H4IIE cells. Rg3 pretreatment reversed GSH depletion by NAPQI. Rg3 resulted in increased mRNA levels of the catalytic and modulatory subunit of glutamate cysteine ligase (GCL, the rate-limiting steps in GSH synthesis and subsequently increased GSH content. Rg3 increased levels of nuclear Nrf2, an essential transcriptional factor of these genes. The knockdown or knockout of the Nrf2 gene abrogated the inductions of mRNA and protein by Rg3. Abolishment of the reversal of GSH depletion by Rg3 against NAPQI was observed in Nrf2-deficient cells. Rg3 induced multidrug resistance-associated protein (Mrp 1 and Mrp3 mRNA levels, but not in Nrf2-deficient cells. Taken together, these results demonstrate that Rg3 is efficacious in protecting hepatocytes against NAPQI insult, due to GSH repletion and coordinated gene regulations of GSH synthesis and Mrp family genes by Nrf2.

  7. Synthesis and structure determination of a stable organometallic uranium(V) imine complex and its isolobal anionic U(IV)-ate complex

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, M.; Botoshanskii, M.; Eisen, M.S. [Schulich Faculty of Chemistry, and Institute of Catalysis Science and Technology, Technion Israel Institute of Technology, Haifa (Israel); Bannenberg, Th.; Tamm, M. [Institut fur Anorganische und Analytische Chemie, Technische Universitat Braunschweig (Germany)

    2010-06-15

    The reaction of one equivalent of Cp*{sub 2}UCl{sub 2} with 2-(trimethylsilyl-imino)-1,3-di-tert-butyl-imidazoline in boiling toluene afforded a one electron oxidation of the uranium metal and the opening of the N-heterocyclic ring, resulting in the formation of an organometallic uranium(V) imine complex. This complex crystallized with one molecule of toluene in the unit cell, and its solid-state structure was determined by X-ray diffraction analysis. When the same reaction was performed in perdeuterated toluene, a myriad of organometallic complexes were obtained, however, when equimolar amounts of water were used in toluene, the same complex was obtained, and its solid state characterization shows two independent molecules in the unit cell with an additional water molecule. For comparison of the geometric parameters, the corresponding isolobal anionic uranium(IV) complex [Cp*{sub 2}UCl{sub 3}]{sup -} was synthesized by the reaction of Cp*{sub 2}UCl{sub 2} with 1,3-di-tert-butyl-imidazolium chloride, and the resulting U(IV)-ate complex was characterized by X-ray diffraction analysis. (authors)

  8. Multivariate analysis of DSC-XRD simultaneous measurement data: a study of multistage crystalline structure changes in a linear poly(ethylene imine) thin film.

    Science.gov (United States)

    Kakuda, Hiroyuki; Okada, Tetsuo; Otsuka, Makoto; Katsumoto, Yukiteru; Hasegawa, Takeshi

    2009-01-01

    A multivariate analytical technique has been applied to the analysis of simultaneous measurement data from differential scanning calorimetry (DSC) and X-ray diffraction (XRD) in order to study thermal changes in crystalline structure of a linear poly(ethylene imine) (LPEI) film. A large number of XRD patterns generated from the simultaneous measurements were subjected to an augmented alternative least-squares (ALS) regression analysis, and the XRD patterns were readily decomposed into chemically independent XRD patterns and their thermal profiles were also obtained at the same time. The decomposed XRD patterns and the profiles were useful in discussing the minute peaks in the DSC. The analytical results revealed the following changes of polymorphisms in detail: An LPEI film prepared by casting an aqueous solution was composed of sesquihydrate and hemihydrate crystals. The sesquihydrate one was lost at an early stage of heating, and the film changed into an amorphous state. Once the sesquihydrate was lost by heating, it was not recovered even when it was cooled back to room temperature. When the sample was heated again, structural changes were found between the hemihydrate and the amorphous components. In this manner, the simultaneous DSC-XRD measurements combined with ALS analysis proved to be powerful for obtaining a better understanding of the thermally induced changes of the crystalline structure in a polymer film.

  9. Spectroscopic, potentiometric and theoretical studies on the binding properties of a novel tripodal polycatechol-imine ligand towards iron(III)

    Science.gov (United States)

    Kanungo, B. K.; Sahoo, Suban K.; Baral, Minati

    2008-12-01

    A novel multidentate tripodal ligand, cis, cis-1,3,5-tris[(2,3-dihydroxybenzylidene)aminomethyl]cyclohexane (TDBAC, L) containing one catechol unit in each arms of a tripodal amine, cis, cis-1,3,5-tris(aminomethyl)cyclohexane was investigated as a chelator for iron(III) through potentiometric and spectrophotometric methods in an aqueous medium of 0.1N ionic strength and 25 ± 1 °C as well as in ethanol by continuous variation method. From pH metric in water, three protonation constants characterized for the three-hydroxyl groups of the catechol units at ortho were used as input data to evaluate the stability constants of the complexes. Formation of monomeric complexes FeLH 3, FeLH 2, FeLH and FeL were depicted. In ethanol, formation of complexes FeL, Fe 2L and Fe 3L were characterized. Structures of the complexes were explained by using the experimental evidences and predicted through molecular modeling calculations. The ligand showed potential to coordinate iron(III) through three imine nitrogens and three catecholic oxygens at ortho to form a tris(iminocatecholate) type complex.

  10. Potential Threats Posed by New or Emerging Marine Biotoxins in UK Waters and Examination of Detection Methodologies Used for Their Control: Cyclic Imines

    Directory of Open Access Journals (Sweden)

    Keith Davidson

    2015-11-01

    Full Text Available Cyclic imines (CIs are a group of phytoplankton produced toxins related to shellfish food products, some of which are already present in UK and European waters. Their risk to shellfish consumers is poorly understood, as while no human intoxication has been definitively related to this group, their fast acting toxicity following intraperitoneal injection in mice has led to concern over their human health implications. A request was therefore made by UK food safety authorities to examine these toxins more closely to aid possible management strategies. Of the CI producers only the spirolide producer Alexandrium ostenfeldii is known to exist in UK waters at present but trends in climate change may lead to increased risk from other organisms/CI toxins currently present elsewhere in Europe and in similar environments worldwide. This paper reviews evidence concerning the prevalence of CIs and CI-producing phytoplankton, together with testing methodologies. Chemical, biological and biomolecular methods are reviewed, including recommendations for further work to enable effective testing. Although the focus here is on the UK, from a strategic standpoint many of the topics discussed will also be of interest in other parts of the world since new and emerging marine biotoxins are of global concern.

  11. Muhammed Esed’de Dini Değişimin Psikolojik Analizi The Psychological Analysis Of Religious Conversion In Muhammad Asad

    Directory of Open Access Journals (Sweden)

    Saffet KARTOPU

    2013-07-01

    Full Text Available At this work on Which religious conversion in Muhammad Asad isstudied, in terms of religious conversion models, first of all the conceptof religious conversion, the Works in this topic and the place of religiousconversion concept in Psychology of Religion are mentioned. Then, abrief life story of Asad is mentioned, by dealing with the religiousconversion in Asad in a theoretical approach, the motives of religiousconversion, the developmental factors in religious conversion, the stagesof religious conversion and the figures of religious conversion arestudied. The religious conversion in Asad is analyzed in terms ofconversion models accepted in Psychology of Religion taking his ownWorks as a base. In this sence, while the motives of religious conversionin Asad are considered by the approaches of Snow & Phillips, Glock andGillespie, the developmental factors in religious conversion areconsidered by Erikson’s thoughts. The stages of religious conversion isconsidered by gradual classification of Lofland & Stark, Clark, Batson &Ventis and Köse. Lofland and Skonovd’s types are used while analyzingthe figures of conversion.When considered the effects of psychological factors on thereligious conversion of Asad, we see that beginning from his earlyadolescence his willing to understanding and his need to mentalsatisfaction are explicit. Asad is in need of reviewing the main pointsimposed by his cultere. He is disturbed by the ambiguities in societyand his own life and he looks for answers to the universal meaning oflife and questions ‘what is right? what is wrong?’. As a result of hisseeking, he accepts Islam as his religion and he gains a feeling ofbelonging, admission and a change of rearranging himself radically. Byaccepting Islam he feels that all his seekings finish and his desire ofdepending on a certain intellectua orbit and being a part of fellowscommunity come true. Dini değişim modelleri açısından Muhammed Esed’de dini değişimin

  12. Polyethylene imine/graphene oxide layer-by-layer surface functionalization for significantly improved limit of detection and binding kinetics of immunoassays on acrylate surfaces.

    Science.gov (United States)

    Miyazaki, Celina M; Mishra, Rohit; Kinahan, David J; Ferreira, Marystela; Ducrée, Jens

    2017-10-01

    Antibody immobilization on polymeric substrates is a key manufacturing step for microfluidic devices that implement sample-to-answer automation of immunoassays. In this work, a simple and versatile method to bio-functionalize poly(methylmethacrylate) (PMMA), a common material of such "Lab-on-a-Chip" systems, is proposed; using the Layer-by-Layer (LbL) technique, we assemble nanostructured thin films of poly(ethylene imine) (PEI) and graphene oxide (GO). The wettability of PMMA surfaces was significantly augmented by the surface treatment with (PEI/GO) 5 film, with an 81% reduction of the contact angle, while the surface roughness increased by 600%, thus clearly enhancing wettability and antibody binding capacity. When applied to enzyme-linked immunosorbent assays (ELISAs), the limit of detection of PMMA surface was notably improved from 340pgmL -1 on commercial grade polystyrene (PS) and 230pgmL -1 on plain PMMA surfaces to 130pgmL -1 on (PEI/GO) 5 treated PMMA. Furthermore, the accelerated antibody adsorption kinetics on the LbL films of GO allowed to substantially shorten incubation times, e.g. for anti-rat IgG adsorption from 2h down to 15min on conventional and treated surfaces, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. The Ruthenostannylene Complex [Cp*(IXy)H2 Ru-Sn-Trip]: Providing Access to Unusual Ru-Sn Bonded Stanna-imine, Stannene, and Ketenylstannyl Complexes.

    Science.gov (United States)

    Liu, Hsueh-Ju; Ziegler, Micah S; Tilley, T Don

    2015-05-26

    Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Formulation of polylactide-co-glycolic acid nanospheres for encapsulation and sustained release of poly(ethylene imine-poly(ethylene glycol copolymers complexed to oligonucleotides

    Directory of Open Access Journals (Sweden)

    Wheatley Margaret A

    2009-04-01

    Full Text Available Abstract Antisense oligonucleotides (AOs have been shown to induce dystrophin expression in muscles cells of patients with Duchenne Muscular Dystrophy (DMD and in the mdx mouse, the murine model of DMD. However, ineffective delivery of AOs limits their therapeutic potential. Copolymers of cationic poly(ethylene imine (PEI and non-ionic poly(ethylene glycol (PEG form stable nanoparticles when complexed with AOs, but the positive surface charge on the resultant PEG-PEI-AO nanoparticles limits their biodistribution. We adapted a modified double emulsion procedure for encapsulating PEG-PEI-AO polyplexes into degradable polylactide-co-glycolic acid (PLGA nanospheres. Formulation parameters were varied including PLGA molecular weight, ester end-capping, and sonication energy/volume. Our results showed successful encapsulation of PEG-PEI-AO within PLGA nanospheres with average diameters ranging from 215 to 240 nm. Encapsulation efficiency ranged from 60 to 100%, and zeta potential measurements confirmed shielding of the PEG-PEI-AO cationic charge. Kinetic measurements of 17 kDa PLGA showed a rapid burst release of about 20% of the PEG-PEI-AO, followed by sustained release of up to 65% over three weeks. To evaluate functionality, PEG-PEI-AO polyplexes were loaded into PLGA nanospheres using an AO that is known to induce dystrophin expression in dystrophic mdx mice. Intramuscular injections of this compound into mdx mice resulted in over 300 dystrophin-positive muscle fibers distributed throughout the muscle cross-sections, approximately 3.4 times greater than for injections of AO alone. We conclude that PLGA nanospheres are effective compounds for the sustained release of PEG-PEI-AO polyplexes in skeletal muscle and concomitant expression of dystrophin, and may have translational potential in treating DMD.

  15. Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing.

    Science.gov (United States)

    Nadella, Sandeep; Selvakumar, Paulraj M; Suresh, Eringathodi; Subramanian, Palani S; Albrecht, Markus; Giese, Michael; Fröhlich, Roland

    2012-12-21

    Phenanthroline-based hexadentate ligands L(1) and L(2) bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La(III), Eu(III), Tb(III), Lu(III), and Y(III) metal ions, were synthesized, and the crystal structures of [ML(1)Cl(3)] (M=La(III), Eu(III), Tb(III), Lu(III), or Y(III)) complexes were determined. Solvent or water molecules act as coligands for the rare-earth metals in addition to halide anions. The big Ln(III) ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu(III), Tb(III), Lu(III), and Y(III) centers with smaller ionic radii show CN=9. Complexes of L(2), namely [ML(2)Cl(3)] (M=Eu(III), Tb(III), Lu(III), or Y(III)) ions could also be prepared. Only the complex of Eu(III) showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine-5'-triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine-5'-diphosphate (ADP) and adenosine-5'-monophosphate (AMP) was found. (31)P NMR spectroscopic studies revealed the formation of a [EuL(2)(ATP)] coordination species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A quantum chemical study of the reactivity of acetaminophen (paracetamol) toxic metabolite N-acetyl-p-benzoquinone imine with deoxyguanosine and glutathione.

    Science.gov (United States)

    Klopčič, Ivana; Poberžnik, Matic; Mavri, Janez; Dolenc, Marija Sollner

    2015-12-05

    Acetaminophen (APAP) forms some reactive metabolites that can react with DNA. APAP is a potentially genotoxic drug and is classified as a Group 3 drug according to International Agency for Research on Cancer (IARC). One of the possible mechanisms of APAP genotoxicity after long term of use is that its reactive quinone imine (QI) metabolite of acetaminophen (NAPQI), can chemically react with DNA after glutathione (GSH) depletion. A quantum chemical study of the reactions between the NAPQI and deoxyguanosine (dG) or GSH was performed. Activation energies (ΔG(ǂ)) for the reactions associated with the 1, 4-Michael addition were calculated on the M062X/6-311++G (d,p) level of theory. We modeled the reaction with dG as a multi-step process. The first step is rate-limiting (ΔG(ǂ) = 26.7 kcal/mol) and consists of formation of a C-N bond between the C3 atom of the QI moiety and the N7 atom of dG. The second step involves proton transfer from the C3 moiety to the nitrogen atom of the QI with ΔG(ǂ) of 13.8 kcal/mol. The depurination reaction that follows has a ΔG(ǂ) of 25.7 kcal/mol. The calculated ΔG(ǂ) for the nucleophilic attack of the deprotonated S atom of GSH on the C3 atom of the NAPQI is 12.9 kcal/mol. Therefore, the QI will react with GSH much faster than with DNA. Our study gives mechanistic insight into the genotoxicity of the APAP metabolite and will be useful for estimating the genotoxic potential of existing drugs with a QI moiety. Our results show that clinical application of APAP is safe, while in the case of severely depleted GSH levels APAP should be administered with caution. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  17. Electronic structure and electron dynamics at an organic molecule/metal interface: interface states of tetra-tert-butyl-imine/Au(111)

    International Nuclear Information System (INIS)

    Hagen, Sebastian; Wolf, Martin; Tegeder, Petra; Luo Ying; Haag, Rainer

    2010-01-01

    Time- and angle-resolved two-photon photoemission (2PPE) spectroscopies have been used to investigated the electronic structure, electron dynamics and localization at the interface between tetra-tert-butyl imine (TBI) and Au(111). At a TBI coverage of one monolayer (ML), the two highest occupied molecular orbitals, HOMO and HOMO-1, are observed at an energy of -1.9 and -2.6 eV below the Fermi level (E F ), respectively, and coincide with the d-band features of the Au substrate. In the unoccupied electronic structure, the lowest unoccupied molecular orbital (LUMO) has been observed at 1.6 eV with respect to E F . In addition, two delocalized states that arise from the modified image potential at the TBI/metal interface have been identified. Their binding energies depend strongly on the adsorption structure of the TBI adlayer, which is coverage dependent in the submonolayer (≤1 ML) regime. Thus the binding energy of the lower interface state (IS) shifts from 3.5 eV at 1.0 ML to 4.0 eV at 0.5 ML, which is accompanied by a pronounced decrease in its lifetime from 100 fs to below 10 fs. This is a result of differences in the wave function overlap with electronic states of the Au(111) substrate at different binding energies. This study shows that in order to fully understand the electronic structure of organic adsorbates at metal surfaces, not only adsorbate- and substrate-induced electronic states have to be considered but also ISs, which are the result of a potential formed by the interaction between the adsorbate and the substrate.

  18. Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

    Science.gov (United States)

    Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

    2017-10-09

    Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH 4 ) n [MMo 6 O 18 (OH) 6 ] (M=Cu 2+ ; Fe 3+ ; Co 3+ ; Ni 2+ ; Zn 2+ , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O 2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo VI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO 6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Metal-free, mild, nonepimerizing, chemo- and enantio- or diastereoselective N-alkylation of amines by alcohols via oxidation/imine-iminium formation/reductive amination: a pragmatic synthesis of octahydropyrazinopyridoindoles and higher ring analogues.

    Science.gov (United States)

    Khan, Imran A; Saxena, Anil K

    2013-12-06

    A mild step and atom-economical nonepimerizing chemo- and enantioselective N-alkylating procedure has been developed via oxidation/imine-iminium formation/reduction cascade using TEMPO-BAIB-HEH-Brønsted acid catalysis in DMPU as solvent and a stoichiometric amount of amine. The optimized conditions were further extended for the nonenzymatic kinetic resolution of the chiral amine thus formed under nonenzymatic in situ hydrogen-transfer conditions using VAPOL-derived phosphoric acid (VAPOL-PA) as the Brønsted acid catalyst. The enantioselective cascade of the presented reaction was successfully utilized in the synthesis of octahydropyrazinopyridoindole and its higher ring analogues.

  20. Intense Chiroptical Switching in a Dicationic Helicene-Like Derivative: Exploration of a Viologen-Type Redox Manifold of a Non-Racemic Helquat

    Czech Academy of Sciences Publication Activity Database

    Pospíšil, Lubomír; Bednárová, Lucie; Štěpánek, Petr; Slavíček, P.; Vávra, Jan; Hromadová, Magdaléna; Dlouhá, Helena; Tarábek, Ján; Teplý, Filip

    2014-01-01

    Roč. 136, č. 31 (2014), s. 10826-10829 ISSN 0002-7863 R&D Projects: GA ČR GA13-19213S Grant - others:GA ČR(CZ) GA13-34168S; GA MŠk(CZ) ED3.2.00/08.0144 Institutional support: RVO:61388963 ; RVO:61388955 Keywords : helicenoids * helquats * helical cations * ECD spectra * redox switching * chiroptical properties * helicene-viologen hybrids Subject RIV: CC - Organic Chemistry Impact factor: 12.113, year: 2014

  1. Sulfinylated Azadecalins act as functional mimics of a pollen germination stimulant in Arabidopsis pistils

    Science.gov (United States)

    Qin, Yuan; Wysocki, Ronald J; Somogyi, Arpad; Feinstein, Yelena; Franco, Jessica Y; Tsukamoto, Tatsuya; Dunatunga, Damayanthi; Levy, Clara; Smith, Steven; Simpson, Robert; Gang, David; Johnson, Mark A; Palanivelu, Ravishankar

    2011-01-01

    SUMMARY Polarized cell elongation is triggered by small molecule cues during development of diverse organisms. During plant reproduction, pollen interactions with the stigma result in the polar outgrowth of a pollen tube, which delivers sperm cells to the female gametophyte to effect double fertilization. In many plants, pistils stimulate pollen germination. However, in Arabidopsis, the effect of pistils on pollen germination and the pistil factors that stimulate pollen germination remain poorly characterized. Here, we demonstrate that stigma, style, and ovules in Arabidopsis pistils stimulate pollen germination. We isolated an Arabidopsis pistil extract fraction that stimulates Arabidopsis pollen germination, and employed ultrahigh resolution ESI FT-ICR and MS/MS techniques to accurately determine the mass (202.126 daltons) of a compound that is specifically present in this pistil extract fraction. Using the molecular formula (C10H19NOS) and tandem mass spectral fragmentation patterns of the m/z (mass to charge ratio) 202.126 ion, we postulated chemical structures, devised protocols, synthesized N-Methanesulfinyl 1- and 2-azadecalins that are close structural mimics of the m/z 202.126 ion, and showed that they are sufficient to stimulate Arabidopsis pollen germination in vitro (30 µM stimulated ~50% germination) and elicit accession-specific response. Although N-Methanesulfinyl 2-azadecalin stimulated pollen germination in three species of Lineage I of Brassicaceae, it did not induce a germination response in Sisymbrium irio (Lineage II of Brassicaceae) and tobacco, indicating that activity of the compound is not random. Our results show that Arabidopsis pistils promote germination by producing azadecalin-like molecules to ensure rapid fertilization by the appropriate pollen. PMID:21801250

  2. Novel and High Affinity 2-[(Diphenylmethyl)sulfinyl]acetamide (Modafinil) Analogues as Atypical Dopamine Transporter Inhibitors

    DEFF Research Database (Denmark)

    Cao, Jianjing; Slack, Rachel D.; Bakare, Oluyomi M.

    2016-01-01

    The development of pharmacotherapeutic treatments of psychostimulant abuse has remained a challenge, despite significant efforts made toward relevant mechanistic targets, such as the dopamine transporter (DAT). The atypical DAT inhibitors have received attention due to their promising pharmacolog...

  3. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphyhaline

    Science.gov (United States)

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-01

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, 1H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

  4. Graphite-supported gold nanoparticles as efficient catalyst for aerobic oxidation of benzylic amines to imines and N-substituted 1,2,3,4-tetrahydroisoquinolines to amides: synthetic applications and mechanistic study.

    Science.gov (United States)

    So, Man-Ho; Liu, Yungen; Ho, Chi-Ming; Che, Chi-Ming

    2009-10-05

    Selective oxidation of amines using oxygen as terminal oxidant is an important area in green chemistry. In this work, we describe the use of graphite-supported gold nanoparticles (AuNPs/C) to catalyze aerobic oxidation of cyclic and acyclic benzylic amines to the corresponding imines with moderate-to-excellent substrate conversions (43-100%) and product yields (66-99%) (19 examples). Oxidation of N-substituted 1,2,3,4-tetrahydroisoquinolines in the presence of aqueous NaHCO3 solution gave the corresponding amides in good yields (83-93%) with high selectivity (up to amide/enamide=93:4) (6 examples). The same protocol can be applied to the synthesis of benzimidazoles from the reaction of o-phenylenediamines with benzaldehydes under aerobic conditions (8 examples). By simple centrifugation, AuNPs/C can be recovered and reused for ten consecutive runs for the oxidation of dibenzylamine to N-benzylidene(phenyl)methanamine without significant loss of catalytic activity and selectivity. This protocol "AuNPs/C+O2" can be scaled to the gram scale, and 8.9 g (84 % isolated yield) of 3,4-dihydroisoquinoline can be obtained from the oxidation of 10 g 1,2,3,4-tetrahydroisoquinoline in a one-pot reaction. Based on the results of kinetic studies, radical traps experiment, and Hammett plot, a mechanism involving the hydrogen-transfer reaction from amine to metal and oxidation of M-H is proposed.

  5. 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.

  6. Polyethylene imine-grafted ACF@BiOI{sub 0.5}Cl{sub 0.5} as a recyclable photocatalyst for high-efficient dye removal by adsorption-combined degradation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongyan [Collaborative Innovation Center of Suzhou Nano Science and Technology, College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou, Jiangsu 215123 (China); Li, Najun, E-mail: linajun@suda.edu.cn [Collaborative Innovation Center of Suzhou Nano Science and Technology, College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou, Jiangsu 215123 (China); State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Suzhou, Jiangsu 215123 (China); Chen, Dongyun; Xu, Qingfeng [Collaborative Innovation Center of Suzhou Nano Science and Technology, College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou, Jiangsu 215123 (China); State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Suzhou, Jiangsu 215123 (China); Lu, Jianmei, E-mail: lujm@suda.edu.cn [Collaborative Innovation Center of Suzhou Nano Science and Technology, College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou, Jiangsu 215123 (China); State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Suzhou, Jiangsu 215123 (China)

    2017-05-01

    Highlights: • A recyclable photocatalyst was facilely fabricated by immobilization and grafting. • Contribution from each component in the composite towards enhanced performance. • High removal efficiency was achieved under adsorption-combined degradation. • The composite photocatalyst can be easily separated from water for direct reuse. - Abstract: A recyclable photocatalyst with adsorption property was prepared for high-efficient complete removal of anionic dyes from water by synergetic adsorption and photocatalytic degradation. Firstly, binary bismuth oxyhalide composed as BiOI{sub 0.5}Cl{sub 0.5} was immobilized on activated carbon fibers (ACF) to get a recyclable photocatalyst (ACF@BiOI{sub 0.5}Cl{sub 0.5}) via one-step solvothermal method. Then it was modified with branched polyethylene imine (PEI) whose abundant amino groups can adsorb contaminants from water by electrostatic interaction. SEM images showed that the nanosheets-based flower-like photocatalytic microspheres uniformly distributed on the ACF surface after grafting of small amount of PEI. But from TGA results we can deduce that the percentage of PEI grafted onto ACF@BiOI{sub 0.5}Cl{sub 0.5} is about 18 wt%. During the synergistic process, the grafted PEI and immobilized BiOI{sub 0.5}Cl{sub 0.5} are worked as the adsorbent and the photocatalyst, respectively. In addition, ACF, as flexible, conductive and corrosion-resistant supports, are beneficial to the photocatalytic degradation process. So the obtained composite PEI-g-ACF@BiOI{sub 0.5}Cl{sub 0.5} has a high removal efficiency of contaminants under visible light irradiation with the synergistic effect of adsorption and photocatalytic degradation. And after facial separation without centrifuge, it can be reused without regeneration because of the real-time complete degradation of the adsorbed contaminants on the surface of the composite photocatalyst.

  7. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline.

    Science.gov (United States)

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-25

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, (1)H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ). Copyright © 2014 Elsevier B.V. All rights reserved.

  8. In-source formation of N-acetyl-p-benzoquinone imine (NAPQI), the putatively toxic acetaminophen (paracetamol) metabolite, after derivatization with pentafluorobenzyl bromide and GC-ECNICI-MS analysis.

    Science.gov (United States)

    Tsikas, Dimitrios; Trettin, Arne; Zörner, Alexander A; Gutzki, Frank-Mathias

    2011-05-15

    Pentafluorobenzyl (PFB) bromide (PFB-Br) is a versatile derivatization reagent for numerous classes of compounds. Under electron-capture negative-ion chemical ionization (ECNICI) conditions PFB derivatives of acidic compounds readily and abundantly ionize to produce intense anions due to [M-PFB](-). In the present article we investigated the PFB-Br derivatization of unlabelled acetaminophen (N-acetyl-p-aminophenol, NAPAP-d(0); paracetamol; MW 151) and tetradeuterated acetaminophen (NAPAP-d(4); MW 155) in anhydrous acetonitrile and their GC-ECNICI-MS behavior using methane as the buffer gas. In addition to the expected anions [M-PFB](-) at m/z 150 from NAPAP-d(0) and m/z 154 from NAPAP-d(4), we observed highly reproducibly almost equally intense anions at m/z 149 and m/z 153, respectively. Selected ion monitoring of these ions is suitable for specific and sensitive quantification of acetaminophen in human plasma and urine. Detailed investigations suggest in-source formation of N-acetyl-p-benzoquinone imine (NAPQI; MW 149), the putatively toxic acetaminophen metabolite, from the PFB ether derivative of NAPAP. GC-ECNICI-MS of non-derivatized NAPAP did not produce NAPQI. The peak area ratio of m/z 149 to m/z 150 and of m/z 153 to m/z 154 decreased with increasing ion-source temperature in the range 100-250°C. Most likely, NAPQI formed in the ion-source captures secondary electrons to become negatively charged (i.e., [NAPQI](-)) and thus detectable. Formation of NAPQI was not observed under electron ionization (EI) conditions, i.e., by GC-EI-MS, from derivatized and non-derivatized NAPAP. NAPQI was not detectable in flow injection analysis LC-MS of native NAPAP in positive electrospray ionization (ESI) mode, whereas in negative ESI mode low extent NAPQI formation was observed (<5%). Our results suggest that oxidation of drug derivatives in the ion-sources of mass spectrometers may form intermediates that are produced from activated drugs in enzyme-catalyzed reactions

  9. Synthesis, crystal structure, and H/D exchange of the inside protonated form of the cage imine 4,8,12-triaza-1-azoniatricyclo[6.6.3.2(4,12)]nonadec-1(15)-ene. A model for proton transfer through an aliphatic membrane

    DEFF Research Database (Denmark)

    Springborg, Johan; Nielsen, Bente; Olsen, Carl Erik

    2002-01-01

    belonging to the triazacyclononane entity. The imine double bond is situated between the N-atom of the triazacyclononane entity and the C-atom belonging to one of the three trimethylene bridges. The imine 2 is stable in acidic solution and the inside coordinated proton is very robust in acidic solution......, which gave K-im = 1.57(1) x 10(-5) M at 25 degreesC, DeltaSdegrees = -83(1) J mol(-1) K-1 and DeltaHdegrees = 2,6(3) kJ mol(-1) at 1 = 1.0 M (NaCl). The inside coordinated proton in 3 is labile in basic solution and the rate for NH/ND exchange was determined by H-1 NMR at three different temperatures....... The reaction followed the expression k(obs) = k(ex)[OD-] with k(ex) = 0.0978(30) dm(3) mol (1) s(-1) at 25 degreesC, DeltaSdegrees = 87(4) J mol(-1) K-1, and DeltaHdegrees = 104.9(11) kJ mol(-1) at I = 1.0 M (NaCl). The exchange rate is more than 5 x 106 times faster than that of the parent saturated cage 1...

  10. Palladium-Catalyzed ortho C-H Arylation of Benzaldehydes Using ortho-Sulfinyl Aniline Transient Auxiliary.

    Science.gov (United States)

    Mu, Delong; He, Gang; Chen, Gong

    2018-05-03

    A PdII-catalyzed ortho-(Csp2)-H arylation reaction of benzaldehydes using catalytic amount of 2-methylsulfinyl-aniline as transient auxiliary was developed. This reaction is compatible with a broad range of benzaldehyde and aryl iodide substrates. Compared with other related reaction systems, an excellent regioselectivity for ortho-C(sp2)-H bonds over benzylic C(sp3)-H bonds was obtained for ortho-alkyl-benzaldehyde substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Novel O N N Pyrazolyl-imine and Imidazolyl-imine Pincer Palladium ...

    African Journals Online (AJOL)

    NICO

    pincer palladium complexes in Heck coupling reactions. The general form of .... while single crystals suitable for X-ray analyses of complexes 1–4 were grown by ...... non-hydrogen atoms were refined with anisotropic displacement coefficients.

  12. Electrochemical Studies of Benzophenone and Fluorenone Imines, Amines and Diphenyldiazomethane.

    Science.gov (United States)

    1982-01-01

    exhaustive, controlled-potential electrolyses has also been described. 2 Cells. electrodes. and electrolysis procedures. All electrochemical experiments...scale electrolyses was monitored periodically by cyclic voltammetry. At the conclusion of the experiment, the electrolysis mixture was protonated in a...stainless steel * column packed with LiChrosorb RP8 or LiChrosorb RP18, 10-pm mean particle size. The eluting solvent was a mixture of methanol and water

  13. Dynamic Combinatorial Chemistry with Diselenides, Disulfides, Imines and Metal Coordination

    DEFF Research Database (Denmark)

    Sørensen, Anne

    combinatorial chemistry, namely the reversible diselenide exchange reaction. The first part of the thesis describes the development of a thermally induced OAr → SeAr migration reaction. Here, it was proven possible to rearrange a variety of substituted O-aryl selenocarbamates into the corresponding Se...

  14. Transition Metal Catalyzed Synthesis of Carboxylic Acids, Imines, and Biaryls

    DEFF Research Database (Denmark)

    Santilli, Carola; Madsen, Robert

    the carboxylate.  Manganese catalyzed radical Kumada-type reaction between aryl halidesand aryl Grignard reagents. The reaction between aryl halides and aryl Grignard reagents catalyzed by MnCl2 has been extended to several methyl-substituted aryl iodide reagents byperforming the reaction at 120 ˚C in a microwave...... oven (Scheme ii). A limitation of the heterocoupling process is the concomitant dehalogenation of the aryl halide and homocoupling of the Grignard reagent leading low to moderate yields of the desired heterocoupling product. The mechanism of the cross-coupling process was investigated by performing two...

  15. Deuterium secondary isotope kinetic effects in imine formation reactions

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1986-01-01

    The kinetic α-deuterium isotope effects, K D /K H , for reaction mechanisms is studied. The reaction of pH function to m-bromobenzaldehyde, semicarbazide nucleophile, methoxy-amine and hydroxylamine are analysed. (M.J.C.) [pt

  16. Current Topics in the Asymmetric Transfer Hydrogenation of Imines

    Czech Academy of Sciences Publication Activity Database

    Januščák, J.; Václavík, Jiří; Šot, P.; Pecháček, J.; Vilhanová, B.; Kuzma, Marek; Kačer, P.

    2015-01-01

    Roč. 109, č. 7 (2015), s. 492-498 ISSN 0009-2770 R&D Projects: GA ČR GAP106/12/1276; GA MŠk(CZ) LO1509 Institutional support: RVO:61388971 Keywords : asymmetric transfer hydrogenation * ruthenium * isoquinoline Subject RIV: EE - Microbiology, Virology Impact factor: 0.279, year: 2015

  17. Cyclic imines evaluation in European commercial shellfish samples

    DEFF Research Database (Denmark)

    Rambla, Maria; Fernandez-Tejedor, Margarita; Miles, Christopher O.

    is much lower (10-100 times less toxic orally, depending on the toxin and how the toxins are administered). In contrast to spirolides, PnTXs have proven to be almost as toxic via oral dosing as they are by i.p. injection to mice. Levels of toxicity of spirolide C and pinnatoxin E+F in feed were 500 and 60...

  18. Üniversite Hastaneleri Çalışanlarının Kalite Anlayışı ve Kalite Çalışmalarında İletişimin Önemi: Bir Uygulama Örneği=Conception of Quality of University Hospitals Employees and the Importance of Quality Work Communication: A Practical Example

    Directory of Open Access Journals (Sweden)

    Huriye Çolaklar

    2013-10-01

    Full Text Available Bu çalışmada, bir kamu kurumunda kalite çalışmalarının anlaşılması ve etkin olabilmesi için kurum çalışanlarının, ortaya çıkabilecek sorunların iletişimle çözülebileceği bilincine sahip olmaları gerektiği vurgulanmıştır. Araştırmada veri toplama yöntemi olarak anket yöntemi kullanılmış ve kurumun yöneticileri ile akademik personeline uygulanmıştır. Toplam 205 kişiye anket gönderilmiş olup, 173 geri bildirim alınmıştır. Anketlerden 4 tanesi eksik ve hatalı doldurulduğu için değerlendirmeye alınmamıştır. Anketleri yanıtlayan 173 kişiden 29’u yöneticidir. Elde edilen verilere göre; yöneticiler “iletişim ve karar mekanizmasını” %23 ile en az önemli; akademik personel ise “örgüt ikliminin motivasyon artırıcı bir nitelikte olmasını” %33 oranla önemli görmektedir. Kurumun kalite yönetimini uygularken karşılaşılan güçlükler arasında yöneticilere göre %39’nun “üst yönetimin yönetim anlayışı” ve %38’nin “kurum içi iletişim eksikleri” en az önemlide, akademik personelde ise %23’nün “iletişim eksikleri” az önemlide yer almıştır. Bu çalışma sonucunda, kalite yönetim sistemi uygulanırken çalışanların, kaliteli hizmet anlayışını ve müşteri memnuniyetini en çok önemli ve iletişimin katkısını da en az önemli seviyesinde değerlendirdikleri saptanmıştır. Ancak kurum içi iletişim eksiklikleri ve birimler arası sürtüşmelerin olması, kalite yönetim sisteminin, etkin olmasını ve kalite bilincinin gelişmesini olumsuz etkilemektedir./In this study, we emphasize that the public institution employees are also that should be aware that problems can be solved by means of communication for the purpose of appreciating the quality of work and making it effective. The survey was used as a method of data collection and that survey was conducted on office managers and academic staff. The survey sheets were sent out to

  19. Preparation and Use of Aziridino Alcohols as Promoters for the Enantioselective Addition of Dialkylzinc Reagents to N-(Diphenylphosphinoyl) IminesImines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Guijarro, David; Andersson, Pher G.

    1997-01-01

    A set of chiral aziridino alcohols has been synthesised, either from amino acids (serine, threonine or allo-threonine) or via Sharpless asymmetric aminohydroxylation/dihydroxylation of simple prochiral olefins. The ligands mediate the addition of diethylzinc to N-phosphinoylimines, with up to 94...

  20. Electroreduction of aromatic oximes: Diprotonation, adsorption, imine formation, and substituent effects

    Czech Academy of Sciences Publication Activity Database

    Celik, H.; Ekmekci, F. G.; Ludvík, Jiří; Pícha, J.; Zuman, P.

    2006-01-01

    Roč. 110, č. 13 (2006), s. 6785-6796 ISSN 1520-6106 R&D Projects: GA AV ČR IAA4040304; GA MŠk 1P05ME785 Institutional research plan: CEZ:AV0Z40400503 Keywords : polarographic reduction * electrochemistry * electroorganic preparations Subject RIV: CG - Electrochemistry Impact factor: 4.115, year: 2006

  1. Two reduction waves of oximes and imine formation in acidic media

    Czech Academy of Sciences Publication Activity Database

    Celik, H.; Ludvík, Jiří; Zuman, P.

    2006-01-01

    Roč. 51, č. 26 (2006), s. 5845-5852 ISSN 0013-4686 R&D Projects: GA MŠk 1P05ME785 Institutional research plan: CEZ:AV0Z40400503 Keywords : oximes * electroreduction * polarography Subject RIV: CG - Electrochemistry Impact factor: 2.955, year: 2006

  2. Silver nanoparticles supported on alumina-​a highly efficient and selective nanocatalyst for imine reduction

    DEFF Research Database (Denmark)

    Poreddy, Raju; Garcia-Suarez, Eduardo J.; Riisager, Anders

    2014-01-01

    in the synthesis of secondary amines from primary amines in a tandem reaction protocol (oxidation–imination–reduction) using air and molecular hydrogen as oxidizing and reducing agents, respectively. The reported synthesis is performed under mild reaction conditions, which complies with the demands of modern...... organic synthesis. Due to the mild reaction conditions and high conversion as well as high selectivity, we consider that the utilization of silver nanoparticles supported on alumina represents an attractive and environmentally friendly alternative to the current synthesis of N-alkyl amines....

  3. Imine-linked receptors decorated ZnO-based dye-sensitized solar cells

    Indian Academy of Sciences (India)

    Continuously, the increasing demand of energy and limited ... boosts the attention of researchers during last decade. The ... The polymer-capped ZnO DSSCs are flexible .... bly enhances the light harvesting capacity and minimizes the.

  4. Catalytic α-arylation of imines leading to N-unprotected indoles and azaindoles

    KAUST Repository

    Marelli, Enrico

    2016-03-30

    A Palladium-N-heterocyclic carbene-catalyzed methodology for the synthesis of substituted, N-unprotected indoles and azaindoles is reported. The protocol permits access to various, highly substituted members of these classes of compounds. Although two possible reactions pathways (deprotonative and Heck-like) can be proposed, control experiments, supported by computational studies, point towards a deprotonative mechanism being operative.

  5. Density functional theory study on the formation of reactive benzoquinone imines by hydrogen abstraction

    DEFF Research Database (Denmark)

    Leth, Rasmus; Rydberg, Patrik; Jørgensen, Flemming Steen

    2015-01-01

    Many drug compounds are oxidized by cytochrome P450 (CYP) enzymes to form reactive metabolites. This study presents density functional theory calculations of the CYP-mediated metabolism of acetaminophen and a series of related compounds that can form reactive metabolites by hydrogen abstraction....... The substitution pattern affects the activation barrier for hydrogen abstraction by up to 30 kJ/mol. A correlation (R(2) = 0.72) between the transition-state energies and the corresponding substrate radical energies has been established. Using this correlation is significantly less time-demanding than using...... the porphyrin model to determine the activation energies. We have used this correlation on monosubstituted phenols to rationalize the effect of the various substituents in the drug compounds. In addition to facilitating a chemical interpretation, the approach is sufficiently fast and reliable to be used...

  6. Complexity in Acid?Base Titrations: Multimer Formation Between Phosphoric Acids and Imines

    OpenAIRE

    Malm, Christian; Kim, Heejae; Wagner, Manfred; Hunger, Johannes

    2017-01-01

    Abstract Solutions of Br?nsted acids with bases in aprotic solvents are not only common model systems to study the fundamentals of proton transfer pathways but are also highly relevant to Br?nsted acid catalysis. Despite their importance the light nature of the proton makes characterization of acid?base aggregates challenging. Here, we track such acid?base interactions over a broad range of relative compositions between diphenyl phosphoric acid and the base quinaldine in dichloromethane, by u...

  7. Complexity in Acid–Base Titrations: Multimer Formation Between Phosphoric Acids and Imines

    Science.gov (United States)

    Malm, Christian; Kim, Heejae; Wagner, Manfred

    2017-01-01

    Abstract Solutions of Brønsted acids with bases in aprotic solvents are not only common model systems to study the fundamentals of proton transfer pathways but are also highly relevant to Brønsted acid catalysis. Despite their importance the light nature of the proton makes characterization of acid–base aggregates challenging. Here, we track such acid–base interactions over a broad range of relative compositions between diphenyl phosphoric acid and the base quinaldine in dichloromethane, by using a combination of dielectric relaxation and NMR spectroscopy. In contrast to what one would expect for an acid–base titration, we find strong deviations from quantitative proton transfer from the acid to the base. Even for an excess of the base, multimers consisting of one base and at least two acid molecules are formed, in addition to the occurrence of proton transfer from the acid to the base and simultaneous formation of ion pairs. For equimolar mixtures such multimers constitute about one third of all intermolecular aggregates. Quantitative analysis of our results shows that the acid‐base association constant is only around six times larger than that for the acid binding to an acid‐base dimer, that is, to an already protonated base. Our findings have implications for the interpretation of previous studies of reactive intermediates in organocatalysis and provide a rationale for previously observed nonlinear effects in phosphoric acid catalysis. PMID:28597513

  8. Complexity in Acid-Base Titrations: Multimer Formation Between Phosphoric Acids and Imines.

    Science.gov (United States)

    Malm, Christian; Kim, Heejae; Wagner, Manfred; Hunger, Johannes

    2017-08-10

    Solutions of Brønsted acids with bases in aprotic solvents are not only common model systems to study the fundamentals of proton transfer pathways but are also highly relevant to Brønsted acid catalysis. Despite their importance the light nature of the proton makes characterization of acid-base aggregates challenging. Here, we track such acid-base interactions over a broad range of relative compositions between diphenyl phosphoric acid and the base quinaldine in dichloromethane, by using a combination of dielectric relaxation and NMR spectroscopy. In contrast to what one would expect for an acid-base titration, we find strong deviations from quantitative proton transfer from the acid to the base. Even for an excess of the base, multimers consisting of one base and at least two acid molecules are formed, in addition to the occurrence of proton transfer from the acid to the base and simultaneous formation of ion pairs. For equimolar mixtures such multimers constitute about one third of all intermolecular aggregates. Quantitative analysis of our results shows that the acid-base association constant is only around six times larger than that for the acid binding to an acid-base dimer, that is, to an already protonated base. Our findings have implications for the interpretation of previous studies of reactive intermediates in organocatalysis and provide a rationale for previously observed nonlinear effects in phosphoric acid catalysis. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  9. HIGHLY ENANTIOSELECTIVE CATALYTIC DIRECT ADDITION OF ALKYNES TO IMINES IN WATER. (R828129)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  10. Novel imines with tunable nucleophilicity and steric properties through metal coordination: applications as ligands and metalloorganocatalysts

    KAUST Repository

    Huang, Kuo-Wei

    2016-03-17

    The invention describes phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes for conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates or preparation of an amide from the combination of an alcohol and an amine.

  11. Imine-linked receptors decorated ZnO-based dye-sensitized solar cells

    Indian Academy of Sciences (India)

    ... Jalandhar 140507, India; Department of Electronics and Communication Engineering, GNDU, Regional Campus, Gurdaspur 143521, India; Department of Electronics and Communication Engineering, Khalsa College of Engineering and Technology, Amritsar 143001, India; Center for Nanoscience and Nanotechnology, ...

  12. Catalytic α-arylation of imines leading to N-unprotected indoles and azaindoles

    KAUST Repository

    Marelli, Enrico; Corpet, Martin; Minenkov, Yury; Neyyappadath, Rifahath; Bismuto, Alessandro; Buccolini, Giulia; Curcio, Massimiliano; Cavallo, Luigi; Nolan, Steven P.

    2016-01-01

    A Palladium-N-heterocyclic carbene-catalyzed methodology for the synthesis of substituted, N-unprotected indoles and azaindoles is reported. The protocol permits access to various, highly substituted members of these classes of compounds. Although two possible reactions pathways (deprotonative and Heck-like) can be proposed, control experiments, supported by computational studies, point towards a deprotonative mechanism being operative.

  13. Novel imines with tunable nucleophilicity and steric properties through metal coordination: applications as ligands and metalloorganocatalysts

    KAUST Repository

    Huang, Kuo-Wei; Zhao, Qianyi

    2016-01-01

    The invention describes phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes for conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates or preparation of an amide from the combination of an alcohol and an amine.

  14. Synthesis and protonation behavior of carboxylate-functionalized poly(propylene imine) dendrimers

    NARCIS (Netherlands)

    Duijvenbode, van R.C.; Rajanayagam, A.; Koper, G.J.M.; Baars, M.W.P.L.; Waal, de B.F.M.; Meijer, E.W.; Borkovec, M.

    2000-01-01

    Five generations of carboxylate-functionalized poly(propyleneimine) dendrimers have been synthesized starting from a double Michael addition of amine-functionalized poly(propyleneimine) dendrimers to methyl acrylate followed by basic hydrolysis using LiOH in a water/methanol mixture. The dendritic

  15. Spectroscopic characterization, antimicrobial activity and molecular docking study of novel azo-imine functionalized sulphamethoxazoles

    Science.gov (United States)

    Sahu, Nilima; Mondal, Sudipa; Naskar, Kaushik; Mahapatra, Ananya Das; Gupta, Suvroma; Slawin, Alexandra M. Z.; Chattopadhyay, Debprasad; Sinha, Chittaranjan

    2018-03-01

    [SMXsbnd Ndbnd Nsbnd C6H3sbnd (p-OH)(msbnd CHO)] (1) reacts with ArNH2 to synthesize Schiff bases, [SMXsbnd Ndbnd Nsbnd C6H3sbnd (psbnd OH)(msbnd HCdbnd Nsbnd Ar)] (Ar = sbnd C6H5 (2a), sbnd C6H4sbnd psbnd CH3 (2b), sbnd C6H4sbnd psbnd OCH3 (2c), sbnd C6H4sbnd psbnd Cl (2d), sbnd C6H4sbnd psbnd NO2 (2e), sbnd C10H7 (2f)) and the products have been assessed for antibacterial properties against Gram positive bacteria, B. subtillis: IC50 (μg/ml): 39.2 (1), 60.1 (2a), 64.0 (2b), 85.6 (2c), 55.1 (2d), 88.4 (2e) and 65.1 (2f); and Gram negative bacteria, E. coli: IC50 (μg/ml): 159.0 (1), 151.4 (2a), 155.3 (2b), 140 (2c), 156.0 (2d), 153.5 (2e) and 157 (2f). The cell line toxicity (Vero cells) has also been evaluated with these compounds and EC50 (μg/ml) values are 129.9 (1), 74.2 (2a) and 93.0 (2b), 191.9 (2c), 99.1 (2d), 93.2 (2e) and 62.0 (2f). The anti-viral efficiency against harpies virus (HSVsbnd 1F ATCC-733) infection demonstrates that the compound 1 has highest selectivity index (CC50/EC50), 5.06 than the compounds 2a-f (CC50/EC50: 1.18 (2a), 1.42 (2b), 3.50 (2c), 1.45 (2d), 1.58 (2e), 1.29 (2f)). The compounds have been spectroscopically characterized and the structural confirmation has been established in one case by single crystal X-ray diffraction studies of 2c. In silico Molecular Docking study has been done using optimized geometries of the compounds to search the most favored binding mode of these drugs and hence useful to explain their competitive drug efficiency.

  16. Keto - enol, imine - enamine, and nitro - aci-nitro tautomerism and their interrelationship in substituted nitroethylenes. Keto, imine, nitro, and vinyl substituent effects, and the importance of H-bonding

    NARCIS (Netherlands)

    Lammertsma, K.; Bharatam, P.V.

    2000-01-01

    Tautomeric isomers and conformers of 2-nitrovinyl alcohol (1), 2-nitrovinylamine (2), and 1-nitropropene (3) are reported at the MP2 and B3LYP levels of theory, using the 6-31G* basis set, with energy evaluation at B3LYP/6-311+G** and G2MP2. The nitroalkenes are the global minima on their respective

  17. Imine derivatives of lathonones. Part I -- Reactions of neodymium (III) isopropoxide with monofunctional bidendtate and bifunctional tridentate aldimines and ketamines

    International Nuclear Information System (INIS)

    Mital, S.P.; Singh, R.V.; Tandon, J.P.

    1980-01-01

    Nd(OPrsup(i))sub(2) (SB) and Nd(Oprsup(i))(SB)sub(2) [where SBH represents the molecule of monofunctional bidentate aldimine] type of derivatives have been synthesised by 1:1 and 1:2 molar reactions of neodymium isopropoxide with the aldimines having the donor system NOH and formed by the condensation of salicylaldehyde with alkylamines. However, bifunctional tridentate Schiff bases (LH) 2 have been found to yield Nd(OPrsup(i)) (L) and Nd 2 (L) 3 type of complexes in 1:1 and 2:3 molar ratio respectively. The isopropoxy groups of the 1:1 complexes have been found to undergo replacement reactions with excess of t-butanol and the resulting complexes are hydrolytically stable. All the newly synthesized complexes have been characterized on the basis of elemental analyses, molecular weight determinations, conductance measurements and infrared and proton magnetic resonance spectral studies. (auth.)

  18. Formation of imines by selective gold-catalysed aerobic oxidative coupling of alcohols and amines under ambient conditions

    DEFF Research Database (Denmark)

    Kegnæs, Søren; Mielby, Jerrik Jørgen; Mentzel, Uffe Vie

    2010-01-01

    with excellent selectivity (above 98%) at moderate conversion under optimized conditions. The effect of catalytic amounts of different bases was studied, along with reaction temperature and time. Utilisation of a selective catalyst system that uses dioxygen as an oxidant and only produces water as by...

  19. Information Mining Technologies to Enable Discovery of Actionable Intelligence to Facilitate Maritime Situational Awareness: I-MINE

    Science.gov (United States)

    2013-01-01

    website). Data mining tools are in-house code developed in Python, C++ and Java . • NGA The National Geospatial-Intelligence Agency (NGA) performs data...as PostgreSQL (with PostGIS), MySQL , Microsoft SQL Server, SQLite, etc. using the appropriate JDBC driver. 14 The documentation and ease to learn are...written in Java that is able to perform various types of regressions, classi- fications, and other data mining tasks. There is also a commercial version

  20. Cobalt-mediated [3 + 2]-annulation reaction of alkenes with alpha,beta-unsaturated ketones and imines.

    Science.gov (United States)

    Schomaker, Jennifer M; Toste, F Dean; Bergman, Robert G

    2009-08-20

    The utility of cobalt dinitrosyl complexes for the [3 + 2] annulation of alkenes with unsaturated enones and ketimines has been demonstrated. Reaction of a series of cobalt dinitrosyl/alkene adducts with conjugate acceptors in the presence of Sc(OTf)(3)/LHMDS formed two new C-C bonds at the carbons alpha to the nitrosyl groups of the substrate, leading to unusual tri- and tetracycles. Retrocycloaddition of these products in the presence of norbornadiene yielded functionalized tetrasubstituted bicyclic olefins.

  1. Cobalt-Mediated [3+2]-Annulation Reaction of Alkenes with α,β-Unsaturated Ketones and Imines

    Science.gov (United States)

    Schomaker, Jennifer M.; Toste, F. Dean; Bergman, Robert G.

    2009-01-01

    The utility of cobalt dinitrosyl complexes for the [3+2] annulation of alkenes with unsaturated enones and ketimines has been demonstrated. Reaction of a series of cobalt dinitrosyl/alkene adducts with conjugate acceptors in the presence of Sc(OTf)3/LHMDS formed two new C-C bonds at the carbons α to the nitrosyl groups of the substrate, leading to unusual tri- and tetracycles. Retrocycloaddition of these products in the presence of norbornadiene yielded functionalized tetrasubstituted bicyclic olefins. PMID:19639989

  2. A First Look on iMiner's Knowledge base and Detecting Hidden Hierarchy of Riyadh Bombing Terrorist Network

    DEFF Research Database (Denmark)

    Memon, Nasrullah

    2007-01-01

      - Data collection is difficult to any network analysis because it is difficult to create a complete network.  It is not easy to gain information on terrorist networks.  It is fact that terrorist organizations do not provide information on their members and the government rarely allows researche...

  3. On the Mechanism of the Copper-Mediated C-S Bond Formation in the Intramolecular Disproportionation of Imine Disulfides

    Czech Academy of Sciences Publication Activity Database

    Rokob, Tibor András; Rulíšek, Lubomír; Šrogl, Jiří; Révész, Agnes; Zins, Emilie-Laure; Schröder, Detlef

    2011-01-01

    Roč. 50, č. 20 (2011), s. 9968-9979 ISSN 0020-1669 R&D Projects: GA MŠk LC512 Grant - others:European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : collision-induced dissociation * DFT calculations * C-S bond formation * Cu(I) catalysis * infrared multiphoton spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.601, year: 2011

  4. Detecting the adsorption of dye molecules in homogenous poly(propylene imine) dendrimer monolayers by surface plasmon resonance sensor

    Czech Academy of Sciences Publication Activity Database

    Chen, S.; Yu, Q.; Li, L.; Boozer, C. L.; Homola, Jiří; Yee, S. S.; Jiang, S.

    2002-01-01

    Roč. 124, č. 13 (2002), s. 3395-3401 ISSN 0002-7863 Grant - others:National Science Foundation(US) CTS-0092699; National Science Foundation(US) CTS-9983895 Keywords : biosensors * surface plasmon resonance * optical sensors Subject RIV: JB - Sensors, Measurment, Regulation Impact factor: 6.201, year: 2002

  5. Towards HIV detection: Novel Poly(propylene imine) Dendrimer-Streptavidin platform for electrochemical DNA and gp120 aptamer biosensors

    CSIR Research Space (South Africa)

    John, SV

    2014-07-01

    Full Text Available to thank Mr Anton of the Laser Research Laboratory, University of Johannesburg for laboratory assistance. References 1. S. Tombelli, M. Minunni, E. Luzi and M. Mascini, Bioelectrochemistry, 67 (2005) 135 2. O. C. Farokhzad, J. Cheng, B. A. Teply..., I. Sherifi, S. Jon, P. W. Kantoff, J. P. Richie and R. Langer, Proc Natl Acad Sci U S A, 103 (2006) 6315 3. E. W. Orava, A. Abdul-Wahidb, E. H.-B. Huang, A. I. Mallick and J. Gariépya, Molecular Oncology, 7 (2013) 799 4. S. Tombelli, M. Minunni...

  6. Diastereoselective Addition of α-Metalated Sulfoxides to Imines Revisited: Mechanism, Computational Studies, and the Effect of External Chiral Ligands

    DEFF Research Database (Denmark)

    Pedersen, Brian; Rein, Tobias; Søtofte, Inger

    2003-01-01

    six-membered "flat chair") was probed by quantum mechanical calculations, which underpinned the idea of using external chiral ligands to enhance the diastereoselectivity of otherwise moderately selective reactions. In this way, the diastereomeric ratio of the product 3a could be raised from (84 : 16...

  7. Enantioselective hydrogenation of cyclic imines catalysed by Noyori-Ikariya half-sandwich complexes and their analogues

    Czech Academy of Sciences Publication Activity Database

    Vilhanová, B.; Václavík, Jiří; Šot, P.; Pecháček, J.; Zápal, J.; Pažout, R.; Maixner, J.; Kuzma, M.; Kačer, P.

    2016-01-01

    Roč. 52, č. 2 (2016), s. 362-365 ISSN 1359-7345 Institutional support: RVO:61388963 Keywords : asymmetric transfer hydrogenation * ruthenium catalysts * aromatic ketones Subject RIV: CC - Organic Chemistry Impact factor: 6.319, year: 2016 http://pubs.rsc.org/en/content/articlepdf/2016/cc/c5cc06712j

  8. Enantioselective hydrogenation of cyclic imines catalysed by Noyori-Ikariya half-sandwich complexes and their analogues

    Czech Academy of Sciences Publication Activity Database

    Vilhanová, B.; Václavík, Jiří; Šot, P.; Pecháček, J.; Zápal, Jakub; Pažout, R.; Maixner, J.; Kuzma, Marek; Kačer, P.

    2016-01-01

    Roč. 52, č. 2 (2016), s. 362-365 ISSN 1359-7345 R&D Projects: GA ČR GAP106/12/1276; GA ČR(CZ) GA15-08992S Institutional support: RVO:61388971 Keywords : ASYMMETRIC TRANSFER HYDROGENATION * RUTHENIUM CATALYSTS * AROMATIC KETONES Subject RIV: EE - Microbiology, Virology Impact factor: 6.319, year: 2016

  9. Miniaturized Lab-on-a-Chip Polarimeter, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Life on Earth is unique in many ways; one of its great mysteries is that all the biomolecules of Earth's life are chiral and non-racemic. In our pursuit of life on...

  10. ESR investigation of the reactions of glutathione, cysteine and penicillamine thiyl radicals: competitive formation of RSOcenter dot, Rcenter dot, RSSRcenter dot-. , and RSScenter dot

    Energy Technology Data Exchange (ETDEWEB)

    Becker, David; Swarts, Steven; Champagne, Mark; Sevilla, M D

    1988-05-01

    The reactions of cysteine, glutathione and penicillamine thiyl radicals with oxygen and their parent thiols in frozen solutions have been elucidated with e.s.r. The major sulfur radicals observed are: (1) thiyl radicals, RS center dot; (2) disulfide radical anions, RSSR anion radicals; (3) perthiyl radicals, RSS center dot and upon introduction of oxygen; (4) sulfinyl radicals, RSO center dot, where R represents the remainder of the cysteine, glutathione or penicillamine moiety. The radical product observed depends on pH, concentration of thiol, and presence or absence of molecular oxygen. The sulfinyl radical is a ubiquitous intermediate, peroxyl radical attack on thiols may lead to sulfinyl radicals. The authors elaborate the observed reaction sequences that lead to sulfinyl radicals and, using /sup 17/O isotopic substitution studies, demonstrate the oxygen atom in sulfinyl radicals originates from dissolved molecular oxygen. The glutathione radical is found to abstract hydrogen from the ..cap alpha..-carbon position on the cysteine residue of glutathione to form a carbon-centred radical.

  11. Synthesis, characterization, spectroscopic and theoretical studies of new zinc(II), copper(II) and nickel(II) complexes based on imine ligand containing 2-aminothiophenol moiety

    Science.gov (United States)

    Shafaatian, Bita; Mousavi, S. Sedighe; Afshari, Sadegh

    2016-11-01

    New dimer complexes of zinc(II), copper(II) and nickel(II) were synthesized using the Schiff base ligand which was formed by the condensation of 2-aminothiophenol and 2-hydroxy-5-methyl benzaldehyde. This tridentate Schiff base ligand was coordinated to the metal ions through the NSO donor atoms. In order to prevent the oxidation of the thiole group during the formation of Schiff base and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structure of the Schiff base ligand showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff base as a new double Schiff base ligand. The molar conductivity values of the complexes in dichloromethane implied the presence of non-electrolyte species. The fluorescence properties of the Schiff base ligand and its complexes were also studied in dichloromethane. The products were characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis, and conductometry. The crystal structure of the double Schiff base was determined by single crystal X-ray diffraction. Furthermore, the density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d,p) level of theory for the determination of the optimized structures of Schiff base complexes.

  12. Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes, structural characterization and catalytic activity on esterification reaction.

    Science.gov (United States)

    Gönül, İlyas; Ay, Burak; Karaca, Serkan; Saribiyik, Oguz Yunus; Yildiz, Emel; Serin, Selahattin

    2017-01-01

    In this study, synthesis of insoluble polymeric ligand (L) and its transition metal complexes [Cu(L)Cl 2 ]·2H 2 O (1) , [Co(L)Cl 2 (H 2 O) 2 ] (2) and [Ni(L)Cl 2 (H 2 O) 2 ] (3) , having the azomethine groups, were synthesized by the condensation reactions of the diamines and dialdehydes. The structural properties were characterized by the analytical and spectroscopic methods using by elemental analysis, Fourier Transform Infrared, Thermo Gravimetric Analysis, Powder X-ray Diffraction, magnetic susceptibility and Inductively Coupled Plasma. The solubilities of the synthesized polymeric materials were also investigated and found as insoluble some organic and inorganic solvents. Additionally, their catalytic performance was carried out for the esterification reaction of acetic acid and butyl acetate. The highest conversion rate is 75.75% by using catalyst 1 . The esterification of butanol gave butyl acetate with 100% selectivity.

  13. Ulrich Beck : ostmine võib olla sama mõjus poliitiline osalusvorm kui valimaskäimine / Ulrich Beck ; interv. Indrek Ibrus

    Index Scriptorium Estoniae

    Beck, Ulrich

    2005-01-01

    Sotsioloog on seisukohal, et tänapäeval, kus teadusest ja majandusest on kujunenud poliitika, saab erasektorit ja teadlasi mõjutada tarbijakäitumise ning riikidevahelise koostöö suurendamisega. Lisa: Ulrich Beck

  14. InIII GaIII complexes of sugar-substituted tripodal trisalicylidene imines: The first68Ga-labelled sugar derivative

    NARCIS (Netherlands)

    Gottschaldt, M.; Bohlender, C.; Pospiech, A.; Görls, H.; Walther, M.; Müller, Dirk; Klette, I.; Baum, R.P.; Schubert, U.S.

    2009-01-01

    Gallium and indium complexes derived from salicylaldimines of 1,1,1-tris(aminomethyl)ethane (TAME) with pendant xylose, glucose and galactose units have been synthesised as model compounds for potential, application as radiotracers, The formed neutral complexes have been characterised by NMR

  15. Synthesis, structure and stability of a chiral imine-based Schiff-based ligand derived from L-glutamic acid and its [Cu4] complex

    Science.gov (United States)

    Muche, Simon; Levacheva, Irina; Samsonova, Olga; Biernasiuk, Anna; Malm, Anna; Lonsdale, Richard; Popiołek, Łukasz; Bakowsky, Udo; Hołyńska, Małgorzata

    2017-01-01

    Studies of the stability of a ligand derived from L-glutamic acid and ortho-vanillin and its new [Cu4] complex are presented. The [Cu4] complex contains a heterocubane [CuII4O4] core and pendant carboxylic groups increasing its solubility in water, also under basic conditions. The stability of the complex in different solvents is confirmed with ESI-MS studies and such experiments as successful recrystallization. The complex is stable also under physiological conditions whereas the ligand is partly decomposed to L-glutamic acid and ortho-vanillin.

  16. Effect of hydroxyl group position at imine structure on corrosion inhibition of mild steel in 0.5 m NaCl

    Science.gov (United States)

    Mohd, Yusairie; Dzolin, Syaidah Athirah; Bahron, Hadariah; Halim, Nurul Huda Abdul

    2017-12-01

    Corrosion is inherent for mild steel and it can be retarded through many approaches including electrodeposition of inert inhibitors in the form of organic molecules. Salicylideneaniline (L1) and 4-hydroxybenzalaniline (L2) were electrodeposited on mild steel using cyclic voltammetry (CV) using 0.1 M inhibitor concentration in 0.3 M NaOH. The scanning potential range for coating via CV was set from 0 - 2 V and back to 0 V for five cycles. A yellow film was observed covering the surface of the mild steel. The corrosion behavior of coated and uncoated mild steel was studied using Linear Polarization Resistance (LPR) in 0.5 M NaCl. Both coated mild steel specimens showed better corrosion resistance than the uncoated, with L1 providing a better inhibition protection with the inhibition efficiency of 80.51 %.

  17. Reduction of tri- and tetra cyclic dihydro indole imines. Control of C-21 stereochemistry of pentacyclic indole alkaloids. NMR and molecular modeling studies

    International Nuclear Information System (INIS)

    Azzouzi, A.; Kerbal, A.; Perrin, B.; Sinibaldi, M.E.; Gardette, D.; Vallee-Goyet, D.; Gramain, J.C.; Lavaud, C.

    1995-01-01

    The synthesis and conformational analysis of dihydroindole tricyclic amines 1a,b and 2a,b and tetracyclic amines 3a,b are reported. Conformational assignments were made using NMR data (including coupling and 2D correlations) and the results of molecular modeling calculations. (author). 14 refs. 14 figs

  18. A green and facile approach for synthesizing imine to develop optical biosensor for wide range detection of bilirubin in human biofluids.

    Science.gov (United States)

    Ellairaja, Sundaram; Shenbagavalli, Kathiravan; Ponmariappan, Sarkaraisamy; Vasantha, Vairathevar Sivasamy

    2017-05-15

    Bilirubin, a key biomarker for the jaundice and its clinical diagnosis needs a better analytical tool. A novel and simple fluorescent platform based on (2,2'-((1E,1'E)-((6-bromopyridine-2,3-diyl) bis(azanylylidene)) bis(methanylylidene diphenol) (BAMD) was designed. BAMD showed a remarkable fluorescent intensity with a very good quantum yield of 0.85 and lifetime of 870ps. Hence, it was applied for the determination of bilirubin using both colorimetric and fluorimetric techniques in physiological and basic pH. Under optimized experimental conditions, the probe detects bilirubin selectively in the presence of other interfering biomolecules and metal ions. The linear range of detection is 1pM-500µM at pH=7.4 and LOD is 2.8 and 3.3 pM at pH=7.4 and 9.0, respectively, which were reported so far. The probe detects the bilirubin through FRET mechanism. The practical application of the probe was successfully tested in the human blood and urine samples. Based on all above advantages, this simple idea can be applied to design a simple clinical diagnostic tool for jaundice. Copyright © 2016. Published by Elsevier B.V.

  19. Modeling cell membrane transport: interaction of guanidinylated poly(propylene imine) dendrimers with a liposomal membrane consisting of phosphate-based lipids.

    Science.gov (United States)

    Tsogas, Ioannis; Tsiourvas, Dimitris; Nounesis, George; Paleos, Constantinos M

    2006-12-19

    Mixed anionic liposomes consisting of dihexadecyl phosphate, phosphatidylcholine, and cholesterol were employed as model systems for assessing the ability of a series of functionalized dendrimers, bearing a varying number of guanidinium groups at their surface, to translocate across the liposomal bilayers. At low guanidinium/phosphate molar ratios or when weakly guanidinylated dendrimeric derivatives were employed, the dendrimeric derivative acted as a kind of "molecular glue" leading to a simple adhesion of the liposomes. Liposomal fusion occurred to a certain extent at high guanidinium/phosphate molar ratios or when highly guanidinylated dendrimeric derivatives were employed. Furthermore, translocation of these dendrimeric derivatives to the liposomal core was observed for low to medium guanidinylation and at low guanidinium/phosphate molar ratios which was, however, enhanced when the lipid bilayer was in its fluid liquid-crystalline phase. Thus, an optimum balance is required between the binding strength of guanidinium with the phosphate groups and the degree of hydrophilicity of the guanidinylated dendrimers for the transport of the latter to the liposomal core to occur.

  20. Elektronik Ağızdan Ağıza İletişimin Pazarlama Literatüründeki Önemi

    OpenAIRE

    ÖZBÜK, Meltem Yetkin; AKSOY, Şafak

    2017-01-01

    Bu çalışmanın amacı, elektronik ağızdan ağızailetişim (E-AAİLT) konusunun pazarlama alanındaki önemini açıklamaktır. Buamaçla, öncelikle, ağızdan ağıza iletişim (AAİLT) ve elektronik ağızdan ağızailetişim (E-AAİLT) süreçleri anlatılmış ve bu süreçler arasındaki farklılıklarortaya koyulmuştur. Sonrasında, yapılan sistematik bir literatür araştırmasıile H indeksine göre belirlenmiş en iyi pazarlama dergilerinde E-AAİLT konusuile ilgili yayınlanmış makaleler incelenmiştir. Bunun sonucunda, E-AAİ...

  1. Reduction of tri- and tetra cyclic dihydro indole imines. Control of C-21 stereochemistry of pentacyclic indole alkaloids. NMR and molecular modeling studies; Reduction d`imines tri- et tetracycliques dihydro-indoliques. Controle de la stereochimie en C-21 des alcaloides indoliques pentacycliques. Etude par resonance magnetique nucleaire et modelisation moleculaire

    Energy Technology Data Exchange (ETDEWEB)

    Azzouzi, A.; Kerbal, A. [Universite Sidi Mohamed Ben Abdellah, Atlas-Fes (Morocco); Perrin, B.; Sinibaldi, M.E.; Gardette, D.; Vallee-Goyet, D.; Gramain, J.C. [Clermont-Ferrand-2 Univ., 63 - Aubiere (France); Lavaud, C. [Reims Univ., 51 (France)

    1995-12-31

    The synthesis and conformational analysis of dihydroindole tricyclic amines 1a,b and 2a,b and tetracyclic amines 3a,b are reported. Conformational assignments were made using NMR data (including coupling and 2D correlations) and the results of molecular modeling calculations. (author). 14 refs. 14 figs.

  2. Synthesis and antiulcer activity of 2-[5-substituted-1-H-benzo(d ...

    Indian Academy of Sciences (India)

    Administrator

    ulcer conditions. 1. In the past few years, research for new antiulcer agents has focused on numerous struc- tural patterns of benzimidazole sulfinyl methyl pyri- ... was heated at 50–60°C under stirring for 8–10 h. Thereafter, the solvent was removed under reduced pressure. Residue was added in ice cold water to ...

  3. Diastereoselective synthesis of pyridyl substituted thiazolidin-4-ones. New ligands for the Cu(I) catalyzed asymmetric conjugate addition of diethylzinc to enones

    NARCIS (Netherlands)

    Vries, André H.M. de; Hof, Robert P.; Staal, Danny; Kellogg, Richard M.; Feringa, Bernard

    1997-01-01

    Several novel thiazolidin-4-ones have been synthesized from chiral non-racemic alpha-mercapto acids by a three component reaction in high yields and with diastereomeric excesses up to 91%. After recrystallization, the thiazolidinones were obtained diastereomerically pure and were employed as chiral

  4. KINETIC RESOLUTION OF ALCOHOLS IN AN ASYMMETRIC MITSUNOBU REACTION USING CHIRAL NONRACEMIC 1,3,2-DIOXAPHOSPHEPANES

    NARCIS (Netherlands)

    Hulst, Ron; Basten, Arjan van; Fitzpatrick, Kevin; Kellogg, Richard M.

    1995-01-01

    Non-racemic chiral trivalent phosphorus derivatives 1 and 2 when employed under Mitsunobu reaction conditions, induce esterification between racemic alcohols and acids with moderate enantiospecificity (up to 39%). At the expense of high conversion, the alcohols can be obtained in high ee (> 99%).

  5. Preparation of 14-C-labelled 1,4-Dideoxy-1,4-imino-D-arabinitol: Cyanosilylation of Cyclic Imines using KCN in a One-Pot Synthesis

    DEFF Research Database (Denmark)

    Lundt, Inge; Malle, Birgitte Mølholm; Foged, Christian

    1999-01-01

    A new method for C-C bond formation was developed based on in situ cyanosilylation of cyclic Schiff bases using KCN, TMSCl, KI and ZnI2. This method was used to prepare the potent -glucosidase inhibitor 1,4-dideoxy-1,4-imino-D-arabinitol 14-C labelled at C-5.Keywords: in situ cyanosilylation; 14-C...

  6. Exploiting the Electrophilic and Nucleophilic Dual Role of Nitrile Imines: One-Pot, Three-Component Synthesis of Furo[2,3-d]pyridazin-4(5H)-ones.

    Science.gov (United States)

    Giustiniano, Mariateresa; Mercalli, Valentina; Amato, Jussara; Novellino, Ettore; Tron, Gian Cesare

    2015-08-21

    An expeditious multicomponent reaction to synthesize tetrasubstituted furo[2,3-d]pyridazin-4(5H)-ones is reported. In brief, hydrazonoyl chlorides react with isocyanoacetamides, in the presence of TEA, to give 1,3-oxazol-2-hydrazones which, without being isolated, can react with dimethylacetylene dicarboxylate to afford furo[2,3-d]pyridazin-4(5H)-ones with an unprecedented level of complexity in a triple domino Diels-Alder/retro-Diels-Alder/lactamization reaction sequence.

  7. Yerel mikorizal türlerle aşılamanın saçlı meşe (Quercus cerris L. fidanı gelişimine etkileri

    Directory of Open Access Journals (Sweden)

    Dr. Sedat TÜFEKÇİ

    2016-07-01

    Full Text Available Bu çalışmada, (1 yarı kurak özellik gösteren doğal meşe meşcerelerinden toplanan mikorizal mantar türlerinden saf kültüre alınabilenlerin laboratuvar ortamında üretilmesi ve (2 elde edilen kültürlerin çoğaltılarak saçlı meşe (Quercus cerris L. fidanlarına aşılanması yoluyla mikorizalı fidan üretimi amaçlanmıştır. Çalışma, 2 mikoriza türü aşılaması, 2 fidan üretim şekli (çıplak köklü ve tüplü ve 2 sterilizasyon uygulaması içeren faktöriyel deneme deseni ile üç yinelemeli olarak kurulmuştur. Çalışmada, laboratuvarda kültüre alınabilen 2 ektomikorizal mantar türü [(Chroogomphus rutilus (Cr ve Rhizopogon luteolous (Rl] fidanlık denemeleri için saf kültüre alınıp çoğaltılmış ve bu aşı kültürü tüp harcına veya fidan yastığına karıştırılarak aşılama yapılmıştır. Ayrıca saf kültürde mikoriza aşılaması yapılmayan, kontrol işlemi de çalışmaya dahil edilmiştir. Birinci vejetasyon dönemi sonunda, çıplak köklü fidanlar mikoriza aşılamanın kontrol uygulamasına göre etkinliği incelendiğinde, Cr türü ile aşılanan fidanlar %29,8 ve Rl türü ile aşılanan fidanlar ise %24,5 oranında Mikorizal Aşılama Etkinliği (MAE değerine ulaşmıştır. Tüplü fidanlarda ise,  C. rutilus türü ile aşılanan fidanlar %9,8 değeri, R. luteolous türü ile aşılanan fidanlar %5,1 MAE değerini elde etmişlerdir. Bu veriler işaret etmektedir ki; sağlıklı ve iyi gelişen meşe fidanları için mikoriza aşılamasının yapılması yerinde olacaktır.Anahtar Kelimeler: Saçlı meşe, mikoriza aşılama, yarıkurak sahalar, ağaçlandırma.

  8. Tüketim Mekanlarının Dönüşümünde Görsel İletişimin Rolü: Küresel Kahve Dükkanları

    Directory of Open Access Journals (Sweden)

    Özlen ÖZGEN

    2014-02-01

    Full Text Available Kapitalizmin varlığını sürdürmesinin önemli bir koşulu mekanın yeniden düzenlenmesidir. Mekanın  hem  iç ve hem de dış yapılanması bu düzenlemede ayırt edici olmakta, kapitalizmin tüketim mekanlarından küresel kahve dükkanları ise bu farklılaşmanın önemli örnekleri arasında yer almaktadır.Yüzyıllar içinde tüm kıtalara yayılarak küreselleşen kahve, günümüzde farklı markalar altında çağımız insanının gündelik yaşamının başat içeceklerinden biri haline gelmiştir. Çalışmada Starbucks, Gloria Jeans, Lavazza, Illy ve Kahve Dünyası gibi küresel kahve markalarının kahve dükkanlarından örneklere yer verilmektedir. Bu markaların kahve dükkanlarının tasarımlarında çoğunlukla  kahveye ilişkin görsellerin kullanıldığı,  Lavazza’nın ise mekan tasarımı açısından diğer markalardan farklılaştığı görülmektedir. Lavazza bu farklılaşmayı, dünyaca ünlü fotoğraf sanatçıları tarafından çekilen takvim fotoğraflarını kahve dükkanlarının tasarımında kullanarak yaratmaktadır. Markanın görsel iletişiminde kullanılan özel fotoğraflar ile Lavazza arasında kurulan özdeşlik mekan aracılığıyla da pekiştirilmektedir. 

  9. Eğitim Seviyesindeki Yükselmenin Geleneksel Aile Anlayışının Değişimine Etkisi: Karabük Üniversitesi Örneği

    Directory of Open Access Journals (Sweden)

    Sinan Yılmaz

    2012-09-01

    Full Text Available ÖzetGünümüzde aile ile ilgili yeni yaklaşımlar ortaya çıkmış ve geleneksel aile anlayışları değişmeye başlamıştır. Evlilik yaşının yükselmesi, boşanmaların artması, nikâhsız birlikte yaşama anlayışının yaygınlaşmaya başlaması, hanehalkı sayısının küçülmesi, çocuk sayısının azalması vb. yeni yaklaşım ve anlayışlar, sıradan bir insanın bile gözlemleyebileceği ölçüde yaygınlaşmıştır. Aile ile ilgili yeni anlayışların ortaya çıkmasını tetikleyen elbette pek çok neden vardır. Bu araştırmada, aile ile ilgili bu yeni anlayışların ortaya çıkmasında eğitimin rolünün ne olduğu araştırılmaktadır. Araştırmada, aile anlayışında meydana gelen değişmelerle ilgili olarak TÜİK verilerinden yararlanıldığı gibi üniversite öğrencileri üzerinde yapmış olduğumuz bir araştırmanın sonuçlarına da yer verilmiştir. İstatistiksel veriler eğitim seviyesinin düşük olduğu dönemlerle karşılaştırılmış, böylece eğitim seviyesindeki yükselmenin nasıl bir değişim ve dönüşüme neden olduğu tespit edilmeye çalışılmıştır. Özellikle ikinci dünya savaşı sonrasında aile ile ilgili olarak Avrupa ve Amerika’da yaşanan gelişmeler de incelenmiş ve Türk ailesindeki gelişmelerle karşılaştırılarak benzer dönüşümlerin yaşanıp yaşanmayacağı tartışılmıştır. AbstractToday, new approaches about the family have emerged, and traditional family patterns have started to change. The increase of marriage age, the increase in the number of divorces, the tendency for cohabitation, the decrease in the number of family members and the decline in the number of offspring have become so wide-spread that these changes could be easily observed even by ordinary people. There are, of course, a lot of reasons that stimulate these new approaches about the family, yet this study focuses upon the role of education concerning the emergence of these new concepts about the family.In the study, the data taken from TUIK, as well as the results of a survey about the changes in the family patterns carried out on the university students are used. The statistical data are compared with the data of the previous periods in which the level of education was low. Additionally, the study examines how the increase in the level of education has brought about transformation in the traditional family patterns. Moreover, the transformations of family patterns in Europe and America, particularly after the Second World War, are studied, and these transformations are compared with the similar changes in the Turkish family patterns. The study also discusses whether the same transformations could be seen in Turkish family.RésuméAujourd’hui, de nouvelles approches ont vu le jour sur la famille et les conceptions de la famille traditionnelle ont commencé à changer. L’augmentation de l’âge du mariage, le nombre croissant de divorces, de personnes vivant en couple sans contrat de mariage, la diminution du nombre d’habitants au sein d’un ménage, la réduction du nombre d’enfants etc… sont des événements que l’on peut observer de plus en plus. Il existe bien sûr de nombreuses raisons qui déclenchent l’émergence de ces nouvelles conceptions au sujet de la famille. Dans cette étude, nous avons étudié le rôle de l’éducation dans l’émergence de ces nouvelles conceptions de la famille moderne.Dans cette étude, en ce qui concerne les changements relatifs à la conception familiale nous avons utilisé les données de TÜİK et aussi celles de notre recherche portant sur les étudiants universitaires. Les données statistiques sont comparées avec les données où le niveau d’éducation est bas dans le but de déterminer comment l’élévation du niveau d’études suscite un changement et une transformation en ce qui concerne la famille. Plus particulièrement, nous avons aussi examiné l' évolutions de la famille en Europe et aux Etats-Unis après la deuxième guerre mondiale et nous avons fait des comparaisons avec l’évolution de la famille Turque pour voir s’il existe des changements et transformations similaires.الملخص:في يومنا الحاضر ظهرت أساليب جديدة حول الأسرة و بدأت مفاهيم "الأسرة التقليدية" تتغير. ارتفاع سن الزواج وزيادة الطلاق، وانتشار مفهوم الاختلاط بين الشباب والشابات بدون نكاح، وتقليل عدد أفراد الأسرة، وتقليل عدد الأطفال في الأسرة، وغير ذلك من المفاهيم الجديدة؛ قد شاعت في المجتمع بقدر حتى يترصدها أي إنسان عادي. لا شك أن هناك أسباب عديدة في تحريك ظهور مفاهيم جديدة تتعلق بالأسرة. في هذه الدراسة، تم البحث عن مدى دور التعليم في ظهور هذه المفاهيم الجديدة المتعلقة بالأسرة... في الدراسة؛ كما تمت الاستفادة من معطيات مؤسسة إحصائيات تركيا، تترق إليه الباحث إلى نتائج البحث الذي قمنا بتطبيقه على طلاب الجامعة أيضًا. و تمت مقارنة البيانات الإحصائية الجديدة بفترات كان فيها مستوى التعليم منخفضًا؛ لذلك حاول الباحث تحديد مدى تأثير مستوى التعليم المرتفع على سبب التغيّر و التحوّل الإجتماعي. ولاسيما، التطوّرات التي شاهدت أوروبا وأمريكا إثر الحرب العالمية الثانية حول الأسرة؛ تمت دراستها ومقارنتها بينها وبين التطوّرات التي شاهدتها الأسرة التركية و نوقشت؛ هل ستعيش نفس المراحل أم لا؟

  10. I2-SDS-H2O System: A highly Efficient Dual Catalytic Green System for Deprotection of Imines and in Situ Preparation of Bis(indolyl)alkanes from Indoles in Water.

    Science.gov (United States)

    Hazarika, Parasa; Pahari, Pallab; Borah, Manash Jyoti; Konwar, Dilip

    2012-01-01

    A novel catalytic system consisting of I2-SDS-H2O has been developed which cleaves 2,3-diaza-1,3-butadiene, 1-aza-1,3-butadienes, oximes and in presence of indoles in the medium uses the corresponding aldehyde products to produce bis(indolyl)alkanes in situ. This one pot simple and mild dual catalytic system works in water at room temperature under neutral conditions.

  11. Eğitim Seviyesindeki Yükselmenin Geleneksel Aile Anlayışının Değişimine Etkisi: Karabük Üniversitesi Örneği

    Directory of Open Access Journals (Sweden)

    Sinan YILMAZ

    2012-09-01

    Full Text Available Günümüzde aile ile ilgili yeni yaklaşımlar ortaya çıkmış ve geleneksel aile anlayışları değişmeye başlamıştır. Evlilik yaşının yükselmesi, boşanmaların artması, nikâhsız birlikte yaşama anlayışının yaygınlaşmaya başlaması, hanehalkı sayısının küçülmesi, çocuk sayısının azalması vb. yeni yaklaşım ve anlayışlar, sıradan bir insanın bile gözlemleyebileceği ölçüde yaygınlaşmıştır. Aile ile ilgili yeni anlayışların ortaya çıkmasını tetikleyen elbette pek çok neden vardır. Bu araştırmada, aile ile ilgili bu yeni anlayışların ortaya çıkmasında eğitimin rolünün ne olduğu araştırılmaktadır. Araştırmada, aile anlayışında meydana gelen değişmelerle ilgili olarak TÜİK verilerinden yararlanıldığı gibi üniversite öğrencileri üzerinde yapmış olduğumuz bir araştırmanın sonuçlarına da yer verilmiştir. İstatistiksel veriler eğitim seviyesinin düşük olduğu dönemlerle karşılaştırılmış, böylece eğitim seviyesindeki yükselmenin nasıl bir değişim ve dönüşüme neden olduğu tespit edilmeye çalışılmıştır. Özellikle ikinci dünya savaşı sonrasında aile ile ilgili olarak Avrupa ve Amerika’da yaşanan gelişmeler de incelenmiş ve Türk ailesindeki gelişmelerle karşılaştırılarak benzer dönüşümlerin yaşanıp yaşanmayacağı tartışılmıştır. Anahtar Kelimeler: Aile, Türk Ailesi, Geleneksel aile, Yeni aile anlayışları, Eğitim ve aile. The Effect of Increasing Education Level on Changes in Traditional Family Patterns: The Case of Karabuk University Today, new approaches about the family have emerged, and traditional family patterns have started to change. The increase of marriage age, the increase in the number of divorces, the tendency for cohabitation, the decrease in the number of family members and the decline in the number of offspring have become so wide-spread that these changes could be easily observed even by ordinary people. There are, of course, a lot of reasons that stimulate these new approaches about the family, yet this study focuses upon the role of education concerning the emergence of these new concepts about the family. In the study, the data taken from TUIK, as well as the results of a survey about the changes in the family patterns carried out on the university students are used. The statistical data are compared with the data of the previous periods in which the level of education was low. Additionally, the study examines how the increase in the level of education has brought about transformation in the traditional family patterns. Moreover, the transformations of family patterns in Europe and America, particularly after the Second World War, are studied, and these transformations are compared with the similar changes in the Turkish family patterns. The study also discusses whether the same transformations could be seen in Turkish family. Effet de l’élévation du niveau/grade d’études au changement de la conception de la famille traditionnelle : Le Cas de l’Université de Karabük Aujourd’hui, de nouvelles approches ont vu le jour sur la famille et les conceptions de la famille traditionnelle ont commencé à changer. L’augmentation de l’âge du mariage, le nombre croissant de divorces, de personnes vivant en couple sans contrat de mariage, la diminution du nombre d’habitants au sein d’un ménage, la réduction du nombre d’enfants etc… sont des événements que l’on peut observer de plus en plus. Il existe bien sûr de nombreuses raisons qui déclenchent l’émergence de ces nouvelles conceptions au sujet de la famille. Dans cette étude, nous avons étudié le rôle de l’éducation dans l’émergence de ces nouvelles conceptions de la famille moderne. Dans cette étude, en ce qui concerne les changements relatifs à la conception familiale nous avons utilisé les données de TÜİK et aussi celles de notre recherche portant sur les étudiants universitaires. Les données statistiques sont comparées avec les données où le niveau d’éducation est bas dans le but de déterminer comment l’élévation du niveau d’études suscite un changement et une transformation en ce qui concerne la famille. Plus particulièrement, nous avons aussi examiné l' évolutions de la famille en Europe et aux Etats-Unis après la deuxième guerre mondiale et nous avons fait des comparaisons avec l’évolution de la famille Turque pour voir s’il existe des changements et transformations similaires. تأثير ارتفاع المستوى التعليمي على تغيّر "مفهوم الأسرة التقليدية" : نموذج جامعة كارابوك في يومنا الحاضر ظهرت أساليب جديدة حول الأسرة و بدأت مفاهيم "الأسرة التقليدية" تتغير. ارتفاع سن الزواج وزيادة الطلاق، وانتشار مفهوم الاختلاط بين الشباب والشابات بدون نكاح، وتقليل عدد أفراد الأسرة، وتقليل عدد الأطفال في الأسرة، وغير ذلك من المفاهيم الجديدة؛ قد شاعت في المجتمع بقدر حتى يترصدها أي إنسان عادي. لا شك أن هناك أسباب عديدة في تحريك ظهور مفاهيم جديدة تتعلق بالأسرة. في هذه الدراسة، تم البحث عن مدى دور التعليم في ظهور هذه المفاهيم الجديدة المتعلقة بالأسرة... في الدراسة؛ كما تمت الاستفادة من معطيات مؤسسة إحصائيات تركيا، تترق إليه الباحث إلى نتائج البحث الذي قمنا بتطبيقه على طلاب الجامعة أيضًا. و تمت مقارنة البيانات الإحصائية الجديدة بفترات كان فيها مستوى التعليم منخفضًا؛ لذلك حاول الباحث تحديد مدى تأثير مستوى التعليم المرتفع على سبب التغيّر و التحوّل الإجتماعي. ولاسيما، التطوّرات التي شاهدت أوروبا وأمريكا إثر الحرب العالمية الثانية حول الأسرة؛ تمت دراستها ومقارنتها بينها وبين التطوّرات التي شاهدتها الأسرة التركية و نوقشت؛ هل ستعيش نفس المراحل أم لا؟

  12. Theoretical investigation of reactions between ammonia and precursors from the ozonolysis of ethane

    DEFF Research Database (Denmark)

    Jørgensen, Solvejg; Gross, Allan

    2009-01-01

    , three reaction channels were found (i) an aldehyde, a hydrogen peroxide and an imine, (ii) two aldehydes and a hydroxylamine, (iii) a hydroxyalkyl hydroperoxide and an imine. For the reaction involving the HSE the reaction products are an aldehyde, carboxylic acid and ammonia. The B3LYP method with 6...

  13. Synthesis of α-alkyl ω-trimethoxysilane polyoxazolines and their application as coatings on glass fibres

    NARCIS (Netherlands)

    Loontjens, Ton; Rique-Lurbet, Laurence

    1999-01-01

    A novel class of telechelic α-alkyl ω-trimethoxysilane poly(N-propionylethylene imine)s (TMS-PPEIs) has been synthesized by living cationic ring-opening polymerization of 2-oxazolines. A new route for the termination reaction of the living polyoxazoline is dcscribed. These block copolymers have been

  14. Metal-Mediated Couplings of Primary Alcohols with Amines and Carbohydrates

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    . The reaction is proposed to proceed by initial dehydrogenation of the alcohol to the aldehyde, which stays coordinated to the ruthenium centre. Then, nucleophilic attack of the amine affords the hemiaminal, which is released from ruthenium and converted into the imine. Project 2: Tin-mediated regioselective 6...... from alcohols and amines catalyzed by a ruthenium N-heterocyclic carbene complex. The successful method development and application of a convenient and direct (one step) synthesis of imines from alcohols and amines is described. The developed method provides quick andextended access to structurally...... and amines have been coupled in the presence of the catalyst to afford the corresponding imines in moderate to good yields. Optically pure amines gave the corresponding imines without any sign of racemization. Moreover, the one-pot diastereoselective addition of different organometallic reagents to the imine...

  15. Outsmarted by nootropics? An investigation into the thermal degradation of modafinil, modafinic acid, adrafinil, CRL-40,940 and CRL-40,941 in the GC injector: formation of 1,1,2,2-tetraphenylethane and its tetra fluoro analog.

    Science.gov (United States)

    Dowling, Geraldine; Kavanagh, Pierce V; Talbot, Brian; O'Brien, John; Hessman, Gary; McLaughlin, Gavin; Twamley, Brendan; Brandt, Simon D

    2017-03-01

    2-[(Diphenylmethyl)sulfinyl]acetamide (modafinil) is commonly prescribed for the treatment of narcolepsy. Increasing popularity and off-label use as a cognitive enhancer has resulted in a reputation as an intelligence boosting 'wonder drug'. Common alternatives available from online shops and other retail outlets include 2-[(diphenylmethyl)sulfinyl]-N-hydroxyacetamide (adrafinil), 2-{[bis(4-fluorophenyl)methyl]sulfinyl}acetamide (CRL-40,940), 2-{[bis(4-fluorophenyl)methyl]sulfinyl}-N-hydroxyacetamide (CRL-40,941), and N-methyl-4,4-difluoro-modafinil (modafiendz), respectively. Gas chromatography-mass spectrometry (GC-MS) is a common tool used in forensic and clinical analysis but there is a potential for inducing analysis-related ambiguities. This study reports on the thermal degradation of modafinil, modafinic acid, adrafinil, CRL-40,940, and CRL-40,941 due to exposure to the heated GC injection port dissolved in a variety of solvents. Key degradation products common to modafinil, modafinic acid, and adrafinil analysis included diphenylmethanol and 1,1,2,2-tetraphenylethane (TPE), the latter of which was verified by its synthesis and characterization by x-ray crystallography. The investigated compounds were also characterized by 1 H and 13 C NMR. Diphenylmethane and thiobenzophenone were also identified in some instances. TPE formation was suggested to involve the generation of a benzhydrylium ion and its reaction with the sulfoxide oxygen of the parent compound to give an oxysulfonium intermediate. Correspondingly, the fluorinated TPE analogue was formed during heat-induced degradation of modafiendz, CRL-40,940 and CRL-40,941, respectively. When a mixture of modafinil (non-fluorinated) and modafiendz (fluorinated) were subjected to GC analysis, 4,4'-(2,2-diphenylethane-1,1-diyl)bis(fluorobenzene) was detected as a third cross reaction product in addition to the two expected TPE analogues. These observations served as a reminder that the seemingly straightforward

  16. Ağızdan Ağıza Çevrimiçi İletişimin Otellerdeki Oda Satışlarına Etkisi Üzerine bir Araştırma = The Impact of Online Word-of-Mouth Communication on Hotels’ Room Sales

    Directory of Open Access Journals (Sweden)

    Olgun KİTAPÇI

    2012-11-01

    Full Text Available Customers have used many components as data source in the purchase decision process. The motivation of being a social existence and the technological progress have featured word-of-mouth communication and have led to realization of this communication online. From this point of view, the present study focuses on hospitality industry and aims to investigate the influence of online consumer-generated reviews on holiday buying behaviour. For the data collecting process of the study, tatilsepeti.com, one of the oldest and mostly used holiday web sites is used. The semi-logarithmic model is used to assess the impact of online reviews. The results underline the significant effects of online reviews on consumer buying decision process.

  17. Tempos de subversões: a iminência de um terrorismo poético. O ativismo artístico e sua influência no cenário político das décadas de 1960 e 1970

    Directory of Open Access Journals (Sweden)

    Richard Augusto Silva

    2014-06-01

    Full Text Available Este trabalho tem como proposta, discorrer sobre contextos históricos de resistência aos poderes hegemônicos do capital no período da década de 1960, destacando o ativismo artístico, no qual atua em conjunto com mobilizações sociais e políticas da época, elucidando novos rumos para as práticas artísticas e políticas. Analisa-se sua influência no pensamento social entre movimentos sociais e artísticos. Em vias das articulações politicas sociais em relação ao ativismo artístico e seus desdobramentos no cotidiano social e cenário político brasileiro

  18. YABANCI DİL OLARAK TÜRKÇE ÖĞRETİMİNDE YAZMA VE KONUŞMA BECERİLERİ KAZANDIRMADA İLETİŞİMSEL YAKLAŞIMIN KULLANIMI İÇİN MODEL ÖNERİSİ

    Directory of Open Access Journals (Sweden)

    İzzet ŞEREF

    2015-12-01

    Full Text Available The language teaching process should not only be restricted with the teacher’s own observations and experiences, but also be based on the scientific and theoretical information. In this research found that communicative approach a big impact in last twenty years language teaching to Turkish teaching to foreigners is dealt with. The activities that have been developed to apply in teaching to foreigners Turkish writing and speaking skill according to communicative approach. The aim of the study is a modern approach to communicative language teaching approach, writing and speaking activities to provide alternative activities to prepare teachers to Turkish teaching to foreigners. Communicative approaches to language teaching techniques used in creating activities (group work and pair work, drama, improvisation, role-playing, simulation, problem solving, communication games are used.

  19. Dual-wavelength β-correction spectrophotometric determination of trace concentrations of cyanide ions based on the nucleophilic addition of cyanide to imine group of the new reagent 4-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-6(3H)-one

    International Nuclear Information System (INIS)

    Hamza, A.; Bashammakh, A.S.; Al-Sibaai, A.A.; Al-Saidi, H.M.; El-Shahawi, M.S.

    2010-01-01

    A simple, fast, low cost and sensitive direct β-correction spectrophotometric assay of cyanide ions based on its reaction with the reagent 4-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1, 3-thiazin-6(3H)-one, abbreviated as HOTT in aqueous media of pH 7-10 is described. The electronic spectrum of the produced brown-red colored species showed well defined and sharp peak at λ max = 466 nm. The effective molar absorptivity for the produced cyano compound was 2.5 x 10 4 L mol -1 cm -1 . Beer's law and Ringbom's plots were obeyed in the concentration range 0.05-2.0 and 0.30-1.5 μg mL -1 cyanide ions, respectively. The proposed method offers 16.0 and 50.3 μg L -1 lower limits of detection (LOD) and quantification (LOQ) of the cyanide ion, respectively. The analytical utility of the method for the analysis of cyanide ions in tap and drinking water samples was demonstrated and the results were compared successfully with the conventional cyanide ion selective electrode. The short time response and the detection by the naked eye make the method available for the detection and quantitative determination of cyanide in a variety of samples e.g. fresh and drinking water. Moreover, the structure of the produced colored species was determined with the aid of spectroscopic measurements (UV-Vis, IR, 1 H and 13 C NMR) and elemental analysis.

  20. Motive edici laboratuvar ortamında bilişüstü gelişimin fen öğretmen adaylarının öğrenme sonuçları açısından verimliliği

    OpenAIRE

    Sarıbaş, Deniz; Bayram, Hale

    2010-01-01

    The aim of this study was to improve pre-service science teachers’ science process skills and attitude towards chemistry by developing their metacognitive skills embedded within a motivating chemistry laboratory. The sample of the study was 54 pre-service science teachers who took the first year chemistry lab course at Marmara University. Both the control (n=27) and the experimental group (n=27) carried out 11 experiments, each of which was performed over a lab course. The students comprising...

  1. Eş Zamanlı Olmayan Gelişimin Üstün Yetenekli Çocuklardaki Görünümü Üzerine Bir Örnek Olay Çalışması

    Directory of Open Access Journals (Sweden)

    Adile Gülşah Saranlı

    2017-04-01

    Full Text Available Üstün yetenekli çocuklar, belirli gelişim alanlarında yaşıtlarından daha üst seviyede performans gösteren çocuklar olarak tanımlanırlar ve gelişimsel olarak tüm alanlarda üstün oldukları önyargısı oldukça yaygındır. Hâlbuki üstün yetenekli bir çocuk bazı gelişimsel alanlarında yaşıtlarından üstün olup, diğerlerinde ortalama, hatta daha geride bir gelişim sergiliyor olabilir. Bu duruma “üstün yeteneklilerde görülen eş zamanlı olmayan gelişim” denmektedir. “Eş zamanlı olmayan gelişim” kavramı özel gereksinimli gruplarda oldukça önemsenmekte ve farklı çalışmalara konu olmaktadır. Buna karşın bu kavramın üstün yetenekliler grubundaki görünümü ve yapılabilecekler hakkında çok fazla derleme, örnek olay çalışması veya uygulama çalışması bulunmamaktadır. Bu çalışmada üstün yetenekli çocukları tanımlayan ve çoğunlukla yeterince bilgi sahibi olunmayan önemli kavramlardan olan eş zamanlı olmayan gelişim kavramı ayrıntılarıyla ele alınarak bu konudaki sorunlar ve çözüm yolları ortaya konmaya çalışılmıştır. Çalışmada 5 yaş 3 aylık Rüzgâr rumuzlu üstün potansiyelli çocuğun eş zamanlı olmayan gelişim örüntüsü örnek olay çalışması yöntemiyle sunulmuştur. Bu çalışmanın özellikle erken yaştaki üstün potansiyelli çocukların tanılanmaları, sosyo-duygusal gelişimlerinin desteklenmesi, ailelerin ve öğretmenlerin akademik ve sosyal anlamda çocuğun davranışlarını anlaması ve oluşabilecek sorunların baştan çözümlenebilmesinde pek çok yararlı bilgiyi sağlayacağı düşünülmektedir. Çalışmanın sonuç kısmında ortaya çıkan tabloya göre oluşturulabilecek erken müdahale yolları tartışılarak bu konularla ilgilenen öğretmenlere, ailelere ve uzmanlara öneriler getirilmiştir. Giftedness is defined as showing superior performance compared to peers in a specific developmental area. In this context, the commonly held preconception is that gifted children are superior in all areas. However, compared to their peers, they may be superior in certain areas, while being typical in others. Such differences in developmental speed in different areas is called “asynchronous development.” This concept is considered to be quite important for groups with special needs and has been the focus of different studies. Despite being one of the defining characteristics of giftedness, asynchronous development is often overlooked, not studied in depth and does not receive sufficient attention, motivating the focus of this paper. In the study, asynchronous development patterns of a child with gifted potential at the age of 5 years and 3 months, to whom we will refer to as Ruzgar, are presented using a case analysis method, thereby concretizing the concepts behind, and the recognition of, typical asynchronous development patterns. It is hoped that this study will support the long-term social-emotional development of gifted children, helping parents and teachers address potential problems before they occur by understanding both academic and social behavioral patterns of gifted children. Possible ways of early intervention are also discussed in light of observations and conclusions from the case study, providing suggestions for experts as well as teachers and parents of gifted children

  2. An example of early childhood music education model and its effects on child development: Music Together® program

    Bir erken çocukluk müzik eğitim modeli ve çocuk gelişimine etkileri: Music Together® programı örneği

    OpenAIRE

    Sezen Özeke

    2017-01-01

    Children learn through games, imitation, and modelling and they acquire most of their learning experiences through their environment and interactions with adults and with other children. Child’s most intense learning experience happens during the period between 0 to 6, so called early childhood or preschool period. Thus, the abilities that can be gained in this period are considered to be important for child’s healthy growth. The effectiveness of music during this period is considered to deve...

  3. Dirhodium(II Carbenes : The Chiral Product Cascade

    Directory of Open Access Journals (Sweden)

    Gregory H. P. Roos

    2000-12-01

    Full Text Available The last decade has witnessed enormous growth in the spectrum of highly efficient asymmetric synthetic transformations. One prominent example of this progress is the application of dirhodium (II carbenes generated from diazo- precursors. Innovative construction of ‘designer’ catalysts has played a integral role in extending the breadth of the synthetic cascade of non-racemic products now available through the range of cyclopropanation, C-X insertion, aromatic cycloaddition-rearrangement, and ylide-based reaction types. This review deals briefly with an overview of the important catalytic systems and maintains as its primary focus the cascade of diverse optically enriched products that flow from their applications.

  4. Circularly polarized luminescence of syndiotactic polystyrene

    Science.gov (United States)

    Rizzo, Paola; Abbate, Sergio; Longhi, Giovanna; Guerra, Gaetano

    2017-11-01

    Syndiotactic polystyrene (s-PS) films, when crystallized from the amorphous state by temporary sorption of non-racemic guest molecules (like carvone) not only exhibit unusually high optical activity, both in the UV-Visible and Infrared ranges, but also present circularly polarized luminescence (CPL) with high dissymmetry ratios (g = ΔI/I values in the range 0.02-0.03). Experimental evidences provide support, rather than to the usual molecular circular dichroism, to a supramolecular chiral optical response being extrinsic to the site of photon absorption and emission, possibly associated with a helical morphology of s-PS crystallites.

  5. Saponification of esters of chiral alpha-amino acids anchored through their amine function on solid support.

    Science.gov (United States)

    Cantel, Sonia; Desgranges, Stéphane; Martinez, Jean; Fehrentz, Jean-Alain

    2004-06-01

    Anchoring an alpha-amino acid residue by its amine function onto a solid support is an alternative to develop chemistry on its carboxylic function. This strategy can involve the use of amino-acid esters as precursors of the carboxylic function. A complete study on the Wang-resin was performed to determine the non racemizing saponification conditions of anchored alpha-amino esters. The use of LiOH, NaOH, NaOSi(Me)3, various solvents and temperatures were tested for this reaction. After saponification and cleavage from the support, samples were examined through their Marfey's derivatives by reversed phase HPLC to evaluate the percentage of racemization.

  6. Solvent-free synthesis of azomethines, spectral correlations and antimicrobial activities of some E-benzylidene-4-chlorobenzenamines

    Directory of Open Access Journals (Sweden)

    R. Suresh

    2015-07-01

    Full Text Available Some azomethines including substituted benzylidene-4-chlorobenzenamines (E-imines have been synthesized by fly-ash: PTS catalyzed microwave assisted condensation of 4-chloroaniline and substituted benzaldehydes under solvent-free conditions. The yield of the imines has been found to be more than 85%. The purity of all imines has been checked using their physical constants and UV, IR and NMR spectral data. These spectral data have been correlated with Hammett substituent constants and F and R parameters using single and multi-linear regression analysis. From the results of statistical analysis, the effect of substituents on the above spectral data has been studied. The antimicrobial activities of all imines have been studied using standard methods.

  7. Construction of an Asymmetric Quaternary Carbon Center via Allylation of Hydrazones

    International Nuclear Information System (INIS)

    Kim, Jin Bum; Satyender, Apuri; Jang, Doo Ok

    2013-01-01

    Asymmetric indium-mediated allylation of imine derivatives bearing a chiral auxiliary is a reliable strategy for the synthesis of chiral homoallylic amines. Various techniques for indium-mediated stereoselective allylation of imines bearing a chiral auxiliary have been reported. In 1997 Loh and co-workers reported indium-mediated allylation with imines derived from L-valine methyl ester. Since then, many forms of indium-mediated allylation bearing a chiral auxiliary have been reported, including imines derived from (S)-valinol, (R)-phenylglycinol, uracil, (R)-phenylglycinol methyl ester, N-tert-butanesufinamide, and (1R,2S)-1-amino-2-indanol. However, the synthesis of chiral auxiliaries often involves a laborious multi-step synthesis with expensive reagents. Therefore, the development of readily accessible chiral auxiliaries for asymmetric indium-mediated all-ylation is in high demand

  8. Synthesis of (R)-(-)-2-fluoronorapomorphine - A precursor for the synthesis of (R)-(-)-2-fluoro-N-[C]propylnorapomorphine for evaluation as a dopamine D agonist ligand for PET investigations

    DEFF Research Database (Denmark)

    Søndergaard, Kåre; Kristensen, Jesper Langgaard; Gillings, Nic

    2005-01-01

    -catalysed rearrangement afforded N-benzylnormorphothebaine which was selectively triflylated at the 2-position and pivaloylated at the 11-position. The triflate underwent palladium-catalysed amination with benzophenone imine. Amination conditions required sequential base addition to give substantial conversion...

  9. Targeting of porous hybrid silica nanoparticles to cancer cells

    NARCIS (Netherlands)

    Rosenholm, J.M.; Meinander, A.; Peuhu, E.; Niemi, R.; Eriksson, J.E.; Sahlgren, C.; Lindén, M.

    2009-01-01

    Mesoporous silica nanoparticles functionalized by surface hyperbranching polymerization of polyethylene imine), PEI, were further modified by introducing both fluorescent and targeting moieties, with the aim of specifically targeting cancer cells. Owing to the high abundance of folate receptors in

  10. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond; Zhong, Fangrui; Zheng, Bin; Meng, Yuezhong; Lu, Yixin; Huang, Kuo-Wei

    2013-01-01

    in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  11. Molecular boxes on a molecular printboard: encapsulation of anionic dyes in immobilized dendrimers

    NARCIS (Netherlands)

    Onclin, S.; Huskens, Jurriaan; Ravoo, B.J.; Reinhoudt, David

    2005-01-01

    Fifth-generation poly(propylene imine) dendrimers, modified with 64 apolar adamantyl groups, have been immobilized on cyclodextrin host monolayers (molecular printboards) on glass by supramolecular microcontact printing. The immobilized dendrimers retain their guest-binding properties and function

  12. New stereoselective intramolecular

    Science.gov (United States)

    Alajarin; Vidal; Tovar; Ramirez De Arellano MC; Cossio; Arrieta; Lecea

    2000-11-03

    Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.

  13. Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels-Alder Reaction.

    Science.gov (United States)

    Kumatabara, Yusuke; Kaneko, Shiho; Nakata, Satoshi; Shirakawa, Seiji; Maruoka, Keiji

    2016-08-05

    A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels-Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a (1) H NMR titration study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Hydrazones as substrates for cycloaddition reactions

    International Nuclear Information System (INIS)

    Belskaya, N P; Eliseeva, A I; Bakulev, V A

    2015-01-01

    The [2+2]-, [4+2]- and [3+2]-cycloaddition reactions of hydrazones and 1,2-diazabuta-1,3-dienes, azomethine imines, nitrile imines and azomethine ylides formed upon hydrazone transformations with dienophiles, dipolarophiles and dienes are considered. The principal issues of structure and reactivity of active substrates and the influence of the reaction conditions and catalysts on the reaction regioselectivity and efficiency are discussed. The bibliography includes 288 references

  15. Intramolecular Azide to Alkene Cycloadditions for the Construction of Pyrrolobenzodiazepines and Azetidino-Benzodiazepines

    Directory of Open Access Journals (Sweden)

    Karl Hemming

    2014-10-01

    Full Text Available The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs, pyrrolo[1,2,5]benzothiadiazepines (PBTDs, and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

  16. Exploiting the CNC side chain in heterocyclic rearrangements: synthesis of 4(5)-acylamino-imidazoles.

    Science.gov (United States)

    Piccionello, Antonio Palumbo; Buscemi, Silvestre; Vivona, Nicolò; Pace, Andrea

    2010-08-06

    A new variation on the Boulton-Katritzky reaction is reported, namely, involving use of a CNC side chain. A novel Montmorillonite-K10 catalyzed nonreductive transamination of a 3-benzoyl-1,2,4-oxadiazole afforded a 3-(alpha-aminobenzyl)-1,2,4-oxadiazole, which was condensed with benzaldehydes to afford the corresponding imines. In the presence of strong base, these imines underwent Boulton-Katritzky-type rearrangement to afford novel 4(5)-acylaminoimidazoles.

  17. 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....

  18. Stereoconversion of amino acids and peptides in uryl-pendant binol schiff bases.

    Science.gov (United States)

    Park, Hyunjung; Nandhakumar, Raju; Hong, Jooyeon; Ham, Sihyun; Chin, Jik; Kim, Kwan Mook

    2008-01-01

    (S)-2-Hydroxy-2'-(3-phenyluryl-benzyl)-1,1'-binaphthyl-3-carboxaldehyde (1) forms Schiff bases with a wide range of nonderivatized amino acids, including unnatural ones. Multiple hydrogen bonds, including resonance-assisted ones, fix the whole orientation of the imine and provoke structural rigidity around the imine C==N bond. Due to the structural difference and the increase in acidity of the alpha proton of the amino acid, the imine formed with an L-amino acid (1-l-aa) is converted into the imine of the D-amino acid (1-D-aa), with a D/L ratio of more than 10 for most amino acids at equilibrium. N-terminal amino acids in dipeptides are also predominantly epimerized to the D form upon imine formation with 1. Density functional theory calculations show that 1-D-Ala is more stable than 1-L-Ala by 1.64 kcal mol(-1), a value that is in qualitative agreement with the experimental result. Deuterium exchange of the alpha proton of alanine in the imine form was studied by (1)H NMR spectroscopy and the results support a stepwise mechanism in the L-into-D conversion rather than a concerted one; that is, deprotonation and protonation take place in a sequential manner. The deprotonation rate of L-Ala is approximately 16 times faster than that of D-Ala. The protonation step, however, appears to favor L-amino acid production, which prevents a much higher predominance of the D form in the imine. Receptor 1 and the predominantly D-form amino acid can be recovered from the imine by simple extraction under acidic conditions. Hence, 1 is a useful auxiliary to produce D-amino acids of industrial interest by the conversion of naturally occurring L-amino acids or relatively easily obtainable racemic amino acids.

  19. New Liquid Phases for the Gas Chromatographic Separation of Strong Bases on Capillary Columns

    OpenAIRE

    Grob, K.

    2017-01-01

    The current practice of pretreating the solid support with free alkali to increase separation efficiency for basic compounds proved to be unsuitable for capillary columns. Instead of this, homogenous organic materials of high base strength are required. We found polyethylene imine (PEI) and polypropylene imine (PPI) to be very efficient as liquid phases of capillary columns for the separation of bases. The preparation of polymers is mentioned. Silanization or acetylation of the free hydroxyl ...

  20. Relationship between Chemical Structure and Antimicrobial Activities of Isothiocyanates from Cruciferous Vegetables against Oral Pathogens.

    Science.gov (United States)

    Ko, Mi-Ok; Kim, Mi-Bo; Lim, Sang-Bin

    2016-12-28

    We evaluated the potentials of 10 isothiocyanates (ITCs) from cruciferous vegetables and radish root hydrolysate for inhibiting the growth of oral pathogens, with an emphasis on assessing any structure-function relationship. Structural differences in ITCs impacted their antimicrobial activities against oral pathogens differently. The indolyl ITC (indol-3-carbinol) was the most potent inhibitor of the growth of oral pathogens, followed by aromatic ITCs (benzyl ITC (BITC) and phenylethyl ITC (PEITC)) and aliphatic ITCs (erucin, iberin, and sulforaphene). Sulforaphene, which is similar in structure, but has one double bond, showed higher antimicrobial activity than sulforaphane. Erucin, which has a thiol group, showed higher antimicrobial activity than sulforaphane, which has a sulfinyl group. BITC and iberin with a short chain exhibited higher antimicrobial potential than PEITC and sulforaphane with a longer chain, respectively. ITCs have strong antimicrobial activities and may be useful in the prevention and management of dental caries.

  1. Synthesis and biological activity of sulfur compounds showing structural analogy with combretastatin A-4

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Edson dos A. dos; Prado, Paulo C.; Carvalho, Wanderley R. de; Lima, Ricardo V. de; Beatriz, Adilson; Lima, Denis P. de, E-mail: denis.lima@ufms.br [Universidade Federal de Mato Grosso do Sul (UFMS), Campo Grande, MS (Brazil). Departamento de Quimica; Hamel, Ernest [Screening Technologies Branch, Developmental Therapeutics Program, Division of Cancer Treatment and Diagnosis, National Cancer Institute at Frederick, National Institutes of Health, Frederick, MD (United States); Dyba, Marzena A. [Basic Science Program , SAIC-Frederick, Inc., Structural Biophysics Laboratory National Cancer Institute, Frederick, MD (United States); Albuquerque, Sergio [Universidade de Sao Paulo (USP), Ribeirao Preto, SP (Brazil). Faculdade de Ciencias Farmaceuticas

    2013-09-01

    We extended our previous exploration of sulfur bridges as bioisosteric replacements for atoms forming the bridge between the aromatic rings of combretastatin A-4. Employing coupling reactions between 5-iodo-1,2,3-trimethoxybenzene and substituted thiols, followed by oxidation to sulfones with m-CPBA, different locations for attaching the sulfur atom to ring A through the synthesis of nine compounds were examined. Antitubulin activity was performed with electrophoretically homogenous bovine brain tubulin, and activity occurred with the 1,2,3-trimethoxy-4-[(4-methoxyphenyl)thio]benzene (12), while the other compounds were inactive. The compounds were also tested for leishmanicidal activity using promastigote forms of Leishmania braziliensis (MHOM/BR175/M2904),and the greatest activity was observed with 1,2,3-trimethoxy-4-(phenylthio)benzene (10) and 1,2,3-trimethoxy-4-[(4-methoxyphenyl) sulfinyl]benzene (15). (author)

  2. Four Thermochromic o-Hydroxy Schiff Bases of α-Aminodiphenylmethane: Solution and Solid State Study

    Directory of Open Access Journals (Sweden)

    Marija Zbačnik

    2017-01-01

    Full Text Available More than a hundred years after the first studies of the photo- and thermochromism of o-hydroxy Schiff bases (imines, it is still an intriguing topic that fascinates several research groups around the world. The reasons for such behavior are still under investigation, and this work is a part of it. We report the solution-based and mechanochemical synthesis of four o-hydroxy imines derived from α-aminodiphenylmethane. The thermochromic properties were studied for the single crystal and polycrystalline samples of the imines. The supramolecular impact on the keto-enol tautomerism in the solid state was studied using SCXRD and NMR, while NMR spectroscopy was used for the solution state. All four imines are thermochromic, although the color changes of the single crystals are not as strong as of the polycrystalline samples. One of the imines shows negative thermochromism, and that one is in keto-amine tautomeric form, both in the solid state as in solution.

  3. Chiral relay: a novel strategy for the control and amplification of enantioselectivity in chiral Lewis acid promoted reactions.

    Science.gov (United States)

    Corminboeuf, Olivier; Quaranta, Laura; Renaud, Philippe; Liu, Mei; Jasperse, Craig P; Sibi, Mukund P

    2003-01-03

    Chiral Lewis acid catalysis has emerged as one of the premiere method to control stereochemistry. Much effort has gone into the design of superior ligands with increasing steric extension to shield distant reactive sites. We report here an alternative and complementary approach based on a "chiral relay". This strategy focuses on the improved design of achiral templates which may relay and amplify the stereochemistry from ligands. The essence of this strategy is that the chiral Lewis acid would effectively convert an achiral template into a chiral non-racemic template. This approach combines the advantages of enantioselective catalysis (substoichiometric amount of the chiral inducer) with the ones of chiral auxiliary control (efficient and predictable stereocontrol).

  4. Enantioselective analysis of ibuprofen and its biotransformation products in water/sediment systems,

    DEFF Research Database (Denmark)

    Sundström, Maria; Escola, Monica; Radke, Michael

    2015-01-01

    of the sediments in the aquatic systems has neither been taken in account previously. In this study, four water-sediment systems were chosen according to anthropogenic exposure and sediment conditions. A low anthropogenic impact lake (Largen), a river receiving wastewater (Fyrisån) and two sediments (anoxic......As ibuprofen degrades enantioselectively in activated sludge, the same process is assumed to occur in surface lake-water and in river-water based biofilms. Yet, the effects of the wastewater inflow, containing non-racemic ibuprofen, into natural systems have never been studied. The role......-7 days in Tvären and B1 respectively. Largen sediments, not impacted by wastewater, degraded ibuprofen faster than Fyrisån sediments did. Yet, these two sediments sediments showed no significant difference with respect to the degradation rates of the ibuprofen enantiomers. A connection between wastewater...

  5. Non-volatile floral oils of Diascia spp. (Scrophulariaceae).

    Science.gov (United States)

    Dumri, Kanchana; Seipold, Lars; Schmidt, Jürgen; Gerlach, Günter; Dötterl, Stefan; Ellis, Allan G; Wessjohann, Ludger A

    2008-04-01

    The floral oils of Diascia purpurea, Diascia vigilis, Diascia cordata, Diascia megathura, Diascia integerrima and Diascia barberae (Scrophulariaceae) were selectively collected from trichome elaiophores. The derivatized floral oils were analyzed by gas chromatography-mass spectrometry (GC-MS), whilst the underivatized samples were analysed by electrospray ionization mass spectrometry (ESI-MS) and Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). The most common constituents of the floral oils investigated are partially acetylated acylglycerols of (3R)-acetoxy fatty acids (C(14), C(16), and C(18)), as was proven with non-racemic synthetic reference samples. The importance of these oils for Rediviva bees is discussed in a co-evolutionary context.

  6. Enantioseparations of amino acids by capillary array electrophoresis with 532 nm laser induced fluorescence detection.

    Science.gov (United States)

    Liu, Kaiying; Wang, Li

    2013-06-21

    Capillary array electrophoresis (CAE) is a promising technique for multiple enantiomeric separations. Carboxytetramethylrhodamine succinimidyl ester (TAMRA SE), a rhodamine-core fluorescent probe, has rarely been applied as an original precolumn derivatization reagent for chiral amino acid (AA) analysis so far. For these purposes, high-throughput enantiomeric separations of 12 TAMRA SE-AAs by a home-made 532 nm CAE-LIF scanner are presented. The effect of cyclodextrins (CDs) and a variety of organic modifiers was quickly investigated. Baseline separations were achieved in 100 mM Tris-borate buffer (pH 10.0) containing 2 mM β-CD and 10 mM hexamethylenediamine (HDA). Multiple determination of the enantiomeric excess (ee) in non-racemic mixtures of alanine is successfully presented. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. A Bioinspired Organocatalytic Cascade for the Selective Oxidation of Amines under Air.

    Science.gov (United States)

    Largeron, Martine; Fleury, Maurice-Bernard

    2017-05-17

    A bioinspired organocatalytic cascade reaction for the selective aerobic oxidative cross-coupling of primary amines to imines is described. This approach takes advantages of commercially available pyrogallol monomeric precursor to deliver low loadings of natural purpurogallin in situ, under air. This is further engaged in a catalytic process with the amine substrate affording, under single turnover, the active biomimetic quinonoid organocatalyst and the homocoupled imine intermediate, which is then converted into cross-coupled imine after dynamic transimination. This organocatalytic cascade inspired by both purpurogallin biosynthesis and copper amine oxidases allows the aerobic oxidation of non-activated primary amines that non-enzymatic organocatalysts were not able to accomplish alone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Controlling the oxidation of bis-tridentate cobalt(ii) complexes having bis(2-pyridylalkyl)amines: ligand vs. metal oxidation.

    Science.gov (United States)

    Anjana, S; Donring, S; Sanjib, P; Varghese, B; Murthy, Narasimha N

    2017-08-22

    Two bis-tridentate chelated cobalt(ii) complexes, which differ in the ligand structure by a methylene group, activate molecular oxygen (O 2 ), and give different oxidation products. The O 2 reaction of [Co II (pepma) 2 ] 2+ (1) with unsymmetrical 2-(2-pyridyl)-N-(2-pyridylmethyl)ethanamine (pepma) results in ligand oxidation, to the corresponding Co(ii) imine complex [Co II (pepmi) 2 ] 2+ (2). Contrastingly, the Co(ii) complex [Co II (bpma) 2 ] 2+ (3) of similar symmetrical bis(2-pyridylmethyl)amine (bpma), undergoes metal oxidation, yielding a cobalt(iii) complex, [Co III (bpma) 2 ] 2+ (4). The reversibility of the amine to imine conversion and the stability of the Co(ii) imine complex (2) are investigated. Furthermore, the solution dynamics of Co(ii) complexes are highlighted with the help of paramagnetic 1 H-NMR spectroscopy.

  9. 3D-printed devices for continuous-flow organic chemistry.

    Science.gov (United States)

    Dragone, Vincenza; Sans, Victor; Rosnes, Mali H; Kitson, Philip J; Cronin, Leroy

    2013-01-01

    We present a study in which the versatility of 3D-printing is combined with the processing advantages of flow chemistry for the synthesis of organic compounds. Robust and inexpensive 3D-printed reactionware devices are easily connected using standard fittings resulting in complex, custom-made flow systems, including multiple reactors in a series with in-line, real-time analysis using an ATR-IR flow cell. As a proof of concept, we utilized two types of organic reactions, imine syntheses and imine reductions, to show how different reactor configurations and substrates give different products.

  10. 3D-printed devices for continuous-flow organic chemistry

    Directory of Open Access Journals (Sweden)

    Vincenza Dragone

    2013-05-01

    Full Text Available We present a study in which the versatility of 3D-printing is combined with the processing advantages of flow chemistry for the synthesis of organic compounds. Robust and inexpensive 3D-printed reactionware devices are easily connected using standard fittings resulting in complex, custom-made flow systems, including multiple reactors in a series with in-line, real-time analysis using an ATR-IR flow cell. As a proof of concept, we utilized two types of organic reactions, imine syntheses and imine reductions, to show how different reactor configurations and substrates give different products.

  11. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Harden, Adrian; Wyatt, Paul

    1996-01-01

    A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines)]. In the b......A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines...

  12. Iridium‐Catalyzed Condensation of Amines and Vicinal Diols to Substituted Piperazines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh; Nordstrøm, Lars Ulrik Rubæk; Madsen, Robert

    2012-01-01

    is believed to involve dehydrogenation of the 1,2‐diol to the α‐hydroxy aldehyde, which condenses with the amine to form the α‐hydroxy imine. The latter rearranges to the corresponding α‐amino carbonyl compound, which then reacts with another amine followed by reduction of the resulting imine.......A straightforward procedure is described for the synthesis of piperazines from amines and 1,2‐diols. The heterocyclization is catalyzed by [Cp*IrCl2]2 and sodium hydrogen carbonate and can be achieved with either toluene or water as solvent. The transformation does not require any stoichiometric...

  13. Discovery of a metalloenzyme-like cooperative catalytic system of metal nanoclusters and catechol derivatives for the aerobic oxidation of amines.

    Science.gov (United States)

    Yuan, Hao; Yoo, Woo-Jin; Miyamura, Hiroyuki; Kobayashi, Shū

    2012-08-29

    We have discovered a new class of cooperative catalytic system, consisting of heterogeneous polymer-immobilized bimetallic Pt/Ir alloyed nanoclusters (NCs) and 4-tert-butylcatechol, for the aerobic oxidation of amines to imines under ambient conditions. After optimization, the desired imines were obtained in good to excellent yields with broad substrate scope. The reaction rate was determined to be first-order with respect to the substrate and catechol and zero-order for the alloyed Pt/Ir NC catalyst. Control studies revealed that both the heterogeneous NC catalyst and 4-tert-butylcatechol are essential and act cooperatively to facilitate the aerobic oxidation under mild conditions.

  14. (E-N-[2-(9-Fluorenylidene-3a,5,7-trimethyl-3,3a-dihydro-2H-indol-3-ylidene]-2,4,6-trimethylaniline

    Directory of Open Access Journals (Sweden)

    Norihiro Tokitoh

    2008-02-01

    Full Text Available The title compound, C33H30N2, has an E configuration at the imine double bond. The angle between the least-squares planes of the imine C=N—C group and the benzene ring of the 2,4,6-trimethylphenyl substituent is 85.38 (11°. The crystal structure is sustained mainly by intermolecular π–π interactions (3.510 Å between the two fluorene rings and some C—H...π interactions.

  15. Allylic azides as potential building blocks for the synthesis of nitrogenated compounds

    Directory of Open Access Journals (Sweden)

    Sá Marcus M.

    2003-01-01

    Full Text Available The synthetic potential of multifunctional allylic azides and imines in attempted intramolecular cyclizations to nitrogen-containing heterocycles was investigated. Tandem Staudinger/aza-Wittig reaction of (E-3-aryl-2-(azidomethylpropenoates with triphenylphosphine and aldehydes yielded N-allylic imines in good yield. The (E-stereochemistry of C=C and C=N bonds was assigned based on NOESY experiments. AlCl3 mediated formation of 3-carbomethoxyquinoline from methyl (E-2-(azidomethyl-3-phenylpropenoate is also described.

  16. Isotope effects in the non enzymic glucation of hemoglobin catalyzed by phosphate

    International Nuclear Information System (INIS)

    Gil, H.; Mata-Segreda, J.; Schowen, R.

    1991-01-01

    The reaction of hemoglobin, mainly at the N-terminal valine, with glucose exhibits identical rates in protium and deuterium oxides, both for the buffer-independent rate and for the first-order rate in phosphate buffer. Under the conditions employed, imine formation is relatively rapid and events in the course of the Amadori rearrangement must limit the rate. A very-slow, phosphate-induced reorganization of hemoglobin-glucose imine may be the most likely candidate for the rate-limiting step. (author)

  17. 4-Methoxy-2-{(E-[(thiophen-2-ylmethylimino]methyl}phenol

    Directory of Open Access Journals (Sweden)

    Esen Nur Kantar

    2012-09-01

    Full Text Available The title Schiff base, C13H13NO2S, adopts the phenol–imine tautomeric form and reveals an intramolecular O—H...N hydrogen bond involving the hydroxy group and the imino N atom, forming an S(6 ring. The molecule is highly twisted with respect to the central imine group, which is reflected in the dihedral angle of 67.83 (10° formed by the thienyl and phenol rings. The crystal packing is characterized by weak C—H...O and C—H...π interactions.

  18. On the possibility of removing of transition metal ions from sewage using polymeric complexes

    International Nuclear Information System (INIS)

    Tazhibaeva, S.M.; Abilov, Zh.A.; Musabekov, K.V.

    1997-01-01

    The possibility of using of complexation in the system polyethylene-imine transition metal ions (Cu 2+ , Ni 2+ , Co 2+ )-surface active substance for removing of metal ions from solution and sewage has been investigated. It is shown, that pH of medium, hydro-fugitive of system and ratio between component of the triply complex effect on purification of solution. (author)

  19. Atom-transfer radical polymerization of methyl methacrylate (MMA) using CuSCN as the catalyst

    NARCIS (Netherlands)

    Singha, N.K.; Klumperman, B.

    2000-01-01

    The effect of CuSCN as a catalyst in atom-transfer radical polymerization (ATRP) was investigated. CuSCN can successfully be used for the ATRP of MMA. Substituted bipyridines as well as imines can be used to stabilize the copper complex in solution. CuSCN induces faster polymerization compared to

  20. Covalent microcontact printing of proteins fro cell patterning

    NARCIS (Netherlands)

    Rozkiewicz, D.I.; Kraan, Yvonne M.; Werten, Marc W.T.; de Wolf, Frits A.; Subramaniam, Vinod; Ravoo, B.J.; Reinhoudt, David

    2006-01-01

    We describe a straightforward approach to the covalent immobilization of cytophilic proteins by microcontact printing, which can be used to pattern cells on substrates. Cytophilic proteins are printed in micropatterns on reactive self-assembled monolayers by using imine chemistry. An

  1. Synthesis and characterization and antibacterial activity of some ...

    African Journals Online (AJOL)

    Some new transition metal complexes of ciprofloxacin-imine derived from ciprofloxacin and o-phenylenediamine were synthesized and characterized on the basis of melting point, magnetic moment, conductance measurements, elemental analysis, infrared, UV/Vis, nuclear magnetic resonance spectroscopy, mass spectra ...

  2. Synthesis of aminocarbonyl N-acylhydrazones by a three-component reaction of isocyanides, hydrazonoyl chlorides, and carboxylic acids.

    Science.gov (United States)

    Giustiniano, Mariateresa; Meneghetti, Fiorella; Mercalli, Valentina; Varese, Monica; Giustiniano, Francesco; Novellino, Ettore; Tron, Gian Cesare

    2014-10-17

    A novel one-pot multicomponent synthesis of α-aminocarbonyl N-acylhydrazones starting from readily available hydrazonoyl chlorides, isocyanides, and carboxylic acids is reported. The strategy exploits the ability of the carboxylic acid as a third component to suppress all competing reactions between nitrile imines and isocyanides, channeling the course of the reaction toward the formation of this novel class of compounds.

  3. Base-mediated generation of ketenimines from ynamides: direct access to azetidinimines by an imino staudinger synthesis

    OpenAIRE

    Romero, Eugénie; Minard, Corinne; Benchekroun, Mohamed; Ventre, Sandrine; Retailleau, Pascal; Dodd, Robert H; Cariou, Kevin

    2017-01-01

    Ynamides were used as precursors for the in situ generation of highly reactive ketenimines which could be trapped with imines in a [2+2] cycloaddition. This imino Staudinger synthesis led to a variety of imino-analogs of β-lactams, namely azetidinimines (20 examples), that could be further functionalized through a broad range of transformations.

  4. ALDOL- AND MANNICH-TYPE REACTIONS VIA IN SITU OLEFIN MIGRATION IN IONIC LIQUID

    Science.gov (United States)

    An aldol-type and a Mannich-type reaction via the cross-coupling of aldehydes and imines with allylic alcohols catalyzed by RuCl2(PPh3)3 was developed with ionic liquid as the solvent. The solvent/catalyst system could be reused for at least five times with no loss of reactiv...

  5. RUTHENIUM-CATALYZED TANDEM OLEFIN MIGRATION-ALDOL AND MANNICH-TYPE REACTIONS IN IONIC LIQUID.

    Science.gov (United States)

    In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

  6. High Pressure Diels Alder Reactions of 1-Vinyl-2,2,6-trimethylcyclohexene Catalyzed by Chiral Lewis Acids; An Enantioselective Route to a Drimane Sesquiterpene Precursor.

    NARCIS (Netherlands)

    Knol, Joop; Meetsma, Auke; Feringa, Bernard

    1995-01-01

    The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with

  7. Chiral 1,3,2-oxazaborolidines in asymmetric synthesis: recent advances

    International Nuclear Information System (INIS)

    Glushkov, Vladimir A; Tolstikov, Alexander G

    2004-01-01

    The use of chiral 1,3,2-oxazaborolidines in asymmetric organic synthesis, particularly, in enantioselective reduction of ketones, imines and oxime ethers, asymmetric Diels-Alder reactions, aldol condensation and atroposelective reduction of lactones is reviewed. Reactions of immobilised 1,3,2-oxazaborolidines are also considered.

  8. Õitsemise tšempionid püsilillepeenral / Kaja Kurg

    Index Scriptorium Estoniae

    Kurg, Kaja, 1959-

    2014-01-01

    Helga Taimeaia perenaine Ülli-Riina Sildnik soovitab pikalt õitsvaid püsililli: mandel-piimalill Purpurea, harilik ussitatar, suureõieline iminõges, harilik tõrvalill, Borisi mõõl, kurerehad, siberi iiris, vene ussilakk jt

  9. Synthesis of new Schiff bases as materials for the design of ...

    African Journals Online (AJOL)

    Synthesis of new Schiff bases as materials for the design of photovoltaics cells. ... We describe the synthesis of new organic Schiff bases chromophores 5 containing a rhodanine-3- acetic as electron accepteur moiety. Imines 3 were obtained by a condensation reaction from a lead molecule, the aminothiazolinethione 1 with ...

  10. Bulletin of Materials Science | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Imine-linked receptors decorated ZnO-based dye-sensitized solar cells ... A maximum solar power to electricity conversion efficiency ( η ) of 3.83% was recorded for .... Dye-sensitized solar cell and photocatalytic performance of nanocomposite ..... Graphene/TiO 2 hydrogel: a potential catalyst to hydrogen evolution reaction.

  11. Fulltext PDF

    Indian Academy of Sciences (India)

    Administrator

    Tridentate Schiff bases are excellent ligands in forming dinuclear complexes of metal ions which prefer square-planar geometry. Deprotonated monobasic arylhydrazones of 2- pyridine-carboxaldehyde can coordinate a metal ion via the pyridine-N, the imine-N and the amide-O atoms. We are interested in amide-O bridged ...

  12. Ligand iron catalysts for selective hydrogenation

    Science.gov (United States)

    Casey, Charles P.; Guan, Hairong

    2010-11-16

    Disclosed are iron ligand catalysts for selective hydrogenation of aldehydes, ketones and imines. A catalyst such as dicarbonyl iron hydride hydroxycyclopentadiene) complex uses the OH on the five member ring and hydrogen linked to the iron to facilitate hydrogenation reactions, particularly in the presence of hydrogen gas.

  13. Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen

    NARCIS (Netherlands)

    Tejel, C.; Ciriano, M.A.; del Río, M.P.; van den Bruele, F.J.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; de Bruin, B.

    2008-01-01

    Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe))(2)] leads to unexpected and unique redox asymmetric dinuclear Rh-I, Rh+I complex [{Rh(ndb)}(2)(bpa-2H)] (2) with a pi-coordinating imine bound to a tetrahedral low valent rhodate(-I). Mono-oxygenation of the deprotonated bpa ligand in 2

  14. Multicomponent Synthesis of a N-Protected Alpha-Amino Ester: Ethyl 2-((4-Methoxyphenyl)Amino)-3-Phenylpropanoate

    Science.gov (United States)

    Le Gall, Erwan; Pignon, Antoine

    2012-01-01

    This laboratory experiment describes the preparation of a N-protected phenylalanine ethyl ester by a zinc-mediated Mannich-like multicomponent reaction between benzyl bromide, "p"-anisidine, and ethyl glyoxylate. The one-step reaction involves the in situ metallation of benzyl bromide into a benzylzinc reagent and its addition onto imine (Barbier…

  15. An expeditious green synthesis of Schiff bases and azetidinones ...

    Indian Academy of Sciences (India)

    phuric acid, phosphoric acid, PPA, HF may also be catalysed by Lewis acids. Magnesium perchlorate has been found to be an efficient catalyst for the synthesis of imines and phenylhydrazones from carbonyl com- pounds with amines and phenylhydrazine in high yields at room temperatures in short times. Especially, the.

  16. Histidine as a catalyst in organic synthesis: A facile in situ synthesis ...

    Indian Academy of Sciences (India)

    Unknown

    They are also used in the synthesis of many nitrogen-containing biologically ... addition to hydroxylamine, results in formation of an imine, azoxy compound 15, ... GC-MS, m/z: 211 (M+), 194 (base peak); 13C NMR (DMSO-d6) δ : 31⋅14 ...

  17. Engineering macrocyclic figure–eight motif

    Indian Academy of Sciences (India)

    TECS

    the helical arrangement is held by intramolecular hydrogen bonding or as a backbone requirement, .... knotted topology through disulfide bonds are called .... Reduction of imine double bond ... of A to NaBH4 in THF transformed to B. B can in.

  18. Renewable glycolaldehyde isolation from pyrolysis oil-derived aqueous solution by reactive extraction with primary amines

    NARCIS (Netherlands)

    Vitasari, C.R.; Meindersma, G.W.; Haan, de A.B.

    2012-01-01

    Glycolaldehyde can be separated from a pyrolysis oil-derived aqueous phase by reactive extraction employing primary amines dissolved in organic diluents. This work investigates the occurrence of solid imine formation from glycolaldehyde and amines and the competitive reactions in the organic extract

  19. Osmium and cobalt complexes incorporating facially coordinated N ...

    Indian Academy of Sciences (India)

    Administrator

    coordinated N,N,O donor azo-imine ligands: Redox and catalytic properties. Poulami Pattanayak, a. Debprasad Patra, a. Jahar Lal Pratihar, a. Andrew Burrows,. Mary F. Mahon b and Surajit Chattopadhyay* a a. Department of Chemistry, University of Kalyani, Kalyani-741235, India b. Department of Inorganic Chemistry, ...

  20. [Mass spectrometric and quantum chemical study of dimeric associates of nucleosides].

    Science.gov (United States)

    Sukhodub, L F; Aksenov, S A; Boldeskul, A I

    1995-01-01

    Deoxyribonucleosides H-bonded pairs were investigated using fast atom bombardment mass spectrometry and MNDO/H quantum chemistry method. It was shown that "rare" (enol or imin) forms of the nitrogen bases could form pairs with energy comparable with "canonical" base pair energy. It was shown that pair stability rows, which are measured using different experimental techniques, were in conformity each with other.

  1. MICROWAVE-ASSISTED CU (I) CATALYZED SOLVENT-FREE THREE COMPONENT COUPLING OF ALDEHYDE, ALKYNE AND AMINE

    Science.gov (United States)

    Direct Grignard type addition of terminal alkynes to in situ generated imines, from aldehydes and amines, occurs under microwave irradiation using CuBr alone in a one-pot operation. This solventless approach provides ready access to propargylamines and is applicable both...

  2. Intramolecular hydrogen bonding and tautomerism in Schiff bases ...

    Indian Academy of Sciences (India)

    Administrator

    C NMR, DEPT and aided by 2D HETCOR and HMBC heteronuclear correlation techniques. The UV-vis spectra of the Schiff bases have been systematically studied in organic solvents of different polarity, acidic and basic media and found useful in understanding of tautomeric equilibria (phenol-imine, O–H...N and ...

  3. A Convergent Enantioselective Total Synthesis of (-)-Perhydrohistrionicotoxin with an Intramolecular Imino Ene-type Reaction as a Key Step

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars

    1998-01-01

    A convergent enantioselective total synthesis of the neurotoxic spirocyclic alkaloid (-)-perhydrohistrionicotoxin (2) is described. A Lewis acid-mediated intramolecular imine ene-type reaction was used for the key spirocyclisation step (14 to 3, with 3 being obtained as a single diastereoisomer...

  4. New dendrimer - peptide host - guest complexes : towards dendrimers as peptide carriers

    NARCIS (Netherlands)

    Boas, U.; Sontjens, S.H.M.; Jensen, K.J.; Christensen, J.B.; Meijer, E.W.

    2002-01-01

    Adamantyl urea and adamantyl thiourea modified poly(propylene imine) dendrimers act as hosts for N-terminal tert-butoxycarbonyl (Boc)-protected peptides and form chloroform-soluble complexes. investigations with NMR spectroscopy show that the peptide is bound to the dendrimer by ionic interactions

  5. Diglycolamide-functionalized dendrimers : Studies on Americium(III) pertraction from radioactive waste

    NARCIS (Netherlands)

    Ansari, Seraj A.; Mohapatra, Prasanta K.; Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem

    2017-01-01

    Diglycolamide (DGA)-functionalized poly(propylene imine) diaminobutane dendrimers were evaluated as the carrier in supported liquid membranes (SLMs) for selective recovery of trivalent actinides over uranium. The 0, 1st, and 2nd generation dendrimers with 2, 4, and 8 DGA moieties, termed as LI, LII,

  6. Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts.

    Science.gov (United States)

    Makio, Haruyuki; Prasad, Aitha Vishwa; Terao, Hiroshi; Saito, Junji; Fujita, Terunori

    2013-07-07

    Bis(phenoxy-imine) Zr and Hf complexes were activated with (i)Bu3Al or (i)Bu2AlH in conjunction with Ph3CB(C6F5)4 and tested as catalysts for propylene polymerization with emphasis on the enantioselectivity of the isospecific species and the single site polymerization characteristics. The isoselective species was identified as the in situ generated bis(phenoxy-amine) complex whose isoselectivity was sensitive to subtle changes in ligand structure. By employing specific substituents at certain key positions the isotacticity reached an extremely high level comparable to high-end commercial isotactic polypropylenes (Tm > 160 °C). Single site polymerization characteristics depended upon the efficiency and selectivity of the in situ imine reduction which is sensitive to the substituent on the imine nitrogen and the reaction conditions. By using (i)Bu2AlH as a reducing agent, quantitative imine reduction can be achieved with a stoichiometric amount of the reducing agent. This lower alkylaluminum loading is beneficial for the catalyst and significantly enhances the polymerization activity and the molecular weight of the resultant polymer.

  7. 2,4-dimethoxybenzyl: An amide protecting group for 2-acetamido glycosyl donors

    DEFF Research Database (Denmark)

    Kelly, N.M.; Jensen, Knud Jørgen

    2001-01-01

    2,4-Dimethoxybenzyl (Dmob) was used as an amide protecting group for 2-acetamido glycosyl donors. The N-Dmob group was introduced by imine formation between 2,4-dimethoxybenzaldehyde and d-glucosamine, followed by per-O-acylation, reduction to form the amine, and finally N-acetylation to give 1...

  8. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    The reaction also produced an unexpected dipyridyl-NH-ketimine organometallic compound. [(η⁵-C₅Me₅)M {(C₅H₄N) ₂C=NH}Cl]PF6 as minor product when the reaction was performed under refluxing acetonitrile. The NH-ketimine compounds were formed via N-C single bond cleavage of imine ligand resulting in ...

  9. Nickel-Catalyzed Synthesis of Primary Aryl and Heteroaryl Amines via C–O Bond Cleavage

    KAUST Repository

    Yue, Huifeng

    2017-03-13

    A nickel-catalyzed protocol for the conversion of aryl and heteroaryl alcohol derivatives to primary and secondary aromatic amines via C(sp2)-O bond cleavage is described. The new amination protocol can be applied to a range of substrates bearing diverse functional groups and uses readily available benzophenone imines as an effective nitrogen source.

  10. Single-Crystal X-ray Structure of Anti- Candida Agent, (E)-3- (1H ...

    African Journals Online (AJOL)

    Purpose: To determine the conformation as well as imine double bond configuration of the anti- Candida oximino ester, 3-(1H-imidazol-1-yl)-1-phenyl- propan-1-one O-3-chlorobenzoyl oxime. Methods: The titled compound was synthesized in a four-step reaction sequence using acetophenone as a starting material.

  11. Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols

    DEFF Research Database (Denmark)

    Fristrup, Peter; Tursky, Matyas; Madsen, Robert

    2012-01-01

    where the intermediate aldehyde stays coordinated to the iridium catalyst and reacts with the amine to give a hemiaminal which is also bound to the catalyst. Dehydration to the imine and reduction to the product amine also takes place without breaking the coordination to the catalyst. The fact...

  12. Molecular Selectivity of Brown Carbon Chromophores

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey; Roach, Patrick J.; Eckert, Peter A.; Gilles, Mary K.; Wang, Bingbing; Lee, Hyun Ji; Hu, Qichi

    2014-10-21

    Complementary methods of high-resolution mass spectrometry and micro-spectroscopy were utilized for molecular analysis of secondary organic aerosol (SOA) generated from ozonolysis of two structural monoterpene isomers: D-limonene (LSOA) and a-pinene (PSOA). Laboratory simulated aging of LSOA and PSOA, through conversion of carbonyls into imines mediated by NH3 vapors in humid air, resulted in selective browning of the LSOA sample, while the PSOA sample remained white. Comparative analysis of the reaction products in the aged LSOA and PSOA samples provided insights into chemistry relevant to formation of brown carbon chromophores. A significant fraction of carbonyl-imine conversion products with identical molecular formulas were detected in both samples. This reflects the high level of similarity in the molecular composition of these two closely related SOA materials. Several highly conjugated products were detected exclusively in the brown LSOA sample and were identified as potential chromophores responsible for the observed color change. The majority of the unique products in the aged LSOA sample with the highest number of double bonds contain two nitrogen atoms. We conclude that chromophores characteristic of the carbonyl- imine chemistry in LSOA are highly conjugated oligomers of secondary imines (Schiff bases) present at relatively low concentrations. Formation of this type of conjugated compounds in PSOA is hindered by the structural rigidity of the a-pinene oxidation products. Our results suggest that the overall light-absorbing properties of SOA may be determined by trace amounts of strong brown carbon chromophores.

  13. A theoretical study on the metabolic activation of paracetamol by cytochrome P-450 : indications for a uniform oxidation mechanism

    NARCIS (Netherlands)

    Koymans, L.; Lenthe, J.H.; Van de Straat, R; Donné-Op den Kelder, G M; Vermeulen, N P

    1989-01-01

    The cytochrome P-450 mediated activation of paracetamol (PAR) to the reactive electrophilic intermediate N-acetyl-p-benzoquinone imine (NAPQI) has been studied by use of SV 6-31G ab initio energy calculations and spin distributions. A simplified model for cytochrome P-450 has been used by

  14. A reaction-based fluorescent sensor for detection of cyanide in aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Shan-Teng; Sie, Yi-Wun [Department of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan (China); Wan, Chin-Feng [School of Applied Chemistry, Chung Shan Medical University, Taichung City 40201, Taiwan (China); Wu, An-Tai, E-mail: antai@cc.ncue.edu.tw [Department of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan (China)

    2016-05-15

    A simple boronic acid derivative was utilized as a reaction-based receptor for CN{sup −} in aqueous solution. The receptor showed a selective and sensitive response to CN{sup −} over other various anions via nucleophilic addition of CN{sup −} to the imine moiety of the boronic-based receptor.

  15. Modern Reduction Methods

    CERN Document Server

    Andersson, Pher G

    2008-01-01

    With its comprehensive overview of modern reduction methods, this book features high quality contributions allowing readers to find reliable solutions quickly and easily. The monograph treats the reduction of carbonyles, alkenes, imines and alkynes, as well as reductive aminations and cross and heck couplings, before finishing off with sections on kinetic resolutions and hydrogenolysis. An indispensable lab companion for every chemist.

  16. Poly[N-(2-aminoethyl)ethyleneimine] as a New Non-Viral Gene Delivery Carrier : The Effect of Two Protonatable Nitrogens in the Monomer Unit on Gene Delivery Efficiency

    NARCIS (Netherlands)

    Khazaie, Yahya; Novo, Luis; van Gaal, Ethlinn; Fassihi, Afshin; Mirahmadi-Zareh, Seyedeh Zohreh; Esfahani, Mohammad Hossein Nasr; van Nostrum, Cornelus F.; Hennink, Wim E.; Dorkoosh, Farid

    2014-01-01

    Purpose. The aim of this study was to investigate the in vitro gene delivery efficiency of poly[N-(2-aminoethyl)ethylene-imine](PAEEI), a polymer with a linear Polyethyleneimine (LPEI) backbone and with aminoethyl side groups that has two protonatable nitrogen atoms per monomer unit instead of one

  17. Nonradical Zinc-Barbier Reaction for Diastereoselective Synthesis of Vicinal Amino Alcohols

    DEFF Research Database (Denmark)

    Keinicke, Lise Edelmann; Fristrup, Peter; Norrby, Per-Ola

    2005-01-01

    A new protocol for the synthesis of vicinal amino alcohols is described. The method employs a Barbier-type reaction between an imine and 3-benzoyloxyallyl bromide in the presence of zinc metal. The addition products are debenzoylated to afford amino alcohols in good yields and with diastereomeric...

  18. Shaibu and Watkins (4)

    African Journals Online (AJOL)

    DELL

    Selected bands of diagnostic importance are listed in Table 3 while the FTIR spectra of the Schiff bases under ... band with lower vibration frequency of between. 1. 3444 – 3420 cm- when compared with free OH. 1 ... These vibrations signify that the eight Schiff bases exist as enol-imine tautomers (Hokelek et al., 2006;. ).

  19. Pyridine synthesis by reactions of allyl amines and alkynes proceeding through a Cu(OAc)2 oxidation and Rh(III)-catalyzed N-annulation sequence.

    Science.gov (United States)

    Kim, Dong-Su; Park, Jung-Woo; Jun, Chul-Ho

    2012-11-28

    A new methodology has been developed for the synthesis of pyridines from allyl amines and alkynes, which involves sequential Cu(II)-promoted dehydrogenation of the allylamine and Rh(III)-catalyzed N-annulation of the resulting α,β-unsaturated imine and alkyne.

  20. Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

    Science.gov (United States)

    Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

    2015-03-20

    A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

  1. Reactivity of Me-pma RhI and IrI Complexes upon Deprotonation and Their Application in Catalytic Carbene Carbonylation Reactions

    NARCIS (Netherlands)

    Tang, Zhou; Tejel, Cristina; Martinez De Sarasa Buchaca, Marc; Lutz, Martin; Van Der Vlugt, Jarl Ivar; De Bruin, Bas

    2016-01-01

    Dehydrogenative oxidation of amines is a relevant process in metal-mediated catalysis, with the amines being either substrates or ligands. Transformation of amine- into imine-type ligands in the coordination sphere of a transition metal can be an important catalyst activation process. The behaviour

  2. Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

    Science.gov (United States)

    Liu, Lianghui; Wang, Zikuan; Fu, Xuefeng; Yan, Chun-Hua

    2012-11-16

    In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide range of "green" oxidation chemistry.

  3. IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

    Science.gov (United States)

    de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A

    2015-10-28

    The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

  4. A concise synthetic route to the conduritols from pentoses

    DEFF Research Database (Denmark)

    Keinicke, Lise Edelmann; Madsen, Robert

    2005-01-01

    -bromopropenyl benzoate and occurs with good diastereoselectivity. An amino group can be introduced in the product by trapping the intermediate aldehyde as the imine prior to the allylation. The functionalised 1,7-octadienes, thus obtained, are converted into protected conduritols by ring-closing olefin...

  5. Adsorption of charged macromolecules at a gold electrode

    NARCIS (Netherlands)

    Kleijn, J.M.; Barten, D.; Cohen Stuart, M.A.

    2004-01-01

    Using an optical reflectometer with impinging-jet system, the adsorption from aqueous solution onto gold of three charged macromolecules has been studied: the strong linear-chain polyelectrolyte polyvinyl pyridine (PVP +), the fifth-generation poly(propylene imine) dendrimer DAB-64, which has a

  6. Synthesis, characterization and anti-tumour activity of iron(III) Schiff ...

    African Journals Online (AJOL)

    The molar conductance measurements reveal the presence of 1:2 electrolytic nature complexes. Infrared spectral data agreed with the coordination to the central metal ion through deprotonated phenolic oxygen, imine and pyridine type nitrogens and the thioether sulfur atoms. From ligand field spectral data an octahedral ...

  7. Synthesis, spectroscopic characterization and biological activities of ...

    African Journals Online (AJOL)

    The elemental and spectral analysis show that ligand coordinate to the central lanthanide(III)ion by its imine nitrogen, phenolic oxygen and carboxylic oxygen in 1:1 stoichemetry. The complexes were found to be electrolytic in nature on basis of ...

  8. Strategy Planning Visualization Tool (SPVT) for the Air Operations Center (AOC). Volume 2: Information Operations (IO) Planning Enhancements

    Science.gov (United States)

    2009-12-31

    NET di rectly bonds i t t o Microsoft Windows machines only, immediately el iminating the possibility of por ting the software t o o ther...requirement to work with OPSWARE and be DoDIIS compliant was to be callable as a “command file” no user interaction installer. IOPC-X leveraged

  9. A concise route to pyrrolizidine alkaloids bearing the 1,2-amino alcohol functionality

    Energy Technology Data Exchange (ETDEWEB)

    Palomo, C.; Aizpurua, J.M.; Roman, P.; Luque, A.; Martinez-Ripoll, M. [Facultad de Quimica, Departamento de Quimica Organica, Universidad del Pais Vascom San Sebastian (Spain)

    1996-10-01

    The first entry to optically pure 4-amino-3-hydroxy-pyrrolizidine and 4-amino-pyrrolizidine alkaloid frameworks is provided by a highly diastereoselective [2+2] cycloaddition of alkoxyketenes to N-Boc-prolinal imines as the key reaction.

  10. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    In this process, quinolin-8-olato (Q) undergoes five-membered chelation, the iminium-phenolato function tautomerizing to the imine-phenol function. In dichloromethane solution, 3 displays a quasireversible 3+/3 couple near 0×50 V vs SCE (3+ is the ruthenium (III) analogue of 3). Coulometrically generated solutions of 3+ ...

  11. Nickel-Catalyzed Synthesis of Primary Aryl and Heteroaryl Amines via C–O Bond Cleavage

    KAUST Repository

    Yue, Huifeng; Guo, Lin; Liu, Xiangqian; Rueping, Magnus

    2017-01-01

    A nickel-catalyzed protocol for the conversion of aryl and heteroaryl alcohol derivatives to primary and secondary aromatic amines via C(sp2)-O bond cleavage is described. The new amination protocol can be applied to a range of substrates bearing diverse functional groups and uses readily available benzophenone imines as an effective nitrogen source.

  12. Sulfonato-imino copper(ii) complexes: fast and general Chan-Evans-Lam coupling of amines and anilines.

    Science.gov (United States)

    Hardouin Duparc, V; Schaper, F

    2017-10-14

    Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.

  13. Asymmetric Transfer Hydrogenation of Acetophenone N-Benzylimine Using [(RuCl)-Cl-II((S,S)-TsDPEN)(eta(6)-p-cymene)]: A DFT Study

    Czech Academy of Sciences Publication Activity Database

    Šot, P.; Kuzma, Marek; Václavík, J.; Pecháček, J.; Přech, J.; Januščák, J.; Kačer, P.

    2012-01-01

    Roč. 31, č. 17 (2012), s. 6496-6499 ISSN 0276-7333 R&D Projects: GA ČR GA104/09/1497; GA ČR GAP106/12/1276 Institutional support: RVO:61388971 Keywords : CARBONYL-COMPOUNDS * KETONES * IMINES Subject RIV: CA - Inorganic Chemistry Impact factor: 4.145, year: 2012

  14. solvent-free synthesis of azomethines, spectral correlations

    African Journals Online (AJOL)

    B. S. Chandravanshi

    attention of organic and medicinal chemists [2, 3]. ... Spectroscopic data is very useful for studying the ground state equilibrium of ... determines the structure of unsaturated systems, such as E- or Z, s-cis and .... The IR and NMR spectra of selective ... The proposed mechanism for the synthesis of E- imines in presence of ...

  15. Optimization of HPLC method for determination of cefixime using 2-thiophenecarboxaldehyde as derivatizing reagent: A new approach

    Science.gov (United States)

    Maheshwari, Madan Lal; Memon, Ayaz Ali; Memon, Shahabuddin; Memon, Fakhar-un-Nisa; Mughal, Ubed Ur Rahman; Dayo, Abdullah; Memon, Naheed; Ghoto, Mohammed Ali; Khan Leghari, M.

    2015-01-01

    The determination of cefixime 1 has clinical and analytical importance due to its broad spectrum antimicrobial activity and stability. Cefixime is a significant member of orally active third generation cephalosporin and has excellent activity against many pathogens. It is for first time that we have developed a new HPLC–DAD method for analysis of imine derivative 3 of cefixime by using reflux method at 100 °C for 50 min without any buffer solution. 2 Thiophenecarboxaldehyde (2TCA) 2 was used first time as a derivatizing reagent for cefixime drug. Furthermore, separation of three components, i.e. drug (cefixime), reagent (2TCA) and derivative was carried out using kromasil 100 C-18 (15 mm × 0.46 mm, 5 μm) column with isocratic elution of methanol: 0.1% aqueous formic acid (70:30 v/v) with flow rate of 1 ml min−1 at retention time of 1.8, 2.4 and 3.3 min, respectively; while, total run time was 5 min. The developed method was repeatable with a relative standard deviation (RSD) of 0.81–1.88% for imine derivative. The limit of detection and quantification of imine derivative 3 were obtained within the range of 0.132–0.401 μg ml−1 and compared with cefixime drug as 0.30–0.90 μg ml−1, respectively. However, the formation of imine derivative 3 was confirmed by comparing peak height, retention time and spectral changes. The method is rapid, simple, very stable and accurate for the separation and determination of imine derivative 3 of cefixime 1. PMID:27134548

  16. Catalysis by Design Using Surface Organometallic Nitrogen-Containing Fragments

    KAUST Repository

    Hamzaoui, Bilel

    2016-06-14

    The aim of this thesis is to explore the chemistry of well-defined silica-supported group 4 and group 5 complexes that contain one or more multiply-bonded nitrogen atoms. Such species have been recognized as crucial intermediates in many catalytic reactions (e.g. hydroaminoalkylation, olefin hydrogenation, imine metathesis…). The first chapter provided a bibliographic overview of the preparation and the reactivity of group 4 and 5 complexes towards hydroaminoalkylation and imine metathesis catalysis. The second chapter deals with the isolation and the characterization of a series of well-defined group 4 ƞ2-imine complexes surfaces species. 2D solid-state NMR (1H–13C HETCOR, Multiple Quantum) experiments have revealed consistently a unique structural rearrangement, viz azametallacycle occurring on the immobilized metal-amido ligands. Hydrogenolysis of the sole Zr-C bond in such species gives selectively a silica-supported zirconium monohydride that can perform the catalytic hydrogenation of olefins. The third chapter examines the mechanistic studies of the intermolecular hydroaminoalkylation using SOMC to identify the key metallacyclic surface intermediates (silica-supported three-membred and five-membered). The catalyst was regenerated by protonolysis and afforded pure amine. Catalytic testing of a selection of amine compounds with variable electronic properties was carried out. The fourth chapter deals with the generation and the characterization of well-defined silica-supported zirconium-imido complexes. The resulting species effectively catalyzes imine/imine cross-metathesis and thus considered as the first heterogeneous catalysts active for imine metathesis reaction. The fifth chapter studies the reaction of SBA15.1100 ºC with dry aniline and derivatives leading to opening strained siloxane bridges into acid-base paired functionalities (formation of N-phenylsilanamine-silanol pairs). This approach was successfully applied to the design of a series of

  17. Syntheses and luminescence properties of two novel lanthanide (III) perchlorate complexes with phenacyl p-tolyl sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Shu-Yan [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Li, Wen-Xian, E-mail: nmglwx@163.com [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Yu-Shan [Inner Mongolia Autonomous Region Product Quality Inspection Institute, Hohhot 010070 (China); Xin, Xiao-Dong; Guo, Feng; Cao, Xiao-Fang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China)

    2015-06-15

    Two novel solid binary complexes of rare earth perchlorate with phenacyl p-tolyl sulfoxide were synthesized and characterized by elemental analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, {sup 1}HNMR and UV spectra. The results indicated that the composition of these complexes was REL{sub 7} (ClO{sub 4}){sub 3}·6H{sub 2}O (RE=Eu (III), Tb (III), L=C{sub 6}H{sub 5}COCH{sub 2}SOC{sub 6}H{sub 4}CH{sub 3}). The study on IR spectra and {sup 1}HNMR spectra revealed that phenacyl p-tolyl sulfoxide bonded with RE{sup 3+} ions by the oxygen atom in sulfinyl group. The emission spectra illustrated that both the Eu (III) and Tb (III) complexes displayed excellent luminescence in solid state, and The most intensive characteristic emission of the Eu(III) and Tb(III) complexes were 245,400 a.u. and 298,000 a.u. respectively. The slit with was 1 nm. By analysis luminescence and phosphorescence spectrum, it was found that the ligand had the advantage to absorb energy and transfer it to the Eu (III) and Tb (III) ions. The fluorescence lifetimes of the complexes were measured as well as the quantum yield of the Eu (III) complex.

  18. Dimethyl Sulfoxide (DMSO) Decreases Cell Proliferation and TNF-α, IFN-γ, and IL-2 Cytokines Production in Cultures of Peripheral Blood Lymphocytes.

    Science.gov (United States)

    de Abreu Costa, Lucas; Henrique Fernandes Ottoni, Marcelo; Dos Santos, Michaelle Geralda; Meireles, Agnes Batista; Gomes de Almeida, Valéria; de Fátima Pereira, Wagner; Alves de Avelar-Freitas, Bethânia; Eustáquio Alvim Brito-Melo, Gustavo

    2017-11-10

    Dimethylsulfoxide (DMSO) is an amphipathic molecule composed of a polar domain characterized by the sulfinyl and two nonpolar methyl groups, for this reason it is able to solubilize polar and nonpolar substances and transpose hydrophobic barriers. DMSO is widely used to solubilize drugs of therapeutic applications and studies indicated that 10% v/v concentration did not modify culture viability when used to treat human peripheral blood mononuclear cells (PBMC). However, some DMSO concentrations could influence lymphocyte activation and present anti-inflammatory effects. Therefore, the objective of this study was to evaluate the effect of DMSO on lymphocyte activation parameters. Cell viability analysis, proliferation, and cytokine production were performed on PBMC from six healthy subjects by flow cytometry. The results indicated that 2.5% v/v DMSO concentrations did not modify lymphocytes viability. DMSO at 1% and 2% v/v concentrations reduced the relative proliferation index of lymphocytes and at 5% and 10% v/v concentrations reduced the percentage of total lymphocytes, cluster of differentiation 4⁺ (CD4⁺) T lymphocytes and CD8⁺ T lymphocytes interferon-γ (IFN-γ), tumor necrosis factor-α (TNF-α) and interleukin-2 (IL-2) producers. Thus, it was concluded that DMSO has an in vitro anti-inflammatory effect by reducing lymphocyte activation demonstrated with proliferation reduction and the decrease of cytokine production.

  19. Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Rodolfo A. (Santa Fe, NM), Unkefer; Clifford J. (Los Alamos, NM), Alvarez; Marc, A [Santa Fe, NM

    2012-06-12

    The present invention is directed to the labeled compounds, ##STR00001## wherein C* is each either .sup.13C and .sup.12C where at least one C* is .sup.13C, each hydrogen of the methylene group is hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is sulfide, sulfinyl, or sulfone, Z is an aryl group such as 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, or a phenyl group ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently either hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group such as NH.sub.2, NHR and NRR' where R and R' are each independently either a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms. The present invention is also directed to the labeled compounds ##STR00003##

  20. Redox regulation of mitochondrial function with emphasis on cysteine oxidation reactions.

    Science.gov (United States)

    Mailloux, Ryan J; Jin, Xiaolei; Willmore, William G

    2014-01-01

    Mitochondria have a myriad of essential functions including metabolism and apoptosis. These chief functions are reliant on electron transfer reactions and the production of ATP and reactive oxygen species (ROS). The production of ATP and ROS are intimately linked to the electron transport chain (ETC). Electrons from nutrients are passed through the ETC via a series of acceptor and donor molecules to the terminal electron acceptor molecular oxygen (O2) which ultimately drives the synthesis of ATP. Electron transfer through the respiratory chain and nutrient oxidation also produces ROS. At high enough concentrations ROS can activate mitochondrial apoptotic machinery which ultimately leads to cell death. However, if maintained at low enough concentrations ROS can serve as important signaling molecules. Various regulatory mechanisms converge upon mitochondria to modulate ATP synthesis and ROS production. Given that mitochondrial function depends on redox reactions, it is important to consider how redox signals modulate mitochondrial processes. Here, we provide the first comprehensive review on how redox signals mediated through cysteine oxidation, namely S-oxidation (sulfenylation, sulfinylation), S-glutathionylation, and S-nitrosylation, regulate key mitochondrial functions including nutrient oxidation, oxidative phosphorylation, ROS production, mitochondrial permeability transition (MPT), apoptosis, and mitochondrial fission and fusion. We also consider the chemistry behind these reactions and how they are modulated in mitochondria. In addition, we also discuss emerging knowledge on disorders and disease states that are associated with deregulated redox signaling in mitochondria and how mitochondria-targeted medicines can be utilized to restore mitochondrial redox signaling.

  1. Redox regulation of mitochondrial function with emphasis on cysteine oxidation reactions☆

    Science.gov (United States)

    Mailloux, Ryan J.; Jin, Xiaolei; Willmore, William G.

    2013-01-01

    Mitochondria have a myriad of essential functions including metabolism and apoptosis. These chief functions are reliant on electron transfer reactions and the production of ATP and reactive oxygen species (ROS). The production of ATP and ROS are intimately linked to the electron transport chain (ETC). Electrons from nutrients are passed through the ETC via a series of acceptor and donor molecules to the terminal electron acceptor molecular oxygen (O2) which ultimately drives the synthesis of ATP. Electron transfer through the respiratory chain and nutrient oxidation also produces ROS. At high enough concentrations ROS can activate mitochondrial apoptotic machinery which ultimately leads to cell death. However, if maintained at low enough concentrations ROS can serve as important signaling molecules. Various regulatory mechanisms converge upon mitochondria to modulate ATP synthesis and ROS production. Given that mitochondrial function depends on redox reactions, it is important to consider how redox signals modulate mitochondrial processes. Here, we provide the first comprehensive review on how redox signals mediated through cysteine oxidation, namely S-oxidation (sulfenylation, sulfinylation), S-glutathionylation, and S-nitrosylation, regulate key mitochondrial functions including nutrient oxidation, oxidative phosphorylation, ROS production, mitochondrial permeability transition (MPT), apoptosis, and mitochondrial fission and fusion. We also consider the chemistry behind these reactions and how they are modulated in mitochondria. In addition, we also discuss emerging knowledge on disorders and disease states that are associated with deregulated redox signaling in mitochondria and how mitochondria-targeted medicines can be utilized to restore mitochondrial redox signaling. PMID:24455476

  2. 2D-QSAR in hydroxamic acid derivatives as peptide deformylase inhibitors and antibacterial agents.

    Science.gov (United States)

    Gupta, Manish K; Mishra, Pradeep; Prathipati, Philip; Saxena, Anil K

    2002-12-01

    Peptide deformylase catalyzes the removal of N-formyl group from the N-formylmethionine of ribosome synthesized polypeptide in eubacteria. Quantitative structure-activity relationship (QSAR) studies have been carried out in a series of beta-sulfonyl and beta-sulfinyl hydroxamic acid derivatives for their PDF enzyme inhibitory and antibacterial activities against Escherichia coli DC2 and Moraxella catarrhalis RA21 which demonstrate that the PDF inhibitory activity in cell free and whole cell system increases with increase in molar refractivity and hydrophobicity. The comparison of the QSARs between the cell free and whole cell system indicate that the active binding sites in PDF isolated from E. coli and in M. catarrhalis RA21 are similar and the whole cell antibacterial activity is mainly due to the inhibition of PDF. Apart from this the QSARs on some matrixmetelloproteins (COL-1, COL-3, MAT and HME) and natural endopeptidase (NEP) indicate the possibilities of introducing selectivity in these hydroxamic acid derivatives for their PDF inhibitory activity.

  3. Apatite formation on organic polymers by biomimetic process using Na2O-SiO2 glasses as nucleating agent

    Energy Technology Data Exchange (ETDEWEB)

    Tanahashi, M; Yao, t; Kokubo, T [Kyoto University, Kyoto (Japan). Faculty of Engineering; Minoda, M; Miyamoto, T [Kyoto University, Kyoto (Japan). Institute for Chemical Research; Nakamura, T [Kyoto University, Kyoto (Japan). Research Center for Biomedical Engineering; Yamamuro, T [Kyoto University, Kyoto (Japan). Faculty of Medicine

    1994-09-01

    In this investigation, CaO-SiO2-based glass, which was previously used as the nucleating agent, was replaced by Na2O-SiO2 glasses, SiO2 glass, and SiO2 gel. The induction period for the apatite nucleation on various organic polymer substrates and the adhesive strength of the apatite layer to the substrates were examined. It was considered that the short induction period for the glasses with high Na2O contents was attributed to high dissolution rates of sodium and silicate ions from them. It was also considered that highly polar carboxyl or sulfinyl groups were formed on the polymer surfaces by the hydrolysis of their ester, amide or sulfonyl group in simulated body fluid with its pH increased by the Na{sup +} dissolution from the glass, and that these polar groups formed a strong bond with the apatite. It is suggested that thus formed apatite-organic polymer composites are useful as the bone-repairing as well as soft tissue-repairing materials. 11 refs., 13 figs., 3 tabs.

  4. Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

    International Nuclear Information System (INIS)

    Li Wenxian; Zheng Yushan; Sun Xiaojun; Chai Wenjuan; Ren Tie; Shi Xiaoyan

    2010-01-01

    Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C 6 H 5 COCH 2 SOCH 2 COC 6 H 5 ), salicylic acid as second ligand (L ' =C 6 H 4 OHCOO - ). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL 5 L'](ClO 4 ) 2 .nH 2 O (RE=Tb, Dy; n=6, 8 ). Based on IR, 1 HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L'), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.

  5. A short synthesis and biological evaluation of potent and nontoxic antimalarial bridged bicyclic beta-sulfonyl-endoperoxides.

    Science.gov (United States)

    Bachi, Mario D; Korshin, Edward E; Hoos, Roland; Szpilman, Alex M; Ploypradith, Poonsakdi; Xie, Suji; Shapiro, Theresa A; Posner, Gary H

    2003-06-05

    The syntheses and in vitro antimalarial screening of 50 bridged, bicyclic endoperoxides of types 9-13 are reported. In contrast to antimalarial trioxanes of the artemisinin family, but like yingzhaosu A and arteflene, the peroxide function of compounds 9-13 is contained in a 2,3-dioxabicyclo[3.3.1]nonane system 6. Peroxides 9 and 10 (R(1) = OH) are readily available through a multicomponent, sequential, free-radical reaction involving thiol-monoterpenes co-oxygenation (a TOCO reaction). beta-Sulfenyl peroxides 9 and 10 (R(1) = OH) are converted into beta-sulfinyl and beta-sulfonyl peroxides of types 11-13 by controlled S-oxidation and manipulation of the tert-hydroxyl group through acylation, alkylation, or dehydration followed by selective hydrogenation. Ten enantiopure beta-sulfonyl peroxides of types 12 and 13 exhibit in vitro antimalarial activity comparable to that of artemisinin (IC(50) = 6-24 nM against Plasmodium falciparum NF54). In vivo testing of a few selected peroxides against Plasmodium berghei N indicates that the antimalarial efficacies of beta-sulfonyl peroxides 39a, 46a, 46b, and 50a are comparable to those of some of the best antimalarial drugs and are higher than artemisinin against chloroquine-resistant Plasmodium yoelii ssp. NS. In view of the nontoxicity of beta-sulfonyl peroxides 39a, 46a, and 46b in mice, at high dosing, these compounds are regarded as promising antimalarial drug candidates.

  6. New anthraquinone derivatives from Geosmithia lavendula.

    Science.gov (United States)

    Malak, Lourin G; Bishay, Daoud W; Abdel-Baky, Afaf M; Moharram, Ahmed M; Cutler, Stephen J; Ross, Samir A

    2013-02-01

    A phytochemical study of Geosmithia lavendula Pitt led to the isolation of three new anthraquinones: 1-acetyl-2,4,6,8-tetrahydroxy-9,10-anthraquinone (1), 2-acetyl-1,4,5,7-tetrahydroxy-9,10-anthraquinone (2), and 1-acetyl-2,4,5,6,7-pentahydroxy-9,10-anthraquinone (3), as well as another new compound named didodecyl thiodipropionate (propionic acid, 3,3-sulfinyl di-1,1'-didodecyl ester) (4), along with ten known compounds: 1-acetyl-2,4,5,7-tetrahydroxy-9,10-anthraquinone (rhodolamprometrin) (5), 1-acetyl-2,4,5,7,8-pentahydroxy-9,10-anthraquinone (6), (22E)-ergosta-6,22-diene-3beta,5alpha,8alpha-triol, p-hydroxybenzyl alcohol, oleic acid, D-mannitol, palmitic acid, stearic acid, cis-vaccenic acid and 2-decenal. The structures of the isolated metabolites were elucidated based on NMR spectroscopic and mass spectrometric data. Compound 1 exhibited moderate activity against methicillin resistant Staphylococcus aureus with an IC50 value of 16.1 microg/mL.

  7. Discovery of the First Interstellar Chiral Molecule: Propylene Oxide

    Science.gov (United States)

    Carroll, Brandon; McGuire, Brett A.; Loomis, Ryan; Finneran, Ian A.; Jewell, Philip; Remijan, Anthony; Blake, Geoffrey

    2016-06-01

    Life on Earth relies on chiral molecules, that is, species not superimposable on their mirror images. This manifests itself as a reliance on a single molecular handedness, or homochirality that is characteristic of life and perhaps most readily apparent in the large enhancement in biological activity of particular amino acid and sugar enantiomers. Yet, the ancestral origin of biological homochirality remains a mystery. The non-racemic ratios in some organics isolated from primitive meteorites hint at a primordial chiral seed but even these samples have experienced substantial processing during planetary assembly, obscuring their complete histories. To determine the underlying origin of any enantiomeric excess, it is critical to understand the molecular gas from which these molecules originated. Here, we present the first extra-solar, astronomical detection of a chiral molecule, propylene oxide (CH_3CHCH_2O), in absorption toward the Galactic Center. With the detection of propylene oxide, we at last have a target for broad-ranging searches for the possible cosmic origin of the homochirality of life.

  8. Life's First Handshake - Discovery of the Interstellar Chiral Molecule Propylene Oxide

    Science.gov (United States)

    McGuire, Brett A.; Carroll, P. Brandon; Loomis, Ryan A.; Finneran, Ian A.; Jewell, Philip R.; Remijan, Anthony J.; Blake, Geoffrey A.

    2016-06-01

    Life on Earth relies on chiral molecules, that is, species not superimposable on their mirror images. This manifests itself in the selection of a single molecular handedness, or homochirality, across the biosphere, and is perhaps most readily apparent in the large enhancement in biological activity of particular amino acid and sugar enantiomers. Yet, the ancestral origin of biological homochirality remains a mystery. The non-racemic ratios in some organics isolated from primitive meteorites hint at a primordial chiral seed, but even these samples have experienced substantial processing during planetary assembly, obscuring their complete histories. To determine the underlying origin of any enantiomeric excess, it is critical to understand the molecular gas from which these molecules originated. Here, we present the first extra-solar, astronomical detection of a chiral molecule, propylene oxide (CH3CHCH2O), in absorption toward the Galactic Center. We discuss the implications of the detection on observational searches to determine a primordial chiral excess, as well as the state of laboratory efforts in these areas.

  9. Temporal and spatial variation in polychlorinated biphenyl chiral signatures of the Greenland shark (Somniosus microcephalus) and its arctic marine food web

    International Nuclear Information System (INIS)

    Lu, Zhe; Fisk, Aaron T.; Kovacs, Kit M.; Lydersen, Christian; McKinney, Melissa A.; Tomy, Gregg T.; Rosenburg, Bruno; McMeans, Bailey C.; Muir, Derek C.G.; Wong, Charles S.

    2014-01-01

    Polychlorinated biphenyls (PCBs) chiral signatures were measured in Greenland sharks (Somniosus microcephalus) and their potential prey in arctic marine food webs from Canada (Cumberland Sound) and Europe (Svalbard) to assess temporal and spatial variation in PCB contamination at the stereoisomer level. Marine mammals had species-specific enantiomer fractions (EFs), likely due to a combination of in vivo biotransformation and direct trophic transfer. Greenland sharks from Cumberland Sound in 2007–2008 had similar EFs to those sharks collected a decade ago in the same location (PCBs 91, 136 and 149) and also similar to their conspecifics from Svalbard for some PCB congeners (PCBs 95, 136 and 149). However, other PCB EFs in the sharks varied temporally (PCB 91) or spatially (PCB 95), suggesting a possible spatiotemporal variation in their diets, since biotransformation capacity was unlikely to have varied within this species from region to region or over the time frame studied. -- Highlights: • Chiral PCB signatures were measured in Greenland sharks and their prey. • Marine mammals accumulated non-racemic PCBs from biotransformation and their diet. • Chiral PCB signatures were similar in sharks at two different arctic locations. • Some changes in chiral PCB signatures in sharks over a decade. -- PCB chiral signatures in Greenland sharks shift over time and space, likely in parallel with dietary variation

  10. In situ coating multiwalled carbon nanotubes with CdS nanoparticles

    International Nuclear Information System (INIS)

    Liu Yangqiao; Gao Lian

    2005-01-01

    CdS nanoparticles were homogeneously coated on multiwalled carbon nanotubes by an in situ method through introducing thiol groups onto the tube wall using a novel method. A cationic polyelectrolyte containing reactive imine groups, polyethyleneimine (PEI), was firstly adsorbed on the surface of nanotubes. 3-Mercaptopropionic acid (MPA) was then anchored by an amidation reaction between its carboxyl group and the imine group of the polyelectrolyte under the activation of carbodiimide reagents. These -SH terminated MWCNTs were coated with CdS nanoparticles by an in situ method. The phase composition, microstructure, and the UV-vis properties of the CdS coated MWCNTs were characterized. The addition of the carbodiimide reagents played an important role in linking the MPA with PEI covalently and subsequently coating the MWCNTs with CdS homogeneously. A blue shift in the absorption edge was observed for the MWCNTs-CdS hybrid material due to the quantum size effect

  11. Nanoscale Assembly of Actuating Cilia-Mimetic

    Science.gov (United States)

    Baird, Lance; Breidenich, Jennifer; Land, Bruce; Hayes, Allen; Benkoski, Jason; Keng, Pei; Pyun, Jeffrey

    2009-03-01

    The cilium is among the smallest mechanical actuators found in nature. We have taken inspiration from this design to create magnetic nanochains, measuring approximately 1-5 μm long and 25 nm in diameter. Fabricated from the self-assembly of cobalt nanoparticles, these flexible filaments actuate in an oscillating magnetic field. The cobalt nanoparticles were functionalized with a polystyrene/benzaldehyde surface coating, thus allowing the particles to form imine bonds with one another in the presence of a diamine terminated polyethylene glycol. These imine bonds effectively cross-linked the particles and held the nanochains together in the absence of a magnetic field. Using design of experiments (DOE) to efficiently screen the effects of cobalt nanoparticle concentration, crosslinker concentration, and surface chemistry, we determined that the morphology of the final structures could be explained primarily by physical interactions (i.e. magnetic forces) rather than chemistry.

  12. Design of expanded bed supports for the recovery of plasmid DNA by anion exchange adsorption

    DEFF Research Database (Denmark)

    Theodossiou, Irini; Søndergaard, M.; Thomas, Owen R. T.

    2001-01-01

    In this study we detail the rational design of new chromatographic adsorbents tailored for the capture of plasmid DNA. Features present on current chromatographic supports that can significantly enhance plasmid binding capacity have been identified in packed bed chromatography experiments...... and blueprints for improved expanded bed adsorbents have been put forward. The characterisation and testing of small (20-40 mum) high density (>3.7 g cm(-3)) pellicular expanded bed materials functionalised with various anion exchange structures is presented. In studies with calf thymus DNA, dynamic binding...... capacities of 1.2 and 3.4 mg ml(-1) were recorded for prototype diethylaminoethyl-and polyethylene imine-linked adsorbents which were respectively 25 and 70 fold higher than those of equivalently derivatised commercial expanded bed materials. The prototype polyethylene imine-coupled material exhibited severe...

  13. Oligomerization of ethylene catalysed by nickel complexes associated with nitrogen ligands in ionic liquids; Oligomerisation de l'ethylene catalysee par des complexes du nickel associes a des ligands azotes dans les liquides ioniques

    Energy Technology Data Exchange (ETDEWEB)

    Lecocq, V.

    2003-09-01

    We report here the use of a new class of catalytic systems based on a nickel active center associated with nitrogen ligands, such as di-imines, or imino-pyridines, for the oligomerization of ethylene in a biphasic medium using ionic liquids as the catalyst solvent. The nickel catalyst is immobilized in the ionic liquid phase in which the olefinic reaction products are poorly miscible. This biphasic system makes possible an easy separation and recycle of the catalyst. Numerous di-imine and imino-pyridine ligands with different steric and electronic properties have been synthesized and their corresponding nickel complexes isolated and characterized. Different ionic liquids, based on chloro-aluminates or non-chloro-aluminates anions, have also been prepared and characterized. The effect of the nature of the ligand, the ionic liquid, the nickel precursor and its mode of activation have been studied and correlated with the selectivity and activity of the transformation of ethylene. (author)

  14. Scandium(III) catalysis of transimination reactions. Independent and constitutionally coupled reversible processes.

    Science.gov (United States)

    Giuseppone, Nicolas; Schmitt, Jean-Louis; Schwartz, Evan; Lehn, Jean-Marie

    2005-04-20

    Sc(OTf)(3) efficiently catalyzes the self-sufficient transimination reaction between various types of C=N bonds in organic solvents, with turnover frequencies up to 3600 h(-)(1) and rate accelerations up to 6 x 10(5). The mechanism of the crossover reaction in mixtures of amines and imines is studied, comparing parallel individual reactions with coupled equilibria. The intrinsic kinetic parameters for isolated reactions cannot simply be added up when several components are mixed, and the behavior of the system agrees with the presence of a unique mediator that constitutes the core of a network of competing reactions. In mixed systems, every single amine or imine competes for the same central hub, in accordance with their binding affinity for the catalyst metal ion center. More generally, the study extends the basic principles of constitutional dynamic chemistry to interconnected chemical transformations and provides a step toward dynamic systems of increasing complexity.

  15. Theoretical investigation of reactions between ammonia and precursors from the ozonolysis of ethene

    Energy Technology Data Exchange (ETDEWEB)

    Jorgensen, Solvejg, E-mail: solvejg@kemi.ku.dk [Copenhagen Center of Atmospheric Research, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen O (Denmark); Gross, Allan, E-mail: agr@dmi.dk [Research Department, Danish Meteorological Institute, Lyngbyvej 100, DK-2100 Copenhagen O (Denmark)

    2009-07-30

    The reaction mechanisms between ammonia and two secondary organic aerosol (SOA) precursors from ozonolysis of alkenes - namely the secondary ozonide (SOZ) and hydroxyl substituted ester (HSE) have been investigated using quantum mechanics calculations. For the reaction between ammonia and SOZ, three reaction channels were found (i) an aldehyde, a hydrogen peroxide and an imine, (ii) two aldehydes and a hydroxylamine, (iii) a hydroxyalkyl hydroperoxide and an imine. For the reaction involving the HSE the reaction products are an aldehyde, carboxylic acid and ammonia. The B3LYP method with 6-311++G(2d,2p) basis set was employed for the geometry optimisation of the stationary points. Gaussian 2 and Gaussian 3 levels of theory have been used to optimise and refine the energy. From an energetic point of view, it is concluded that the reaction between ammonia and HSE is in favour compared to the one with the SOZ.

  16. Highly efficient induction of chirality in intramolecular

    Science.gov (United States)

    Cossio; Arrieta; Lecea; Alajarin; Vidal; Tovar

    2000-06-16

    Highly stereocontrolled, intramolecular [2 + 2] cycloadditions between ketenimines and imines leading to 1,2-dihydroazeto[2, 1-b]quinazolines have been achieved. The source of stereocontrol is a chiral carbon atom adjacent either to the iminic carbon or nitrogen atom. In the first case, the stereocontrol stems from the preference for the axial conformer in the first transition structure. In the second case, the origin of the stereocontrol lies on the two-electron stabilizing interaction between the C-C bond being formed and the sigma orbital corresponding to the polar C-X bond, X being an electronegative atom. These models can be extended to other related systems for predicting the stereochemical outcome in this intramolecular reaction.

  17. Ethyl 2-[(2-hydroxybenzylideneamino]-6-methyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate

    Directory of Open Access Journals (Sweden)

    Naki Çolak

    2013-07-01

    Full Text Available The title compound, C18H20N2O3S, exists as the phenol–imine form in the crystal and there are bifurcated intramolecular O—H...(N/O hydrogen bonds present. The conformation about the C=N bond is anti (1E; the C=N imine bond length is 1.287 (4 Å and the C=N—C angle is 122.5 (3°. In the tetrahydrothienopyridine moiety, the six-membered ring has a flattened-boat conformation. In the crystal, molecules are stacked nearly parallel to (110 and a weak C—H...π interaction is observed. The carbonyl O atom is disordered over two positions and was refined with a fixed occupancy ratio of 0.7:0.3.

  18. Ethyl 2-{3-[(2-chloro-1,3-thiazol-5-ylmethyl]-4-nitroimino-1,3,5-triazinan-1-yl}acetate

    Directory of Open Access Journals (Sweden)

    Chuan-wen Sun

    2010-06-01

    Full Text Available In the title compound, C11H15ClN6O4S, which belongs to the neonicotinoid class of insecticidally active heterocyclic compounds, the six-membered triazine ring adopts an opened envolope conformation. The planar nitro imine group [dihedral angle between nitro and imine groups = 1.07 (7°] and the thiazole ring are oriented at a dihedral angle of 69.62 (8°. A classical intramolecular N—H...O hydrogen bond is found in the molecular structure. Moreover, one classical intermolecular N—H...N and four non-classical C—H...O and C—H...N hydrogen bonds are also present in the crystal structure. Besides intermolecular hydrogen bonds, the Cl atom forms an intermolecular short contact [3.020 (2 Å] with one of the nitro O atoms.

  19. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    Directory of Open Access Journals (Sweden)

    Zong Guan

    2014-04-01

    Full Text Available Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes which can be trapped as rhodium complexes (X-ray analysis. In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis. Results of DFT calculations are presented.

  20. 1,4-Bis{(+-(S-[1-(1-naphthylethyl]iminomethyl}benzene

    Directory of Open Access Journals (Sweden)

    Armando Espinosa Leija

    2009-10-01

    Full Text Available The title compound, C32H28N2, is a chiral bis-imine in which both imine groups display the common E configuration. The naphthyl groups present different orientations with respect to the central core, as reflected in the dihedral angles of 21.4 (2 and 78.83 (14° between the benzene and naphthyl mean planes, thus the highest possible C2 local molecular symmetry is not attained. This C1 molecular conformation allows multiple C—H...π intermolecular contacts involving all aromatic rings, while no π–π interactions are available for the stabilization of the crystal structure. The resulting packing structure is based on molecules stacked along [100].

  1. Removal of some organic pollutants in water employing ceramic membranes impregnated with cross-linked silylated dendritic and cyclodextrin polymers.

    Science.gov (United States)

    Allabashi, Roza; Arkas, Michael; Hörmann, Gerold; Tsiourvas, Dimitris

    2007-01-01

    Triethoxysilylated derivatives of poly(propylene imine) dendrimer, polyethylene imine and polyglycerol hyperbranched polymers and beta-cyclodextrin have been synthesized and characterized. These compounds impregnated ceramic membranes made from Al(2)O(3), SiC and TiO(2) and subsequently sol-gel reaction led to their polymerization and chemical bond formation with the ceramic substrates. The resulting organic-inorganic filters were tested for the removal of a variety of organic pollutants from water. They were found to remove of polycyclic aromatic hydrocarbons (up to 99%), of monocyclic aromatic hydrocarbons (up to 93%), trihalogen methanes (up to 81%), pesticides (up to 43%) and methyl-tert-butyl ether (up to 46%).

  2. Organic/inorganic hybrid filters based on dendritic and cyclodextrin "nanosponges" for the removal of organic pollutants from water.

    Science.gov (United States)

    Arkas, Michael; Allabashi, Roza; Tsiourvas, Dimitris; Mattausch, Eva-Maria; Perfler, Reinhard

    2006-04-15

    Long-alkyl chain functionalized poly(propylene imine) dendrimer, poly(ethylene imine) hyperbranched polymer, and beta-cyclodextrin derivatives, which are completely insoluble in water, have the property of encapsulating organic pollutants from water. Ceramic porous filters can be impregnated with these compounds resulting in hybrid organic/ inorganic filter modules. These hybrid filter modules were tested for the effective purification of water, by continuous filtration experiments, employing a variety of water pollutants. It has been established that polycyclic aromatic hydrocarbons (PAHs) can be removed very efficiently (more than 95%), and final concentrations of several ppb (microg/ L) are easily obtained. Representatives of the pollutant group of trihalogen methanes (THMs), monoaromatic hydrocarbons (BTX), and pesticides (simazine) can also be removed (>80%), although the filters are saturated considerably faster in these cases.

  3. Selective Hydrogen Generation from Formic Acid with Well-Defined Complexes of Ruthenium and Phosphorus-Nitrogen PN3-Pincer Ligand

    KAUST Repository

    Pan, Yupeng

    2016-04-22

    An unsymmetrically protonated PN3-pincer complex in which ruthenium is coordinated by one nitrogen and two phosphorus atoms was employed for the selective generation of hydrogen from formic acid. Mechanistic studies suggest that the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved. Grabbing hold: A PN3-pincer complex was employed for the selective hydrogen generation from formic acid. Mechanistic studies suggest the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Continuous-flow oxidative cyanation of primary and secondary amines using singlet oxygen.

    Science.gov (United States)

    Ushakov, Dmitry B; Gilmore, Kerry; Kopetzki, Daniel; McQuade, D Tyler; Seeberger, Peter H

    2014-01-07

    Primary and secondary amines can be rapidly and quantitatively oxidized to the corresponding imines by singlet oxygen. This reactive form of oxygen was produced using a variable-temperature continuous-flow LED-photoreactor with a catalytic amount of tetraphenylporphyrin as the sensitizer. α-Aminonitriles were obtained in good to excellent yields when trimethylsilyl cyanide served as an in situ imine trap. At 25°C, primary amines were found to undergo oxidative coupling prior to cyanide addition and yielded secondary α-aminonitriles. Primary α-aminonitriles were synthesized from the corresponding primary amines for the first time, by an oxidative Strecker reaction at -50 °C. This atom-economic and protecting-group-free pathway provides a route to racemic amino acids, which was exemplified by the synthesis of tert-leucine hydrochloride from neopentylamine. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.

    Science.gov (United States)

    Largeron, Martine; Chiaroni, Angèle; Fleury, Maurice-Bernard

    2008-01-01

    Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.

  6. Reactions of ethyl diazoacetate catalyzed by methylrhenium trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Z.; Espenson, H. [Iowa State Univ., Ames, IA (United States)

    1995-11-03

    Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) has found wise use in catalysis, including the epoxidation and metathesis of olefins, aldehyde olefination, and oxygen transfer. Extensive reports have now appeared in the area of MTO-catalyzed substrate oxidations with hydrogen peroxide. Certain catalytic applications of MTO for organic reactions that do not utilize peroxide have now been realized. In particular, a catalytic amount of MTO with ethyl diazoacetate (EDA) will convert aromatic imines to aziridines and convert aldehydes and ketones to epoxides. The aziridine preparation proceeds in high yields under anaerobic conditions more conveniently than with existing methods. Compounds with a three-membered heterocyclic ring can be obtained with the EDA/MTO catalytic system. Aromatic imines undergo cycloaddition reactions to give aziridines under mild conditions.

  7. Highly Efficient Catalytic Cyclic Carbonate Formation by Pyridyl Salicylimines.

    Science.gov (United States)

    Subramanian, Saravanan; Park, Joonho; Byun, Jeehye; Jung, Yousung; Yavuz, Cafer T

    2018-03-21

    Cyclic carbonates as industrial commodities offer a viable nonredox carbon dioxide fixation, and suitable heterogeneous catalysts are vital for their widespread implementation. Here, we report a highly efficient heterogeneous catalyst for CO 2 addition to epoxides based on a newly identified active catalytic pocket consisting of pyridine, imine, and phenol moieties. The polymeric, metal-free catalyst derived from this active site converts less-reactive styrene oxide under atmospheric pressure in quantitative yield and selectivity to the corresponding carbonate. The catalyst does not need additives, solvents, metals, or co-catalysts, can be reused at least 10 cycles without the loss of activity, and scaled up easily to a kilogram scale. Density functional theory calculations reveal that the nucleophilicity of pyridine base gets stronger due to the conjugated imines and H-bonding from phenol accelerates the reaction forward by stabilizing the intermediate.

  8. Iminoboronate Formation Leads to Fast and Reversible Conjugation Chemistry of α-Nucleophiles at Neutral pH.

    Science.gov (United States)

    Bandyopadhyay, Anupam; Gao, Jianmin

    2015-10-12

    Bioorthogonal reactions that are fast and reversible under physiological conditions are in high demand for biological applications. Herein, it is shown that an ortho boronic acid substituent makes aryl ketones rapidly conjugate with α-nucleophiles at neutral pH. Specifically, 2-acetylphenylboronic acid and derivatives were found to conjugate with phenylhydrazine with rate constants of 10(2) to 10(3) M(-1) s(-1) , comparable to the fastest bioorthogonal conjugations known to date. (11) B NMR analysis revealed the varied extent of iminoboronate formation of the conjugates, in which the imine nitrogen forms a dative bond with boron. The iminoboronate formation activates the imines for hydrolysis and exchange, rendering these oxime/hydrazone conjugations reversible and dynamic under physiological conditions. The fast and dynamic nature of the iminoboronate chemistry should find wide applications in biology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Effect of medium acidity on the thermodynamics and kinetics of the reaction of pyridoxal 5'-phosphate with isoniazid in an aqueous solution

    Science.gov (United States)

    Gamov, G. A.; Zavalishin, M. N.; Usacheva, T. R.; Sharnin, V. A.

    2017-05-01

    Thermodynamic characteristics of the formation of the Schiff base between isoniazid and pyridoxal 5'-phosphate in an aqueous solution at different pH values of a medium are determined by means of spectrophotometry and calorimetric titration. The process kinetics is studied spectrophotometrically, and the reaction rate constants for the formation of the imine at different acidities of a medium are determined. Biochemical aspects of the binding of pyridoxal 5'-phosphate into stable compounds are discussed.

  10. Crystal and Molecular Structure of 2-Aminoacetophenone-N(3)-dimethylthiosemicarbazone

    OpenAIRE

    Nassar, Amal A.; Hernández-Ortega, Simón; Valdés-Martínez, Jesús; West, Douglas X.

    2002-01-01

    Condensation of N(3)-dimethylthiosemicarbazide with 2-aminoacetophenone in anhydrous ethanol produces 2-aminoacetophenone-N(3)-dimethylthiosemicarbazone, 1, which is planar with the S1 and N1 atoms in a syn conformation. The amino group forms a bifurcated intramolecular hydrogen bond with the sulfur and the imine nitrogen, and an intermolecular hydrogen bond with the thione sulfur of a second molecule. La condensación de la N(3)-dimetiltiosemicarbazida con la 2-aminoacetofenona en etanol a...

  11. Bromido(2-{1-[2-(morpholin-4-yl)ethylimino]ethyl}phenolato)copper(II)

    OpenAIRE

    Xiao-Fan Zhao; Fang Li

    2010-01-01

    In the title complex, [CuBr(C14H19N2O2)], the CuII atom is coordinated by one phenolate O, one imine N and one amine N atom of the tridentate Schiff base ligand and by one bromide ion, resulting in a distorted CuBrN2O square-planar geometry, with the N atoms in a cis arrangement. The morpholine ring adopts a chair conformation.

  12. Bromido(2-{1-[2-(piperidin-1-yl)ethyl?imino]?eth?yl}phenolato)copper(II)

    OpenAIRE

    Zhao, Xiao-Fan; Li, Fang

    2010-01-01

    In the title complex, [CuBr(C15H21N2O)], the CuII atom is coordinated by one phenolate O, one imine N and one amine N atom of the tridentate Schiff base ligand and by one bromide ion, resulting in a distorted CuBrN2O square-planar geometry for the metal ion, with the N atoms in a cis conformation.

  13. Synthesis of polyhydroxylated compounds from Derythrose: enzymatic inhibition studies

    OpenAIRE

    Noro, Jennifer Martins

    2015-01-01

    Dissertação de mestrado em Química Medicinal This thesis is divided into two parts. At first, two starting synthon compounds were obtained: the benzylidene acetal D-erythrose aldehyde and the unsaturated lactone derived from this aldehyde. Both compounds were obtained following methods reported in the literature. The first part of the work focuses on aldehyde reactions with different primary aliphatic amines, yielding the respective imines. These were reduced to afford the ...

  14. Base-Mediated Generation of Ketenimines from Ynamides: Direct Access to Azetidinimines by an Imino-Staudinger Synthesis.

    Science.gov (United States)

    Romero, Eugénie; Minard, Corinne; Benchekroun, Mohamed; Ventre, Sandrine; Retailleau, Pascal; Dodd, Robert H; Cariou, Kevin

    2017-09-21

    Ynamides were used as precursors for the in situ generation of highly reactive ketenimines that could be trapped with imines in a [2+2] cycloaddition. This imino-Staudinger synthesis led to a variety of imino-analogs of β-lactams, namely azetidinimines (20 examples), that could be further functionalized through a broad range of transformations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Valuable fenugreek (Trigonella foenum-graecum L.) mutants induced by gamma rays and alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Floria, F [Biotechnology and Molecular Genetics Group, ' Stejarul' Research Centre for Biological Sciences, Piatra Neamt (Romania); Ichim, M C [Biotechnology and Molecular Genetics Group, ' Stejarul' Research Centre for Biological Sciences, Piatra Neamt (Romania)

    2006-12-15

    Seeds of fenugreek (Trigonella foenum-graecum L.) were treated with either gamma rays (25-15 kR) or ethyl methanesulphonate (EMS 0.1-0.5%, 2h) or ethylene imine (EI, 0.01- 0.1%, 2h). After repeated selection for better morphological performance from M{sub 2} to M{sub 4} generation, 11 mutant lines were identified with better yield potential and higher diosgenin content than their parent. (author)

  16. Peeter Kreitzberg : võtame vaestelt lapsed ära! / Peeter Kreitzberg ; interv. Helen Urbanik

    Index Scriptorium Estoniae

    Kreitzberg, Peeter, 1948-2011

    2001-01-01

    Endine haridusminister tuli märtsi keskel konverentsil "Teine võimalus hariduses" välja ettepanekuga, et lastele peaks koolis käimine olema kohustuslik 18. eluaastani, riigi pansionidesse ja internaatidesse tuleks panna need lapsed, kelle pered ei jaksa neid üleval pidada. Autori täiendus 3. mai Eesti Ekspressi kirjade rubriigis (lk. A6) pealkirja all: Pakkusin vanematele võimalust, mitte vaeste laste konfiskeerimist. Autor: Keskerakond. Parlamendisaadik

  17. A Highly Efficient Catalyst for Oxime Ligation and Hydrazone-Oxime Exchange Suitable for Bioconjugation

    OpenAIRE

    Rashidian, Mohammad; Mahmoodi, Mohammad M.; Shah, Rachit; Dozier, Jonathan K.; Wagner, Carston R.; Distefano, Mark D.

    2013-01-01

    Imine-based reactions are useful for a wide range of bioconjugation applications. Although aniline is known to catalyze the oxime ligation reaction under physiological conditions, it suffers from slow reaction kinetics, specifically when a ketone is being used or when hydrazone-oxime exchange is performed. Here, we report on the discovery of a new catalyst that is up to 15 times more efficient than aniline. That catalyst, m-phenylenediamine (mPDA), was initially used to analyze the kinetics o...

  18. Heavy metal contamination in the environs of the Zn-pB Mine in North-West of Tunisia

    International Nuclear Information System (INIS)

    Ben Guirat, S.; Ben Aissa, N.; Mhiri, A.

    2009-01-01

    The impact of industrial heavy metals (HM) pollution on soil quality and plant growth has become a public concern. To evaluate heavy metals concentration a Zn-Pb mine site was selected, as source of pollution, localized in BouGrine (BG) region at 120 km North-west of Tunis characterized by calcareous soils. Soils of the imine site are occupied by forest pine. (Author)

  19. In silico design of supramolecules from their precursors: odd-even effects in cage-forming reactions.

    Science.gov (United States)

    Jelfs, Kim E; Eden, Edward G B; Culshaw, Jamie L; Shakespeare, Stephen; Pyzer-Knapp, Edward O; Thompson, Hugh P G; Bacsa, John; Day, Graeme M; Adams, Dave J; Cooper, Andrew I

    2013-06-26

    We synthesize a series of imine cage molecules where increasing the chain length of the alkanediamine precursor results in an odd-even alternation between [2 + 3] and [4 + 6] cage macrocycles. A computational procedure is developed to predict the thermodynamically preferred product and the lowest energy conformer, hence rationalizing the observed alternation and the 3D cage structures, based on knowledge of the precursors alone.

  20. Synthesis of 2,5-Disubstituted Octahydroquinolin-4-ones via anIntramolecular Hetero Diels-Alder Reaction

    Directory of Open Access Journals (Sweden)

    J. Antonio Palenzuela

    2007-02-01

    Full Text Available A route for the preparation of 2,5-disubstituted octahydroquinolin-4-ones, synthetic precursors of the decahydroquinoline-type toxins, is presented. The key steps are an asymmetric epoxidation and an intramolecular hetero Diels-Alder reaction between an activated diene and an imine. The presence of an allylic stereogenic center induces some selectivity and thus only two cycloadducts are obtained in 70:30 ratio and good yield.

  1. Photo-patterning of non-fouling polymers and biomolecules on paper

    Czech Academy of Sciences Publication Activity Database

    Tischer, T.; Rodriguez-Emmenegger, Cesar; Trouillet, V.; Welle, A.; Schueler, V.; Mueller, J. O.; Goldmann, A. S.; Brynda, Eduard; Barner-Kowollik, C.

    2014-01-01

    Roč. 26, č. 24 (2014), s. 4087-4092 ISSN 0935-9648 R&D Projects: GA ČR GAP205/12/1702; GA MŠk(CZ) LH13178; GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:61389013 Keywords : bioactive paper * micropatterning * nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) Subject RIV: CD - Macromolecular Chemistry Impact factor: 17.493, year: 2014

  2. 3-[(2,4-Dichlorophenyliminomethyl]-2-hydroxy-5-methylbenzaldehyde

    Directory of Open Access Journals (Sweden)

    Işın Kılıç

    2009-06-01

    Full Text Available The title compound, C15H11Cl2NO2, is a Schiff base which adopts the phenol–imine tautomeric form in the solid state, being stabilized by a strong intramolecular O—H...N hydrogen bond. The molecule is almost planar (r.m.s. deviation for all non-H atoms = 0.049 Å, displaying a dihedral angle of 3.1 (3° between the planes of the two aromatic rings.

  3. A review exploring biological activities of hydrazones

    Directory of Open Access Journals (Sweden)

    Garima Verma

    2014-01-01

    Full Text Available The development of novel compounds, hydrazones has shown that they possess a wide variety of biological activities viz. antimicrobial, anticonvulsant, antidepressant, anti-inflammatory, analgesic, antiplatelet, antimalarial, anticancer, antifungal, antitubercular, antiviral, cardio protective etc., Hydrazones/azomethines/imines possess-NHN = CH- and constitute an important class of compounds for new drug development. A number of researchers have synthesized and evaluated the biological activities of hydrazones. This review aims at highlighting the diverse biological activities of hydrazones.

  4. Optimal income taxation with endogenous participation and search unemployment

    OpenAIRE

    Lehmann, Etienne; Parmentier, Alexis; van der Linden, Bruno

    2011-01-01

    This paper characterizes the optimal redistributive taxation when individuals are hetero- geneous in two exogenous dimensions: their skills and their values of non-market activities. Search-matching frictions on the labor markets create unemployment. Wages, labor demand and participation are endogenous. The government only observes wage levels. Under a Max- imin objective, if the elasticity of participation decreases along the distribution of skills, at the optimum, the average tax rate is in...

  5. Synthesis, characterization and thermogravimetric study of zinc and cadmium acetates-polyaniline hybrids

    International Nuclear Information System (INIS)

    Fernandes de Farias, Robson

    2004-01-01

    By dissolution of respective acetates and conducting polymer in dimethylformamide, homogeneous zinc acetate and cadmium acetate-polyaniline (PANI) hybrids were synthesized and characterized by infrared spectroscopy, thermogravimetry and SEM microscopy. The infrared spectra suggests that there are interactions between PANI and the metal cations involving both, imine and amine nitrogens in a typical Lewis acid-base reaction. The thermogravimetric degradation profile of the synthesized hybrids resembles those exhibited by PANI samples

  6. Electrospun complexes - functionalised nanofibres

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, T.; Wolf, M.; Dreyer, B.; Unruh, D.; Krüger, C.; Menze, M. [Leibniz University Hannover, Institute of Inorganic Chemistry (Germany); Sindelar, R. [University of Applied Science Hannover, Faculty II (Germany); Klingelhöfer, G. [Gutenberg-University, Institute of Inorganic and Analytic Chemistry (Germany); Renz, F., E-mail: renz@acd.uni-hannover.de [Leibniz University Hannover, Institute of Inorganic Chemistry (Germany)

    2016-12-15

    Here we present a new approach of using iron-complexes in electro-spun fibres. We modify poly(methyl methacrylate) (PMMA) by replacing the methoxy group with Diaminopropane or Ethylenediamine. The complex is bound covalently via an imine-bridge or an amide. The resulting polymer can be used in the electrospinning process without any further modifications in method either as pure reagent or mixed with small amounts of not functionalised polymer resulting in fibres of different qualities (Fig. 1).

  7. A Stress Test to Evaluate the Physical Capacity of Performing L-1 Anti-G Straining Maneuvers

    Science.gov (United States)

    1988-09-01

    similar to hyperventilation can produce respiratory alkalosis . Therefore, lowered G-tolerance may result from decreased cerebral blood flow. Another...VE), respiratory exchange ratio (RER) and heart rate (HR were determined for steady state exercise at AGSM duty cyclEs cf 2,, 215%, 33% and 50%. Thesc...V02, ml/kg/min), minute pulmonary ventilation (VE, I/min) and respiratory exchange ratio (RER, VCO 2/VO2) at each duty cycle of discontinuous AGSM

  8. Degradable conjugated polymers for the selective sorting of semiconducting carbon nanotubes

    Science.gov (United States)

    Gopalan, Padma; Arnold, Michael Scott; Kansiusarulsamy, Catherine Kanimozhi; Brady, Gerald Joseph; Shea, Matthew John

    2018-04-10

    Conjugated polymers composed of bi-pyridine units linked to 9,9-dialkyl fluorenyl-2,7-diyl units via imine linkages along the polymer backbone are provided. Also provided are semiconducting single-walled carbon nanotubes coated with the conjugated polymers and methods of sorting and separating s-SWCNTs from a sample comprising a mixture of s-SWCNTs and metallic single-walled carbon nanotubes using the conjugated polymers.

  9. Synthesis, structure and study of azo-hydrazone tautomeric equilibrium of 1,3-dimethyl-5-(arylazo)-6-amino-uracil derivatives

    Science.gov (United States)

    Debnath, Diptanu; Roy, Subhadip; Li, Bing-Han; Lin, Chia-Her; Misra, Tarun Kumar

    2015-04-01

    Azo dyes, 1,3-dimethyl-5-(arylazo)-6-aminouracil (aryl = -C6H5 (1), -p-CH3C6H4 (2), -p-ClC6H4 (3), -p-NO2C6H4 (4)) were prepared and characterized by UV-vis, FT-IR, 1H NMR, 13C NMR spectroscopic techniques and single crystal X-ray crystallographic analysis. In the light of spectroscopic analysis it evidences that of the tautomeric forms, the azo-enamine-keto (A) form is the predominant form in the solid state whereas in different solvents it is the hydrazone-imine-keto (B) form. The study also reveals that the hydrazone-imine-keto (B) form exists in an equilibrium mixture with its anionic form in various organic solvents. The solvatochromic and photophysical properties of the dyes in various solvents with different hydrogen bonding parameter were investigated. The dyes exhibit positive solvatochromic property on moving from polar protic to polar aprotic solvents. They are fluorescent active molecules and exhibit high intense fluorescent peak in some solvents like DMSO and DMF. It has been demonstrated that the anionic form of the hydrazone-imine form is responsible for the high intense fluorescent peak. In addition, the acid-base equilibrium in between neutral and anionic form of hydrazone-imine form in buffer solution of varying pH was investigated and evaluated the pKa values of the dyes by making the use of UV-vis spectroscopic methods. The determined acid dissociation constant (pKa) values increase according to the sequence of 2 > 1 > 3 > 4.

  10. Controlled cell adhesion on poly(dopamine) interfaces photopatterned with non-fouling brushes

    Czech Academy of Sciences Publication Activity Database

    Rodriguez-Emmenegger, C.; Preuss, C. M.; Yameen, B.; Pop-Georgievski, Ognen; Bachmann, M.; Mueller, J. O.; Bruns, M.; Goldmann, A. S.; Bastmeyer, M.; Barner-Kowollik, C.

    2013-01-01

    Roč. 25, č. 42 (2013), s. 6123-6127 ISSN 0935-9648 R&D Projects: GA ČR GAP205/12/1702; GA ČR GAP106/12/1451; GA ČR GAP108/11/1857 Institutional support: RVO:61389013 Keywords : micropatterning * nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) * photoligation Subject RIV: CD - Macromolecular Chemistry Impact factor: 15.409, year: 2013

  11. preparation, spectroscopic studies and x-ray structure of ...

    African Journals Online (AJOL)

    Administrator

    interest in this chemistry is stimulated by their low toxicity, their potential uses as diagnostic tools in biology and their .... C=O) and imine (C=N) bonds and a band at 1018 cm-1 is characteristic of N-N vibrations. In the .... due to the O-H stretching vibration of the phenolic groups and the non-coordinated water molecules [14].

  12. Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

    Science.gov (United States)

    Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

    2016-12-19

    We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Carbamoyl anion-initiated cascade reaction for stereoselective synthesis of substituted α-hydroxy-β-amino amides.

    Science.gov (United States)

    Lin, Chao-Yang; Ma, Peng-Ju; Sun, Zhao; Lu, Chong-Dao; Xu, Yan-Jun

    2016-01-18

    A carbamoyl anion-initiated cascade reaction with acylsilanes and imines has been used to rapidly construct substituted α-hydroxy-β-amino amides. The Brook rearrangement-mediated cascade allows the formation of two C-C bonds and one O-Si bond in a single pot. Using this approach, a range of α-aryl α-hydroxy-β-amino amides has been synthesized in high yields with excellent diastereoselectivities.

  14. One-pot, two-step synthesis of imidazo[1,2-a]benzimidazoles via a multicomponent [4 + 1] cycloaddition reaction.

    Science.gov (United States)

    Hsiao, Ya-Shan; Narhe, Bharat D; Chang, Ying-Sheng; Sun, Chung-Ming

    2013-10-14

    A one-pot, two-step synthesis of imidazo[1,2-a]benzimidazoles has been achieved by a three-component reaction of 2-aminobenzimidazoles with an aromatic aldehyde and an isocyanide. The reaction involving condensation of 2-aminobenzimidazole with an aldehyde is run under microwave activation to generate an imine intermediate under basic conditions which then undergoes [4 + 1] cycloaddition with an isocyanide.

  15. 5-Diethylamino-2-[(E-(2,4-dimethoxyphenyliminomethyl]phenol

    Directory of Open Access Journals (Sweden)

    Esen Nur Kantar

    2012-06-01

    Full Text Available The title Schiff base, C19H24N2O3, exists in the crystal structure in the phenol–imine tautomeric form with an intramolecular O—H...N hydrogen bond. The planes of the aromatic rings form a dihedral angle of 36.8 (8°. The crystal packing is characterized by C—H...O hydrogen bonds and π–π stacking interactions [centroid–centroid distance = 3.478 (4Å].

  16. A modular approach to neutral P,N-ligands: synthesis and coordination chemistry

    Directory of Open Access Journals (Sweden)

    Vladislav Vasilenko

    2016-04-01

    Full Text Available We report the modular synthesis of three different types of neutral κ2-P,N-ligands comprising an imine and a phosphine binding site. These ligands were reacted with rhodium, iridium and palladium metal precursors and the structures of the resulting complexes were elucidated by means of X-ray crystallography. We observed that subtle changes of the ligand backbone have a significant influence on the binding geometry und coordination properties of these bidentate P,N-donors.

  17. Supramolecular Influence on Keto-Enol Tautomerism and Thermochromic Properties of o-Hydroxy Schiff Bases

    Directory of Open Access Journals (Sweden)

    Marija Zbačnik

    2016-06-01

    Full Text Available This work presents a study on thermo-optical properties of three Schiff bases (imines in the solid state. The Schiff bases were obtained by means of mechanochemical synthesis using monosubstituted o-hydroxy aromatic aldehydes and monosubstituted aromatic amines. The keto-enol tautomerism and proton transfer via intramolecular O∙∙∙N hydrogen bond of the reported compounds was found to be influenced more by supramolecular interactions than by a temperature change. All products were characterised by powder X-ray diffraction (PXRD, FT-IR spectroscopy, thermogravimetric (TG analysis and differential scanning calorimetry (DSC. Molecular and crystal structures of compounds 1, 2 and 3 were determined by single crystal X-ray diffraction (SCXRD. The molecules of 1 appear to be present as the enol-imine, the molecules of 2 as the keto-amine tautomer and the molecules of 3 exhibit keto-enol tautomeric equilibrium in the solid state. An analysis of Cambridge structural database (CSD data on similar imines has been used for structural comparison. This work is licensed under a Creative Commons Attribution 4.0 International License.

  18. 3-{(E-[4-(4-Hydroxy-3-methoxyphenylbutan-2-ylidene]amino}-1-phenylurea: crystal structure and Hirshfeld surface analysis

    Directory of Open Access Journals (Sweden)

    Ming Yueh Tan

    2018-01-01

    Full Text Available Two independent molecules (A and B comprise the asymmetric unit of the title compound, C18H21N3O3. The urea moiety is disubstituted with one amine being linked to a phenyl ring, which is twisted out of the plane of the CN2O urea core [dihedral angles = 25.57 (11 (A and 29.13 (10° (B]. The second amine is connected to an imine (E conformation, which is linked in turn to an ethane bridge that links a disubstituted benzene ring. Intramolecular amine-N—H...N(imine and hydroxyl-O—H...O(methoxy hydrogen bonds close S(5 loops in each case. The molecules have twisted conformations with the dihedral angles between the outer rings being 38.64 (81 (A and 48.55 (7° (B. In the crystal, amide-N—H...O(amide hydrogen bonds link the molecules A and B via an eight-membered {...HNCO}2 synthon. Further associations between molecules, leading to supramolecular layers in the ac plane, are hydrogen bonds of the type hydroxyl-O—H...N(imine and phenylamine-N—H...O(methoxy. Connections between layers, leading to a three-dimensional architecture, comprise benzene-C—H...O(hydroxy interactions. A detailed analysis of the calculated Hirshfeld surfaces shows molecules A and B participate in very similar intermolecular interactions and that any variations relate to conformational differences between the molecules.

  19. Chemical structure of the adducts formed by the oxidation of benzidine in the presence of phenols

    International Nuclear Information System (INIS)

    Josephy, P.D.; Mason, R.P.; Eling, T.

    1982-01-01

    Bioactivation of carcinogens by peroxidases has received increasing attention since the discovery of the oxidation of carcinogens by prostaglandin hydroperoxidase. Benzidine and 3,5,3',5'-tetramethylbenzidine are oxidized by horseradish peroxidase and prostaglandin synthase to two-electron oxidation products (di-imines). Di-imines readily react with the phenolic anti-oxidant butylated hydroxyanisole to form adducts. In this paper, we have studied the oxidation of benzidine by horseradish peroxidase in the presence of phenolic compounds and characterized the resultant benzidine/phenol adducts. A benzidine/2,6-dimethylphenol adduct was isolated and characterized by mass spectrometry and high field n.m.r. The reaction of [ 14 C]benzidine in the presence of horseradish peroxidase and phenol yielded only the benzidine/phenol adduct. Our results indicate that the benzidine/phenol adducts are analogous to the indoaniline dyes, differing only in substitution of a biphenyl group for a benzene ring. The reaction of benzidine di-imine with endogenous phenols may represent a new pathway for detoxication, removing potentially harmful metabolites of benzidine

  20. Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents

    Directory of Open Access Journals (Sweden)

    Gennari Cesare

    1998-01-01

    Full Text Available We have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of synthetic importance. The force field model was used to assist the design and preparation of new chiral boron ligands derived from menthone. The chiral boron enolates were employed in various stereoselective processes, including the addition to chiral aldehydes and the reagent-controlled total synthesis of (3S,4S-statine. The chiral enolates derived from alpha-halo and alpha-oxysubstituted thioacetates were added to aldehydes and imines. Addition to imines leads to the enantioselective synthesis of chiral aziridines, a formal total synthesis of (+-thiamphenicol, and a new highly efficient synthesis of the paclitaxel (taxol® C-13 side-chain and taxol semisynthesis from baccatin III. The stereochemical outcome of the addition to imines was rationalised with the aid of computational studies. Enantioselective addition reactions of the chiral boron enolate derived from thioacetate have successfully been applied to solid phase bound aldehydes to give aldol products in comparable yields and enantioselectivities to the usual solution conditions.

  1. 15N NMR investigation of the covalent binding of reduced TNT amines to soil humic acid, model compounds, and lignocellulose

    Science.gov (United States)

    Thorn, K.A.; Kennedy, K.R.

    2002-01-01

    The five major reductive degradation products of TNT-4ADNT (4-amino-2,6-dinitrotoluene), 2ADNT (2-amino-4,6-dinitrotoluene), 2,4DANT (2,4-diamino-6-nitrotoluene), 2,6DANT (2,6-diamino-4-nitrotoluene), and TAT (2,4,6-triaminotoluene)-labeled with 15N in the amine positions, were reacted with the IHSS soil humic acid and analyzed by 15N NMR spectrometry. In the absence of catalysts, all five amines underwent nucleophilic addition reactions with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and nonheterocyclic condensation products. Imine formation via 1,2-addition of the amines to quinone groups in the soil humic acid was significant with the diamines and TAT but not the monoamines. Horseradish peroxidase (HRP) catalyzed an increase in the incorporation of all five amines into the humic acid. In the case of the diamines and TAT, HRP also shifted the binding away from heterocyclic condensation product toward imine formation. A comparison of quantitative liquid phase with solid-state CP/MAS 15N NMR indicated that the CP experiment underestimated imine and heterocyclic nitrogens in humic acid, even with contact times optimal for observation of these nitrogens. Covalent binding of the mono- and diamines to 4-methylcatechol, the HRP catalyzed condensation of 4ADNT and 2,4DANT to coniferyl alcohol, and the binding of 2,4DANT to lignocellulose with and without birnessite were also examined.

  2. Crystal structure of {(R-N2-[(benzo[h]quinolin-2-ylmethyl]-N2′-[(benzo[h]quinolin-2-ylmethylidene]-1,1′-binaphthyl-2,2′-diamine-κ4N,N′,N′′,N′′′}(trifluoromethanesulfonato-κOzinc(II} trifluoromethanesulfonate dichloromethane 1.5-solvate

    Directory of Open Access Journals (Sweden)

    Shayna R. Skokan

    2017-07-01

    Full Text Available The zinc(II atom in the title compound, [Zn(C48H31N4(CF3SO3](CF3SO3·1.5CH2Cl2, adopts a distorted five-coordinate square-pyramidal geometry. It is coordinated by one trifluoromethanesulfonate ligand and four N atoms of the N2-[(benzo[h]quinolin-2-ylmethyl]-N2′-[(benzo[h]quinolin-2-ylmethylidene]-1,1′-binaphthyl-2,2′-diamine ligand. The complex is present as a single-stranded P-helimer monohelical structure incorporating π–π and/or σ–π interactions. One of the imine bonds present in the original ligand framework is reduced, leading to variations in bond lengths and torsion angles for each side of the ligand motif. The imine-bond reduction also affects the bond lengths involving the metal atom with the N-donor atoms located on the imine bond. There are two molecules of the complex in the asymmetric unit. One of the molecules exhibits positional disorder within the coordinating trifluoromethanesulfonate ion making the molecules symmetrically non-equivalent.

  3. H-shaped supra-amphiphiles based on a dynamic covalent bond.

    Science.gov (United States)

    Wang, Guangtong; Wang, Chao; Wang, Zhiqiang; Zhang, Xi

    2012-10-16

    The imine bond, a kind of dynamic covalent bond, is used to bind two bolaform amphiphiles together with spacers, yielding H-shaped supra-amphiphiles. Micellar aggregates formed by the self-assembly of the H-shaped supra-amphiphiles are observed. When pH is tuned down from basic to slightly acidic, the benzoic imine bond can be hydrolyzed, leading to the dissociation of H-shaped supra-amphiphiles. Moreover, H-shaped supra-amphiphiles have a lower critical micelle concentration than their building blocks, which is very helpful in enhancing the stability of the benzoic imine bond being hydrolyzed by acid. The surface tension isotherms of the H-shaped supra-amphiphiles with different spacers indicate their twisty conformation at a gas-water interface. The study of H-shaped supra-amphiphiles can enrich the family of amphiphiles, and moreover, the pH-responsiveness may make them apply to controlled or targetable drug delivery in a biological environment.

  4. Synthesis of New 4-Aminoquinolines and Evaluation of Their In Vitro Activity against Chloroquine-Sensitive and Chloroquine-Resistant Plasmodium falciparum.

    Directory of Open Access Journals (Sweden)

    Chandima S K Rajapakse

    Full Text Available The efficacy of chloroquine, once the drug of choice in the fight against Plasmodium falciparum, is now severely limited due to widespread resistance. Amodiaquine is one of the most potent antimalarial 4-aminoquinolines known and remains effective against chloroquine-resistant parasites, but toxicity issues linked to a quinone-imine metabolite limit its clinical use. In search of new compounds able to retain the antimalarial activity of amodiaquine while circumventing quinone-imine metabolite toxicity, we have synthesized five 4-aminoquinolines that feature rings lacking hydroxyl groups in the side chain of the molecules and are thus incapable of generating toxic quinone-imines. The new compounds displayed high in vitro potency (low nanomolar IC50, markedly superior to chloroquine and comparable to amodiaquine, against chloroquine-sensitive and chloroquine-resistant strains of P. falciparum, accompanied by low toxicity to L6 rat fibroblasts and MRC5 human lung cells, and metabolic stability comparable or higher than that of amodiaquine. Computational studies indicate a unique mode of binding of compound 4 to heme through the HOMO located on a biphenyl moeity, which may partly explain the high antiplasmodial activity observed for this compound.

  5. Proton transfers in the Strecker reaction revealed by DFT calculations

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2014-08-01

    Full Text Available The Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT calculations for the first time, which involves two reaction stages. In the first reaction stage, the aminonitrile was formed. The rate-determining step is the deprotonation of the NH3+ group in MeCH(OH-NH3+ to form 1-aminoethanol, which occurs with an activation energy barrier (ΔE≠ of 9.6 kcal/mol. The stereochemistry (R or S of the aminonitrile product is determined at the NH3 addition step to the carbonyl carbon of the aldehyde. While the addition of CN− to the carbon atom of the protonated imine 7 appears to scramble the stereochemistry, the water cluster above the imine plane reinforces the CN− to attack the imine group below the plane. The enforcement hinders the scrambling. In the second stage, the aminonitrile transforms to alanine, where an amide Me-CH(NH2-C(=O-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the cyano group of N(amino-protonated aminonitrile which occurs with an ΔE≠ value of 34.7 kcal/mol. In the Strecker reaction, the proton transfer along the hydrogen bonds plays a crucial role.

  6. Sintesis Ramah Lingkungan Senyawa Imina Turunan Vanilin dan 2-Hidroksi Asetofenon Serta Uji Aktivitas Biologi dan Antioksidan

    Directory of Open Access Journals (Sweden)

    Putri Pratiwi

    2015-04-01

    Full Text Available Eco-friendly synthesis of imine derivative compound from 2-hydroxy acetophenone and vanillin had been conducted by using a method of stirring (with stirrer in a water solvent. The whole experiment began with the synthesis of imine compounds, followed by purification and characterization of the synthesis products and finally analysis on their biological and antioxidant activities. The experiments showed that imine compounds could be synthesized by a chemical reaction of 4-amino antipirin aqueous solution with 2-hydroxy acetophenone and vanillin at magnetic stirrer speed of 250 and 450 rpm, respectively, which produced product A, (E-4-(1-(2-hydroxyphenyl ethylideneamino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H-one and product B, (E-4-(4-hydroxy-3-(vinyloxy benzylideneamino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H-one. Yield percentage (% obtained from the synthesis of product A and B were 40.68% and 19.76% respectively. Toxicity and antioxidant activity tests showed that the product B were toxic and more active as an antioxidant than product A. While the antibacterial activity test showed that both products had a response to Staphyllococcus aureus bacteria and Escherechia coli bacteria.

  7. Preparation of Chitosan-based Injectable Hydrogels and Its Application in 3D Cell Culture.

    Science.gov (United States)

    Li, Yongsan; Zhang, Yaling; Wei, Yen; Tao, Lei

    2017-09-29

    The protocol presents a facile, efficient, and versatile method to prepare chitosan-based hydrogels using dynamic imine chemistry. The hydrogel is prepared by mixing solutions of glycol chitosan with a synthesized benzaldehyde terminated polymer gelator, and hydrogels are efficiently obtained in several minutes at room temperature. By varying ratios between glycol chitosan, polymer gelator, and water contents, versatile hydrogels with different gelation times and stiffness are obtained. When damaged, the hydrogel can recover its appearances and modulus, due to the reversibility of the dynamic imine bonds as crosslinkages. This self-healable property enables the hydrogel to be injectable since it can be self-healed from squeezed pieces to an integral bulk hydrogel after the injection process. The hydrogel is also multi-responsive to many bio-active stimuli due to different equilibration statuses of the dynamic imine bonds. This hydrogel was confirmed as bio-compatible, and L929 mouse fibroblast cells were embedded following standard procedures and the cell proliferation was easily assessed by a 3D cell cultivation process. The hydrogel can offer an adjustable platform for different research where a physiological mimic of a 3D environment for cells is profited. Along with its multi-responsive, self-healable, and injectable properties, the hydrogels can potentially be applied as multiple carriers for drugs and cells in future bio-medical applications.

  8. Simulation of the oxidative metabolism of diclofenac by electrochemistry/(liquid chromatography/)mass spectrometry.

    Science.gov (United States)

    Faber, Helene; Melles, Daniel; Brauckmann, Christine; Wehe, Christoph Alexander; Wentker, Kristina; Karst, Uwe

    2012-04-01

    Diclofenac is a frequently prescribed drug for rheumatic diseases and muscle pain. In rare cases, it may be associated with a severe hepatotoxicity. In literature, it is discussed whether this toxicity is related to the oxidative phase I metabolism, resulting in electrophilic quinone imines, which can subsequently react with nucleophiles present in the liver in form of glutathione or proteins. In this work, electrochemistry coupled to mass spectrometry is used as a tool for the simulation of the oxidative pathway of diclofenac. Using this purely instrumental approach, diclofenac was oxidized in a thin layer cell equipped with a boron doped diamond working electrode. Sum formulae of generated oxidation products were calculated based on accurate mass measurements with deviations below 2 ppm. Quinone imines from diclofenac were detected using this approach. It could be shown for the first time that these quinone imines do not react with glutathione exclusively but also with larger molecules such as the model protein β-lactoglobulin A. A tryptic digest of the generated drug-protein adduct confirms that the protein is modified at the only free thiol-containing peptide. This simple and purely instrumental set-up offers the possibility of generating reactive metabolites of diclofenac and to assess their reactivity rapidly and easily.

  9. AĞ TOPLUMUNUN İLETİŞİMİ EKSENİNDE YEREL YÖNETİMLERİN SOSYAL MEDYA KULLANIM DÜZEYİ: KADIKÖY BELEDİYESİ ÖRNEĞİ

    Directory of Open Access Journals (Sweden)

    Alper DEĞERLİ

    2016-08-01

    Full Text Available Yeni iletişim ortamlarının sunduğu sayısız olanaklar sayesinde ağ toplumu formunda yeniden şekillenen insanoğlu, bu yeni yapıdaki ilişkiler düzeninin değişimine de tanıklık etmektedir. Etki bağlamındaki kitle iletişim yorumlamalarından etkileşimin ön planda olduğu yatay iletişime doğru bir yol alıştır bu. Bu noktada kamusal iletişimin bu değişimden bağımsız kalacağını düşünmek olanaksızdır. Parasosyal etkileşimin yeniden tanımlandığı, kitle iletişimin monolojik yapısından diyalojik iletişime doğru geçildiği bu yeni kamu-yönetim ilişkisinde kamunun rolü de edilgenden etkene doğru evrilmektedir. Ağ toplumunun kamusal alanları olarak karşımıza çıkan sosyal ağlar vasıtasıyla yönetim ile kamu arasındaki ilişki yeniden yorumlanmakta, kamu kısıtlı da olsa erişebilirlik ve hesap sorabilirlik hakkına yeniden yaklaşabilmektedir.Bu çalışma kapsamında; bireylerde çok daha hızlı gerçeklesen bu zihinsel dönüşümün kamu kurumları açısından doğru yorumlanıp yorumlanmadığı sorusuna, Twitter sosyal ağı üzerinde İstanbul ilçe belediyeleri arasında açık ara en fazla takipçiye sahip belediye olan Kadıköy belediyesi özelinde cevaplar aranmaya çalışılmıştır.

  10. Facile Synthesis of Well-Defined MDMO-PPV Containing (TriBlock—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

    Directory of Open Access Journals (Sweden)

    Neomy Zaquen

    2015-02-01

    Full Text Available A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene (PPV materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ·mol−1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC. PPVs with molecular weights ranging from thousands to ten thousands g·mol−1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark–Houwink–Kuhn–Sakurada (MHKS parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy]-1,4-phenylenevinylene to α = 0.809 and k = 0.00002 mL·g−1. Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP. In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene-block-poly(tert-butyl acrylate-block-poly(ethylene glycol (PPV-b-PtBuA-b-PEG.

  11. Two novel bioactive glucosinolates from Broccoli (Brassica oleracea L. var. italica) florets.

    Science.gov (United States)

    Survay, Nazneen Shaik; Kumar, Brajesh; Jang, Mi; Yoon, Do-Young; Jung, Yi-Sook; Yang, Deok-Chun; Park, Se Won

    2012-09-01

    Two novel glucosinolates along with one known glucosinolate were isolated from Broccoli (Brassica oleracea L. var. italica) florets. Their structures were established mainly by 1D ((1)H and (13)C NMR), 2D NMR ((1)H-(1)H COSY, DEPT 135°, HSQC and HMBC), and Tandem MS-MS spectrometric data as 2-mercaptomethyl sulfinyl glucosinolate [(Z)-4-(methylsulfinyl)-N-(sulfooxy)-2-((2'S,3'R,4'S,5'S,6'R)-3',4',5'-trihydroxy-6'(hydroxylmethyl)-2'-mercapto tetrahydro-2H-pyran-2-yl) butane amide] 1, (Z)-1-((2S,5S)-5-hydroxytetra-hydro-2H-pyran-2-ylthio)-2-(1H-indol-3-yl) ethylidene amino sulfate 2 and a known cinnamoyl [6'-O-trans-(4″-hydroxy cinnamoyl)4-(methylsulphinyl)butyl glucosinolate] 3. Compound 1 exhibited scavenging activity against DPPH with an inhibitory concentration IC(50) of 20 mM, whereas compound 3 was a weak antioxidant when compared to the standard quercetin (5 mM) as a positive control. Both the compounds showed a significant and similar antimicrobial activity against Staphylococcus aureus with an IC(50) of <625 μg/mL when compared to antibiotic duricef. Against Salmonella typhimurium the IC(50) of 1 and 3 was determined as <625 μg/mL and <1250 μg/mL, respectively, when compared to ampicillin (IC(50) ≤ 39 μg/mL) as a positive control. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. Determination of chiral pharmaceuticals and illicit drugs in wastewater and sludge using microwave assisted extraction, solid-phase extraction and chiral liquid chromatography coupled with tandem mass spectrometry.

    Science.gov (United States)

    Evans, Sian E; Davies, Paul; Lubben, Anneke; Kasprzyk-Hordern, Barbara

    2015-07-02

    This is the first study presenting a multi-residue method allowing for comprehensive analysis of several chiral pharmacologically active compounds (cPACs) including beta-blockers, antidepressants and amphetamines in wastewater and digested sludge at the enantiomeric level. Analysis of both the liquid and solid matrices within wastewater treatment is crucial to being able to carry out mass balance within these systems. The method developed comprises filtration, microwave assisted extraction and solid phase extraction followed by chiral liquid chromatography coupled with tandem mass spectrometry to analyse the enantiomers of 18 compounds within all three matrices. The method was successfully validated for 10 compounds within all three matrices (amphetamine, methamphetamine, MDMA, MDA, venlafaxine, desmethylvenlafaxine, citalopram, metoprolol, propranolol and sotalol), 7 compounds validated for the liquid matrices only (mirtazapine, salbutamol, fluoxetine, desmethylcitalopram, atenolol, ephedrine and pseudoephedrine) and 1 compound (alprenolol) passing the criteria for solid samples only. The method was then applied to wastewater samples; cPACs were found at concentration ranges in liquid matrices of: 1.7 ng L(-1) (metoprolol) - 1321 ng L(-1) (tramadol) in influent, non-racemic composition. Furthermore, enantiomeric composition of studied analytes differed in liquid and solid matrices. This demonstrates that not analysing the solid fraction of wastewater may lead to over-estimation of the removal rates of cPACs as well as possible misrepresentation of the enantiomeric fraction of the compounds as they leave the wastewater treatment plant. Consequently risks from cPACs entering the environment might be higher than

  13. Synthesis and reactions of cyclovalence isomers of azo-keto-carbenes

    International Nuclear Information System (INIS)

    Rettenbacher, A.S.

    2001-09-01

    Novel types of cycloaddition products with an azomethine imine functionality have been prepared from ω-azo-α'-diazo ketones with a carbon chain of variable length between the azo- and the keto-group; the reaction is induced by catalytical amounts of rhodium(II) acetate and occurs with the concomitant extrusion of dinitrogen. The synthesis of these cyclic azomethine imines succeeded in the course of the intramolecular reaction of the azo nitrogen atoms with a carbene/carbenoid carbon atom, in situ generated from the α-diazoketone functionality; this is a novel cyclization reaction. Some of the resulting cyclization products are stable and have been isolated, others could only be trapped with dipolarophiles as [3+2] cycloadducts. The ring-size of the heterocyclic products depends on the one hand on the length of the carbon-chain (for n = 0, 1, 2) between the carbonyl carbon atom and the quaternary aliphatic or aromatic carbon atom that blocks the tautomerization of the azo-group in the starting material. On the other hand, the ring size depends on which of the two nitrogen atoms of the azo-group undergoes the ring closure with the carbene/carbenoid carbon atom generated from the α-diazoketon functionality in the course of the reaction. By far the most serious problem in the preparation of the cyclic azomethine imines is the synthesis of the required ω-azo-α'-diazo ketones. A so far unknown property of the azo-group is its intramolecularly directed nucleophilicity toward ketenes, which emerge from acid chlorides and anhydrides, or from α-diazo ketones in the course of the Wolff rearrangement. This complicated the approach to the required ω-azo-α'-diazo ketones via these functionalities as precursors and with the desired chain length between the azo- and diazo-keto-groups. Nevertheless, these problems could be overcome by using alternative strategies. Utilizing ω-azo-α'-diazo ketones a largely commonly applicable approach to endocyclic and N

  14. Semi-Targeted Analysis of Complex Matrices by ESI FT-ICR MS or How an Experimental Bias may be Used as an Analytical Tool

    Science.gov (United States)

    Hertzog, Jasmine; Carré, Vincent; Dufour, Anthony; Aubriet, Frédéric

    2018-03-01

    Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H]-. Nevertheless, NH3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous CxHyOz bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. [Figure not available: see fulltext.

  15. Tautomerism in quinoxalines derived from the 1,4-naphthoquinone nucleus: acid mediated synthesis, X-ray molecular structure of 5-chlorobenzo[f]quinoxalin-6-ol and density functional theory calculations

    International Nuclear Information System (INIS)

    Gomez, Javier A.G.; Lage, Mateus R.; Carneiro, Jose Walkimar de M.; Resende, Jackson A.L.C.; Vargas, Maria D.

    2013-01-01

    The reaction of tert-butyl 2-(3-chloro-1,4-dioxo-1,4-dihydronaphthalen-2-ylamino) ethylcarbamate with CF 3 COOH/CH 2 Cl 2 yields 5-chloro-3,4-dihydrobenzo[f]quinoxalin-6(2H)-one which undergoes acid-promoted dehydrogenation in the presence of water to give novel 5-chlorobenzo[f]quinoxalin-6-ol. The molecular structure of 5-chlorobenzo[f]quinoxalin-6-ol in the solid state, determined by an X-ray diffraction (XRD) study, and the solution data confirm that it exists as the enol-imine tautomer, both in the solid state and in solution, differently from 5-chloro-3,4-dihydrobenzo[f]quinoxalin-6(2H)-one, which exhibits the keto-amine arrangement. Density functional theory (DFT) calculations confirmed the preference of 5-chlorobenzo[f]quinoxalin-6-ol and of the derivatives containing H and CH 3 groups in place of the Cl atom for the enol-imine tautomer. It is suggested that the enol-imine structure is preferred for 5-chlorobenzo[f]quinoxalin-6-ol as a consequence of the higher aromatic character of this structure in comparison with the keto-amine form. DFT calculations carried out on the two tautomers of the benzo[a]phenazin-5(7H)-ones analogous to the benzo[f]quinoxalin-6(4H)-ones showed that the relative stabilities are dominated by solvation effects in the first case and the degree of aromaticity, in the latter. (author)

  16. Experimental and theoretical studies on tautomeric structures of a newly synthesized 2,2‧(hydrazine-1,2-diylidenebis(propan-1-yl-1-ylidene))diphenol

    Science.gov (United States)

    Karakurt, Tuncay; Cukurovali, Alaaddin; Subasi, Nuriye Tuna; Onaran, Abdurrahman; Ece, Abdulilah; Eker, Sıtkı; Kani, Ibrahim

    2018-02-01

    In the present study, a single crystal of a Schiff base, 2,2‧(hydrazine-1,2-diylidenebis(propan-1-yl-1-ylidene))diphenol, was synthesized. The structure of the synthesized crystal was confirmed by 1H and 13C NMR spectroscopic and X-ray diffraction analysis techniques. Experimental and theoretical studies were carried out on two tautomeric structures. It has been observed that the title compound studied can be in two different tautomeric forms, phenol-imine and keto-amine. Theoretical calculations have been performed to support experimental results. Accordingly, the geometric parameters of the compound were optimized by the density functional theory (DFT) method using the Gaussian 09 and Quantum Espresso (QE) packet program was used for periodic boundary conditions (PBC) studies. Furthermore, the compound was also tested for in vitro antifungal activity against Sclerotinia sclerotiorum, Alternaria solani, Fusarium oxysporum f. sp. lycopersici and Monilinia fructigena plant pathogens. Promising inhibition profiles were observed especially towards A. solani. Finally, molecular docking studies and post-docking procedure based on Molecular Mechanics-Generalized Born Surface Area (MM-GBSA) were also carried out to get insight into the compound's binding interactions with the potential. Although theoretical calculations showed that the phenol-imine form was more stable, keto-amine form was predicted to have better binding affinity which was concluded to result from loss of rotational entropy in phenol-imine upon binding. The results obtained here from both experimental and computational methods might serve as a potential lead in the development of novel anti-fungal agents.

  17. Determination of NH2 concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

    Science.gov (United States)

    Manakhov, Anton; Čechal, Jan; Michlíček, Miroslav; Shtansky, Dmitry V.

    2017-08-01

    The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH2 groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH2/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH2 fraction ∼8.5%. This value is closely matching the NH2/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH2/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA derivatization is probably related to the side reaction of benzaldehydes with conjugated imines, the proposed IFA derivatization of primary amines can be an alternative procedure for the quantification of surface amine groups.

  18. Graphene-poly aniline by oxidative electro polymerization

    International Nuclear Information System (INIS)

    Pa-a, Jonathan E.; Enriquez, Erwin P.

    2013-01-01

    In this work , the photochemically synthesized NH 2 - graphene is doped with poly aniline through oxidative electro polymerization to form the NH 2 -graphene/poly aniline composites. These composites with varying amounts of NH 2 -graphene are investigated using Fourier Transform-infrared (FTIR) spectroscopy, ultraviolet-visible (UV)absorption spectroscopy , scanning electron microscopy (SEM-EDX), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and electrochemical measurements. FTIR analysis strongly suggests incorporation of NH 2 -graphene sheets on poly aniline via imine (C=N) formation. UV/visible analysis of composites containing varying amounts of NH 2 -graphene in PANI shows different extent of modification on the oxidation state of the emeraldine base form to leuco emeraldine form of the PANI chain segments with possible formation of imine (C=N) units at other positions of the aniline ring in the composite, Time evolution UV/visible spectra by UV-irradiation of composites tend to proceed further with imine and phenazine-like microstructure formation. TEM and SEM images show patterns on aggregation of regular to deformed fibers surrounding planar surfaces which may indicate interior surface of NH 2 -graphene sheets not being grafted with polymers. Improved thermal stability of poly aniline in the presence of minimum amount of NH 2 -graphene sheets further confirms structural transformation within the microstructures. Electrochemical measurements by cyclic voltammetry show enhanced capacitive behavior relative to pure poly aniline. The route of synthesis using NH 2 -graphene and poly aniline offers a simple but controlled synthetic route for electrochemical doping and welding of N-containing heterocyclic structures onto pristine graphene sheets for possible use in sensing and energy storage applications. (author)

  19. Distinguishing tautomerism in the crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide using DFT-D calculations and {sup 13}C solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaozhou; Bond, Andrew D.; Johansson, Kristoffer E.; Van de Streek, Jacco, E-mail: jacco.vandestreek@sund.ku.dk [Department of Pharmacy, University of Copenhagen, Universitetsparken 2, Copenhagen DK-2100 (Denmark)

    2014-08-01

    The crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide contains an imine tautomer, rather than the previously reported amine tautomer. The tautomers can be distinguished using dispersion-corrected density functional theory calculations and by comparison of calculated and measured {sup 13}C solid-state NMR spectra. The crystal structure of the title compound, C{sub 11}H{sub 13}N{sub 3}O{sub 2}S{sub 2}, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated {sup 13}C solid-state NMR spectra [Hangan et al. (2010 ▶). Acta Cryst. B66, 615–621]. The mol@@ecule is tautomeric, and was reported as an amine tautomer [systematic name: N-(5-ethyl-1,3,4-thia@@diazol-2-yl)-p-toluene@@sulfonamide], rather than the correct imine tautomer. The protonation site on the mol@@ecule’s 1,3,4-thia@@diazole ring is indicated by the inter@@molecular contacts in the crystal structure: N—H⋯O hydrogen bonds are established at the correct site, while the alternative protonation site does not establish any notable inter molecular inter@@actions. The two tautomers provide essentially identical Rietveld fits to laboratory PXRD data, and therefore they cannot be directly distinguished in this way. However, the correct tautomer can be distinguished from the incorrect one by previously reported qu@@anti@@tative criteria based on the extent of structural distortion on optimization of the crystal structure using dispersion-corrected density functional theory (DFT-D) calculations. Calculation of the {sup 13}C SS-NMR spectrum based on the correct imine tautomer also provides considerably better agreement with the measured {sup 13}C SS-NMR spectrum.

  20. Prorocentrolide-A from Cultured Prorocentrum lima Dinoflagellates Collected in Japan Blocks Sub-Types of Nicotinic Acetylcholine Receptors

    Directory of Open Access Journals (Sweden)

    Muriel Amar

    2018-02-01

    Full Text Available Prorocentrolides are members of the cyclic imine phycotoxins family. Their chemical structure includes a 26-membered carbo-macrocycle and a 28-membered macrocyclic lactone arranged around a hexahydroisoquinoline that incorporates the characteristic cyclic imine group. Six prorocentrolides are already known. However, their mode of action remains undetermined. The aim of the present work was to explore whether prorocentrolide-A acts on nicotinic acetylcholine receptors (nAChRs, using competition-binding assays and electrophysiological techniques. Prorocentrolide-A displaced [125I]α-bungarotoxin binding to Torpedo membranes, expressing the muscle-type (α12β1γδ nAChR, and in HEK-293 cells, expressing the chimeric chick neuronal α7-5HT3 nAChR. Functional studies revealed that prorocentrolide-A had no agonist action on nAChRs, but inhibited ACh-induced currents in Xenopus oocytes that had incorporated the muscle-type α12β1γδ nAChR to their membranes, or that expressed the human α7 nAChR, as revealed by voltage-clamp recordings. Molecular docking calculations showed the absence of the characteristic hydrogen bond between the iminium group of prorocentrolide-A and the backbone carbonyl group of Trp147 in the receptor, explaining its weaker affinity as compared to all other cyclic imine toxins. In conclusion, this is the first study to show that prorocentrolide-A acts on both muscle and neuronal nAChRs, but with higher affinity on the muscle-type nAChR.

  1. Cyclometalation and coupling of a rigid 4,5-bis(imino)acridanide pincer ligand on yttrium.

    Science.gov (United States)

    Wong, Edwin W Y; Emslie, David J H

    2015-07-07

    An extremely rigid NNN-donor proligand, 4,5-bis{(diphenylmethylene)amino}-2,7,9,9-tetramethylacridan, H[AIm2] was prepared in five steps starting from 5-methyl-2-aminobenzoic acid and 4-bromotoluene. Reaction of intensely orange H[AIm2] with LiCH2SiMe3 formed deep blue Li(x)[AIm2]x (x = 2 in the solid state), while reaction with [Y(CH2SiMe3)3(THF)2] (0.5 equiv.) afforded deep blue [Y(AIm2)(AIm)] (1; AIm = an AIm2 ligand cyclometalated at the ortho-position of one of the phenyl rings). Compound 1 slowly isomerizes to form green-brown 2, which contains a single trianionic, hexadentate ligand that features one amine, two imine, and three amido donors. The acridanide backbone and one imine group in each of the original AIm2 ligands is intact, but the two acridanide backbones are now linked by an isoindoline heterocycle. Yttrium in 2 is coordinated to six nitrogen donors and the ortho carbon of an isoindoline phenyl substituent. The intense colours of H[AIm2], Li(x)[AIm2]x and 1 were shown by TD-DFT calculations to arise from charge transfer transitions from the HOMO, which is localized on the acridanide ligand backbone, to the LUMO and LUMO+1, which are localized on the imine substituents. The conversion of 1 to 2 was studied by UV-Visible absorption spectroscopy and is first-order with a half-life of 7.8 hours at room temperature.

  2. Tautomerism in quinoxalines derived from the 1,4-naphthoquinone nucleus: acid mediated synthesis, X-ray molecular structure of 5-chlorobenzo[f]quinoxalin-6-ol and density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, Javier A.G.; Lage, Mateus R.; Carneiro, Jose Walkimar de M.; Resende, Jackson A.L.C.; Vargas, Maria D., E-mail: mdvargas@vm.uff.br, E-mail: walk@vm.uff.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Instituto de Quimica

    2013-02-15

    The reaction of tert-butyl 2-(3-chloro-1,4-dioxo-1,4-dihydronaphthalen-2-ylamino) ethylcarbamate with CF{sub 3}COOH/CH{sub 2}Cl{sub 2} yields 5-chloro-3,4-dihydrobenzo[f]quinoxalin-6(2H)-one which undergoes acid-promoted dehydrogenation in the presence of water to give novel 5-chlorobenzo[f]quinoxalin-6-ol. The molecular structure of 5-chlorobenzo[f]quinoxalin-6-ol in the solid state, determined by an X-ray diffraction (XRD) study, and the solution data confirm that it exists as the enol-imine tautomer, both in the solid state and in solution, differently from 5-chloro-3,4-dihydrobenzo[f]quinoxalin-6(2H)-one, which exhibits the keto-amine arrangement. Density functional theory (DFT) calculations confirmed the preference of 5-chlorobenzo[f]quinoxalin-6-ol and of the derivatives containing H and CH{sub 3} groups in place of the Cl atom for the enol-imine tautomer. It is suggested that the enol-imine structure is preferred for 5-chlorobenzo[f]quinoxalin-6-ol as a consequence of the higher aromatic character of this structure in comparison with the keto-amine form. DFT calculations carried out on the two tautomers of the benzo[a]phenazin-5(7H)-ones analogous to the benzo[f]quinoxalin-6(4H)-ones showed that the relative stabilities are dominated by solvation effects in the first case and the degree of aromaticity, in the latter. (author)

  3. The ozonolysis of primary aliphatic amines in single and multicomponent fine particles

    Science.gov (United States)

    Zahardis, J.; Geddes, S.; Petrucci, G. A.

    2007-10-01

    The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2- and NO3- ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitro alkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3-(HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10-7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides was shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10-3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g. NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

  4. The ozonolysis of primary aliphatic amines in fine particles

    Science.gov (United States)

    Zahardis, J.; Geddes, S.; Petrucci, G. A.

    2008-02-01

    The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2- and NO3- ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3- (HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10-7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10-3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

  5. New donor-acceptor-donor molecules based on quinoline acceptor unit with Schiff base bridge: synthesis and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Kotowicz, Sonia [Institute of Chemistry, University of Silesia, 9 Szkolna Street, 40-006 Katowice (Poland); Siwy, Mariola [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland); Filapek, Michal; Malecki, Jan G. [Institute of Chemistry, University of Silesia, 9 Szkolna Street, 40-006 Katowice (Poland); Smolarek, Karolina; Grzelak, Justyna; Mackowski, Sebastian [Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, 5 Grudziadzka Str., 87-100 Torun (Poland); Slodek, Aneta, E-mail: aneta.slodek@us.edu.pl [Institute of Chemistry, University of Silesia, 9 Szkolna Street, 40-006 Katowice (Poland); Schab-Balcerzak, Ewa, E-mail: ewa.schab-balcerzak@us.edu.pl [Institute of Chemistry, University of Silesia, 9 Szkolna Street, 40-006 Katowice (Poland); Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland)

    2017-03-15

    Three solution-processable small organic molecules bearing quinoline as electron-accepting moiety were synthesized via condensation reaction of novel 6-amino-2-(2,2’-bithiophen-5-yl)-4-phenylquinoline with 2,2’-bithiophene-5-carboxaldehyde, 9-ethyl-9H-carbazole-3-carbaldehyde and 9-phenanthrenecarboxaldehyde. The presence of alternating electron-donating and accepting units results in a donor-acceptor-donor architecture of these molecular systems. Thermal, photophysical, and electrochemical properties of these small molecules were examined and the experimental results were supported by the density functional theory calculations. The obtained molecular systems exhibited high thermal stability with decomposition temperatures (5% weight loss) exceeding 330 °C in nitrogen atmosphere. It was found, based on DSC measurements, that investigated Schiff bases form amorphous material with glass transition temperatures between 88 and 190 °C. They also showed a UV–vis absorption in the range of 250–500 nm both in solution and in solid state as film and blend with PMMA and PVK. Photoluminescence measurements revealed moderately strong blue-light emission of the imines in solution as well as in PMMA blend with quantum yields in the range of 2–26%. In the case of imines dispersed in PVK matrix the emission of green light was mainly observed. In addition, when mixed with plasmonically active silver nanowires, the compounds exhibit relatively strong electroluminescence signal, associated with plasmonics enhancement, as evidenced by high-resolution photoluminescence imaging. The energy band gap estimated based on cyclic voltammetry was between 2.38 and 2.61 eV. - Highlights: • New Schiff bases possess donor-acceptor-imine-bridge-donor architecture were synthesized and examined. • Thorough characterization of optical and electrochemical properties of novel Schiff bases has been carried out. • Optical and electrochemical measurements were compared with DFT

  6. The ozonolysis of primary aliphatic amines in fine particles

    Directory of Open Access Journals (Sweden)

    J. Zahardis

    2008-02-01

    Full Text Available The oxidative processing by ozone of the particulate amines octadecylamine (ODA and hexadecylamine (HDA is reported. Ozonolysis of these amines resulted in strong NO2 and NO3 ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3 (HNO3. For ozonized mixed particles containing ODA or HDA + oleic acid (OL, with pO3≥3×10–7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines and stabilized Criegee intermediates (SCI or secondary ozonides (for amides from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10−3 atm for 17 s. This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3, formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

  7. Cross-linking by protein oxidation in the rapidly setting gel-based glues of slugs

    Science.gov (United States)

    Bradshaw, Andrew; Salt, Michael; Bell, Ashley; Zeitler, Matt; Litra, Noelle; Smith, Andrew M.

    2011-01-01

    SUMMARY The terrestrial slug Arion subfuscus secretes a glue that is a dilute gel with remarkable adhesive and cohesive strength. The function of this glue depends on metals, raising the possibility that metal-catalyzed oxidation plays a role. The extent and time course of protein oxidation was measured by immunoblotting to detect the resulting carbonyl groups. Several proteins, particularly one with a relative molecular mass (Mr) of 165×103, were heavily oxidized. Of the proteins known to distinguish the glue from non-adhesive mucus, only specific size variants were oxidized. The oxidation appears to occur within the first few seconds of secretion. Although carbonyls were detected by 2,4-dinitrophenylhydrazine (DNPH) in denatured proteins, they were not easily detected in the native state. The presence of reversible cross-links derived from carbonyls was tested for by treatment with sodium borohydride, which would reduce uncross-linked carbonyls to alcohols, but stabilize imine bonds formed by carbonyls and thus lead to less soluble complexes. Consistent with imine bond formation, sodium borohydride led to a 20–35% decrease in the amount of soluble protein with a Mr of 40–165 (×103) without changing the carbonyl content per protein. In contrast, the nucleophile hydroxylamine, which would competitively disrupt imine bonds, increased protein solubility in the glue. Finally, the primary amine groups on a protein with a Mr of 15×103 were not accessible to acid anhydrides. The results suggest that cross-links between aldehydes and primary amines contribute to the cohesive strength of the glue. PMID:21525316

  8. Selectivity in inter polymer complexation involving phenolic copolymer, poly electrolytes, non-ionic polymers and transition metal ions

    International Nuclear Information System (INIS)

    Vasheghani Farahani, B.; Hosseinpour Rajabi, F.

    2006-01-01

    Selectivity in inter polymer complex formation involving a typical four-component phenolic copolymer (ρ-chloro phenol-ρ-aminophenol-ρ-toluidine-ρ-cresol- HCHO copolymer), poly electrolytes such as polyethylene imine and polyacrylic acid, a non-ionic homopolymer polyvinyl pyrrolidone, and some transition metal ions (e.g., Cu (II), Ni (11)) have been studied in dimethylformamide-methanol solvents mixture. The coordinating groups of phenolic copolymer form complexes through hydrogen bonding and ion-dipole interactions. The different stages of interactions have been studied by several experimental techniques, e.g., viscometry, potentiometry and conductometry. Some schemes have been suggested to explain the mode of interaction between these components

  9. Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

    Directory of Open Access Journals (Sweden)

    Patrícia M. Dias

    2010-01-01

    Full Text Available Herein, the immobilization of some Schiff base-copper(II complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

  10. Festivais Matsuris como referencial cultural e turístico da etnia japonesa em Curitiba (Paraná, Brasil

    Directory of Open Access Journals (Sweden)

    Miguel Bahl

    2013-12-01

    Full Text Available O artigo trata sobre Matsuris, festivais da etnia japonesa realizados na cidade de Curitiba, Paraná (Brasil. É um estudo de caso de caráter descritivo com a intenção de resgatar parte do histórico de imigração japonesa no Brasil, a fim de perceber a importância dos festivais Matsuris como referencial da etnia e como forma de inserção social do grupo na capital paranaense. Utilizando pesquisa bibliográfica, busca eletrônica e observação direta intensiva, o estudo traz como resultado a descrição dos três festivais mais importantes da etnia na cidade (Hana Matsuri, Imin Matsuri e Haru Matsuri, demonstrando a relação dos mesmos como referencial étnico japonês e a apresentação do resultado de pesquisa de campo empreendida em 2009, junto ao Hana Matsuri e ao Imin Matsuri. Também evidencia a importância da existência de produtos étnicos culturais para um grupo de imigrantes, principalmente em uma capital cosmopolita como Curitiba, que contemplem o significado real de sua cultura, sem que se tornem apenas um bem de consumo.  Matsuris Festivals as cultural and turistic benchmark of japonese ethnicity in Curitiba (Paraná, Brazil. The article discusses about the Matsuris, Japanese ethnic festivals realized in Curitiba, Paraná (Brazil. It is a descriptive case study that intends to briefly redeem part of the history of Japanese immigration in Brazil, in order to understand the importance of Matsuris festivals as an ethnic referential and as a kind of social insertion of the group at the capital of Paraná. Using literature search, electronic search and intensive direct observation, the study results in a description of the three most important festivals of the ethnic group in the city (Hana Matsuri, Imin Matsuri and Haru Matsuri, showing their relation as an ethnic Japanese referential and showing the result from the field research applied in 2009, during the Hana Matsuri and Imin Matsuri Festivals. It also highlights the

  11. 1-[(E-(3-Hydroxy-4-methoxybenzylideneamino]-3-methylthiourea

    Directory of Open Access Journals (Sweden)

    Md. Azharul Arafath

    2016-10-01

    Full Text Available In the title thiosemicarbazone Schiff base compound, C10H13N3O2S, the dihedral angle between the benzene ring and methyl carbothioamide side arm was found to be 17.4 (4°. The presence of two intramolecular hydrogen bonds is noted, namely hydroxy-O—H...O(methoxy and amine-N—H...N(imine. In the crystal, pairwise amine-N—H...S hydrogen bonds give rise to centrosymmetric {...HNCS}2 synthons, which lead to dimeric aggregates.

  12. A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3(2H-furanones

    Directory of Open Access Journals (Sweden)

    Jubi John

    2014-06-01

    Full Text Available A facile route towards highly functionalized 3(2H-furanones via a sequential Mannich addition–palladium catalyzed ring closing has been elaborated. The reaction of 4-chloroacetoacetate esters with imines derived from aliphatic and aromatic aldehydes under palladium catalysis afforded 4-substituted furanones in good to excellent yields. 4-Hydrazino-3(2H-furanones could also be synthesized from diazo esters in excellent yields by utilising the developed strategy. We could also efficiently transform the substituted furanones to aza-prostaglandin analogues.

  13. Protestos pela ótica do Google Glass: uma análise das potencialidades de amplificação da vigilância do cidadão │ Protests seen through Google Glass: an analysis of potential amplification of citizen surveillance

    OpenAIRE

    Eduardo Campos Pellanda

    2014-01-01

    RESUMO O contexto da mobilidade da informação inaugurou uma nova perspectiva para diferentes formas de protestos. Agora, com a iminência de produtos comerciais que fazem parte de uma categoria chamada “computação de vestir”, ou wearables, temos novos debates de potencialidades. Este texto usa como exemplo desta categoria o Google Glass que está em testes por diversas pessoas e deve se tornar um produto comercial em breve. O artigo analisa os protestos e manifestações urbanas no contexto da mo...

  14. A Short Synthetic Route to the Calystegine Alkaloids

    DEFF Research Database (Denmark)

    Skaanderup, Philip Robert; Madsen, Robert

    2003-01-01

    An efficient strategy is described for the synthesis of enantiopure calystegine alkaloids. The key step employs a zinc-mediated fragmentation of benzyl-protected methyl 6-iodo-glycosides followed by in situ formation of the benzyl imine and Barbier-type allylation with zinc, magnesium, or indium...... metal. Stereochemistry in the pivotal allylation is controlled by the choice of the metal. The functionalized 1,8-nonadienes, thus formed, are converted into cycloheptenes by ring-closing metathesis. Regioselective hydroboration and oxidation give the corresponding cycloheptanones, which are deprotected...

  15. Detecting Hidden Hierarchy of Non Hierarchical Terrorist Networks

    DEFF Research Database (Denmark)

    Memon, Nasrullah

    measures (and combinations of them) to identify key players (important nodes) in terrorist networks. Our recently introduced techniques and algorithms (which are also implemented in the investigative data mining toolkit known as iMiner) will be particularly useful for law enforcement agencies that need...... to analyze terrorist networks and prioritize their targets. Applying recently introduced mathematical methods for constructing the hidden hierarchy of "nonhierarchical" terrorist networks; we present case studies of the terrorist attacks occurred / planned in the past, in order to identify hidden hierarchy...

  16. A turn-on indole-based sensor for hydrogen sulfate ion.

    Science.gov (United States)

    Wan, Chin-Feng; Yang, Shih-Tse; Lin, Hsiang-Yi; Chang, Ya-Ju; Wu, An-Tai

    2014-08-01

    A simple indole-based receptor 1 was prepared by a simple Schiff-base reaction of 1H-indole-3-carbaldehyde with ethane 1,2-diamine and its fluoroionophoric properties toward anions were investigated. Indole-based receptor 1 acts as a selective turn-on fluorescent sensor for HSO4(-) in methanol among a series of tested anions. Fluorescence spectroscopy, ultraviolet and nuclear magnetic resonance imaging support that the HSO4(-) indeed interacted with imine nitrogen and the proton of nitrogen in indole ring. Copyright © 2013 John Wiley & Sons, Ltd.

  17. Macrocyclic effects upon isomeric Cu M and M Cu cores. Formation ...

    Indian Academy of Sciences (India)

    Administrator

    from the iminic site to the aminic site in the synthesis of 10 is explained by ... Our previous studies suggest that isomeric MIICuII ... Calcd. for C24H27Br2ClCuN4NiO8: C 35⋅28; H 3⋅33; N 6⋅86; Cu 7⋅78; Ni .... Electronic absorption spectra in .... 3. 1497(1). 1452. ⋅3(5). 2992(1). 1860(2). 3206(1). Z. 2. 2. 4. 2. 4. D calcd. /g.

  18. The synthesis of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides by the microwave-assisted Pudovik reaction

    Directory of Open Access Journals (Sweden)

    Erika Bálint

    2017-01-01

    Full Text Available A family of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides was synthesized by the microwave-assisted solvent-free addition of dialkyl phosphites and diphenylphosphine oxide, respectively, to imines formed from benzaldehyde derivatives and primary amines. After optimization, the reactivity was mapped, and the fine mechanism was evaluated by DFT calculations. Two α-aminophosphonates were subjected to an X-ray study revealing a racemic dimer formation made through a N–H···O=P intermolecular hydrogen bridges pair.

  19. Bis({tris[2-(3,5-di-tert-butyl-2-oxidobenzylideneaminoethyl]amine}cerium(III diethyl ether solvate

    Directory of Open Access Journals (Sweden)

    Peter Dröse

    2010-11-01

    Full Text Available The title compound, 2[Ce(C51H75N4O3]·C4H10O, was obtained in high yield (92% by reduction of (TRENDSALCeIVCl [TRENDSAL is N,N′,N′′-tris(3,5-di-tert-butylsalicylidenatoaminotriethylamine] with potassium in THF. The bulky tripodal TRENDSAL ligand effectively encapsulates the central CeIII cation with a Ce—N(imine distance of 2.860 (2 Å and an average C—N(amine distance of 2.619 Å within a distorted monocapped octahedral coordination.

  20. Effects of scallop shell extract on scopolamine-induced memory impairment and MK801-induced locomotor activity

    OpenAIRE

    HASEGAWA, Yasushi; INOUE, Tatsuro; KAWAMINAMI, Satoshi; FUJITA, Miho

    2016-01-01

    ObjectiveTo evaluate the neuroprotective effects of the organic components of scallop shells (scallop shell extract) on memory impairment and locomotor activity induced by scopolamine or 5-methyl-10,11-dihydro-5H-dibenzo (a,d) cyclohepten-5,10-imine (MK801).MethodsEffect of the scallop shell extract on memory impairment and locomotor activity was investigated using the Y-maze test, the Morris water maze test, and the open field test.ResultsScallop shell extract significantly reduced scopolami...

  1. Copper hexacyanoferrate formation on the modified silica surface with DAB-Am-16 dendrimer

    International Nuclear Information System (INIS)

    Carmo, Devaney R. do; Gabriel Junior, Suelino; Bicalho, Urquisa O.; Paim, Leonardo L.

    2009-01-01

    The dendrimer hexadecamine poly(propylene)imine (DAB-Am-16) of third generation (G-3) was anchored on the silica gel surface. The modified silica interact easily with Cu 2+ and then with hexacyanoferrate to form copper hexacyanoferrate. The modified silica was characterized by following techniques: nuclear magnetic resonance (NMR), infrared (FTIR), energy dispersive X-ray (EDX) and cyclic voltammetry. As application of the composite obtained, the modified silica containing copper hexacyanoferrate (CuHCFSD) was tested for a voltammetric determination of nitrite using a graphite paste modified electrode. The modified graphite paste electrode can be applied also to the determination of others biological substances with success. (author)

  2. A Base Promoted Synthesis of N,N-dimethylformamidines

    International Nuclear Information System (INIS)

    Li, Bao Lin; Ding, Si Yi; Ren, Yu Fei; Wang, Liu Chang; Jia, Yu Cai; Zhang, Xi Quan; Gu, Hong Mei

    2013-01-01

    In conclusion, this report supplies a base promoted synthesis of N'-aryl-N,N-dimethylformamidines straight from arylamines bearing strong electron withdrawing group at o-position and imine complex from DMF and Me 2 SO 4 . The key advantage of the procedure is to avoid the preparation of N,N-dimethylformamide dimethyl acetal from DMF and Me 2 SO 4 . Using this method, some important intermediates shown as entry 1-4, 9-11 in Table 3 were efficiently prepared. With these intermediates in hand, various antitumor drugs containing quinazoline moiety such as gefitinib, erlotinib and lapatinib etc. can be synthesized conveniently

  3. Quantum chemical study of penicillin: Reactions after acylation

    Science.gov (United States)

    Li, Rui; Feng, Dacheng; Zhu, Feng

    The density functional theory methods were used on the model molecules of penicillin to determine the possible reactions after their acylation on ?-lactamase, and the results were compared with sulbactam we have studied. The results show that, the acylated-enzyme tetrahedral intermediate can evolves with opening of ?-lactam ring as well as the thiazole ring; the thiazole ring-open products may be formed via ?-lactam ring-open product or from tetrahedral intermediate directly. Those products, in imine or enamine form, can tautomerize via hydrogen migration. In virtue of the water-assisted, their energy barriers are obviously reduced.

  4. A Highly Stereocontrolled, One-Pot Approach toward Pyrrolobenzoxazinones and Pyrroloquinazolinones through a Lewis Acid-Catalyzed [3 + 2]-Cycloannulation Process.

    Science.gov (United States)

    Boomhoff, Michael; Ukis, Rostyslav; Schneider, Christoph

    2015-08-21

    We report herein a stereocontrolled [3 + 2]-cycloheteroannulation of bis-silyl dienediolate 1 with 2-aminobenzoic acid- and 2-aminobenzamide-derived imines to furnish highly substituted pyrrolo[1,2-a]benzoxazinones 3 and pyrrolo[1,2-a]quinazolinones 4, respectively, in good overall yields. This one-pot process rapidly generates molecular complexity and comprises a Lewis acid-catalyzed, vinylogous Mannich reaction of 1 followed by an intramolecular N,O-acetal- and N,N-aminal formation, respectively, which proceeds with good to excellent stereocontrol.

  5. Hydrogen atom in momentum space with a minimal length

    International Nuclear Information System (INIS)

    Bouaziz, Djamil; Ferkous, Nourredine

    2010-01-01

    A momentum representation treatment of the hydrogen atom problem with a generalized uncertainty relation, which leads to a minimal length ΔX imin =(ℎ/2π)√(3β+β ' ), is presented. We show that the distance squared operator can be factorized in the case β ' =2β. We analytically solve the s-wave bound-state equation. The leading correction to the energy spectrum caused by the minimal length depends on √(β). An upper bound for the minimal length is found to be about 10 -9 fm.

  6. The effect of dendrimer on cotton dyeability with direct dyes

    Directory of Open Access Journals (Sweden)

    Khakzar Bafrooei F.

    2014-01-01

    Full Text Available Pretreatment of cotton fabric with poly(propylene imine dendrimer enhanced its colour strength using C.I. Direct Red 81 and C.I. Direct Blue 78. Application of this dendrimer and the direct dye simultaneously on cotton fabric by the exhaust and the continuous dyeing method were studied; slight improvements in the dyeing results were obtained. Pretreatment of the cotton fabric with dendrimer in an emulsion form using the pad-dry method followed by continuous dyeing markedly increased the colour strength. In addition, level dyeing was obtained, and no negative effects on the fastness properties of the dyes used were observed.

  7. C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

    OpenAIRE

    Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

    2012-01-01

    We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexib...

  8. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond

    2013-01-01

    l-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  9. 1,2,3,3-Tetramethyl-7-nitro-3,4-dihydroisoquinolinium tetrafluoroborate

    Directory of Open Access Journals (Sweden)

    Mouna Bouzid

    2016-04-01

    Full Text Available The title salt, C13H17N2O2+·BF4−, was prepared by the methylation of the imine with Meerwein salt in dichloromethane. The asymmetric unit comprises a 1,3,3-trimethyl-7-nitro-3,4-dihydroisoquinolinium cation and a tetrafluoroborate anion. The coordination around the boron atom in the tetrafluoroborate anion is tetrahedral. The heterocyclic ring adopts a half-chair conformation. The crystal packing is governed by means of C—H...F contacts, which lead to the formation of a three-dimensional network.

  10. Regioselective Synthesis of Some Pyrazole Scaffolds Attached to Benzothiazole and Benzimidazole Moieties

    Directory of Open Access Journals (Sweden)

    Nabila A. Kheder

    2014-01-01

    Full Text Available Condensation of 2-(benzothiazol-2-ylacetonitrile (1 or 2-(1-methyl-1H-benzimidazol-2-ylacetonitrile (2 with thiophene-2-carbaldehyde afforded the corresponding acrylonitrile derivatives 3 or 4, respectively. The 1,3-dipolar cycloaddition reaction of the acrylonitrile 3 or 4 with nitrile-imine 6 gave novel pyrazole derivatives pendant to benzothiazole and benzimidazole. The pyrazoline derivative 7 was converted into the corresponding pyrazole derivative 11 via thermal elimination of hydrogen cyanide upon heating in sodium ethoxide solution. The structures of the synthesized products were confirmed by IR, 1H NMR, and mass spectral techniques.

  11. Chiral Organic Cages with a Triple-Stranded Helical Structure Derived from Helicene.

    Science.gov (United States)

    Malik, Abaid Ullah; Gan, Fuwei; Shen, Chengshuo; Yu, Na; Wang, Ruibin; Crassous, Jeanne; Shu, Mouhai; Qiu, Huibin

    2018-02-28

    We report the use of helicene with an intrinsic helical molecular structure to prepare covalent organic cages via imine condensation. The organic cages revealed a [3+2]-type architecture containing a triple-stranded helical structure with three helicene units arranged in a propeller-like fashion with the framework integrally twisted. Such structural chirality was retained upon dissolution in organic solvents, as indicated by a strong diastereotopy effect in proton NMR and unique Cotton effects in circular dichroism spectra. Further study on chiral adsorption showed that the chiral organic cages possess considerable enantioselectivity toward a series of aromatic racemates.

  12. Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines

    Science.gov (United States)

    Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.

    2017-09-01

    Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.

  13. Solventless Lactam Synthesis by Intramolecular Cyclizations of α-Iminoester Derivatives under Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Aicha Derdour

    2007-03-01

    Full Text Available We have previously reported a new synthesis of amides from esters and amines under microwave irradiation, offering much higher yields than those achieved with conventional heating [1]. We have now extended these studies to the ring closure of neat iminoesters I2, I3 and I4-I6 to give five- and six-membered ring lactams L5, L6 and larger lactams L7-L9 (where I means imine and L means lactam, respectively, under both classical heating conditions and microwave irradiation.

  14. Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

    Directory of Open Access Journals (Sweden)

    Matthias Leven

    2013-01-01

    Full Text Available Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

  15. cis-Dichlorido(dimethyl sulfoxide-κS(N,N,N′,N′-tetramethylguanidine-κN′′platinum(II

    Directory of Open Access Journals (Sweden)

    Ivan I. Eliseev

    2013-02-01

    Full Text Available In the title compound, cis-[PtCl2(C5H13N3(C2H6OS], the four-coordinate PtII atom is bonded to one N atom of the N,N,N′,N′-tetramethylguanidine ligand, one dimethyl sulfoxide S atom and two chloride ligands, forming a cis-square-planar geometry. The bond lengths and angles of the N—Pt—Cl functionality are typical for imine dichloridoplatinum(II complexes. The H atom of the imino group is oriented towards the O atom of the sulfoxide group of a neighboring molecule and forms an N—H...O hydrogen bond.

  16. Stereocontrolled Synthesis of Methyl Silanediol Peptide Mimics

    DEFF Research Database (Denmark)

    Nielsen, Lone; Lindsay, Karl; Faber, Jesper

    2007-01-01

     The treatment of chiral sulfinimines with (methyldiphenylsilyl)lithium gives R-(methyldiphenylsilyl)-sulfinamides with excellent diastereoselectivity, and in good yield. The presence of α-protons on the imines is also well tolerated. The sulfinamide auxiliary is easily removed via treatment with...... corresponding bis-TMS siloxane via protection with TMSCl, and converted back to the desired silanediol via hydrolysis with aqueous KOH. Efforts to apply this approach to biologically relevant silanediol peptide mimics, with a view to protease inhibition, are described....

  17. Reaction of the diimine pyridine ligand with aluminum alkyls: An unexpectedly complex reaction

    NARCIS (Netherlands)

    Knijnenburg, Q.; Smits, J.M.M.; Budzelaar, P.H.M.

    2006-01-01

    The diimine pyridine ligand 2,6-{2,6-(Pr2C6H3N)-Pr-i=CMe}(2)C5H3N (1) was reacted with a series of aluminum alkyls (Me3Al, Et3Al, (Bu3Al)-Bu-i, (Bu2AlH)-Bu-i, Et2AlCl). Depending on the choice of alkyl, addition to the imine carbon and the pyridine C2 and C4 positions was observed. Addition to C2

  18. 4-(2,3-Dihydroxybenzylideneamino-3-methyl-1H-1,2,4-triazol-5(4H-one

    Directory of Open Access Journals (Sweden)

    Şamil Işık

    2009-12-01

    Full Text Available All the non-H atoms of the title compound, C10H10N4O3, are almost coplanar, the maximum deviation from planarity being 0.065 (3 Å. The dihedral angle between the aromatic rings is 1.66 (6°. The molecule adopts the enol–imine tautomeric form with an intramolecular hydrogen-bonding interaction between the Schiff base N atom and the hydroxy group. In the crystal, intermolecular N—H...O and O—H...O hydrogen bonds link the molecules into a three-dimensional network.

  19. 8-{(E-[(4-Chlorophenylimino]methyl}-1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-9-ol

    Directory of Open Access Journals (Sweden)

    Esen Nur Kantar

    2013-06-01

    Full Text Available The title Schiff base, C23H27ClN2O adopts the phenol–imine tautomeric form, with an intramolecular O—H...N hydrogen bond, which generates an S(6 ring motif. Three C atoms of the heterocyclic moiety of the hexahydropyridoquinoline unit, as well as the two methyl groups bonded to one of these C atoms, are disordered over two set of sites, with anoccupancy ratio of 0.740 (4:0.260 (4.

  20. Bis[2-(cyclopentyliminomethyl-5-methoxyphenolato]copper(II

    Directory of Open Access Journals (Sweden)

    Xiao-Hui Ji

    2010-08-01

    Full Text Available The title compound, [Cu(C13H16NO22], is a mononuclear copper(II complex derived from the Schiff base ligand 2-(cyclopentyliminomethyl-5-methoxyphenol and copper acetate. The CuII atom is four-coordinated by the phenolate O atoms and imine N atoms from two Schiff base ligands, in a highly distorted square-planar geometry. The O- and N-donor atoms are mutually trans and the dihedral angle between the two benzene rings is 55.8 (3°.

  1. Şiddet içerikli bilgisayar oyunlarının çocuklarda saldırganlığa etkisi

    OpenAIRE

    KARS, Gözde Bahar

    2010-01-01

    Teknolojik gelişmeler çoğunlukla insan yaşamını kolaylaştırmaya yönelik olmakla birlikte, kulanım biçimine bağlı olarak bazı olumsuz sonuçlarla da karşılaşılabilmektedir. Kullanım biçimine bağlı olarak olumlu ve olumsuz sonuçlar doğurabileceği öne sürülen teknoloji ürünleri arasında bilgisayar oyunları da bulunmaktadır. Özellikle son yıllarda çocukların bilgisayar oyunu oynama taleplerinde ve bilgisayar oyunu oynamak için ayırdıkları zamanda büyük artış görülmektedir.Bu a...

  2. Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles.

    Science.gov (United States)

    Wentrup, Curt

    2017-03-08

    Flash vacuum pyrolysis (FVP) of azides is an extremely valuable method of generating nitrenes and studying their thermal rearrangements. The nitrenes can in many cases be isolated in low-temperature matrices and observed spectroscopically. NH and methyl, alkyl, aralkyl, vinyl, cyano, aryl and N-heteroaryl, acyl, carbamoyl, alkoxycarbonyl, imidoyl, boryl, silyl, phosphonyl, and sulfonyl nitrenes are included. FVP of triazoloazines generates diazomethylazines and azinylcarbenes, which often rearrange to the energetically more stable arylnitrenes. N 2 elimination from monocyclic 1,2,3-triazoles can generate iminocarbenes, 1H-azirines, ketenimines, and cyclization products, and 1,2,4-triazoles are precursors of nitrile ylides. Benzotriazoles are preparatively useful precursors of cyanocyclopentadienes, carbazoles, and aza-analogues. FVP of 5-aryltetrazoles can result in double N 2 elimination with formation of arylcarbenes or of heteroarylcarbenes, which again rearrange to arylnitrenes. Many 5-substituted and 2,5-disubstituted tetrazoles are excellent precursors of nitrile imines (propargylic, allenic, or carbenic), which are isolable at low temperatures in some cases (e.g., aryl- and silylnitrile imines) or rearrange to carbodiimides. 1,5-Disubstituted tetrazoles are precursors of imidoylnitrenes, which also rearrange to carbodiimides or add intramolecularly to aryl substituents to yield indazoles and related compounds. Where relevant for the mechanistic understanding, pyrolysis under flow conditions or in solution or the solid state will be mentioned. Results of photolysis reactions and computational chemistry complementing the FVP results will also be mentioned in several places.

  3. Evaluation of Antitrypanosomal Dihydroquinolines for Hepatotoxicity, Mutagenicity, and Methemoglobin Formation In Vitro.

    Science.gov (United States)

    Werbovetz, Karl A; Riccio, Edward S; Furimsky, Anna; Richard, Julian V; He, Shanshan; Iyer, Lalitha; Mirsalis, Jon

    2014-07-01

    N1-Benzylated dihydroquinolin-6-ols and their corresponding esters display exceptional activity against African trypanosomes in vitro, and administration of members of this class of compounds to trypanosome-infected mice results in cures in a first-stage African trypanosomiasis model. Since a quinone imine intermediate has been implicated in the antiparasitic mechanism of action of these compounds, evaluation of the hepatotoxic, mutagenic, and methemoglobin-promoting effects of these agents was performed. 1-Benzyl-1,2-dihydro-2,2,4-trimethylquinolin-6-ol hydrochloride and 1-benzyl-1,2-dihydro-2,2,4-trimethylquinolin-6-yl acetate showed outstanding in vitro selectivity for Trypanosoma brucei compared to the HepG2, Hep3B, Huh7, and PLC5 hepatocyte cell lines. 1-Benzyl-1,2-dihydro-2,2,4-trimethylquinolin-6-ol hydrochloride and 1-(2-methoxybenzyl)-1,2-dihydro-2,2,4-trimethylquinolin-6-yl acetate were not mutagenic when screened in the Ames assay, with or without metabolic activation. The latter 2 compounds promoted time- and dose-dependent formation of methemoglobin when incubated in whole human blood, but such levels were below those typically required to produce symptoms of methemoglobinemia in humans. Although compounds capable of quinone imine formation require careful evaluation, these in vitro studies indicate that antitrypanosomal dihydroquinolines merit further study as drug candidates against the neglected tropical disease human African trypanosomiasis. © The Author(s) 2014.

  4. Application of the aza-Diels-Alder reaction in the synthesis of natural products.

    Science.gov (United States)

    Cao, Min-Hui; Green, Nicholas J; Xu, Sheng-Zhen

    2017-04-11

    The Diels-Alder reaction that involves a nitrogen atom in the diene or dienophile is termed the aza-Diels-Alder reaction. As well as the powerful all-carbon Diels-Alder reaction, the aza-Diels-Alder reaction has also played an important role in the total synthesis of natural products. Herein, we review various natural products using an aza-Diels-Alder reaction as a key step to their total synthesis, and divide the syntheses into inter- and intra-molecular aza-Diels-Alder reactions and a retro-aza-Diels-Alder reaction. Inter- and intra-molecular aza-Diels-Alder reactions involve an imine as an electron deficient dienophile and an imine as an electron deficient azadiene. The significance of the aza-Diels-Alder reaction for the construction of a six-membered ring containing nitrogen is tremendous, but the development of asymmetric, in particular catalytic enantioselective intramolecular aza-Diels-Alder reaction in the total synthesis of natural products remains highly challenging, and will no doubt see enormous advances in the future.

  5. Latent Hardeners for the Assembly of Epoxy Composites

    Science.gov (United States)

    Palmieri, Frank; Wohl, Christopher J.; Connell, John W.; Mercado, Zoar; Galloway, Jordan

    2016-01-01

    Large-scale composite structures are commonly joined by secondary bonding of molded-and-cured thermoset components. This approach may result in unpredictable joint strengths. In contrast, assemblies made by co-curing, although limited in size by the mold, result in stable structures, and are certifiable for commercial aviation because of structural continuity through the joints. Multifunctional epoxy resins were prepared that should produce fully-cured subcomponents with uncured joining surfaces, enabling them to be assembled by co-curing in a subsequent out-of-autoclave process. Aromatic diamines were protected by condensation with a ketone or aldehyde to form imines. Properties of the amine-cured epoxy were compared with those of commercially available thermosetting epoxy resins and rheology and thermal analysis were used to demonstrate the efficacy of imine protection. Optimum conditions to reverse the protecting chemistry in the solid state using moisture and acid catalysis were determined. Alternative chemistries were also investigated. For example, chain reaction depolymerization and photoinitiated catalysts would be expected to minimize liberation of volatile organic content upon deprotection and avoid residual reactive species that could damage the resin. Results from the analysis of protected and deprotected resins will be presented.

  6. A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

    Science.gov (United States)

    Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

    2013-12-14

    Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

  7. Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Black, Hayden T; Harrison, Katharine Lee

    2016-10-01

    The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Li+ ions, and that the mobility of polymer associated Li+ was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li+ within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.

  8. SYNTHESIS AND EVALUATION OF NEW PHTHALAZINE SUBSTITUTED β-LACTAM DERIVATIVES AS CARBONIC ANHYDRASE INHIBITORS.

    Science.gov (United States)

    Berber, Nurcan; Arslan, Mustafa; Bilen, Çiğdem; Sackes, Zübeyde; Gençer, Nahit; Arslan, Oktay

    2015-01-01

    A new series of phthalazine substituted β-lactam derivatives were synthesized and their inhibitory effects on the activity of purified human carbonic anhydrase (hCA I and II) were evaluated. 2H-Indazolo[2,1-b]phthala- zine-trione derivative was prepared with 4-nitrobenzaldehyde, dimedone, and phthalhydrazide in the presence of TFA in DMF, and the nitro group was reduced to 13-(4-aminophenyl)-3,3-dimethyl-3,4-dihydro- 2H-indazolo[1,2-b]phthalazine-1,6,11(13H)-trione with SnCl2 · 2H2O. The reduced compound was re- acted with different aromatic aldehydes, and phthalazine substituted imines were synthesized. The imine compounds undergo (2+2) cycloaddition reactions with ketenes to produce 2H-indazolo[2,1-b]phthala-zine-trione substituted β-lactam derivatives. The β-lactam compounds were tested as inhibitors of the CA isoenzyme activity. The results showed that all the synthesized compounds inhibited the CA isoenzyme activity. 1-(4-(3,3-dimethyl- 1,6,1 1-trioxo-2,3,4,6,11,13-hexahydro-1H-indazolo[1,2-b]phthalazin-13- yl)phenyl)-2-oxo-4-p-tolylazetidin-3-yl acetate (IC50 = 6.97 µM for hCA I and 8.48 µM for hCA II) had the most inhibitory effect.

  9. Ternary iron(II) complex with an emissive imidazopyridine arm from Schiff base cyclizations and its oxidative DNA cleavage activity.

    Science.gov (United States)

    Mukherjee, Arindam; Dhar, Shanta; Nethaji, Munirathinam; Chakravarty, Akhil R

    2005-01-21

    The ternary iron(II) complex [Fe(L')(L")](PF6)3(1) as a synthetic model for the bleomycins, where L' and L" are formed from metal-mediated cyclizations of N,N'-(2-hydroxypropane-1,3-diyl)bis(pyridine-2-aldimine)(L), is synthesized and structurally characterized by X-ray crystallography. In the six-coordinate iron(ii) complex, ligands L' and L" show tetradentate and bidentate chelating modes of bonding. Ligand L' is formed from an intramolecular attack of the alcoholic OH group of L to one imine moiety leading to the formation of a stereochemically constrained five-membered ring. Ligand L" which is formed from an intermolecular reaction involving one imine moiety of L and pyridine-2-carbaldehyde has an emissive cationic imidazopyridine pendant arm. The complex binds to double-stranded DNA in the minor groove giving a Kapp value of 4.1 x 10(5) M(-1) and displays oxidative cleavage of supercoiled DNA in the presence of H2O2 following a hydroxyl radical pathway. The complex also shows photo-induced DNA cleavage activity on UV light exposure involving formation of singlet oxygen as the reactive species.

  10. Synthesis and Biological Assessment of Racemic Benzochromenopyrimidinimines as Antioxidant, Cholinesterase, and Aβ1-42 Aggregation Inhibitors for Alzheimer's Disease Therapy.

    Science.gov (United States)

    Dgachi, Youssef; Ismaili, Lhassane; Knez, Damijan; Benchekroun, Mohamed; Martin, Hélène; Szałaj, Natalia; Wehle, Sarah; Bautista-Aguilera, Oscar M; Luzet, Vincent; Bonnet, Alexandre; Malawska, Barbara; Gobec, Stanislav; Chioua, Mourad; Decker, Michael; Chabchoub, Fakher; Marco-Contelles, José

    2016-06-20

    Given the complex nature of Alzheimer's disease (AD), compounds that are able to simultaneously address two or more AD-associated targets show greater promise for development into drugs for AD therapy. Herein we report an efficient two-step synthesis and biological evaluation of new racemic benzochromene derivatives as antioxidants, inhibitors of cholinesterase and β-amyloid (Aβ1-42 ) aggregation. Based on the results of the primary screening, we identified 15-(3-methoxyphenyl)-9,11,12,15-tetrahydro-10H,14H-benzo[5,6]chromeno[2,3-d]pyrido[1,2-a]pyrimidin-14-imine (3 e) and 16-(3-methoxyphenyl)-9,10,11,12,13,16-hexahydro-15H-benzo[5',6']chromeno[2',3':4,5]pyrimido[1,2-a]azepin-15-imine (3 f) as new potential multitarget-directed ligands for AD therapy. Further in-depth biological analysis showed that compound 3 f is a good human acetylcholinesterase inhibitor [IC50 =(0.36±0.02) μm], has strong antioxidant activity (3.61 μmol Trolox equivalents), and moderate Aβ1-42 antiaggregating power (40.3 %). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Autonomous model protocell division driven by molecular replication.

    Science.gov (United States)

    Taylor, J W; Eghtesadi, S A; Points, L J; Liu, T; Cronin, L

    2017-08-10

    The coupling of compartmentalisation with molecular replication is thought to be crucial for the emergence of the first evolvable chemical systems. Minimal artificial replicators have been designed based on molecular recognition, inspired by the template copying of DNA, but none yet have been coupled to compartmentalisation. Here, we present an oil-in-water droplet system comprising an amphiphilic imine dissolved in chloroform that catalyses its own formation by bringing together a hydrophilic and a hydrophobic precursor, which leads to repeated droplet division. We demonstrate that the presence of the amphiphilic replicator, by lowering the interfacial tension between droplets of the reaction mixture and the aqueous phase, causes them to divide. Periodic sampling by a droplet-robot demonstrates that the extent of fission is increased as the reaction progresses, producing more compartments with increased self-replication. This bridges a divide, showing how replication at the molecular level can be used to drive macroscale droplet fission.Coupling compartmentalisation and molecular replication is essential for the development of evolving chemical systems. Here the authors show an oil-in-water droplet containing a self-replicating amphiphilic imine that can undergo repeated droplet division.

  12. Size effects on cation heats of formation. I. Methyl substitutions in nitrogenous compounds

    International Nuclear Information System (INIS)

    Leach, Sydney

    2012-01-01

    Graphical abstract: Heat of formation of cations as a function of ln(n) where n is the number of atoms in the ion: methyl substituted immonium cations. N = substitution at nitrogen sites, C = substitution at carbon sites. Highlights: ► Heats of formation of nitrogenous cations by graphical method relating to ion size. ► Methyl substitution in formamides, acetamides, immonium, amine, and imine cations. ► Methyl substitution in ammonium and amino cations. ► New studies ionization energies and heats of formation required in several cases. - Abstract: The heats of formation of molecular ions are often not known to better than 10 or 20 kJ/mol. The present study on nitrogenous compounds adopts the graphical approach of Holmes and Lossing which relates cation heats of formation to cation size. A study of methyl substitution in formamides and acetamides is followed by an examination of heat of formation data on carbon-site and nitrogen-site methyl substitution in immonium, amine, imine, ammonium and amino cations. The results provide tests of the validity of this graphical method and also suggest investigating or re-investigating the ionization energies and the heats of formation of several of the molecules studied.

  13. Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products

    Science.gov (United States)

    Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

    2018-01-01

    The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1H, 13C and 15N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH3salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO2salDAMN and naphDAMN only one form (X) was observed.

  14. Aldehyde-functionalized chitosan-montmorillonite films as dynamically-assembled, switchable-chemical release bioplastics.

    Science.gov (United States)

    Chabbi, Jamal; Jennah, Oumayma; Katir, Nadia; Lahcini, Mohamed; Bousmina, Mosto; El Kadib, Abdelkrim

    2018-03-01

    Temporal release of synergistic and/or complementary chemicals (e.g.: drugs) is recognized as extremely challenging because of their frequently intertwined kinetic delivery and presently, straightforward concepts enabling to circumvent this bottleneck are missing in the open literature. In this framework, we report herein on aldehyde-functionalized, transparent and flexible chitosan-montmorillonite hybrid films that act as a new generation of eco-friendly, controlled-chemical release bioplastics. These dynamically-assembled nanomaterials are designed by a ternary assembly from biowaste derived chitin biopolymer, aromatic aldehydes and layered clay nanoparticles. On the basis of their geometrical and conformational properties, the oxygenated groups on the grafted aromatics interact preferentially with either the base Schiff belonging to the carbohydrate (via intramolecular CNHO-Ar known as "imine clip") or with the hydroxyl groups belonging to the clay surface (via intermolecular Si-OHO-Ar). The exfoliated clay nanoparticles within the carbohydrate polymer enables either accelerating or slowing down of the imine (CN) hydrolysis depending on the interaction of the conjugated aromatics. This provides the driving force for fine tuning host-guest interactions at the molecular level and constitutes an entry toward subtle discrimination of different chemicals (e.g. complementary fertilizers, synergistic drugs) during their sequential release. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Dissociation of protonated N-(3-phenyl-2H-chromen-2-ylidene)-benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer.

    Science.gov (United States)

    Wang, Shanshan; Dong, Cheng; Yu, Lian; Guo, Cheng; Jiang, Kezhi

    2016-01-15

    In the tandem mass spectrometry of protonated N-(3-phenyl-2H-chromen-2-ylidene)benzenesulfonamides, the precursor ions have been observed to undergo gas-phase dissociation via two competing channels: (a) the predominant channel involves migration of the sulfonyl cation to the phenyl C atom and the subsequent loss of benzenesulfinic acid along with cyclization reaction, and (b) the minor one involves dissociation of the precursor ion to give an ion/neutral complex of [sulfonyl cation/imine], followed by decomposition to afford sulfonyl cation or the INC-mediated electron transfer to give an imine radical cation. The proposed reaction channels have been supported by theoretical calculations and D-labeling experiments. The gas-phase cyclization reaction originating from the N- to C-sulfonyl cation transfer has been first reported to the best of our knowledge. For the substituted sulfonamides, the presence of electron-donating groups (R(2) -) at the C-ring effectively facilitates the reaction channel of cyclization reaction, whereas that of electron-withdrawing groups inhibits this pathway. Copyright © 2015 John Wiley & Sons, Ltd.

  16. Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework

    KAUST Repository

    Chen, Chen

    2017-12-20

    We have characterized the local electronic structure of a porphyrin-containing single-layer covalent organic framework (COF) exhibiting a square lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMA) and 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) onto a Au(111) surface in ultrahigh vacuum followed by annealing to facilitate Schiff-base condensations between monomers. Scanning tunneling spectroscopy (STS) experiments conducted on isolated TAPP precursor molecules and the covalently linked COF networks yield similar transport (HOMO-LUMO) gaps of 1.85 ± 0.05 eV and 1.98 ± 0.04 eV, respectively. The COF orbital energy alignment, however, undergoes a significant downward shift compared to isolated TAPP molecules due to the electron-withdrawing nature of the imine bond formed during COF synthesis. Direct imaging of the COF local density of states (LDOS) via dI/dV mapping reveals that the COF HOMO and LUMO states are localized mainly on the porphyrin cores and that the HOMO displays reduced symmetry. DFT calculations reproduce the imine-induced negative shift in orbital energies and reveal that the origin of the reduced COF wave function symmetry is a saddle-like structure adopted by the porphyrin macrocycle due to its interactions with the Au(111) substrate.

  17. Chiral multichromic single crystals for optical devices (LDRD 99406).

    Energy Technology Data Exchange (ETDEWEB)

    Kemp, Richard Alan; Felix, Ana M. (University of New Mexico, Albuquerque, NM)

    2006-12-01

    This report summarizes our findings during the study of a novel system that yields multi-colored materials as products. This system is quite unusual as it leads to multi-chromic behavior in single crystals, where one would expect that only a single color would exist. We have speculated that these novel solids might play a role in materials applications such as non-linear optics, liquid crystal displays, piezoelectric devices, and other similar applications. The system examined consisted of a main-group alkyl compound (a p block element such as gallium or aluminum) complexed with various organic di-imines. The di-imines had substituents of two types--either alkyl or aromatic groups attached to the nitrogen atoms. We observed that single crystals, characterized by X-ray crystallography, were obtained in most cases. Our research during January-July, 2006, was geared towards understanding the factors leading to the multi-chromic nature of the complexes. The main possibilities put forth initially considered (a) the chiral nature of the main group metal, (b) possible reduction of the metal to a lower-valent, radical state, (c) the nature of the ligand(s) attached to the main group metal, and (d) possible degradation products of the ligand leading to highly-colored products. The work carried out indicates that the most likely explanation considered involves degradation of the aromatic ligands (a combination of (c) and (d)), as the experiments performed can clearly rule out (a) and (b).

  18. Gelation-driven selection in dynamic covalent C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C/CN exchange.

    Science.gov (United States)

    Liang, Chunshuang; Kulchat, Sirinan; Jiang, Shimei; Lehn, Jean-Marie

    2017-10-01

    Knoevenagel barbiturate derivatives bearing long alkyl chains were proven to form organogels in suitable solvents based on supramolecular interactions. Their reaction with imines allows for component exchange through CC/CN recombination. The effect of various parameters (solvents, chain length, and temperature) on the CC/CN exchange reaction has been studied. Mixing Knoevenagel compound K and imine I-16 in a 1 : 1 ratio generated a constitutional dynamic library containing the four constituents K , I-16 , K'-16 , and I' . The reversible exchange reaction was monitored by 1 H-NMR, showing marked changes in the fractions of the four constituents on sol-gel interconversion as a function of temperature. The library composition changed from statistical distribution of the four constituents in the sol state to selective amplification of the gel forming K'-16 constituent together with that of its agonist I' . The process amounts to self-organization driven component selection in a constitutional dynamic organogel system undergoing gelation. This process displays up-regulation of the gel-forming constituent by component redistribution through reversible covalent connections.

  19. Ionic liquid mediated stereoselective synthesis of alanine linked hybrid quinazoline-4(3H)-one derivatives perturbing the malarial reductase activity in folate pathway.

    Science.gov (United States)

    Patel, Tarosh S; Bhatt, Jaimin D; Vanparia, Satish F; Patel, Urmila H; Dixit, Ritu B; Chudasama, Chaitanya J; Patel, Bhavesh D; Dixit, Bharat C

    2017-12-15

    Grimmel's method was optimized as well as modified leading to the cyclization and incorporation of alanine linked sulphonamide in 4-quinazolin-(3H)-ones. Further, the generation of heterocyclic motif at position-3 of 4-quinazolinones was explored by synthesis of imines, which unfortunately led to an isomeric mixture of stereoisomers. The hurdle of diastereomers encountered on the path was eminently rectified by development of new rapid and reproducible methodology involving the use of imidazolium based ionic liquid as solvents as well as catalyst for cyclization as well as synthesis of imines in situ at position-3 leading to procurement of single E-isomer as the target hybrid heterocyclic molecules. The purity and presence of single isomer was also confirmed by HPLC and spectroscopic techniques. Further, the synthesized sulphonamide linked 4-quinazolin-(3H)-ones hybrids were screened for their antimalarial potency rendering potent entities (4b, 4c, 4 l, 4 t and 4u). The active hybrids were progressively screened for enzyme inhibitory efficacy against presumed receptor Pf-DHFR and h-DHFR computationally as well as in vitro, proving their potency as dihydrofolate reductase inhibitors. The ADME properties of these active molecules were also predicted to enhance the knowhow of the oral bioavailability, indicating good bioavailability of the active entities. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. A simple approach to design chitosan functionalized Fe3O4 nanoparticles for pH responsive delivery of doxorubicin for cancer therapy

    Science.gov (United States)

    Adimoolam, Mahesh G.; Amreddy, Narsireddy; Nalam, Madhusudana Rao; Sunkara, Manorama V.

    2018-02-01

    The use of magnetic nanoparticles (MNPs) in cancer therapy offer many advantages due to their unique size, physical and biocompatible properties. In this study we have developed a formulation, comprising of anti-cancer drug doxorubicin (Dox) conjugated to iron oxide nanoparticles via a pH sensitive imine linker. Different amounts of chitosan functionalized superparamagnetic iron oxide nanoparticles (Fe3O4-CHI) were synthesized in-situ by a simple hydrolysis method at room temperature. The synthesized nanoparticles were well characterized by TEM, Zeta Potential, TOC, XPS, TGA and VSM for their physicochemical properties. Dox was conjugated to the Fe3O4-CHI nanoparticles via a glutaraldehyde cross linker with the imine (sbnd Cdbnd Nsbnd) bond, which is sensitive to cleavage in the pH range of 4.4-6.4. The synthesized Fe3O4-Dox nanoparticles exhibited enhanced drug release in lower pH conditions which mimics the tumor microenvironment or intracellular organelles such as endosomes/lysosomes. The cell uptake and therapeutic efficacy of Fe3O4-Dox nanoparticles carried out in ovarian cancer cell (SK-OV-3) and breast cancer cell line (MCF7) showed improved therapeutic efficacy of Dox by nearly four-fold with Fe3O4-Dox nanoparticles.

  1. Ruthenium(II) Complexes Containing Lutidine-Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of C-N bonds.

    Science.gov (United States)

    Hernández-Juárez, Martín; López-Serrano, Joaquín; Lara, Patricia; Morales-Cerón, Judith P; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

    2015-05-11

    A series of Ru complexes containing lutidine-derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver-carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N-heterocyclic carbene fragments. In the presence of tBuOK, the Ru-CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand-assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru-CNC complex 5 e(BF4 ) is able to add aldimines to the metal-ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer-sphere stepwise hydrogen transfer to the C-N bond assisted either by the pincer ligand or a second coordinated H2 molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Diallyl 5-[(4-hexyloxyphenyliminomethyl]-m-phenylene dicarbonate

    Directory of Open Access Journals (Sweden)

    Ana María Herrera-González

    2009-11-01

    Full Text Available The title molecule, C27H31NO7, an imine derivative bearing both carbonate and allyl functionalities, was synthesized in the hope of obtaining a mesogenic polymerizable material. The allylcarbonate arms are fully disordered over two sets of sites, reflecting a large degree of rotational freedom about σ bonds [occupancies: 0.665 (9/0.335 (9 for one substituent, 0.564 (9/0.436 (9 for the other]. In contrast, the hexyl chain is ordered, and presents the common all-trans extended conformation. The benzene rings connected via the imine group make a dihedral angle of 9.64 (11°. In the crystal, the Y-shaped molecules are weakly associated into centrosymmetric dimers through pairs of C—H...O(hexyl contacts. The resulting layers of dimers, approximately parallel to (2overline{2}5, are closely packed in the crystal, allowing π...π interactions between benzene rings of neighboring layers: the separation between the centroid of the benzene ring substituted by allylcarbonate and the centroid of the benzene ring bearing the hexyloxy group in the adjacent layer is 3.895 (1 Å.

  3. Diallyl 5-[(4-hexyl-oxyphen-yl)imino-meth-yl]-m-phenyl-ene dicarbonate.

    Science.gov (United States)

    Herrera-González, Ana María; López-Velázquez, Delia; Bernès, Sylvain

    2009-10-23

    The title mol-ecule, C(27)H(31)NO(7), an imine derivative bearing both carbonate and allyl functionalities, was synthesized in the hope of obtaining a mesogenic polymerizable material. The allyl-carbonate arms are fully disordered over two sets of sites, reflecting a large degree of rotational freedom about σ bonds [occupancies: 0.665 (9)/0.335 (9) for one substituent, 0.564 (9)/0.436 (9) for the other]. In contrast, the hexyl chain is ordered, and presents the common all-trans extended conformation. The benzene rings connected via the imine group make a dihedral angle of 9.64 (11)°. In the crystal, the Y-shaped mol-ecules are weakly associated into centrosymmetric dimers through pairs of C-H⋯O(hex-yl) contacts. The resulting layers of dimers, approximately parallel to (25), are closely packed in the crystal, allowing π⋯π inter-actions between benzene rings of neighboring layers: the separation between the centroid of the benzene ring substituted by allyl-carbonate and the centroid of the benzene ring bearing the hex-yloxy group in the adjacent layer is 3.895 (1) Å.

  4. Glucosinolate diversity within a phylogenetic framework of the tribe Cardamineae (Brassicaceae) unraveled with HPLC-MS/MS and NMR-based analytical distinction of 70 desulfoglucosinolates.

    Science.gov (United States)

    Olsen, Carl Erik; Huang, Xiao-Chen; Hansen, Cecilie I C; Cipollini, Don; Ørgaard, Marian; Matthes, Annemarie; Geu-Flores, Fernando; Koch, Marcus A; Agerbirk, Niels

    2016-12-01

    As a basis for future investigations of evolutionary trajectories and biosynthetic mechanisms underlying variations in glucosinolate structures, we screened members of the crucifer tribe Cardamineae by HPLC-MS/MS, isolated and identified glucosinolates by NMR, searched the literature for previous data for the tribe, and collected HPLC-MS/MS data for nearly all glucosinolates known from the tribe as well as some related structures (70 in total). This is a considerable proportion of the approximately 142 currently documented natural glucosinolates. Calibration with authentic references allowed distinction (or elucidation) of isomers in many cases, such as distinction of β-hydroxyls, methylthios, methylsulfinyls and methylsulfonyls. A mechanism for fragmentation of secondary β-hydroxyls in MS was elucidated, and two novel glucosinolates were discovered: 2-hydroxy-3-methylpentylglucosinolate in roots of Cardamine pratensis and 2-hydroxy-8-(methylsulfinyl)octylglucosinolate in seeds of Rorippa amphibia. A large number of glucosinolates (ca. 54 with high structural certainty and a further 28 or more suggested from tandem MS), representing a wide structural variation, is documented from the tribe. This included glucosinolates apparently derived from Met, Phe, Trp, Val/Leu, Ile and higher homologues. Normal side chain elongation and side chain decoration by oxidation or methylation was observed, as well as rare abnormal side chain decoration (hydroxylation of aliphatics at the δ rather than β-position). Some species had diverse profiles, e.g. R. amphibia and C. pratensis (19 and 16 individual glucosinolates, respectively), comparable to total diversity in literature reports of Armoracia rusticana (17?), Barbarea vulgaris (20-24), and Rorippa indica (>20?). The ancestor or the tribe would appear to have used Trp, Met, and homoPhe as glucosinolate precursor amino acids, and to exhibit oxidation of thio to sulfinyl, formation of alkenyls, β-hydroxylation of aliphatic

  5. Notch activation is dispensable for D, L-sulforaphane-mediated inhibition of human prostate cancer cell migration.

    Directory of Open Access Journals (Sweden)

    Eun-Ryeong Hahm

    Full Text Available D, L-Sulforaphane (SFN, a synthetic racemic analog of broccoli constituent L-sulforaphane, is a highly promising cancer chemopreventive agent with in vivo efficacy against chemically-induced as well as oncogene-driven cancer in preclinical rodent models. Cancer chemopreventive effect of SFN is characterized by G(2/M phase cell cycle arrest, apoptosis induction, and inhibition of cell migration and invasion. Moreover, SFN inhibits multiple oncogenic signaling pathways often hyperactive in human cancers, including nuclear factor-κB, Akt, signal transducer and activator of transcription 3, and androgen receptor. The present study was designed to determine the role of Notch signaling, which is constitutively active in many human cancers, in anticancer effects of SFN using prostate cancer cells as a model. Exposure of human prostate cancer cells (PC-3, LNCaP, and/or LNCaP-C4-2B to SFN as well as its naturally-occurring thio-, sulfinyl-, and sulfonyl-analogs resulted in cleavage (activation of Notch1, Notch2, and Notch4, which was accompanied by a decrease in levels of full-length Notch forms especially at the 16- and 24-hour time points. The SFN-mediated cleavage of Notch isoforms was associated with its transcriptional activation as evidenced by RBP-Jk-, HES-1A/B- and HEY-1 luciferase reporter assays. Migration of PC-3 and LNCaP cells was decreased significantly by RNA interference of Notch1 and Notch2, but not Notch4. Furthermore, SFN-mediated inhibition of PC-3 and LNCaP cell migration was only marginally affected by knockdown of Notch1 and Notch2. Strikingly, SFN administration to Transgenic Adenocarcinoma of Mouse Prostate transgenic mice failed to increase levels of cleaved Notch1, cleaved Notch2, and HES-1 proteins in vivo in prostatic intraepithelial neoplasia, well-differentiated carcinoma or poorly-differentiated prostate cancer lesions. These results indicate that Notch activation is largely dispensable for SFN-mediated inhibition of cell

  6. From synthesis to function via iterative assembly of N-methyliminodiacetic acid boronate building blocks.

    Science.gov (United States)

    Li, Junqi; Grillo, Anthony S; Burke, Martin D

    2015-08-18

    The study and optimization of small molecule function is often impeded by the time-intensive and specialist-dependent process that is typically used to make such compounds. In contrast, general and automated platforms have been developed for making peptides, oligonucleotides, and increasingly oligosaccharides, where synthesis is simplified to iterative applications of the same reactions. Inspired by the way natural products are biosynthesized via the iterative assembly of a defined set of building blocks, we developed a platform for small molecule synthesis involving the iterative coupling of haloboronic acids protected as the corresponding N-methyliminodiacetic acid (MIDA) boronates. Here we summarize our efforts thus far to develop this platform into a generalized and automated approach for small molecule synthesis. We and others have employed this approach to access many polyene-based compounds, including the polyene motifs found in >75% of all polyene natural products. This platform further allowed us to derivatize amphotericin B, the powerful and resistance-evasive but also highly toxic last line of defense in treating systemic fungal infections, and thereby understand its mechanism of action. This synthesis-enabled mechanistic understanding has led us to develop less toxic derivatives currently under evaluation as improved antifungal agents. To access more Csp(3)-containing small molecules, we gained a stereocontrolled entry into chiral, non-racemic α-boryl aldehydes through the discovery of a chiral derivative of MIDA. These α-boryl aldehydes are versatile intermediates for the synthesis of many Csp(3) boronate building blocks that are otherwise difficult to access. In addition, we demonstrated the utility of these types of building blocks in accessing pharmaceutically relevant targets via an iterative Csp(3) cross-coupling cycle. We have further expanded the scope of the platform to include stereochemically complex macrocyclic and polycyclic molecules

  7. Determination of NH_2 concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

    International Nuclear Information System (INIS)

    Manakhov, Anton; Čechal, Jan; Michlíček, Miroslav; Shtansky, Dmitry V.

    2017-01-01

    Highlights: • A new method for primary amines derivatization is proposed and validated. • The chemical structure of APTES layer is studied. • The derivatization by 5-iodo 2-furaldehyde allowed to avoid side reactions in contrast to 4-trifluoromethyl benzaldehyde derivatization. - Abstract: The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH_2 groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH_2/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH_2 fraction ∼8.5%. This value is closely matching the NH_2/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH_2/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA derivatization is probably

  8. The synthesis and preliminary pharmacological evaluation of the racemic cis and trans 3-alkylfentanyl analogues

    Directory of Open Access Journals (Sweden)

    LJ. DOSEN-MICOVIC

    2004-07-01

    Full Text Available A general, five step method for the synthesis of 3-alkylfentanyl analogues (i.e., cis and trans 3-alkyl-4-anilidopiperidines 6.1–6.6 has been developed. The starting N-phenethyl-4-piperidone 1 was first converted into the cyclohexylimine derivative 2, a-deprotonated with butyllithium and the resulting imine anion efficiently monoalkylated with primary and secondary alkyl halides. After mild acid hydrolysis, the obtained 3-alkyl-4-piperidones 3.1–3.6 were isolated in good yields (79–85 %, then condensed with aniline to form imines 4.1–4.6. Subsequent reduction of the imines (LiAlH4/THF yielded cis/trans mixtures of 3-alkyl-4-anilinopiperidines 5.1–5.6. Quantitative separation of the diastereoisomers by column chromatography of Al2O3 gave pure cis 5.1–5.6 (29–51 % yield and trans 5.1–5.6 (19–27 % yield, with the cis/trans ratio in the range 7/3–6/4. The synthesis was concluded by N-acylation of the purified 5.1–5.6, with propionyl chloride, to afford cis and trans 3-alkyl-4-anilidopiperidines 6.1–6.6 (~95 % yield, as monooxalate salts. No enatioseparation was attempted at any stage. The relative cis/trans stereochemistry was provisionally assigned from the 1H-NMR spectra. Of the twelve synthesized 3-alkylfentanyls, ten compounds (two known and eight novel derivatives, all as the monooxalate salts were preliminarily tested as analgesics in rats, comparing the potency to fentanyl. Except for the known (±-cis-3-Me fentanyl 6.1cis, (8 × fentanyl, and the novel (±-cis-3-Et fentanyl 6.2cis, (1.5 × fentanyl, all of the others were less active than fentanyl or inactive. Some tentative conclusions on the structure-activity relationship (SAR in this series of derivatives have been made.

  9. Determination of NH{sub 2} concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Manakhov, Anton, E-mail: ant-manahov@ya.ru [National University of Science and Technology “MISiS”, Leninsky pr. 4, Moscow 119049 (Russian Federation); RG Plasma Technologies, CEITEC—Central European Institute of Technology, Masaryk University, Kotlářská, 2, 61137 Brno (Czech Republic); Čechal, Jan [CEITEC—Central European Institute of Technology, Brno University of Technology, Purkyňova 123, 612 00 Brno (Czech Republic); Institute of Physical Engineering, Brno University of Technology, Technická 2896/2, 616 69 Brno (Czech Republic); Michlíček, Miroslav [RG Plasma Technologies, CEITEC—Central European Institute of Technology, Masaryk University, Kotlářská, 2, 61137 Brno (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, 61137 Brno (Czech Republic); Shtansky, Dmitry V. [National University of Science and Technology “MISiS”, Leninsky pr. 4, Moscow 119049 (Russian Federation)

    2017-08-31

    Highlights: • A new method for primary amines derivatization is proposed and validated. • The chemical structure of APTES layer is studied. • The derivatization by 5-iodo 2-furaldehyde allowed to avoid side reactions in contrast to 4-trifluoromethyl benzaldehyde derivatization. - Abstract: The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH{sub 2} groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH{sub 2}/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH{sub 2} fraction ∼8.5%. This value is closely matching the NH{sub 2}/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH{sub 2}/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA

  10. Primary ethynamines (HC similarly ordered CNH2, PhC similarly ordere CNH2), aminopropadienone (H2NCH=C=C=O), and imidoylketene (NH=CHCH=C=O). Preparation and identification of molecules of cosmochemical interest

    International Nuclear Information System (INIS)

    Wentrup, C.; Briehl, H.; Lorencak, P.; Vogelbacher, U.J.; Winter, H.W.; Maquestiau, A.; Flammang, R.

    1988-01-01

    Ethynamine (HC similarly ordered CNH 2 ) has been prepared from three different precursors by flash vacuum pyrolysis (FVP) and observed by low-temperature infrared spectroscopy for the first time. The collision activation mass spectra (CAMS) strongly support the assignments. The Meldrum's acid derivative also gives rise to equilibrating imidoylketene and aminopropadienone observable by both IR and CAMS. Ethynamine isomerizes in part to acetonitrile in the gas phase but polymerizes in the solid state between -70 and -50 0 C. Both ketene imine (H 2 C=C=NH) and acrylonitrile are formed on FVP of 3-hydroxypropionitrile. 2-Phenylethynamine (PhC similarly ordered CNH 2 ) is readily produced by FVP of the isoxazolone

  11. Platinum Group Thiophenoxyimine Complexes: Syntheses,Crystallographic and Computational Studies of Structural Properties

    Energy Technology Data Exchange (ETDEWEB)

    Krinsky, Jamin L.; Arnold, John; Bergman, Robert G.

    2006-10-03

    Monomeric thiosalicylaldiminate complexes of rhodium(I) and iridium(I) were prepared by ligand transfer from the homoleptic zinc(II) species. In the presence of strongly donating ligands, the iridium complexes undergo insertion of the metal into the imine carbon-hydrogen bond. Thiophenoxyketimines were prepared by non-templated reaction of o-mercaptoacetophenone with anilines, and were complexed with rhodium(I), iridium(I), nickel(II) and platinum(II). X-ray crystallographic studies showed that while the thiosalicylaldiminate complexes display planar ligand conformations, those of the thiophenoxyketiminates are strongly distorted. Results of a computational study were consistent with a steric-strain interpretation of the difference in preferred ligand geometries.

  12. In Situ Formation of Steroidal Supramolecular Gels Designed for Drug Release

    Directory of Open Access Journals (Sweden)

    Hana Bunzen

    2013-03-01

    Full Text Available In this work, a steroidal gelator containing an imine bond was synthesized, and its gelation behavior as well as a sensitivity of its gels towards acids was investigated. It was shown that the gels were acid-responsive, and that the gelator molecules could be prepared either by a conventional synthesis or directly in situ during the gel forming process. The gels prepared by both methods were studied and it was found that they had very similar macro- and microscopic properties. Furthermore, the possibility to use the gels as carriers for aromatic drugs such as 5-chloro-8-hydroxyquinoline, pyrazinecarboxamide, and antipyrine was investigated and the prepared two-component gels were studied with regard to their potential applications in drug delivery, particularly in a pH-controlled drug release.

  13. Reaction of Tosylmethyl Isocyanide with N-Heteroaryl Formamidines: an Alternative Approach to the Synthesis of N-Heteroaryl Tosylimidazoles

    Energy Technology Data Exchange (ETDEWEB)

    Gomezgarcia, Omar; Salgadozamora, Hector; Reyesarellano, Aliciam; Camposaldrete, Elena; Peraltacruz, Javier [Departamento Quimica Organica, Colonia (Mexico)

    2013-09-15

    In conclusion, an alternative procedure was developed under mild conditions for the synthesis of 2-(4-tosylimidazo-1-yl)pyridines and pyrimidines by the reaction of TosMIC with the corresponding heteroaryl N,N'-dimethyl form-amidines. This approach does not involve a nucleophilic displacement of a leaving group and constitutes a further application of amidines, in which TosMIC acts as both a nucleophile and an electrophile on the heteroaryl formamidine. This process offers advantages over previously reported procedures. Tosyl methyl isocyanide (TosMIC), a multipurpose commercially available 3-unit synthon introduced by Van Leusen, reacts with a variety of groups to give heterocycles. It is important to emphasize that treatment of TosMIC with various functional groups leads to the formation of the imidazole nucleus, such as is the case with imines, imidoyl chlorides, isothiocyanates, nitrile and ethoxy methylene amino. However, only the latter group yields N-heterocycle imidazoles.

  14. Synthesis and characterization of a novel mucoadhesive derivative of xyloglucan.

    Science.gov (United States)

    Madgulkar, Ashwini R; Bhalekar, Mangesh R; Asgaonkar, Kalyani D; Dikpati, Amrita A

    2016-01-01

    A novel polymer in the form of a thiolated derivative of natural tamarind seed polysaccharide or xyloglucan was synthesized and its chacteristics as a mucoadhesive polymer were studied as a part of the study undertaken herein. The synthetic route followed involves a two-step reaction mechanism of firstly oxidizing xyloglucan and then further conjugating it with l-cysteine to form thiolated xyloglucan or thiomer via imine linkage. The thiomer thus formed was characterized using various analytical techniques as differential scanning calorimetry (DSC), X-ray diffraction analysis (XRD), and nuclear magnetic resonance (NMR). Ellman's method was used to determine the numbers of thiol groups/g of thiolated xyloglucan. Zeta potential measurements were carried out for thiolated xyloglucan. Viscosities of the formulated xyloglucan and thiolated xyloglucan gels were comparatively evaluated along with the evaluation of mucoadhesive properties of the gels using ex vivo bioadhesion study employing freshly excised sheep intestinal mucosa. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Debromination of endo-(+)-3-bromocamphor with primary amines

    Energy Technology Data Exchange (ETDEWEB)

    Markovic, Svetlana; Markovic, Violeta; Joksovic, Milan D.; Joksovic, Ljubinka, E-mail: ljubinka@kg.ac.rs [Department of Chemistry, Faculty of Science, University of Kragujevac (Serbia); Todorovic, Nina [Institute for Chemistry, Technology and Metallurgy, Belgrade (Serbia); Divjakovic, Vladimir [Department of Physics, University of Novi Sad (Serbia); Trifunovic, Snezana [Faculty of Chemistry, University of Belgrade, Belgrade, (Serbia)

    2013-07-15

    Reductive debromination of endo-(+)-3-bromocamphor with different primary amines followed by imine formation was investigated. This reaction requires simple experimental procedure without any organic solvent, metal or conventional reducing agent. A strong influence of amine polarity on the efficacy of debromination process was observed, and ethanolamine and ethylene diamine having sufficiently high boiling points can debrominate 3-bromocamphor giving corresponding camphanimines in good isolated yields. The mechanisms of debromination of 3-bromocamphor with ethanolamine and n-hexylamine were investigated at the B3LYP/6-311+G(d,p) level of theory. The radical mechanism was revealed, and it was shown that the reaction with more polar ethanolamine is energetically more favorable. (author)

  16. A one-pot chemoselective synthesis of secondary amines by using a biomimetic electrocatalytic system

    International Nuclear Information System (INIS)

    Largeron, Martine

    2009-01-01

    A one-pot electrochemically induced oxidation-imine formation-reduction route to secondary amines is described in detail. The key step of the process consists of the o-iminoquinone-mediated chemoselective catalytic oxidation of a primary aliphatic amine substrate, in the presence of a second amine used as the alkylating agent. Through the examination of the scope of the reaction by systematically varying both amine substrate and amine alkylating agent, it can be shown that this reaction sequence, leaving ammonia as the sole by-product, allows the rapid synthesis of various secondary amines in moderate to good yields. This process, that highlights the pre-eminent green advantages of electrochemical synthesis, especially the utilization of electricity as energy instead of chemical reagents, high atom economy as well as ambient temperature and pressure, could be a mild alternative to already reported synthetic methods.

  17. A one-pot chemoselective synthesis of secondary amines by using a biomimetic electrocatalytic system

    Energy Technology Data Exchange (ETDEWEB)

    Largeron, Martine [UMR CNRS 8638, Synthese et Structure de Molecules d' nteret Pharmacologique, Universite Paris Descartes, Faculte des Sciences Pharmaceutiques et Biologiques, 4 Avenue de l' Observatoire, 75270 Paris Cedex 06 (France)], E-mail: martine.largeron@parisdescartes.fr

    2009-09-01

    A one-pot electrochemically induced oxidation-imine formation-reduction route to secondary amines is described in detail. The key step of the process consists of the o-iminoquinone-mediated chemoselective catalytic oxidation of a primary aliphatic amine substrate, in the presence of a second amine used as the alkylating agent. Through the examination of the scope of the reaction by systematically varying both amine substrate and amine alkylating agent, it can be shown that this reaction sequence, leaving ammonia as the sole by-product, allows the rapid synthesis of various secondary amines in moderate to good yields. This process, that highlights the pre-eminent green advantages of electrochemical synthesis, especially the utilization of electricity as energy instead of chemical reagents, high atom economy as well as ambient temperature and pressure, could be a mild alternative to already reported synthetic methods.

  18. {4-Phenyl-1-[1-(1,3-thiazol-2-ylethylidene]thiosemicarbazidato}{4-phenyl-1-[1-(1,3-thiazol-2-ylethylidene]thiosemicarbazide}nickel(II chloride monohydrate

    Directory of Open Access Journals (Sweden)

    Ramaiyer Venkatraman

    2010-05-01

    Full Text Available In the title compound, [Ni(C12H11N4S2(C12H12N4S2]Cl·H2O, the NiII ion is chelated by two 2-acetylthiazole-3-phenylthiosemicarbazone ligands, forming a distorted octahedral complex. The metal ion is coordinated via the thiazole nitrogen, imine nitrogen and thione sulfur atoms from each thiosemicarbazone ligand, and two coordinating units lie almost perpendicular to each other give dihedral angle = 81.89 (1°]. One thiosemicarbazone unit is found to bind a chloride anion through two hydrogen bonds, while the other is linked with the disordered crystal water molecule. Two molecules are connected to each other through an intermolecular N—H...S interaction, forming a centrosymmetric dimer. Dimers are linked into sheets by π–π stacking of two phenyl rings [shortest C...C distance = 4.041 (3 Å].

  19. Özgün İslami Finansal Kurumlar İnşa Etmek

    Directory of Open Access Journals (Sweden)

    Asad Zaman Çeviren: Mustafa Kenan ERKAN

    2016-11-01

    Full Text Available Özet İslam’ın ruhunun kapitalizmin ruhuyla sert ve keskin bir uyuşmazlık içinde olmasından dolayı, İslam’ın ruhunu ifade etmek üzere tasarlanmış kurumların almış olduğu biçimin de ayrıca farklı olması zorunludur. Kapitalist finansal kurumlar kapitalist toplumların özünde yer alan servet biriktirme sürecini desteklemek üzere tasarlanmışlardır. İslam’da esas olan, kapitalist toplumlarda baskın olanlardan radikal bir şekilde farklı çeşitli hizmet-odaklı kurumlardaki hizmet ruhu ve başkalarına infak etmektir.

  20. Fractionation of whey proteins with high-capacity superparamagnetic ion-exchangers

    DEFF Research Database (Denmark)

    Heebøll-Nielsen, Anders; Justesen, S.F.L.; Thomas, Owen R. T.

    2004-01-01

    to particles activated in sequential reactions with allyl bromide and N-bromosuccinimide yielded a maximum bovine serum albumin binding capacity of 156 mg g(-1) combined with a dissociation constant of 0.60 muM, whereas ion-exchangers created by linking polyethylene imine through superficial aldehydes bound up...... was then contacted with the anion-exchanger. For both adsorbent classes of ion-exchanger, desorption selectivity was subsequently studied by sequentially increasing the concentration of NaCl in the elution buffer. In the initial cation-exchange step quantitative removal of lactoferrin (LF) and lactoperoxidase (LPO......) was achieved with some simultaneous binding of immunoglobulins (1g). The immunoglobulins were separated from the other two proteins by desorbing with a low concentration of NaCl (less than or equal to0.4 M), whereas lactoferrin and lactoperoxidase were co-eluted in significantly purer form, e...

  1. A novel conversion of C(19)-diterpenoid alkaloids into aconane-type diterpenes with eight-membered ring system via skeletal rearrangement of corresponding diazonium derivatives.

    Science.gov (United States)

    Ji, Hong; Chen, Qiao-Hong; Wang, Feng-Peng

    2009-03-01

    A new and efficient approach toward the conversion of C(19)-diterpenoid alkaloids into diterpenes with [6+8+5+6] ring system is reported. Treatment of imines 5, 14, and 24 derived from the C(19)-diterpenoid alkaloids with NaNO(2)-NaOAc-HOAc afforded a series of novel rearrangement diterpenes 6-8, 15-19, and 25-27, respectively. The lactone 11 was obtained in 41% yield by treating 5 with NaNO(2)-HBr-Br(2). The formation of diazonium intermediate is postulated, which was subsequently subjected to skeletal rearrangement, leading to the enlargement of B ring. All the new compounds were isolated and fully characterized.

  2. Sensitive detection of strong acidic condition by a novel rhodamine-based fluorescent pH chemosensor.

    Science.gov (United States)

    Tan, Jia-Lian; Yang, Ting-Ting; Liu, Yu; Zhang, Xue; Cheng, Shu-Jin; Zuo, Hua; He, Huawei

    2016-05-01

    A novel rhodamine-based fluorescent pH probe responding to extremely low pH values has been synthesized and characterized. This probe showed an excellent photophysical response to pH on the basis that the colorless spirocyclic structure under basic conditions opened to a colored and highly fluorescent form under extreme acidity. The quantitative relationship between fluorescence intensity and pH value (1.75-2.62) was consistent with the equilibrium equation pH = pKa + log[(Imax - I)/(I - Imin)]. This sensitive pH probe was also characterized with good reversibility and no interaction with interfering metal ions, and was successfully applied to image Escherichia coli under strong acidity. Copyright © 2015 John Wiley & Sons, Ltd.

  3. Molecular recognition: Comparative study of a tunable host-guest system by using a fluorescent model system and collision-induced dissociation mass spectrometry on dendrimers

    DEFF Research Database (Denmark)

    Pittelkow, M.; Nielsen, C.B.; Broeren, A.C.

    2005-01-01

    Host-guest interactions between the periphery of adamantylurea-functionalized dendrimers (host) and ureido acetic acid derivatives (guest) were shown to be specific, strong and spatially well-defined. The binding becomes stronger when using phosphonic or sulfonic acid derivatives. In the present...... work we have quantified the binding constants for the host-guest interactions between two different host motifs and six different guest molecules. The host molecules, which resemble the periphery of a poly(propylene imine) dendrimer, have been fitted with an anthracene-based fluorescent probe. The two...... host motifs differ in terms of the length of the spacer between a tertiary amine and two ureido functionalities. The guest molecules all contain an acidic moiety (either a carboxylic acid, a phosphonic acid, or a sulfonic acid) and three of them also contain an ureido moiety capable of forming multiple...

  4. Synthesis and characterization of thorium(IV) and uranium(IV) complexes with Schiff bases

    Energy Technology Data Exchange (ETDEWEB)

    Radoske, Thomas; Maerz, Juliane; Kaden, Peter; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements

    2017-06-01

    We report herein the synthesis and characterization of several imine complexes of tetravalent thorium (Th(IV)) and uranium (U(IV)). The ligands investigated in this study are a Schiff base type, including the well-known salen ligand (H{sub 2}Le, Fig. 1). The complexation in solution was investigated by NMR measurements indicating paramagnetic effects of unpaired f-electrons of U(IV) on the ligand molecule. We also determined the solid-state molecular structures of the synthesized complexes by single crystal X-ray diffraction. The synthesized complexes show an eight-fold coordination geometry around the actinide center surrounded by two tetradentate ligands with 2N- and 2O-donor atoms.

  5. Catalytic behaviors of Co{sup II} and Mn{sup II} compounds bearing α-Diimine ligands for oxidative polymerization or drying oils

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Gilvan E.S.; Nunes, Everton V.; Dantas, Roberta C.; Meneghetti, Mario R.; Meneghetti, Simoni M.P., E-mail: simoni.plentz@gmail.com [Universidade Federal de Alagoas (UFAL), Maceió, AL (Brazil). Grupo de Catálise e Reatividade Química; Simone, Carlos A. de [Universidade de Sao Paulo (USP), São Carlos, USP, SP (Brazil). Instituto de Física

    2018-05-01

    The oxidative polymerization of linseed oil was investigated comparing the classical catalysts cobalt(II) 2-ethylhexanoate and manganese(II) 2-ethylhexanoate and their derivatives modified by the presence of chelating nitrogen ligands, i.e., 2,2’-bipyridyl, 2-(acetyl-2,6-diisopropylphenylimine)- pyridine and [N-(2,6-diisopropylphenyl)imine]acenaphthoquinone. The suitable stoichiometries between the two precursor complexes with the three ligands were determined by UV-visible spectroscopy. All complexes were characterized by infrared spectroscopy, and one complex was characterized also by X-ray diffraction. The apparent kinetic constants of oxidative polymerization of linseed oil was determined, for each catalytic system, via the periodic measurements of the oil viscosity during the oxidation reaction. The results indicated that the modifications of the classical two complexes with the chelating nitrogen ligands improved the catalytic efficiency at least to the manganese complex. (author)

  6. Inheritance and gene expression of a root-growth inhibiting mutant in rice (Oryza sativa L.)

    International Nuclear Information System (INIS)

    Kitano, H.; Futsuhara, Y.

    1990-01-01

    Full text: A root-growth inhibiting mutant was induced in the dwarf mutant line, 'Fukei 71', through ethylene-imine. The mutant is characterised by the excessive inhibition of both seminal and crown roots elongation just after germination, although its shoots grow nearly normal. To study the genetics, the mutant was crossed with its original line 'Fukei 71' and some other normal cultivars. Results show that the root-growth inhibition is controlled by a recessive gene (rt), independent of the dwarf gene, d-50(t) locus in Fukei 71. For elucidating the gene action on root morphogenesis, histological and cytological experiments were carried out using a longitudinal and transverse thin section of seminal and/or crown root tips. Observations suggest that the rt gene affects the normal formation of the epidermal system which is differentiated from the protoderm of the root apical meristem. (author)

  7. 3-[(E-(4-Chlorobenzylideneamino]-1-phenylthiourea

    Directory of Open Access Journals (Sweden)

    Nur Nadia Dzulkifli

    2011-04-01

    Full Text Available In the title compound, C14H12ClN3S, the dihedral angle between the terminal benzene rings is 56.6 (2°; the benzene rings lie to the same side of the molecule. The major twist in the molecule occurs around the Car—N bond (ar is aromatic [C—N—C—C = 49.9 (5°]. The configuration about the N=C bond [1.271 (4 Å] is E. The amine H atoms lie on opposite sides of the molecule with one forming an intramolecular N—H...N(imine hydrogen bond and an S(5 ring. In the crystal, centrosymmetric dimers are formed via {...HNC=S}2 synthons.

  8. Simple preparation of new N-aryl-N-(3-indolmethyl acetamides and their spectroscopic analysis

    Directory of Open Access Journals (Sweden)

    José A. Henao

    2009-12-01

    Full Text Available To prepare new indolic molecules and characterize them by spectroscopic methods. Materials and methods: All reagentswere purchased from Aldrich, commercial grade. The purity of the products and the composition of the reaction mixtures were monitoredby thin layer chromatography over Silufol UV254 0.25 mm-thick chromatoplates. Product isolation and purification were performed bycolumn chromatography (SiO2, using ethyl acetate-petroleum ether mixtures as eluents. Results. The synthesis of new N-aryl-N-(3-indolmethyl acetamides based on first step iminization reaction of indol-3-carbaldehyde is accomplished. The structures of the C-3substituted indoles were confirmed by 1H-NMR and 13C-NMR studies supported by inverse-detected 2D NMR experiments and alsothrough monocrystal X-ray diffraction. Conclusions. An efficient, economic, and fast synthetic route was designed to the construction ofthe N-aryl-N-(3-indolmethyl acetamides, structural analogues of some alkaloids.

  9. Synthesis of furan-based DNA binders and their interaction with DNA

    International Nuclear Information System (INIS)

    Voege, Andrea; Hoffmann, Sascha; Gabel, Detlef

    2006-01-01

    In recent years, many substances, based on naturally occurring DNA-binding molecules have been developed for the use in cancer therapy and as virostatica. Most of these substances are binding specifically to A-T rich sequences in the DNA minor groove. Neutral and positively charged DNA-binders are known. BNCT is most effective, which the boron is directly located in the cellular nucleus, so that the intercation with thermal neutrons can directly damage the DNA. To reach this aim, we have connected ammonioundecahydrododecaborate(1-) to DNA-binding structures such as 2,5-bis(4-formylphenyl)furan via a Schiff-Base reaction followed by a reduction of the imine to a secondary amine. In a following step the amine can be alkylated to insert positive charges to prevent repulsion between the compounds and the negatively charged sugar-phosphate-backbone of the DNA. (author)

  10. SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

    KAUST Repository

    Falivene, Laura; Credendino, Raffaele; Poater, Albert; Petta, Andrea; Serra, Luigi; Oliva, Romina; Scarano, Vittorio; Cavallo, Luigi

    2016-01-01

    Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.

  11. Use of Biosensors as Alternatives to Current Regulatory Methods for Marine Biotoxins

    Directory of Open Access Journals (Sweden)

    Luis M. Botana

    2009-11-01

    Full Text Available Marine toxins are currently monitored by means of a bioassay that requires the use of many mice, which poses a technical and ethical problem in many countries. With the exception of domoic acid, there is a legal requirement for the presence of other toxins (yessotoxin, saxitoxin and analogs, okadaic acid and analogs, pectenotoxins and azaspiracids in seafood to be controlled by bioassay, but other toxins, such as palytoxin, cyclic imines, ciguatera and tetrodotoxin are potentially present in European food and there are no legal requirements or technical approaches available to identify their presence. The need for alternative methods to the bioassay is clearly important, and biosensors have become in recent years a feasible alternative to animal sacrifice. This review will discuss the advantages and disadvantages of using biosensors as alternatives to animal assays for marine toxins, with particular focus on surface plasmon resonance (SPR technology.

  12. Computational investigation of rearrangements in huisgen cycloadducts of azolium N-dicyanomethanide 1,3-dipoles with alkynes: a mechanistic panoply.

    Science.gov (United States)

    Burke, Luke A; Butler, Richard N

    2009-08-07

    The reaction surfaces leading to rearrangements and ring expansions of azapentalene cycloadducts of imidazolo- and triazolodicyanomethanide 1,3-dipoles with alkynes are studied with the B3LYP DFT method using the 6-31G(d) and 6-311+G(2d,p) basis sets. The surprisingly complex surface involves (1) consecutive but not combined pericyclic steps, a coarctate TS, and pseudopericyclic mechanisms, (2) anchimerically assisted H-atom transfer competing effectively with concerted symmetry-allowed sigmatropic steps, and (3) azolium methanide zwitterions and ketenimines as key intermediates. The azolium methanide is identified as the intermediate detected previously in a variable-temperature NMR experiment that converted the unstable cycloadduct to product imine.

  13. Nitrogen Fixation by Photochemistry in the Atmosphere of Titan and Implications for Prebiotic Chemistry

    Science.gov (United States)

    Balucani, Nadia

    The observation of N-containing organic molecules and the composition of the haze aerosols, as determined by the Aerosol Collector and Pyrolyser (ACP) on-board Huygens, are clear indications that some chemistry involving nitrogen active forms and hydrocarbons is operative in the upper atmosphere of Titan. Neutral-neutral reactions involving the first electronically excited state of atomic nitrogen, N(2D), and small hydrocarbons have the right prerequisites to be among the most significant pathways to formation of nitriles, imines and other simple N-containing organic molecules. The closed-shell products methanimine, ethanimine, ketenimine, 2H-azirine and the radical products CH3N, HCCN and CH2NCH can be the intermediate molecular species that, via addition reactions, polymerization and copolymerization form the N-rich organic aerosols of Titan as well as tholins in bulk reactors simulating Titan's atmosphere.

  14. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Science.gov (United States)

    Malloy, Q. G. J.; Qi, Li; Warren, B.; Cocker, D. R., III; Erupe, M. E.; Silva, P. J.

    2009-03-01

    Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

  15. Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter.

    Science.gov (United States)

    Liu, Pengfei; Li, Yong Jie; Wang, Yan; Bateman, Adam P; Zhang, Yue; Gong, Zhaoheng; Bertram, Allan K; Martin, Scot T

    2018-02-28

    Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet-visible spectrophotometry, was kinetically inhibited for RH atmospheric brown carbon production and associated influences on energy balance.

  16. Synthesis, Characterization, and Catalytic Activity of Pd(II Salen-Functionalized Mesoporous Silica

    Directory of Open Access Journals (Sweden)

    Rotcharin Sawisai

    2017-01-01

    Full Text Available Salen ligand synthesized from 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde was used as a palladium chelating ligand for the immobilization of the catalytic site. Mesoporous silica supported palladium catalysts were prepared by immobilizing Pd(OAc2 onto a mesoporous silica gel through the coordination of the imine-functionalized mesoporous silica gel. The prepared catalysts were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray (EDX, inductivity couple plasma (ICP, nitrogen adsorption-desorption, and Fourier transform infrared (FT-IR spectroscopy. The solid catalysts showed higher activity for the hydroamination of C-(tetra-O-acetyl-β-D-galactopyranosylallene with aromatic amines compared with the corresponding homogenous catalyst. The heterogeneous catalytic system can be easily recovered by simple filtration and reused for up to five cycles with no significant loss of catalytic activity.

  17. The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

    Science.gov (United States)

    Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

    2017-01-12

    We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Nephelauxetic and hypersensitive nature of neodymium(III) complexes with α-pyridyl-thiosemicarbazide and its furfural-2-aldehyde and thiophene-2-aldehyde derivatives

    International Nuclear Information System (INIS)

    Jain, C.L.; Mundley, P.N.; Khandelwal, B.E.

    1986-01-01

    A new series of octahedral Nd(III) complexes with recently synthesised α-pyridylthiosemicarbazide (C 6 H 8 N 4 S or 'PT'), N-(α-pyridyl)furfural-2-aldehyde-thiosemicarbazone (C 11 H 10 N 4 SO or 'PFT') and N-(α-pyridyl)thiophene-2-aldehyde-thiosemicarbazone (C 11 H 10 N 4 S 2 or 'PTT'), have been isolated and characterised on the basis of their elemental analysis, magnetic and reflectance and ir spectral data revealing 'PT' as bidentate (pyridinic-N and thioketo-S) and 'PFT' and 'PTT' as tetradentate with pyridinic-N, thioketo-S, imine-N and furfuryl-O/thiophenyl-S as donor sites. Isolation and characterisation of Nd(III) complexes with 'PT', 'PFT' and 'PTT' and their nephelauxetic and hypersensitive nature are studied in order to evaluate the stereochemistry of the ligands around Nd(III) ion. (author). 12 refs., 2 tables

  19. A stereoselective, catalytic strategy for the in-flow synthesis of advanced precursors of rasagiline and tamsulosin.

    Science.gov (United States)

    Brenna, Davide; Pirola, Margherita; Raimondi, Laura; Burke, Anthony J; Benaglia, Maurizio

    2017-12-01

    The diastereoselective, trichlorosilane-mediate reduction of imines, bearing different and removable chiral auxiliaries, in combination either with achiral bases or catalytic amounts of chiral Lewis bases, was investigated to afford immediate precursors of chiral APIs (Active Pharmaceutical Ingredients). The carbon-nitrogen double bond reduction was successfully performed in batch and in flow mode, in high yields and almost complete stereocontrol. By this metal-free approach, the formal synthesis of rasagiline and tamsulosin was successfully accomplished in micro(meso) flow reactors, under continuous flow conditions. The results of these explorative studies represent a new, important step towards the development of automated processes for the preparation of enantiopure biologically active compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Low-Mode Conformational Search Method with Semiempirical Quantum Mechanical Calculations: Application to Enantioselective Organocatalysis.

    Science.gov (United States)

    Kamachi, Takashi; Yoshizawa, Kazunari

    2016-02-22

    A conformational search program for finding low-energy conformations of large noncovalent complexes has been developed. A quantitatively reliable semiempirical quantum mechanical PM6-DH+ method, which is able to accurately describe noncovalent interactions at a low computational cost, was employed in contrast to conventional conformational search programs in which molecular mechanical methods are usually adopted. Our approach is based on the low-mode method whereby an initial structure is perturbed along one of its low-mode eigenvectors to generate new conformations. This method was applied to determine the most stable conformation of transition state for enantioselective alkylation by the Maruoka and cinchona alkaloid catalysts and Hantzsch ester hydrogenation of imines by chiral phosphoric acid. Besides successfully reproducing the previously reported most stable DFT conformations, the conformational search with the semiempirical quantum mechanical calculations newly discovered a more stable conformation at a low computational cost.