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Sample records for tertiary amine oxides

  1. 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.

  2. 2,2,2-Trifluoroacetophenone as an organocatalyst for the oxidation of tertiary amines and azines to N-oxides.

    Science.gov (United States)

    Limnios, Dimitris; Kokotos, Christoforos G

    2014-01-07

    A cheap, mild and environmentally friendly oxidation of tertiary amines and azines to the corresponding N-oxides is reported by using polyfluoroalkyl ketones as efficient organocatalysts. 2,2,2-Trifluoroacetophenone was identified as the optimum catalyst for the oxidation of aliphatic tertiary amines and azines. This oxidation is chemoselective and proceeds in high-to-quantitative yields utilizing 10 mol % of the catalyst and H2 O2 as the oxidant. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Complementation of biotransformations with chemical C-H oxidation: copper-catalyzed oxidation of tertiary amines in complex pharmaceuticals.

    Science.gov (United States)

    Genovino, Julien; Lütz, Stephan; Sames, Dalibor; Touré, B Barry

    2013-08-21

    The isolation, quantitation, and characterization of drug metabolites in biological fluids remain challenging. Rapid access to oxidized drugs could facilitate metabolite identification and enable early pharmacology and toxicity studies. Herein, we compared biotransformations to classical and new chemical C-H oxidation methods using oxcarbazepine, naproxen, and an early compound hit (phthalazine 1). These studies illustrated the low preparative efficacy of biotransformations and the inability of chemical methods to oxidize complex pharmaceuticals. We also disclose an aerobic catalytic protocole (CuI/air) to oxidize tertiary amines and benzylic CH's in drugs. The reaction tolerates a broad range of functionalities and displays a high level of chemoselectivity, which is not generally explained by the strength of the C-H bonds but by the individual structural chemotype. This study represents a first step toward establishing a chemical toolkit (chemotransformations) that can selectively oxidize C-H bonds in complex pharmaceuticals and rapidly deliver drug metabolites.

  4. (E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

    Science.gov (United States)

    Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

    2015-02-21

    A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

  5. Tailoring Enzyme-Like Activities of Gold Nanoclusters by Polymeric Tertiary Amines for Protecting Neurons Against Oxidative Stress.

    Science.gov (United States)

    Liu, Ching-Ping; Wu, Te-Haw; Lin, Yu-Lung; Liu, Chia-Yeh; Wang, Sabrina; Lin, Shu-Yi

    2016-08-01

    The cytotoxicity of nanozymes has drawn much attention recently because their peroxidase-like activity can decompose hydrogen peroxide (H2 O2 ) to produce highly toxic hydroxyl radicals (•OH) under acidic conditions. Although catalytic activities of nanozymes are highly associated with their surface properties, little is known about the mechanism underlying the surface coating-mediated enzyme-like activities. Herein, it is reported for the first time that amine-terminated PAMAM dendrimer-entrapped gold nanoclusters (AuNCs-NH2 ) unexpectedly lose their peroxidase-like activity while still retaining their catalase-like activity in physiological conditions. Surprisingly, the methylated form of AuNCs-NH2 (i.e., MAuNCs-N(+) R3 , where R = H or CH3 ) results in a dramatic recovery of the intrinsic peroxidase-like activity while blocking most primary and tertiary amines (1°- and 3°-amines) of dendrimers to form quaternary ammonium ions (4°-amines). However, the hidden peroxidase-like activity is also found in hydroxyl-terminated dendrimer-encapsulated AuNCs (AuNCs-OH, inside backbone with 3°-amines), indicating that 3°-amines are dominant in mediating the peroxidase-like activity. The possible mechanism is further confirmed that the enrichment of polymeric 3°-amines on the surface of dendrimer-encapsulated AuNCs provides sufficient suppression of the critical mediator •OH for the peroxidase-like activity. Finally, it is demonstrated that AuNCs-NH2 with diminished cytotoxicity have great potential for use in primary neuronal protection against oxidative damage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Oxidation of tertiary amines by cytochrome p450-kinetic isotope effect as a spin-state reactivity probe.

    Science.gov (United States)

    Li, Chunsen; Wu, Wei; Cho, Kyung-Bin; Shaik, Sason

    2009-08-24

    Two types of tertiary amine oxidation processes, namely, N-dealkylation and N-oxygenation, by compound I (Cpd I) of cytochrome P450 are studied theoretically using hybrid DFT calculations. All the calculations show that both N-dealkylation and N-oxygenation of trimethylamine (TMA) proceed preferentially from the low-spin (LS) state of Cpd I. Indeed, the computed kinetic isotope effects (KIEs) for the rate-controlling hydrogen abstraction step of dealkylation show that only the KIE(LS) fits the experimental datum, whereas the corresponding value for the high-spin (HS) process is much higher. These results second those published before for N,N-dimethylaniline (DMA), and as such, they further confirm the conclusion drawn then that KIEs can be a sensitive probe of spin state reactivity. The ferric-carbinolamine of TMA decomposes most likely in a non-enzymatic reaction since the Fe-O bond dissociation energy (BDE) is negative. The computational results reveal that in the reverse reaction of N-oxygenation, the N-oxide of aromatic amine can serve as a better oxygen donor than that of aliphatic amine to generate Cpd I. This capability of the N-oxo derivatives of aromatic amines to transfer oxygen to the heme, and thereby generate Cpd I, is in good accord with experimental data previously reported.

  7. 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.

  8. Saturated amine oxides: Part 8. Hydroacridines: Part 27. Effects of N-oxidation and of N-quaternization on the 15N NMR chemical shifts of N-methylpiperidine-derived mono-, bi-, and tricycloaliphatic tertiary amines.

    Science.gov (United States)

    Potmischil, Francisc; Duddeck, Helmut; Nicolescu, Alina; Deleanu, Calin

    2007-03-01

    The (15)N chemical shifts of 13 N-methylpiperidine-derived mono-, bi- and tricycloaliphatic tertiary amines, their methiodides and their N-epimeric pairs of N-oxides were measured, and the contributions of specific structural parameters to the chemical shifts were determined by multilinear regression analysis. Within the examined compounds, the effects of N-oxidation upon the (15)N chemical shifts of the amines vary from +56 ppm to +90 ppm (deshielding), of which approx. +67.7 ppm is due to the inductive effect of the incoming N(+)--O(-) oxygen atom, whereas the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The effects of quaternization vary from -3.1 ppm to +29.3 ppm, of which approx. +8.9 ppm is due to the inductive effect of the incoming N(+)--CH(3) methyl group, and the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The shift effects of the C-alkyl substituents in the amines, the N-oxides and the methiodides are discussed. Copyright (c) 2007 John Wiley & Sons, Ltd.

  9. Probing the Compound I-like reactivity of a bare high-valent oxo iron porphyrin complex: the oxidation of tertiary amines.

    Science.gov (United States)

    Chiavarino, Barbara; Cipollini, Romano; Crestoni, Maria Elisa; Fornarini, Simonetta; Lanucara, Francesco; Lapi, Andrea

    2008-03-12

    The mechanisms of oxidative N-dealkylation of amines by heme enzymes including peroxidases and cytochromes P450 and by functional models for the active Compound I species have long been studied. A debated issue has concerned in particular the character of the primary step initiating the oxidation sequence, either a hydrogen atom transfer (HAT) or an electron transfer (ET) event, facing problems such as the possible contribution of multiple oxidants and complex environmental effects. In the present study, an oxo iron(IV) porphyrin radical cation intermediate 1, [(TPFPP)*+ Fe(IV)=O]+ (TPFPP = meso-tetrakis (pentafluorophenyl)porphinato dianion), functional model of Compound I, has been produced as a bare species. The gas-phase reaction with amines (A) studied by ESI-FT-ICR mass spectrometry has revealed for the first time the elementary steps and the ionic intermediates involved in the oxidative activation. Ionic products are formed involving ET (A*+, the amine radical cation), formal hydride transfer (HT) from the amine ([A(-H)]+, an iminium ion), and oxygen atom transfer (OAT) to the amine (A(O), likely a carbinolamine product), whereas an ionic product involving a net initial HAT event is never observed. The reaction appears to be initiated by an ET event for the majority of the tested amines which included tertiary aliphatic and aromatic amines as well as a cyclic and a secondary amine. For a series of N,N-dimethylanilines the reaction efficiency for the ET activated pathways was found to correlate with the ionization energy of the amine. A stepwise pathway accounts for the C-H bond activation resulting in the formal HT product, namely a primary ET process forming A*+, which is deprotonated at the alpha-C-H bond forming an N-methyl-N-arylaminomethyl radical, A(-H)*, readily oxidized to the iminium ion, [A(-H)]+. The kinetic isotope effect (KIE) for proton transfer (PT) increases as the acidity of the amine radical cation increases and the PT reaction to the base

  10. Formation mechanism of NDMA from ranitidine, trimethylamine, and other tertiary amines during chloramination: a computational study.

    Science.gov (United States)

    Liu, Yong Dong; Selbes, Meric; Zeng, Chengchu; Zhong, Rugang; Karanfil, Tanju

    2014-01-01

    Chloramination of drinking waters has been associated with N-nitrosodimethylamine (NDMA) formation as a disinfection byproduct. NDMA is classified as a probable carcinogen and thus its formation during chloramination has recently become the focus of considerable research interest. In this study, the formation mechanisms of NDMA from ranitidine and trimethylamine (TMA), as models of tertiary amines, during chloramination were investigated by using density functional theory (DFT). A new four-step formation pathway of NDMA was proposed involving nucleophilic substitution by chloramine, oxidation, and dehydration followed by nitrosation. The results suggested that nitrosation reaction is the rate-limiting step and determines the NDMA yield for tertiary amines. When 45 other tertiary amines were examined, the proposed mechanism was found to be more applicable to aromatic tertiary amines, and there may be still some additional factors or pathways that need to be considered for aliphatic tertiary amines. The heterolytic ONN(Me)2-R(+) bond dissociation energy to release NDMA and carbocation R(+) was found to be a criterion for evaluating the reactivity of aromatic tertiary amines. A structure-activity study indicates that tertiary amines with benzyl, aromatic heterocyclic ring, and diene-substituted methenyl adjacent to the DMA moiety are potentially significant NDMA precursors. The findings of this study are helpful for understanding NDMA formation mechanism and predicting NDMA yield of a precursor.

  11. Oxidation of amines by flavoproteins.

    Science.gov (United States)

    Fitzpatrick, Paul F

    2010-01-01

    Many flavoproteins catalyze the oxidation of primary and secondary amines, with the transfer of a hydride equivalent from a carbon-nitrogen bond to the flavin cofactor. Most of these amine oxidases can be classified into two structural families, the D-amino acid oxidase/sarcosine oxidase family and the monoamine oxidase family. This review discusses the present understanding of the mechanisms of amine and amino acid oxidation by flavoproteins, focusing on these two structural families. Copyright 2009 Elsevier Inc. All rights reserved.

  12. Concise Redox Deracemization of Secondary and Tertiary Amines with a Tetrahydroisoquinoline Core via a Nonenzymatic Process.

    Science.gov (United States)

    Ji, Yue; Shi, Lei; Chen, Mu-Wang; Feng, Guang-Shou; Zhou, Yong-Gui

    2015-08-26

    A concise deracemization of racemic secondary and tertiary amines with a tetrahydroisoquinoline core has been successfully realized by orchestrating a redox process consisted of N-bromosuccinimide oxidation and iridum-catalyzed asymmetric hydrogenation. This compatible redox combination enables one-pot, single-operation deracemization to generate chiral 1-substituted 1,2,3,4-tetrahydroisoquinolines with up to 98% ee in 93% yield, offering a simple and scalable synthetic technique for chiral amines directly from racemic starting materials.

  13. Catalyst Deactivation Reactions : The Role of Tertiary Amines Revisited

    NARCIS (Netherlands)

    Novarino, Elena; Rios, Itzel Guerrero; van der Veer, Siebe; Meetsma, Auke; Hessen, Bart; Bouwkamp, Marco W.

    2011-01-01

    Decamethylzirconocene cation [Cp*2ZrMe](+) (2) decomposes in bromobenzene-d(5) solution to generate sigma-aryl species [Cp*Zr-2(2-C6H4Br-kappa Br,C)][B(C6F5)(4)] (3). This a-bond metathesis reaction is catalyzed by tertiary amines via a two-step mechanism, in which the amine acts as a proton relay.

  14. Sodium Perborate Oxidation of an Aromatic Amine

    Science.gov (United States)

    Juestis, Laurence

    1977-01-01

    Describes an experiment involving the oxidation of aromatic primary amines to the corresponding azo compound; suggests procedures for studying factors that influence the yield of such a reaction, including the choice of solvent and the oxidant-amine ratio. (MLH)

  15. Yb(OTf){sub 3}-catalyzed one-pot three component synthesis for tertiary amines

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Bum Seok; Kim, Ji Hye; Nam, Tae Kyu; Jang, Doo Ok [Dept. of Chemistry, Yonsei University, Wonju (Korea, Republic of)

    2015-07-15

    Tertiary amine functionality is found in many natural bioactive products such as alkaloids, amino acids, nucleic acids, pharmaceuticals, and agrochemicals. Tertiary amines have also been used as building blocks for nitrogen-containing organic compounds and synthetic polymers. A one-pot method for direct reductive amination of aldehydes has been developed to synthesize tertiary amines using HMDS as a nitrogen source in the presence of Yb(OTf ){sub 3}. With a stoichiometric amount of HMDS, the reaction afforded the desired tertiary amines without competitive reduction of the parent carbonyl compounds. This reaction offers a convenient and efficient protocol for synthesizing aromatic and aliphatic tertiary amines under mild reaction conditions.

  16. Tandem catalytic allylic amination and [2,3]-Stevens rearrangement of tertiary amines.

    Science.gov (United States)

    Soheili, Arash; Tambar, Uttam K

    2011-08-24

    We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.

  17. Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

    Science.gov (United States)

    Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

    2012-01-14

    Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

  18. Tertiary-amine-containing thermo- and pH-sensitive hydrophilic ABA triblock copolymers: effect of different tertiary amines on thermally induced sol-gel transitions.

    Science.gov (United States)

    Henn, Daniel M; Wright, Roger A E; Woodcock, Jeremiah W; Hu, Bin; Zhao, Bin

    2014-03-11

    This Article reports on the synthesis of a series of well-defined, tertiary-amine-containing ABA triblock copolymers, composed of a poly(ethylene oxide) (PEO) central block and thermo- and pH-sensitive outer blocks, and the study of the effect of different tertiary amines on thermally induced sol-gel transition temperatures (T(sol-gel)) of their 10 wt % aqueous solutions. The doubly responsive ABA triblock copolymers were prepared from a difunctional PEO macroinitiator by atom transfer radical polymerization of methoxydi(ethylene glycol) methacrylate and ethoxydi(ethylene glycol) methacrylate at a feed molar ratio of 30:70 with ∼5 mol % of either N,N-diethylaminoethyl methacrylate (DEAEMA), N,N-diisopropylaminoethyl methacrylate, or N,N-di(n-butyl)aminoethyl methacrylate. The chain lengths of thermosensitive outer blocks and the molar contents of tertiary amines were very similar for all copolymers. Using rheological measurements, we determined the pH dependences of T(sol-gel) of 10 wt % aqueous solutions of these copolymers in a phosphate buffer. The T(sol-gel) versus pH curves of all polymers exhibited a sigmoidal shape. The T(sol-gel) increased with decreasing pH; the changes were small on both high and low pH sides. At a specific pH, the T(sol-gel) decreased with increasing the hydrophobicity of the tertiary amine, and upon decreasing pH the onset pH value for the T(sol-gel) to begin to increase noticeably was lower for the more hydrophobic tertiary amine-containing copolymer. In addition, we studied the effect of different tertiary amines on the release behavior of FITC-dextran from 10 wt % micellar gels in an acidic medium at 37 and 27 °C. The release profiles for three studied hydrogels at 37 °C were essentially the same, suggesting that the release was dominated by the diffusion of FITC-dextran. At 27 °C, the release was significantly faster for the DEAEMA-containing copolymer, indicating that both diffusion and gel dissolution contributed to the

  19. Berkelium (4) and cerium (4) extraction with tertiary amines

    International Nuclear Information System (INIS)

    Milyukova, M.S.; Malikov, D.A.; Myasoedov, B.V.

    1978-01-01

    Oxidation of indicator quantities of berkelium and cerium by a mixture of silver nitrate and ammonium persulfate in the solutions of nitric and sulfuric acid has been examined. The stability of the elements in a tetravalent state and their extraction by the solutions of ternary amines have been investigated. It has been established that berkelium and cerium oxidation under these conditions occurs under the effect of ions of divalent silver which is formed owing to oxidation of monovalent silver by peroxide sulfate ions. The following supposition has been put forward: a difference in the behaviour of tetravalent berkelium and cerium during their extraction by ternary amines is explained by their different stability in this state, but not by the formation of complex compounds with nitrate ions

  20. Equilibrium and Transport Properties of Primary, Secondary and Tertiary Amines by Molecular Simulation

    International Nuclear Information System (INIS)

    Orozco, Gustavo A.; Nieto-Draghi, Carlos; Lachet, Veronique; Mackie, Allan D.

    2014-01-01

    Using molecular simulation techniques such as Monte Carlo (MC) and molecular dynamics (MD), we present several simulation results of thermodynamic and transport properties for primary, secondary and tertiary amines. These calculations are based on a recently proposed force field for amines that follows the Anisotropic United Atom approach (AUA). Different amine molecules have been studied, including n-Butylamine, di-n-Butylamine, tri-n-Butylamine and 1,4-Butanediamine for primary, secondary, tertiary and multi-functional amines respectively. For the transport properties, we have calculated the viscosity coefficients as a function of temperature using the isothermal-isobaric (NPT) ensemble. In the case of the pure components, we have investigated different thermodynamic properties using NVT Gibbs ensemble simulations such as liquid-vapor phase equilibrium diagrams, vaporization enthalpies, vapor pressures, normal boiling points, critical temperatures and critical densities. We have also calculated the excess enthalpies for water-n-Butylamine and n-heptane-n-Butylamine mixtures using Monte Carlo simulations in the NPT ensemble. In addition, we present the calculation of liquid-vapor surface tensions of n-Butylamine using a two-phase NVT simulation as well as the radial distribution functions. Finally, we have investigated the physical Henry constants of nitrous oxide (N 2 O) and nitrogen (N 2 ) in an aqueous solutions of n-Butylamine. In general, we found a good agreement between the available experimental information and our simulation results for all the studied properties, ratifying the predictive capability of the AUA force field for amines. (authors)

  1. Oxidations of N-(3-indoleethyl) cyclic aliphatic amines by horseradish peroxidase: the indole ring binds to the enzyme and mediates electron-transfer amine oxidation.

    Science.gov (United States)

    Ling, Ke-Qing; Li, Wen-Shan; Sayre, Lawrence M

    2008-01-23

    Although oxidations of aromatic amines by horseradish peroxidase (HRP) are well-known, typical aliphatic amines are not substrates of HRP. In this study, the reactions of N-benzyl and N-methyl cyclic amines with HRP were found to be slow, but reactions of N-(3-indoleethyl) cyclic amines were 2-3 orders of magnitude faster. Analyses of pH-rate profiles revealed a dominant contribution to reaction by the amine-free base forms, the only species found to bind to the enzyme. A metabolic study on a family of congeneric N-(3-indoleethyl) cyclic amines indicated competition between amine and indole oxidation pathways. Amine oxidation dominated for the seven- and eight-membered azacycles, where ring size supports the change in hybridization from sp3 to sp2 that occurs upon one-electron amine nitrogen oxidation, whereas only indole oxidation was observed for the six-membered ring congener. Optical difference spectroscopic binding data and computational docking simulations suggest that all the arylalkylamine substrates bind to the enzyme through their aromatic termini with similar binding modes and binding affinities. Kinetic saturation was observed for a particularly soluble substrate, consistent with an obligatory role of an enzyme-substrate complexation preceding electron transfer. The significant rate enhancements seen for the indoleethylamine substrates suggest the ability of the bound indole ring to mediate what amounts to medium long-range electron-transfer oxidation of the tertiary amine center by the HRP oxidants. This is the first systematic investigation to document aliphatic amine oxidation by HRP at rates consistent with normal metabolic turnover, and the demonstration that this is facilitated by an auxiliary electron-rich aromatic ring.

  2. Direct electrochemical imidation of aliphatic amines via anodic oxidation.

    Science.gov (United States)

    Zhang, Li; Su, Ji-Hu; Wang, Sujing; Wan, Changfeng; Zha, Zhenggen; Du, Jiangfeng; Wang, Zhiyong

    2011-05-21

    Direct electrochemical synthesis of sulfonyl amidines from aliphatic amines and sulfonyl azides was realized with good to excellent yields. Traditional tertiary amine substrates were broadened to secondary and primary amines. The reaction intermediates were observed and a reaction mechanism was proposed and discussed. © The Royal Society of Chemistry 2011

  3. Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

    Science.gov (United States)

    Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

    2010-05-17

    Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

  4. Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

    Science.gov (United States)

    Lee, Melissa; Sanford, Melanie S

    2015-10-14

    This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.

  5. Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.

    Science.gov (United States)

    Zultanski, Susan L; Zhao, Jingyi; Stahl, Shannon S

    2016-05-25

    A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available.

  6. Ruthenium-Catalyzed Aerobic Oxidation of Amines.

    Science.gov (United States)

    Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

    2018-01-18

    Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Factors influencing phase-disengagement rates in solvent-extraction systems employing tertiary amine extractants

    International Nuclear Information System (INIS)

    Moyer, B.A.; McDowell, W.J.

    1981-01-01

    The primary purpose of the present investigation was to examine the effects of amine size and structure on phase disengagement. Nine commercial tertiary amines were tested together with four laboratory-quality amines for uranium extraction and both organic-continuous (OC) and aqueous-continuous (AC) phase disengagement under Amex-type conditions. Synthetic acid sulfate solutions with and without added colloidal silica and actual ore leach solutions were used as the aqueous phases. Phase disengagement results were correlated with amine size and branching and solution wetting behavior on a silicate (glass) surface. The results suggest that the performance of some Amex systems may be improved by using branched chain tertiary amine extractants of higher molecular weight than are now normally used

  8. Characterization of molybdenum interfacial crud in a uranium mill that employs tertiary-amine solvent extraction

    International Nuclear Information System (INIS)

    Moyer, B.; McDowell, W.J.

    1983-01-01

    In the present work, samples of a molybdenum-caused green gummy interfacial crud from an operating western US uranium mill have been physically and chemically examined. Formaton of cruds of this description has been a long-standing problem in the use of tertiary amine solvent extraction for the recovery of uranium from low-grade ores (Amex Process). The crud is essentially an organic-continuous dispersion containing about 10 wt % aqueous droplets and about 37 wt % greenish-yellow crystalline solids suspended in kerosene-amine process solvent. The greenish-yellow crystals were found to be a previously unknown double salt of tertiary amine molybdophosphate with three tertiary amine chlorides having the empirical formula (R 3 NH) 3 [PMo 12 O 40 ].3(R 3 NH)Cl. To confirm the identification of the compound, a pure trioctylamine (TOA) analog was synthesized. In laboratory extraction experiments, it was demonstrated that organic-soluble amine molydophosphate forms slowly upon contact of TOA solvent with dilute sulfuric acid solutions containing low concentrations of molybdate and phosphate. If the organic solutions of amine molybdophosphate were then contacted with aqueous NaCl solutions, a greenish-yellow precipitate of (TOAH) 3 [PMo 12 O 40 ].3(TOAH)Cl formed at the interface. The proposed mechanism for the formation of the crud under process conditions involves build up of molybdenum in the solvent, followed by reaction with extracted phosphate to give dissolved amine molybdophosphate. The amine molybdophosphate then co-crystallizes with amine chloride, formed during the stripping cycle, to give the insoluble double salt, which precipitates as a layer of small particles at the interface. The proposed solution to the problem is the use of branched-chain, instead of straight-chain, tertiary amine extractants under the expectation that branching would increase the solubility of the double salt. 2 figures, 5 tables

  9. Aliphatic amine oxides as ligands

    International Nuclear Information System (INIS)

    Garla, L.C.; Betarello, V.H.; Chiericato Junior, G.; De Giovani, W.F.

    1984-01-01

    The reaction between some hydrated lanthanide perchlorates with trimethylamine oxide (TMAO) was studied. Compounds of general formula Ln(Cl 4 ) 3 : . 5,5 TMAO (Ln = La, Pr, Er and Y) were isolated. (Author) [pt

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-15

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

  12. Metal-Free Conversion of Carboxamides to Ureas Using Tertiary Amines and Iodosylmesitylene

    Energy Technology Data Exchange (ETDEWEB)

    Han, Hoon; Chang, Suk Bok [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)

    2010-03-15

    A new synthetic route has been developed for the preparation of ureas from the reaction of carboxamides with tertiary amines with the use of iodosylmesitylene as a stoichiometric oxidant. Although the reaction proceeds under the mild conditions to afford urea products in moderate yields, further optimization studies are required to improve the reaction efficiency and regioselectivity in the dealkylative pathway. Ureas are recognized as an important synthetic building unit, finding a wide range of applications in the preparation of agrochemicals, petrochemicals, and pharmaceuticals. In addition, hydrogen bond-mediated communication between ureas and certain types of compounds is an important structural motif in asymmetric catalysis, molecular recognition, and crystal engineering. Although numerous procedures have been developed for the urea synthesis, the most commonly employed strategy involves the reaction of amine precursors with phosgene, or its surrogates, isocyanates, or carbamates. Whereas these traditional methods are operative under conventional reaction conditions, they often lead to incomplete conversion. Additional drawback of these protocols is that unsymmetric ureas are difficult to prepare in many cases.

  13. The roles of tertiary amine structure, background organic matter and chloramine species on NDMA formation.

    Science.gov (United States)

    Selbes, Meric; Kim, Daekyun; Ates, Nuray; Karanfil, Tanju

    2013-02-01

    N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated and chlorinated drinking waters and wastewaters. Formation mechanisms and precursors of NDMA are still not well understood. The main objectives of this study were to systematically investigate (i) the effect of tertiary amine structure, (ii) the effect of background natural organic matter (NOM), and (iii) the roles of mono vs. dichloramine species on the NDMA formation. Dimethylamine (DMA) and 20 different tertiary aliphatic and aromatic amines were carefully examined based on their functional groups attached to the basic DMA structure. The wide range (0.02-83.9%) of observed NDMA yields indicated the importance of the structure of tertiary amines, and both stability and electron distribution of the leaving group of tertiary amines on NDMA formation. DMA associated with branched alkyl groups or benzyl like structures having only one carbon between the ring and DMA structure consistently gave higher NDMA yields. Compounds with electron withdrawing groups (EWG) reacted preferentially with monochloramine, whereas compounds with electron donating group (EDG) showed tendency to react with dichloramine to form NDMA. When the selected amines were present in NOM solutions, NDMA formation increased for compounds with EWG while decreased for compounds with EDG. This impact was attributed to the competitions between NOM and amines for chloramine species. The results provided additional information to the commonly accepted mechanism for NDMA formation including chloramine species reacting with tertiary amines and the role of the leaving group on overall NDMA conversion. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

    Science.gov (United States)

    Lee, Melissa; Sanford, Melanie S.

    2016-01-01

    This paper describes the terminal-selective Pt-catalyzed C(sp3)–H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol %. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251

  15. Extraction separation studies of uranium(VI) by amine oxides

    International Nuclear Information System (INIS)

    Ejaz, M.

    1975-01-01

    The extraction of uranium(VI) by two amine oxides, 4-(5-nonyl)pyridine oxide and trioctylamine oxide has been studied. The extraction behavior of these two N-oxides is compared. The dependence of extraction on the type of amine oxide and acid, nature of organic diluent, and amine oxide concentration has been investigated. The influence of the concentration of the metal and salting-out agents is described. The possible mechanism of extraction is discussed in the light of the results of extraction isotherms, loading radiodata, and log-log plots of amine oxide concentration vs distribution ratio. The separation factors for a number of metal ions are reported, and the separation of uranium from some fission elements has also been achieved

  16. A study of structure–activity relationships of commercial tertiary amines for post-combustion CO_2 capture

    International Nuclear Information System (INIS)

    Xiao, Min; Liu, Helei; Idem, Raphael; Tontiwachwuthikul, Paitoon; Liang, Zhiwu

    2016-01-01

    Highlights: • Ethyl group is beneficial for tertiary amines of CO_2 absorption. • The existence of side carbon chain may promote the activity of tertiary amine. • Hydroxyl group reduces the equilibrium CO_2 solubility, k_2 and pKa. • Heterocyclic structure decrease the equilibrium CO_2 solubility, k_2 and pKa. • Hydroxyl group results in higher CO_2 absorption heat. - Abstract: This work examined the relationship between the structure of various commercial tertiary amines and their activity in CO_2 absorption/desorption in terms of rate of CO_2 absorption, equilibrium CO_2 loading, pKa and heat of CO_2 absorption in order to establish possible guidelines for selection of tertiary amine components for amine blends. Results show that any electron donating group linked directly to the nitrogen atom increases their reactivity with CO_2. In addition, the presence of steric hindrance effect and good water solubility also show enhancements in activity. In contrast, the existence of a hydroxyl group leads to a decrease in all the activity of the tertiary amine. The heat of CO_2 absorption of tertiary amines, which is closely related to the regeneration energy, can be reduced by decreasing the number of hydroxyethyl groups or by positing the hydroxyl group at the proper carbon relative to the nitrogen atom.

  17. Homologation of methanol catalyzed by transition metal complexes in the presence of tertiary amines

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Masato; Ogata, Ikuei

    1987-12-18

    This paper describes the homologation of methanol by transition metal carbonyl catalysts in the presence of tertiary amines. Methanol was reacted with amine using a catalyst at 180/sup 0/C under 100 atm in the atmosphere of CO and H/sub 2/ mixed at the ratio of 4 in an autoclave. The reaction activities and selectivities of ethanol using iron carbonyl and Co carbonyl catalysts are superior. Only the iron catalyst was used hereafter because phosphine is required for the latter catalyst. N-methyl- piperidine, a cyclic amine, is superior to the other amines. The selectivity of ethanol is higher under higher partial pressure of H/sub 2/ and lower partial pressure of CO. The conversion rate is optimum at 180/sup 0/ and it goes down with increasing the temperature from it. Since the selectivity is markedly decreased with increasing amine, the reaction activity must be balanced with the amount of amine. The presence of solvent affects it. (3 figs, 6 tabs, 15 refs)

  18. Ozone Promotes Chloropicrin Formation by Oxidizing Amines to Nitro Compounds.

    Science.gov (United States)

    McCurry, Daniel L; Quay, Amanda N; Mitch, William A

    2016-02-02

    Chloropicrin formation has been associated with ozonation followed by chlorination, but the reaction pathway and precursors have been poorly characterized. Experiments with methylamine demonstrated that ozonation converts methylamine to nitromethane at ∼100% yield. Subsequent chlorination converts nitromethane to chloropicrin at ∼50% yield under the conditions evaluated. Similarly high yields from other primary amines were limited to those with functional groups on the β-carbon (e.g., the carboxylic acid in glycine) that facilitate carbon-carbon bond cleavage to release nitromethyl anion. Secondary amines featuring these reactive primary amines as functional groups (e.g., secondary N-methylamines) formed chloropicrin at high yields, likely by facile dealkylation to release the primary nitro compound. Chloropicrin yields from tertiary amines were low. Natural water experiments, including derivatization to transform primary and secondary amines to less reactive carbamate functional groups, indicated that primary and secondary amines were the dominant chloropicrin precursors during ozonation/chlorination. Ozonation followed by chlorination of the primary amine side chain of lysine demonstrated low yields (∼0.2%) of chloropicrin, but high yields (∼17%) of dichloronitrolysine, a halonitroalkane structural analogue to chloropicrin. However, chloropicrin yields increased and dichloronitrolysine yields decreased in the absence of hydroxyl radical scavengers, suggesting that future research should characterize the potential occurrence of such halonitroalkane analogues relative to natural radical scavenger (e.g., carbonate) concentrations.

  19. Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines.

    Science.gov (United States)

    Pronin, Sergey V; Reiher, Christopher A; Shenvi, Ryan A

    2013-09-12

    The SN2 reaction (bimolecular nucleophilic substitution) is a well-known chemical transformation that can be used to join two smaller molecules together into a larger molecule or to exchange one functional group for another. The SN2 reaction proceeds in a very predictable manner: substitution occurs with inversion of stereochemistry, resulting from the 'backside attack' of the electrophilic carbon by the nucleophile. A significant limitation of the SN2 reaction is its intolerance for tertiary carbon atoms: whereas primary and secondary alcohols are viable precursor substrates, tertiary alcohols and their derivatives usually either fail to react or produce stereochemical mixtures of products. Here we report the stereochemical inversion of chiral tertiary alcohols with a nitrogenous nucleophile facilitated by a Lewis-acid-catalysed solvolysis. The method is chemoselective against secondary and primary alcohols, thereby complementing the selectivity of the SN2 reaction. Furthermore, this method for carbon-nitrogen bond formation mimics a putative biosynthetic step in the synthesis of marine terpenoids and enables their preparation from the corresponding terrestrial terpenes. We expect that the general attributes of the methodology will allow chiral tertiary alcohols to be considered viable substrates for stereoinversion reactions.

  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. Amine Functionalization via Oxidative Photoredox Catalysis: Methodology Development and Complex Molecule Synthesis

    Science.gov (United States)

    2016-01-01

    Conspectus While the use of visible light to drive chemical reactivity is of high importance to the development of environmentally benign chemical transformations, the concomitant use of a stoichiometric electron donor or acceptor is often required to steer the desired redox behavior of these systems. The low-cost and ubiquity of tertiary amine bases has led to their widespread use as reductive additives in photoredox catalysis. Early use of trialkylamines in this context was focused on their role as reductive excited state quenchers of the photocatalyst, which in turn provides a more highly reducing catalytic intermediate. In this Account, we discuss some of the observations and thought processes that have led from our use of amines as reductive additives to their use as complex substrates and intermediates for natural product synthesis. Early attempts by our group to construct key carbon–carbon bonds via free-radical intermediates led to the observation that some trialkylamines readily behave as efficient hydrogen atom donors under redox-active photochemical conditions. In the wake of in-depth mechanistic studies published in the 1970s, 1980s and 1990s, this understanding has in turn allowed for a systematic approach to the design of a number of photochemical methodologies through rational tuning of the amine component. Minimization of the C–H donicity of the amine additive was found to promote desired C–C bond formation in a number of contexts, and subsequent elucidation of the amine’s redox fate has sparked a reevaluation of the amine’s role from that of reagent to that of substrate. The reactivity of tertiary amines in these photochemical systems is complex, and allows for a number of mechanistic possibilities that are not necessarily mutually exclusive. A variety of combinations of single-electron oxidation, C–H abstraction, deprotonation, and β-scission result in the formation of reactive intermediates such as α-amino radicals and iminium ions

  2. OXIDATION OF CYCLIC AMINES BY MOLYBDENUM(II) AND ...

    African Journals Online (AJOL)

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    metal is in formal oxidation state +2. Since no reduction can take place without oxidation and vice versa, we can reasonably say the reduction of Mo(II) and W(II) species is accompanied by oxidation of the amine. At this juncture, we should point out that C=N bonds are also known to absorb IR radiation in the same spectral ...

  3. Highly efficient and diastereoselective gold(I)-catalyzed synthesis of tertiary amines from secondary amines and alkynes: substrate scope and mechanistic insights.

    Science.gov (United States)

    Liu, Xin-Yuan; Guo, Zhen; Dong, Sijia S; Li, Xiao-Hua; Che, Chi-Ming

    2011-11-11

    An efficient method for the synthesis of tertiary amines through a gold(I)-catalyzed tandem reaction of alkynes with secondary amines has been developed. In the presence of ethyl Hantzsch ester and [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %), a variety of secondary amines bearing electron-deficient and electron-rich substituents and a wide range of alkynes, including terminal and internal aryl alkynes, aliphatic alkynes, and electron-deficient alkynes, underwent a tandem reaction to afford the corresponding tertiary amines in up to 99 % yield. For indolines bearing a preexisting chiral center, their reactions with alkynes in the presence of ethyl Hantzsch ester catalyzed by [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %) afforded tertiary amines in excellent yields and with good to excellent diastereoselectivity. All of these organic transformations can be conducted as a one-pot reaction from simple and readily available starting materials without the need of isolation of air/moisture-sensitive enamine intermediates, and under mild reaction conditions (mostly room temperature and mild reducing agents). Mechanistic studies by NMR spectroscopy, ESI-MS, isotope labeling studies, and DFT calculations on this gold(I)-catalyzed tandem reaction reveal that the first step involving a monomeric cationic gold(I)-alkyne intermediate is more likely than a gold(I)-amine intermediate, a three-coordinate gold(I) intermediate, or a dinuclear gold(I)-alkyne intermediate. These studies also support the proposed reaction pathway, which involves a gold(I)-coordinated enamine complex as a key intermediate for the subsequent transfer hydrogenation with a hydride source, and reveal the intrinsic stereospecific nature of these transformations observed in the experiments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Thermodynamic study of (heptane + amine) mixtures. III: Excess and partial molar volumes in mixtures with secondary, tertiary, and cyclic amines at 298.15 K

    International Nuclear Information System (INIS)

    Lepori, Luciano; Gianni, Paolo; Spanedda, Andrea; Matteoli, Enrico

    2011-01-01

    Graphical abstract: Highlights: → Excess volumes of (sec., tert., or cyclic amines + heptane) mixtures. → Excess volumes are positive for small size amines and decrease as the size increases. → Group contributions to predict the partial molar volumes of amines in heptane. → The void volume is larger for sec. and tert. than for linear amines in heptane. → The void volume is much smaller for cyclic than for linear amines in heptane. - Abstract: Excess molar volumes V E at 298.15 K were determined by means of a vibrating tube densimeter for binary mixtures of {heptane + open chain secondary (diethyl to dibutyl) and tertiary (triethyl to tripentyl) amines} as well as for cyclic imines (C 2 , C 3 , C 4 , C 6 , and C 7 ) and primary cycloalkylamines (C 5 , C 6 , C 7 , and C 12 ). The V E values were found positive for mixtures involving small size amines, with V E decreasing as the size increases. Negative V E 's were found for tributyl- and tripentylamine, heptamethylenimine, and cyclododecylamine. Mixtures of heptane with cycloheptylamine showed an s-shaped curve. Partial molar volumes V 0 of amines at infinite dilution in heptane were obtained from V E and compared with V 0 of hydrocarbons and other classes of organic compounds taken from literature. An additivity scheme, based on the intrinsic volume approach, was applied to estimate group (CH 3 , CH 2 , CH, C, NH 2 , NH, N, OH, O, CO, and COO) contributions to V 0 . These contributions, the effect of cyclization on V 0 , and the limiting slope of the apparent excess molar volumes were discussed in terms of solute-solvent and solute-solute interactions.

  5. Synthesis of Tertiary and Quaternary Amine Derivatives from Wood Resin as Chiral NMR Solvating Agents

    Directory of Open Access Journals (Sweden)

    Tiina Laaksonen

    2015-11-01

    Full Text Available Chiral tertiary and quaternary amine solvating agents for NMR spectroscopy were synthesized from the wood resin derivative (+-dehydroabietylamine (2. The resolution of enantiomers of model compounds [Mosher’s acid (3 and its n-Bu4N salt (4] (guests by (+-dehydroabietyl-N,N-dimethylmethanamine (5 and its ten different ammonium salts (hosts was studied. The best results with 3 were obtained using 5 while with 4 the best enantiomeric resolution was obtained using (+-dehydroabietyl-N,N-dimethylmethanaminium bis(trifluoromethane-sulfonimide (6. The compounds 5 and 6 showed a 1:1 complexation behaviour between the host and guest. The capability of 5 and 6 to recognize the enantiomers of various α-substituted carboxylic acids and their n-Bu4N salts in enantiomeric excess (ee determinations was demonstrated. A modification of the RES-TOCSY NMR pulse sequence is described, allowing the enhancement of enantiomeric discrimination when the resolution of multiplets is insufficient.

  6. Regulation of carbon partitioning into carotenes by MPTA, a substituted tertiary amine

    Energy Technology Data Exchange (ETDEWEB)

    Madhavan, S.; Rosenfield, C.L.; Benedict, C.R.

    1986-04-01

    In mature citrus fruits, synthesis and turnover of carotenes appears to be low. Treatment of lemon pieces with the substituted tertiary amine, 2-(4-methylphenoxyl)triethylamine, MPTA, induces the synthesis of carotenes. Exposure of tissue slices (lemon flavedo) to MPTA for 72 hrs results in the production of 29.6 ..mu..g gfrwt/sup -1/ lycopene whereas control slices showed only trace amounts of lycopene. An identical incorporation of /sup 14/C-glucose into sugars, amino acids and organic acids, in both treated and control tissue slices indicates the non-disturbance of fruit respiration by MPTA treatment. Incorporation of /sup 14/C-glucose into carotenes is negligible in mature citrus fruits, but in MPTA treated tissue slices there is a pronounced incorporation of /sup 14/C-glucose into carotenes. MPTA treatment induces the synthesis of carotene enzymes, thus effecting an increased partitioning of glucose into the MVA pathway for carotene synthesis.

  7. Regulation of carbon partitioning into carotenes by MPTA, a substituted tertiary amine

    International Nuclear Information System (INIS)

    Madhavan, S.; Rosenfield, C.L.; Benedict, C.R.

    1986-01-01

    In mature citrus fruits, synthesis and turnover of carotenes appears to be low. Treatment of lemon pieces with the substituted tertiary amine, 2-(4-methylphenoxyl)triethylamine, MPTA, induces the synthesis of carotenes. Exposure of tissue slices (lemon flavedo) to MPTA for 72 hrs results in the production of 29.6 μg gfrwt -1 lycopene whereas control slices showed only trace amounts of lycopene. An identical incorporation of 14 C-glucose into sugars, amino acids and organic acids, in both treated and control tissue slices indicates the non-disturbance of fruit respiration by MPTA treatment. Incorporation of 14 C-glucose into carotenes is negligible in mature citrus fruits, but in MPTA treated tissue slices there is a pronounced incorporation of 14 C-glucose into carotenes. MPTA treatment induces the synthesis of carotene enzymes, thus effecting an increased partitioning of glucose into the MVA pathway for carotene synthesis

  8. Thermodynamic properties of donor-acceptor complexes of tertiary amine with aryl ketones in hexane medium

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, R. [Department of Physics, The New College, Chennai 600 014 (India); Jayakumar, S. [Department of Physics, R.K.M. Vivekananda College, Chennai 600 004 (India); Kannappan, V., E-mail: vkannappan@hotmail.com [Department of Chemistry, Presidency College, Chennai 600 005 (India)

    2012-05-20

    Highlights: Black-Right-Pointing-Pointer Ultrasonic scan is carried out on ternary systems of aromatic tertiary amine and three aryl ketones. Black-Right-Pointing-Pointer Formation of CT complexes is found between tertiary amine with aryl ketones. Black-Right-Pointing-Pointer Stability constant values are computed by ultrasonic and spectral methods are compared. Black-Right-Pointing-Pointer The trend in the 'K' suggests that substituents in ketones influence the stabilities of these complexes. Black-Right-Pointing-Pointer The thermodynamic parameters suggest CT interaction is exothermic and the complexes are thermodynamically stable. - The thermodynamic stability of complexes formed between N,N-dimethylaniline (DMANI) and three ketones, namely, acetophenone (ACP), 4-chloroactophenone (ClACP) and 4-methylacetophenone (MACP) in n-hexane is extensively investigated by spectral and ultrasonic methods. The ultrasound scan was carried out in the temperature range 208.15-313.15 K and at atmospheric pressure on solutions containing equimolar concentrations of components ranging from 0.025 to 0.2 M. The existence of solute-solute interactions has also been confirmed through electronic absorption spectra analyzed with Benesi-Hildebrand theory at 303.15 K. The stability constants of the donor-acceptor complexes determined both by spectroscopic and ultrasonic methods are comparable and follow similar trends. The trend in the formation constants is discussed with structures of the components. The thermodynamic behavior of the systems was explained through the computed values of the free energy ({Delta}G), enthalpy ({Delta}H) and entropy ({Delta}S) changes for complex formation are computed and discussed.

  9. Deacidification of oils and fats of biological origine by aqueous solutions of tertiary amines*

    Directory of Open Access Journals (Sweden)

    Peter Siegfried

    2001-01-01

    Full Text Available Deacidification of triacylglycerols by extraction is investigated using aqueous solutions of amines as extractants. Tertiary amines with boiling points ranging between 100° and 170°C, such as 2-methylamino-diethanol, 2-dimethylamino-ethanol, 4-methylmorpholine, 1-dimethylamino-2-propanol etc. were found to be suitable substances. Especially the deacidification by aqueous solutions of 2-dimethylamino-ethanol (DMAE was amply investigated as it is used as an active agent in remedies. Amazingly gelatinous soap stocks are not formed, when the concentration of DMAE exceeds 20% if the free fatty acid content of the oil is below 15%. Two liquid phases are formed in systems composed of triacylglyceroles and aqueous solutions containing 20 to 80% DMAE. Palm oil containing 4.3 wt.% free fatty acids was mixed with an equal amount of an aqueous solution of 30 wt.% DMAE at 60°C. In equilibrium an extract containing 86 wt.% free fatty acids (solvents deducted and a raffinate of 0.09 wt.% free fatty acids are obtained. Loss of neutral oil being 0.7 wt.%.

  10. Dual C-H functionalization of N-aryl amines: synthesis of polycyclic amines via an oxidative Povarov approach.

    Science.gov (United States)

    Min, Chang; Sanchawala, Abbas; Seidel, Daniel

    2014-05-16

    Iminium ions generated in situ via copper(I) bromide catalyzed oxidation of N-aryl amines readily undergo [4 + 2] cycloadditions with a range of dienophiles. This method involves the functionalization of both a C(sp(3))-H and a C(sp(2))-H bond and enables the rapid construction of polycyclic amines under relatively mild conditions.

  11. Factors influencing the regioselectivity of the oxidation of asymmetric secondary amines with singlet oxygen.

    Science.gov (United States)

    Ushakov, Dmitry B; Plutschack, Matthew B; Gilmore, Kerry; Seeberger, Peter H

    2015-04-20

    Aerobic amine oxidation is an attractive and elegant process for the α functionalization of amines. However, there are still several mechanistic uncertainties, particularly the factors governing the regioselectivity of the oxidation of asymmetric secondary amines and the oxidation rates of mixed primary amines. Herein, it is reported that singlet-oxygen-mediated oxidation of 1° and 2° amines is sensitive to the strength of the α-C-H bond and steric factors. Estimation of the relative bond dissociation energy by natural bond order analysis or by means of one-bond C-H coupling constants allowed the regioselectivity of secondary amine oxidations to be explained and predicted. In addition, the findings were utilized to synthesize highly regioselective substrates and perform selective amine cross-couplings to produce imines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Copper(II)-catalyzed electrophilic amination of quinoline N-oxides with O-benzoyl hydroxylamines.

    Science.gov (United States)

    Li, Gang; Jia, Chunqi; Sun, Kai; Lv, Yunhe; Zhao, Feng; Zhou, Kexiao; Wu, Hankui

    2015-03-21

    Copper acetate-catalyzed C-H bond functionalization amination of quinoline N-oxides was achieved using O-benzoyl hydroxylamine as an electrophilic amination reagent, thereby affording the desired products in moderate to excellent yields. Electrophilic amination can also be performed in good yield on a gram scale.

  13. Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

    Science.gov (United States)

    Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

    2012-05-14

    The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Assessment of the combined approach of N-alkylation and salt formation to enhance aqueous solubility of tertiary amines using bupivacaine as a model drug

    DEFF Research Database (Denmark)

    Nielsen, Anders Bach; Frydenvang, Karla Andrea; Liljefors, Tommy

    2005-01-01

    as their iodide salts. Chloride, mesylate, formate, acetate, glycolate, and tosylate salts were obtained by anion exchange of the N-methyl-bupivacaine derivative. N-Alkylation and salt formation afforded quaternary ammonium salts possessing pH-independent aqueous solubilities far exceeding that of the parent......Quaternary prodrug types of poorly water-soluble tertiary amines have been shown to exhibit significantly enhanced solubilities as compared to the parent amine. In the present study the combined effect of N-alkylation and salt formation to enhance aqueous solubility of tertiary amines have been...

  15. Extraction and purification of plutonium by a tertiary amine; Extraction et purification du plutonium par une amine tertiaire

    Energy Technology Data Exchange (ETDEWEB)

    Trentinian, M de; Chesne, A [Commissariat a l' Energie Atomique, Fontenay aux Roses, Section de Chimie des Actimides (France).Centre d' Etudes Nucleaires; Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    Trilaurylamine diluted with a paraffinic solvent (dodecane) was studied as part of the research dealing with the separation and purification of plutonium. The physical properties (solubility of nitrates in the amine as a function of temperature) and the resistance to radiations of this substance were examined. The extraction characteristics of nitric solutions of plutonium, uranium and certain fission products are given as a function of the following factors: concentration of the various ions in solution, valency states. A method of plutonium purification based on these results is presented. (author) [French] La trilaurylamine diluee par un solvant paraffinique (dodecane) a ete etudiee dans le cadre des recherches concernant la separation et la purification du plutonium. Une etude des caracteres physiques (solubilite des nitrates dans l'amine en fonction de la temperature) s'ajoute a celle de la tenue aux radiations de ce corps. Les caracteristiques d'extraction de solutions nitriques de plutonium, uranium, et certains produits de fission, sont donnes en fonction des facteurs suivants: concentration des differents ions en solution, etats de valence. On presente une methode de purification du plutonium basee sur ces resultats. (auteur)

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

    Science.gov (United States)

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

    2014-01-15

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

  17. The stability study of myristyl dimethyl amine oxide as an amphoteric ...

    African Journals Online (AJOL)

    The stability study of myristyl dimethyl amine oxide as an amphoteric surfactant in strong oxidant media containing 5 % m/m sodium hypochlorite through measurement of decomposing rate using high performance liquid chromatography and two phase titration.

  18. Palladium-catalysed anti-Markovnikov selective oxidative amination

    Science.gov (United States)

    Kohler, Daniel G.; Gockel, Samuel N.; Kennemur, Jennifer L.; Waller, Peter J.; Hull, Kami L.

    2018-03-01

    In recent years, the synthesis of amines and other nitrogen-containing motifs has been a major area of research in organic chemistry because they are widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to a reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a palladium-catalysed oxidative amination reaction in which the addition of the nitrogen occurs at the less-substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide through trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favoured products. Both the scope of the transformation and mechanistic investigations are reported.

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

    DEFF Research Database (Denmark)

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

    2015-01-01

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

  20. Visible-Light-Promoted Metal-Free Aerobic Oxidation of Primary Amines to Acids and Lactones.

    Science.gov (United States)

    Cheng, Xiaokai; Yang, Bo; Hu, Xingen; Xu, Qing; Lu, Zhan

    2016-12-05

    A unique metal-free aerobic oxidation of primary amines via visible light photocatalytic double carbon-carbon bonds cleavage and multi carbon-hydrogen bonds oxidation was observed. Aerobic oxidation of primary amines could be controlled to afford acids by using dioxane with 18 W CFL, and lactones by using DMF with 8 W green LEDs, respectively. A plausible mechanism was proposed based on control experiments. This observation showed direct evidences for the fragmentation in the aerobic oxidation of aliphatic primary amines. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. Changing of the electron structure of dispersed iron oxide during interaction with amines and borofluoride

    International Nuclear Information System (INIS)

    Hobert, H.; Arnold, D.

    1975-01-01

    The mechanism of chemisorption on the surface of iron oxide was studied by Moessbauer spectroscopy performed on samples of iron oxide finely dispersed in SiO 2 . It was found from Moessbauer spectra that the interaction of the oxide with amines resulted in a reversible electron transition from the amine to the adsorbent. The interaction with BF 3 brought about an irreversible electron transition from iron to boron. (A.K.)

  3. Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

    Science.gov (United States)

    Wendlandt, Alison E; Stahl, Shannon S

    2014-01-08

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

  4. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    Directory of Open Access Journals (Sweden)

    Worawan Bhanthumnavin

    2010-02-01

    Full Text Available Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009.

  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. Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide.

    Science.gov (United States)

    Salter-Blanc, Alexandra J; Bylaska, Eric J; Lyon, Molly A; Ness, Stuart C; Tratnyek, Paul G

    2016-05-17

    New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. In this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ(-)), pKas of the amines, and energies of the highest occupied molecular orbital (EHOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (Eox)]. The selection of calculated descriptors (pKa, EHOMO, and Eox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to EHOMO (calculated with a modest level of theory).

  7. Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide

    International Nuclear Information System (INIS)

    Salter-Blanc, Alexandra J.; Lyon, Molly A.; Science University, Portland, OR; Ness, Stuart C.; Science University, Portland, OR; Tratnyek, Paul G.; Science University, Portland, OR

    2016-01-01

    New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO 2 ) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here in this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ − ), pK a s of the amines, and energies of the highest occupied molecular orbital (E HOMO )] to specific for the likely rate-limiting step [one-electron oxidation potentials (E ox )]. The selection of calculated descriptors (pK a ), E HOMO , and E ox ) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO 2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to E HOMO (calculated with a modest level of theory).

  8. Effect of Amine Adlayer on Electrochemical Uric Acid Sensor Conducted on Electrochemically Reduced Graphene Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sumi; Kim, Kyuwon [Incheon National University, Incheon (Korea, Republic of)

    2016-03-15

    The electrochemical biosensing efficiency of uric acid (UA) detection on an electrochemically reduced graphene oxide (ERGO)-decorated electrode surface was studied by using various amine linkers used to immobilize ERGO. The amine linkers aminoethylphenyldiazonium , 2,2'-(ethylenedioxy)bis(ethylamine), 3-aminopro-pyltriethoxysilane, and polyethyleneimine were coated on indium-tin-oxide electrode surfaces through chemical or electrochemical deposition methods. ERGO-decorated surfaces were prepared by the electrochemical reduction of graphene oxide (GO), which was immobilized on the amine-coated electrode surfaces through the electrostatic interaction between GO and the ammonium ion of the linker on the surface. We monitored the sensing results of electrochemical UA detection with differential pulse voltammetry. The ERGO-modified surface presented electrocatalytic oxidation of UA and ascorbic acid. Among the different amines tested, 3-aminopropyltriethoxysilane provided the best biosensing performance in terms of sensitivity and reproducibility.

  9. Effect of Amine Adlayer on Electrochemical Uric Acid Sensor Conducted on Electrochemically Reduced Graphene Oxide

    International Nuclear Information System (INIS)

    Park, Sumi; Kim, Kyuwon

    2016-01-01

    The electrochemical biosensing efficiency of uric acid (UA) detection on an electrochemically reduced graphene oxide (ERGO)-decorated electrode surface was studied by using various amine linkers used to immobilize ERGO. The amine linkers aminoethylphenyldiazonium , 2,2'-(ethylenedioxy)bis(ethylamine), 3-aminopro-pyltriethoxysilane, and polyethyleneimine were coated on indium-tin-oxide electrode surfaces through chemical or electrochemical deposition methods. ERGO-decorated surfaces were prepared by the electrochemical reduction of graphene oxide (GO), which was immobilized on the amine-coated electrode surfaces through the electrostatic interaction between GO and the ammonium ion of the linker on the surface. We monitored the sensing results of electrochemical UA detection with differential pulse voltammetry. The ERGO-modified surface presented electrocatalytic oxidation of UA and ascorbic acid. Among the different amines tested, 3-aminopropyltriethoxysilane provided the best biosensing performance in terms of sensitivity and reproducibility.

  10. Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

    Science.gov (United States)

    Shanker, Uma; Singh, Gurinder; Kamaluddin

    2013-06-01

    The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.

  11. Determination of rate constants of N-alkylation of primary amines by 1H NMR spectroscopy.

    Science.gov (United States)

    Li, Chenghong

    2013-09-05

    Macromolecules containing N-diazeniumdiolates of secondary amines are proposed scaffolds for controlled nitrogen oxide (NO) release medical applications. Preparation of these compounds often involves converting primary amine groups to secondary amine groups through N-alkylation. However, N-alkylation results in not only secondary amines but tertiary amines as well. Only N-diazeniumdiolates of secondary amines are suitable for controlled NO release; therefore, the yield of secondary amines is crucial to the total NO load of the carrier. In this paper, (1)H NMR spectroscopy was used to estimate the rate constants for formation of secondary amine (k1) and tertiary amine (k2) for alkylation reagents such as propylene oxide (PO), methyl acrylate (MA), and acrylonitrile (ACN). At room temperature, the ratio of k2/k1 for the three reactions was found to be around 0.50, 0.026, and 0.0072.

  12. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    OpenAIRE

    Worawan Bhanthumnavin; Tirayut Vilaivan

    2010-01-01

    Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects ...

  13. Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

    International Nuclear Information System (INIS)

    Hayon, E.; Rao, P.S.

    1975-01-01

    The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N 1 ,N 1 - tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N 1 ,N 1 -tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 μsec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD. + , PD. + , DMPD. + , TMB. + , and DPA. + . The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH. 2+ , PDH. 2+ , DMPDH. 2+ , TMBH. 2+ , and DPAH. 2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

  14. Amine-oxide hybrid materials for acid gas separations

    KAUST Repository

    Bollini, Praveen; Didas, Stephanie A.; Jones, Christopher W.

    2011-01-01

    Organic-inorganic hybrid materials based on porous silica materials functionalized with amine-containing organic species are emerging as an important class of materials for the adsorptive separation of acid gases from dilute gas streams

  15. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    –titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Furthermore, we report that pure titania is in fact itself a catalyst for the oxidation of amines with molecular oxygen under very mild conditions. We demonstrate that these new methodologies open up for two......Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold...

  16. Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Jisheng [Iowa State Univ., Ames, IA (United States)

    1996-01-08

    This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

  17. Effect of tertiary amines on the synthesis and photovoltaic properties of TiO2 nanoparticles in dye sensitized solar cells

    International Nuclear Information System (INIS)

    Mir, Noshin; Salavati-Niasari, Masoud

    2013-01-01

    Highlights: • TiO 2 nanoparticles were synthesized via a two-step sol–gel method. • Two tertiary amines were selected as complexing agents. • Size control was achieved by selection of long chained amine. • The total conversion efficiency of 5.04% was reported as the best result. -- Abstract: Two different amines as complexing agents were used in a two-step sol–gel method to prepare TiO 2 nanoparticles. The effect of amines on the size of the TiO 2 nanocrystals and its influence on the performance of corresponding dye-sensitized solar cell (DSSC) were investigated. It is shown that using a tertiary long chained monoamine as a complexing agent is beneficial in two ways; one is producing the particles with smaller size and the other is slightly sticking the particles in order to have a film with higher reflectivity which both is beneficial to photovoltaic performance. The obtained products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, and ultraviolet-visible (UV–vis) spectroscopy. The overall conversion efficiency of the long-chain-based DSSC (5.04%) appeared to be 45% higher than that obtained for the tertiary short-chain diamine

  18. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk [Kyung Hee Univ., Seoul (Korea, Republic of)

    2012-11-15

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O{sub 2} might be the main reason for the activity of the selenium catalyst for this reaction.

  19. 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.

  20. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    International Nuclear Information System (INIS)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk

    2012-01-01

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O 2 might be the main reason for the activity of the selenium catalyst for this reaction

  1. Grafting of model primary amine compounds to cellulose nanowhiskers through periodate oxidation

    Science.gov (United States)

    Rajalaxmi Dash; Thomas Elder; Arthur Ragauskas

    2012-01-01

    This study demonstrates regioselective oxidation of cellulose nanowhiskers using 2.80–10.02 mmols of sodium periodate per 5 g of whiskers followed by grafting with methyl and butyl amines through a Schiff base reaction to obtain their amine derivatives in 80–90 % yield. We found a corresponding increase in carbonyl content (0.06–0.14 mmols/g) of the dialdehyde...

  2. 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.

  3. A metal-free general procedure for oxidation of secondary amines to nitrones.

    Science.gov (United States)

    Gella, Carolina; Ferrer, Eric; Alibés, Ramon; Busqué, Félíx; de March, Pedro; Figueredo, Marta; Font, Josep

    2009-08-21

    An efficient and metal-free protocol for direct oxidation of secondary amines to nitrones has been developed, using Oxone in a biphasic basic medium as the sole oxidant. The method is general and tolerant with other functional groups or existing stereogenic centers, providing rapid access to enantiomerically pure compounds in good yields.

  4. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Science.gov (United States)

    2010-07-01

    ..., alkali and amine salts. 721.2565 Section 721.2565 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

  5. A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.

    Science.gov (United States)

    Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M

    2016-06-17

    The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

  6. High production volume chemical Amine Oxide [C8-C20] category environmental risk assessment

    DEFF Research Database (Denmark)

    Sanderson, Hans; Tibazarwa, Caritas; Greggs, William

    2009-01-01

    and personal care products. Given the lack of persistence or bioaccumulation, and the low likelihood of these chemicals partitioning to soil, the focus of the environmental assessment is on the aquatic environment. In the United States, the E-FAST model is used to estimate effluent concentrations in the United......An environmental assessment of amine oxides has been conducted under the OECD SIDS High Production Volume (HPV) Program via the Global International Council of Chemical Associations (ICCA) Amine Oxides Consortium. Amine oxides are primarily used in conjunction with surfactants in cleaning...... States from manufacturing facilities and from municipal facilities resulting from consumer product uses. Reasonable worst-case ratios of predicted environmental concentration (PEC) to predicted no effect concentration (PNEC) range from 0.04 to 0.003, demonstrating that these chemicals are a low risk...

  7. 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.

  8. A redox-assisted molecular assembly of molybdenum oxide amine composite nanobelts

    International Nuclear Information System (INIS)

    Luo Haiyan; Wei Mingdeng; Wei Kemei

    2011-01-01

    Research highlights: → Nanobelts of molybdenum oxide amine were first synthesized via a redox-assisted molecular assembly route. → These nanobelts are highly crystalline with a several tens of micrometers in length and 20-30 nm in thickness. - Abstract: In this paper, the nanobelts of molybdenum oxide amine composite were successfully synthesized via a redox-assisted molecular assembly route under the hydrothermal conditions. The synthesized nanobelts were characterized by XRD, SEM, TEM, TG and FT-IR measurements. The thickness of nanobelts is found to be ca. 20-30 nm and their lengths are up to several tens of micrometers. Based on a series of the experimental results, a possible model, redox-intercalation-exfoliation, was suggested for the formation of nanobelts of molybdenum oxide amine composite.

  9. Modification Of Poly(glycidyl Methacrylate) Grafted Onto Crosslinked Pvc With Tertiary Amine Group And Use For Removing Acidic Dyes From Water

    OpenAIRE

    Yorgun, Gülden

    2009-01-01

    In this study, glycidylmethacrylate is grafted onto partially dehydrochlorinated poly(vinyl chloride) (DHPVC) using ATRP method and polymerization kinetics of the reaction is studied. Then, the polymeric resin was interacted with excess of diethylamine, giving a tertiary amine containing sorbent. Surface initiated polymerizations have been widely used to overcome inadequate properties of poly(vinylchloride) (PVC). Epoxy group is one of the most important type to be integrated into polymers. T...

  10. Kinetic determinations of accurate relative oxidation potentials of amines with reactive radical cations.

    Science.gov (United States)

    Gould, Ian R; Wosinska, Zofia M; Farid, Samir

    2006-01-01

    Accurate oxidation potentials for organic compounds are critical for the evaluation of thermodynamic and kinetic properties of their radical cations. Except when using a specialized apparatus, electrochemical oxidation of molecules with reactive radical cations is usually an irreversible process, providing peak potentials, E(p), rather than thermodynamically meaningful oxidation potentials, E(ox). In a previous study on amines with radical cations that underwent rapid decarboxylation, we estimated E(ox) by correcting the E(p) from cyclic voltammetry with rate constants for decarboxylation obtained using laser flash photolysis. Here we use redox equilibration experiments to determine accurate relative oxidation potentials for the same amines. We also describe an extension of these experiments to show how relative oxidation potentials can be obtained in the absence of equilibrium, from a complete kinetic analysis of the reversible redox kinetics. The results provide support for the previous cyclic voltammetry/laser flash photolysis method for determining oxidation potentials.

  11. Nanoscale assembly of amine-functionalized colloidal iron oxide

    Energy Technology Data Exchange (ETDEWEB)

    Barick, K.C. [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400076 (India); Aslam, M. [Department of Physics, Indian Institute of Technology Bombay, Mumbai 400076 (India); Centre for Research in Nanotechnology and Science, Indian Institute of Technology Bombay, Mumbai 400076 (India); Prasad, Pottumarthi V. [Department of Radiology, Evanston Northwestern Healthcare, Evanston, IL 60201 (United States); Dravid, Vinayak P. [Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208 (United States); International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208 (United States)], E-mail: v-dravid@northwestern.edu; Bahadur, Dhirendra [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400076 (India); Centre for Research in Nanotechnology and Science, Indian Institute of Technology Bombay, Mumbai 400076 (India)], E-mail: dhirenb@iitb.ac.in

    2009-05-15

    We demonstrate a single-step facile approach for highly water-stable assembly of amine-functionalized Fe{sub 3}O{sub 4} nanoparticles using thermal decomposition of Fe-chloride precursors in ethylene glycol medium in the presence of ethylenediamine. The average size of nanoassemblies is 40{+-}1 nm, wherein the individual nanoparticles are about 6 nm. Amine-functionalized properties are evident from Fourier transform infrared spectrometer (FTIR), thermal and elemental analyses. The saturation magnetization and spin-echo r{sub 2} of the nanoassemblies were measured to be 64.3 emu/g and 314.6 mM{sup -1} s{sup -1}, respectively. The higher value of relaxivity ratio (r{sub 2}/r{sub 1}=143) indicates that nanoassemblies are a promising high-efficiency T2 contrast agent platform.

  12. Nanoscale assembly of amine-functionalized colloidal iron oxide

    International Nuclear Information System (INIS)

    Barick, K.C.; Aslam, M.; Prasad, Pottumarthi V.; Dravid, Vinayak P.; Bahadur, Dhirendra

    2009-01-01

    We demonstrate a single-step facile approach for highly water-stable assembly of amine-functionalized Fe 3 O 4 nanoparticles using thermal decomposition of Fe-chloride precursors in ethylene glycol medium in the presence of ethylenediamine. The average size of nanoassemblies is 40±1 nm, wherein the individual nanoparticles are about 6 nm. Amine-functionalized properties are evident from Fourier transform infrared spectrometer (FTIR), thermal and elemental analyses. The saturation magnetization and spin-echo r 2 of the nanoassemblies were measured to be 64.3 emu/g and 314.6 mM -1 s -1 , respectively. The higher value of relaxivity ratio (r 2 /r 1 =143) indicates that nanoassemblies are a promising high-efficiency T2 contrast agent platform.

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

    Science.gov (United States)

    Kim, Jinho; Stahl, Shannon S

    2013-07-05

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

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

    OpenAIRE

    Kim, Jinho; Stahl, Shannon S.

    2013-01-01

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

  15. 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.

  16. 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.

  17. Photocatalytic oxidation of aromatic amines using MnO2@g-C3N4

    Data.gov (United States)

    U.S. Environmental Protection Agency — An efficient and direct oxidation of aromatic amines to aromatic azo-compounds has been achieved using a MnO2@g-C3N4 catalyst under visible light as a source of...

  18. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    International Nuclear Information System (INIS)

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  19. Photocatalytic oxidation of aromatic amines using MnO2@g ...

    Science.gov (United States)

    An efficient and direct oxidation of aromatic amines to aromatic azo-compounds has been achieved using a MnO2@g-C3N4 catalyst under visible light as a source of energy at room temperature Prepared for submission to the journal, Advanced Materials Letters.

  20. Amine-oxide hybrid materials for acid gas separations

    KAUST Repository

    Bollini, Praveen

    2011-01-01

    Organic-inorganic hybrid materials based on porous silica materials functionalized with amine-containing organic species are emerging as an important class of materials for the adsorptive separation of acid gases from dilute gas streams. In particular, these materials are being extensively studied for the adsorption of CO 2 from simulated flue gas streams, with an eye towards utilizing these materials as part of a post-combustion carbon capture process at large flue gas producing installations, such as coal-fired electricity-generating power plants. In this Application Article, the utilization of amine-modified organic-inorganic hybrid materials is discussed, focusing on important attributes of the materials, such as (i) CO 2 adsorption capacities, (ii) adsorption and desorption kinetics, and (iii) material stability, that will determine if these materials may one day be useful adsorbents in practical CO 2 capture applications. Specific research needs and limitations associated with the current body of work are identified. © 2011 The Royal Society of Chemistry.

  1. Amine binding and oxidation at the catalytic site for photosynthetic water oxidation

    Science.gov (United States)

    Ouellette, Anthony J. A.; Anderson, Lorraine B.; Barry, Bridgette A.

    1998-01-01

    Photosynthetic water oxidation occurs at the Mn-containing catalytic site of photosystem II (PSII). By the use of 14C-labeled amines and SDS-denaturing PAGE, covalent adducts derived from primary amines and the PSII subunits, CP47, D2/D1, and the Mn-stabilizing protein, can be observed. When PSII contains the 18- and 24-kDa extrinsic proteins, which restrict access to the active site, no 14C labeling is obtained. NaCl, but not Na2SO4, competes with 14C labeling in Mn-containing PSII preparations, and the concentration dependence of this competition parallels the activation of oxygen evolution. Formation of 14C-labeled adducts is observed in the presence or in the absence of a functional manganese cluster. However, no significant Cl− effect on 14C labeling is observed in the absence of the Mn cluster. Isolation and quantitation of the 14C-labeled aldehyde product, produced from [14C]benzylamine, gives yields of 1.8 ± 0.3 mol/mol PSII and 2.9 ± 0.2 mol/mol in Mn-containing and Mn-depleted PSII, respectively. The corresponding specific activities are 0.40 ± 0.07 μmol(μmol PSII-hr)−1 and 0.64 ± 0.04 μmol(μmol PSII-hr)−1. Cl− suppresses the production of [14C]benzaldehyde in Mn-containing PSII, but does not suppress the production in Mn-depleted preparations. Control experiments show that these oxidation reactions do not involve the redox-active tyrosines, D and Z. Our results suggest the presence of one or more activated carbonyl groups in protein subunits that form the active site of PSII. PMID:9482863

  2. Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

    KAUST Repository

    Ghosh, Subhash Chandra; Li, Cheng Chao; Zeng, Hua Chun; Ngiam, Joyce S Y; Seayad, Abdul M.; Chen, Anqi

    2014-01-01

    Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  3. Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

    KAUST Repository

    Ghosh, Subhash Chandra

    2014-02-06

    Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  4. Third phase formation in organic solutions in the extraction of mono-acids by tertiary trialcoyl-amines diluted in very slightly polar organic solvents

    International Nuclear Information System (INIS)

    Robaglia, Michele

    1973-01-01

    The phenomena of third phase formation which can occur during the extraction of an acid with a tertiary amine diluted in a low polarity diluent are studied. In the first part a system including water (TnOA - C 6 H 12 - HCl - H 2 O) is compared with an anhydrous system (TnOA - C 6 H 12 - HCl - N 2 ). There are two kinds of gaps. One during amine salification, another one during the extraction of excess acid. The important part of the water content of the organic phase is demonstrated. The presence of water enhances the gaps. The polar water molecules are dissolved inside the tri-octylamine salt micelles. The heavy phase is formed by aggregates, the light phase represents the solubility of the non soluble species in the medium. In the second part are studied the influence of some parameters (like nature of diluent, acid, amine and temperature) on the gaps formation and on the extraction of excess acid and water. In every cases the part played by water remains the same. Finally some comparisons are made between tertiary systems and binary systems which formed them. The binary systems were studied by the mean of crystallization curves. (author) [fr

  5. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    Science.gov (United States)

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this minireview. PMID:25044821

  6. Studies on the formation of volatile amines from trimethylamine oxide by gamma-irradiation, (1)

    International Nuclear Information System (INIS)

    Uchiyama, Sadao; Kondo, Tatsuo; Uchiyama, Mitsuru

    1976-01-01

    The fundamental investigation concerning the formation of volatile amines from trimethylamine oxide (TMAO) by gamma-irradiation was carried out as a model of the irradiation of fish-meat products like Kamaboko. By the irradiation of 5.8 Mrad, 5 x 10 -6 mol of dimethylamine (DMA) was produced from 1 x 10 -4 mol of TMAO in a phosphate buffer (pH 6.5). Fe 2+ , Fe 3+ , Zn 2+ and Al 3+ promoted the formation of amines but Ca 2+ , Mg 2+ and Na + scarcely affected it. On the other hand, cysteine, which is known as a protecting agent against gamma-ray, promoted the formation of DMA. However, protain worked repressibly for amine formation even when Fe 3+ was contained. (auth.)

  7. Mechanism of Oxidative Amidation of Nitroalkanes with Oxygen and Amine Nucleophiles by Using Electrophilic Iodine.

    Science.gov (United States)

    Li, Jing; Lear, Martin J; Kwon, Eunsang; Hayashi, Yujiro

    2016-04-11

    Recently, we developed a direct method to oxidatively convert primary nitroalkanes into amides that entailed mixing an iodonium source with an amine, base, and oxygen. Herein, we systematically investigated the mechanism and likely intermediates of such methods. We conclude that an amine-iodonium complex first forms through N-halogen bonding. This complex reacts with aci-nitronates to give both α-iodo- and α,α-diiodonitroalkanes, which can act as alternative sources of electrophilic iodine and also generate an extra equimolar amount of I(+) under O2. In particular, evidence supports α,α-diiodonitroalkane intermediates reacting with molecular oxygen to form a peroxy adduct; alternatively, these tetrahedral intermediates rearrange anaerobically to form a cleavable nitrite ester. In either case, activated esters are proposed to form that eventually reacts with nucleophilic amines in a traditional fashion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Amine functionalized graphene oxide/CNT nanocomposite for ultrasensitive electrochemical detection of trinitrotoluene

    Energy Technology Data Exchange (ETDEWEB)

    Sablok, Kavita; Bhalla, Vijayender; Sharma, Priyanka; Kaushal, Roohi; Chaudhary, Shilpa [Institute of Microbial Technology (CSIR) Sector-39A, Chandigarh160036 (India); Suri, C. Raman, E-mail: raman@imtech.res.in [Institute of Microbial Technology (CSIR) Sector-39A, Chandigarh160036 (India)

    2013-03-15

    Highlights: ► Binding of electron-deficient trinitrotoluene to the electron rich amino groups to form JM complexes. ► rGO/CNT based platform for enhanced electrochemical detection. ► Functionalization and characterization of rGO/CNT with amine derivative. ► Ultrasenstitive and specific detection of TNT. -- Abstract: Binding of electron-deficient trinitrotoluene (TNT) to the electron rich amine groups on a substrate form specific charge-transfer Jackson–Meisenheimer (JM) complex. In the present work, we report formation of specific JM complex on amine functionalized reduced graphene oxide/carbon nanotubes- (a-rGO/CNT) nanocomposite leading to sensitive detection of TNT. The CNT were dispersed using graphene oxide that provides excellent dispersion by attaching to CNT through its hydrophobic domains and solubilizes through the available -OH and -COOH groups on screen printed electrode (SPE). The GO was reduced electrochemically to form reduced graphene that remarkably increases electrochemical properties owing to the intercalation of high aspect CNT on graphene flakes as shown by TEM micrograph. The surface amine functionalization of dropcasted and rGO/CNT was carried out using a bi-functional cross linker ethylenediamine. The extent of amine functionalization on modified electrodes was confirmed using energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and confocal microscopy. The FTIR and Raman spectra further suggested the formation of JM complex between amine functionalized electrodes and TNT leading to a shift in peak intensity together with peak broadening. The a-rGO/CNT nanocomposite prepared electrode surface leads to ultra-trace detection of TNT upto 0.01 ppb with good reproducibility (n = 3). The a-rGO/CNT sensing platform could be an alternate for sensitive detection of TNT explosive for various security and environmental applications.

  9. Amine functionalized graphene oxide/CNT nanocomposite for ultrasensitive electrochemical detection of trinitrotoluene

    International Nuclear Information System (INIS)

    Sablok, Kavita; Bhalla, Vijayender; Sharma, Priyanka; Kaushal, Roohi; Chaudhary, Shilpa; Suri, C. Raman

    2013-01-01

    Highlights: ► Binding of electron-deficient trinitrotoluene to the electron rich amino groups to form JM complexes. ► rGO/CNT based platform for enhanced electrochemical detection. ► Functionalization and characterization of rGO/CNT with amine derivative. ► Ultrasenstitive and specific detection of TNT. -- Abstract: Binding of electron-deficient trinitrotoluene (TNT) to the electron rich amine groups on a substrate form specific charge-transfer Jackson–Meisenheimer (JM) complex. In the present work, we report formation of specific JM complex on amine functionalized reduced graphene oxide/carbon nanotubes- (a-rGO/CNT) nanocomposite leading to sensitive detection of TNT. The CNT were dispersed using graphene oxide that provides excellent dispersion by attaching to CNT through its hydrophobic domains and solubilizes through the available -OH and -COOH groups on screen printed electrode (SPE). The GO was reduced electrochemically to form reduced graphene that remarkably increases electrochemical properties owing to the intercalation of high aspect CNT on graphene flakes as shown by TEM micrograph. The surface amine functionalization of dropcasted and rGO/CNT was carried out using a bi-functional cross linker ethylenediamine. The extent of amine functionalization on modified electrodes was confirmed using energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and confocal microscopy. The FTIR and Raman spectra further suggested the formation of JM complex between amine functionalized electrodes and TNT leading to a shift in peak intensity together with peak broadening. The a-rGO/CNT nanocomposite prepared electrode surface leads to ultra-trace detection of TNT upto 0.01 ppb with good reproducibility (n = 3). The a-rGO/CNT sensing platform could be an alternate for sensitive detection of TNT explosive for various security and environmental applications

  10. 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.

  11. Preparation and characterization of aminated graphite oxide for CO2 capture

    International Nuclear Information System (INIS)

    Zhao Yunxia; Ding Huiling; Zhong Qin

    2012-01-01

    Adsorption with solid sorbents is one of the most promising options for postcombustion carbon dioxide (CO 2 ) capture. In this study, aminated graphite oxide used for CO 2 adsorption was synthesized, based on the intercalation reaction of graphite oxide (GO) with amines, including ethylenediamine (EDA), diethylenetriamine (DETA) and triethylene tetramine (TETA). The structural information, surface chemistry and thermal behavior of the adsorbent samples were characterized by X-ray powder diffraction (XRD), infrared spectroscopy (IR), transmission electron microscope (TEM), elemental analysis, particle size analysis, nitrogen adsorption as well as differential thermal and thermogravimetric analysis (DSC-TGA). CO 2 capture was investigated by dynamic adsorption experiments with N 2 -CO 2 mixed gases at 30 °C. The three kinds of graphite oxide samples modified by excess EDA, DETA and TETA showed similar adsorption behaviors seen from their breakthrough curves. Among them, the sample aminated by EDA exhibited the highest adsorption capacity with the longest breakthrough time of CO 2 . Before saturation, its adsorption capacity was up to 53.62 mg CO 2 /g sample. In addition, graphite oxide samples modified by different amount of EDA (EDA/GO raw ratio 10 wt%, 50 wt% and 100 wt%) were prepared in the ethanol. Their CO 2 adsorption performance was investigated. The experimental results demonstrated that graphite oxide with 50 wt% EDA had the largest adsorption capacity 46.55 mg CO 2 /g sample.

  12. Application of ultraviolet, ozone, and advanced oxidation treatments to washwaters to destroy nitrosamines, nitramines, amines, and aldehydes formed during amine-based carbon capture.

    Science.gov (United States)

    Shah, Amisha D; Dai, Ning; Mitch, William A

    2013-03-19

    Although amine-based CO(2) absorption is a leading contender for full-scale postcombustion CO(2) capture at power plants, concerns have been raised about the potential release of carcinogenic N-nitrosamines and N-nitramines formed by reaction of exhaust gas NO(x) with the amines. Experiments with a laboratory-scale pilot unit suggested that washwater units meant to scrub contaminants from absorber unit exhaust could potentially serve as a source of N-nitrosamines via reactions of residual NO(x) with amines accumulating in the washwater. Dosage requirements for the continuous treatment of the washwater recycle line with ultraviolet (UV) light for destruction of N-nitrosamines and N-nitramines, and with ozone or hydroxyl radical-based advanced oxidation processes (AOPs) for destruction of amines and aldehydes, were evaluated. Although amine destruction. Ozone achieved 90% amine removal in washwaters at 5-12 molar excess of ozone, indicating transferred dosage levels of ∼100 mg/L for 90% removal in a first-stage washwater unit, but likely only ∼10 mg/L if applied to a second-stage washwater. Accurate dosage and cost estimates would require pilot testing to capture synergies between UV and ozone treatments.

  13. THE EFFECT OF SULPHURIC ACID CONCENTRATION ON SOLVENT EXTRACTION OF ReO4 - BY THE LONG-CHAIN ALIPHATIC TERTIARY AMINES AND ALCOHOLS

    Directory of Open Access Journals (Sweden)

    Aleksander G. Kasikov

    2010-06-01

    Full Text Available The effect of sulphuric acid concentration on solvent extraction of ReO4- by the long-chain aliphatic tertiary amines and alcohols in a wide range of H2SO4 concentrations in initial solutions is discussed. It has been established that the influence of the sulphuric acid concentration on rhenium solvent extraction is largely due to the extraction process mechanism. In the case of the anion-exchange mechanism, ReO4- is best extracted from weakly acidic solutions, whereas when the hydrate-solvate mechanism takes place – from solutions containing 4-7 mole/l H2SO4.

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

    Science.gov (United States)

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

    2016-04-04

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

  15. 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.

  16. Study of interaction and adsorption of aromatic amines by manganese oxides and their role in chemical evolution

    Science.gov (United States)

    Bhushan, Brij; Nayak, Arunima; Kamaluddin

    2017-04-01

    The role of manganese oxides in concentrating organic moieties and offering catalytic activity for prebiotic reactions is investigated by studying their interaction with different aromatic amines such as aniline, p-chloroaniline, p-toluidine and p-anisidine. For all amines, metal oxides showed highest adsorption at neutral pH. The order of their adsorption capacity and affinity as revealed by the Langmuir constants was found to be manganosite (MnO) > bixbyite (Mn2O3) > hausmannite (Mn3O4) > and pyrolusite (MnO2). At alkaline pH, these manganese oxides offered their surfaces for oxidation of amines to form coloured oligomers. Analysis of the oxidation products by gas chromatography-mass spectrometry showed the formation of a dimer from p-anisidine and p-chloroaniline, while a trimer and tetramer is formed from p-toluidine and aniline, respectively. A reaction mechanism is proposed for the formation of the oligomers. While field-emission scanning electron microscopic studies confirm the binding phenomenon, the Fourier transform infrared spectroscopy analysis suggests that the mechanism of binding of amines on the manganese oxides was primarily electrostatic. The adsorption behaviour of the studied aromatic amines followed the order: p-anisidine > p-toluidine > aniline > p-chloroaniline, which is related to the basicities and structure of the amines. Our studies confirmed the significance of the role of manganese oxides in prebiotic chemistry.

  17. Catalytic oxidation of 2-aminophenols and ortho hydroxylation of aromatic amines by tyrosinase

    International Nuclear Information System (INIS)

    Toussaint, O.; Lerch, K.

    1987-01-01

    The usual substrates of tyrosinase, a copper-containing monooxygenase (EC 1.14.18.1), are monophenols and o-diphenols which are both converted to o-quinones. In this paper, the authors studied the reaction of this enzyme with two new classes of substrates: aromatic amines and o-aminophenols, structural analogues of monophenols and o-diphenols, respectively. They undergo the same catalytic reactions (ortho hydroxylation and oxidation), as documented by product analysis and kinetic studies. In the presence of tyrosinase, arylamines and o-aminophenols are converted to o-quinone imines, which are isolated as quinone anils or phenoxazones. As an example, in the presence of tyrosinase, 2-amino-3-hydroxybenzoic acid (an o-aminophenol) is converted to cinnabarinic acid, a well-known phenoxazone, while p-aminotoluene (an aromatic amine) gives rise to the formation of 5-amino-2-methyl-1,4-benzoquinone 1-(4-methylanil). Kinetic studies using an oxygen electrode show that arylamines and the corresponding monophenols exhibit similar Michaelis constants. In contrast, the reaction rates observed for aromatic amines are relatively slow as compared to monophenols. The enzymatic conversion of arylamines by tryosinase is different from the typical ones: N-oxidation and ring hydroxylation without further oxidation. This difference originates from the regiospecific hydroxylation (ortho position) and subsequent oxidation of the intermediate o-aminophenol to the corresponding o-quinone imine. Finally, the well-know monooxygenase activity of tyrosinase was also confirmed for the aromatic amine p-aminotoluene, with 18 O 2

  18. DFT Rationalization of the Diverse Outcomes of the Iodine(III)-Mediated Oxidative Amination of Alkenes.

    Science.gov (United States)

    Funes-Ardoiz, Ignacio; Sameera, W M C; Romero, R Martín; Martínez, Claudio; Souto, José A; Sampedro, Diego; Muñiz, Kilian; Maseras, Feliu

    2016-05-23

    A computational study of the mechanism for the iodine(III)-mediated oxidative amination of alkenes explains the experimentally observed substrate dependence on product distribution. Calculations with the M06 functional have been carried out on the reaction between PhI(N(SO2 Me)2 )2 and three different representative substrates: styrene, α-methylstyrene, and (E)-methylstilbene. All reactions start with electrophilic attack by a cationic PhI(N(SO2 Me)2 )(+) unit on the double bond, and formation of an intermediate with a single C-I bond and a planar sp(2) carbocationic center. The major path, leading to 1,2-diamination, proceeds through a mechanism in which the bissulfonimide initially adds to the alkene through an oxygen atom of one sulfonyl group. This behavior is now corroborated by experimental evidence. An alternative path, leading to an allylic amination product, takes place through deprotonation at an allylic C-H position in the common intermediate. The regioselectivity of this amination depends on the availability of the resonant structures of an alternate carbocationic intermediate. Only in cases where a high electronic delocalization is possible, as in (E)-methylstilbene, does the allylic amination occur without migration of the double bond. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Monomer-to-polymer conversion and micro-tensile bond strength to dentine of experimental and commercial adhesives containing diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide or a camphorquinone/amine photo-initiator system.

    Science.gov (United States)

    Miletic, Vesna; Pongprueksa, Pong; De Munck, Jan; Brooks, Neil R; Van Meerbeek, Bart

    2013-10-01

    To compare the degree of conversion (DC) of adhesives initiated by diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) or a camphorquinone/tertiary amine system (CQ/Amine) as well as their 'immediate' micro-tensile bond strength (μTBS) to bur-cut dentine. DC of Scotchbond Universal ('SBU'; 3M ESPE), its experimental counterpart containing TPO as photo-initiator system, an experimental G-aenial Bond ('Ga-B'; GC) adhesive formulation, and an experimental LUB-102 adhesive formulation ('LUB', Kuraray Noritake), containing as photo-initiatior system either 2wt% CQ along with 2wt% tertiary amine ('SBU_CQ/Amine'; 'Ga-B_CQ/Amine'; 'LUB_CQ/Amine'), or 2wt% TPO ('SBU_TPO'; 'Ga-B_TPO'; 'LUB_TPO'), was determined using Fourier-transform infrared spectroscopy (FTIR), after being cured with a dual-wavelength light-curing unit (bluephase 20i, Ivoclar Vivadent). The same adhesive formulations were applied to bur-cut mid-coronal dentine of intact human molars, and subjected to a μTBS test after 1-week water storage. Besides being applied following a self-etch (SE) application mode, the adhesive formulations SBU_CQ/Amine and SBU_TPO were also applied following an etch-and-rinse (E&R) mode, this both for DS and μTBS measurement. No significant difference in DC was found for any of the adhesive formulations, except for SBU_CQ/Amine_SE and SBU_TPO_SE. For both SBU formulations, a significantly higher DC was reached for the E&R than the SE approach. Regarding μTBS, no significant differences were recorded, except for the significantly higher μTBS measured for SBU_CQ/Amine_E&R and SBU_TPO_E&R. In self-etch adhesives, the photo-initiator TPO may be used instead of CQ/Amine. The curing and 'immediate' bonding efficiency depended on the application protocol (E&R versus SE), but not on the photo-initiator system. The photo-initiator TPO may be used in self-etch adhesives instead of CQ/Amine with similar curing and 'immediate' bonding efficiency. Copyright © 2013 Elsevier Ltd. All

  20. Chain radiation-chemical oxidation of aromatic amines in polyvinylchloride films

    International Nuclear Information System (INIS)

    Kolninov, O.V.; Lisovskaya, I.A.; Milinchuk, V.K.

    1983-01-01

    Radiation-chemical oxidation of tetramethyldiaminediphenylmethane in polyvinylchloride (PVC) and polystyrene (PS) films was investigated in the presence of CBr 4 at 300 K. Radiation yields (G) of 70 and 1 were obtained for an oxidized amine form (Am + ) in PVC and PS, resp. High yields of Am + in PVC matrix indicate the chain character of an oxidation reaction. Triplet states, which form exciplexes with CBr 4 were established to participate in oxidation reactions. The kinetic scheme suggested for the chain radiation oxidation of Am takes into account energy transfer, formation and degradation of the excited states of molecules resulting in the initiation and propagation of the chain on the account of active particles. (author)

  1. Complexation of Phenol and Thiophenol by Amine N-Oxides: Isothermal Titration Caloritmetry and ab Initio Calculations

    NARCIS (Netherlands)

    Cuypers, R.; Sukumaran, M.; Marcelis, A.T.M.; Sudhölter, E.J.R.; Zuilhof, H.

    2010-01-01

    To develop a new solvent-impregnated resin (SIR) system for removal of phenols from water the complex formation of dimethyldodecylamine. N-oxide (DMDAO), trioctylamine N-oxide (TOAO), and tris(2-ethylhexyl)amine N-oxide (TEHAO) with phenol (PhOH) and thiophenol (PhSH) is studied To this end we use

  2. Anaerobic digestion of amine-oxide-based surfactants: biodegradation kinetics and inhibitory effects.

    Science.gov (United States)

    Ríos, Francisco; Lechuga, Manuela; Fernández-Arteaga, Alejandro; Jurado, Encarnación; Fernández-Serrano, Mercedes

    2017-08-01

    Recently, anaerobic degradation has become a prevalent alternative for the treatment of wastewater and activated sludge. Consequently, the anaerobic biodegradability of recalcitrant compounds such as some surfactants require a thorough study to avoid their presence in the environment. In this work, the anaerobic biodegradation of amine-oxide-based surfactants, which are toxic to several organisms, was studied by measuring of the biogas production in digested sludge. Three amine-oxide-based surfactants with structural differences in their hydrophobic alkyl chain were tested: Lauramine oxide (AO-R 12 ), Myristamine oxide (AO-R 14 ) and Cocamidopropylamine oxide (AO-cocoamido). Results show that AO-R 12 and AO-R 14 inhibit biogas production, inhibition percentages were around 90%. AO-cocoamido did not cause inhibition and it was biodegraded until reaching a percentage of 60.8%. Otherwise, we fitted the production of biogas to two kinetic models, to a pseudo first-order model and to a logistic model. Production of biogas during the anaerobic biodegradation of AO-cocoamido was pretty good adjusted to the logistics model. Kinetic parameters were also determined. This modelling is useful to predict their behaviour in wastewater treatment plants and under anaerobic conditions in the environment.

  3. Hemoglobin binding of aromatic amines: molecular dosimetry and quantitative structure-activity relationships for N-oxidation.

    Science.gov (United States)

    Sabbioni, G

    1993-01-01

    Aromatic amines are important intermediates in industrial manufacturing. N-Oxidation to N-hydroxyarylamines is a key step in determining the genotoxic properties of aromatic amines. N-Hydroxyarylamines can form adducts with DNA, with tissue proteins, and with the blood proteins albumin and hemoglobin in a dose-dependent manner. The determination of hemoglobin adducts is a useful tool for biomonitoring exposed populations. We have established the hemoglobin binding index (HBI) [(mmole compound/mole hemoglobin)/(mmole compound/kg body weight)] of several aromatic amines in female Wistar rats. Including the values from other researchers obtained in the same rat strain, the logarithm of hemoglobin binding (logHBI) was plotted against the following parameters: the sum of the Hammett constants(sigma sigma = sigma p + sigma m), pKa, logP (octanol/water), the half-wave oxidation potential (E1/2), and the electronic descriptors of the amines and their corresponding nitrenium ions obtained by semi-empirical calculations (MNDO, AMI, and PM3), such as atomic charge densities, energies of the highest occupied molecular orbit and lowest occupied molecular orbit and their coefficients, the bond order of C-N, the dipole moments, and the reaction enthalpy [MNDOHF, AM1HF or PM3HF = Hf(nitrenium) - Hf(amine)]. The correlation coefficients were determined from the plots of all parameters against log HBI for all amines by means of linear regression analysis. The amines were classified in three groups: group 1, all parasubstituted amines (maximum, n = 9); group 2, all amines with halogens (maximun, n = 11); and group 3, all amines with alkyl groups (maximum, n = 13).(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8319626

  4. Practical aerobic oxidations of alcohols and amines with homogeneous copper/TEMPO and related catalyst systems.

    Science.gov (United States)

    Ryland, Bradford L; Stahl, Shannon S

    2014-08-18

    Oxidations of alcohols and amines are common reactions in the synthesis of organic molecules in the laboratory and industry. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Self-assembly of a superparamagnetic raspberry-like silica/iron oxide nanocomposite using epoxy-amine coupling chemistry.

    Science.gov (United States)

    Cano, Manuel; de la Cueva-Méndez, Guillermo

    2015-02-28

    The fabrication of colloidal nanocomposites would benefit from controlled hetero-assembly of ready-made particles through covalent bonding. Here we used epoxy-amine coupling chemistry to promote the self-assembly of superparamagnetic raspberry-like nanocomposites. This adaptable method induced the covalent attachment of iron oxide nanoparticles sparsely coated with amine groups onto epoxylated silica cores in the absence of other reactants.

  6. Artifacts Generated During Azoalkane Peroxy Radical Oxidative Stress Testing of Pharmaceuticals Containing Primary and Secondary Amines.

    Science.gov (United States)

    Nefliu, Marcela; Zelesky, Todd; Jansen, Patrick; Sluggett, Gregory W; Foti, Christopher; Baertschi, Steven W; Harmon, Paul A

    2015-12-01

    We report artifactual degradation of pharmaceutical compounds containing primary and secondary amines during peroxy radical-mediated oxidative stress carried out using azoalkane initiators. Two degradation products were detected when model drug compounds dissolved in methanol/water were heated to 40°C with radical initiators such as 2,2'-azobis(2-methylpropionitrile) (AIBN). The primary artifact was identified as an α-aminonitrile generated from the reaction of the amine group of the model drug with formaldehyde and hydrogen cyanide, generated as byproducts of the stress reaction. A minor artifact was generated from the reaction between the amine group and isocyanic acid, also a byproduct of the stress reaction. We report the effects of pH, initiator/drug molar ratio, and type of azoalkane initiator on the formation of these artifacts. Mass spectrometry and nuclear magnetic resonance were used for structure elucidation, whereas mechanistic studies, including stable isotope labeling experiments, cyanide analysis, and experiments exploring the effects of butylated hydroxyanisole addition, were employed to support the degradation pathways. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

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

    Science.gov (United States)

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

    2015-01-01

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

  8. Highly Chemoselective Reduction of Amides (Primary, Secondary, Tertiary) to Alcohols using SmI2/Amine/H2O under Mild Conditions

    Science.gov (United States)

    2014-01-01

    Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C–N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C–O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → π*C=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C–N/C–O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions. PMID:24460078

  9. Ozonization, Amination and Photoreduction of Graphene Oxide for Triiodide Reduction Reaction: An Experimental and Theoretical Study

    International Nuclear Information System (INIS)

    Jing, Hongyu; Ren, Suzhen; Shi, Yantao; Song, Xuedan; Yang, Ying; Guo, Yanan; An, Yonglin; Hao, Ce

    2017-01-01

    This work proposes a mild and environmentally-friendly approach to prepare a highly efficient functional graphene (termed as AGO-hv) using methods of ozone oxidation, solvothermal synthesis, and photoreduction. The use of ozone oxidation in the first step can effectively increase the interlaminar distance between graphite oxide sheets, and create active sites for nucleophilic attack on the epoxy carbon from ammonia. The amino groups were successfully grafted on the surface of graphene as evidenced by the amidation reaction, with a maximum nitrogen content of 10.46 wt% and a C/N molar ratio of 8.46. After further photoreduction of the aminated graphite oxide (AGO), the residual oxygen functionalities, such as C-OH, were effectively removed and the conductivity of the graphene sheet was further recovered. The dye-sensitized solar cell (DSC) exhibited a power conversion efficiency (PCE) of 7.51% based on AGO-hv counter electrode (CE), close to that of Pt counterpart (7.79%). The experimental results indicated that the amidation and photoreduction processes were significantly facilitated by the initial ozonization of graphene oxide, and this process significantly improved the electrochemical activity and the conductivity of graphene oxide. Density functional theory (DFT) calculations revealed that AGO-hv had the lowest ionization energy (a better electron-donating ability) and also suitable binding energy with I atoms as well. The combination of ozonization, amination and photoreduction is an efficient route to obtain electrocatalysts with desired compositional distributions and performance for triiodide reduction reaction in DSCs.

  10. Mechanism of the extraction of nitric acid and water by organic solutions of tertiary alkyl-amines

    International Nuclear Information System (INIS)

    Gourisse, D.

    1966-06-01

    The micellar aggregation of tri-alkyl-ammonium nitrates in low polarity organic solvents has been verified by viscosity, conductivity and sedimentation velocity measurements. The aggregation depends upon the polarity of solvent, the length of the alkyl radicals and the organic concentration of the various constituents (tri-alkyl-ammonium nitrate, tri-alkyl-amine, nitric acid, water). The amine salification law has been established and the excess nitric acid and water solubilities in the organic solutions have been measured. Nitric acid and water are slightly more soluble in micellar organic solutions than in molecular organic solutions. A description of excess nitric acid containing tri-alkyl-ammonium nitrate solutions is proposed. (author) [fr

  11. Hydrogenation of unactivated enamines to tertiary amines: rhodium complexes of fluorinated phosphines give marked improvements in catalytic activity

    Directory of Open Access Journals (Sweden)

    Sergey Tin

    2015-05-01

    Full Text Available In the hydrogenation of sluggish unactivated enamine substrates, Rh complexes of electron-deficient phosphines are demonstrated to be far more reactive catalysts than those derived from triphenylphosphine. These operate at low catalyst loadings (down to 0.01 mol % and are able to reduce tetrasubstituted enamines. The use of the sustainable and environmentally benign solvent (R-limonene for the reaction is also reported with the amine isolated by acid extraction.

  12. Moving protons with pendant amines: proton mobility in a nickel catalyst for oxidation of hydrogen.

    Science.gov (United States)

    O'Hagan, Molly; Shaw, Wendy J; Raugei, Simone; Chen, Shentan; Yang, Jenny Y; Kilgore, Uriah J; DuBois, Daniel L; Bullock, R Morris

    2011-09-14

    Proton transport is ubiquitous in chemical and biological processes, including the reduction of dioxygen to water, the reduction of CO(2) to formate, and the production/oxidation of hydrogen. In this work we describe intramolecular proton transfer between Ni and positioned pendant amines for the hydrogen oxidation electrocatalyst [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+) (P(Cy)(2)N(Bn)(2) = 1,5-dibenzyl-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane). Rate constants are determined by variable-temperature one-dimensional NMR techniques and two-dimensional EXSY experiments. Computational studies provide insight into the details of the proton movement and energetics of these complexes. Intramolecular proton exchange processes are observed for two of the three experimentally observable isomers of the doubly protonated Ni(0) complex, [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+), which have N-H bonds but no Ni-H bonds. For these two isomers, with pendant amines positioned endo to the Ni, the rate constants for proton exchange range from 10(4) to 10(5) s(-1) at 25 °C, depending on isomer and solvent. No exchange is observed for protons on pendant amines positioned exo to the Ni. Analysis of the exchange as a function of temperature provides a barrier for proton exchange of ΔG(‡) = 11-12 kcal/mol for both isomers, with little dependence on solvent. Density functional theory calculations and molecular dynamics simulations support the experimental observations, suggesting metal-mediated intramolecular proton transfers between nitrogen atoms, with chair-to-boat isomerizations as the rate-limiting steps. Because of the fast rate of proton movement, this catalyst may be considered a metal center surrounded by a cloud of exchanging protons. The high intramolecular proton mobility provides information directly pertinent to the ability of pendant amines to accelerate proton transfers during catalysis of hydrogen oxidation. These results may also have broader implications for proton movement in

  13. Mild and Efficient Deoxygenation of Amine-N-Oxides with FeCl{sub 3}·6H{sub 2}O-Indium System under Ultrasonication

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Hwang, Sun Kyun; Kim, Dong Yoon; Choi, Jin Woo; Kang, Sang Ook [Korea University, Jochiwon (Korea, Republic of); Yoo, Byoung Seung [Dongguk University, Seoul (Korea, Republic of); Choi, Kyung Il; Kim, Joong Hyup [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2004-11-15

    We believe that the mild and efficient method described here will present an attractive alternative to the existing methods available for the reduction of amine-N-oxides to the corresponding amines. Further investigations of FeCl{sub 3}·6H{sub 2}O/In system as reducing agent in organic synthesis are currently in progress. The deoxygenation of amine-N-oxides to amines in the presence of other functional groups is an important transformation in the synthesis of nitrogenous aromatic heterocycles. Many reagents have been employed for the deoxygenation of amine-N-oxides, including agents such as: low-valent titanium, phosphorous and sulphur compounds, tributyltin hydride, Pd/C, tetrathiomolybdate, SmI{sub 2}, indium/NH{sub 4}Cl. Recently we reported that Cp{sub 2}TiCl{sub 2}/In system could be used for the deoxygenation of various amine-N-oxides.

  14. Mild and Efficient Deoxygenation of Amine-N-Oxides with FeCl3·6H2O-Indium System under Ultrasonication

    International Nuclear Information System (INIS)

    Yoo, Byung Woo; Hwang, Sun Kyun; Kim, Dong Yoon; Choi, Jin Woo; Kang, Sang Ook; Yoo, Byoung Seung; Choi, Kyung Il; Kim, Joong Hyup

    2004-01-01

    We believe that the mild and efficient method described here will present an attractive alternative to the existing methods available for the reduction of amine-N-oxides to the corresponding amines. Further investigations of FeCl 3 ·6H 2 O/In system as reducing agent in organic synthesis are currently in progress. The deoxygenation of amine-N-oxides to amines in the presence of other functional groups is an important transformation in the synthesis of nitrogenous aromatic heterocycles. Many reagents have been employed for the deoxygenation of amine-N-oxides, including agents such as: low-valent titanium, phosphorous and sulphur compounds, tributyltin hydride, Pd/C, tetrathiomolybdate, SmI 2 , indium/NH 4 Cl. Recently we reported that Cp 2 TiCl 2 /In system could be used for the deoxygenation of various amine-N-oxides

  15. High intake of heterocyclic amines from meat is associated with oxidative stress.

    Science.gov (United States)

    Carvalho, A M; Miranda, A M; Santos, F A; Loureiro, A P M; Fisberg, R M; Marchioni, D M

    2015-04-28

    High meat intake has been related to chronic diseases such as cancer and CVD. One hypothesis is that heterocyclic amines (HCA), which are formed during the cooking process of meat, can generate reactive species. These compounds can cause oxidation of lipids, proteins and DNA, resulting in oxidative stress, cell damage and loss of biological function. This association has been seen in vitro; however, it remains unclear in vivo. The aim of the present study was to investigate the association between oxidative stress and HCA intake, and oxidative stress and meat intake. Data were from the Health Survey for Sao Paulo--ISA-Capital (561 adult and elderly). Food intake was estimated by one 24-h dietary recall (24HR) complemented by a detailed FFQ with preferences of cooking methods and level of doneness for meat. HCA intake was estimated linking the meat from the 24HR to a database of HCA. Oxidative stress was estimated by malondialdehyde (MDA) concentration in the plasma, after derivatisation with thiobarbituric acid and quantification by HPLC/diode array. Analyses were performed using multivariate logistic regressions adjusted for smoking, sex, age, BMI, skin colour, energy intake, fruit and vegetable intake, and physical activity. A positive association between HCA intake and MDA concentration (OR 1·17; 95% CI 1·01, 1·38) was observed, showing that HCA from meat may contribute to increase oxidative stress, and may consequently increase the risk of chronic diseases.

  16. Nitrogen inversion barriers affect the N-oxidation of tertiary alkylamines by cytochromes P450

    DEFF Research Database (Denmark)

    Rydberg, Patrik; Jørgensen, Martin S.; Jacobsen, T.A.

    2013-01-01

    Calculations: Cytochrome P450 enzymes facilitate a number of chemically different reactions. For example, amines can be either N-dealkylated or N-oxidized, but it is complex to rationalize which of these competing reactions occurs. It is shown that the barrier for inversion of the alkylamine...... nitrogen atom seems to be of vital importance for the amount of N-oxidized product formed relative to dealkylation and hydroxylation products....

  17. RuO4-mediated oxidation of secondary amines: Part 1. Are hydroxylamines main intermediates?

    Directory of Open Access Journals (Sweden)

    Florea Cristina A.

    2016-01-01

    Full Text Available The RuO4-catalyzed oxidation of secondary amines Bn-NH-CH2R (1a-b; R=H, Me gave mainly amides, but minute amounts of nitrones PhCH=N(O-CH2R (9a-b and traces of Bn-N(OH-CH2R (R=H, 4a were also detected. In the presence of cyanide, up to 22 reaction products were identified, but mainly α-aminonitriles. Comparison of the oxidation products of 1a-b with those of 4a-b, 9a-b, and Bn-N(O=CHR (10a-b showed that 4a-b cannot be main reaction intermediates formed from 1a-b.

  18. Oxidation of tertiary homoallylic alcohols by thallium trinitrate: fragmentation versus ring contraction

    International Nuclear Information System (INIS)

    Silva Junior, Luiz F.; Quintiliano, Samir A.P.; Ferraz, Helena M.C.; Santos, Leonardo S.; Eberlin, Marcos N.

    2006-01-01

    The oxidation of tertiary homoallylic alcohols with thallium trinitrate (TTN) was investigated. The alcohols bearing an allylic methyl group lose a molecule of acetone via a fragmentation reaction that leads to isomeric secondary allylic alcohols as major products, together with their corresponding acetylated derivatives. On the other hand, treating analogous tertiary alcohols without the allylic methyl group with TTN gives indans, through a ring contraction reaction. (author)

  19. Transition Metal-Free Selective Double sp(3) C-H Oxidation of Cyclic Amines to 3-Alkoxyamine Lactams.

    Science.gov (United States)

    Osorio-Nieto, Urbano; Chamorro-Arenas, Delfino; Quintero, Leticia; Höpfl, Herbert; Sartillo-Piscil, Fernando

    2016-09-16

    The first chemical method for selective dual sp(3) C-H functionalization at the alpha-and beta positions of cyclic amines to their corresponding 3-alkoxyamine lactams is reported. Unlike traditional Cα-H oxidation of amines to amides mediated by transition metals, the present protocol, which involves the use of NaClO2/TEMPO/NaClO in either aqueous or organic solvent, not only allows the Cα-H oxidation but also the subsequent functionalization of the unreactive β-methylene group in an unprecedented tandem fashion and using environmentally friendly reactants.

  20. 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.

  1. Studies of interaction of amines with TOPO/TOP capped CdSe quantum dots: Role of crystallite size and oxidation potential

    International Nuclear Information System (INIS)

    Sharma, Shailesh N.; Sharma, Himani; Singh, Gurmeet; Shivaprasad, S.M.

    2008-01-01

    This work reports the interaction of aliphatic (triethyl amine, butyl amine) and aromatic amines (PPD, aniline) with CdSe quantum dots of varied sizes. The emission properties and lifetime values of CdSe quantum dots were found to be dependent on the oxidation potential of amines and crystallite sizes. Smaller CdSe quantum dots (size ∼5 nm) ensure better surface coverage of amines and hence higher quenching efficiency of amines could be realized as compared to larger CdSe quantum dots (size ∼14 nm). Heterogeneous quenching of amines due to the presence of accessible and inaccessible set of CdSe fluorophores is indicated. PPD owing to its lowest oxidation potential (∼0.26 V) has been found to have higher quenching efficiency as compared to other amines TEA and aniline having oxidation potentials ∼0.66 and >1.0 V, respectively. Butyl amine on the other hand, plays a dual role: its post-addition acts as a quencher for smaller and enhances emission for larger CdSe quantum dots, respectively. The beneficial effect of butyl amine in enhancing emission intensity could be attributed to enhance capping effect and better passivation of surface-traps

  2. Mechanistic investigation of the one-pot formation of amides by oxidative coupling of alcohols with amines in methanol

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Riisager, Anders; Fristrup, Peter

    2013-01-01

    The one-pot formation of amides by oxidative coupling of alcohols and amines via intermediate formation of methyl ester using supported gold and base as catalysts was studied using the Hammett methodology. Determining the relative reactivity of four different para-substituted benzyl alcohol deriv...... a theoretical Hammett plot that was in good agreement with the one obtained experimentally....

  3. Improving the scratch resistance of sol-gel metal oxide coatings cured at 250 C through use of thermogenerated amines

    NARCIS (Netherlands)

    Langanke, J.; Arfsten, N.; Buskens, P.; Habets, R.; Klankermayer, J.; Leitner, W.

    2013-01-01

    Scratch resistant sol-gel metal oxide coatings typically require a thermal post-treatment step (curing process) at temperatures between 400 and 700 C. In this report, we demonstrate that the in situ generation of amines within sol-gel films facilitates the preparation of scratch resistant metal

  4. Aldehyde Selective Wacker Oxidations of Phthalimide Protected Allylic Amines : A New Catalytic Route to beta(3)-Amino Acids

    NARCIS (Netherlands)

    Weiner, Barbara; Baeza Garcia, Alejandro; Jerphagnon, Thomas; Feringa, Ben L.

    2009-01-01

    A new method for the synthesis of B-3-amino acids is presented. Phthalimide protected allylic amines are oxidized under Wacker conditions selectively to aldehydes using PdCl2 and CuCl or Pd(MeCN)(2)Cl(NO2) and CuCl2 as complementary catalyst systems. The aldehydes are produced in excellent yields

  5. Simple one-pot synthesis of thioureas from amine, carbon disulfide and oxidants in water

    Directory of Open Access Journals (Sweden)

    Milosavljević Milutin M.

    2016-01-01

    Full Text Available The present study reports the new facile methodology for synthesis of symmetrical and asymmetrical thioureas by an one-pot reaction of amine, carbon disulfide and oxidants: hydrogen peroxide, ethylenediamine tetraacetic acid (EDTA/sodium percarbonate system or air. The structures of the synthesized compounds were confirmed by IR, 1H and 13C NMR and MS methods. Reaction mechanism has been proposed on the basis of reaction intermediate isolation and their structure determination. The synthetic benefits of the presented methods is reflected in the operational simplicity, mild reaction conditions, short reaction times, recycling of solvent, high purity and yield of products, absence of dangerous by-products and technological applicability at industrial scale. Considering commercial importance of the thioureas, it can be emphasized that implementation of the optimal synthesis of thiourea, based on presented methods, at industrial level of production would provide concurrent alternative to existing technologies in use. [Projekat Ministarstva nauke Republike Srbije, br. 172013

  6. Interaction of amines with native aluminium oxide layers in non-aqueous environment: Application to the understanding of the formation of epoxy-amine/metal interphases

    International Nuclear Information System (INIS)

    Mercier, D.; Rouchaud, J.-C.; Barthes-Labrousse, M.-G.

    2008-01-01

    Interaction of propylamine (PA), 1,2-diaminoethane (DAE) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophorone diamine, IPDA) with native aluminium oxide layers in non-aqueous environment has been studied using time-resolved inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray photoelectron spectroscopy (XPS). The formation of several surface complexes has been evidenced. Monodentate and bidentate metal-bond surface complexes (MBSC) result from interactions between the amine terminations of the molecule and aluminium cations by donation of the N lone electron pair to the metal ion (Lewis-like mechanism leading to O-Al...N bonds). Monodentate and bidentate hydrogen-bond surface complexes (HBSC) are due to interaction of the amino group with surface hydroxyl groups by protonation of the amine termination (Bronsted-like mechanism leading to the formation of Al-OH...N bonds) or interaction with carbonaceous contamination (C x O y H z ...N bonds). Diamines can also form mixed complexes with one amino group forming an O-Al...N bond and the other group forming an Al-OH...N or C x O y H z ...N bond. Al-OH...N and C x O y H z ...N bonds are less stable under vacuum than O-Al...N bonds, leading to partial desorption of the DAE molecules in vacuum and modification of the interaction modes. Only DAE and IPDA can lead to partial dissolution of the aluminium native (hydr)oxide films. A detailed mechanism of dissolution has been proposed based on the formation of mononuclear bidentate (chelate) MBSC by ligand exchange between the terminal η 1 -OH and bridged μ 2 -OH surface sites and the amino terminations of the molecule. The detachment of this complex from the surface is likely to be the precursor step to the formation of the interphase in epoxy-amine/metal systems

  7. Aerobic biodegradation of amphoteric amine-oxide-based surfactants: Effect of molecular structure, initial surfactant concentration and pH.

    Science.gov (United States)

    Ríos, Francisco; Lechuga, Manuela; Fernández-Serrano, Mercedes; Fernández-Arteaga, Alejandro

    2017-03-01

    The present study was designed to provide information regarding the effect of the molecular structure of amphoteric amine-oxide-based surfactants and the initial surfactant concentration on their ultimate biodegradation. Moreover, given this parameter's pH-dependence, the effect of pH was also investigated. Three amine-oxide-based surfactants with structural differences in their hydrophobic alkyl chain were tested: Lauramine oxide (AO-R 12 ), Myristamine oxide (AO-R 14 ) and Cocamidopropylamine oxide (AO-Cocoamido). We studied the ultimate biodegradation using the Modified OECD Screening Test at initial surfactant concentrations ranged from 5 to 75 mg L -1 and at pH levels from 5 to 7.4. The results demonstrate that at pH 7.4, amine-oxide-based surfactants are readily biodegradable. In this study, we concluded that ω-oxidation can be assumed to be the main biodegradation pathway of amine-oxides and that differences in the biodegradability between them can be explained by the presence of an amide group in the alkyl chain of AO-Cocoamido; the CN fission of the amide group slows down their mineralization process. In addition, the increase in the concentration of the surfactant from 5 to 75 mg L -1 resulted in an increase in the final biodegradation of AO-R 12 and AO-R 14 . However, in the case of AO-Cocoamido, a clear relationship between the concentration and biodegradation cannot be stated. Conversely, the biodegradability of AO-R 12 and AO-R 14 was considerably lower in an acid condition than at a pH of 7.4, whereas AO-Cocoamido reached similar percentages in acid conditions and at a neutral pH. However, microorganisms required more time to acclimate. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Extraction and separation of molybdenum and vanadium from acidic and alkaline media using tertiary and quaternary amines

    International Nuclear Information System (INIS)

    Stas, J.; Dahdouh, A.; Rizkallah, I.

    2010-01-01

    The extraction of vanadium and molybdenum from alkaline leaching solutions coming from the leaching of fly ash of fired electrical power stations by tri-n dodecylamine (TDA) and metyl trioctyl ammonium chloride (QA) in the presence of octanol-2 as modifier in kerosene has been investigated. Some parameters influencing the extraction process have been studied (agitation time, octanol-2 percentage in the organic phase, pH of the aqueous phase, concentration of TDA and QA, concentration of vanadium in the aqueous phase and temperature). It has been shown that the extraction capacity of both V and Mo by TDA increases by decreasing the pH of the aqueous phase and reaches a maximum extraction at pH=2. The concentration of TDA plays an important role on the separation selectivity between these two elements, where the selectivity of Mo vs V (S M o, v=[Mo] o rg/[V] o rg) increases with the decrease of TDA concentration to reach a maximum selectivity value of S M o, v = 0.37 for [TDA]=1.5 M. It has been also shown that, whatever vanadium concentration in the aqueous phase, molybdenum will be first extracted, then the remaining free TDA will be occupied by vanadium. Concerning the quaternary amine QA, the pH value of the aqueous phase plays an important role in the separation process between vanadium and molybdenum, where the value of the selectivity of V vs Mo (S v , Mo=[V] o rg/[Mo] o rg) is maximal for pH>8 and the pH=8.5 is the best value which permit a good separation between these two elements at QA concentration equal to 6%, especially at high vanadium concentration. It is very important to note that for low vanadium concentration and at pH=1.5 the value of the selectivity of Mo vs V (S M o,v) increases with increasing Mo concentration in the aqueous phase which enable us the separation between these two elements under these experimental conditions, where Mo will be much more extracted than vanadium. The stripping of vanadium and molybdenum from the loaded organic

  9. A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

    Science.gov (United States)

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-01-01

    Aerobic oxidative C–H functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. PMID:26206475

  10. Simultaneous analysis of fourteen tertiary amine stimulants in human urine for doping control purposes by liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry

    International Nuclear Information System (INIS)

    Lu Jianghai; Wang San; Dong Ying; Wang Xiaobing; Yang Shuming; Zhang Jianli; Deng Jing; Qin Yang; Xu Youxuan; Wu Moutian; Ouyang Gangfeng

    2010-01-01

    A method for the simultaneous screening and confirmation of the presence of fourteen tertiary amine stimulants in human urine by gas chromatography-mass spectrometry (GC-MS) in combination with liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed and validated. Solid phase extraction (SPE) and liquid-liquid extraction (LLE) approaches were utilized for the pre-treatment of the urine samples. The study indicated that the capillary temperature played a significant role in the signal abundances of the protonated molecules of cropropamide and crotethamide under positive ion electrospray ionization (ESI) conditions. In addition, comparison studies of two different pre-treatment approaches as well as the two ionization modes were conducted. The LODs of the developed method for all the analytes were lower than the minimum required performance limit (MRPL) as set forth in the World Anti-Doping Agency (WADA) technical document for laboratories. The human urine sample obtained after oral administration of prolintane.HCl was successfully analyzed by the developed method, which demonstrated the applicability and reliability of the method for routine doping control analysis.

  11. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    International Nuclear Information System (INIS)

    Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira; Abuin, Senen Paz; Soulé, Ezequiel R.; Williams, Roberto J.J.

    2015-01-01

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted

  12. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Abuin, Senen Paz, E-mail: senen@gairesa.com [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Soulé, Ezequiel R. [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina); Williams, Roberto J.J., E-mail: williams@fi.mdp.edu.ar [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina)

    2015-09-20

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.

  13. 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 

  14. Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

    Science.gov (United States)

    Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

    2017-12-18

    Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Curing characteristics of an epoxy resin in the presence of functional graphite oxide with amine-rich surface

    Energy Technology Data Exchange (ETDEWEB)

    Li, Le [The State Key Lab of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu 610065 (China); Zeng, Zhong [Safety Environment Quality Surveillance and Inspection Research Institute of CNPC Chuanqing Drilling & Exploration Corporation, Chengdu 618300 (China); Zou, Huawei, E-mail: hwzou@163.com [The State Key Lab of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu 610065 (China); Liang, Mei, E-mail: liangmeiww@163.com [The State Key Lab of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu 610065 (China)

    2015-08-20

    Highlights: • Functional graphite oxide with amine-rich surface was prepared and characterized. • Kinetic parameters were calculated by Kissinger method and autocatalytic model. • The incorporation of GO and DGO brings in an effect of inhibition on curing. • The inhibition effect weakens for its good compatibility and catalytic effect of DGO. - Abstract: Functional graphite oxide (DGO) with amine-rich surface was successfully prepared through the amidation reaction and characterized by X-ray diffraction analyses (XRD), Fourier transform infrared spectra (FTIR) and Raman spectra. The effects of functional graphite oxide on the curing kinetics of epoxy (EP) were investigated by means of differential scanning calorimetry (DSC). The curing kinetic parameters of EP, EP/graphite oxide (GO) and EP/functional graphite oxide were obtained. There was not much difference in total heat of reaction ΔH and peak temperature T{sub p} with the incorporation of GO or DGO. However, the activation energy, E{sub a}, and the overall order of reaction m + n were enhanced. Comprehensive kinetic analyses indicated that the incorporation of GO sheets brought in an effect of inhibition on curing process. While the inhibition effect weaken when the GO is modified with amine-rich surface. The possible curing mechanism and reaction pathways were proposed to provide a reasonable explanation.

  16. Curing characteristics of an epoxy resin in the presence of functional graphite oxide with amine-rich surface

    International Nuclear Information System (INIS)

    Li, Le; Zeng, Zhong; Zou, Huawei; Liang, Mei

    2015-01-01

    Highlights: • Functional graphite oxide with amine-rich surface was prepared and characterized. • Kinetic parameters were calculated by Kissinger method and autocatalytic model. • The incorporation of GO and DGO brings in an effect of inhibition on curing. • The inhibition effect weakens for its good compatibility and catalytic effect of DGO. - Abstract: Functional graphite oxide (DGO) with amine-rich surface was successfully prepared through the amidation reaction and characterized by X-ray diffraction analyses (XRD), Fourier transform infrared spectra (FTIR) and Raman spectra. The effects of functional graphite oxide on the curing kinetics of epoxy (EP) were investigated by means of differential scanning calorimetry (DSC). The curing kinetic parameters of EP, EP/graphite oxide (GO) and EP/functional graphite oxide were obtained. There was not much difference in total heat of reaction ΔH and peak temperature T p with the incorporation of GO or DGO. However, the activation energy, E a , and the overall order of reaction m + n were enhanced. Comprehensive kinetic analyses indicated that the incorporation of GO sheets brought in an effect of inhibition on curing process. While the inhibition effect weaken when the GO is modified with amine-rich surface. The possible curing mechanism and reaction pathways were proposed to provide a reasonable explanation

  17. A DNA biosensor based on the electrocatalytic oxidation of amine by a threading intercalator

    International Nuclear Information System (INIS)

    Gao Zhiqiang; Tansil, Natalia

    2009-01-01

    An electrochemical biosensor for the detection of DNA based a peptide nucleic acid (PNA) capture probe (CP) modified indium tin oxide electrode (ITO) is described in this report. After hybridization, a threading intercalator, N,N'-bis[(3-propyl)-imidazole]-1,4,5,8-naphthalene diimide (PIND) imidazole complexed with Ru(bpy) 2 Cl (PIND-Ru, bpy = 2,2'-bipyridine), was introduced to the biosensor. PIND-Ru selectively intercalated to double-stranded DNA (ds-DNA) and became immobilized on the biosensor surface. Voltammetric tests showed highly stable and reversible electrochemical oxidation/reduction processes and the peak currents can directly be utilized for DNA quantification. When the tests were conducted in an amine-containing medium, Tris-HCl buffer for example, a remarkable improvement in the voltammetric response and noticeable enhancements of voltammetric and amperometric sensitivities were observed due to the electrocatalytic activity of the [Ru(bpy) 2 Cl] redox moieties. Electrocatalytic current was observed when as little as 3.0 attomoles of DNA was present in the sample solution

  18. Mesoporous tertiary oxides via a novel amphiphilic approach

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, Natasha; Hall, Simon R., E-mail: simon.hall@bristol.ac.uk, E-mail: Annela.Seddon@bristol.ac.uk [Bristol Centre for Functional Nanomaterials, Centre for Nanoscience and Quantum Information, Tyndall Avenue, Bristol BS8 1FD, United Kingdom and Complex Functional Materials Group, School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Seddon, Annela M., E-mail: simon.hall@bristol.ac.uk, E-mail: Annela.Seddon@bristol.ac.uk; Hallett, James E. [H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Kockelmann, Winfried [STFC Rutherford Appleton Laboratory, Chilton OX11 0QX (United Kingdom); Ting, Valeska P. [Department of Chemical Engineering, University of Bath, Bath BA2 7AY (United Kingdom); Sadasivan, Sajanikumari; Tooze, Robert P. [Sasol Technology (UK) Ltd, Purdie Building, North Haugh, St Andrews, Fife KY16 9ST (United Kingdom)

    2016-01-01

    We report a facile biomimetic sol-gel synthesis using the sponge phase formed by the lipid monoolein as a structure-directing template, resulting in high phase purity, mesoporous dysprosium- and gadolinium titanates. The stability of monoolein in a 1,4-butanediol and water mixture complements the use of a simple sol-gel metal oxide synthesis route. By judicious control of the lipid/solvent concentration, the sponge phase of monoolein can be directly realised in the pyrochlore material, leading to a porous metal oxide network with an average pore diameter of 10 nm.

  19. Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Wang, Pei; He, Yi-Liang; Huang, Ching-Hua

    2010-12-01

    Fluoroquinolones (FQs) are a group of widely prescribed antibiotics and have been frequently detected in the aquatic environment. The reaction kinetics and transformation of seven FQs (ciprofloxacin (CIP), enrofloxacin (ENR), norfloxacin (NOR), ofloxacin (OFL), lomefloxacin (LOM), pipemidic acid (PIP) and flumequine (FLU)) and three structurally related amines (1-phenylpiperazine (PP), N-phenylmorpholine (PM) and 4-phenylpiperidine (PD)) toward chlorine dioxide (ClO(2)) were investigated to elucidate the behavior of FQs during ClO(2) disinfection processes. The reaction kinetics are highly pH-dependent, can be well described by a second-order kinetic model incorporating speciation of FQs, and follow the trend of OFL > ENR > CIP ∼ NOR ∼ LOM > > PIP in reactivity. Comparison among FQs and related amines and product characterization indicate that FQs' piperazine ring is the primary reactive center toward ClO(2). ClO(2) likely attacks FQ's piperazinyl N4 atom followed by concerted fragmentation involving piperazinyl N1 atom, leading to dealkylation, hydroxylation and intramolecular ring closure at the piperazine moiety. While FQs with tertiary N4 react faster with ClO(2) than FQs with secondary N4, the overall reactivity of the piperazine moiety also depends strongly on the quinolone ring through electronic effects. The reaction rate constants obtained in clean water matrix can be used to model the decay of CIP by ClO(2) in surface water samples, but overestimate the decay in wastewater samples. Overall, transformation of FQs, particularly for those with tertiary N4 amines, could be expected under typical ClO(2) disinfection conditions. However, the transformation may not eliminate antibacterial activity because of little destruction at the quinolone ring. Copyright © 2010 Elsevier Ltd. All rights reserved.

  20. [Age-related changes in biogenic amine content and oxidative stress profile in the rat hypothalamus in hyperhomocysteinemia].

    Science.gov (United States)

    Milyutina, Yu P; Pustygina, A V; Zaloznyaya, I V; Arutjunyan, A V

    2016-01-01

    The article presents a detailed analysis of correlations between the content of a variety of biogenic amines in the hypothalamic structures responsible for the luteinizing hormone releasing hormone synthesis and secretion (the medial preoptic area and median eminence) and such independent factors as total L-homocysteine plasma level elevation induced by L-methionine loading and aging. Both a nature and a pattern of changes in oxidative stress profile were evaluated. It was shown that ageing, when compared to hyperhomocysteinemia, is a determining factor influencing biogenic amine content in the studied hypothalamic structures. Unlike antioxidant defense system profile, considerable changes in macromolecule oxidative modification were not found, which evidences a balanced activity of pro- and antioxidant systems in the hypothalamus.

  1. Oxidation of primary amines to oximes with molecular oxygen using 1,1-diphenyl-2-picrylhydrazyl and WO3/Al2O3 as catalysts.

    Science.gov (United States)

    Suzuki, Ken; Watanabe, Tomonari; Murahashi, Shun-Ichi

    2013-03-15

    The oxidative transformation of primary amines to their corresponding oximes proceeds with high efficiency under molecular oxygen diluted with molecular nitrogen (O2/N2 = 7/93 v/v, 5 MPa) in the presence of the catalysts 1,1-diphenyl-2-picrylhydrazyl (DPPH) and tungusten oxide/alumina (WO3/Al2O3). The method is environmentally benign, because the reaction requires only molecular oxygen as the terminal oxidant and gives water as a side product. Various alicyclic amines and aliphatic amines can be converted to their corresponding oximes in excellent yields. It is noteworthy that the oxidative transformation of primary amines proceeds chemoselectively in the presence of other functional groups. The key step of the present oxidation is a fast electron transfer from the primary amine to DPPH followed by proton transfer to give the α-aminoalkyl radical intermediate, which undergoes reaction with molecular oxygen and hydrogen abstraction to give α-aminoalkyl hydroperoxide. Subsequent reaction of the peroxide with WO3/Al2O3 gives oximes. The aerobic oxidation of secondary amines gives the corresponding nitrones. Aerobic oxidative transformation of cyclohexylamines to cyclohexanone oximes is important as a method for industrial production of ε-caprolactam, a raw material for Nylon 6.

  2. N-formylation of amines via the aerobic oxidation of methanol over supported gold nanoparticles.

    Science.gov (United States)

    Ishida, Tamao; Haruta, Masatake

    2009-01-01

    Dress code: formyl. Gold nanoparticles supported on NiO catalyze the one-pot N-formylation of amines with methanol and molecular oxygen to produce formamide at a selectivity of 90 %. This process generates methyl formate in situ, followed by reaction with amines.

  3. Sequential continuous flow processes for the oxidation of amines and azides by using HOF·MeCN.

    Science.gov (United States)

    McPake, Christopher B; Murray, Christopher B; Sandford, Graham

    2012-02-13

    The generation and use of the highly potent oxidising agent HOF·MeCN in a controlled single continuous flow process is described. Oxidations of amines and azides to corresponding nitrated systems by using fluorine gas, water and acetonitrile by sequential gas-liquid/liquid-liquid continuous flow procedures are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Role of Chlorine Dioxide in N-Nitrosodimethylamine Formation from Oxidation of Model Amines.

    Science.gov (United States)

    Gan, Wenhui; Bond, Tom; Yang, Xin; Westerhoff, Paul

    2015-10-06

    N-Nitrosodimethylamine (NDMA) is an emerging disinfection byproduct, and we show that use of chlorine dioxide (ClO2) has the potential to increase NDMA formation in waters containing precursors with hydrazine moieties. NDMA formation was measured after oxidation of 13 amines by monochloramine and ClO2 and pretreatment with ClO2 followed by postmonochloramination. Daminozide, a plant growth regulator, was found to yield 5.01 ± 0.96% NDMA upon reaction with ClO2, although no NDMA was recorded during chloramination. The reaction rate was estimated to be ∼0.0085 s(-1), and on the basis of our identification by mass spectrometry of the intermediates, the reaction likely proceeds via the hydrolytic release of unsymmetrical dimethylhydrazine (UDMH), with the hydrazine structure a key intermediate in NDMA formation. The presence of UDMH was confirmed by gas chromatography-mass spectrometry analysis. For 10 of the 13 compounds, ClO2 preoxidation reduced NDMA yields compared with monochloramination alone, which is explained by our measured release of dimethylamine. This work shows potential preoxidation strategies to control NDMA formation may not impact all organic precursors uniformly, so differences might be source specific depending upon the occurrence of different precursors in source waters. For example, daminozide is a plant regulator, so drinking water that is heavily influenced by upstream agricultural runoff could be at risk.

  5. One-pot synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines using supported gold and base as catalysts

    DEFF Research Database (Denmark)

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

    2012-01-01

    Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol.......Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol....

  6. Removal of cobalt ions from aqueous solution by an amination graphene oxide nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Fang [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000 (China); Kong, Lingtao, E-mail: ltkong@iim.ac.cn [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Huang, Jiarui [College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000 (China); Wu, Shibiao [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); School of Chemistry and Chemical Engineering, Anhui University, Hefei, Anhui 230039 (China); Zhang, Kaisheng [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Wang, Xuelong [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); School of Chemistry and Chemical Engineering, Anhui University, Hefei, Anhui 230039 (China); Sun, Bai; Jin, Zhen; Wang, Jin [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Huang, Xing-Jiu, E-mail: xjhuang@iim.ac.cn [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Liu, Jinhuai, E-mail: jhliu@iim.ac.cn [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031 (China)

    2014-04-01

    Highlights: • A newly designed GO-NH{sub 2}: Higher adsorption capability than that of activated carbon. • Very quick adsorption property: More than 90% of Co(II) can be removed within 5 min. • One of the highest adsorption capabilities of today's nanomaterials for Co(II) (116.35 mg/g). • GO-NH{sub 2} membrane can remove more than 98% Co(II) from the water. - Abstract: A newly designed amination graphene oxide (GO-NH{sub 2}), a superior adsorption capability to that of activated carbon, was fabricated by graphene oxide (GO) combining with aromatic diazonium salt. The resultant GO-NH{sub 2} maintained a high surface area of 320 m{sup 2}/g. When used as an adsorbent, the GO-NH{sub 2} demonstrated a very quick adsorption property for the removal of Co(II) ions, more than 90% of Co(II) ions could be removed within 5 min for dilute solutions at 0.3 g/L adsorbent dose. The adsorption capability approaches 116.35 mg/g, which is one of the highest capabilities of today's materials. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that the Co(II) ions adsorption on GO-NH{sub 2} was a spontaneous process. Considering the superior adsorption capability, the GO-NH{sub 2} filter membrane was fabricated for the removal of Co(II) ions. Membrane filtration experiments revealed that the removal capabilities of the materials for cobalt ions depended on the membrane's thickness, flow rate and initial concentration of Co(II) ions. The highest percentage removal of Co(II) exceeds 98%, indicating that the GO-NH{sub 2} is one of the very suitable membrane materials in environmental pollution management.

  7. Structure and Oxidation of Pyrrole Adducts Formed between Aflatoxin B2a and Biological Amines.

    Science.gov (United States)

    Rushing, Blake R; Selim, Mustafa I

    2017-06-19

    Aflatoxin B 2a has been shown to bind to proteins through a dialdehyde intermediate under physiological conditions. The proposed structure of this adduct has been published showing a Schiff base interaction, but adequate verification using structural elucidation instrumental techniques has not been performed. In this work, we synthesized the aflatoxin B 2a amino acid adduct under alkaline conditions, and the formation of a new product was determined using high performance liquid chromatography-time-of-flight mass spectrometry. The resulting accurate mass was used to generate a novel proposed chemical structure of the adduct in which the dialdehyde forms a pyrrole ring with primary amines rather than the previously proposed Schiff base interaction. The pyrrole structure was confirmed using 1 H, 13 C, correlation spectroscopy, heteronuclear single quantum correlation, and heteronuclear multiple bond correlation NMR and tandem mass spectrometry. Reaction kinetics show that the reaction is overall second order and that the rate increases as pH increases. Additionally, this study shows for the first time that aflatoxin B 2a dialdehyde forms adducts with phosphatidylethanolamines and does so through pyrrole ring formation, which makes it the first aflatoxin-lipid adduct to be structurally identified. Furthermore, oxidation of the pyrrole adduct produced a product that was 16 m/z heavier. When the aflatoxin B 2a -lysine (ε) adduct was oxidized, it gave a product with an accurate mass, mass fragmentation pattern, and 1 H NMR spectrum that match aflatoxin B 1 -lysine, which suggest the transformation of the pyrrole ring to a pyrrolin-2-one ring. These data give new insight into the fate and chemical properties of biological adducts formed from aflatoxin B 2a as well as possible interferences with known aflatoxin B 1 exposure biomarkers.

  8. Kinetic Effects Of Increased Proton Transfer Distance On Proton-Coupled Oxidations Of Phenol-Amines

    Science.gov (United States)

    Rhile, Ian J.

    2011-01-01

    To test the effect of varying the proton donor-acceptor distance in proton-coupled electron transfer (PCET) reactions, the oxidation of a bicyclic amino-indanol (2) is compared with that of a closely related phenol with an ortho CPh2NH2 substituent (1). Spectroscopic, structural, thermochemical and computational studies show that the two amino-phenols are very similar, except that the O⋯N distance (dON) is >0.1 Å longer in 2 than in 1. The difference in dON is 0.13 ± 0.03 Å from X-ray crystallography and 0.165 Å from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations •OAr–NH3+ by concerted proton-electron transfer (CPET). Simple tunneling and classical kinetic models both predict that the longer donor-acceptor distance in 2 should lead to slower reactions, by ca. two orders of magnitude, as well as larger H/D kinetic isotope effects (KIEs). However, kinetic studies show that the compound with the longer proton-transfer distance, 2, exhibits smaller KIEs and has rate constants that are quite close to those of 1. For example, the oxidation of 2 by the triarylamminium radical cation N(C6H4OMe)3•+ (3a+) occurs at (1.4 ± 0.1) × 104 M-1 s-1, only a factor of two slower than the closely related reaction of 1 with N(C6H4OMe)2(C6H4Br)•+ (3b+). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ΔG°(2 + 3a+) = +0.078 V vs. ΔG°(1 + 3b+) = +0.04 V. The two phenol-amines do display some subtle kinetic differences: for instance, compound 2 has a shallower dependence of CPET rate constants on driving force (Brønsted α, Δln(k)/Δln(Keq)). These results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Computational analysis of the observed similarity of the two phenols emphasizes the importance of the highly

  9. 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.

  10. Microwave-Accelerated Iodination of Some Aromatic Amines, Using Urea-Hydrogen Peroxide Addition Compound (UHP as the Oxidant

    Directory of Open Access Journals (Sweden)

    Lech Skulski

    2002-12-01

    Full Text Available A fast and simple method for the oxidative iodination of some aromatic amines, under microwave irradiation, is reported, using diiodine and the the strongly Hbonded urea-hydrogen peroxide addition compound (H2NCONH2···H2O2, UHP as the oxidant. The reactions were carried out in boiling CHCl3 under a reflux condenser to afford, within 10 minutes, the purified monoiodinated products in 40-80% yields.

  11. Oxidative Degradation of Aminosilica Adsorbents Relevant to Postcombustion CO 2 Capture

    KAUST Repository

    Bollini, Praveen

    2011-05-19

    Coal-fired power plant flue gas exhaust typically contains 3-10% oxygen. While it is known that the monoethanolamine (MEA) oxidative degradation rate is a critical parameter affecting liquid amine absorption processes, the effect of oxygen on the stability of solid amine adsorbents remains unexplored. Here, oxidative degradation of aminosilica materials is studied under accelerated oxidizing conditions to assess the stability of different supported amine structures to oxidizing conditions. Adsorbents constructed using four different silane coupling agents are evaluated, three with a single primary, secondary, or tertiary amine at the end of a propyl surface linker, with the fourth having one secondary propylamine separated from a primary amine by an ethyl linker. Under the experimental conditions used in this study, it was found that both amine type and proximity had a significant effect on oxidative degradation rates. In particular, the supported primary and tertiary amines proved to be stable to the oxidizing conditions used, whereas the secondary amines degraded at elevated treatment temperatures. Because secondary amines are important components of many supported amine adsorbents, it is suggested that the oxidative stability of such species needs to be carefully considered in assessments of postcombustion CO2 capture processes based on supported amines. © 2011 American Chemical Society.

  12. Oxidative Degradation of Aminosilica Adsorbents Relevant to Postcombustion CO 2 Capture

    KAUST Repository

    Bollini, Praveen; Choi, Sunho; Drese, Jeffrey H.; Jones, Christopher W.

    2011-01-01

    Coal-fired power plant flue gas exhaust typically contains 3-10% oxygen. While it is known that the monoethanolamine (MEA) oxidative degradation rate is a critical parameter affecting liquid amine absorption processes, the effect of oxygen on the stability of solid amine adsorbents remains unexplored. Here, oxidative degradation of aminosilica materials is studied under accelerated oxidizing conditions to assess the stability of different supported amine structures to oxidizing conditions. Adsorbents constructed using four different silane coupling agents are evaluated, three with a single primary, secondary, or tertiary amine at the end of a propyl surface linker, with the fourth having one secondary propylamine separated from a primary amine by an ethyl linker. Under the experimental conditions used in this study, it was found that both amine type and proximity had a significant effect on oxidative degradation rates. In particular, the supported primary and tertiary amines proved to be stable to the oxidizing conditions used, whereas the secondary amines degraded at elevated treatment temperatures. Because secondary amines are important components of many supported amine adsorbents, it is suggested that the oxidative stability of such species needs to be carefully considered in assessments of postcombustion CO2 capture processes based on supported amines. © 2011 American Chemical Society.

  13. A bioinspired catalytic aerobic oxidative C-H functionalization of primary aliphatic amines: synthesis of 1,2-disubstituted benzimidazoles.

    Science.gov (United States)

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-09-01

    Aerobic oxidative CH functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons Attribution NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  14. OMS-2-Supported Cu Hydroxide-Catalyzed Benzoxazoles Synthesis from Catechols and Amines via Domino Oxidation Process at Room Temperature.

    Science.gov (United States)

    Meng, Xu; Wang, Yanmin; Wang, Yuanguang; Chen, Baohua; Jing, Zhenqiang; Chen, Gexin; Zhao, Peiqing

    2017-07-07

    In the presence of manganese oxide octahedral molecular sieve (OMS-2) supported copper hydroxide Cu(OH) x /OMS-2, aerobic synthesis of benzoxazoles from catechols and amines via domino oxidation/cyclization at room temperature is achieved. This heterogeneous benzoxazoles synthesis initiated by the efficient oxidation of catechols over Cu(OH) x /OMS-2 tolerates a variety of substrates, especially amines containing sensitive groups (hydroxyl, cyano, amino, vinyl, ethynyl, ester, and even acetyl groups) and heterocycles, which affords functionalized benzoxazoles in good to excellent yields by employing low catalyst loading (2 mol % Cu). The characterization and plausible catalytic mechanism of Cu(OH) x /OMS-2 are described. The notable features of our catalytic protocol such as the use of air as the benign oxidant and EtOH as the solvent, mild conditions, ease of product separation, being scalable up to the gram level, and superior reusability of catalyst (up to 10 cycles) make it more practical and environmentally friendly for organic synthesis.

  15. Oxidation using quaternary ammonium polyhalides VII. Oxidation of primary amines and hydrazo compounds by use of benzyltrimethylammonium tribromide

    OpenAIRE

    Nishida, Akiko; Kohro, Noriaki; Fujisaki, Shizuo; Kajigaeshi, Shoji

    1990-01-01

    The reactions of primary amines and hydrazo compounds with benzyltrimethylammonium tribromide in aqueous sodium hydroxide or in water gave the corresponding nitriles and azo compounds in satisfactory yields, respectively.

  16. Evaluating Metabolite-Related DNA Oxidation and Adduct Damage from Aryl Amines Using a Microfluidic ECL Array.

    Science.gov (United States)

    Bist, Itti; Bhakta, Snehasis; Jiang, Di; Keyes, Tia E; Martin, Aaron; Forster, Robert J; Rusling, James F

    2017-11-21

    Damage to DNA from the metabolites of drugs and pollutants constitutes a major human toxicity pathway known as genotoxicity. Metabolites can react with metal ions and NADPH to oxidize DNA or participate in S N 2 reactions to form covalently linked adducts with DNA bases. Guanines are the main DNA oxidation sites, and 8-oxo-7,8-dihydro-2-deoxyguanosine (8-oxodG) is the initial product. Here we describe a novel electrochemiluminescent (ECL) microwell array that produces metabolites from test compounds and measures relative rates of DNA oxidation and DNA adduct damage. In this new array, films of DNA, metabolic enzymes, and an ECL metallopolymer or complex assembled in microwells on a pyrolytic graphite wafer are housed in dual microfluidic chambers. As reactant solution passes over the wells, metabolites form and can react with DNA in the films to form DNA adducts. These adducts are detected by ECL from a RuPVP polymer that uses DNA as a coreactant. Aryl amines also combine with Cu 2+ and NADPH to form reactive oxygen species (ROS) that oxidize DNA. The resulting 8-oxodG was detected selectively by ECL-generating bis(2,2'-bipyridine)-(4-(1,10-phenanthrolin-6-yl)-benzoic acid)Os(II). DNA/enzyme films on magnetic beads were oxidized similarly, and 8-oxodG determined by LC/MS/MS enabled array standardization. The array limit of detection for oxidation was 720 8-oxodG per 10 6 nucleobases. For a series of aryl amines, metabolite-generated DNA oxidation and adduct formation turnover rates from the array correlated very well with rodent 1/TD 50 and Comet assay results.

  17. 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.

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

    Science.gov (United States)

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

    2017-04-01

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

  19. Synergism and Physicochemical Properties of Anionic/Amphoteric Surfactant Mixtures with Nonionic Surfactant of Amine Oxide Type

    Science.gov (United States)

    Blagojević, S. M.; Pejić, N. D.; Blagojević, S. N.

    2017-12-01

    The physicochemical properties of initial formulation, that is anionic/amphoteric surfactants mixture SLES/AOS/CAB (sodium lauryl ether sulfate (SLES), α-olefin sulfonates (AOS) and cocamidopropyl betaine (CAB) at ratio 80 : 15 : 5) with nonionic surfactant of amine oxide type (lauramine oxide (AO)) in various concentration (1-5%) were studied. To characterize the surfactants mixture, the critical micelle concentration (CMC), surface tension (γ), foam volume, biodegradability and irritability were determined. This study showed that adding of AO in those mixtures lowered both γ and CMC as well as enhanced SLES/AOS/CAB foaming properties, but did not significantly affect biodegradability and irritability of initial formulation. Moreover, an increase in AO concentration has a meaningful synergistic effect on the initial formulation properties. All those results indicates that a nonionic surfactant of amine oxide type significantly improves the performance of anionic/amphoteric mixed micelle systems, and because of that anionic/amphoteric/nonionic mixture can be used in considerably lower concentrations as a cleaning formulation.

  20. Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal-organic frameworks for catalytic oxidative desulfurization.

    Science.gov (United States)

    Wang, Xu-Sheng; Huang, Yuan-Biao; Lin, Zu-Jin; Cao, Rong

    2014-08-21

    Highly dispersed Keggin-type phosphotungstic acid (H3PW12O40, PTA) encapsulated in the mesocages of amine-functionalized metal-organic frameworks MIL-101(Cr)-NH2 has been prepared by an anion-exchange method. PTA anions (PW12O40(3-)) are stabilized in the mesocages via the electrostatic interaction with amino groups of the MIL-101(Cr)-NH2. The obtained catalyst (denoted PTA@MIL-101(Cr)-NH2) exhibits high catalytic activity in the extractive and catalytic oxidative desulfurization (ECODS) system under mild conditions. Moreover, it can be easily recovered and recycled several times without leaching and loss of activity.

  1. Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

    Science.gov (United States)

    Fitzpatrick, Paul F.

    2014-01-01

    Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

  2. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

    Science.gov (United States)

    Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

    2014-09-14

    An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

  3. Electro-oxidation of reverse osmosis concentrates generated in tertiary water treatment.

    Science.gov (United States)

    Pérez, G; Fernández-Alba, A R; Urtiaga, A M; Ortiz, I

    2010-05-01

    This work investigates the application of the electro-oxidation technology provided with boron doped diamond (BDD), an electrode material which has shown outstanding properties in oxidation of organic and inorganic compounds, for the treatment of reverse osmosis (RO) concentrates generated in tertiary wastewater treatment plants (WWTP). Chemical oxygen demand (COD), ammonium and several anions were measured during the electro-oxidation process, and the influence of the applied current density (20-200A/m(2)) was analysed on process kinetics. Analytical assessment showed that several emerging pollutants (pharmaceuticals, personal care products, stimulants, etc.) were presented both in the effluent of the secondary WWTP as well as in the RO concentrate. For this reason, a group of 10 emerging pollutants, those found with higher concentrations, was selected in order to test whether electro-oxidation can be also applied for their mitigation. In the removal of emerging pollutants the electrical current density in the range 20-100A/m(2) did not show influence likely due to the mass transfer resistance developed in the process when the oxidized solutes are present in such low concentrations. Their removal rates were fitted to first order expressions, and the apparent kinetic constants for the anodic oxidation of each compound were calculated. Finally, the formation of trihalomethanes (THMs) has been checked; concluding that after selecting the appropriate operational conditions the attained concentration is lower than the standards for drinking water established in European and EPA regulations. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  4. Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation.

    Science.gov (United States)

    Mirza-Aghayan, Maryam; Tavana, Mahdieh Molaee; Boukherroub, Rabah

    2016-03-01

    Sulfonated reduced graphene oxide nanosheets (rGO-SO3H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO3H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO3H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56-95%) the corresponding amides in short reaction times. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Influence of cooking methods and storage time on lipid and protein oxidation and heterocyclic aromatic amines production in bacon.

    Science.gov (United States)

    Soladoye, O P; Shand, P; Dugan, M E R; Gariépy, C; Aalhus, J L; Estévez, M; Juárez, M

    2017-09-01

    This study aimed to examine the influence of cooking methods and pre-determined refrigerated storage days on the production of lipid oxidation (TBARS), protein oxidation (PROTOX) and heterocyclic aromatic amines (HAA) in bacon. Forty-four pork bellies selected from pigs varying in breed, sex and diets to introduce variability in composition were processed as bacon. Sliced-bacon was stored at 4°C either for 2 or 28days and these storage groups were cooked either with microwave or frying pan. Microwave led to significantly higher PROTOX (P0.05) by the cooking methods and storage times. Similarly, the fatty acid composition of pork belly did not significantly influence the production of HAA, TBARS and PROTOX produced in bacon during cooking. Overall, microwave cooking had lesser impact on the production of carcinogenic compounds in bacon with only minor impact on sensory attributes. Copyright © 2017. Published by Elsevier Ltd.

  6. Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

    Science.gov (United States)

    Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

    2013-07-07

    A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

  7. Selective and Efficient Deoxygenation of Amine-N-Oxides with CeCl{sub 3}·7H{sub 2}O/Zinc System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Jung, Ha Il; Kim, Se Heon; Ahn, Young Sun; Choi, Ji Yong [Korea Univ., Seoul (Korea, Republic of)

    2013-02-15

    A number of methods have been developed for the deoxygenation of amine-N-oxides, including agents such as low-valent titanium, Zn/HCOONH{sub 4}, InCl{sub 3}, tributyltin hydride, Pd/C, tetrathiomolybdate, SmI{sub 2}, indium/NH{sub 4}Cl, and Mo(CO){sub 6}, Cu(I)-Zn or Cu(I)-Al,11 RuCl{sub 3}·xH{sub 2}O, Zn/Cu-triflates. In conclusion, we have discovered that CeCl{sub 3}·7H{sub 2}O/Zn system mediates a selective and efficient deoxygenation of amine-N-oxides to the corresponding amines. Although the scope and limitations have not been fully established, the present procedure offers an attractive alternative to the conventional methods with its mildness and chemoselectivity as well as high yields. Further investigations of more useful applications with this system are currently in progress.

  8. The coupling of ω-transaminase and Oppenauer oxidation reactions via intra-membrane multicomponent diffusion – A process model for the synthesis of chiral amines

    DEFF Research Database (Denmark)

    Esparza-Isunza, T.; González-Brambila, M.; Gani, Rafiqul

    2015-01-01

    amine product. Using 2-propylamine as the amine donor of the ω-transaminase reaction, gives acetone as a by-product, which in turn allows the coupling of the ω-transaminase reaction with the Oppenauer oxidation. The Oppenauer reaction converts secondary alcohols into ketones, and these can subsequently......In this study we consider the theoretical coupling of an otherwise thermodynamically limited ω-transaminase reaction to an Oppenauer oxidation, in order to shift the equilibria of both reactions, with the aim of achieving a significant (and important) increase in the yield of the desired chiral...... of this paper is to report the development of a mathematical model as a tool for the simulation and potential design of such a process for the production of a range of chiral amines. The mathematical model developed considers that each reaction is performed in a single ideally mixed isothermal reactor operating...

  9. 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.

  10. 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.

  11. 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.

  12. Cu(OAc)2/TFA-promoted formal [3 + 3] cycloaddition/oxidation of enamines and enones for synthesis of multisubstituted aromatic amines.

    Science.gov (United States)

    Li, Liang; Zhao, Mi-Na; Ren, Zhi-Hui; Li, Jian-Li; Guan, Zheng-Hui

    2012-07-06

    New strategies for the oxidative cycloaddition of enones with enamines are developed. These cycloaddition reactions directly afford substituted aromatic amines, which are important in organic chemistry, in moderate to good yield. Cu(OAc)(2)/TFA is shown to be essential to achieve high reaction efficiency.

  13. N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation

    Science.gov (United States)

    2015-01-01

    A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C–H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C–H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C–H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration. PMID:24999765

  14. N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.

    Science.gov (United States)

    Osberger, Thomas J; White, M Christina

    2014-08-06

    A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

  15. Ni-Catalyzed Carbon-Carbon Bond-Forming Reductive Amination.

    Science.gov (United States)

    Heinz, Christoph; Lutz, J Patrick; Simmons, Eric M; Miller, Michael M; Ewing, William R; Doyle, Abigail G

    2018-02-14

    This report describes a three-component, Ni-catalyzed reductive coupling that enables the convergent synthesis of tertiary benzhydryl amines, which are challenging to access by traditional reductive amination methodologies. The reaction makes use of iminium ions generated in situ from the condensation of secondary N-trimethylsilyl amines with benzaldehydes, and these species undergo reaction with several distinct classes of organic electrophiles. The synthetic value of this process is demonstrated by a single-step synthesis of antimigraine drug flunarizine (Sibelium) and high yielding derivatization of paroxetine (Paxil) and metoprolol (Lopressor). Mechanistic investigations support a sequential oxidative addition mechanism rather than a pathway proceeding via α-amino radical formation. Accordingly, application of catalytic conditions to an intramolecular reductive coupling is demonstrated for the synthesis of endo- and exocyclic benzhydryl amines.

  16. Oxidation of cyclic amines by molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br

    Directory of Open Access Journals (Sweden)

    H.M. Mbuvi

    2013-05-01

    Full Text Available The molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br react with a large excess of the nitrogen bases, 1-methylpyrrolidine, 1-methylpiperidine, 1-ethylpiperidine and 2-ethylpiperidine to give aminecarbonyl complexes of the type M(CO3L3 (L= alkylamine. Excess piperidine reacts with the tungsten halocarbonyls, [W(CO4X2]2 (X = Cl, Br, to give the trans isomer of the complex, W(CO3(C5H11N3. The halogens were recovered as the amminium salts, amine, HX. The oxidized amine dimerized to form a yellow product which was recovered as an oily liquid but in very small amounts. However, in the reaction between Mo(CO4Br2 and 1-ethylpiperidine, a yellow crystalline solid, with a melting point of 224 oC was recovered in sufficient amounts for elemental analysis, melting point and spectral data. Its mass spectrum showed a molecular ion peak at m+/z = 222, a clear evidence that the oxidized amine dimerizes. The cyclic dibasic amine piperazine, C4H10N2 is not, however, oxidized by these halocarbonyls but rather it reacts by substituting some CO groups to form products of the type, M(CO3(C4H10N22X2 (M = Mo, W; X = Cl, Br. Products were characterized by elemental analysis, IR, UV, 1H NMR and mass spectrometry.

  17. Factors affecting the photovoltaic behavior of inverted polymer solar cells using various indium tin oxide electrodes modified by amines with simple chemical structures

    Energy Technology Data Exchange (ETDEWEB)

    Kusumi, Takuji [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Kuwabara, Takayuki, E-mail: tkuwabar@se.kanazawa-u.ac.jp [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Research Center for Sustainable Energy and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Yamaguchi, Takahiro [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Taima, Tetsuya [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Research Center for Sustainable Energy and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Takahashi, Kohshin, E-mail: ktakaha@se.kanazawa-u.ac.jp [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Research Center for Sustainable Energy and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan)

    2015-09-30

    In a glass–indium tin oxide (ITO)/amine/regioregular poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C{sub 61} butyric acid methyl ester (PCBM)/poly(3,4-ethylenedioxylenethiophene):poly(4-styrene sulfonic acid) (PEDOT:PSS)/Au cell, which uses small molecule amine-modified ITO as the electron collection electrode, a light-soaking effect under irradiation of simulated sunlight was restrained considerably compared with in an ITO/P3HT:PCBM/PEDOT:PSS/Au cell containing bare ITO. That is, the time taken to arrive at a saturated V{sub oc} from the initial V{sub oc} became short when the ionization potential (I{sub P}) of ITO reduced by the amine modification, and consequently both of its saturated V{sub oc} and power conversion efficiency (PCE) improved. The I{sub P} decreased with an increase in the number (N) of amino groups in a single amine molecule, because the basic amino groups can efficiently neutralize any acidic hydroxyl groups on ITO through a multipoint interaction. The superior performance of the cell containing the amine-modified electrode with large N was perhaps because the energy mismatch formed by a contact between ITO and acceptor PCBM reduced, and consequently the rate of electron collection at ITO increased. - Highlights: • Surface-modification of ITO electrode with low molecular weight amines • Ionization potential of ITO was decreased by forming an electrical double layer. • Light-soaking effect has been observed by irradiating white light. • The light-soaking effect mainly improved the open-circuit photovoltage. • Open-circuit photovoltage was limited by ionization potential of amine-modified ITO.

  18. Factors affecting the photovoltaic behavior of inverted polymer solar cells using various indium tin oxide electrodes modified by amines with simple chemical structures

    International Nuclear Information System (INIS)

    Kusumi, Takuji; Kuwabara, Takayuki; Yamaguchi, Takahiro; Taima, Tetsuya; Takahashi, Kohshin

    2015-01-01

    In a glass–indium tin oxide (ITO)/amine/regioregular poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C_6_1 butyric acid methyl ester (PCBM)/poly(3,4-ethylenedioxylenethiophene):poly(4-styrene sulfonic acid) (PEDOT:PSS)/Au cell, which uses small molecule amine-modified ITO as the electron collection electrode, a light-soaking effect under irradiation of simulated sunlight was restrained considerably compared with in an ITO/P3HT:PCBM/PEDOT:PSS/Au cell containing bare ITO. That is, the time taken to arrive at a saturated V_o_c from the initial V_o_c became short when the ionization potential (I_P) of ITO reduced by the amine modification, and consequently both of its saturated V_o_c and power conversion efficiency (PCE) improved. The I_P decreased with an increase in the number (N) of amino groups in a single amine molecule, because the basic amino groups can efficiently neutralize any acidic hydroxyl groups on ITO through a multipoint interaction. The superior performance of the cell containing the amine-modified electrode with large N was perhaps because the energy mismatch formed by a contact between ITO and acceptor PCBM reduced, and consequently the rate of electron collection at ITO increased. - Highlights: • Surface-modification of ITO electrode with low molecular weight amines • Ionization potential of ITO was decreased by forming an electrical double layer. • Light-soaking effect has been observed by irradiating white light. • The light-soaking effect mainly improved the open-circuit photovoltage. • Open-circuit photovoltage was limited by ionization potential of amine-modified ITO.

  19. Adsorption of poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) polymers on zinc, zinc oxide, iron, and iron oxide surfaces.

    Science.gov (United States)

    Seifert, Susan; Simon, Frank; Baumann, Giesela; Hietschold, Michael; Seifert, Andreas; Spange, Stefan

    2011-12-06

    The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions. © 2011 American Chemical Society

  20. Influence of nature, concentration and pH of buffer acid-base system on rate determining step of the electrochemiluminescence of Ru(bpy){sub 3} {sup 2+} with tertiary aliphatic amines

    Energy Technology Data Exchange (ETDEWEB)

    Pastore, Paolo [Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova (Italy)]. E-mail: paolo.pastore@unipd.it; Badocco, Denis [Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova (Italy); Zanon, Francesco [Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova (Italy)

    2006-07-28

    The electrogenerated chemiluminescence (ECL) of Ru(bpy){sub 3} {sup 2+} (bpy 2,2'-bipyridyl) with tertiary aliphatic amines as co-reactants, was theoretically and experimentally studied as a function of the pre-equilibria involved in the ammonium proton lost and in relation to the nature of the rate determining step. Transient potential steps were used with a 3-mm glassy carbon disk electrode or carbon fiber ultramicroelectrodes array to investigate emission behavior in a variety of aqueous solution types, containing phosphate, tartrate and phthalate acid-base systems at differing pH values. The emission of Ru(bpy){sub 3} {sup 2+} resulting from the reaction with n-tripropylamine (TPrA), tri-isobutylamine (TisoBuA), n-tributylamine (TBuA), methyl-di-n-propylamine (MeDPrA) and triethylamine (TEtA) in varying acid-base media was interpreted on the basis of the quoted pre-equilibria, ammonium pK {sub a} being known. The nature of the rate determining steps changes depending on pH. Above pH {approx} 5 the amine neutral radical formation is the rate determining step and, is independent of pH with rate constant close to 10{sup 3} s{sup -1}; below pH {approx} 5 the rate determining step becomes the deprotonation of the ammonium ion, operated by different bases present in solution. Different amines in the same acid-base system showed analogous ECL behavior, conditioned by the chosen acid base system. A single amine in different acid-base systems showed different kinetic behaviors, due to the dissociation constants of the chosen buffers. The concentration of the acid-base system also played an important role and influenced emission intensity and shape. ECL emission were simulated by finite difference methods, implementing a previously proposed mechanism by including the relevant pre-equilibria. Simulation may also give estimates of the pK {sub a} values of the ammonium ions. An ion pair formation between R{sub 3}N{center_dot} {sup +} and the mostly charged species

  1. Influence of nature, concentration and pH of buffer acid-base system on rate determining step of the electrochemiluminescence of Ru(bpy)32+ with tertiary aliphatic amines

    International Nuclear Information System (INIS)

    Pastore, Paolo; Badocco, Denis; Zanon, Francesco

    2006-01-01

    The electrogenerated chemiluminescence (ECL) of Ru(bpy) 3 2+ (bpy 2,2'-bipyridyl) with tertiary aliphatic amines as co-reactants, was theoretically and experimentally studied as a function of the pre-equilibria involved in the ammonium proton lost and in relation to the nature of the rate determining step. Transient potential steps were used with a 3-mm glassy carbon disk electrode or carbon fiber ultramicroelectrodes array to investigate emission behavior in a variety of aqueous solution types, containing phosphate, tartrate and phthalate acid-base systems at differing pH values. The emission of Ru(bpy) 3 2+ resulting from the reaction with n-tripropylamine (TPrA), tri-isobutylamine (TisoBuA), n-tributylamine (TBuA), methyl-di-n-propylamine (MeDPrA) and triethylamine (TEtA) in varying acid-base media was interpreted on the basis of the quoted pre-equilibria, ammonium pK a being known. The nature of the rate determining steps changes depending on pH. Above pH ∼ 5 the amine neutral radical formation is the rate determining step and, is independent of pH with rate constant close to 10 3 s -1 ; below pH ∼ 5 the rate determining step becomes the deprotonation of the ammonium ion, operated by different bases present in solution. Different amines in the same acid-base system showed analogous ECL behavior, conditioned by the chosen acid base system. A single amine in different acid-base systems showed different kinetic behaviors, due to the dissociation constants of the chosen buffers. The concentration of the acid-base system also played an important role and influenced emission intensity and shape. ECL emission were simulated by finite difference methods, implementing a previously proposed mechanism by including the relevant pre-equilibria. Simulation may also give estimates of the pK a values of the ammonium ions. An ion pair formation between R 3 N· + and the mostly charged species present in solution is hypothesized to explain the contradictory experimental

  2. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H2O2

    International Nuclear Information System (INIS)

    Dong, Xinbo; Wang, Danjun; Li, Kebin; Zhen, Yanzhong; Hu, Huaiming; Xue, Ganglin

    2014-01-01

    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H 2 O 2 , featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH 2 ) are prepared and characterized by FT-IR, XRD, N 2 adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H 2 O 2 as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H 5 [PV 2 W 10 O 40 ] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H 2 O 2

  3. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Xinbo [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Wang, Danjun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Li, Kebin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Zhen, Yanzhong [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Hu, Huaiming [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Xue, Ganglin, E-mail: xglin707@163.com [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China)

    2014-09-15

    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.

  4. Catalytic oxidation of o-aminophenols and aromatic amines by mushroom tyrosinase.

    Science.gov (United States)

    Muñoz-Muñoz, Jose Luis; Garcia-Molina, Francisco; Garcia-Ruiz, Pedro Antonio; Varon, Ramon; Tudela, Jose; Rodriguez-Lopez, Jose N; Garcia-Canovas, Francisco

    2011-12-01

    The kinetics of tyrosinase acting on o-aminophenols and aromatic amines as substrates was studied. The catalytic constants of aromatic monoamines and o-diamines were both low, these results are consistent with our previous mechanism in which the slow step is the transfer of a proton by a hydroxyl to the peroxide in oxy-tyrosinase (Fenoll et al., Biochem. J. 380 (2004) 643-650). In the case of o-aminophenols, the hydroxyl group indirectly cooperates in the transfer of the proton and consequently the catalytic constants in the action of tyrosinase on these compounds are higher. In the case of aromatic monoamines, the Michaelis constants are of the same order of magnitude than for monophenols, which suggests that the monophenols bind better (higher binding constant) to the enzyme to facilitate the π-π interactions between the aromatic ring and a possible histidine of the active site. In the case of aromatic o-diamines, both the catalytic and Michaelis constants are low, the values of the catalytic constants being lower than those of the corresponding o-diphenols. The values of the Michaelis constants of the aromatic o-diamines are slightly lower than those of their corresponding o-diphenols, confirming that the aromatic o-diamines bind less well (lower binding constant) to the enzyme. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Henegar, A.J., E-mail: henegar1@umbc.edu; Gougousi, T., E-mail: gougousi@umbc.edu

    2016-12-30

    Graphical abstract: The interaction of the native oxides of GaAs(100) and InAs(100) with alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition (ALD) of Al{sub 2}O{sub 3} and TiO{sub 2} is compared. Al{sub 2}O{sub 3} if found to be a significantly better barrier against the transport of the surface native oxide during the film deposition as well as after post-deposition heat treatment. This superior blocking ability also limits the removal of the native oxides during the Al{sub 2}O{sub 3} ALD process. - Highlights: • Native oxide diffusion is required for continuous native oxide removal. • The diffusion barrier capabilities of Al{sub 2}O{sub 3} limits native oxide removal during ALD. • Arsenic oxide exhibits higher mobility from InAs compared to GaAs substrates. • Oxygen scavenging from the surface by trimethyl aluminum is confirmed. - Abstract: In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al{sub 2}O{sub 3} and TiO{sub 2}, using H{sub 2}O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al{sub 2}O{sub 3} ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO{sub 2} and the native oxides continues well after the surface has been covered with 2 nm of TiO{sub 2}. This difference is traced to the superior properties of Al{sub 2}O{sub 3} as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to

  6. Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

    International Nuclear Information System (INIS)

    Henegar, A.J.; Gougousi, T.

    2016-01-01

    Graphical abstract: The interaction of the native oxides of GaAs(100) and InAs(100) with alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition (ALD) of Al_2O_3 and TiO_2 is compared. Al_2O_3 if found to be a significantly better barrier against the transport of the surface native oxide during the film deposition as well as after post-deposition heat treatment. This superior blocking ability also limits the removal of the native oxides during the Al_2O_3 ALD process. - Highlights: • Native oxide diffusion is required for continuous native oxide removal. • The diffusion barrier capabilities of Al_2O_3 limits native oxide removal during ALD. • Arsenic oxide exhibits higher mobility from InAs compared to GaAs substrates. • Oxygen scavenging from the surface by trimethyl aluminum is confirmed. - Abstract: In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al_2O_3 and TiO_2, using H_2O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al_2O_3 ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO_2 and the native oxides continues well after the surface has been covered with 2 nm of TiO_2. This difference is traced to the superior properties of Al_2O_3 as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to lower native oxide stability as well as an initial diffusion path formation by the indium oxides.

  7. Copper/ascorbic acid dyad as a catalytic system for selective aerobic oxidation of amines

    Czech Academy of Sciences Publication Activity Database

    Šrogl, Jiří; Voltrová, Svatava

    2009-01-01

    Roč. 11, č. 4 (2009), s. 843-845 ISSN 1523-7060 Institutional research plan: CEZ:AV0Z40550506 Keywords : copper * ascorbic acid * oxidative deamination Subject RIV: CC - Organic Chemistry Impact factor: 5.420, year: 2009

  8. In vitro lipofection with novel series of symmetric 1,3-dialkoylamidopropane-based cationic surfactants containing single primary and tertiary amine polar head groups.

    Science.gov (United States)

    Sheikh, Mohammad; Feig, Jennifer; Gee, Becky; Li, Song; Savva, Michalakis

    2003-06-01

    A novel series of symmetric double-chained primary and tertiary 1,3-dialkoylamido monovalent cationic lipids were synthesized and evaluated for their transfection activities. In the absence of the helper lipid DOPE (1,2-dioleoyl-sn-glycero-3-phosphoethanolamine), only the primary and tertiary dioleoyl derivatives 1,3lmp5 and 1,3lmt5, respectively elicited transfection activity. This is a striking difference between symmetrical 1,2-diacyl glycerol-based monovalent cationic lipids that always found both dioleoyl and dimyristoyl analogues being efficient transfection reagents. In the presence of helper lipid, all cationic derivatives induced marker gene expression, except the dilauroyl analogues 1,3lmp1 and 1,3lmt1 that elicited no transfection activity. Combining electrophoretic mobility data of the lipoplexes at different charge ratios with transfection activity suggested two requirements for high transfection activity with monovalent double-chained cationic lipids, that is, binding/association of the lipid to the plasmid DNA and membrane fusion properties of the lipid layers surrounding the DNA.

  9. Thermal Oxidation of Polyolefins by Mild Pro-Oxidant Additives Based on Iron Carboxylates and Lipophilic Amines: Degradability in the Absence of Light and Effect on the Adhesion to Paperboard

    Directory of Open Access Journals (Sweden)

    Tuan-Anh Nguyen

    2015-08-01

    Full Text Available Marine and inland pollution by non-degradable plastic bags and other plastic articles is a topic of great concern. Natural degradation processes based on oxidation of plastic pollutants could possibly contribute to limit the extent of pollution. Thermal degradation of polyolefins in the absence of light by non-polluting pro-oxidants has not been presented before. In this study, we show that two amines, stearyl amine and [(3-(11-aminoundecanoyl amino propane-1-] silsesquioxane (amino-POSS in combination with ferric stearate (FeSt3 tremendously accelerate the thermal oxidation of polyolefins compared with reference samples. Both amines and FeSt3 are to a large extent based on renewable resources. Polyethylene and polypropylene samples containing less than 100 ppm of iron and 1% of amine were extremely brittle after 10 days in a circulation oven in the absence of light. No significant degradation could be seen with samples containing iron but no amine. In a different application, the initial oxidation of polyethylene can be used in order to increase its adhesion to cardboard. Excellent adhesion between polyethylene and cardboard is important for liquid packaging based on renewable resources. Amino-POSS has been chosen for food packaging applications due to its expected lower leakage from polyethylene (PE compared with stearyl amine. Film samples of PE/amino-POSS/FeSt3 blends were partly oxidized in a circulation oven. The oxidation was documented by increased carbonyl index (CI and melt flow index (MFI. The limited extent of oxidation has been proved by unchanged tensile strength and only moderate changes in elongation at break when compared to reference polyethylene films containing no FeSt3 or amino-POSS. The PE/amino-POSS/FeSt3 blends were compression moulded to paperboard. The adhesion of non-aged blends to paperboard decreased with increasing amino-POSS content which is in good compliance with an earlier reported lubricant effect of high

  10. Free terminal amines in DNA-binding peptides alter the product distribution from guanine radicals produced by single electron oxidation.

    Science.gov (United States)

    Konigsfeld, Katie M; Lee, Melissa; Urata, Sarah M; Aguilera, Joe A; Milligan, Jamie R

    2012-03-01

    Electron deficient guanine radical species are major intermediates produced in DNA by the direct effect of ionizing irradiation. There is evidence that they react with amine groups in closely bound ligands to form covalent crosslinks. Crosslink formation is very poorly characterized in terms of quantitative rate and yield data. We sought to address this issue by using oligo-arginine ligands to model the close association of DNA and its binding proteins in chromatin. Guanine radicals were prepared in plasmid DNA by single electron oxidation. The product distribution derived from them was assayed by strand break formation after four different post-irradiation incubations. We compared the yields of DNA damage produced in the presence of four ligands in which neither, one, or both of the amino and carboxylate termini were blocked with amides. Free carboxylate groups were unreactive. Significantly higher yields of heat labile sites were observed when the amino terminus was unblocked. The rate of the reaction was characterized by diluting the unblocked amino group with its amide blocked derivative. These observations provide a means to develop quantitative estimates for the yields in which these labile sites are formed in chromatin by exposure to ionizing irradiation.

  11. 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.

  12. Amine synergism in uranium extraction

    International Nuclear Information System (INIS)

    Rinelli, G.; Abbruzzese, C.

    1977-01-01

    Commercial products based on C 8 to C 12 tertiary amine mixtures are now widely used in the solvent extraction of uranium from sulphuric pregnant solutions. The satisfactory results generally obtained have never required an analysis of the synergistic effects of amine combinations similar to that carried out for the organo-phosphorus compounds. In the research described the increase in the extraction power of an organic phase composed of an amine binary mixture was studied with regard to an aqueous solution from the sulphuric acid treatment of uranium ore. On the basis of the experimental results obtained, it is possible to select the best composition of the amine mixture to ensure a percentage increase in uranium recovery. Bearing in mind the tendency for the yellow-cake price to rise, the study is considered to be a useful contribution in the context of commercial products currently available on the market. (author)

  13. Impact of primary amine group from aminophospholipids and amino acids on marine phospholipids stability: Non-enzymatic browning and lipid oxidation

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline P.

    2013-01-01

    The main objective of this study was to investigate the oxidative stability and non-enzymatic browning reactions of marine PL in the presence or in the absence of primary amine group from aminophospholipids and amino acids. Marine phospholipids liposomal dispersions were prepared from two authentic......) Strecker derived volatiles, (ii) yellowness index (YI), (iii) hydrophobic and (iv) hydrophilic pyrroles content. The oxidative stability of the samples was assessed through measurement of secondary lipid derived volatile oxidation products. The result showed that the presence of PE and amino acids caused...... the formation of pyrroles, generated Strecker derived volatiles, decreased the YI development and lowered lipid oxidation. The lower degree of lipid oxidation in liposomal dispersions containing amino acids might be attributed to antioxidative properties of pyrroles or amino acids....

  14. A Hydrazone-Based exo-Directing-Group Strategy for β C-H Oxidation of Aliphatic Amines.

    Science.gov (United States)

    Huang, Zhongxing; Wang, Chengpeng; Dong, Guangbin

    2016-04-18

    Described is a new hydrazone-based exo-directing group (DG) strategy developed for the functionalization of unactivated primary β C-H bonds of aliphatic amines. Conveniently synthesized from protected primary amines, the hydrazone DGs are shown to site-selectively promote the β-acetoxylation and tosyloxylation via five-membered exo-palladacycles. Amines with a wide scope of skeletons and functional groups are tolerated. Moreover, the hydrazone DG can be readily removed, and a one-pot C-H acetoxylation/DG removal protocol was also discovered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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.

  16. Effects of Graphene Oxide and Chemically-Reduced Graphene Oxide on the Dynamic Mechanical Properties of Epoxy Amine Composites

    Directory of Open Access Journals (Sweden)

    Cristina Monteserín

    2017-09-01

    Full Text Available Composites based on epoxy/graphene oxide (GO and epoxy/reduced graphene oxide (rGO were investigated for thermal-mechanical performance focusing on the effects of the chemical groups present on nanoadditive-enhanced surfaces. GO and rGO obtained in the present study have been characterized by Fourier transform infrared spectroscopy (FTIR, X-ray photoelectron spectroscopy (XPS, and X-ray powder diffraction (XRD demonstrating that materials with different oxidation degrees have been obtained. Thereafter, GO/epoxy and rGO/epoxy nanocomposites were successfully prepared and thoroughly characterized by dynamic mechanical thermal analysis (DMTA and transmission electron microscopy (TEM. A significant increase in the glass transition temperature was found in comparison with the neat epoxy. The presence of functional groups on the graphene surface leads to chemical interactions between these functional groups on GO and rGO surfaces with the epoxy, contributing to the possible formation of covalent bonds between GO and rGO with the matrix. The presence of oxidation groups on GO also contributes to an improved exfoliation, intercalation, and distribution of the GO sheets in the composites with respect to the rGO based composites.

  17. Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

    Science.gov (United States)

    Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

    2016-05-21

    Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs.

  18. Anodic selective functionalization of cyclic amine derivatives

    OpenAIRE

    Onomura, Osamu

    2012-01-01

    Anodic reactions are desirable methods from the viewpoint of Green Chemistry, since no toxic oxidants are necessary for the oxidation of organic molecules. This review introduces usefulness of anodic oxidation and successive reaction for selective functionalization of cyclic amine derivatives.

  19. Solvent effects on the magnetic shielding of tertiary butyl alcohol

    African Journals Online (AJOL)

    )4 and tetramethyl ammonium cation N(CH3)4(+) have also been presented. KEY WORDS: Solvent effects, Magnetic shielding, Tertiary butyl alcohol, Tertiary butyl amine, Continuum solvation calculations, Chemical shift estimation methods

  20. Observation of new particle formation and measurement of sulfuric acid, ammonia, amines and highly oxidized organic molecules at a rural site in central Germany

    Directory of Open Access Journals (Sweden)

    A. Kürten

    2016-10-01

    Full Text Available The exact mechanisms for new particle formation (NPF under different boundary layer conditions are not known yet. One important question is whether amines and sulfuric acid lead to efficient NPF in the atmosphere. Furthermore, it is not clear to what extent highly oxidized organic molecules (HOMs are involved in NPF. We conducted field measurements at a rural site in central Germany in the proximity of three larger dairy farms to investigate whether there is a connection between NPF and the presence of amines and/or ammonia due to the local emissions from the farms. Comprehensive measurements using a nitrate chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF mass spectrometer, a proton-transfer-reaction mass spectrometer (PTR-MS, particle counters and differential mobility analyzers (DMAs, as well as measurements of trace gases and meteorological parameters, were performed. We demonstrate here that the nitrate CI-APi-TOF is suitable for sensitive measurements of sulfuric acid, amines, a nitrosamine, ammonia, iodic acid and HOMs. NPF was found to correlate with sulfuric acid, while an anti-correlation with RH, amines and ammonia is observed. The anti-correlation between NPF and amines could be due to the efficient uptake of these compounds by nucleating clusters and small particles. Much higher HOM dimer (C19/C20 compounds concentrations during the night than during the day indicate that these HOMs do not efficiently self-nucleate as no nighttime NPF is observed. Observed iodic acid probably originates from an iodine-containing reservoir substance, but the iodine signals are very likely too low to have a significant effect on NPF.

  1. N-oxide as a traceless oxidizing directing group: mild rhodium(III)-catalyzed C-H olefination for the synthesis of ortho-alkenylated tertiary anilines.

    Science.gov (United States)

    Huang, Xiaolei; Huang, Jingsheng; Du, Chenglong; Zhang, Xingyi; Song, Feijie; You, Jingsong

    2013-12-02

    Double role: A traceless directing group also acts as an internal oxidant in a novel Rh(III) -catalyzed protocol developed for the synthesis of ortho-alkenylated tertiary anilines. A five-membered cyclometalated Rh(III) complex is proposed as a plausible intermediate and confirmed by X-ray crystallographic analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. Direct evidence of charge separation in a metal-organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer.

    Science.gov (United States)

    Xu, Caiyun; Liu, Hang; Li, Dandan; Su, Ji-Hu; Jiang, Hai-Long

    2018-03-28

    The selective aerobic oxidative coupling of amines under mild conditions is an important laboratory and commercial procedure yet a great challenge. In this work, a porphyrinic metal-organic framework, PCN-222, was employed to catalyze the reaction. Upon visible light irradiation, the semiconductor-like behavior of PCN-222 initiates charge separation, evidently generating oxygen-centered active sites in Zr-oxo clusters indicated by enhanced porphyrin π-cation radical signals. The photogenerated electrons and holes further activate oxygen and amines, respectively, to give the corresponding redox products, both of which have been detected for the first time. The porphyrin motifs generate singlet oxygen based on energy transfer to further promote the reaction. As a result, PCN-222 exhibits excellent photocatalytic activity, selectivity and recyclability, far superior to its organic counterpart, for the reaction under ambient conditions via combined energy and charge transfer.

  4. Determination of biogenic amines from electrocatalytic responses of graphite electrodes modified with metallic osmium or an osmium oxide-ruthenium cyanide film

    International Nuclear Information System (INIS)

    Shajdarova, L.G.; Gedmina, A.V.; Chelnokova, I.A.; Budnikov, G.K.

    2008-01-01

    Particles of osmium or an inorganic polymeric film of osmium oxide-ruthenium cyanide (OsO-RuCN) electrodeposited on glassy carbon (GC) electrocatalyze the oxidation of dopamine (DA), adrenaline (AD), and noradrenaline (NAD). It is found that these biogenic amines are determined with a high sensitivity by oxidation at an electrode with an OsO-RuCN film. Procedures for the voltammetric determination of DA, AD, or NAD at a composite film electrode are developed. The currents of the substrate oxidation are linear functions of the concentrations in the ranges from 5x10 -7 to 1x10 -3 M for DA and from 1x10 -6 to 1x10 -3 M for AD and NAD [ru

  5. Effect of γ-Aminobutyric Acid (GABA Producing Bacteria on Rumen Fermentation, Biogenic Amine Production and Anti-oxidation Using Corn Meal as Substrate

    Directory of Open Access Journals (Sweden)

    Bum Seung Ku

    2013-06-01

    Full Text Available The effects and significance of γ-amino butyric acid (GABA producing bacteria (GPB on in vitro rumen fermentation and reduction of biogenic amines (histamine, methylamine, ethylamine, and tyramine using corn meal as a substrate were determined. Ruminal samples collected from ruminally fistulated Holstein cows served as inoculum and corn was used as substrate at 2% dry matter (DM. Different inclusion rates of GPB and GABA were evaluated. After incubation, addition of GPB had no significant effect on in vitro fermentation pH and total gas production, but significantly increased the ammonia nitrogen (NH3-N concentration and reduced the total biogenic amines production (p<0.05. Furthermore, antioxidation activity was improved as indicated by the significantly higher concentration of superoxide dismutase (SOD and glutathione peroxidase (GSH-Px among treated samples when compared to the control (p<0.05. Additionally, 0.2% GPB was established as the optimum inclusion level. Taken together, these results suggest the potential of utilizing GPB as feed additives to improve growth performance in ruminants by reducing biogenic amines and increasing anti-oxidation.

  6. Integration of biofiltration and advanced oxidation processes for tertiary treatment of an oil refinery wastewater aiming at water reuse.

    Science.gov (United States)

    Nogueira, A A; Bassin, J P; Cerqueira, A C; Dezotti, M

    2016-05-01

    The combination of biological and chemical oxidation processes is an interesting approach to remove ready, poor, and non-biodegradable compounds from complex industrial wastewaters. In this study, biofiltration followed by H2O2/UV oxidation (or microfiltration) and final reverse osmosis (RO) step was employed for tertiary treatment of an oil refinery wastewater. Biofiltration alone allowed obtaining total organic carbon (TOC), chemical oxygen demand (COD), UV absorbance at 254 nm (UV254), ammonium, and turbidity removal of around 46, 46, 23, 50, and 61 %, respectively. After the combined biological-chemical oxidation treatment, TOC and UV254 removal amounted to 88 and 79 %, respectively. Whereas, the treatment performance achieved with different UV lamp powers (55 and 95 W) and therefore distinct irradiance levels (26.8 and 46.3 mW/cm(2), respectively) were very similar and TOC and UV254 removal rates were highly affected by the applied C/H2O2 ratio. Silt density index (SDI) was effectively reduced by H2O2/UV oxidation, favoring further RO application. C/H2O2 ratio of 1:4, 55 W UV lamp, and 20-min oxidation reaction corresponded to the experimental condition which provided the best cost/benefit ratio for TOC, UV254, and SDI reduction from the biofilter effluent. The array of treatment processes proposed in this study has shown to be adequate for tertiary treatment of the oil refinery wastewater, ensuring the mitigation of membrane fouling problems and producing a final effluent which is suitable for reuse applications.

  7. 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.

  8. Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multi-pesticide residues analysis of tea.

    Science.gov (United States)

    Ma, Guicen; Zhang, Minglu; Zhu, Li; Chen, Hongping; Liu, Xin; Lu, Chengyin

    2018-01-05

    Amine-functional reduced graphene oxide (amine-rGO) with different carbon chain length amino groups were successfully synthesized. The graphene oxides (GO) reduction as well as amino grafting were achieved simultaneously in one step via a facile solvothermal synthetic strategy. The obtained materials were characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectrometry and X-ray photoelectron spectroscopy to confirm the modification of GO with different amino groups. The adsorption performance of catechins and caffeine from tea acetonitrile extracts on different amine functional rGO samples were evaluated. It was found that tributylamine-functional rGO (tri-BuA-rGO) exhibited the highest adsorption ability for catechins and caffeine compared to GO and other amino group functional rGO samples. It was worth to note that the adsorption capacity of catechins on tri-BuA-rGO was 11 times higher than that of GO (203.7mgg -1 vs 18.7mgg -1 ). Electrostatic interaction, π-π interaction and surface hydrophilic-hydrophobic properties of tri-BuA-rGO played important roles in the adsorption of catechins as well as caffeine. The gravimetric analysis confirmed that the tri-BuA-rGO achieved the highest efficient cleanup preformance compared with traditional dispersive solid phase extraction (dSPE) adsorbents like primary-secondary amine (PSA), graphitized carbon black (GCB) or C18. A multi-pesticides analysis method based on tri-BuA-rGO is validated on 33 representative pesticides in tea using gas chromatography coupled to tandem mass spectrometry or high-performance liquid chromatography coupled with tandem mass spectrometry. The analysis method gave a high coefficient of determination (r 2 >0.99) for each pesticide and satisfactory recoveries in a range of 72.1-120.5%. Our study demonstrated that amine functional rGO as a new type of QuEChERS adsorbent is expected to be widely applied for analysis of pesticides at trace levels. Copyright © 2017

  9. Magnetic amine-functionalized graphene oxide as a novel and recyclable bifunctional nanocatalyst for solvent-free synthesis of pyrano[3,2-c]pyridine derivatives

    Directory of Open Access Journals (Sweden)

    Shahnaz Rostamizadeh

    2017-01-01

    Full Text Available The new magnetic amine-functionalized graphene oxide (Fe3O4-GO-NH2 nanocatalyst was prepared through the reaction of 3-aminopropyltriethoxysilane (APTES with magnetic graphene oxide (Fe3O4-GO. It was characterized by XRD, TEM, SEM, FT-IR and EDX techniques. The intrinsic carboxylic acids on the edges of Fe3O4-GO along with the amine groups post grafted to the surface of Fe3O4-GO led to preparation of an acid-base bifunctional magnetically recyclable nanocatalyst. It proved to be efficient nanocatalyst for solvent-free synthesis of pyrano[3,2-c]pyridine derivatives under mild reaction conditions with good to excellent yields. This heterogeneous catalyst also exhibited higher activities than acid or base functionalized mesoporous silica, magnetic GO or basic Al2O3 an even higher than some basic homogeneous catalysts such as triethylamine and piperazine. More importantly, due to the loaded iron oxide nanoparticles, this catalyst could be easily recovered from the reaction mixture using an external magnet and reused without significant decrease in activity even after 7 runs.

  10. Low-fat frankfurters formulated with a healthier lipid combination as functional ingredient: microstructure, lipid oxidation, nitrite content, microbiological changes and biogenic amine formation.

    Science.gov (United States)

    Delgado-Pando, Gonzalo; Cofrades, Susana; Ruiz-Capillas, Claudia; Solas, Maria Teresa; Triki, Mehdi; Jiménez-Colmenero, Francisco

    2011-09-01

    Oil (healthier lipid combination of olive, linseed and fish oils)-in-water emulsions stabilized with different protein systems (prepared with sodium caseinate (SC), soy protein isolate (SPI), and microbial transglutaminase (MTG)) were used as pork backfat replacers in low-fat frankfurters. Microstructure, lipid oxidation, nitrite content, microbiological changes and biogenic amine formation of frankfurters were analyzed and found to be affected by the type of oil-in-water emulsion and by chilling storage (2° C, 41 days). Although the lipid oxidation levels attained were low, replacement of animal fat by healthier oil combinations in frankfurter formulation did promote a slight increase in lipid oxidation. Residual nitrite was affected (P nitrite was detectable in the product after processing and 17-46% at the end of storage. The microbial population was low in all formulations during chilling storage. Spermine was the most abundant amine (19-20 mg/kg), but similar in level to all samples. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    Energy Technology Data Exchange (ETDEWEB)

    Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)

    2011-01-01

    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

  12. Fluorinated Amine Stereotriads via Allene Amination.

    Science.gov (United States)

    Liu, Lu; Gerstner, Nels C; Oxtoby, Lucas J; Guzei, Ilia A; Schomaker, Jennifer M

    2017-06-16

    The incorporation of fluorine into organic scaffolds often improves the bioactivity of pharmaceutically relevant compounds. C-F/C-N/C-O stereotriad motifs are prevalent in antivirals, neuraminidase inhibitors, and modulators of androgen receptors, but are challenging to install. An oxidative allene amination strategy using Selectfluor rapidly delivers triply functionalized triads of the form C-F/C-N/C-O, exhibiting good scope and diastereoselectivity for all syn products. The resulting stereotriads are readily transformed into fluorinated pyrrolidines and protected α-, β-, and γ-amino acids.

  13. Removal of organic contaminants from secondary effluent by anodic oxidation with a boron-doped diamond anode as tertiary treatment

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Segura, Sergi, E-mail: sergigarcia@ub.edu [Advanced Water Management Centre, The University of Queensland, Level 4, Gehrmann Bld. (60), St Lucia, QLD 072 (Australia); Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain); Keller, Jürg [Advanced Water Management Centre, The University of Queensland, Level 4, Gehrmann Bld. (60), St Lucia, QLD 072 (Australia); Brillas, Enric [Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain); Radjenovic, Jelena, E-mail: j.radjenovic@awmc.uq.edu.au [Advanced Water Management Centre, The University of Queensland, Level 4, Gehrmann Bld. (60), St Lucia, QLD 072 (Australia)

    2015-02-11

    Graphical abstract: - Highlights: • Mineralization of secondary effluent by anodic oxidation with BDD anode. • Complete removal of 29 pharmaceuticals and pesticides at trace level concentrations. • Organochlorine and organobromine byproducts were formed at low μM concentrations. • Chlorine species evolution assessed to evaluate the anodic oxidation applicability. - Abstract: Electrochemical advanced oxidation processes (EAOPs) have been widely investigated as promising technologies to remove trace organic contaminants from water, but have rarely been used for the treatment of real waste streams. Anodic oxidation with a boron-doped diamond (BDD) anode was applied for the treatment of secondary effluent from a municipal sewage treatment plant containing 29 target pharmaceuticals and pesticides. The effectiveness of the treatment was assessed from the contaminants decay, dissolved organic carbon and chemical oxygen demand removal. The effect of applied current and pH was evaluated. Almost complete mineralization of effluent organic matter and trace contaminants can be obtained by this EAOP primarily due to the action of hydroxyl radicals formed at the BDD surface. The oxidation of Cl{sup −} ions present in the wastewater at the BDD anode gave rise to active chlorine species (Cl{sub 2}/HClO/ClO{sup −}), which are competitive oxidizing agents yielding chloramines and organohalogen byproducts, quantified as adsorbable organic halogen. However, further anodic oxidation of HClO/ClO{sup −} species led to the production of ClO{sub 3}{sup −} and ClO{sub 4}{sup −} ions. The formation of these species hampers the application as a single-stage tertiary treatment, but posterior cathodic reduction of chlorate and perchlorate species may reduce the risks associated to their presence in the environment.

  14. SEDIMENT-ASSOCIATED REACTIONS OF AROMATIC AMINES. 2. QSAR DEVELOPMENT

    Science.gov (United States)

    The fate of aromatic amines in soils and sediments is dominated by irreversible binding through nucleophilic addition and oxidative radical coupling. Despite the common occurrence of the aromatic amine functional group in organic chemicals, the molecular properties useful for pr...

  15. Tertiary treatment of landfill leachate by an integrated Electro-Oxidation/Electro-Coagulation/Electro-Reduction process: Performance and mechanism.

    Science.gov (United States)

    Ding, Jing; Wei, Liangliang; Huang, Huibin; Zhao, Qingliang; Hou, Weizhu; Kabutey, Felix Tetteh; Yuan, Yixing; Dionysiou, Dionysios D

    2018-06-05

    This study presents an integrated Electro-Oxidation/Electro-Coagulation/Electro-Reduction (EO/EC/ER) process for tertiary landfill leachate treatment. The influence of variables including leachate characteristics and operation conditions on the performance of EO/EC/ER process was evaluated. The removal mechanisms were explored by comparing results of anode, cathode, and bipolar electrode substitution experiments. The performance of the process in a scaled-up reactor was investigated to assure the feasibility of the process. Results showed that simultaneous removal of carbonaceous and nitrogenous pollutants was achieved under optimal conditions. Ammonia removal was due to the free chlorine generation of EO while organic matter degradation was achieved by both EO and EC processes. Nitrate removal was attributed to both ER and EC processes, with the higher removal achieved by ER process. In a scaled-up reactor, the EO/EC/ER process was able to remove 50-60% organic matter and 100% ammonia at charge of 1.5 Ah/L with energy consumption of 15 kW h/m 3 . Considering energy cost, the process is more efficient to meet the requirement of organic removal efficiency less than 70%. These results show the feasibility and potential of the EO/EC/ER process as an alternative tertiary treatment to achieve the simultaneous removal of organic matter, ammonia, nitrate, and color of leachate. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. New potential of the reductive alkylation of amines

    International Nuclear Information System (INIS)

    Gusak, K N; Ignatovich, Zh V; Koroleva, E V

    2015-01-01

    Available data on the reductive alkylation of amines with carbonyl compounds — a key method for the preparation of secondary and tertiary amines — are described systematically. The review provides information on the relevant reducing agents and catalysts and on the use of chiral catalysts in stereo- and enantiocontrolled reactions of amine synthesis. The effect of the reactant and catalyst structures on the reaction rates and chemo- and stereo(enantio)selectivity is considered. The bibliography includes 156 references

  17. N-nitrosodimethylamine (NDMA) formation potential of amine-based water treatment polymers: Effects of in situ chloramination, breakpoint chlorination, and pre-oxidation.

    Science.gov (United States)

    Park, Sang Hyuck; Padhye, Lokesh P; Wang, Pei; Cho, Min; Kim, Jae-Hong; Huang, Ching-Hua

    2015-01-23

    Recent studies show that cationic amine-based water treatment polymers may be important precursors that contribute to formation of the probable human carcinogen N-nitrosodimethylamine (NDMA) during water treatment and disinfection. To better understand how water treatment parameters affect NDMA formation from the polymers, the effects of in situ chloramination, breakpoint chlorination, and pre-oxidation on the NDMA formation from the polymers were investigated. NDMA formation potential (NDMA-FP) as well as dimethylamine (DMA) residual concentration were measured from poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) solutions upon reactions with oxidants including free chlorine, chlorine dioxide, ozone, and monochloramine under different treatment conditions. The results supported that dichloramine (NHCl2) formation was the critical factor affecting NDMA formation from the polymers during in situ chloramination. The highest NDMA formation from the polymers occurred near the breakpoint of chlorination. Polymer chain breakdown and transformation of the released DMA and other intermediates were important factors affecting NDMA formation from the polymers in pre-oxidation followed by post-chloramination. Pre-oxidation generally reduced NDMA-FP of the polymers; however, the treatments involving pre-ozonation increased polyDADMAC's NDMA-FP and DMA release. The strategies for reducing NDMA formation from the polymers may include the avoidance of the conditions favorable to NHCl2 formation and the avoidance of polymer exposure to strong oxidants such as ozone. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. The Azomethine Ylide Route to Amine C–H Functionalization: Redox-Versions of Classic Reactions and a Pathway to New Transformations

    Science.gov (United States)

    2016-01-01

    Conspectus Redox-neutral methods for the functionalization of amine α-C–H bonds are inherently efficient because they avoid external oxidants and reductants and often do not generate unwanted byproducts. However, most of the current methods for amine α-C–H bond functionalization are oxidative in nature. While the most efficient variants utilize atmospheric oxygen as the terminal oxidant, many such transformations require the use of expensive or toxic oxidants, often coupled with the need for transition metal catalysts. Redox-neutral amine α-functionalizations that involve intramolecular hydride transfer steps provide viable alternatives to certain oxidative reactions. These processes have been known for some time and are particularly well suited for tertiary amine substrates. A mechanistically distinct strategy for secondary amines has emerged only recently, despite sharing common features with a range of classic organic transformations. Among those are such widely used reactions as the Strecker, Mannich, Pictet–Spengler, and Kabachnik–Fields reactions, Friedel–Crafts alkylations, and iminium alkynylations. In these classic processes, condensation of a secondary amine with an aldehyde (or a ketone) typically leads to the formation of an intermediate iminium ion, which is subsequently attacked by a nucleophile. The corresponding redox-versions of these transformations utilize identical starting materials but incorporate an isomerization step that enables α-C–H bond functionalization. Intramolecular versions of these reactions include redox-neutral amine α-amination, α-oxygenation, and α-sulfenylation. In all cases, a reductive N-alkylation is effectively combined with an oxidative α-functionalization, generating water as the only byproduct. Reactions are promoted by simple carboxylic acids and in some cases require no additives. Azomethine ylides, dipolar species whose usage is predominantly in [3 + 2] cycloadditions and other pericyclic

  19. The azomethine ylide route to amine C-H functionalization: redox-versions of classic reactions and a pathway to new transformations.

    Science.gov (United States)

    Seidel, Daniel

    2015-02-17

    Conspectus Redox-neutral methods for the functionalization of amine α-C-H bonds are inherently efficient because they avoid external oxidants and reductants and often do not generate unwanted byproducts. However, most of the current methods for amine α-C-H bond functionalization are oxidative in nature. While the most efficient variants utilize atmospheric oxygen as the terminal oxidant, many such transformations require the use of expensive or toxic oxidants, often coupled with the need for transition metal catalysts. Redox-neutral amine α-functionalizations that involve intramolecular hydride transfer steps provide viable alternatives to certain oxidative reactions. These processes have been known for some time and are particularly well suited for tertiary amine substrates. A mechanistically distinct strategy for secondary amines has emerged only recently, despite sharing common features with a range of classic organic transformations. Among those are such widely used reactions as the Strecker, Mannich, Pictet-Spengler, and Kabachnik-Fields reactions, Friedel-Crafts alkylations, and iminium alkynylations. In these classic processes, condensation of a secondary amine with an aldehyde (or a ketone) typically leads to the formation of an intermediate iminium ion, which is subsequently attacked by a nucleophile. The corresponding redox-versions of these transformations utilize identical starting materials but incorporate an isomerization step that enables α-C-H bond functionalization. Intramolecular versions of these reactions include redox-neutral amine α-amination, α-oxygenation, and α-sulfenylation. In all cases, a reductive N-alkylation is effectively combined with an oxidative α-functionalization, generating water as the only byproduct. Reactions are promoted by simple carboxylic acids and in some cases require no additives. Azomethine ylides, dipolar species whose usage is predominantly in [3 + 2] cycloadditions and other pericyclic processes, have been

  20. A versatile family of degradable non-viral gene carriers based on hyperbranched poly(ester amine)s

    NARCIS (Netherlands)

    Zhong, Zhiyuan; Song, Y.; Engbersen, Johannes F.J.; Lok, Martin C.; Hennink, Wim E.; Feijen, Jan

    2005-01-01

    A variety of degradable hyperbranched poly(ester amine)s containing primary, secondary and tertiary amino groups, were synthesized and evaluated as non-viral gene carriers. The polymers were obtained in high yields through a Michael-type conjugate addition of diacrylate monomers with trifunctional

  1. 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

  2. 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

  3. Effects of plant polyphenols and a-tocopherol on lipid oxidation, residual nitrites, biogenic amines, and N-nitrosamines formation during ripening and storage of dry-cured bacon

    Science.gov (United States)

    Effects of plant polyphenols (green tea polyphenols (GTP) and grape seed extract (GSE) and a-tocopherol on physicochemical parameters, lipid oxidation, residual nitrite, microbiological counts, biogenic amines, and N-nitrosamines were determined in bacons during dry-curing and storage. Results show ...

  4. Method for the production of primary amines

    NARCIS (Netherlands)

    Baldenius, Kai-Uwe; Ditrich, Klaus; Breurer, Michael; Navickas, Vaidotas; Janssen, Dick; Crismaru, Ciprian; Bartsch, Sebastian

    2014-01-01

    The present invention relates to a novel enzymatically catalyzed method for the production of aliphatic primary amines, which method comprises the enzymatic oxidation of a primary aliphatic alcohol catalyzed by an alcohol dehydrogenase, amination of the resulting oxocompound catalyzed by a

  5. An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I2 and TBHP: access to lead molecules for biomedical applications.

    Science.gov (United States)

    Mahato, Karuna; Arora, Neha; Ray Bagdi, Prasanta; Gattu, Radhakrishna; Ghosh, Siddhartha Sankar; Khan, Abu T

    2018-02-06

    A metal-free I 2 /TBHP induced highly atom economic and operationally simple oxidative cross-coupling reaction has been developed for the direct synthesis of sulfenamides/sulfanes/disulfides from the reaction of 4-hydroxydithiocoumarin and amines/thiols. The novelties of the present protocol are unprecedented S-C bond formation in addition to S-N and S-S bonds, shorter reaction time, mild and environmentally benign reaction conditions, functional group tolerance and moderate to excellent yields. Moreover, the four newly synthesized compounds namely 4q, 6d, 6e and 7a exhibit anti-proliferative activity against the breast cancer cell line MCF7, and may be lead molecules for future drug development.

  6. 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.

  7. Intensification of UV-C tertiary treatment: Disinfection and removal of micropollutants by sulfate radical based Advanced Oxidation Processes.

    Science.gov (United States)

    Rodríguez-Chueca, J; García-Cañibano, C; Lepistö, R-J; Encinas, Á; Pellinen, J; Marugán, J

    2018-04-21

    This study explores the enhancement of UV-C tertiary treatment by sulfate radical based Advanced Oxidation Processes (SR-AOPs), including photolytic activation of peroxymonosulfate (PMS) and persulfate (PS) and their photocatalytic activation using Fe(II). Their efficiency was assessed both for the inactivation of microorganisms and the removal or micropollutants (MPs) in real wastewater treatment plant effluents. Under the studied experimental range (UV-C dose 5.7-57 J/L; UV-C contact time 3 to 28 s), the photolysis of PMS and PS (0.01 mM) increased up to 25% the bacterial removal regarding to UV-C system. The photolytic activation of PMS led to the total inactivation of bacteria (≈ 5.70 log) with the highest UV-C dose (57 J/L). However, these conditions were insufficient to remove the MPs, being required oxidant's dosages of 5 mM to remove above 90% of carbamazepine, diclofenac, atenolol and triclosan. The best efficiencies were achieved by the combination of PMS or PS with Fe(II), leading to the total removal of the MPs using a low UV-C dosage (19 J/L), UV-C contact time (9 s) and reagent's dosages (0.5 mM). Finally, high mineralization was reached (>50%) with photocatalytic activation of PMS and PS even with low reagent's dosages. Copyright © 2018 Elsevier B.V. All rights reserved.

  8. Conformations of double-headed, triple-tailed phospholipid oxidation lipid products in model membranes

    DEFF Research Database (Denmark)

    Hermetter, Albin; Kopec, Wojciech; Khandelia, Himanshu

    2013-01-01

    Products of phospholipid oxidation can produce lipids with a carbonyl moiety at the end of a shortened lipid acyl tail, such as 1-palmitoyl-2-(5-oxovaleroyl)-sn-glycero-3-phosphocholine (POVPC). The carbonyl tail of POVPC can covalently bond to the free tertiary amine of a phosphatidylethanolamine...

  9. Two pathways for electrocatalytic oxidation of hydrogen by a nickel bis(diphosphine) complex with pendant amines in the second coordination sphere.

    Science.gov (United States)

    Yang, Jenny Y; Smith, Stuart E; Liu, Tianbiao; Dougherty, William G; Hoffert, Wesley A; Kassel, W Scott; Rakowski DuBois, M; DuBois, Daniel L; Bullock, R Morris

    2013-07-03

    A nickel bis(diphosphine) complex containing pendant amines in the second coordination sphere, [Ni(P(Cy)2N(t-Bu)2)2](BF4)2 (P(Cy)2N(t-Bu)2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex gives three isomers of the doubly protonated Ni(0) complex [Ni(P(Cy)2N(t-Bu)2H)2](BF4)2. Using the pKa values and Ni(II/I) and Ni(I/0) redox potentials in a thermochemical cycle, the free energy of hydrogen addition to [Ni(P(Cy)2N(t-Bu)2)2](2+) was determined to be -7.9 kcal mol(-1). The catalytic rate observed in dry acetonitrile for the oxidation of H2 depends on base size, with larger bases (NEt3, t-BuNH2) resulting in much slower catalysis than n-BuNH2. The addition of water accelerates the rate of catalysis by facilitating deprotonation of the hydrogen addition product before oxidation, especially for the larger bases NEt3 and t-BuNH2. This catalytic pathway, where deprotonation occurs prior to oxidation, leads to an overpotential that is 0.38 V lower compared to the pathway where oxidation precedes proton movement. Under the optimal conditions of 1.0 atm H2 using n-BuNH2 as a base and with added water, a turnover frequency of 58 s(-1) is observed at 23 °C.

  10. Effect of molecular chain length on the mechanical and thermal properties of amine-functionalized graphene oxide/polyimide composite films prepared by in situ polymerization.

    Science.gov (United States)

    Liao, Wei-Hao; Yang, Shin-Yi; Wang, Jen-Yu; Tien, Hsi-Wen; Hsiao, Sheng-Tsung; Wang, Yu-Sheng; Li, Shin-Ming; Ma, Chen-Chi M; Wu, Yi-Fang

    2013-02-01

    This study fabricates amine (NH(2))-functionalized graphene oxide (GO)/polyimide(PI) composite films with high performance using in situ polymerization. Linear poly(oxyalkylene)amines with two different molecular weights 400 and 2000 (D400 and D2000) have been grafted onto the GO surfaces, forming two types of NH(2)-functionalized GO (D400-GO/D2000-GO). NH(2)-functionalized GO, especially D400-GO, demonstrated better reinforcing efficiency in mechanical and thermal properties. The observed property enhancement are due to large aspect ratio of GO sheets, the uniform dispersion of the GO within the PI matrix, and strong interfacial adhesion due to the chemical bonding between GO and the polymeric matrix. The Young's modulus of the composite films with 0.3 wt % D400-GO loading is 7.4 times greater than that of neat PI, and tensile strength is 240% higher than that of neat PI. Compared to neat PI, 0.3 wt % D400-GO/PI film exhibits approximately 23.96 °C increase in glass transition temperature (T(g)). The coefficient of thermal expansion below T(g) is significantly decreased from 102.6 μm/°C (neat PI) to 53.81 μm/°C (decreasing 48%) for the D400-GO/PI composites with low D400-GO content (0.1 wt %). This work not only provides a method to develop the GO-based polyimide composites with superior performances but also conceptually provides a chance to modulate the interfacial interaction between GO and the polymer through designing the chain length of grafting molecules on NH(2)-functionalized GO.

  11. Oxidation of DNA, proteins and lipids by DOPA, protein-bound DOPA, and related catechol(amine)s

    DEFF Research Database (Denmark)

    Pattison, David I; Dean, Roger T; Davies, Michael Jonathan

    2002-01-01

    Incubation of free 3,4-dihydroxyphenylalanine (DOPA), protein-bound DOPA (PB-DOPA) and related catechols with DNA, proteins and lipids has been shown to result in oxidative damage to the target molecule. This article reviews these reactions with particular emphasis on those that occur in the pres......Incubation of free 3,4-dihydroxyphenylalanine (DOPA), protein-bound DOPA (PB-DOPA) and related catechols with DNA, proteins and lipids has been shown to result in oxidative damage to the target molecule. This article reviews these reactions with particular emphasis on those that occur...... in the presence of molecular O(2) and redox-active metal ions (e.g. Fe(3+), Cu(2+), Cr(6+)), which are known to increase the rate of DOPA oxidation. The majority of oxidative damage appears to be mediated by reactive oxygen species (ROS) such as superoxide and HO(.) radicals, though other DOPA oxidation products...

  12. Biogenic amines and radiosensitivity of solitary cells

    International Nuclear Information System (INIS)

    Goncharenko, E.N.

    1978-01-01

    Different stability of cells to ionizing radiation is considered from a position of the ''elevated biochemical radioresistance background'' concept. Experimental evidence presented indicates an important role of endogenic amines (serotonin and histamine) possessing radioprotector properties in the cell radioresistance formation. The concept about their effect as being solely a result of circulatory hypoxia is critically discussed. The experimental results favor the existence of a ''cellular'' component, along with the ''hypoxic'' one, in the mechanism of action of biogenic amines. These compounds can affect the initial stages of peroxide oxidation of lipids, thereby favoring a less intensive oxidation induced by radiation. Biogenic amines can also exert influence on the cyclic nucleotide system

  13. Blue-light photoelectrochemical sensor based on nickel tetra-amined phthalocyanine-graphene oxide covalent compound for ultrasensitive detection of erythromycin.

    Science.gov (United States)

    Peng, Jinyun; Huang, Qing; Zhuge, Wenfeng; Liu, Yuxia; Zhang, Cuizong; Yang, Wei; Xiang, Gang

    2018-05-30

    In this study, we developed a novel photoelectrochemical (PEC) sensor for the highly sensitive detection of erythromycin by functionalising graphene oxide (GO) with nickel tetra-amined phthalocyanine (NiTAPc) through covalent bonding, which resulted in the formation of NiTAPc-Gr. The fabricated sensor showed a higher PEC efficiency under blue light, exhibiting a peak wavelength of 456 nm, as compared to that of the monomer. Further, the NiTAPc-Gr/indium tin oxide (ITO) sensor exhibited a photocurrent that was 50-fold higher than that for a GO/ITO sensor under the same conditions. Under optimal conditions, the NiTAPc-Gr PEC sensor showed a linear response for erythromycin concentrations ranging from 0.40 to 120.00 μmol L -1 , with the minimum limit for detection being 0.08 μmol L -1 . Thus, the NiTAPc-Gr sensor exhibited superior performance and excellent PEC characteristics, high stability, and good reproducibility with respect to the sensing of erythromycin. Moreover, it is convenient to use, fast, small, and cheap to produce. Hence, it should find wide use in the analysis of erythromycin in real-world applications. Copyright © 2018 Elsevier B.V. All rights reserved.

  14. Sensitive electrochemical sensing for polycyclic aromatic amines based on a novel core-shell multiwalled carbon nanotubes@ graphene oxide nanoribbons heterostructure.

    Science.gov (United States)

    Zhu, Gangbing; Yi, Yinhui; Han, Zhixiang; Wang, Kun; Wu, Xiangyang

    2014-10-03

    Being awfully harmful to the environment and human health, the qualitative and quantitative determinations of polycyclic aromatic amines (PAAs) are of great significance. In this paper, a novel core-shell heterostructure of multiwalled carbon nanotubes (MWCNTs) as the core and graphene oxide nanoribbons (GONRs) as the shell (MWCNTs@GONRs) was produced from longitudinal partially unzipping of MWCNTs side walls using a simple wet chemical strategy and applied for electrochemical determination of three kinds of PAAs (1-aminopyrene (1-AP), 1-aminonaphthalene and 3,3'-diaminobiphenyl). Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and electrochemical methods were used to characterize the as-prepared MWCNTs@GONRs. Due to the synergistic effects from MWCNTs and GONRs, the oxidation currents of PAAs at the MWCNTs@GONRs modified glassy carbon (GC) electrode are much higher than that at the MWCNTs/GC, graphene/GC and bare GC electrodes. 1-AP was used as the representative analyte to demonstrate the sensing performance of the MWCNTs@GONRs/GC electrode, and the proposed modified electrode has a linear response range of 8.0-500.0 nM with a detection limit of 1.5 nM towards 1-AP. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Susceptibility of dry-cured tuna to oxidative deterioration and biogenic amines generation: I. Effect of NaCl content, antioxidant type and ageing.

    Science.gov (United States)

    Roseiro, L C; Santos, C; Gonçalves, H; Serrano, C; Aleixo, C; Partidário, A; Lourenço, A R; Dias, M Abreu; da Ponte, D J B

    2017-08-01

    This study aimed to assess lipid oxidation and biogenic amine (BA) development in "muxama", a dry-cured tuna muscle product, as affected by salt content, antioxidant type and ageing time. Overall, BA contents decreased with NaCl level (2785.1mgkg -1 , 1148.1mgkg -1 and 307.7mgkg -1 ) and increased with ageing time (366.2mgkg -1 , 1711.8mgkg -1 and 2959.2mgkg -1 in the final product (T0), and after 1 (T1) and 3 (T3) months of ageing, respectively). Regardless of the test conditions, the most concentrated BA was always tyramine. For the ageing periods considered in the present study, malondialdehyde formation was affected by the NaCl level, with the saltiest samples exhibiting lower content. Rosemary and sage extracts represented promising technological options for preserving muxama from oxidation and to minimize the presence of a fishy flavour and odour, but this treatment may cause the colour to lose some of its redness and become less appealing. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Sensitive electrochemical sensing for polycyclic aromatic amines based on a novel core–shell multiwalled carbon nanotubes@ graphene oxide nanoribbons heterostructure

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Gangbing, E-mail: zhgb1030@ujs.edu.cn [School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Yi, Yinhui; Han, Zhixiang [School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Wang, Kun [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Wu, Xiangyang, E-mail: wuxy@ujs.edu.cn [School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China)

    2014-10-03

    Highlights: • A core–shell heterostructure MWCNTs@GONRs was produced from unzipping MWCNTs. • A new electrochemical sensor for PAAs was developed based on MWCNTs@GONRs hybrids. • The sensor shows good analytical performance for PAAs detection. - Abstract: Being awfully harmful to the environment and human health, the qualitative and quantitative determinations of polycyclic aromatic amines (PAAs) are of great significance. In this paper, a novel core–shell heterostructure of multiwalled carbon nanotubes (MWCNTs) as the core and graphene oxide nanoribbons (GONRs) as the shell (MWCNTs@GONRs) was produced from longitudinal partially unzipping of MWCNTs side walls using a simple wet chemical strategy and applied for electrochemical determination of three kinds of PAAs (1-aminopyrene (1-AP), 1-aminonaphthalene and 3,3′-diaminobiphenyl). Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and electrochemical methods were used to characterize the as-prepared MWCNTs@GONRs. Due to the synergistic effects from MWCNTs and GONRs, the oxidation currents of PAAs at the MWCNTs@GONRs modified glassy carbon (GC) electrode are much higher than that at the MWCNTs/GC, graphene/GC and bare GC electrodes. 1-AP was used as the representative analyte to demonstrate the sensing performance of the MWCNTs@GONRs/GC electrode, and the proposed modified electrode has a linear response range of 8.0–500.0 nM with a detection limit of 1.5 nM towards 1-AP.

  17. Sensitive electrochemical sensing for polycyclic aromatic amines based on a novel core–shell multiwalled carbon nanotubes@ graphene oxide nanoribbons heterostructure

    International Nuclear Information System (INIS)

    Zhu, Gangbing; Yi, Yinhui; Han, Zhixiang; Wang, Kun; Wu, Xiangyang

    2014-01-01

    Highlights: • A core–shell heterostructure MWCNTs@GONRs was produced from unzipping MWCNTs. • A new electrochemical sensor for PAAs was developed based on MWCNTs@GONRs hybrids. • The sensor shows good analytical performance for PAAs detection. - Abstract: Being awfully harmful to the environment and human health, the qualitative and quantitative determinations of polycyclic aromatic amines (PAAs) are of great significance. In this paper, a novel core–shell heterostructure of multiwalled carbon nanotubes (MWCNTs) as the core and graphene oxide nanoribbons (GONRs) as the shell (MWCNTs@GONRs) was produced from longitudinal partially unzipping of MWCNTs side walls using a simple wet chemical strategy and applied for electrochemical determination of three kinds of PAAs (1-aminopyrene (1-AP), 1-aminonaphthalene and 3,3′-diaminobiphenyl). Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and electrochemical methods were used to characterize the as-prepared MWCNTs@GONRs. Due to the synergistic effects from MWCNTs and GONRs, the oxidation currents of PAAs at the MWCNTs@GONRs modified glassy carbon (GC) electrode are much higher than that at the MWCNTs/GC, graphene/GC and bare GC electrodes. 1-AP was used as the representative analyte to demonstrate the sensing performance of the MWCNTs@GONRs/GC electrode, and the proposed modified electrode has a linear response range of 8.0–500.0 nM with a detection limit of 1.5 nM towards 1-AP

  18. Amines as extracting agents for the quantitative determinations of actinides in biological samples

    International Nuclear Information System (INIS)

    Singh, N.P.

    1987-01-01

    The use of amines (primary, secondary and tertiary chains and quaternary ammonium salts) as extracting agents for the quantitative determination of actinides in biological samples is reviewed. Among the primary amines, only Primene JM-T is used to determine Pu in urine and bone. No one has investigated the possibility of using secondary amines to quantitatively extract actinides from biological samples. Among the tertiary amines, tri-n-octylamine, tri-iso-octylamine, tyricaprylamine (Alamine) and trilaurylamine (tridodecylamine) are used extensively to extract and separate the actinides from biological samples. Only one quaternary ammonium salt, methyltricapryl ammonium chloride (Aliquat-336), is used to extract Pu from biological samples. (author) 28 refs

  19. 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...

  20. A nanocomposite disk prepared from reduced graphene oxide and gold nanoparticles for the preconcentration of heterocyclic aromatic amines prior to their determination by HPLC

    International Nuclear Information System (INIS)

    Tan, Connieal; Wang, Yiru; Deng, Zhuo; Xu, Na; Song, Xinhong; Liu, Haihong; Rong, Mingcong; Chen, Xi

    2014-01-01

    We report on a preconcentration disk for the determination of trace amounts of heterocyclic aromatic amines (HAAs) in the groups of quinoline and quinoxaline congeners as possible human carcinogens. The disk is based on nanocomposite (NC) prepared from graphene oxide as the precursor and from gold nanoparticles that act as building blocks to form a three-dimensional NC. If deposited in the sampling valve of a HPLC system, the material displays excellent extraction capability for HAAs owing to its large surface and π-π stacking interaction. Following an optimization of the extraction parameters, the method was successfully applied to the simultaneous determination of polar HAAs in meat samples with detection limit of 0.09 to 0.16 ng g −1 and recoveries of 69.5 to 122.7 %. The disk was used in more than 150 subsequent preconcentration cycles without obvious loss of the absorption capability. The results reveal that this new NC represents an excellent sorbent for purposes of preconcentration. (author)

  1. Triplet-State Dissolved Organic Matter Quantum Yields and Lifetimes from Direct Observation of Aromatic Amine Oxidation.

    Science.gov (United States)

    Schmitt, Markus; Erickson, Paul R; McNeill, Kristopher

    2017-11-21

    Excited triplet state chromophoric dissolved organic matter ( 3 CDOM*) is a short-lived mixture of excited-state species that plays important roles in aquatic photochemical processes. Unlike the study of the triplet states of well-defined molecules, which are amenable to transient absorbance spectroscopy, the study of 3 CDOM* is hampered by it being a complex mixture and its low average intersystem crossing quantum yield (Φ ISC ). This study is an alternative approach to investigating 3 CDOM* using transient absorption laser spectroscopy. The radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), formed through oxidation by 3 CDOM*, was directly observable by transient absorption spectroscopy and was used to probe basic photophysical properties of 3 CDOM*. Quenching and control experiments verified that TMPD •+ was formed from 3 CDOM* under anoxic conditions. Model triplet sensitizers with a wide range of excited triplet state reduction potentials and CDOM oxidized TMPD at near diffusion-controlled rates. This gives support to the idea that a large cross-section of 3 CDOM* moieties are able to oxidize TMPD and that the complex mixture of 3 CDOM* can be simplified to a single signal. Using the TMPD •+ transient, the natural triplet lifetime and Φ ISC for different DOM isolates and natural waters were quantified; values ranged from 12 to 26 μs and 4.1-7.8%, respectively.

  2. Mechanism of the extraction of nitric acid and water by organic solutions of tertiary alkyl-amines; Mecanisme d'extraction de l'acide nitrique et de l'eau par les solutions organiques d'alcoylamines tertiaires

    Energy Technology Data Exchange (ETDEWEB)

    Gourisse, D

    1966-06-01

    The micellar aggregation of tri-alkyl-ammonium nitrates in low polarity organic solvents has been verified by viscosity, conductivity and sedimentation velocity measurements. The aggregation depends upon the polarity of solvent, the length of the alkyl radicals and the organic concentration of the various constituents (tri-alkyl-ammonium nitrate, tri-alkyl-amine, nitric acid, water). The amine salification law has been established and the excess nitric acid and water solubilities in the organic solutions have been measured. Nitric acid and water are slightly more soluble in micellar organic solutions than in molecular organic solutions. A description of excess nitric acid containing tri-alkyl-ammonium nitrate solutions is proposed. (author) [French] Mecanisme d'extraction de l'acide nitrique et de l'eau par les solutions organiques d'alcoylamines tertiaires. L'agregation micellaire des nitrates de trialcoylammonium dans les solvants peu polaires a ete verifiee par viscosimetrie, conductimetrie et ultracentrifugation des solutions organiques. L'agregation depend de la polarite du solvant, de la longueur des radicaux alcoyle, et des concentrations des differents constituants de la solution organique (nitrate de trialcoylammonium, alcoylamine tertiaire, acide nitrique, eau). La loi de salification de l'amine a ete determinee et les solubilites de l'acide nitrique en exces et de l'eau dans les solutions organiques ont ete mesurees. L'acide nitrique et l'eau sont legerement plus solubles dans les organiques micellaires que dans les solutions organiques moleculaires. Une description des solutions de nitrate de trialcoylammonium contenant de l'acide nitrique en exces est proposee. (auteur)

  3. Adsorption and Oxidation of Aromatic Amines on Metal(II Hexacyanocobaltate(III Complexes: Implication for Oligomerization of Exotic Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Rachana Sharma

    2017-03-01

    Full Text Available Based on the hypothesis on the presence of double metal cyanides in the primordial oceans, a series of nano-sized metal(II hexacyanocobaltate(III (MHCCo with the general formula: M3[Co(CN6]2•xH2O (where M = Zn, Fe, Ni and Mn has been synthesized. Surface interaction of aromatic amines, namely aniline, 4-chloroaniline, 4-methylaniline and 4-methoxyaniline with MHCCo particles has been carried out at the concentration range of 100–400 μM at pH~7.0. The percentage binding of aromatic amines on MHCCo surface was found to be in the range of 84%–44%. The trend in adsorption was in accordance to the relative basicity of the studied amines. At the experimental pH, amines reacted rapidly with the surface of the iron(II hexacyanocobaltate, producing colored products that were analyzed by Gas Chromatography Mass Spectroscopy (GC-MS. GC-MS analysis of the colored products demonstrated the formation of dimers of the studied aromatic amines. Surface interaction of aromatic amines with MHCCo was studied by Fourier Transform Infrared (FT-IR spectroscopy and Field Emission Scanning Electron Microscopy (FE-SEM. The change in amine characteristic frequencies, as observed by FT-IR, suggests that interaction took place through the NH2 group on amines with metal ions of hexacyanocobaltate complexes. FE-SEM studies revealed the adherence of 4-methoxyaniline on zinc hexacyanocobaltate particles surface. We proposed that MHCCo might have been formed under the conditions on primitive Earth and may be regarded as an important candidate for concentrating organic molecules through the adsorption process.

  4. Amine Measurements in Boreal Forest Air

    Science.gov (United States)

    Hemmilä, Marja; Hellén, Heidi; Makkonen, Ulla; Hakola, Hannele

    2015-04-01

    Amines are reactive, volatile bases in the air with a general formula of RNH2, R2NH or R3N. Especially small amines can stabilize sulphuric acid clusters and hence affect nucleation. Amines react rapidly with hydroxyl radical (OH˙) thus affecting oxidative capacity of the atmosphere. The amine concentrations are higher in forest air than in urban air (Hellén et al., 2014), but the sources are not known. In order to get more information concerning amine sources, we conducted a measurement campaign in a boreal forest. At SMEAR II station at Hyytiälä, Southern Finland (61°510'N, 24°170'E, 180 m a.s.l.) The measurements cover seven months, from June to December 2014. For sampling and measuring we used MARGA (The instrument for Measuring AeRosols and Gases in Ambient air) which is an on-line ion chromatograph (IC) connected to a sampling system. The IC component of the MARGA system was coupled to an electrospray ionization quadrupole mass spectrometer (MS) to improve sensitivity of amine measurements. This new set-up enabled amine concentration measurements in ambient air both in aerosol and gas phases with a time resolution of only 1 hour. With MARGA-MS we analysed 7 different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA) and butylamine (BA). In preliminary data-analysis we found out, that in June and July most of the measured amines were in gas phase, and particle phase amine concentrations were mostly under detection limits (<1.7 pptv). In June the gaseous amine concentrations were higher than in July. The measured concentrations of gaseous amines followed temperature variation, which could indicate that amines are produced and emitted from the environment or re-emitted from the surfaces as temperature rises after deposition during night-time. All measured amines had similar diurnal variation with maxima during afternoon and minima during night. Results from other months will also

  5. Synthesis and Application of Amine Functionalized Iron Oxide Nanoparticles on Menaquinone-7 Fermentation: A Step towards Process Intensification

    Directory of Open Access Journals (Sweden)

    Alireza Ebrahiminezhad

    2015-12-01

    Full Text Available Industrial production of menaquione-7 by Bacillus subtilis natto is associated with major drawbacks. To address the current challenges in menaquione-7 fermentation, studying the effect of magnetic nanoparticles on the bacterial cells can open up a new domain for intensified menqainone-7 process. This article introduces the new concept of production and application of l-lysine coated iron oxide nanoparticles (l-Lys@IONs as a novel tool for menaquinone-7 biosynthesis. l-Lys@IONs with the average size of 7 nm were successfully fabricated and were examined in a fermentation process of l-Lys@IONs decorated Bacillus subtilis natto. Based on the results, higher menaquinone-7 specific yield was observed for l-Lys@IONs decorated bacterial cells as compared to untreated bacteria. In addition, more than 92% removal efficacy was achieved by using integrated magnetic separation process. The present study demonstrates that l-Lys@IONs can be successfully applied during a fermentation of menaquinone-7 without any negative consequences on the culture conditions. This study provides a novel biotechnological application for IONs and their future role in bioprocess intensification.

  6. Syntheses of the enantiomers of 1-deoxynojirimycin and 1-deoxyaltronojirimycin via chemo- and diastereoselective olefinic oxidation of unsaturated amines.

    Science.gov (United States)

    Bagal, Sharan K; Davies, Stephen G; Lee, James A; Roberts, Paul M; Scott, Philip M; Thomson, James E

    2010-12-03

    Oxidation of enantiomerically pure (R)-N(1)-1'-(1''-naphthyl)ethyl-2,7-dihydro-1H-azepine with m-CPBA in the presence of HBF(4) and BnOH gave (3S,4R,5S,6S,1'R)-N(1)-1'-(1''-naphthyl)ethyl-3-hydroxy-4-benzyloxy-5,6-epoxyazepane as the major product and as a single diastereoisomer after chromatography. Elaboration of this highly functionalized intermediate via ring contraction to (2S,3R,4S,5S,1'R)-N(1)-benzyl-2-chloromethyl-3-benzyloxy-4,5-epoxypiperidine followed by regioselective epoxide ring opening, functional group manipulation, and deprotection gave (+)-1-deoxyaltronojirimycin. Alternatively, resolution of (RS,RS)-N(1)-benzyl-3-hydroxy-4-benzyloxy-2,3,4,7-tetrahydro-1H-azepine or (3RS,4SR,5RS,6RS)-N(1)-benzyl-3-hydroxy-4-benzyloxy-5,6-epoxyazepane by preparative chiral HPLC and subsequent elaboration allows access to the enantiomers of 1-deoxynojirimycin and 1-deoxyaltronojirimycin, respectively.

  7. Amine-modified magnetic iron oxide nanoparticle as a promising carrier for application in bio self-healing concrete.

    Science.gov (United States)

    Seifan, Mostafa; Ebrahiminezhad, Alireza; Ghasemi, Younes; Samani, Ali Khajeh; Berenjian, Aydin

    2018-01-01

    Self-healing mechanisms are a promising solution to address the concrete cracking issue. Among the investigated self-healing strategies, the biotechnological approach is distinguished itself by inducing the most compatible material with concrete composition. In this method, the potent bacteria and nutrients are incorporated into the concrete matrix. Once cracking occurs, the bacteria will be activated, and the induced CaCO 3 crystals will seal the concrete cracks. However, the effectiveness of a bio self-healing concrete strictly depends on the viability of bacteria. Therefore, it is required to protect the bacteria from the resulted shear forces caused by mixing and drying shrinkage of concrete. Due to the positive effects on mechanical properties and the high compatibility of metallic nanoparticles with concrete composition, for the first time, we propose 3-aminopropyltriethoxy silane-coated iron oxide nanoparticles (APTES-coated IONs) as a biocompatible carrier for Bacillus species. This study was aimed to investigate the effect of APTES-coated IONs on the bacterial viability and CaCO 3 yield for future application in the concrete structures. The APTES-coated IONs were successfully synthesized and characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The results show that the presence of 100 μg/mL APTES-coated IONs could increase the bacterial viability. It was also found that the CaCO 3 -specific yield was significantly affected in the presence of APTES-coated IONs. The highest CaCO 3 -specific yield was achieved when the cells were decorated with 50 μg/mL of APTES-coated IONs. This study provides new insights for the application of APTES-coated IONs in designing bio self-healing strategies.

  8. Tandem Oxidative Derivatization of Nitrene Insertion Products for the Highly Diastereoselective Synthesis of 1,3-aminoalcohols.

    Science.gov (United States)

    Alderson, Juliet M; Schomaker, Jennifer M

    2017-06-27

    Transition-metal-catalyzed nitrene insertion into tertiary C-H bonds located at stereogenic carbons often results in mixtures of diastereomeric products, especially if the reaction proceeds through a concerted pathway. In this communication, we report a solution to this problem that invokes a one-pot, silver-catalyzed C-H nitrene transfer reaction. Nitrene insertion is followed by facile oxidation of the amine to an imine and nucleophilic addition to furnish α-tertiary amine 1,3-aminoalcohol products in high diastereoselectivities. The silver catalyst, PhIO oxidant, and TEMPO additive are crucial to success in this unusual oxidation, which is proposed to occur via hydrogen-atom abstraction from pre-activation of the initial nitrene insertion product by additional oxidant. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Study on synthesis, application and mechanism of benzophenone/amine initiator

    International Nuclear Information System (INIS)

    Xiong Wei; Liu Jinshui; Wen Yinjun; Wan Qizhong; Zhou Xianyan; Xiao Hanling; Yang Jianwen

    1999-01-01

    Through Michael addition reaction of trimethylolpropane triacrylate (TMPTA) with diethylamine (DEA), a new kind of tertiary amine derivative was synthesized and its structure was identified by 'H-NMR. When used in combination with benzophenone, this amine presented excellent curing speed and could be a substitute for initiator Darocur R 1173, which is effective but expensive. If so, the cost of UV-curable coatings can descend apparently. The functioning mechanism of benzophenone/amine bimolecular initiator was studied

  10. Effects of plant polyphenols and α-tocopherol on lipid oxidation, microbiological characteristics, and biogenic amines formation in dry-cured bacons.

    Science.gov (United States)

    Wang, Yongli; Li, Feng; Zhuang, Hong; Li, Lianghao; Chen, Xiao; Zhang, Jianhao

    2015-03-01

    Effects of plant polyphenols (tea polyphenol [TP], grape seed extract [GSE], and gingerol) and α-tocopherol on physicochemical parameters, microbiological counts, and biogenic amines were determined in dry-cured bacons at the end of ripening. Results showed that plant polyphenols and α-tocopherol significantly decreased pH, thiobarbituric acid reactive substances content, and total volatile basic nitrogen (TVBN) compared with the control (P amine contents in dry-cured bacons were affected by plant polyphenols or α-tocopherol, with TP being the most effective (P amines, and spoilage microorganisms, whereas PC2 grouped the TVBN, tyramine, 2-phenylethylamine, yeast, and molds. These findings suggest that plant polyphenols, especially TP, could be used to process dry-cured bacons to improve the quality and safety of finished products. © 2015 Institute of Food Technologists®

  11. Aracyl triflates for preparing fluorescent and UV absorbing derivatives of unreactive carboxylates, amines and other metabolites

    Energy Technology Data Exchange (ETDEWEB)

    Storer, Malina K. [Biochemistry Unit, Canterbury Health Laboratories, P.O. Box 151, Christchurch (New Zealand); Department of Pathology, Christchurch School of Medicine and Health Sciences, University of Otago, Christchurch (New Zealand); Lever, Michael [Biochemistry Unit, Canterbury Health Laboratories, P.O. Box 151, Christchurch (New Zealand) and Department of Pathology, Christchurch School of Medicine and Health Sciences, University of Otago, Christchurch (New Zealand)]. E-mail: michael.lever@chmeds.ac.nz

    2006-02-03

    Aracyl trifluoromethanesulfonate (triflate) reagents alkylate the unreactive carboxyl groups of betaines. The reagents also derivatise tertiary amines, amine oxides, phosphates and thioethers. A general derivatisation procedure is to dilute the sample with a polar aprotic organic solvent containing a trace of water, followed by adding an appropriate base and the aracyl triflate reagent. Limits of detection were 40 nM for glycine betaine (GB) and carnitine, 0.14 {mu}M for N,N-dimethylglycine, 70 nM for trimethylamine (TMA), and 5.9 {mu}M trimethylamine-N-oxide (TMAO). Limits of detection were improved when derivatisation yield was optimised for different analytes by changing solvent, base and water content of the reaction mixture. Solvents used include acetonitrile, acetone, butanone, dimethoxyethane and dimethoxyethyl ether, with the presence of some water or alcohol tolerated. Suitable bases include the inorganic bases magnesium hydroxide, silver oxide and lithium phosphate. These bases are sparingly soluble in the reaction solvent so sustain weakly basic conditions during derivatisation and can be removed by centrifugation to stop the reaction. This is particularly important for betaine assays since the derivatives are base-sensitive. The information presented here can be used to develop assays for many metabolites using these versatile reagents.

  12. Aracyl triflates for preparing fluorescent and UV absorbing derivatives of unreactive carboxylates, amines and other metabolites

    International Nuclear Information System (INIS)

    Storer, Malina K.; Lever, Michael

    2006-01-01

    Aracyl trifluoromethanesulfonate (triflate) reagents alkylate the unreactive carboxyl groups of betaines. The reagents also derivatise tertiary amines, amine oxides, phosphates and thioethers. A general derivatisation procedure is to dilute the sample with a polar aprotic organic solvent containing a trace of water, followed by adding an appropriate base and the aracyl triflate reagent. Limits of detection were 40 nM for glycine betaine (GB) and carnitine, 0.14 μM for N,N-dimethylglycine, 70 nM for trimethylamine (TMA), and 5.9 μM trimethylamine-N-oxide (TMAO). Limits of detection were improved when derivatisation yield was optimised for different analytes by changing solvent, base and water content of the reaction mixture. Solvents used include acetonitrile, acetone, butanone, dimethoxyethane and dimethoxyethyl ether, with the presence of some water or alcohol tolerated. Suitable bases include the inorganic bases magnesium hydroxide, silver oxide and lithium phosphate. These bases are sparingly soluble in the reaction solvent so sustain weakly basic conditions during derivatisation and can be removed by centrifugation to stop the reaction. This is particularly important for betaine assays since the derivatives are base-sensitive. The information presented here can be used to develop assays for many metabolites using these versatile reagents

  13. Role of amine structure on carbon dioxide adsorption from ultradilute gas streams such as ambient air.

    Science.gov (United States)

    Didas, Stephanie A; Kulkarni, Ambarish R; Sholl, David S; Jones, Christopher W

    2012-10-01

    A fundamental study on the adsorption properties of primary, secondary, and tertiary amine materials is used to evaluate what amine type(s) are best suited for ultradilute CO(2) capture applications. A series of comparable materials comprised of primary, secondary, or tertiary amines ligated to a mesoporous silica support via a propyl linker are used to systematically assess the role of amine type. Both CO(2) and water adsorption isotherms are presented for these materials in the range relevant to CO(2) capture from ambient air and it is demonstrated that primary amines are the best candidates for CO(2) capture from air. Primary amines possess both the highest amine efficiency for CO(2) adsorption as well as enhanced water affinity compared to other amine types or the bare silica support. The results suggest that the rational design of amine adsorbents for the extraction of CO(2) from ambient air should focus on adsorbents rich in primary amines. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Effects of plant polyphenols and a-tocopherol on lipid oxidation, microbiological characteristics, and biogenic amines formation in dry-cured bacons

    Science.gov (United States)

    Effects of plant polyphenols (tea polyphenol, grape seed extract, and gingerol) and a-tocopherol on physicochemical parameters, microbiological counts, and biogenic amines were determined in dry-cured bacons at the end of ripening. Results showed that plant polyphenols and a-tocopherol significantly...

  15. Ligand-Centred Reactivity of Bis(picolyl)amine Iridium: Sequential Deprotonation, Oxidation and Oxygenation of a "Non-Innocent" Ligand

    Czech Academy of Sciences Publication Activity Database

    Tejel, C.; del Río, M. P.; Ciriano, M. A.; Reijerse, E. J.; Hartl, F.; Záliš, Stanislav; Hetterscheid, D. G. H.; Tsichlis i Spithas, N.; de Bruin, B.

    2009-01-01

    Roč. 15, č. 44 (2009), s. 11878-11889 ISSN 0947-6539 R&D Projects: GA MŠk OC 139; GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : bis(picolyl)amine * iridium * ligand radical * oxygenation Subject RIV: CG - Electrochemistry Impact factor: 5.382, year: 2009

  16. 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.

  17. Amines, Astrocytes and Arousal

    OpenAIRE

    Bazargani, N.; Attwell, D.

    2017-01-01

    Amine neurotransmitters, such as noradrenaline, mediate arousal, attention, and reward in the CNS. New data suggest that, from flies to mammals, a major mechanism for amine transmitter action is to raise astrocyte [Ca2+]i and release gliotransmitters that modulate neuronal activity and behavior.

  18. Synthesis and bioelectrochemical behavior of aromatic amines.

    Science.gov (United States)

    Shabbir, Muhammad; Akhter, Zareen; Ahmad, Iqbal; Ahmed, Safeer; Bolte, Michael; McKee, Vickie

    2017-12-01

    Four aromatic amines 1-amino-4-phenoxybenzene (A 1 ), 4-(4-aminophenyloxy) biphenyl (A 2 ), 1-(4-aminophenoxy) naphthalene (A 3 ) and 2-(4-aminophenoxy) naphthalene (A 4 ) were synthesized and characterized by elemental, spectroscopic (FTIR, NMR), mass spectrometric and single crystal X-ray diffraction methods. The compounds crystallized in monoclinic crystal system with space group P2 1 . Intermolecular hydrogen bonds were observed between the amine group and amine/ether acceptors of neighboring molecules. Electrochemical investigations were done using cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). CV studies showed that oxidation of aromatic amines takes place at about 0.9 V (vs. Ag/AgCl) and the electron transfer (ET) process has irreversible nature. After first scan reactive intermediate were generated electrochemically and some other cathodic and anodic peaks also appeared in the succeeding scans. DPV study revealed that ET process is accompanied by one electron. DNA binding study of aromatic amines was performed by CV and UV-visible spectroscopy. These investigations revealed groove binding mode of interaction of aromatic amines with DNA. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. The chemistry of amine radical cations produced by visible light photoredox catalysis

    Directory of Open Access Journals (Sweden)

    Jie Hu

    2013-10-01

    Full Text Available Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.

  20. Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

    Science.gov (United States)

    Sharma, Pankaj; Liu, Rai-Shung

    2015-03-16

    A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Polymeric film of 6-arm-poly(ethylene glycol) amine graphene oxide with poly (ε-caprolactone): Adherence and growth of adipose derived mesenchymal stromal cells culture on rat bladder

    Science.gov (United States)

    Durán, Marcela; Durán, Nelson; Luzo, Angela C. M.; Duarte, Adriana S. S.; Volpe, Bruno B.; Ceragioli, Helder J.; Andrade, Patricia F.; De Souza, Joel G.; Fávaro, Wagner J.

    2017-06-01

    Nanotechnology has been more present in different fields related to health. The need to find a durable material, of easy use, and which does not interfere significantly in the growth and differentiation of stem cells for the construction of a scaffold for use in urologic surgery, with the purpose of reducing infections, regeneration times and even graft rejection during reconstitution in patients with urethral stricture was conducted a broad survey of information about this and came to the consensus of this project: using graphene oxide, a widely studied nanomaterials which has been presenting numerous beneficial results when in contact with the adipose-derived stem cells. Advanced techniques for the growth, differentiation and proliferation of adipose-derived stem cells were used, as well as the characterization of graphene oxide sheets. For this study, it was prepared the graphene oxide/6 ARM-Poly (ethylene glycol) amine films with poly (ε-caprolactone). The graphene suspension in organic solvent was prepared by using an ultrasonicator bath and subsequently, the film was formed by solvent evaporation. Total characterization of graphene oxide/6 ARM-PEG-amine/ poly (ε-caprolactone) film was carried out. It was tested growth and adhesion of adipose-derived stem cells on the film, as well as, were verified the histopathological effects of this scaffold when implanted in the urinary bladder to repair the lesion. Our results demonstrated that this scaffold with adipose-derived stem cells enhanced the repair in rat urinary bladder defect model, resulting in a regular bladder. Improved organized muscle bundles and urothelial layer were observed in animals treated with this scaffold with adipose-derived stem cells compared with those treated only suture thread or scaffold. Thus, our biomaterial could be suitable for tissue engineered urinary tract reconstruction.

  2. Polymeric film of 6-arm-poly(ethylene glycol) amine graphene oxide with poly (ε-caprolactone): Adherence and growth of adipose derived mesenchymal stromal cells culture on rat bladder

    International Nuclear Information System (INIS)

    Durán, Marcela; Durán, Nelson; Fávaro, Wagner J.; Luzo, Angela C.M.; Duarte, Adriana S. S.; Volpe, Bruno B.; Ceragioli, Helder J.; Andrade, Patricia F.; De Souza, Joel G.

    2017-01-01

    Nanotechnology has been more present in different fields related to health. The need to find a durable material, of easy use, and which does not interfere significantly in the growth and differentiation of stem cells for the construction of a scaffold for use in urologic surgery, with the purpose of reducing infections, regeneration times and even graft rejection during reconstitution in patients with urethral stricture was conducted a broad survey of information about this and came to the consensus of this project: using graphene oxide, a widely studied nanomaterials which has been presenting numerous beneficial results when in contact with the adipose-derived stem cells. Advanced techniques for the growth, differentiation and proliferation of adipose-derived stem cells were used, as well as the characterization of graphene oxide sheets. For this study, it was prepared the graphene oxide/6 ARM-Poly (ethylene glycol) amine films with poly (ε-caprolactone). The graphene suspension in organic solvent was prepared by using an ultrasonicator bath and subsequently, the film was formed by solvent evaporation. Total characterization of graphene oxide/6 ARM-PEG-amine/ poly (ε-caprolactone) film was carried out. It was tested growth and adhesion of adipose-derived stem cells on the film, as well as, were verified the histopathological effects of this scaffold when implanted in the urinary bladder to repair the lesion. Our results demonstrated that this scaffold with adipose-derived stem cells enhanced the repair in rat urinary bladder defect model, resulting in a regular bladder. Improved organized muscle bundles and urothelial layer were observed in animals treated with this scaffold with adipose-derived stem cells compared with those treated only suture thread or scaffold. Thus, our biomaterial could be suitable for tissue engineered urinary tract reconstruction. (paper)

  3. Preparation of Benzo[c]carbazol-6-amines via Manganese-Catalyzed Enaminylation of 1-(Pyrimidin-2-yl)-1H-indoles with Ketenimines and Subsequent Oxidative Cyclization.

    Science.gov (United States)

    Zhou, Xiaorong; Li, Zhenmin; Zhang, Zhiyin; Lu, Ping; Wang, Yanguang

    2018-03-02

    Manganese-catalyzed C 2 -H enaminylation of 1-(pyrimidin-2-yl)-1H-indoles with ketenimines is reported. The reaction provided 2-enaminylated indole derivatives in moderate to excellent yields with a broad substrate scope. A migration of the directing group pyrimidinyl occurred during this process. The synthesized 2-enaminyl indoles could be conveniently converted into 5-aryl-7H-benzo[c]carbazol-6-amines.

  4. Amine Functionalized Porous Network

    KAUST Repository

    Eddaoudi, Mohamed; Guillerm, Vincent; Weselinski, Lukasz Jan; Alkordi, Mohamed H.; Mohideen, Mohamed Infas Haja; Belmabkhout, Youssef

    2015-01-01

    Amine groups can be introduced in porous materials by a direct (one pot) or post-synthetic modification (PSM) process on aldehyde groups, and the resulting porous materials have increased gas affinity.

  5. Amine Functionalized Porous Network

    KAUST Repository

    Eddaoudi, Mohamed

    2015-05-28

    Amine groups can be introduced in porous materials by a direct (one pot) or post-synthetic modification (PSM) process on aldehyde groups, and the resulting porous materials have increased gas affinity.

  6. Controlling Nitrosamines, Nitramines, and Amines in Amine-Based CO₂ Capture Systems with Continuous Ultraviolet and Ozone Treatment of Washwater.

    Science.gov (United States)

    Dai, Ning; Mitch, William A

    2015-07-21

    Formation of nitrosamines and nitramines from reactions between flue gas NOx and the amines used in CO2 capture units has arisen as a significant concern. Washwater scrubbers can capture nitrosamines and nitramines. They can also capture amines, preventing formation of nitrosamines and nitramines downwind by amine reactions with ambient NOx. The continuous application of UV alone, or a combination of UV and ozone to the return line of a washwater treatment unit was evaluated to control the accumulation of nitrosamines, nitramines and amines in a laboratory-scale washwater unit. With model secondary amine solvents ranging from nonvolatile diethanolamine to volatile morpholine, application of 272-537 mJ/cm(2) UV incident fluence alone reduced the accumulation of nitrosamines and nitramines by approximately an order of magnitude. Modeling indicated that the gains achieved by UV treatment should increase over time, because UV treatment converts the time dependence of nitrosamine accumulation from a quadratic to a linear function. Ozone (21 mg/L) maintained low steady-state concentrations of amines in the washwater. While modeling indicated that more than 80% of nitrosamine accumulation in the washwater was associated with reaction of washwater amines with residual NOx, a reduction in nitrosamine accumulation rates due to ozone oxidation of amines was not fully realized because the ozonation products of amines reduced nitrosamine photolysis rates by competing for photons.

  7. Drugs for stroke: action of nitrone (Z)-N-(2-bromo-5-hydroxy-4-methoxybenzylidene)-2-methylpropan-2-amine oxide on rat cortical neurons in culture subjected to oxygen-glucose-deprivation.

    Science.gov (United States)

    Arce, Carmen; Diaz-Castroverde, Sabela; Canales, María J; Marco-Contelles, José; Samadi, Abdelouahid; Oset-Gasque, María J; González, María P

    2012-09-01

    The action of (Z)-N-(2-bromo-5-hydroxy-4-methoxybenzylidene)-2-methylpropan-2-amine oxide (RP6) on rat cortical neurons in culture, under oxygen-glucose-deprivation conditions, is reported. Cortical neurons in culture were treated during 1 h with OGD. After, they were placed under normal conditions during 24 h (reperfusion) in absence and presence of RP6. Different parameters were measured under each condition (control, 1 h OGD and 1 h OGD + reperfusion in absence and presence of RP6). RP6 protects neurons against ROS generation, lipid peroxidation levels, LDH release and mitochondrial membrane potential alteration, when administered during reperfusion after the OGD damage. Consequently, these results show that nitrone RP6 protects cells against ischemia injury produced during the reoxygenation, and could be a potential drug for the ictus therapy. Copyright © 2012. Published by Elsevier Masson SAS.

  8. Catalyst- and Reagent-free Electrochemical Azole C-H Amination.

    Science.gov (United States)

    Qiu, Youai; Struwe, Julia; Meyer, Tjark H; Oliveira, Joao Carlos Agostinho Carlos Agostinho; Ackermann, Lutz

    2018-06-14

    Catalyst-, and chemical oxidant-free electrochemical azole C-H aminations were accomplished via cross-dehydrogenative C-H/N-H functionalization. The catalyst-free electrochemical C-H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp3)-H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C-H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Nucleophilic addition of amines to the activated ethylene bond in non-aqueous media

    International Nuclear Information System (INIS)

    Perepichka, Igor F.; Popov, Anatolii F.

    1995-01-01

    The kinetics of addition of a number of primary and secondary aliphatic amines to trans-(2-furyl) nitro ethylene (1) has been studied in solvents of various polarities (from acetonitrile, ε 37.5, to heptane, ε 1.89). It has been shown that the reaction is catalysed both by the amine reagent and by tertiary amines. On the basis of analyzing the observed kinetic regularities a stepwise reaction mechanism has been proposed which involves formation of zwitterionic intermediate (3) at the first equilibrium step (k 1 , K 1 ) which is then converted into the reaction product by means of proton transfer in parallel routes, the non-catalytic one (k 2 ) and that catalysed by the initial (K 3 ) or tertiary (K 4 ) amine. The observed high values of the deuterium isotope effects in the reaction (K H /K D ∼ 2.3 - 8.9) confirm that proton transfer occurs in the rate-limiting step of the reaction (primary kinetic isotope effect). The third order by amine kinetic route is observed in low polar media which is due to participation of amine dimers (R 2 NH HNR 2 ) in the reaction. The observed kinetic regularities are compared with those for the nucleophilic aromatic substitution reactions in low-polar media, and the conclusion has been made that the reaction route of the third order by amine proceeds as reversible nucleophilic attack by amine dimer and following base-catalysed transformation of the intermediate into the product. (author)

  10. Hydrothermal oxidation of an epoxy resin through the study of two model molecules: N-methyl-acetamide and N,N-di[1(phenoxy)2-hydroxy propyl-3] propyl-amine

    International Nuclear Information System (INIS)

    Moutonnet-Fromonteil, C.

    2000-01-01

    The study consists in choosing and developing a technology to realize damage experiments of an epoxy resin which is used as coating of embedded nuclear samples. Hydrothermal oxidation is the chosen method. We first identified the chemical composition of the epoxy resin. Then we studied hydrolysis and oxidation of a molecule which contains a function of the epoxy network: N-methyl-acetamide. The comparison between our results and those already existing allowed to validate this degradation method. In a second part, we studied a model molecule of the polymer network: N, N-di[1(phenoxy)2-hydroxy propyl-3] propyl-amine. The hydrolysis temperatures are relatively high: the compound is totally destroyed at 300 deg C. Its oxidation leads to the formation of acetic acid from 220 deg C. In the third study, we determined the best experimental conditions to destroy the epoxy resin. Experiments were performed at different temperatures between 200 deg C and 410 deg C. The degradation rates are classically defined by amounts of constituents in liquid and gaseous phases. (author)

  11. Structure and activity of Aspergillus nidulans copper amine oxidase

    DEFF Research Database (Denmark)

    McGrath, Aaron P; Mithieux, Suzanne M; Collyer, Charles A

    2011-01-01

    Aspergillus nidulans amine oxidase (ANAO) has the unusual ability among the family of copper and trihydroxyphenylalanine quinone-containing amine oxidases of being able to oxidize the amine side chains of lysine residues in large peptides and proteins. We show here that in common with the related...... enzyme from the yeast Pichia pastoris, ANAO can promote the cross-linking of tropoelastin and oxidize the lysine residues in α-casein proteins and tropoelastin. The crystal structure of ANAO, the first for a fungal enzyme in this family, has been determined to a resolution of 2.4 Å. The enzyme is a dimer...... with the archetypal fold of a copper-containing amine oxidase. The active site is the most open of any of those of the structurally characterized enzymes in the family and provides a ready explanation for its lysine oxidase-like activity....

  12. Tertiary lithofacies and paleo-geographic framework and interlayer oxidation zone sandstone uranium deposits in Longjiang-Zhaozhou area

    International Nuclear Information System (INIS)

    Zhang Zhenqiang

    2003-01-01

    The main points of views for the experiment are: (1) Yi'an formation is mainly composed of limnetic facies of siltstone and fine sandstone, due to weak surface water, limited sedimentation and simple material source; (2) strengthened surface water and enormous material brought from north and west-north and enlarged sedimentation from north to south, the major deposition during Da'an period are channel facies of conglomerate and river bed facies of sandstone; (3) stronger surface water during Taikang period, led alluvial-flood plain facies brown-yellow conglomerate to develop along western margin of the basin, the channel facies of conglomerate and river bed facies of grey-green sandstone, pelitic siltstone were widely formed southward and eastward; (4) according to the lithofacies criterion for in-situ leachable sandstone uranium ore, Taikang formation is an ideal horizon, river bed facies is suitable for interlayer oxidation type uranium deposit. (author)

  13. Selective fluorescence quenching of nitrogen-containing polycyclic aromatic hydrocarbons by aliphatic amines

    International Nuclear Information System (INIS)

    Li Xiaoping; McGuffin, Victoria L.

    2004-01-01

    In this investigation, primary, secondary, and tertiary amines are evaluated for their efficiency and selectivity as fluorescence quenchers for polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). In general, the quenching efficiency tends to increase from primary to tertiary amine due to a greater number of alkyl groups that increase the electron-donating ability. However, the selectivity decreases from primary to tertiary amine. The effect of low concentrations of water is also examined. Because water can form hydrogen bonds with amines, the nonbonding electron pair is not available for interaction with the fluorophore, thus the quenching constant is decreased. These aliphatic amines are then applied to PAHs and N-PAHs and some interesting trends are observed. Whereas amino-PAHs remain virtually unquenched by different amines, aza-PAHs are all quenched well. The selectivity between aza-PAHs and amino-PAHs is as high as several hundred. This trend provides an easy and effective method to discriminate between these classes of N-PAHs. Moreover, the alternant aza-PAHs are quenched more than their corresponding alternant PAHs

  14. Complexes of vanadium (V) oxotrichloride with amides and tertiary amines

    International Nuclear Information System (INIS)

    Paul, R.C.; Sharma, N.C.; Sahi, Y.P.; Chadha, S.L.; Sharma, A.K.

    1975-01-01

    Vanadium(V) oxotrichloride forms dark brown hygroscopic solid complexes of the composition VOCl 3 .3B and VOCl 3 .2B' where B represents pyridine, α-, β-, and γ-picolines, quinoline, isoquinoline, urea, N-methylformamide or acetanilide while B' represents N, N'-dimethylformamide, N-methylacetamide or dimethylacetamide. These complexes have been characterized on the basis of their analytical and IR spectral data. (author)

  15. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Anita S.; Kitchin, John R.

    2012-10-24

    Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.

  16. A practical and catalyst-free trifluoroethylation reaction of amines using trifluoroacetic acid

    Science.gov (United States)

    Andrews, Keith G.; Faizova, Radmila; Denton, Ross M.

    2017-06-01

    Amines are a fundamentally important class of biologically active compounds and the ability to manipulate their physicochemical properties through the introduction of fluorine is of paramount importance in medicinal chemistry. Current synthesis methods for the construction of fluorinated amines rely on air and moisture sensitive reagents that require special handling or harsh reductants that limit functionality. Here we report practical, catalyst-free, reductive trifluoroethylation reactions of free amines exhibiting remarkable functional group tolerance. The reactions proceed in conventional glassware without rigorous exclusion of either moisture or oxygen, and use trifluoroacetic acid as a stable and inexpensive fluorine source. The new methods provide access to a wide range of medicinally relevant functionalized tertiary β-fluoroalkylamine cores, either through direct trifluoroethylation of secondary amines or via a three-component coupling of primary amines, aldehydes and trifluoroacetic acid. A reduction of in situ-generated silyl ester species is proposed to account for the reductive selectivity observed.

  17. Characterization of particulate amines

    International Nuclear Information System (INIS)

    Gundel, L.A.; Chang, S.G.; Clemenson, M.S.; Markowitz, S.S.; Novakov, T.

    1979-01-01

    The reduced nitrogen compounds associated with ambient particulate matter are chemically characterized by means of ESCA and proton activation analysis. Ambient particulate samples collected on silver filters in Berkeley, California were washed with water and organic solvents, and ESCA and proton activation analysis were performed in order to determine the composition of various nitrogen compounds and the total nitrogen content. It is found that 85% of the amines originally present in ambient particulate matter can be removed by water extraction, whereas the ammonium and nitrate are completely removed. An observed increase in ammonium ion in the extract, compared with its concentration in the original sample, coupled with the commensurate decrease in amine concentration, is attributed to the hydrolysis of amide groups, which may cause analytical methods based on extraction to yield erroneous results

  18. Solvent-free functionalization of carbon nanotube buckypaper with amines

    International Nuclear Information System (INIS)

    Basiuk, Elena V.; Ramírez-Calera, Itzel J.; Meza-Laguna, Victor; Abarca-Morales, Edgar; Pérez-Rey, Luis A.; Re, Marilena; Prete, Paola; Lovergine, Nico

    2015-01-01

    Graphical abstract: - Abstract: We demonstrate the possibility of fast and efficient solvent-free functionalization of buckypaper (BP) mats prefabricated from oxidized multiwalled carbon nanotubes (MWCNTs-ox), by using three representative amines of different structure: one monofunctional aliphatic amine, octadecylamine (ODA), one monofunctional aromatic amine, 1-aminopyrene (AP), and one aromatic diamine, 1,5-diaminonaphthalene (DAN). The functionalization procedure, which relies on the formation of amide bonds with carboxylic groups of MWCNTs-ox, is performed at 150–180 °C under reduced pressure and takes about 4 h including auxiliary degassing. The amine-treated BP samples (BP-ODA, BP-AP and BP-DAN, respectively) were characterized by means of a variety of analytical techniques such as Fourier-transform infrared and Raman spectroscopy, thermogravimetric and differential thermal analysis, scanning and transmission electron microscopy, scanning helium ion microscopy, and atomic force microscopy. The highest amine content was found for BP-ODA, and the lowest one was observed for BP-DAN, with a possible contribution of non-covalently bonded amine molecules in all three cases. Despite of some differences in spectral and morphological characteristics for amine-functionalized BP samples, they have in common a dramatically increased stability in water as compared to pristine BP and, on the other hand, a relatively invariable electrical conductivity.

  19. Microfluidic photoinduced chemical oxidation for Ru(bpy)33 + chemiluminescence - A comprehensive experimental comparison with on-chip direct chemical oxidation

    Science.gov (United States)

    Kadavilpparampu, Afsal Mohammed; Al Lawati, Haider A. J.; Suliman, Fakhr Eldin O.

    2017-08-01

    For the first time, the analytical figures of merit in detection capabilities of the very less explored photoinduced chemical oxidation method for Ru(bpy)32 + CL has been investigated in detail using 32 structurally different analytes. It was carried out on-chip using peroxydisulphate and visible light and compared with well-known direct chemical oxidation approaches using Ce(IV). The analytes belong to various chemical classes such as tertiary amine, secondary amine, sulphonamide, betalactam, thiol and benzothiadiazine. Influence of detection environment on CL emission with respect to method of oxidation was evaluated by changing the buffers and pH. The photoinduced chemical oxidation exhibited more universal nature for Ru(bpy)32 + CL in detection towards selected analytes. No additional enhancers, reagents, or modification in instrumental configuration were required. Wide detectability and enhanced emission has been observed for analytes from all the chemical classes when photoinduced chemical oxidation was employed. Some of these analytes are reported for the first time under photoinduced chemical oxidation like compounds from sulphonamide, betalactam, thiol and benzothiadiazine class. On the other hand, many of the selected analytes including tertiary and secondary amines such as cetirizine, azithromycin fexofenadine and proline did not produced any analytically useful CL signal (S/N = 3 or above for 1 μgmL- 1 analyte) under chemical oxidation. The most fascinating observations was in the detection limits; for example ofloxacin was 15 times more intense with a detection limit of 5.81 × 10- 10 M compared to most lowest ever reported 6 × 10- 9 M. Earlier, penicillamine was detected at 0.1 μg mL- 1 after derivatization using photoinduced chemical oxidation, but in this study, we improved it to 5.82 ng mL- 1 without any prior derivatization. The detection limits of many other analytes were also found to be improved by several orders of magnitude under

  20. 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.

  1. 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.

  2. Ultrasound-assisted oxidative desulfurization process of liquid fuel by phosphotungstic acid encapsulated in a interpenetrating amine-functionalized Zn(II)-based MOF as catalyst.

    Science.gov (United States)

    Afzalinia, Ahmad; Mirzaie, Abbas; Nikseresht, Ahmad; Musabeygi, Tahereh

    2017-01-01

    In this work, ultrasound-assisted oxidative desulfurization (UAOD) of liquid fuels performed with a novel heterogeneous highly dispersed Keggin-type phosphotungstic acid (H 3 PW 12 O 40 , PTA) catalyst that encapsulated into an amino-functionalized MOF (TMU-17-NH 2 ). The prepared composite exhibits high catalytic activity and reusability in oxidative desulfurization of model fuel. Ultrasound-assisted oxidative desulfurization (UAOD) is a new way to performed oxidation reaction of sulfur-contain compounds rapidly, economically, environment-friendly and safely, under mild conditions. Ultrasound waves can be apply as an efficient tool to decrease the reaction time and improves oxidative desulfurization system performance. PTA@TMU-17-NH 2 could be completely performed desulfurization of the model oil by 20mg of catalyst, O/S molar ratio of 1:1 in presence of MeCN as extraction solvent. The obtained results indicated that the conversions of DBT to DBTO 2 achieve 98% after 15min in ambient temperature. In this work, we prepared TMU-17-NH 2 and PTA/TMU-17-NH 2 composite by ultrasound irradiation for first time and employed in UAOD process. Prepared catalyst exhibit an excellent reusability without PTA leaching and loss of activity. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  3. Redox reactions of Cu(II)-amine complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Kumbhar, A.G.; Kishore, Kamal

    2003-01-01

    A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu 2+ and Ni 2+ ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e aq - with a number of Cu(II)-amine complexes have been determined by following the decay of e aq - absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the λ max of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron oxidation of Cu(II) amine complexes was studied using azidyl radicals for the oxidation reaction as OH radicals react with the alcohol groups present in the amines used in this study. Cu(III)-amine complexes were found to be unstable and decayed by second-order kinetics

  4. The economics of amine usage

    International Nuclear Information System (INIS)

    Fountain, M.J.

    1994-01-01

    The EPRI computer programm, 'Aminemod', a PWR chemistry model, has been used to compare the technical advantages of the 'advanced' amines, ethanolamine, 1,2 diaminoethane and 5 aminopentanol over morpholine in generating an elevated pH in the moisture separator and the economics of using these amines has been assessed by using an MS Excel spreadsheet in conjunction with Aminemod. The advanced amines are capable of achieving 1 pH unit above neutrality, the EPRI target for prevention of erosion-corrison, at acceptable cost and, compared with 'conventional' amines, at considerably reduced ionic load on the condensate polisher. The exercise demonstrates that it is essential to evaluate the effect of an amine dosing regime on the total operating cost and that it is not possible to prejudge the economic outcome on the basis of an amine's purchase price. (orig.)

  5. Oxidative versus Non-oxidative Decarboxylation of Amino Acids: Conditions for the Preferential Formation of Either Strecker Aldehydes or Amines in Amino Acid/Lipid-Derived Reactive Carbonyl Model Systems.

    Science.gov (United States)

    Zamora, Rosario; León, M Mercedes; Hidalgo, Francisco J

    2015-09-16

    Comparative formation of both 2-phenylethylamine and phenylacetaldehyde as a consequence of phenylalanine degradation by carbonyl compounds was studied in an attempt to understand if the amine/aldehyde ratio can be changed as a function of reaction conditions. The assayed carbonyl compounds were selected because of the presence in the chain of both electron-donating and electron-withdrawing groups and included alkenals, alkadienals, epoxyalkenals, oxoalkenals, and hydroxyalkenals as well as lipid hydroperoxides. The obtained results showed that the 2-phenylethylamine/phenylacetaldehyde ratio depended upon both the carbonyls and the reaction conditions. Thus, it can be increased using electron-donating groups in the chain of the carbonyl compound, small amounts of carbonyl compound, low oxygen content, increasing the pH, or increasing the temperature at pH 6. Opposed conditions (use of electron-withdrawing groups in the chain of the carbonyl compound, large amounts of carbonyl compound, high oxygen contents, low pH values, and increasing temperatures at low pH values) would decrease the 2-phenylethylamine/phenylacetaldehyde ratio, and the formation of aldehydes over amines in amino acid degradations would be favored.

  6. Using Amines and Alkanes as Thermal-Runaway Retardants for Lithium-Ion Battery

    Science.gov (United States)

    Shi, Yang

    Thermal runaway imposes major challenges to large-scale lithium-ion batteries (LIBs). The working temperature of a LIB is usually around room temperature. However, upon mechanical abuse such as an impact or nail penetration, LIB cell components may fail and internal short circuits could be formed. As a result, a series of exothermic electrochemical reactions and decompositions would take place and the local temperature can rapidly increase. In this thesis, a few novel techniques are investigated to mitigate thermal runaway of LIBs. Mechanically triggered approach has been employed. Thermal-runaway retardant (TRR) is encapsulated in mechanically responsive packages made of materials inert to the battery environment, and upon external mechanical loadings the packages can be broken apart and release the TRR. This mechanism allows for the use of aggressive chemicals to suppress the short circuit discharge and reduce the subsequent exothermic phenomena, immediately after the battery is damaged even before temperature increase begins. The best TRR candidates are identified to be amines and alkanes. Among amines, secondary amines and tertiary amines perform better than primary amines. The reduction in electrolyte ionic conductivity and the displacement of electrolyte are the thermal-runaway-mitigation mechanisms of the secondary and the tertiary amines, respectively. Pentadecane is the best candidate among the alkanes under investigation, with the major working mechanism being electrolyte displacement. Impact tests on large pouch cells and high-energy battery chemistry were also performed; the results were quite encouraging.

  7. 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.

  8. Ligand-Enabled γ-C(sp(3))-H Olefination of Amines: En Route to Pyrrolidines.

    Science.gov (United States)

    Jiang, Heng; He, Jian; Liu, Tao; Yu, Jin-Quan

    2016-02-17

    Pd(II)-catalyzed olefination of γ-C(sp(3))-H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp(3))-H olefination reactions. The use of Ns protecting group to direct C(sp(3))-H activation of alkyl amines is also a significant step toward practical C-H functionalizations of alkyl amines.

  9. Molecular Evolution and Functional Divergence of Trace Amine-Associated Receptors.

    Directory of Open Access Journals (Sweden)

    Seong-Il Eyun

    Full Text Available Trace amine-associated receptors (TAARs are a member of the G-protein-coupled receptor superfamily and are known to be expressed in olfactory sensory neurons. A limited number of molecular evolutionary studies have been done for TAARs so far. To elucidate how lineage-specific evolution contributed to their functional divergence, we examined 30 metazoan genomes. In total, 493 TAAR gene candidates (including 84 pseudogenes were identified from 26 vertebrate genomes. TAARs were not identified from non-vertebrate genomes. An ancestral-type TAAR-like gene appeared to have emerged in lamprey. We found four therian-specific TAAR subfamilies (one eutherian-specific and three metatherian-specific in addition to previously known nine subfamilies. Many species-specific TAAR gene duplications and losses contributed to a large variation of TAAR gene numbers among mammals, ranging from 0 in dolphin to 26 in flying fox. TAARs are classified into two groups based on binding preferences for primary or tertiary amines as well as their sequence similarities. Primary amine-detecting TAARs (TAAR1-4 have emerged earlier, generally have single-copy orthologs (very few duplication or loss, and have evolved under strong functional constraints. In contrast, tertiary amine-detecting TAARs (TAAR5-9 have emerged more recently and the majority of them experienced higher rates of gene duplications. Protein members that belong to the tertiary amine-detecting TAAR group also showed the patterns of positive selection especially in the area surrounding the ligand-binding pocket, which could have affected ligand-binding activities and specificities. Expansions of the tertiary amine-detecting TAAR gene family may have played important roles in terrestrial adaptations of therian mammals. Molecular evolution of the TAAR gene family appears to be governed by a complex, species-specific, interplay between environmental and evolutionary factors.

  10. Potential occupational risk of amines in carbon capture for power generation.

    Science.gov (United States)

    Gentry, P Robinan; House-Knight, Tamara; Harris, Angela; Greene, Tracy; Campleman, Sharan

    2014-08-01

    While CO2 capture and storage (CCS) technology has been well studied in terms of its efficacy and cost of implementation, there is limited available data concerning the potential for occupational exposure to amines, mixtures of amines, or degradation of by-products from the CCS process. This paper is a critical review of the available data concerning the potential effects of amines and CCS-degradation by-products. A comprehensive review of the occupational health and safety issues associated with exposure to amines and amine by-products at CCS facilities was performed, along with a review of the regulatory status and guidelines of amines, by-products, and CCS process vapor mixtures. There are no specific guidelines or regulations regarding permissible levels of exposure via air for amines and degradation products that could form atmospheric oxidation of amines released from post-combustion CO2 capture plants. While there has been a worldwide effort to develop legal and regulatory frameworks for CCS, none are directly related to occupational exposures. By-products of alkanolamine degradation may pose the most significant health hazard to workers in CCS facilities, with several aldehydes, amides, nitramines, and nitrosamines classified as either known or potential/possible human carcinogens. The absence of large-scale CCS facilities; absence and unreliability of reported data in the literature from pilot facilities; and proprietary amine blends make it difficult to estimate potential amine exposures and predict formation and exposure to degradation products.

  11. Carbon Dioxide-Mediated C(sp3)-H Arylation of Amine Substrates.

    Science.gov (United States)

    Kapoor, Mohit; Liu, Daniel; Young, Michael C

    2018-05-25

    Elaborating amines via C-H functionalization has been an important area of research over the past decade but has generally relied on an added directing group or sterically hindered amine approach. Since free-amine-directed C(sp 3 )-H activation is still primarily limited to cyclization reactions and to improve the sustainability and reaction scope of amine-based C-H activation, we present a strategy using CO 2 in the form of dry ice that facilitates intermolecular C-H arylation. This methodology has been used to enable an operationally simple procedure whereby 1° and 2° aliphatic amines can be arylated selectively at their γ-C-H positions. In addition to potentially serving as a directing group, CO 2 has also been demonstrated to curtail the oxidation of sensitive amine substrates.

  12. Novel acid-base hybrid membrane based on amine-functionalized reduced graphene oxide and sulfonated polyimide for vanadium redox flow battery

    International Nuclear Information System (INIS)

    Cao, Li; Sun, Qingqing; Gao, Yahui; Liu, Luntao; Shi, Haifeng

    2015-01-01

    A series of novel acid-base hybrid membranes (SPI/PEI-rGO) based on sulfonated polyimide (SPI) with polyethyleneimine-functionalized reduced graphene oxide (PEI-rGO) are prepared by a solution-casting method for vanadium redox flow battery (VRB). FT-IR and XPS results prove the successful fabrication of PEI-rGO and SPI/PEI-rGO hybrid membranes, which show a dense and homogeneous structure observed by SEM. The physicochemical properties such as water uptake, swelling ratio, ion exchange capacity, proton conductivity and vanadium ion permeability are well controlled by the incorporated PEI-rGO fillers. The interfacial-formed acid-base pairs between PEI-rGO and SPI matrix effectively reduce the swelling ratio and vanadium ion permeability, increasing the stability performance of the hybrid membranes. SPI/PEI-rGO-2 hybrid membrane exhibits a higher coulombic efficiency (CE, 95%) and energy efficiency (EE, 75.6%) at 40 mA cm −2 , as compared with Nafion 117 membrane (CE, 91% and EE, 66.8%). The self-discharge time of the VRB with SPI/PEI-rGO-2 hybrid membrane (80 h) is longer than that of Nafion 117 membrane (26 h), demonstrating the excellent blocking ability for vanadium ion. After 100 charge-discharge cycles, SPI/PEI-rGO-2 membrane exhibits the good stability under strong oxidizing and acid condition, proving that SPI/PEI-rGO acid-base hybrid membranes could be used as the promising candidates for VRB applications

  13. Modular functionalization of allenes to aminated stereotriads.

    Science.gov (United States)

    Adams, Christopher S; Boralsky, Luke A; Guzei, Ilia A; Schomaker, Jennifer M

    2012-07-04

    Nitrogen-containing stereotriads, compounds with three adjacent stereodefined carbons, are commonly found in biologically important molecules. However, the preparation of molecules bearing these motifs can be challenging. Herein, we describe a modular oxidation protocol which converts a substituted allene to a triply functionalized amine of the form C-X/C-N/C-Y. The key step employs a Rh-catalyzed intramolecular conversion of the allene to a strained bicyclic methylene aziridine. This reactive intermediate is further elaborated to the target products, often in one reaction vessel and with effective transfer of the axial chirality of the allene to point chirality in the stereotriad.

  14. 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.

  15. 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.

  16. Structural Influence on Excited State Dynamics in Simple Amines

    DEFF Research Database (Denmark)

    Klein, Liv Bærenholdt

    experiments with calculations, provides new insight into the nature of the internal conversion processes that mediate the dynamical evolution between Rydberg states, and how structural variations in simple amine system have a large impact on the non-adiabatic processes. The experimental method of choice...... is femtosecond time-resolved photoelectron velocity map imaging (VMI), which is a newtechnique in the Copenhagen lab. The design, building and implementation of the VMI spectrometer has been a very substantial part of the thesis work. This techniques oers enhanced information content in the form of ecient...... and sensitive collection of photoelectron spectra. In particular, the angleresolved data available from the VMI approach provides highly detailed mechanistic insight about the relaxation pathways. One striking novel nding is that for tertiary amines, the critical factor driving the non-adiabatic dynamics...

  17. Cloud condensation nuclei activity of aliphatic amine secondary aerosol

    Science.gov (United States)

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

  18. Enzymatic network for production of ether amines from alcohols

    NARCIS (Netherlands)

    Palacio, Cyntia M.; Crismaru, Gica Ciprian; Bartsch, Sebastian; Navickas, Vaidotas; Ditrich, Klaus; Breuer, Michael; Abu, Rohana; Woodley, John; Baldenius, Kai-Uwe; Wu, Bian; Janssen, Dick

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production of the

  19. The economics of amine usage

    International Nuclear Information System (INIS)

    Fountain, M.J.

    1994-01-01

    Research carried out over the past decade in the USA (funded by EPRI) and by the CEGB/Nuclear Electric in the UK has identified several thermally stable, low-toxicity 'advanced' amines with good high-temperature basicity and low steam-water distribution ratio. As a direct result of this work several US PWR stations are now evaluating monoethanolamine (ETA) and Nuclear Electric's Wylfa Power Station (magnox) now doses 5 aminopentanol (5AP) instead of AMP, which had successfully combated erosion-corrosion for the past nine years. It has recently been stated that the use of 5AP ''...could save Nuclear Electric up to 1.5M pounds per year''. To provide US power station chemists with a tool for tailoring amine dosage to their own plant requirements EPRI has developed a computer model, Aminmod, which can, with user-defined circuit parameters and amine feed concentrations, calculate amine concentrations and pH(t) values at various points around the circuit. To complement this model a user-friendly spreadsheet program is being developed which will work in conjunction with Aminmod, via active links, to calculate the total operating cost associated with the selected amine dosing regime and compare alternative scenarios. This paper discusses the relationship between the technical and economic aspects of choosing an amine dosing regime and draws on combined Aminmod/spreadsheet results to illustrate how differences in amine properties can influence the optimum economic solution for a typical PWR. (author). 3 figs., 2 tabs., 5 refs

  20. 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.

  1. Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization.

    Science.gov (United States)

    Clark, Joseph R; Feng, Kaibo; Sookezian, Anasheh; White, M Christina

    2018-06-01

    Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Brønsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

  2. Fishmeal with different levels of biogenic amines in Aquafeed: Comparison of feed protein quality, fish growth performance, and metabolism

    DEFF Research Database (Denmark)

    Jasour, Mohammad Sedigh; Wagner, Liane; Sundekilde, Ulrik Kræmer

    2018-01-01

    The current study investigated the effects of fishmeal quality (low (LB) and high (HB) levels of endogenous biogenic amines) and feed extrusion temperatures (100 and 130 °C) on protein oxidation indicators and amino acids racemization (AAR) in extruded fish feed. Furthermore, the study investigated......, secondary oxidation products, and racemized methionine correlated positively with a low content of biogenic amines, whereas the primary oxidation product, protein hydroperoxides, and in vivo AAs digestibility correlated positively with high content of biogenic amines. At an extrusion temperature of 100 °C......, the growth performance of the fish decreased when the content of biogenic amines increased. In contrast, at an extrusion temperature of 130 °C, the growth performance was unaffected by the level of biogenic amines. The latter could be a consequence of the higher level of protein oxidation of LB fishmeal...

  3. Enzymatic network for production of ether amines from alcohols

    DEFF Research Database (Denmark)

    Palacio, Cyntia M.; Crismaru, Ciprian G.; Bartsch, Sebastian

    2016-01-01

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production...... of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed...... for reactions containing 10mM alcohol and up to 280mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up....

  4. Devulcanization of Waste Tire Rubber Using Amine Based Solvents and Ultrasonic Energy

    Directory of Open Access Journals (Sweden)

    Walvekar Rashmi

    2018-01-01

    Full Text Available This research project focuses on an alternative pathway of devulcanizing waste tire rubber by using amine based chemicals. Waste tire rubbers are known to be as toxic, non-degradable material due to their vulcanized crosslink carbon structure, and disposing of such waste could impose hazardous impacts on the environment. The current rubber recycling methods that are practiced today are rather uneconomical, non-environmentally friendly, and also producing recycled rubber with low quality due to the alteration in the main polymeric chains of waste rubber. This project aims to answer the question of whether the usage of amine can produce high quality rubber, where the properties of recycled rubber is almost the same as new/virgin rubber. With known potential of amine, it is a challenge for the chemical to selectively cleave the sulfur bonds without affecting the main carbon backbone chain in the rubber structure and diminishing much of the rubber properties. To study this research, amine-treated rubber must undergo devulcanisation process by applying heat and sonication energy. Then, the properties of the amine-treated rubber were determined through a set of characterization tests and analysis which are: gel content test to determine the weight of rubber before and after devulcanization, the thermogravimetric analysis (TGA to determine the thermal degradation and stability of rubber, and Fourier Transform Infrared Spectroscopy (FTIR to determine any structural change of the rubber. In this research so far, the first two preliminary analysis tests have been performed. The gel content test has shown that tertiary amine samples possessed a lower gel content (% of (77 – 63 %, compared to primary amine samples (falls within the range of 80%, as well as the TGA test in which tertiary amine samples degrade faster than primary amine samples (suggesting a higher degree of rubber structure breakdown. For each type of amine, the concertation of amine did

  5. Reaction constants, in cyclohexane, of lauryl-amines with tetrabromo-phenolphthalein magenta E acid

    International Nuclear Information System (INIS)

    Perez, J.J.

    1966-11-01

    Trilauryl amine is an extracting agent used for plutonium purification. Its main degradation product is di-laurylamine. The titration of this impurity is carried out by spectro-colorimetry in cyclohexane using bromophtalein Magenta E as coloured acid indicator. The reported dissociation constants for alcoylammonium salts are too closed to lead to a discrimination between secondary and tertiary amines. The present spectrophotometric study shows that the ratios of various dissociation constants for bromophtalein Magenta E salts are notably different from those for salts of simple coloured acids like 2,4 dinitro phenol. The structural changes accompanying the colorations are discussed in order to explain this phenomenon. (author) [fr

  6. Degradation of amine-based water treatment polymers during chloramination as N-nitrosodimethylamine (NDMA) precursors.

    Science.gov (United States)

    Park, Sang-Hyuck; Wei, Shuting; Mizaikoff, Boris; Taylor, Amelia E; Favero, Cedrick; Huang, Ching-Hua

    2009-03-01

    Recent studies indicated that water treatment polymers such as poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) may form N-nitrosodimethylamine (NDMA) when in contact with chloramine water disinfectants. To minimize such potential risk and improve the polymer products, the mechanisms of how the polymers behave as NDMA precursors need to be elucidated. Direct chloramination of polymers and intermediate monomers in reagent water was conducted to probe the predominant mechanisms. The impact of polymer properties including polymer purity, polymer molecular weight and structure, residual dimethylamine (DMA), and other intermediate compounds involved in polymer synthesis, and reaction conditions such as pH, oxidant dose, and contact time on the NDMA formation potential (NDMA-FP) was investigated. Polymer degradation after reaction with chloramines was monitored at the molecular level using FT-IR and Raman spectroscopy. Overall, polyamines have greater NDMA-FP than polyDADMAC, and the NDMA formation from both polymers is strongly related to polymer degradation and DMA release during chloramination. Polyamines' tertiary amine chain ends play a major role in their NDMA-FP, while polyDADMACs' NDMA-FP is related to degradation of the quaternary ammonium ring group.

  7. Amine Swingbed Payload Project Management

    Science.gov (United States)

    Walsch, Mary; Curley, Su

    2013-01-01

    The International Space Station (ISS) has been designed as a laboratory for demonstrating technologies in a microgravity environment, benefitting exploration programs by reducing the overall risk of implementing such technologies in new spacecraft. At the beginning of fiscal year 2010, the ISS program manager requested that the amine-based, pressure-swing carbon dioxide and humidity absorption technology (designed by Hamilton Sundstrand, baselined for the Orion Multi-Purpose Crew Vehicle, and tested at the Johnson Space Center in relevant environments, including with humans, since 2005) be developed into a payload for ISS Utilization. In addition to evaluating the amine technology in a flight environment before the first launch of the Orion vehicle, the ISS program wanted to determine the capability of the amine technology to remove carbon dioxide from the ISS cabin environment at the metabolic rate of the full 6 ]person crew. Because the amine technology vents the absorbed carbon dioxide and water vapor to space vacuum (open loop), additional hardware needed to be developed to minimize the amount of air and water resources lost overboard. Additionally, the payload system would be launched on two separate Space Shuttle flights, with the heart of the payload-the swingbed unit itself-launching a full year before the remainder of the payload. This paper discusses the project management and challenges of developing the amine swingbed payload in order to accomplish the technology objectives of both the open -loop Orion application as well as the closed-loop ISS application.

  8. Electrodeposition of amine-terminatedpoly(ethylene glycol) to titanium surface

    International Nuclear Information System (INIS)

    Tanaka, Yuta; Doi, Hisashi; Iwasaki, Yasuhiko; Hiromoto, Sachiko; Yoneyama, Takayuki; Asami, Katsuhiko; Imai, Hachiro; Hanawa, Takao

    2007-01-01

    The immobilization of poly(ethylene glycol), PEG, to a solid surface is useful to functionalize the surface, e.g., to prevent the adsorption of proteins. No successful one-stage technique for the immobilization of PEG to base metals has ever been developed. In this study, PEG in which both terminals or one terminal had been modified with amine bases was immobilized onto a titanium surface using electrodeposition. PEG was dissolved in a NaCl solution, and electrodeposition was carried out at 310 K with - 5 V for 300 min. The thickness of the deposited PEG layer was evaluated using ellipsometry, and the bonding manner of PEG to the titanium surface was characterized using X-ray photoelectron spectroscopy after electrodeposition. The results indicated that a certain amount of PEG was adsorbed on titanium through both electrodeposition and immersion when PEG was terminated by amine. However, terminated amines existed at the surface of titanium and were combined with titanium oxide as N-HO by electrodeposition, while amines randomly existed in the molecule and showed an ionic bond with titanium oxide by immersion. The electrodeposition of PEG was effective for the inhibition of albumin adsorption. This process is useful for materials that have electroconductivity and a complex morphology

  9. Cheminformatics Modeling of Amine Solutions for Assessing their CO2 Absorption Properties.

    Science.gov (United States)

    Kuenemann, Melaine A; Fourches, Denis

    2017-07-01

    As stricter regulations on CO 2 emissions are adopted worldwide, identifying efficient chemical processes to capture and recycle CO 2 is of critical importance for industry. The most common process known as amine scrubbing suffers from the lack of available amine solutions capable of capturing CO 2 efficiently. Tertiary amines characterized by low heats of reaction are considered good candidates but their absorption properties can significantly differ from one analogue to another despite high structural similarity. Herein, after collecting and curating experimental data from the literature, we have built a modeling set of 41 amine structures with their absorption properties. Then we analyzed their chemical composition using molecular descriptors and non-supervised clustering. Furthermore, we developed a series of quantitative structure-property relationships (QSPR) to assess amines' CO 2 absorption properties from their structural characteristics. These models afforded reasonable prediction performances (e. g., Q 2 LOO =0.63 for CO 2 absorption amount) even though they are solely based on 2D chemical descriptors and individual machine learning techniques (random forest and neural network). Overall, we believe the chemical analysis and the series of QSPR models presented in this proof-of-concept study represent new knowledge and innovative tools that could be very useful for screening and prioritizing hypothetical amines to be synthesized and tested experimentally for their CO 2 absorption properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Tris{2-[(2-aminobenzylideneamino]ethyl}amine

    Directory of Open Access Journals (Sweden)

    Perla Elizondo Martínez

    2010-12-01

    Full Text Available The title Schiff base, C27H33N7, is a tripodal amine displaying C3 symmetry, with the central tertiary N atom lying on the threefold crystallographic axis. The N—CH2—CH2—N conformation of the pendant arms is gauche [torsion angle = 76.1 (3°], which results in a claw-like molecule, with the terminal aniline groups wrapped around the symmetry axis. The lone pair of the apical N atom is clearly oriented inwards towards the cavity, and should thus be chemically inactive. The amine NH2 substituents lie in the plane of the benzene ring to which they are bonded. With such an arrangement, one amine H atom forms an S(6 motif through a weak N—H...N hydrogen bond with the imine N atom, while the other is engaged in an intermolecular N—H...π contact involving the benzene ring of a neighbouring molecule related by inversion. The benzene rings also participate in an intramolecular C—H...π contact of similar strength. In the crystal structure, molecules are separated by empty voids (ca 5% of the crystal volume, although the crystal seems to be unsolvated.

  11. Regularities of synthesis and mechanism of polycondensation of aromatic amines

    International Nuclear Information System (INIS)

    Matnishyan, Hagob

    2002-01-01

    Full text.Aniline polymers and its derivatives are widely used in modern electronics, electrical engineering and manufacturing of various appliances. They are used for production of electrical power sources, probes and sensors, composite materials absorbing high frequency radiations, anticorrosion coatings, nonlinear optical devices-such as lasers, cathode ray tubes, photodiodes etc. Such a wide usage of aromatic amine polymers brings up new demands to their structure and properties, which is dependent on conditions of synthesis and forming of the hard phase. The presented article describes regularities and mechanisms of oxidative polycondensation of aromatic amines. Several types of polymers have been synthesized by chemical and electrochemical oxidation of aniline and its chlor-, brom-, iodo-, nitro-, p-substituted derivatives; diphenylamine, benzidine and phenylenediamines in nonwater media. On the basis of kinetic and electrochemical studies and literature analysis we suggested a mechanism of polycondensation of aromatic amines. According to it, oxidation of amines starts with the electron transfer with cation-radical formation on the first stage, which stabilizes in acid environments due to complex formation with initial amine. Dimer formation and further growth of chain takes place upon another electron transfer from formed complex, which results in forming of macromolecules. We also suggested a scheme for obtaining of structures defect in media assisting in deprotonizing of cation radicals and formation of arylamine radical centers. Those processes lead to formation of azo- and diphenyl fragments in the main chain of the polymer and predetermine the possibility of chain disruption. We also considered reactions leading to formation of branched polymers and cyclic structures, such as phenazine in particular. The peculiarity of electrochemical process lies in regulation of concentration of active centres on the positive electrode surface

  12. Characterization of the in vitro binding and inhibition kinetics of primary amine oxidase/vascular adhesion protein-1 by glucosamine.

    LENUS (Irish Health Repository)

    Olivieri, Aldo

    2012-04-01

    Primary-amine oxidase (PrAO) catalyzes the oxidative deamination of endogenous and exogenous primary amines and also functions, in some tissues, as an inflammation-inducible endothelial factor, known as vascular adhesion protein-1. VAP-1 mediates the slow rolling and adhesion of lymphocytes to endothelial cells in a number of inflammatory conditions, including inflammation of the synovium.

  13. Supported polytertiary amines: highly efficient and selective SO2 adsorbents.

    Science.gov (United States)

    Tailor, Ritesh; Abboud, Mohamed; Sayari, Abdelhamid

    2014-01-01

    Tertiary amine containing poly(propyleneimine) second (G2) and third (G3) generation dendrimers as well as polyethyleneimine (PEI) were developed for the selective removal of SO2. N-Alkylation of primary and secondary amines into tertiary amines was confirmed by FTIR and NMR analysis. Such modified polyamines were impregnated on two nanoporous supports, namely, SBA-15PL silica with platelet morphology and ethanol-extracted pore-expanded MCM-41 (PME) composite. In the presence of 0.1% SO2/N2 at 23 °C, the uptake of modified PEI, G2, and G3 supported on SBA-15PL was 2.07, 2.35, and 1.71 mmol/g, respectively; corresponding to SO2/N ratios of 0.22, 0.4, and 0.3. Under the same conditions, the SO2 adsorption capacity of PME-supported modified PEI and G3 was significantly higher, reaching 4.68 and 4.34 mmol/g, corresponding to SO2/N ratios of 0.41 and 0.82, respectively. The working SO2 adsorption capacity decreased with increasing temperature, reflecting the exothermic nature of the process. The adsorption capacity of these materials was enhanced dramatically in the presence of humidity in the gas mixture. FTIR data before SO2 adsorption and after adsorption and regeneration did not indicate any change in the materials. Nonetheless, the SO2 working capacity decreased in consecutive adsorption/regeneration cycles due to evaporation of impregnated polyamines, rather than actual deactivation. FTIR and (13)C and (15)N CP-MAS NMR of fresh and SO2 adsorbed modified G3 on PME confirmed the formation of a complexation adduct.

  14. Interaction of biogenic amines with ethanol.

    Science.gov (United States)

    Smith, A A

    1975-01-01

    Ethanol through its primary catabolite, acetaldehyde, competitively inhibits oxidation of aldehyde dehydrogenase substrates. As a consequence biogenic amines form increased quantities of alcohols rather than the corresponding acids. During this biotransformation, condensation reactions between deaminated and intact amines may occur which can yield tetrahydropapaverolines. These compounds are closely related to precursors of opioids which is cause to link ethanol abuse to morphine addiction. There is, however, no pharmacological or clinical evidence suggesting similarities between ethanol dependence or opiod addiction. Acetaldehyde plays an additional role in alkaloidal formation in vitro. Biogenic amines may react with acetaldehyde to form isoquinoline or carboline compounds. Some of these substances have significant pharmacological activity. Furthermore, they may enter neural stores and displace the natural neurotransmitter. Thus, they can act as false neurotransmitters. Some investigators believe that chronic ethanol ingestion leads to significant formation of such aberrant compounds which may then upset autonomic nervous system balance. This disturbance may explain the abnormal sympathetic activity seen in withdrawal. While these ideas about the etiology of alcohol abuse have a definite appeal, they are naturally based on in vitro preliminary work. Much study of the quantitative pharmacology of these compounds in animals is required before judgement can be made as to the merits of the proposed hypotheses. In the meantime, pharmacological studies on the ability of ethanol to depress respiration in the mouse has revealed that unlike opioids or barbituates, respiratory depression induced by ethanol requires the presence in brain of serotonin. This neurotransmitter also mediates the respiratory effects of several other alcohols but curiously, not chloral hydrate, yet this compound is purported to alter biogenic amine metabolism much like ethanol. Thus, the response

  15. Deposition of stable amine coating onto polycaprolactone nanofibers by low pressure cyclopropylamine plasma polymerization

    International Nuclear Information System (INIS)

    Manakhov, Anton; Nečas, David; Čechal, Jan; Pavliňák, David; Eliáš, Marek

    2015-01-01

    Amine-rich films are of high interest for the bio-applications including drug delivery and tissue engineering thanks to their high reactivity allowing the formation of the covalent linkages between biomolecules and a surface. However, the bio-applications of amine-rich films require their good stability in water which is often achieved at large expenses of the amine concentration. Recently, non-toxic cyclopropylamine (CPA) has been applied for the plasma polymerization of films bearing high NH x environment combined with the moderate thickness loss (20%) after water immersion for 48 h. In this work, the amine-rich film with the NH x concentration over 7 at.% was deposited on Si substrates and polycaprolactone nanofiber meshes by using CPA plasma polymerization (pulsed mode) in a vertically oriented stainless steel reactor. The substrates were placed at the radio frequency electrode and the ion bombardment caused by direct-current self-bias was suppressed by using high pressure of 50 Pa. Analysis of samples by scanning electron microscopy did not reveal any cracks in the deposited layer formed during a sample immersion in water. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed a slight oxidation of amine groups in water but the film still contained 5 at.% of NH x (according to the N1s XPS fitting) after the immersion. The rapid oxidation of amine groups was observed during the aging experiment carried out in air at room temperature because FTIR revealed an increase of amide peaks that increased progressively with aging time. However, this oxidation was significantly reduced if the plasma polymer was stored at − 20 °C. Since the films exhibit high amine concentration and very good water stability they have great potential for applications as biocompatible functional coatings. - Highlights: • Cyclopropylamine plasma polymers deposited on polycaprolactone nanofibers • Amine-rich films with high water stability

  16. Bacterial degradation of monocyclic aromatic amines

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora

    2015-08-01

    Full Text Available Aromatic amines are an important group of industrial chemicals, which are widely used for manufacturing of dyes, pesticides, drugs, pigments, and other industrial products. These compounds have been considered highly toxic to human beings due to their carcinogenic nature. Three groups of aromatic amines have been recognized: monocyclic, polycyclic and heterocyclic aromatic amines. Bacterial degradation of several monocyclic aromatic compounds has been studied in a variety of bacteria, which utilizes monocyclic aromatic amines as their sole source of carbon and energy. Several degradation pathways have been proposed and the related enzymes and genes have also been characterized. Many reviews have been reviewed toxicity of monocyclic aromatic amines; however, there is lack of review on biodegradation of monocyclic aromatic amines. The aim of this review is to summarize bacterial degradation of monocyclic aromatic amines. This review will increase our current understanding of biochemical and molecular basis of bacterial degradation of monocyclic aromatic amines.

  17. Dimethylzinc-Initiated Radical Coupling of β-Bromostyrenes with Ethers and Amines

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Ahlburg, Andreas; Madsen, Robert

    2015-01-01

    A new coupling reaction has been developed in which β-bromostyrenes react with ethers and tertiary amines to introduce the styryl group in the α-position. The transformation is mediated by Me2Zn/O2 with 10 % MnCl2 and is believed to proceed by a radical addition-elimination mechanism. The ether...... and the amine are employed as solvent and the coupling takes place through the most stable α radical for unsymmetrical substrates. The products are obtained in moderate to good yields as the pure E isomers. The coupling can be achieved with a range of smaller cyclic and acyclic ethers/amines as well as various...

  18. Electron beam induced electronic transport in alkyl amine-intercalated VOx nanotubes

    International Nuclear Information System (INIS)

    O'Dwyer, C.; Lavayen, V.; Clavijo-Cedeno, C.; Torres, C.M.S.

    2008-01-01

    The electron beam induced electronic transport in primary alkyl amine-intercalated V 2 O 5 nanotubes is investigated where the organic amine molecules are employed as molecular conductive wires to an aminosilanized substrate surface and contacted to Au interdigitated electrode contacts. The results demonstrate that the high conductivity of the nanotubes is related to the non-resonant tunnelling through the amine molecules and a reduced polaron hopping conduction through the vanadium oxide itself. Both nanotube networks and individual nanotubes exhibit similarly high conductivities where the minority carrier transport is bias dependent and nanotube diameter invariant. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. New insights into controlling tube-bundle fouling using alternative amines

    Energy Technology Data Exchange (ETDEWEB)

    Turner, C.W.; Klimas, S.J.; Guzonas, D.A.; Fruzzetti, K. [Atomic Energy of Canada Ltd. (Canada); Frattini, P.L. [Electric Power Research Inst. (United States)

    2002-07-01

    A volatile amine is added to the secondary heat-transport system of a nuclear power plant to reduce the rate of corrosion and corrosion product transport in the feedwater and to protect steam generator (SG) crevices and materials exposed to steam condensate. Volatility and base strength of the amine at the SG operating temperature are two important considerations when choosing the optimum amine (or mixture of amines) for corrosion control in the steam cycle. The investigation has found that the rate of tube-bundle fouling is strongly dependent upon the surface chemistry of the corrosion products. For example, the fouling rates of fully oxidized iron oxides, such as hematite and lepidocrocite, are at least an order of magnitude greater than the fouling rate of magnetite under identical operating conditions. The difference is related to the sign of the surface charge on the corrosion products at temperature. The choice of amine for pH-control also influences the fouling rate. This was originally thought to be a surface-charge effect as well, but recent tests have suggested that it is related to the role that the amine plays in governing the rate of deposit consolidation on the heat-transfer surface. Amines that promote a high rate of deposit consolidation result in a low rate of deposit removal and a high fouling rate. Conversely, amines that tend to inhibit deposit consolidation produce a higher rate of deposit removal and a lower fouling rate. Dimethyl-amine and dodecyl-amine have been identified as two amines that inhibit the rate of deposit consolidation and, consequently, result in fouling rates that are up to 5 times lower than rates measured for amines that promote consolidation. A significant difference between morpholine (high fouling rate) and dimethyl-amine (low fouling rate) is that the latter desorbs more slowly from the surface of magnetite. How to account for a correlation between slow desorption kinetics and lower rate constants for deposition and

  20. New insights into controlling tube-bundle fouling using alternative amines

    International Nuclear Information System (INIS)

    Turner, C.W.; Klimas, S.J.; Guzonas, D.A.; Frattini, P.L.; Fruzzetti, K.

    2002-01-01

    A volatile amine is added to the secondary heat-transport system of a nuclear power plant to reduce the rate of corrosion and corrosion product transport in the feedwater and to protect steam generator (SG) crevices and materials exposed to steam condensate. Volatility and base strength of the amine at the SG operating temperature are two important considerations when choosing the optimum amine (or mixture of amines) for corrosion control in the steam cycle. Atomic Energy of Canada Limited (AECL) and Electric Power Research Institute (EPRI) have been collaborating in an extensive investigation of the effectiveness of amines at controlling the rate of tube-bundle fouling under SG operating conditions. Tests have been performed using a radiotracing technique in a high-temperature fouling loop facility at Chalk River Laboratories operated by AECL. This investigation has provided new insights into the role played by the amine in determining the rate of tube-bundle fouling in the SG. These insights are being used by AECL and EPRI to develop criteria for the selection of an amine that has optimum properties for both corrosion control and deposit control in the secondary heat transport system. The investigation has found that the rate of tube-bundle fouling is strongly dependent upon the surface chemistry of the corrosion products. For example, the fouling rates of fully oxidized iron oxides, such as hematite and lepidocrocite, are at least an order of magnitude greater than the fouling rate of magnetite under identical operating conditions. The difference is related to the sign of the surface charge on the corrosion products at temperature. The choice of amine for pH-control also influences the fouling rate. This was originally thought to be a surface-charge effect as well, but recent tests have suggested that it is related to the role that the amine plays in governing the rate of deposit consolidation on the heat-transfer surface. Amines that promote a high rate of

  1. New insights into controlling tube-bundle fouling using alternative amines

    International Nuclear Information System (INIS)

    Turner, C.W.; Klimas, S.J.; Guzonas, D.A.; Fruzzetti, K.; Frattini, P.L.

    2002-01-01

    A volatile amine is added to the secondary heat-transport system of a nuclear power plant to reduce the rate of corrosion and corrosion product transport in the feedwater and to protect steam generator (SG) crevices and materials exposed to steam condensate. Volatility and base strength of the amine at the SG operating temperature are two important considerations when choosing the optimum amine (or mixture of amines) for corrosion control in the steam cycle. The investigation has found that the rate of tube-bundle fouling is strongly dependent upon the surface chemistry of the corrosion products. For example, the fouling rates of fully oxidized iron oxides, such as hematite and lepidocrocite, are at least an order of magnitude greater than the fouling rate of magnetite under identical operating conditions. The difference is related to the sign of the surface charge on the corrosion products at temperature. The choice of amine for pH-control also influences the fouling rate. This was originally thought to be a surface-charge effect as well, but recent tests have suggested that it is related to the role that the amine plays in governing the rate of deposit consolidation on the heat-transfer surface. Amines that promote a high rate of deposit consolidation result in a low rate of deposit removal and a high fouling rate. Conversely, amines that tend to inhibit deposit consolidation produce a higher rate of deposit removal and a lower fouling rate. Dimethyl-amine and dodecyl-amine have been identified as two amines that inhibit the rate of deposit consolidation and, consequently, result in fouling rates that are up to 5 times lower than rates measured for amines that promote consolidation. A significant difference between morpholine (high fouling rate) and dimethyl-amine (low fouling rate) is that the latter desorbs more slowly from the surface of magnetite. How to account for a correlation between slow desorption kinetics and lower rate constants for deposition and

  2. Secondary and tertiary hyperparathyroidism.

    Science.gov (United States)

    Jamal, Sophie A; Miller, Paul D

    2013-01-01

    We reviewed the etiology and management of secondary and tertiary hyperparathyroidism. Secondary hyperparathyroidism is characterized by an increase in parathyroid hormone (PTH) that is appropriate and in response to a stimulus, most commonly low serum calcium. In secondary hyperparathyroidism, the serum calcium is normal and the PTH level is elevated. Tertiary hyperparathyroidism is characterized by excessive secretion of PTH after longstanding secondary hyperparathyroidism, in which hypercalcemia has ensued. Tertiary hyperparathyroidism typically occurs in men and women with chronic kidney disease usually after kidney transplant. The etiology and treatment of secondary hyperparathyroidism is relatively straightforward whereas data on the management of tertiary hyperparathyroidism is limited to a few small trials with short follow-up. Copyright © 2013 The International Society for Clinical Densitometry. Published by Elsevier Inc. All rights reserved.

  3. ADVANCED OXIDATION PROCESS TECHNOLOGY (ULTRAVIOLET RADIATION/OZONE TREATMENT) FOR REMOVAL OF METHYL TERTIARY BUTYL ETHER (MTBE) IN GROUND WATER SUPPLIES.

    Science.gov (United States)

    U.S. EPA’s Office of Research and Development in Cincinnati, Ohio has been testing and evaluating MTBE removal in dechlorinated tap water using three oxidant combinations: hydrogen peroxide/ozone, ultraviolet irradiation (UV)/ozone, and UV/ozone/hydrogen peroxide. Pilot-scale st...

  4. Electrochemical degradation of aromatic amines on BDD electrodes

    International Nuclear Information System (INIS)

    Pacheco, M.J.; Santos, V.; Ciriaco, L.; Lopes, A.

    2011-01-01

    The electrochemical oxidation of four aromatic amines, with different substituent groups, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid (A1), 5-amino-2-methoxybenzenesulfonic acid (A2), 2,4-dihydroxyaniline hydrochloride (A3) and benzene-1,4-diamine (A4), was performed using as anode a boron-doped diamond electrode, commercially available at Adamant Technologies. Tests were run at room temperature with model solutions of the different amines, with concentrations of 200 ppm, using as electrolyte 0.035 M Na 2 SO 4 aqueous solutions, in a batch cell with recirculation, at different current densities (200 and 300 A m -2 ). The following analyses were performed with the samples collected during the assays: UV-Vis spectrophotometry, chemical oxygen demand (COD), total organic carbon (TOC), total Kjeldahl nitrogen, ammonia nitrogen, nitrates and HPLC. Results have shown a good electrodegradation of all the amines tested, with COD removals, after 6 h assays, higher than 90% and TOC removals between 60 and 80%. Combustion efficiency (η C ), which measures the tendency to convert organic carbon to CO 2 , was also determined for all the amines, being η CA1 CA2 CA3 CA4 = 0.99.

  5. Amine oxidases as important agents of pathological processes of rhabdomyolysis in rats.

    Science.gov (United States)

    Gudkova, O O; Latyshko, N V; Shandrenko, S G

    2016-01-01

    In this study we have tested an idea on the important role of amine oxidases (semicarbazide-sensitive amine oxidase, diamine oxidase, polyamine oxidase) as an additional source of oxidative/carbonyl stress under glycerol-induced rhabdomyolysis, since the enhanced formation of reactive oxygen species and reactive carbonyl species in a variety of tissues is linked to various diseases. In our experiments we used the sensitive fluorescent method devised for estimation of amine oxidases activity in the rat kidney and thymus as targeted organs under rhabdomyolysis. We have found in vivo the multiple rises in activity of semicarbazide-sensitive amine oxidase, diamine oxidase, polyamine oxidase (2-4.5 times) in the corresponding cell fractions, whole cells or their lysates at the 3-6th day after glycerol injection. Aberrant antioxidant activities depended on rhabdomyolysis stage and had organ specificity. Additional treatment of animals with metal chelator ‘Unithiol’ adjusted only the activity of antioxidant enzymes but not amine oxidases in both organs. Furthermore the in vitro experiment showed that Fenton reaction (hydrogen peroxide in the presence of iron) products alone had no effect on semicarbazide-sensitive amine oxidase activity in rat liver cell fraction whereas supplementation with methylglyoxal resulted in its significant 2.5-fold enhancement. Combined action of the both agents had additive effect on semicarbazide-sensitive amine oxidase activity. We can assume that biogenic amine and polyamine catabolism by amine oxidases is upregulated by oxidative and carbonyl stress factors directly under rhabdomyolysis progression, and the increase in catabolic products concentration contributes to tissue damage in glycerol-induced acute renal failure and apoptosis stimulation in thymus.

  6. High surface area V-Mo-N materials synthesized from amine intercalated foams

    International Nuclear Information System (INIS)

    Krawiec, Piotr; Narayan Panda, Rabi; Kockrick, Emanuel; Geiger, Dorin; Kaskel, Stefan

    2008-01-01

    Nanocrystalline ternary V-Mo nitrides were prepared via nitridation of amine intercalated oxide foams or bulk ternary oxides. Specific surface areas were in the range between 40 and 198 m 2 g -1 and strongly depended on the preparation method (foam or bulk oxide). Foamed precursors were favorable for vanadium rich materials, while for molybdenum rich samples bulk ternary oxides resulted in higher specific surface areas. The materials were characterized via nitrogen physisorption at 77 K, X-ray diffraction patterns, electron microscopy, and elemental analysis. - Graphical abstract: Nanocrystalline ternary V-Mo nitrides were prepared via nitridation of amine intercalated oxide foams or bulk ternary oxides. Foamed precursors were favorable for vanadium rich materials, while for molybdenum rich samples bulk ternary oxides resulted in higher specific surface areas

  7. Processing method for drained water containing ethanol amine

    International Nuclear Information System (INIS)

    Wakuta, Kuniharu; Ogawa, Naoki; Sagawa, Hiroshi; Kamiyoshi, Hideki; Fukunaga, Kazuo; Iwamoto, Ken; Miki, Tsuyoshi; Hirata, Toshio

    1998-01-01

    Drained water containing ethanol amine is processed with microorganisms such as hydrazine resistant denitrification bacteria in a biodegrading vessel (A) in the coexistence of nitrous ions and/or nitric ions under an anaerobic condition, and then it is processed with microorganisms such as nitrification bacteria in another biotic oxidation vessel (B) under an aerobic condition to generate the coexistent nitrate ion and/or nitric ion, and returned to the biodegrading vessel (A). Further, they are exposed to air or incorporated with an oxidant and optionally a copper compound such as copper sulfate as a catalyst is added in a step of removing hydrazine. (T.M.)

  8. Biogenic Amines in Insect Antennae

    Directory of Open Access Journals (Sweden)

    Marianna I. Zhukovskaya

    2017-06-01

    Full Text Available Insect antenna is a multisensory organ, each modality of which can be modulated by biogenic amines. Octopamine (OA and its metabolic precursor tyramine (TA affect activity of antennal olfactory receptor neurons. There is some evidence that dopamine (DA modulates gustatory neurons. Serotonin can serve as a neurotransmitter in some afferent mechanosensory neurons and both as a neurotransmitter and neurohormone in efferent fibers targeted at the antennal vessel and mechanosensory organs. As a neurohormone, serotonin affects the generation of the transepithelial potential by sensillar accessory cells. Other possible targets of biogenic amines in insect antennae are hygro- and thermosensory neurons and epithelial cells. We suggest that the insect antenna is partially autonomous in the sense that biologically active substances entering its hemolymph may exert their effects and be cleared from this compartment without affecting other body parts.

  9. Aqueous amine solution characterization for post-combustion CO_2 capture process

    International Nuclear Information System (INIS)

    El Hadri, Nabil; Quang, Dang Viet; Goetheer, Earl L.V.; Abu Zahra, Mohammad R.M.

    2017-01-01

    Highlights: • The CO_2 solubility of 30 aqueous amine solutions was measured at 30 wt% and 313.15 K. • The CO_2 loading of HMD is the highest, and that of TEA is the lowest. • 2DMAE, 3DMA1P, 1DMA2P, MDEA, TMPAD and 2EAE have a low heat of absorption with CO_2. • 2EAE can be used as an alternative to MEA in the CO_2 capture process. - Abstract: This article presents a thermodynamic and kinetic characterization of CO_2 absorption by 30 aqueous amine solutions. A solvent screening setup (S.S.S.) was used to find the CO_2 loading (α) for 30 different aqueous amine solutions (30 wt%) at a pressure of 1 bar with feed gas containing 15 vol% CO_2 and 85 vol% N_2 at 313.15 K to provide reliable absorber parameters. The structures of various amines (linear, non-linear, polyamines, sterically hindered, etc.) were tested and the S.S.S. results showed that hexamethylenediamine (HMD) has higher CO_2 loading at 1.35 moles of CO_2/mole of amine, and triethanolamine (TEA) has the lowest at 0.39 mole of CO_2/mole of amine. The heat of absorption indicates that MDEA has the lowest and HMD has the highest at −52.51 kJ/mole of CO_2 and −98.39 kJ/mole of CO_2, respectively. The combined data for the CO_2 loading and the absorption heat generated 6 amines that have good properties for the post-combustion CO_2 capture process in comparison with that of MEA. These amines are made up of one secondary amine (2-ethylaminoethanol, 2EAE) and 5 tertiary amines (N-methyldiethanolamine, MDEA, 1-dimethylamino-2-propanol, 1DMA2P, 2-dimethylaminoethanol, 2DMAE, 3-dimethylamino-1-propanol, 3DMA1P and N,N,N′,N′-tetramethyl-1,3-propanediamine, TMPDA). In comparison with the amine reference MEA (ΔH = −85.13 kJ/mole of CO_2 and α = 0.58 mole CO_2/mole of amine), the 6 amines have heats of absorption that are between −68.95 kJ/mole of CO_2 and −52.51 kJ/mole of CO_2, and their CO_2 loading is between 0.52 and 1.16 mole of CO_2/mole amine. The third important parameter, namely the

  10. Microfluidic photoinduced chemical oxidation for Ru(bpy)33+ chemiluminescence - A comprehensive experimental comparison with on-chip direct chemical oxidation.

    Science.gov (United States)

    Kadavilpparampu, Afsal Mohammed; Al Lawati, Haider A J; Suliman, Fakhr Eldin O

    2017-08-05

    For the first time, the analytical figures of merit in detection capabilities of the very less explored photoinduced chemical oxidation method for Ru(bpy) 3 2+ CL has been investigated in detail using 32 structurally different analytes. It was carried out on-chip using peroxydisulphate and visible light and compared with well-known direct chemical oxidation approaches using Ce(IV). The analytes belong to various chemical classes such as tertiary amine, secondary amine, sulphonamide, betalactam, thiol and benzothiadiazine. Influence of detection environment on CL emission with respect to method of oxidation was evaluated by changing the buffers and pH. The photoinduced chemical oxidation exhibited more universal nature for Ru(bpy) 3 2+ CL in detection towards selected analytes. No additional enhancers, reagents, or modification in instrumental configuration were required. Wide detectability and enhanced emission has been observed for analytes from all the chemical classes when photoinduced chemical oxidation was employed. Some of these analytes are reported for the first time under photoinduced chemical oxidation like compounds from sulphonamide, betalactam, thiol and benzothiadiazine class. On the other hand, many of the selected analytes including tertiary and secondary amines such as cetirizine, azithromycin fexofenadine and proline did not produced any analytically useful CL signal (S/N=3 or above for 1μgmL -1 analyte) under chemical oxidation. The most fascinating observations was in the detection limits; for example ofloxacin was 15 times more intense with a detection limit of 5.81×10 -10 M compared to most lowest ever reported 6×10 -9 M. Earlier, penicillamine was detected at 0.1μgmL -1 after derivatization using photoinduced chemical oxidation, but in this study, we improved it to 5.82ngmL -1 without any prior derivatization. The detection limits of many other analytes were also found to be improved by several orders of magnitude under photoinduced

  11. Metal-Free α-C(sp3–H Functionalized Oxidative Cyclization of Tertiary N,N-Diaryl Amino Alcohols: Theoretical Approach for Mechanistic Pathway

    Directory of Open Access Journals (Sweden)

    Zakir Ullah

    2017-03-01

    Full Text Available The mechanistic pathway of TEMPO/I2-mediated oxidative cyclization of N,N-diaryl amino alcohols 1 was investigated. Based on direct empirical experiments, three key intermediates (aminium radical cation 3, α-aminoalkyl radical 4, and iminium 5, four types of reactive species (radical TEMPO, cationic TEMPO, TEMPO-I, and iodo radical, and three types of pathways ((1 SET/PCET mechanism; (2 HAT/1,6-H transfer mechanism; (3 ionic mechanism were assumed. Under the assumption, nine free energy diagrams were acquired through density functional theory calculations. From the comparison of solution-phase free energy, some possible mechanisms were excluded, and then the chosen plausible mechanisms were concretized using the more stable intermediate 7.

  12. The effect of amine protonation on the electrical properties of spin-assembled single-walled carbon nanotube networks

    Energy Technology Data Exchange (ETDEWEB)

    Opatkiewicz, Justin P; LeMieux, Melburne C; Bao Zhenan [Department of Chemical Engineering, Stanford University, Stanford, CA 94305 (United States); Patil, Nishant P; Wei Hai; Mitra, Subhasish, E-mail: zbao@stanford.edu [Department of Electrical Engineering, Stanford University, Stanford, CA 94305 (United States)

    2011-03-25

    Amine-terminated self-assembled monolayers (SAMs) have been shown to selectively adsorb semiconducting single-walled carbon nanotubes (sc-SWNTs). Previous studies have shown that when deposited by spin coating, the resulting nanotube networks (SWNTnts) can be strongly influenced by the charge state of the amine (primary, secondary, and tertiary). When the amine surfaces were exposed to varying pH solutions, the conductivity and overall quality of the resulting fabricated networks were altered. Atomic force microscopy (AFM) topography had shown that the density of the SWNTnts was reduced as the amine protonation decreased, indicating that the electrostatic attraction between the SWNTs in solution and the surface influenced the adsorption. Simultaneously, {mu}-Raman analysis had suggested that when exposed to more basic conditions, the resulting networks were enhanced with sc-SWNTs. To directly confirm this enhancement, Ti/Pd contacts were deposited and devices were tested in air. Key device characteristics were found to match the enhancement trends previously observed by spectroscopy. For the primary and secondary amines, on/off current ratios were commensurate with the Raman trends in metallic contribution, while no trends were observed on the tertiary amine (due to weaker interactions). Finally, differing SWNT solution volumes were used to compensate for adsorption differences and yielded identical SWNTnt densities on the various pH-treated samples to eliminate the influence of network density. These results further the understanding of the amine-SWNT interaction during the spin coating process. Overall, we provide a convenient route to provide SWNT-based TFTs with highly tunable electronic charge transport through better understanding of the influence of these specific interactions.

  13. The effect of amine protonation on the electrical properties of spin-assembled single-walled carbon nanotube networks

    International Nuclear Information System (INIS)

    Opatkiewicz, Justin P; LeMieux, Melburne C; Bao Zhenan; Patil, Nishant P; Wei Hai; Mitra, Subhasish

    2011-01-01

    Amine-terminated self-assembled monolayers (SAMs) have been shown to selectively adsorb semiconducting single-walled carbon nanotubes (sc-SWNTs). Previous studies have shown that when deposited by spin coating, the resulting nanotube networks (SWNTnts) can be strongly influenced by the charge state of the amine (primary, secondary, and tertiary). When the amine surfaces were exposed to varying pH solutions, the conductivity and overall quality of the resulting fabricated networks were altered. Atomic force microscopy (AFM) topography had shown that the density of the SWNTnts was reduced as the amine protonation decreased, indicating that the electrostatic attraction between the SWNTs in solution and the surface influenced the adsorption. Simultaneously, μ-Raman analysis had suggested that when exposed to more basic conditions, the resulting networks were enhanced with sc-SWNTs. To directly confirm this enhancement, Ti/Pd contacts were deposited and devices were tested in air. Key device characteristics were found to match the enhancement trends previously observed by spectroscopy. For the primary and secondary amines, on/off current ratios were commensurate with the Raman trends in metallic contribution, while no trends were observed on the tertiary amine (due to weaker interactions). Finally, differing SWNT solution volumes were used to compensate for adsorption differences and yielded identical SWNTnt densities on the various pH-treated samples to eliminate the influence of network density. These results further the understanding of the amine-SWNT interaction during the spin coating process. Overall, we provide a convenient route to provide SWNT-based TFTs with highly tunable electronic charge transport through better understanding of the influence of these specific interactions.

  14. Iridium-Catalyzed Condensation of Primary Amines To Form Secondary Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh; Jensen, Paw; Madsen, Robert

    2009-01-01

    Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields.......Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields....

  15. Novel bioreducible poly(amido amine)s for highly efficient gene delivery

    NARCIS (Netherlands)

    Lin, C.; Zhong, Zhiyuan; Lok, Martin C.; Jiang, Xulin; Hennink, Wim E.; Feijen, Jan; Engbersen, Johannes F.J.

    2007-01-01

    A series of novel bioreducible poly(amido amine)s containing multiple disulfide linkages (SS-PAAs) were synthesized and evaluated as nonviral gene vectors. These linear SS-PAAs could be easily obtained by Michael-type polyaddition of various primary amines to the disulfide-containing cystamine

  16. 2. Tertiary Foraminifera

    NARCIS (Netherlands)

    Umbgrove, J.H.F.

    1931-01-01

    In his review of the palaeozoology of Java, K. Martin could in 1919, record 49 foraminifera from tertiary strata of Java, on the strength of a critical study of the existant literature, and especially on the strength of his own studies and knowledge of the above mentioned fossils (Bibl. 49). In

  17. Pd-Catalyzed Acetoxylation of γ-C(sp3)-H Bonds of Amines Directed by a Removable Bts-Protecting Group.

    Science.gov (United States)

    Zheng, Yong; Song, Weibin; Zhu, Yefu; Wei, Bole; Xuan, Lijiang

    2018-02-16

    Pd-catalyzed acetoxylation of γ-C(sp 3 )-H bonds directed by Bts-protected amines using inexpensive PhI(OAc) 2 as oxidant is reported. The Bts-protecting group is easily introduced and removed under mild conditions. This protocol provides an important strategy for the construction of γ-hydroxyl amine derivatives.

  18. Intolerance to dietary biogenic amines: A review

    NARCIS (Netherlands)

    Jansen, S.C.; Dusseldorp, M. van; Bottema, K.C.; Dubois, A.E.J.

    2003-01-01

    Objective: To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. Data Sources: MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allerg*, intoler*, and

  19. Intolerance to dietary biogenic amines : a review

    NARCIS (Netherlands)

    Jansen, SC; van Dusseldorp, M; Bottema, KC; Dubois, AEJ

    Objective: To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. Data Sources: MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allergen intoler*, and

  20. Sillica Gel-Amine from Geothermal Sludge

    Science.gov (United States)

    Muljani, S.; Pujiastuti, C.; Wicaksono, P.; Lutfianingrum, R.

    2018-01-01

    Silica Gel-Amine (SGA) has been made from geothermal sludge by grafting amine method. Sodium silicate solution is prepared by extracted geothermal sludge powder using sodium hidroxide solution then acidification in the range of pH 5 - 9 by using tartaric acid 1N. The grafting process uses 1 ml of ammonia solution and 10 ml of toluene at a rate of 0.1 ml min-1 accompanied by a reflux process. The amine grafting is done in two methods. The first method is grafting amine in silicate solution and the second method is grafting amine in washed gel. Product SGA was confirmed by FTIR, TGA-DTG and BET characterization. The results show that the pH affects the amount of amine that is grafted onto silica gel. Differences in grafting method affect the size of the pore and surface area. SGA product prepared by grafting washed gel at pH 8 have pore diameter of 12.06 nm, surface area of 173.44 m2g-1, and mass of decomposed amine compound 0.4 mg. In the presence of amine groups on the silica gel surface, these adsorbents may be able to selectively adsorb CO2 gas from natural gas.

  1. Redox self-sufficient whole cell biotransformation for amination of alcohols.

    Science.gov (United States)

    Klatte, Stephanie; Wendisch, Volker F

    2014-10-15

    Whole cell biotransformation is an upcoming tool to replace common chemical routes for functionalization and modification of desired molecules. In the approach presented here the production of various non-natural (di)amines was realized using the designed whole cell biocatalyst Escherichia coli W3110/pTrc99A-ald-adh-ta with plasmid-borne overexpression of genes for an l-alanine dehydrogenase, an alcohol dehydrogenase and a transaminase. Cascading alcohol oxidation with l-alanine dependent transamination and l-alanine dehydrogenase allowed for redox self-sufficient conversion of alcohols to the corresponding amines. The supplementation of the corresponding (di)alcohol precursors as well as amino group donor l-alanine and ammonium chloride were sufficient for amination and redox cofactor recycling in a resting buffer system. The addition of the transaminase cofactor pyridoxal-phosphate and the alcohol dehydrogenase cofactor NAD(+) was not necessary to obtain complete conversion. Secondary and cyclic alcohols, for example, 2-hexanol and cyclohexanol were not aminated. However, efficient redox self-sufficient amination of aliphatic and aromatic (di)alcohols in vivo was achieved with 1-hexanol, 1,10-decanediol and benzylalcohol being aminated best. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Extraction of sulphates by long chain amines

    International Nuclear Information System (INIS)

    Boirie, Ch.

    1959-05-01

    The extraction of sulphuric acid by long chain amines in organic solution has been studied with a view to determining the value of the stability constants of the amine sulphates and bi-sulphates formed. We have concentrated chiefly on uranium sulphate and thorium sulphate. The formulae of the complexes extractable with amines have been established, as well as the corresponding dissociation constants. We have observed that for uranium sulphate the formula of the complex depends only on the nature of the amine, whereas for thorium this formula varies with the amine structure. From the formulae determined and the value of the constants calculated, we have been able to establish the best conditions for uranium and thorium extraction and also for a separation of these two elements. Finally we propose an application of this study to the determination of uranium in ores, where the separation of uranium by this method is particularly easy and complete. (author) [fr

  3. Spectroscopic Studies of the Chan-Lam Amination: A Mechanism-Inspired Solution to Boronic Ester Reactivity.

    Science.gov (United States)

    Vantourout, Julien C; Miras, Haralampos N; Isidro-Llobet, Albert; Sproules, Stephen; Watson, Allan J B

    2017-04-05

    We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, including off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxidation/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I) → Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.

  4. Mode of action of ethyl tertiary-butyl ether hepatotumorigenicity in the rat: Evidence for a role of oxidative stress via activation of CAR, PXR and PPAR signaling pathways

    Energy Technology Data Exchange (ETDEWEB)

    Kakehashi, Anna, E-mail: anna@med.osaka-cu.ac.jp [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan); Hagiwara, Akihiro; Imai, Norio [DIMS Institute of Medical Science, Inc., 64 Goura, Nishiazai, Azai-cho, Ichinomiya, Aichi 491-0113 (Japan); Nagano, Kasuke [Nagano Toxicologic-Pathology Consulting, Ochiai, Hadano, Kanagawa 257-0025 (Japan); Nishimaki, Fukumi [Biofuel Assessment Group, New Fuels Dept., Japan Petroleum Energy Center (JPEC), 4-3-9 Toranomon, Minato-ku, Tokyo 105-0001 (Japan); Banton, Marcy [Toxicology and Risk Assessment, LyondellBasell Industries, LyondellBasell Corporate HSE/Product Safety, One Houston Center, Suite 700, 1221 McKinney Street, Houston, TX 770 10 (United States); Wei, Min [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan); Fukushima, Shoji [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan); Japan Bioassay Research Center, Japan Industrial Safety and Health Association, 2445 Hirasawa, Hadano, Kanagawa 257-0011 (Japan); Wanibuchi, Hideki [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan)

    2013-12-01

    To elucidate possible mode of action (MOA) and human relevance of hepatotumorigenicity in rats for ethyl tertiary-butyl ether (ETBE), male F344 rats were administered ETBE at doses of 0, 150 and 1000 mg/kg body weight twice a day by gavage for 1 and 2 weeks. For comparison, non-genotoxic carcinogen phenobarbital (PB) was applied at a dose of 500 ppm in diet. Significant increase of P450 total content and hydroxyl radical levels by low, high doses of ETBE and PB treatments at weeks 1 and 2, and 8-OHdG formation at week 2, accompanied accumulation of CYP2B1/2B2, CYP3A1/3A2 and CYP2C6, and downregulation of DNA oxoguanine glycosylase 1, induction of apoptosis and cell cycle arrest in hepatocytes, respectively. Up-regulation of CYP2E1 and CYP1A1 at weeks 1 and 2, and peroxisome proliferation at week 2 were found in high dose ETBE group. Results of proteome analysis predicted activation of upstream regulators of gene expression altered by ETBE including constitutive androstane receptor (CAR), pregnane-X-receptor (PXR) and peroxisome proliferator-activated receptors (PPARs). These results indicate that the MOA of ETBE hepatotumorigenicity in rats may be related to induction of oxidative stress, 8-OHdG formation, subsequent cell cycle arrest, and apoptosis, suggesting regenerative cell proliferation after week 2, predominantly via activation of CAR and PXR nuclear receptors by a mechanism similar to that of PB, and differentially by activation of PPARs. The MOA for ETBE hepatotumorigenicity in rats is unlikely to be relevant to humans. - Highlights: • We focus on MOA and human relevance of hepatotumorigenicity in rats for ETBE. • ETBE was administered to F344 rats for 1 and 2 weeks. • Oxidative stress formation, proliferation and apoptosis in the liver are analyzed. • ETBE-induced changes of gene and protein expression in the liver are examined. • The effects are compared with those induced by non-genotoxic carcinogen PB.

  5. Thermodynamics of mixtures containing amines

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez, Juan Antonio [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain)], E-mail: jagl@termo.uva.es; Mozo, Ismael; Garcia de la Fuente, Isaias; Cobos, Jose Carlos [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain); Riesco, Nicolas [Department of Chemical Engineering, Loughborough University, Loughborough, LE113TU Leicestershire (United Kingdom)

    2008-01-30

    Mixtures with dimethyl or trimethylpyridines and alkane, aromatic compound or 1-alkanol have been examined using different theories: DISQUAC, Flory, the concentration-concentration structure factor, S{sub CC}(0), or the Kirkwood-Buff formalism. DISQUAC represents fairly well the available experimental data, and improves theoretical calculations from Dortmund UNIFAC. Two important effects have been investigated: (i) the effect of increasing the number of methyl groups attached to the aromatic ring of the amine; (ii) the effect of modifying the position of the methyl groups in this ring. The molar excess enthalpy, H{sup E}, and the molar excess volume, V{sup E}, decrease in systems with alkane or methanol as follows: pyridine > 3-methylpyridine > 3,5-dimethylpyridine and pyridine > 2-methylpyridine > 2,4-dimethylpyridine > 2,4,6-trimethylpyridine, which has been attributed to a weakening of the amine-amine interactions in the same sequences. This is in agreement with the relative variation of the effective dipole moment, {mu}-bar, and of the differences between the boiling temperature of a pyridine base and that of the homomorphic alkane. For heptane solutions, the observed H{sup E} variation, H{sup E} (3,5-dimethylpyridine) > H{sup E} (2,4-dimethylpyridine) > H{sup E} (2,6-dimethylpyridine), is explained similarly. Calculations on the basis of the Flory model confirm that orientational effects become weaker in systems with alkane in the order: pyridine > methylpyridine > dimethylpyridine > trimethylpyridine. S{sub CC}(0) calculations show that steric effects increase with the number of CH{sub 3}- groups in the pyridine base, and that the steric effects exerted by methyl groups in positions 2 and 6 are higher than when they are placed in positions 3 and 5. The hydrogen bond energy in methanol mixtures is independent of the pyridine base, and it is estimated to be -35.2 kJ mol{sup -1}. Heterocoordination in these solutions is due in part to size effects. Their

  6. From caffeine to fish waste: amine compounds present in food and drugs and their interactions with primary amine oxidase.

    LENUS (Irish Health Repository)

    Olivieri, Aldo

    2011-07-01

    Tissue bound primary amine oxidase (PrAO) and its circulating plasma-soluble form are involved, through their catalytic activity, in important cellular roles, including the adhesion of lymphocytes to endothelial cells during various inflammatory conditions, the regulation of cell growth and maturation, extracellular matrix deposition and maturation and glucose transport. PrAO catalyses the oxidative deamination of several xenobiotics and has been linked to vascular toxicity, due to the generation of cytotoxic aldehydes. In this study, a series of amines and aldehydes contained in food and drugs were tested via a high-throughput assay as potential substrates or inhibitors of bovine plasma PrAO. Although none of the compounds analyzed were found to be substrates for the enzyme, a series of molecules, including caffeine, the antidiabetics phenformin and tolbutamide and the antimicrobial pentamidine, were identified as PrAO inhibitors. Although the inhibition observed was in the millimolar and micromolar range, these data show that further work will be necessary to elucidate whether the interaction of ingested biogenic or xenobiotic amines with PrAO might adversely affect its biological roles.

  7. Environmental impact of atmospheric fugitive emissions from amine based post combustion CO{sub 2} capture

    Energy Technology Data Exchange (ETDEWEB)

    Attalla, M.I.; Azzi, M.; Jackson, P.; Angove, D. [CSIRO, Newcastle, NSW (Australia). Energy Technology Div

    2009-07-01

    Amine solvent-based chemical absorption of CO{sub 2} is the most mature technology for post combustion capture (PCC) and will likely to be the first to reach commercial scale application. As such, potentially millions of tonnes of solvent will be used per year. In order to ensure the viability of PCC, the potential environmental impacts of fugitive emissions on terrestrial, aquatic and atmospheric environments must be investigated. This study used controlled laboratory/ pilot scale experiments to determine the major chemical components emitted under different operating conditions. As well, the atmospheric photo-oxidation products of amines were studied in a smog chamber under ambient conditions. The environmental concerns associated with these emissions include entrainment of the amine/ammonia with the treated flue gas and their associated atmospheric chemical reaction pathways; formation of ammonia and other amine degradation products can be entrained with the flue gas to the atmosphere; nitrosamines may form as a result of the reaction between an amine and nitrogen oxide; and the mounting evidence of the presence of amines in particulate phase. The chemical compositions of potential fugitive emissions in the flue gases from the CO{sub 2} capture system were estimated. The CSIRO smog chamber was then used to assess the potential environmental impact of selected relevant compounds in terms of their reactivities to produce secondary products. These secondary products were then characterized to determine their potential health risk factors. An air quality model was used to evaluate the potential impact of using amine solutions for CO{sub 2} capture and to determine the trade-off between CO{sub 2} capture and local and regional air quality.

  8. Enrichment Mechanism of Semiconducting Single-walled Carbon Nanotubes by Surfactant Amines

    Science.gov (United States)

    Ju, Sang-Yong; Utz, Marcel; Papadimitrakopoulos, Fotios

    2009-01-01

    Utilization of single-walled carbon nanotubes (SWNTs) in high-end applications hinges on separating metallic (met-) from semiconducting (sem-) SWNTs. Surfactant amines, like octadecylamine (ODA) have proven instrumental for the selective extraction of sem-SWNTs from tetrahydrofuran (THF) nanotube suspensions. The chemical shift differences along the tail of an asymmetric, diacetylenic surfactant amine were used to probe the molecular dynamics in the presence and absence of nanotubes via NMR. The results suggest that the surfactant amine head is firmly immobilized onto the nanotube surface together with acidic water, while the aliphatic tail progressively gains larger mobility as it gets farther from the SWNT. X-ray and high-resolution TEM studies indicate that the sem-enriched sample is populated mainly by small nanotube bundles containing ca. three SWNTs. Molecular simulations in conjunction with previously determined HNO3/H2SO4 oxidation depths for met- and sem-SWNTs indicate that the strong pinning of the amine surfactants on the sem-enriched SWNTs bundles is a result of a well-ordered arrangement of nitrate/amine salts separated with a monomolecular layer of H2O. Such continuous 2D arrangement of nitrate/amine salts shields the local environment adjacent to sem-enriched SWNTs bundles and maintains an acidic pH that preserves nanotube oxidation (i.e. SWNTn+). This, in turn, results in strong interactions with charge-balancing NO3- counter ions that through their association with neutralized surfactant amines provide effective THF dispersion and consequent sem-enrichment. PMID:19397291

  9. STUDIES ON RADICAL POLYMERIZATION OF METHYL METHACRYLATE INITIATED WITH ORGANIC PEROXIDE-AMINE SYSTEMS

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; SHUI Li; FENG Xinde

    1984-01-01

    Radical polymerization of methyl methacrylate (MMA) initiated with various diacyl peroxideamine systems was studied. Benzoyl peroxide (BPO) and lauroyl peroxide (LPO) were used as diacyl peroxide component, N,N-dimethyl aniline (DMA) and its para substituted derivatives, i.e., N,N-dimethyl-p-toluidine (DMT), p-hydroxymethyl-N,N-dimethyl aniline (HDMA), p-nitro-N,N-dimethyl aniline (NDMA) and p-dimethylamino benzaldehyde (DMAB) were used as amine components. It was found that the peroxide-DMT systems give higher rates of bulk polymerization Rp of MMA than the organic hydroperoxide-DMT systems with the following descending order BPO-DMT>LPO-DMT>CHP (cumene hydroperoxide)-DMT>TBH (tert-butyl hydroperoxide)-DMT.The aromatic tertiary amines possess obvious structural effect on the Rp values in the diacyl peroxideamine system. The overall activation energy of MMA polymerization was determined and the kinetics of polymerization of MMA initiated with BPO-DMT system was investigated.

  10. Amine terminated SAMs: Investigating why oxygen is present in these films

    International Nuclear Information System (INIS)

    Baio, J.E.; Weidner, T.; Brison, J.; Graham, D.J.; Gamble, Lara J.; Castner, David G.

    2009-01-01

    Self-assembled monolayers (SAMs) on gold prepared from amine-terminated alkanethiols have long been employed as model positively charged surfaces. Yet in previous studies significant amounts of unexpected oxygen containing species are always detected in amine terminated SAMs. Thus, the goal of this investigation was to determine the source of these oxygen species and minimize their presence in the SAM. The surface composition, structure, and order of amine-terminated SAMs on Au were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), sum frequency generation (SFG) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. XPS determined compositions of amine-terminated SAMs in the current study exhibited oxygen concentrations of 2.4 ± 0.4 atomic %, a substantially lower amount of oxygen than reported in previously published studies. High-resolution XPS results from the S 2p , C 1s and N 1s regions did not detect any oxidized species. Angle-resolved XPS indicated that the small amount of oxygen detected was located at or near the amine head group. Small amounts of oxidized nitrogen, carbon and sulfur secondary ions, as well as ions attributed to water, were detected in the ToF-SIMS data due to the higher sensitivity of ToF-SIMS. The lack of N-O, S-O, and C-O stretches in the SFG spectra are consistent with the XPS and ToF-SIMS results and together show that oxidation of the amine-terminated thiols alone can only account for, at most, a small fraction of the oxygen detected by XPS. Both the SFG and angle-dependent NEXAFS indicated the presence of gauche defects in the amine SAMs. However, the SFG spectral features near 2865 cm -1 , assigned to the stretch of the methylene group next to the terminal amine unit, demonstrate the SAM is reasonably ordered. The SFG results also show another broad feature near 3200 cm -1 related to hydrogen-bonded water. From this multi-technique investigation it is

  11. Deposition of stable amine coating onto polycaprolactone nanofibers by low pressure cyclopropylamine plasma polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Manakhov, Anton [Plasma Technologies, CEITEC — Central European Institute of Technology, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Nečas, David [Plasma Technologies, CEITEC — Central European Institute of Technology, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Čechal, Jan [CEITEC — Central European Institute of Technology, Brno University of Technology, Technická 3058/10, 616 00 Brno (Czech Republic); Pavliňák, David [Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Eliáš, Marek [Plasma Technologies, CEITEC — Central European Institute of Technology, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); and others

    2015-04-30

    Amine-rich films are of high interest for the bio-applications including drug delivery and tissue engineering thanks to their high reactivity allowing the formation of the covalent linkages between biomolecules and a surface. However, the bio-applications of amine-rich films require their good stability in water which is often achieved at large expenses of the amine concentration. Recently, non-toxic cyclopropylamine (CPA) has been applied for the plasma polymerization of films bearing high NH{sub x} environment combined with the moderate thickness loss (20%) after water immersion for 48 h. In this work, the amine-rich film with the NH{sub x} concentration over 7 at.% was deposited on Si substrates and polycaprolactone nanofiber meshes by using CPA plasma polymerization (pulsed mode) in a vertically oriented stainless steel reactor. The substrates were placed at the radio frequency electrode and the ion bombardment caused by direct-current self-bias was suppressed by using high pressure of 50 Pa. Analysis of samples by scanning electron microscopy did not reveal any cracks in the deposited layer formed during a sample immersion in water. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed a slight oxidation of amine groups in water but the film still contained 5 at.% of NH{sub x} (according to the N1s XPS fitting) after the immersion. The rapid oxidation of amine groups was observed during the aging experiment carried out in air at room temperature because FTIR revealed an increase of amide peaks that increased progressively with aging time. However, this oxidation was significantly reduced if the plasma polymer was stored at − 20 °C. Since the films exhibit high amine concentration and very good water stability they have great potential for applications as biocompatible functional coatings. - Highlights: • Cyclopropylamine plasma polymers deposited on polycaprolactone nanofibers • Amine-rich films with high

  12. Tunable, chemoselective amination via silver catalysis.

    Science.gov (United States)

    Rigoli, Jared W; Weatherly, Cale D; Alderson, Juliet M; Vo, Brian T; Schomaker, Jennifer M

    2013-11-20

    Organic N-containing compounds, including amines, are essential components of many biologically and pharmaceutically important molecules. One strategy for introducing nitrogen into substrates with multiple reactive bonds is to insert a monovalent N fragment (nitrene or nitrenoid) into a C-H bond or add it directly to a C═C bond. However, it has been challenging to develop well-defined catalysts capable of promoting predictable and chemoselective aminations solely through reagent control. Herein, we report remarkable chemoselective aminations that employ a single metal (Ag) and a single ligand (phenanthroline) to promote either aziridination or C-H insertion by manipulating the coordination geometry of the active catalysts.

  13. Lactoperoxidase, an Antimicrobial Milk Protein, as a Potential Activator of Carcinogenic Heterocyclic Amines in Breast Cancer.

    Science.gov (United States)

    Sheikh, Ishfaq Ahmad; Jiffri, Essam Hussain; Kamal, Mohammad Amjad; Ashraf, Ghulam Md; Beg, Mohd Amin

    2017-11-01

    Lactoperoxidase (LPO) is an antimicrobial protein secreted from mammary, salivary and other mucosal glands. It is an important member of heme peroxidase enzymes and the primary peroxidase enzyme present in breast tissues. In addition to the antimicrobial properties, LPO has been shown to be associated with breast cancer etiology. Heterocyclic amines, an important class of environmental and dietary carcinogens, have been increasingly associated with breast cancer etiology. Heterocyclic amines undergo activation in breast tissue as a result of oxidation by LPO. The current study includes three important heterocyclic amines, 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-1-methy-6-phenylimidazo[4,5-b]-pyridine (PhIP), that have carcinogenic activity. The structural binding characterization of IQ, MeIQx and PhIP with LPO was done using in silico approaches. Their binding pattern and interactions with LPO amino acid residues were analyzed. The three compounds bound in the distal heme cavity of LPO without replacing the important water molecule required for oxidation of substrate compounds. PhIP displayed lesser binding affinity for LPO in comparison to IQ and MeIQx. The binding mode of heterocyclic amines in distal heme cavity of LPO resembled to that of substrate binding pattern. The three heterocyclic amines are suggested to act as LPO substrate. The undisturbed water molecule present in distal heme cavity of the LPO is expected to facilitate the oxidation and activation of the three heterocyclic amines. These activated compounds may potentially bind with DNA in breast tissues forming DNA adducts and may subsequently lead to breast cancer initiation. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

  14. Amine-catalyzed direct aldol reactions of hydroxy- and dihydroxyacetone: biomimetic synthesis of carbohydrates.

    Science.gov (United States)

    Popik, Oskar; Pasternak-Suder, Monika; Leśniak, Katarzyna; Jawiczuk, Magdalena; Górecki, Marcin; Frelek, Jadwiga; Mlynarski, Jacek

    2014-06-20

    This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.

  15. Novel vanillin derivatives: Synthesis, anti-oxidant, DNA and cellular protection properties.

    Science.gov (United States)

    Scipioni, Matteo; Kay, Graeme; Megson, Ian; Kong Thoo Lin, Paul

    2018-01-01

    Antioxidants have been the subject of intense research interest mainly due to their beneficial properties associated with human health and wellbeing. Phenolic molecules, such as naturally occurring Resveratrol and Vanillin, are well known for their anti-oxidant properties, providing a starting point for the development of new antioxidants. Here we report, for the first time, the synthesis of a number of new vanillin through the reductive amination reaction between vanillin and a selection of amines. All the compounds synthesised, exhibited strong antioxidant properties in DPPH, FRAP and ORAC assays, with compounds 1b and 2c being the most active. The latter also demonstrated the ability to protect plasmid DNA from oxidative damage in the presence of the radical initiator AAPH. At cellular level, neuroblastoma SH-SY5Y cells were protected from oxidative damage (H 2 O 2 , 400 μM) with both 1b and 2c. The presence of a tertiary amino group, along with the number of vanillin moieties in the molecule contribute for the antioxidant activity. Furthermore, the delocalization of the electron pair of the nitrogen and the presence of an electron donating substituent to enhance the antioxidant properties of this new class of compounds. In our opinion, vanillin derivatives 1b and 2c described in this work can provide a viable platform for the development of antioxidant based therapeutics. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  16. Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

    Science.gov (United States)

    Corbin, Joshua R; Schomaker, Jennifer M

    2017-04-13

    Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

  17. 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.

  18. Transition metals in the amination of chloroarenes

    Energy Technology Data Exchange (ETDEWEB)

    Serdyuk, O V [Leibniz-Institut fuer Katalyse an der Universitaet Rostock (Germany); Abaev, Vladimir T [North-Ossetia State University, Vladikavkaz (Russian Federation)

    2009-11-30

    The review is devoted to the catalytic amination of chloroarenes and chlorohetarenes. Examples of the formation of the C-N bond in the presence of iron-, nickel- and copper-based catalytic systems are given.

  19. Tris[2-(2H-indazol-2-ylethyl]amine

    Directory of Open Access Journals (Sweden)

    Saúl Ovalle

    2012-06-01

    Full Text Available The title tertiary amine, C27H27N7, a potential tripodal ligand for coordination chemistry, crystallizes with the central N atom located on a threefold axis of a trigonal cell. The gauche conformation of the N(amime—CH2—CH2—N(indazole chain [torsion angle = −64.2 (2°] places the pendant 2H-indazole heterocycles surrounding the symmetry axis, affording a claw-like shaped molecule. Two symmetry-related indazole planes in the molecule make an acute angle of 60.39 (4°. The lone pair of the tertiary N atom is located inside the cavity, and should thus be inactive (as a ligand. In the crystal, neither significant π–π nor C—H...π interactions between molecules are found.

  20. General Dialdehyde Click Chemistry for Amine Bioconjugation.

    Science.gov (United States)

    Elahipanah, Sina; O'Brien, Paul J; Rogozhnikov, Dmitry; Yousaf, Muhammad N

    2017-05-17

    The development of methods for conjugating a range of molecules to primary amine functional groups has revolutionized the fields of chemistry, biology, and material science. The primary amine is a key functional group and one of the most important nucleophiles and bases used in all of synthetic chemistry. Therefore, tremendous interest in the synthesis of molecules containing primary amines and strategies to devise chemical reactions to react with primary amines has been at the core of chemical research. In particular, primary amines are a ubiquitous functional group found in biological systems as free amino acids, as key side chain lysines in proteins, and in signaling molecules and metabolites and are also present in many natural product classes. Due to its abundance, the primary amine is the most convenient functional group handle in molecules for ligation to other molecules for a broad range of applications that impact all scientific fields. Because of the primary amine's central importance in synthetic chemistry, acid-base chemistry, redox chemistry, and biology, many methods have been developed to efficiently react with primary amines, including activated carboxylic acids, isothiocyanates, Michael addition type systems, and reaction with ketones or aldehydes followed by in situ reductive amination. Herein, we introduce a new traceless, high-yield, fast click-chemistry method based on the rapid and efficient trapping of amine groups via a functionalized dialdehyde group. The click reaction occurs in mild conditions in organic solvents or aqueous media and proceeds in high yield, and the starting dialdehyde reagent and resulting dialdehyde click conjugates are stable. Moreover, no catalyst or dialdehyde-activating group is required, and the only byproduct is water. The initial dialdehyde and the resulting conjugate are both straightforward to characterize, and the reaction proceeds with high atom economy. To demonstrate the broad scope of this new click

  1. Metal Monolithic Amine-grafted Zeolite for CO{sub 2} Capture

    Energy Technology Data Exchange (ETDEWEB)

    Chuang, Steven

    2011-03-31

    The solid amine sorbent for CO{sub 2} capture process has advantages of simplicity and low operating cost compared to the MEA (monoethanolamine) process. Solid amine sorbents reported so far suffered from either low CO{sub 2} capture capacity or low stability. The solid amine sorbent developed in this project exhibited more than 3.2 mmol/g and degraded less than 10% even after 500 cycles of heating and cooling in absence of steam. The presence of steam further enhanced CO{sub 2} capture capacity. The cost of the sorbent is estimated to be less than $7.00/lb. This sorbent was developed using the results of in situ infrared spectroscopic study. Infrared results showed that CO{sub 2} adsorbs on TEPA (tetraethylenepentamine)/PEG (polyethylene glycol) as carbamates and bicarbonates. The CO{sub 2} adsorption capacity and oxidation resistance of the amine sorbent can be enhanced by the interactions between NH{sub 2} of TEPA molecules with the OH group of PEG molecules. PEG was also found to be effectively disperse and immobilize the aromatic amines for SO{sub 2} adsorption. The infrared study also showed that SiO{sub 2} is a significantly better support than zeolites due to its proper hydrophobicity. The results of this study led to the development of a high performance solid amine sorbent under simulated gas flow condition in a fixed bed, a fluidized bed, and a metal monolith unit. This study showed heat transfer could become a major technical issue in scaling up a fixed bed adsorber. The use of the fluidized bed and metal monoliths can alleviate the heat transfer issue. The metal monolith could be suitable for small scale applications due to the high cost of manufacturing; the fluidized bed mode would be most suitable for large scale applications. Preliminary economic analysis suggested that the Akron solid amine process would cost 45% less than that of MEA process.

  2. Diamond surface functionalization with biomimicry – Amine surface tether and thiol moiety for electrochemical sensors

    Energy Technology Data Exchange (ETDEWEB)

    Sund, James B., E-mail: jim@jamessund.com [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States); Causey, Corey P. [Departments of Chemistry and Biochemistry, Duke University, Durham, NC (United States); Wolter, Scott D. [Department of Physics, Elon University, Elon, NC 27244 (United States); Parker, Charles B., E-mail: charles.parker@duke.edu [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States); Stoner, Brian R. [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States); Research Triangle Institute (RTI) International, Research Triangle Park, NC (United States); Toone, Eric J. [Departments of Chemistry and Biochemistry, Duke University, Durham, NC (United States); Glass, Jeffrey T. [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States)

    2014-05-01

    Highlights: • Diamond surfaces were functionalized with organic molecules using a novel approach. • Used biomimicry to select a molecule to bind NO, similar to the human body. • Molecular orbital theory predicted the molecule-analyte oxidation behavior. • A thiol moiety was attached to an amine surface tether on the diamond surface. • XPS analysis verified each surface functionalization step. - Abstract: The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen–oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis.

  3. Diamond surface functionalization with biomimicry – Amine surface tether and thiol moiety for electrochemical sensors

    International Nuclear Information System (INIS)

    Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

    2014-01-01

    Highlights: • Diamond surfaces were functionalized with organic molecules using a novel approach. • Used biomimicry to select a molecule to bind NO, similar to the human body. • Molecular orbital theory predicted the molecule-analyte oxidation behavior. • A thiol moiety was attached to an amine surface tether on the diamond surface. • XPS analysis verified each surface functionalization step. - Abstract: The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen–oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis

  4. Magnetic particles-based biosensor for biogenic amines using an optical oxygen sensor as a transducer

    International Nuclear Information System (INIS)

    Pospiskova, K.; Sebela, M.; Safarik, I.; Kuncova, G.

    2013-01-01

    We have developed a fibre optic biosensor with incorporated magnetic microparticles for the determination of biogenic amines. The enzyme diamine oxidase from Pisum sativum was immobilized either on chitosan-coated magnetic microparticles or on commercial microbeads modified with a ferrofluid. Both the immobilized enzyme and the ruthenium complex were incorporated into a UV-cured inorganic-organic polymer composite and deposited on a lens that was connected, by optical fibres, to an electro-optical detector. The enzyme catalyzes the oxidation of amines under consumption of oxygen. The latter was determined by measuring the quenched fluorescence lifetime of the ruthenium complex. The limits of detection for the biogenic amines putrescine and cadaverine are 25-30 μmol L -1 , and responses are linear up to a concentration of 1 mmol L -1 . (author)

  5. Enhancing amine terminals in an amine-deprived collagen matrix.

    LENUS (Irish Health Repository)

    Tiong, William H C

    2008-10-21

    Collagen, though widely used as a core biomaterial in many clinical applications, is often limited by its rapid degradability which prevents full exploitation of its potential in vivo. Polyamidoamine (PAMAM) dendrimer, a highly branched macromolecule, possesses versatile multiterminal amine surface groups that enable them to be tethered to collagen molecules and enhance their potential. In this study, we hypothesized that incorporation of PAMAM dendrimer in a collagen matrix through cross-linking will result in a durable, cross-linked collagen biomaterial with free -NH 2 groups available for further multi-biomolecular tethering. The aim of this study was to assess the physicochemical properties of a G1 PAMAM cross-linked collagen matrix and its cellular sustainability in vitro. Different amounts of G1 PAMAM dendrimer (5 or 10 mg) were integrated into bovine-derived collagen matrices through a cross-linking process, mediated by 5 or 25 mM 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) in 5 mM N-hydroxysuccinimide (NHS) and 50 mM 2-morpholinoethane sulfonic acid buffer at pH 5.5. The physicochemical properties of resultant matrices were investigated with scanning electron microscopy (SEM), collagenase degradation assay, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectra, and ninhydrin assay. Cellular sustainability of the matrices was assessed with Alamar Blue assay and SEM. There was no significant difference in cellular behavior between the treated and nontreated groups. However, the benefit of incorporating PAMAM in the cross-linking reaction was limited when higher concentrations of either agent were used. These results confirm the hypothesis that PAMAM dendrimer can be incorporated in the collagen cross-linking process in order to modulate the properties of the resulting cross-linked collagen biomaterial with free -NH 2 groups available for multi-biomolecular tethering.

  6. On the formation of protected gold nanoparticles from AuCl4- by the reduction using aromatic amines

    International Nuclear Information System (INIS)

    Subramaniam, Chandramouli; Tom, Renjis T.; Pradeep, T.

    2005-01-01

    Amines are used extensively as reductants and subsequent capping agents in the synthesis of metal nanoparticles, especially gold, due to its affinity to nitrogen. Taking 2-methyl aniline as an example, we show that metal reduction is followed by polymerization of the amine, while part of it covers the nanoparticle surface another fraction deposits in the solution. It is found that the oxidative polymerization of the amine goes in step with the formation of gold nanoparticles. The gold nanoparticles thus formed have a mean diameter of 20 nm. The polymerized amine encapsulates the gold nanoparticle forming a robust shell of about 5 nm thickness, making the gold core inert towards mineralizing agents such as chloroform, bromoform, sodium cyanide, benzylchloride, etc. which react with the naked gold nanoparticles. The deposited polymer is largely protonated, taking up protons from the medium during its formation. Similar results have been observed in the case of aniline also. The materials have been fully characterized by spectroscopy and microscopy

  7. Ligand-Enabled γ-C(sp3)–H Olefination of Amines: En Route to Pyrrolidines

    Science.gov (United States)

    Jiang, Heng; He, Jian; Liu, Tao

    2016-01-01

    Pd(II)-catalyzed olefination of γ-C(sp3)–H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp3)–H olefination reaction. The use of Ns protecting group to direct C(sp3)–H activation of alkyl amine is also a significant step towards practical C–H functionalizations of alkyl amines. PMID:26796676

  8. Examination of Amine-Functionalised Anion-Exchange Membranes for Possible Use in the All-Vanadium Redox Flow Battery

    International Nuclear Information System (INIS)

    Mallinson, Sarah L.; Varcoe, John R.; Slade, Robert C.T.

    2014-01-01

    The applicability of amine-functionalised anion-exchange membranes (AEMs) for use in the all-vanadium redox flow battery has been studied. A selection of radiation-grafted aminated membranes functionalised with dimethylamine, trimethylamine or diazabicyclo(2,2,2)octane were extensively tested. The success of each grafting process was confirmed by Raman and infrared spectroscopies, titrimetry and ionic conductivity measurements. The amine-functionalised membranes were found to have poor thermo-oxidative stability and high vanadium cation permeabilities. The results highlight the importance of balancing ionic conductivity with vanadium cation permeability and indicate that amine-based functional groups may not be suitably stable for the membranes to remain true AEMs when in use in the all-vanadium redox flow battery

  9. Oxidative activation of dihydropyridine amides to reactive acyl donors

    DEFF Research Database (Denmark)

    Funder, Erik Daa; Trads, Julie Brender; Gothelf, Kurt Vesterager

    2015-01-01

    Amides of 1,4-dihydropyridine (DHP) are activated by oxidation for acyl transfer to amines, alcohols and thiols. In the reduced form the DHP amide is stable towards reaction with amines at room temperature. However, upon oxidation with DDQ the acyl donor is activated via a proposed pyridinium...

  10. Bioreducible poly(amido amine)s for non-viral gene delivery

    NARCIS (Netherlands)

    Lin, C.

    2008-01-01

    This thesis describes the design and development of bioreducible poly(amido amine)s as non-viral vectors for gene delivery in vitro and in vivo. The structural influences of these polymers on their physico-chemical properties and gene delivery properties, transfection capability and cytotoxicity in

  11. Myeloperoxidase-catalyzed incorporation of amines into proteins: role of hypochlorous acid and dichloramines.

    Science.gov (United States)

    Thomas, E L; Jefferson, M M; Grisham, M B

    1982-11-23

    Myeloperoxidase-catalyzed oxidation of chloride (Cl-) to hypochlorous acid (HOCl) resulted in formation of mono- and dichloramine derivatives (RNHCl and RNCl2) of primary amines. The RNCl2 derivatives could undergo a reaction that resulted in incorporation of the R moiety into proteins. The probable mechanism was attack of RNCl2 or an intermediate formed in the decomposition of RNCl2 on histidine, tyrosine, and cystine residues and on lysine residues at high pH. Incorporation of radioactivity from labeled amines into stable, high molecular weight derivatives of proteins was measured by acid or acetone precipitation and by gel chromatography and electrophoresis. Whereas formation of RNCl2 was favored at low pH, the subsequent incorporation reaction was favored at high pH. Up to several hours were required for the maximum amount of incorporation, which was less than 10% of the label in RNCl2. For the amines tested, incorporation was in the order histamine greater than 1,2-diaminoethane greater than putrescine greater than taurine greater than lysine greater than glucosamine greater than leucine greater than methylamine. Initiation of the reaction required HOCl, and oxidized forms of bromide, iodide, or thiocyanate did not substitute. Inhibitors of incorporation fell into three classes. First, ammonia or amines competed with the labeled amine for reaction with HOCl, so that larger amounts of HOCl were required. Second, readily oxidized substances such as sulfhydryl or diketo compounds or thioethers (methionine) reduced RNCl2. Third, certain compounds competed with protein as the acceptor for the incorporation reaction. The amount required to block incorporation into protein depended on protein concentration. Among these inhibitors were imidazole compounds (histidine), phenols (tyrosine), and disulfides (glutathione disulfide, GSSG). Low yields of derivatives of histidine, tyrosine, and GSSG were detected by thin-layer chromatography. Acid-precipitable derivatives were

  12. Oxidation of suspected N-nitrosodimethylamine (NDMA) precursors by ferrate (VI): kinetics and effect on the NDMA formation potential of natural waters.

    Science.gov (United States)

    Lee, Changha; Lee, Yunho; Schmidt, Carsten; Yoon, Jeyong; Von Gunten, Urs

    2008-01-01

    The potential of ferrate (Fe(VI)) oxidation to remove N-nitrosodimethylamine (NDMA) precursors during water treatment was assessed. Apparent second-order rate constants (k(app)) for the reactions of NDMA and its suspected precursors (dimethylamine (DMA) and 7 tertiary amines with DMA functional group) with Fe(VI) were determined in the range of pH 6-12. Four model NDMA precursors (dimethyldithiocarbamate, dimethylaminobenzene, 3-(dimethylaminomethyl)indole and 4-dimethylaminoantipyrine) showed high reactivity toward Fe(VI) with k(app) values at pH 7 between 2.6 x 10(2) and 3.2 x 10(5)M(-1)s(-1). The other NDMA precursors (DMA, trimethylamine, dimethylethanolamine, dimethylformamide) and NDMA had k(app) values ranging from 0.55 to 9.1M(-1)s(-1) at pH 7. In the second part of the study, the NDMA formation potentials (NDMA-FP) of the model NDMA precursors and natural waters were measured with and without pre-oxidation by Fe(VI). For most of the NDMA precursors with the exception of DMA, a significant reduction of the NDMA-FP (>95%) was observed after complete transformation of the NDMA precursor. This result was supported by low yields of DMA from the Fe(VI) oxidation of tertiary amine NDMA precursors. Pre-oxidation of several natural waters (rivers Rhine, Neckar and Pfinz) with a high dose of Fe(VI) (0.38 mM = 21 mg L(-1) as Fe) led to removals of the NDMA-FP of 46-84%. This indicates that the NDMA precursors in these waters have a low reactivity toward Fe(VI) because it has been shown that for fast-reacting NDMA precursors Fe(VI) doses of 20 microM (1.1 mg L(-1) as Fe) are sufficient to completely oxidize the precursors.

  13. BIOGENIC AMINES CONTENT IN DIFFERENT WINE SAMPLES

    Directory of Open Access Journals (Sweden)

    Attila Kántor

    2015-02-01

    Full Text Available Twenty-five samples of different Slovak wines before and after filtration were analysed in order to determine the content of eight biogenic amines (tryptamine, phenylalanine, putrescine, cadaverine, histamine, tyramine, spermidine and spermine. The method involves extraction of biogenic amines from wine samples with used dansyl chloride. Ultra-high performance liquid chromatography (UHPLC was used for determination of biogenic amines equipped with a Rapid Resolution High Definition (RRHD, DAD detectors and Extend-C18 LC column (50 mm x 3.0 mm ID, 1.8 μm particle size. In this study the highest level of biogenic amine in all wine samples represent tryptamine (TRM with the highest content 170.9±5.3 mg/L in Pinot Blanc wine. Phenylalanine (PHE cadaverine (CAD, histamine (HIS and spermidine (SPD were not detected in all wines; mainly SPD was not detected in 16 wines, HIS not detected in 14 wines, PHE and CAD not detected in 2 wines. Tyramine (TYR, spermine (SPN and putrescine (PUT were detected in all wines, but PUT and SPN in very low concentration. The worst wine samples with high biogenic amine content were Saint Laurent (BF, Pinot Blanc (S and Pinot Noir (AF.

  14. Nano ZnO/amine composites antimicrobial additives to acrylic paints

    Directory of Open Access Journals (Sweden)

    H.B. Kamal

    2015-12-01

    Full Text Available Nano ZnO has been widely used as an antimicrobial agent not only for food packaging purposes but also in many coating processes. The present work is meant to enhance such functions through the preparation of sustainable and safe conduct of nano ZnO composites with amine derivatives that are characterized by their antimicrobial and anti-fouling functional activities. The results obtained revealed a more comprehensive approach to the antimicrobial function based on the reported active oxide species role. The oxide/amine composites and the acrylic emulsion paint were characterized chemically and structurally through FT-IR, TGA and TEM supported by biological assessment of each ZnO/amine composite action. Results of the study concluded that equilibrium between the nano ZnO particles size, their dispersion form, and amine ability to stabilize the actively produced oxygen species responsible for the antimicrobial function, should all be accounted for when persistence of antimicrobial agent efficiency is regarded.

  15. Novel primary amine diazeniumdiolates-Chemical and biological characterization.

    Science.gov (United States)

    Puglisi, Melany P; Bradaric, Michael J; Pontikis, John; Cabai, Jonathan; Weyna, Theodore; Tednes, Patrick; Schretzman, Robert; Rickert, Karl; Cao, Zhao; Andrei, Daniela

    2018-05-02

    Hit, Lead & Candidate Discovery Diazeniumdiolates, also known as NONOates, are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release nitric oxide (NO . ) and/or their congeneric nitroxyl (HNO). The purpose of this work was to synthesize a series of primary amine-based diazeniumdiolates as HNO/NO donors and to determine their efficacy as anticancer and antifungal agents in vivo. The seven compounds (3a-3g) were successfully synthesized and characterized, one of which had been previously reported in the literature (3g). Two compounds showed anti-proliferative effects against ovarian (ES2 and SKOV3) and AML monocyte-derived cancer cells (THP-1) when tested with standard MTT assays. Compounds 3a and 3g demonstrated reduced ovarian cancer cell proliferation when treated at doses from 0.033 to 1.0 mg/mL at the 24 hr time point. These compounds also exhibited moderate and selective antifungal activity against Fusarium oxysporum f.sp. lycopersici, one cause of opportunistic infections of immunocompromised patients, inhibiting the growth of the fungi at LD 50 at 10 mg/mL. A third compound (3e) did not exhibit similar activities, possibly due to the alkyl chain. Our results suggest that the primary amine diazeniumdiolates may offer a versatile platform for the development of HNO/NO donors for biomedical applications. © 2018 Wiley Periodicals, Inc.

  16. Extraction of some acids using aliphatic amines

    International Nuclear Information System (INIS)

    Matutano, L.

    1964-06-01

    Hydrochloric, nitric, sulphuric, perchloric, phosphoric, acetic and formic acids in aqueous solution (0.05 to 10 M) are extracted by amberlite LA2 and trilaurylamine in solution, 5 per cent by volume, in kerosene and xylene respectively. The extraction process consists of: neutralization of the amine salt; a 'molecular extraction', i.e. an extraction using an excess of acid with respect to the stoichiometry of the amine salt. According to the behaviour of the acid during the extraction, three groups may be distinguished: completely dissociated acids, carboxylic acids, phosphoric acid. This classification is also valid for the extraction of the water which occurs simultaneously with that of the acid. An extraction mechanism is put forward for formic acid and the formation constant of its amine salt is calculated. (author) [fr

  17. Base metal dehydrogenation of amine-boranes

    Science.gov (United States)

    Blacquiere, Johanna Marie [Ottawa, CA; Keaton, Richard Jeffrey [Pearland, TX; Baker, Ralph Thomas [Los Alamos, NM

    2009-06-09

    A method of dehydrogenating an amine-borane having the formula R.sup.1H.sub.2N--BH.sub.2R.sup.2 using base metal catalyst. The method generates hydrogen and produces at least one of a [R.sup.1HN--BHR.sup.2].sub.m oligomer and a [R.sup.1N--BR.sup.2].sub.n oligomer. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources, such as, but not limited to, fuel cells.

  18. Catalyst for hydrogen-amine D exchange

    International Nuclear Information System (INIS)

    Holtslander, W.J.; Johnson, R.E.

    1976-01-01

    A process is claimed for deuterium isotopic enrichment (suitable for use in heavy water production) by amine-hydrogen exchange in which the exchange catalyst comprises a mixture of alkyl amides of two metals selected from the group consisting of the alkali metals. Catalyst mixtures comprising at least one of the alkali amides of lithium and potassium are preferred. At least one of the following benefits are obtained: decreased hydride formation, decreased thermal decomposition of alkyl amide, increased catalyst solubility in the amine phase, and increased exchange efficiency. 11 claims

  19. Corrosion inhibition of brass by aliphatic amines

    International Nuclear Information System (INIS)

    Taha, K. K.; Sheshadri, B. S; Ahmed, M. F.

    2005-01-01

    Aliphatic amines hexylamine (HCA), octylamine (OCA) and decylamine (DCA) have been used as corrosion inhibitors for (70/30) brass in 0.I M HCIO 4 . The inhibitor efficiency (%P) calculated using weight loss, Tafel extrapolation, linear polarization and impedance methods was found to be in the order DCA> OCA> HCA. These adsorb on brass surface following bockris-swinkels' isotherm. DCA, OCA and HCA displaced 4, 3 and 2 molecules of water from interface respectively. Displacement of water molecules brought a great reorganization of double layer at the interface. These amines during corrosion form complexes with dissolved zinc and copper ions.(Author)

  20. Extraction of uranyl sulfate with primary amine

    International Nuclear Information System (INIS)

    Mrnka, M.; Bizek, V.; Nekovar, P.; Cizevska, S.; Schroetterova, D.

    1984-01-01

    PRIMENE JM-T was used for extraction. Its composition was found to approach the general formula C 21 H 43 NH 2 . It was found that the extraction of uranyl sulfate is lower in case of a higher steady-state concentration of sulfuric acid in the aqueous phase. Extraction is accompanied with coextraction of water. The results obtained showed that uranyl sulfate passes into the organic phase by two mechanisms: extraction with amine sulfate and extraction with free amine. A mathematical description of the process was made based on the obtained results. (E.S.)

  1. Kinetics of nitrosamine and amine reactions with NO3 radical and ozone related to aqueous particle and cloud droplet chemistry

    Science.gov (United States)

    Weller, Christian; Herrmann, Hartmut

    2015-01-01

    Aqueous phase reactivity experiments with the amines dimethylamine (DMA), diethanolamine (DEA) and pyrrolidine (PYL) and their corresponding nitrosamines nitrosodimethylamine (NDMA), nitrosodiethanolamine (NDEA) and nitrosopyrrolidine (NPYL) have been performed. NO3 radical reaction rate coefficients for DMA, DEA and PYL were measured for the first time and are 3.7 × 105, 8.2 × 105 and 8.7 × 105 M-1 s-1, respectively. Rate coefficients for NO3 + NDMA, NDEA and NPYL are 1.2 × 108, 2.3 × 108 and 2.4 × 108 M-1 s-1. Compared to OH radical rate coefficients for reactions with amines, the NO3 radical will most likely not be an important oxidant but it is a potential nighttime oxidant for nitrosamines in cloud droplets or deliquescent particles. Ozone is unreactive towards amines and nitrosamines and upper limits of rate coefficients suggest that aqueous ozone reactions are not important in atmospheric waters.

  2. Enantioselective catalytic syntheses of alpha-branched chiral amines

    DEFF Research Database (Denmark)

    Brase, S.; Baumann, T.; Dahmen, S.

    2007-01-01

    Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials.......Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials....

  3. Facilitated transport of HNO3 through a supported liquid membrane containing a tertiary amine as carrier

    International Nuclear Information System (INIS)

    Cianetti, C.; Danesi, P.R.

    1983-01-01

    The facilitated transport of HNO 3 through a supported liquid membrane consisting of a porous polypropylene film containing a solution of trilaurylamine in diethylbenzene as carrier was studied as a function of the stirring speed of the aqueous solutions and the membrane composition. A physico-chemical model which takes into account diffusion through an aqueous boundary layer, a fast interfacial chemical reaction leading to the formation of a membrane soluble alkylammonium salt and diffusion through the membrane was proposed. In this way, equations were derived which describe how composition changes, occurring in the course of the permeation process, influence the membrane permeability. The experimental data were quantitatively explained by the derived equations. The results indicate that the monomeric form of the trilaurylammonium nitrate salt is the species which is mainly responsible for the acid transport through the membrane. The diffusion coefficient of the permeating species and the order of magnitude of the thickness of the aqueous boundary layer were evaluated. 8 figures

  4. PHOTOINITIATED POLYMERIZATION BY ARYLIODONIUM SALT/BENZOPHENONE / TERTIARY AMINE BINARY PHOTOSENSITIZATION SYSTEM

    Institute of Scientific and Technical Information of China (English)

    HE Junhui; WANG Erjian

    1990-01-01

    A novel binary photosensitization system composed of benzophenone (BP) /diphenyliodonium chloride ( DPIOC )/triethylamine (TEA), exhibiting a good photoresponse at near UV and visible light regions, was used as the initiator for photopolymerization of MMA. The radical photogeneration in the binary system consists mainly of two parallel reactions, i. e., BP/TEA photohydrogen-abstraction and DPIOC/TEA complex photodecomposition, but the latter is more active than the former. The results of comparative study indicate that the rate of polymerization induced by the binary system (BDT) is remarkably higher than those by the corresponding single systems The polymerization rates are proportional to[BP] 0. 16, [ DPIOC] 0.32, [ TEA ] 0.45 and [MMA ] . The mechanism is also discussed.

  5. Emissions to the Atmosphere from Amine-Based Post Combustion CO2 Capture Plant - Regulatory Aspects

    International Nuclear Information System (INIS)

    Azzi, Merched; Angove, Dennys; Dave, Narendra; Day, Stuart; Do, Thong; Feron, Paul; Sharma, Sunil; Attalla, Moetaz; Abu Zahra, Mohammad

    2014-01-01

    Amine-based Post Combustion Capture (PCC) of CO 2 is a readily available technology that can be deployed to reduce CO 2 emissions from coal fired power plants. However, PCC plants will likely release small quantities of amine and amine degradation products to the atmosphere along with the treated flue gas. The possible environmental effects of these emissions have been examined through different studies carried out around the world. Based on flue gas from a 400 MW ultra-supercritical coal fired power plant Aspen-Plus PCC process simulations were used to predict the potential atmospheric emissions from the plant. Different research initiatives carried out in this area have produced new knowledge that has significantly reduced the risk perception for the release of amine and amine degradation products to the atmosphere. In addition to the reduction of the CO 2 emissions, the PCC technology will also help in reducing SO x and NO 2 emissions. However, some other pollutants such as NH 3 and aerosols will increase if appropriate control technologies are not adopted. To study the atmospheric photo-oxidation of amines, attempts are being made to develop chemical reaction schemes that can be used for air quality assessment. However, more research is still required in this area to estimate the reactivity of amino solvents in the presence of other pollutants such as NO x and other volatile organic compounds in the background air. Current air quality guidelines may need to be updated to include limits for the additional pollutants such as NH 3 , nitrosamines and nitramines once more information related to their emissions is available. This paper focuses on describing the predicted concentrations of major pollutants that are expected to be released from a coal fired power plant obtained by ASPEN-Plus PCC process simulations in terms of current air quality regulations and other regulatory aspects. (authors)

  6. Removing sulphur oxides from a fluid stream

    Science.gov (United States)

    Katz, Torsten; Riemann, Christian; Bartling, Karsten; Rigby, Sean Taylor; Coleman, Luke James Ivor; Lail, Marty Alan

    2014-04-08

    A process for removing sulphur oxides from a fluid stream, such as flue gas, comprising: providing a non-aqueous absorption liquid containing at least one hydrophobic amine, the liquid being incompletely miscible with water; treating the fluid stream in an absorption zone with the non-aqueous absorption liquid to transfer at least part of the sulphur oxides into the non-aqueous absorption liquid and to form a sulphur oxide-hydrophobic amine-complex; causing the non-aqueous absorption liquid to be in liquid-liquid contact with an aqueous liquid whereby at least part of the sulphur oxide-hydrophobic amine-complex is hydrolyzed to release the hydrophobic amine and sulphurous hydrolysis products, and at least part of the sulphurous hydrolysis products is transferred into the aqueous liquid; separating the aqueous liquid from the non-aqueous absorption liquid. The process mitigates absorbent degradation problems caused by sulphur dioxide and oxygen in flue gas.

  7. Oxyfunctionalization of the Remote C-H Bonds of Aliphatic Amines by Decatungstate Photocatalysis.

    Science.gov (United States)

    Schultz, Danielle M; Lévesque, François; DiRocco, Daniel A; Reibarkh, Mikhail; Ji, Yining; Joyce, Leo A; Dropinski, James F; Sheng, Huaming; Sherry, Benjamin D; Davies, Ian W

    2017-11-27

    Aliphatic amines, oxygenated at remote positions within the molecule, represent an important class of synthetic building blocks to which there are currently no direct means of access. Reported herein is an efficient and scalable solution that relies upon decatungstate photocatalysis under acidic conditions using either H 2 O 2 or O 2 as the terminal oxidant. By using these reaction conditions a series of simple and unbiased aliphatic amine starting materials can be oxidized to value-added ketone products. Lastly, NMR spectroscopy using in situ LED-irradiated samples was utilized to monitor the kinetics of the reaction, thus enabling direct translation of the reaction into flow. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Recyclable surfaces for amine conjugation chemistry via redox reaction

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Inseong; Yeo, Woon Seok [Dept. of Bioscience and Biotechnology, Bio/Molecular Informatics Center, Konkuk University, Seoul (Korea, Republic of); Bae, Se Won [Green Materials and Process Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

    2017-02-15

    In this study, we extended this strategy to present a switchable surface that allows surface functionalization and removal of functional groups repeatedly. The substrate presenting a benzoquinone acid group is first used to immobilize with an amine-containing (bio)molecule using well-known conjugation chemistry. The benzoquinone group is then converted to the corresponding hydroquinone by treating with a reducing agent. We have described a strategy for the dynamic control of surface properties with recyclability via a simple reduction/ oxidation reaction. A stimuli-responsive quinone derivative was harnessed for the repeated immobilization and release of (bio)molecules, and thus, for the repeated dynamic change of the surface properties according to the characteristics of the immobilized (bio)molecules.

  9. Purification and characterization of amine oxidase from soybean seedlings.

    Science.gov (United States)

    Vianello, F; Di Paolo, M L; Stevanato, R; Gasparini, R; Rigo, A

    1993-11-15

    A simple and rapid procedure for purification of soybean seedling amine oxidase is reported. The crude enzyme, obtained by ammonium sulfate fractionation was purified by ion-exchange chromatography on a cellulose phosphate column and batch affinity chromatography on 6-aminohexyl-Sepharose. Cyclohexylamine, a competitive inhibitor, was utilized to elute the enzyme. A homogeneous enzyme was obtained with a yield higher than 25%, the content of minor components being lauryl sulfate-polyacrylamide gel electrophoresis. The enzyme is a dimer and contains two Cu2+ ion per molecule. Its EPR spectrum is typical of Cu2+ in a tetragonal symmetry. The enzyme oxidizes cadaverine at high rate, the specific activity being 4.3 mukat/mg. Molecular, spectroscopic, and kinetic properties of this enzyme are reported.

  10. Reductive amination with zinc powder in aqueous media

    Directory of Open Access Journals (Sweden)

    Giovanni B. Giovenzana

    2011-08-01

    Full Text Available Zinc powder in aqueous alkaline media was employed to perform reductive amination of aldehydes with primary amines. The corresponding secondary amines were obtained in good yields along with minor amounts of hydrodimerization byproducts. The protocol is a green alternative to the use of complex hydrides in chlorinated or highly flammable solvents.

  11. The Synthesis of Methyl Salicylate: Amine Diazotization.

    Science.gov (United States)

    Zanger, Murray; McKee, James R.

    1988-01-01

    Notes that this experiment takes safety and noncarcinogenic reactants into account. Demonstrates the use of diazonium salts for the replacement of an aromatic amine group by a phenolic hydroxyl. Involves two pleasant-smelling organic compounds, methyl anthranilate (grape) and methyl salicylate (oil of wintergreen). (MVL)

  12. Microbiological, physicochemical properties and biogenic amine ...

    African Journals Online (AJOL)

    Thirty three strained yoghurt samples were collected from local open markets in different provinces of Turkey (Afyon [AF], Aydın [AY], Burdur [B], Isparta [I] and Muğla [M]). Physicochemical and microbiological properties, as well as biogenic amine content, were examined in each of the samples. The dry matter (17.90 to ...

  13. Direct amination of secondary alcohols using Ammonia

    NARCIS (Netherlands)

    Pingen, D.L.L.; Müller, C.; Vogt, D.

    2010-01-01

    Hydrogen shuttle: For the first time secondary alcohols and ammonia can be directly converted into primary amines with a selectivity of up to 99¿% by using a simple ruthenium/phosphine catalyst (see scheme; R1, R2= alkyl, aryl, alkenyl; M=[Ru3(CO)12]; and L=phosphine ligand).

  14. Direct Amination of alpha-Hydroxy Amides

    NARCIS (Netherlands)

    Chandgude, Ajay L.; Dömling, Alexander

    A TiCl4-mediated reaction for the direct amination of alpha-hydroxy amides has been developed. This simple, general, additive/base/ligand-free reaction is mediated by economical TiCl4. The reaction runs under mild conditions. This highly efficient C-N bond formation protocol is valid for diverse

  15. One-Pot Two-Step Multicomponent Process of Indole and Other Nitrogenous Heterocycles or Amines toward α-Oxo-acetamidines.

    Science.gov (United States)

    Martinez-Ariza, Guillermo; McConnell, Nicholas; Hulme, Christopher

    2016-04-15

    A cesium carbonate promoted three-component reaction of N-H containing heterocycles, primary or secondary amines, arylglyoxaldehydes, and anilines is reported. The key step involves a tandem sequence of N-1 addition of a heterocycle or an amine to preformed α-iminoketones, followed by an air- or oxygen-mediated oxidation to form α-oxo-acetamidines. The scope of the reaction is enticingly broad, and this novel methodology is applied toward the synthesis of various polycyclic heterocycles.

  16. Uranium diphosphonates templated by interlayer organic amines

    International Nuclear Information System (INIS)

    Nelson, Anna-Gay D.; Alekseev, Evgeny V.; Albrecht-Schmitt, Thomas E.; Ewing, Rodney C.

    2013-01-01

    The hydrothermal treatment of uranium trioxide and methylenediphosphonic acid with a variety of amines (2,2-dipyridyl, triethylenediamine, ethylenediamine, and 1,10-phenanthroline) at 200 °C results in the crystallization of a series of layered uranium diphosphonate compounds, [C 10 H 9 N 2 ]{UO 2 (H 2 O)[CH 2 (PO 3 )(PO 3 H)]} (Ubip2), [C 6 H 14 N 2 ]{(UO 2 ) 2 [CH 2 (PO 3 )(PO 3 H)] 2 ·2H 2 O} (UDAB), [C 2 H 10 N 2 ] 2 {(UO 2 ) 2 (H 2 O) 2 [CH 2 (PO 3 ) 2 ] 2 ·0.5H 2 O} (Uethyl), and [C 12 H 9 N 2 ]{UO 2 (H 2 O)[CH 2 (PO 3 )(PO 3 H)]} (Uphen). The crystal structures of the compounds are based on UO 7 units linked by methylenediphosphonate molecules to form two-dimensional anionic sheets in Ubip2 and UDAB, and one-dimensional anionic chains in Uethyl and Uphen, which are charge balanced by protonated amine molecules. Interaction of the amine molecules with phosphonate oxygens and water molecules results in extensive hydrogen bonding in the interlayer. These amine molecules serve both as structure-directing agents and charge-balancing cations for the anionic uranium phosphonate sheets and chains in the formation of the different coordination geometries and topologies of each structure. Reported herein are the syntheses, structural and spectroscopic characterization of the synthesized compounds. - Graphical abstract: The Raman spectra of the synthesized compounds and an illustration of the stacking of the layers with the diprotonated triethylenediamine molecules in [C 6 H 14 N 2 ]{(UO 2 ) 2 [CH 2 (PO 3 )(PO 3 H)] 2 ·2H 2 O} UDAB. Solvent water molecules are removed for clarity. The corresponding Raman spectra for the complexes synthesized is also shown. The structure is constructed from UO 7 pentagonal bipyramids (yellow), oxygen=red, phosphorus=magenta, carbon=black, and nitrogen=blue. Highlights: ► Organic amines act both as charge-balancing and as structure-directing agents. ► Extensive hydrogen bonding interactions with solvent water molecules and amines

  17. Extraction and selective stripping of uranium and molybdenum in sulfate solution using amines

    International Nuclear Information System (INIS)

    Sialino, E.; Mignot, C.; Michel, P.; Vial, J.

    1977-01-01

    The uranium solutions issued from leaching of AKOUTA ores and containing lot of molybdenum are purified using solvent extraction. During the first test run precipitation of complexes such as amine phosphomolybdate was observed. It was pointed out that the precipitation could be prevented if the molybdenum is oxidized in the feed prior to solvent extraction. Informations on the basic studies carried out to ensure the reliability of the process are given in the complete paper

  18. Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation.

    Science.gov (United States)

    Zheng, Yi-Wen; Chen, Bin; Ye, Pan; Feng, Ke; Wang, Wenguang; Meng, Qing-Yuan; Wu, Li-Zhu; Tung, Chen-Ho

    2016-08-17

    We present a blueprint for aromatic C-H functionalization via a combination of photocatalysis and cobalt catalysis and describe the utility of this strategy for benzene amination and hydroxylation. Without any sacrificial oxidant, we could use the dual catalyst system to produce aniline directly from benzene and ammonia, and phenol from benzene and water, both with evolution of hydrogen gas under unusually mild conditions in excellent yields and selectivities.

  19. Intolerance to dietary biogenic amines: a review.

    Science.gov (United States)

    Jansen, Sophia C; van Dusseldorp, Marijke; Bottema, Kathelijne C; Dubois, Anthony E J

    2003-09-01

    To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allerg*, intoler*, and adverse. Additionally, the keywords histamine, tyramine, and phenylethylamine were combined with headache, migraine, urticaria, oral challenge, and oral provocation. Articles were also selected from references in relevant literature. Only oral challenge studies in susceptible patients were considered. Studies with positive results (ie, studies in which an effect was reported) were only eligible when a randomized, double-blind, placebo-controlled design was used. Eligible positive result studies were further evaluated according to a number of scientific criteria. Studies with negative results (ie, studies in which no effect was reported) were examined for factors in their design or methods that could be responsible for a false-negative outcome. Results of methodologically weak or flawed studies were considered inconclusive. A total of 13 oral challenge studies (5 with positive results and 8 with negative results) were found. Three of them (all with positive results) were considered ineligible. By further evaluation of the 10 eligible studies, 6 were considered inconclusive. The 4 conclusive studies all reported negative results. One conclusive study showed no relation between biogenic amines in red wine and wine intolerance. Two conclusive studies found no effect of tyramine on migraine. One conclusive study demonstrated no relation between the amount of phenylethylamine in chocolate and headache attacks in individuals with headache. The current scientific literature shows no relation between the oral ingestion of biogenic amines and food intolerance reactions. There is therefore no scientific basis for dietary recommendations concerning biogenic amines in such patients.

  20. Degree of conversion and monomer elution of CQ/amine and TPO adhesives.

    Science.gov (United States)

    Pongprueksa, Pong; Miletic, Vesna; Janssens, Henriette; Van Landuyt, Kirsten L; De Munck, Jan; Godderis, Lode; Van Meerbeek, Bart

    2014-06-01

    To evaluate the effect of photo-initiator on the degree of conversion (DC) and elution of Bis-GMA and HEMA for 8 one-step adhesive formulations. We used Scotchbond Universal ('SBU-CQ/amine_4.0', 3M ESPE), containing about 2wt% camphorquinone (CQ) and 2wt% ethyl-4-dimethylamino benzoate (EDMAB), an experimental 'SBU-TPO_2.1' version, containing 2.1wt% diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), and 6 experimental LUB adhesives (Kuraray Noritake), namely 'LUB-CQ/amine_0.7', 'LUB-CQ/amine_1.4', 'LUB-CQ/amine_4.0', 'LUB-TPO_0.35', 'LUB-TPO_0.7' and 'LUB-TPO_2.0', respectively containing 0.35wt% CQ and 0.35wt% EDMAB, 0.7wt% CQ and 0.7wt% EDMAB, 2.0wt% CQ and 2.0wt% EDMAB, 0.35wt% TPO, 0.7wt% TPO, and 2.0wt% TPO. DC was measured using micro-Raman spectroscopy. Additional specimens were immersed in ethanol for 24h to determine the elution of Bis-GMA and HEMA using HPLC. DC of the respective SBU and LUB adhesives was alike at high photo-initiator concentration. At low concentration, TPO was significantly more efficient than CQ/amine (LUB adhesives only). A statistically significant positive photo-initiator concentration effect on DC was noted for both CQ/amine and TPO (LUB adhesives only). A statistically significant inverse photo-initiator concentration effect on HEMA elution was noted for both the CQ/amine- and TPO-containing LUB adhesives. A significantly strong correlation was found between DC and Bis-GMA elution (R(2)=0.744, p=0.026), and between DC and HEMA elution (R(2)=0.913, p=0.002) for the LUB adhesives. The photo-initiator kind and concentration affect DC and the Bis-GMA/HEMA elution. TPO can be used as an alternative photo-initiator for CQ/amine. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  1. Hydrothermal oxidation of an epoxy resin through the study of two model molecules: N-methyl-acetamide and N,N-di[1(phenoxy)2-hydroxy propyl-3] propyl-amine; Oxydation hydrothermale d'une resine epoxyde au travers de l'etude de deux molecules modeles: le N-methylacetamide et la N,N-di[1-(phenoxy) 2-hydroxy propyl-3] propylamine

    Energy Technology Data Exchange (ETDEWEB)

    Moutonnet-Fromonteil, C. [CEA/Cadarache, Dept. d' Etudes des Combustibles (DEC), 13 - Saint-Paul-lez-Durance (France)]|[Bordeaux-1 Univ., 33 (France)

    2000-07-01

    The study consists in choosing and developing a technology to realize damage experiments of an epoxy resin which is used as coating of embedded nuclear samples. Hydrothermal oxidation is the chosen method. We first identified the chemical composition of the epoxy resin. Then we studied hydrolysis and oxidation of a molecule which contains a function of the epoxy network: N-methyl-acetamide. The comparison between our results and those already existing allowed to validate this degradation method. In a second part, we studied a model molecule of the polymer network: N, N-di[1(phenoxy)2-hydroxy propyl-3] propyl-amine. The hydrolysis temperatures are relatively high: the compound is totally destroyed at 300 deg C. Its oxidation leads to the formation of acetic acid from 220 deg C. In the third study, we determined the best experimental conditions to destroy the epoxy resin. Experiments were performed at different temperatures between 200 deg C and 410 deg C. The degradation rates are classically defined by amounts of constituents in liquid and gaseous phases. (author)

  2. Biotransformation and bioactivation reactions of alicyclic amines in drug molecules.

    Science.gov (United States)

    Bolleddula, Jayaprakasam; DeMent, Kevin; Driscoll, James P; Worboys, Philip; Brassil, Patrick J; Bourdet, David L

    2014-08-01

    Aliphatic nitrogen heterocycles such as piperazine, piperidine, pyrrolidine, morpholine, aziridine, azetidine, and azepane are well known building blocks in drug design and important core structures in approved drug therapies. These core units have been targets for metabolic attack by P450s and other drug metabolizing enzymes such as aldehyde oxidase and monoamine oxidase (MAOs). The electron rich nitrogen and/or α-carbons are often major sites of metabolism of alicyclic amines. The most common biotransformations include N-oxidation, N-conjugation, oxidative N-dealkylation, ring oxidation, and ring opening. In some instances, the metabolic pathways generate electrophilic reactive intermediates and cause bioactivation. However, potential bioactivation related adverse events can be attenuated by structural modifications. Hence it is important to understand the biotransformation pathways to design stable drug candidates that are devoid of metabolic liabilities early in the discovery stage. The current review provides a comprehensive summary of biotransformation and bioactivation pathways of aliphatic nitrogen containing heterocycles and strategies to mitigate metabolic liabilities.

  3. Tertiary climatic fluctuations and methods of analysis of tertiary floras

    Science.gov (United States)

    Wolfe, J.A.

    1971-01-01

    On theoretical grounds, an analysis of the physiognomy of a Tertiary leaf assemblage is more direct and reliable than a circuitous floristic analysis in assigning thermal regimes to fossil assemblages. Using primarily foliar physiognomy and secondarily floristic composition, it can be shown that: (1) some middle latitude Tertiary assemblages probably lived under meteoroligically tropical climates; (2) a major and rapid climatic deterioration occurred in the Oligocene; and (3) a major climatic fluctuation probably occurred in the Late Eocene. These analyses thus substantiate the conclusions of several other paleobotanists regarding climatic fluctuations. Recent criticisms of these analyses are shown to be invalid and to be based largely on misinterpretations. ?? 1971.

  4. Extraction of sulphates by long chain amines; Extraction des sulfates par les amines a longues chaines

    Energy Technology Data Exchange (ETDEWEB)

    Boirie, Ch [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1959-05-15

    The extraction of sulphuric acid by long chain amines in organic solution has been studied with a view to determining the value of the stability constants of the amine sulphates and bi-sulphates formed. We have concentrated chiefly on uranium sulphate and thorium sulphate. The formulae of the complexes extractable with amines have been established, as well as the corresponding dissociation constants. We have observed that for uranium sulphate the formula of the complex depends only on the nature of the amine, whereas for thorium this formula varies with the amine structure. From the formulae determined and the value of the constants calculated, we have been able to establish the best conditions for uranium and thorium extraction and also for a separation of these two elements. Finally we propose an application of this study to the determination of uranium in ores, where the separation of uranium by this method is particularly easy and complete. (author) [French] L'extraction de l'acide sulfurique par des amines a longues chaines en solution organique a ete etudiee en vue de la determination de la valeur des constantes de stabilite des sulfates et bisulfates d'amines formes. Parmi les sulfates, nous nous sommes particulierement interesses au sulfate d'uranium et au sulfate de thorium. Nous avons determine les formules des complexes extractibles avec les amines, ainsi que les constantes de dissociation correspondantes. Nous avons remarque que pour le sulfate d'uranium, la formule du complexe ne depend que de la nature de l'amine, alors que pour le thorium cette formule varie avec la structure de l'amine. Les formules determinees et la valeur des constantes calculees, nous ont permis de decrire les meilleures conditions d'extraction de l'uranium et du thorium ainsi que celles d'une separation de ces deux elements. Nous proposons enfin une application de cette etude au dosage de l'uranium dans les minerais, ou la separation de l'uranium par cette methode est

  5. Green Preparation of Epoxy/Graphene Oxide Nanocomposites Using a Glycidylamine Epoxy Resin as the Surface Modifier and Phase Transfer Agent of Graphene Oxide.

    Science.gov (United States)

    Tang, Xinlei; Zhou, Yang; Peng, Mao

    2016-01-27

    In studies of epoxy/graphene oxide (GO) nanocomposites, organic solvents are commonly used to disperse GO, and vigorous mechanical processes and complicated modification of GO are usually required, increasing the cost and hindering the development and application of epoxy nanocomposites. Here, we report a green, facile, and efficient method of preparing epoxy/GO nanocomposites. When triglycidyl para-aminophenol (TGPAP), a commercially available glycidyl amine epoxy resin with one tertiary amine group per molecule, is used as both the surface modifier and phase transfer agent of GO, GO can be directly and rapidly transferred from water to diglycidyl ether of bisphenol A and other types of epoxy resins by manual stirring under ambient conditions, whereas GO cannot be transferred to these epoxy resins in the absence of TGPAP. The interaction between TGPAP and GO and the effect of the TGPAP content on the dispersion of GO in the epoxy matrix were investigated systematically. Superior dispersion and exfoliation of GO nanosheets and remarkably improved mechanical properties, including tensile and flexural properties, toughness, storage modulus, and microhardness, of the epoxy/GO nanocomposites with a suitable amount of TGPAP were demonstrated. This method is organic-solvent-free and technically feasible for large-scale preparation of high-performance nanocomposites; it opens up new opportunities for exploiting the unique properties of graphene or even other nanofillers for a wide range of applications.

  6. Extraction of some acids using aliphatic amines; Extraction de quelques acides par des amines aliphatiques

    Energy Technology Data Exchange (ETDEWEB)

    Matutano, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-06-01

    Hydrochloric, nitric, sulphuric, perchloric, phosphoric, acetic and formic acids in aqueous solution (0.05 to 10 M) are extracted by amberlite LA2 and trilaurylamine in solution, 5 per cent by volume, in kerosene and xylene respectively. The extraction process consists of: neutralization of the amine salt; a 'molecular extraction', i.e. an extraction using an excess of acid with respect to the stoichiometry of the amine salt. According to the behaviour of the acid during the extraction, three groups may be distinguished: completely dissociated acids, carboxylic acids, phosphoric acid. This classification is also valid for the extraction of the water which occurs simultaneously with that of the acid. An extraction mechanism is put forward for formic acid and the formation constant of its amine salt is calculated. (author) [French] Les acides chlorhydrique, nitrique, sulfurique, perchlorique, phosphorique, acetique et formique, en solution aqueuse - 0,05 a 10 M - sont extraits par l'amberlite LA2 et la trilaurylamine en solution, a 5 pour cent en volume, dans le kerosene et le xylene respectivement. L'extraction comprend: une neutralisation de l'amine par l'acide avec formation d'un sel d'amine; une 'extraction moleculaire', c'est-a-dire une extraction d'acide en exces par rapport a la stoechiometrie du sel d'amine. Suivant le comportement des acides au cours de l'extraction nous distinguons trois groupes: acides entierement dissocies, acides carboxyliques, acide phosphorique. Cette classification est egalement valable pour l'extraction de l'eau qui est simultanee a celle de l'acide. Un mecanisme d'extraction pour l'acide formique est propose et nous calculons la constante de formation de son sel d'amine. (auteur)

  7. Metabolism and Biomarkers of Heterocyclic Aromatic Amines in Molecular Epidemiology Studies: Lessons Learned from Aromatic Amines

    Science.gov (United States)

    2011-01-01

    Aromatic amines and heterocyclic aromatic amines (HAAs) are structurally related classes of carcinogens that are formed during the combustion of tobacco or during the high-temperature cooking of meats. Both classes of procarcinogens undergo metabolic activation by N-hydroxylation of the exocyclic amine group, to produce a common proposed intermediate, the arylnitrenium ion, which is the critical metabolite implicated in toxicity and DNA damage. However, the biochemistry and chemical properties of these compounds are distinct and different biomarkers of aromatic amines and HAAs have been developed for human biomonitoring studies. Hemoglobin adducts have been extensively used as biomarkers to monitor occupational and environmental exposures to a number of aromatic amines; however, HAAs do not form hemoglobin adducts at appreciable levels and other biomarkers have been sought. A number of epidemiologic studies that have investigated dietary consumption of well-done meat in relation to various tumor sites reported a positive association between cancer risk and well-done meat consumption, although some studies have shown no associations between well-done meat and cancer risk. A major limiting factor in most epidemiological studies is the uncertainty in quantitative estimates of chronic exposure to HAAs and, thus, the association of HAAs formed in cooked meat and cancer risk has been difficult to establish. There is a critical need to establish long-term biomarkers of HAAs that can be implemented in molecular epidemioIogy studies. In this review article, we highlight and contrast the biochemistry of several prototypical carcinogenic aromatic amines and HAAs to which humans are chronically exposed. The biochemical properties and the impact of polymorphisms of the major xenobiotic-metabolizing enzymes on the biological effects of these chemicals are examined. Lastly, the analytical approaches that have been successfully employed to biomonitor aromatic amines and HAAs, and

  8. Study of the degradation mechanisms of amines used for the capture of CO{sub 2} in industrial fumes; Etude des mecanismes de degradation des amines utilisees pour le captage du CO{sub 2} dans les fumees

    Energy Technology Data Exchange (ETDEWEB)

    Lepaumier, H

    2008-10-15

    Global warming leads to reduce greenhouse gas emissions. Post combustion CO{sub 2} capture with solvent is the most advanced technology to reduce CO{sub 2} emissions in industrial fumes. A major problem associated with chemical absorption of CO{sub 2} using the benchmark ethanolamine (MEA) is solvent degradation through irreversible side reactions with CO{sub 2} and O{sub 2} which leads to numerous harmful impacts to the process: corrosion, solvent loss, foaming, fouling, and viscosity increase. So, developing new amines with higher chemical stability is essential. This work is based on the chemical stability study of 17 different molecules. Their structures have been chosen in order to establish structure-property relationships: alkanolamines, known for gas treatment application (MEA, DEA, MDEA, AMP...), di-amines, and tri-amines without alcohol function. Impact of temperature, CO{sub 2}, and O{sub 2} on degradation has been studied. Strong experimental conditions have been used to observe significant degradation after a 15 days experiment. Separation, identification and quantification of degradation products have been performed by using different testing instructions such as gas chromatography, mass spectrometry, ionic chromatography and NMR. Different mechanisms are proposed to explain most of degradation compounds. Radical reactions (dealkylation, alkylation, ring-closure reactions and piperazinones formation) are involved under O{sub 2} pressure whereas CO{sub 2} induces ionic reactions (dealkylation, alkylation, addition, ring-closure reactions and oxazolidinones or imidazolidinones formation). Large discrepancies of stability are noticed among the different amines. Knowledge of degradation products and reaction mechanisms has thus permitted to establish some relationships between structure and chemical stability: for example, role of the amine function (primary, secondary, tertiary), impact of alkyl chain length between the two amino groups and steric

  9. Deuterium exchange between hydrofluorocarbons and amines

    International Nuclear Information System (INIS)

    Hammond, W.B.; Bigeleisen, J.; Tuccio, S.A.

    1983-01-01

    The invention consists of a process for obtaining a compound enriched in deuterium which comprises the known method of exposing a gaseous hydrofluorocarbon to infrared laser radiation of a predetermined frequency to selectively cause a chemical reaction involving hydrofluorocarbon molecules containing deuterium without substantially affecting hydrofluorocarbon molecules not containing deuterium, thereby producing, as reaction products, a compound enriched in deuterium and hydrofluorocarbon depleted in deuterium; combined with a new method, which comprises enriching the deuterium content of the depleted hydrofluorocarbon by contacting the depleted hydrofluorocarbon with an alkali metal amide and an amine having a concentration of deuterium at least that which will yield an increase in deuterium concentration of the hydrofluorocarbon upon equilibration, whereby the amine becomes depleted in deuterium

  10. Amine chemistry. Update on impact on resin

    International Nuclear Information System (INIS)

    Bachman, Gregory; Kellogg, Douglas; Wilkes, Marty

    2012-01-01

    Impurity removal in the steam cycle and the associated prevention of corrosion and/or fouling of system components are the goals of ion exchange resins. However, in many instances (such as a switch to amine chemistry or a change in product specifications), resins do not remove, and, in fact, contribute impurities to the steam cycle. This paper reviews recent data compiled to determine the direct and indirect effects of amines on ion exchange resins used in the power industry. Water chemistries have improved in recent years, in large part due to changes in chemistry and resins, but it is necessary to continue to develop products, processes and techniques to reduce impurities and improve overall water chemistry in power plant systems. (orig.)

  11. Amine chemistry. Update on impact on resin

    Energy Technology Data Exchange (ETDEWEB)

    Bachman, Gregory; Kellogg, Douglas [Siemens Industry, Inc., Rockford, IL (United States). Technology and Lab Services; Wilkes, Marty [Siemens Industry, Inc., Rockford, IL (United States). Water Technologies Div.

    2012-03-15

    Impurity removal in the steam cycle and the associated prevention of corrosion and/or fouling of system components are the goals of ion exchange resins. However, in many instances (such as a switch to amine chemistry or a change in product specifications), resins do not remove, and, in fact, contribute impurities to the steam cycle. This paper reviews recent data compiled to determine the direct and indirect effects of amines on ion exchange resins used in the power industry. Water chemistries have improved in recent years, in large part due to changes in chemistry and resins, but it is necessary to continue to develop products, processes and techniques to reduce impurities and improve overall water chemistry in power plant systems. (orig.)

  12. Rate phenomena in uranium extraction by amines

    International Nuclear Information System (INIS)

    Coleman, C.F.; McDowell, W.J.

    1979-01-01

    Kinetics studies and other rate measurements are reviewed in the amine extraction of uranium and of some other related and associated metal ions. Equilibration is relatively fast in the uranium sulfate systems most important to uranium hydrometallurgy. Significantly slow equilibration has been encountered in some other systems. Most of the recorded rate information, both qualitative and quantitative, has come from exploratory and process-development work, while some kinetics studies have been directed specifically toward elucidation of extraction mechanisms. 71 references

  13. Study of the degradation mechanisms of amines used for the capture of CO2 in industrial fumes

    International Nuclear Information System (INIS)

    Lepaumier, H.

    2008-10-01

    Global warming leads to reduce greenhouse gas emissions. Post combustion CO 2 capture with solvent is the most advanced technology to reduce CO 2 emissions in industrial fumes. A major problem associated with chemical absorption of CO 2 using the benchmark ethanolamine (MEA) is solvent degradation through irreversible side reactions with CO 2 and O 2 which leads to numerous harmful impacts to the process: corrosion, solvent loss, foaming, fouling, and viscosity increase. So, developing new amines with higher chemical stability is essential. This work is based on the chemical stability study of 17 different molecules. Their structures have been chosen in order to establish structure-property relationships: alkanolamines, known for gas treatment application (MEA, DEA, MDEA, AMP...), di-amines, and tri-amines without alcohol function. Impact of temperature, CO 2 , and O 2 on degradation has been studied. Strong experimental conditions have been used to observe significant degradation after a 15 days experiment. Separation, identification and quantification of degradation products have been performed by using different testing instructions such as gas chromatography, mass spectrometry, ionic chromatography and NMR. Different mechanisms are proposed to explain most of degradation compounds. Radical reactions (dealkylation, alkylation, ring-closure reactions and piperazinones formation) are involved under O 2 pressure whereas CO 2 induces ionic reactions (dealkylation, alkylation, addition, ring-closure reactions and oxazolidinones or imidazolidinones formation). Large discrepancies of stability are noticed among the different amines. Knowledge of degradation products and reaction mechanisms has thus permitted to establish some relationships between structure and chemical stability: for example, role of the amine function (primary, secondary, tertiary), impact of alkyl chain length between the two amino groups and steric hindrance. (author)

  14. Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent.

    Science.gov (United States)

    Gündüz, T; Kiliç, E; Cakirer, O

    1996-05-01

    Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.

  15. Rethinking the Tertiary Mathematics Curriculum

    Science.gov (United States)

    Petocz, Peter; Reid, Anna

    2005-01-01

    Mathematics curriculum at the tertiary level is located within a range of social and cultural theories, and is often constructed by academics seeking to promulgate a particular view of mathematics. We argue that such a curriculum should incorporate a real acknowledgement of the different ways in which students understand the nature of mathematics…

  16. Single-walled carbon nanotube/metalloporphyrin composites for the chemiresistive detection of amines and meat spoilage.

    Science.gov (United States)

    Liu, Sophie F; Petty, Alexander R; Sazama, Graham T; Swager, Timothy M

    2015-05-26

    Chemiresistive detectors for amine vapors were made from single-walled carbon nanotubes by noncovalent modification with cobalt meso-arylporphyrin complexes. We show that through changes in the oxidation state of the metal, the electron-withdrawing character of the porphyrinato ligand, and the counteranion, the magnitude of the chemiresistive response to ammonia could be improved. The devices exhibited sub-ppm sensitivity and high selectivity toward amines as well as good stability to air, moisture, and time. The application of these chemiresistors in the detection of various biogenic amines (i.e. putrescine, cadaverine) and in the monitoring of spoilage in raw meat and fish samples (chicken, pork, salmon, cod) over several days was also demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Isotopes in oxidation reactions

    International Nuclear Information System (INIS)

    Stewart, R.

    1976-01-01

    The use of isotopes in the study of organic oxidation mechanisms is discussed. The help provided by tracer studies to demonstrate the two-equivalent path - hydride transfer, is illustrated by the examples of carbonium oxidants and the Wacker reaction. The role of kinetic isotope effects in the study of the scission of carbon-hydrogen bonds is illustrated by hydride abstraction, hydrogen atom abstraction, proton abstraction and quantum mechanical tunnelling. Isotopic studies on the oxidation of alcohols, carbonyl compounds, amines and hydrocarbons are discussed. The role of isotopes in the study of biochemical oxidation is illustrated with a discussion on nicotinamide and flavin coenzymes. (B.R.H.)

  18. Oxidative allene amination for the synthesis of azetidin-3-ones.

    Science.gov (United States)

    Burke, Eileen G; Schomaker, Jennifer M

    2015-10-05

    Regioselectivity in the aziridination of silyl-substituted homoallenic sulfamates is readily diverted to the distal double bond of the allene to yield endocyclic bicyclic methyleneaziridines with excellent stereocontrol. Subsequent reaction with electrophilic oxygen sources initiates facile rearrangement to densely functionalized, fused azetidin-3-ones in excellent d.r., effectively transferring the axial chirality of the allene to central chirality in the products. The steric nature of the silyl group dictates which of the two rings of the fused azetidin-3-one will undergo further functionalization, providing an additional element of diversity for the preparation of enantioenriched azetidine scaffolds with potential biological activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Uranium diphosphonates templated by interlayer organic amines

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Anna-Gay D., E-mail: nelsoa@umich.edu [Department of Civil Engineering and Geological Sciences, University of Notre Dame, IN 46556 (United States); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Alekseev, Evgeny V. [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Juelich Wilhelm-Johnen-Strasse, 52428 Juelich (Germany); Institut fuer Kristallographie, RWTH Aachen University, D-52066 Aachen (Germany); Albrecht-Schmitt, Thomas E. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, IN 46556 (United States); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States)

    2013-02-15

    The hydrothermal treatment of uranium trioxide and methylenediphosphonic acid with a variety of amines (2,2-dipyridyl, triethylenediamine, ethylenediamine, and 1,10-phenanthroline) at 200 Degree-Sign C results in the crystallization of a series of layered uranium diphosphonate compounds, [C{sub 10}H{sub 9}N{sub 2}]{l_brace}UO{sub 2}(H{sub 2}O)[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{r_brace} (Ubip2), [C{sub 6}H{sub 14}N{sub 2}]{l_brace}(UO{sub 2}){sub 2}[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{sub 2}{center_dot}2H{sub 2}O{r_brace} (UDAB), [C{sub 2}H{sub 10}N{sub 2}]{sub 2}{l_brace}(UO{sub 2}){sub 2}(H{sub 2}O){sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sub 2}{center_dot}0.5H{sub 2}O{r_brace} (Uethyl), and [C{sub 12}H{sub 9}N{sub 2}]{l_brace}UO{sub 2}(H{sub 2}O)[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{r_brace} (Uphen). The crystal structures of the compounds are based on UO{sub 7} units linked by methylenediphosphonate molecules to form two-dimensional anionic sheets in Ubip2 and UDAB, and one-dimensional anionic chains in Uethyl and Uphen, which are charge balanced by protonated amine molecules. Interaction of the amine molecules with phosphonate oxygens and water molecules results in extensive hydrogen bonding in the interlayer. These amine molecules serve both as structure-directing agents and charge-balancing cations for the anionic uranium phosphonate sheets and chains in the formation of the different coordination geometries and topologies of each structure. Reported herein are the syntheses, structural and spectroscopic characterization of the synthesized compounds. - Graphical abstract: The Raman spectra of the synthesized compounds and an illustration of the stacking of the layers with the diprotonated triethylenediamine molecules in [C{sub 6}H{sub 14}N{sub 2}]{l_brace}(UO{sub 2}){sub 2}[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{sub 2}{center_dot}2H{sub 2}O{r_brace} UDAB. Solvent water molecules are removed for clarity. The corresponding Raman spectra for the complexes synthesized is also

  20. Amine promoted, metal enhanced degradation of Mirex under high temperature conditions

    Energy Technology Data Exchange (ETDEWEB)

    Jallad, Karim N. [American University of Sharjah, Department of Chemistry, P.O. Box 26666, Sharjah (United Arab Emirates)]. E-mail: kjallad@runbox.com; Lynn, Bert C. [University of Kentucky, Department of Chemistry, Lexington, KY 40506-055 (United States); Alley, Earl G. [Mississippi State University, Department of Chemistry, MS State, MS 39762 (United States)

    2006-07-31

    In this study, zero-valent metal dehalogenation of mirex was conducted with amine solvents at high temperatures. Mirex was treated with excess amine in sealed glass tube reactors under nitrogen. The amines used were n-butyl amine (l), ethyl amine (l), dimethyl amine (g), diethyl amine (l), triethyl amine (l), trimethyl amine (g) and ammonia (g). The metals used were copper, zinc, magnesium, aluminum and calcium. The most suitable amine solvent and metal were selected by running a series of reactions with different amines and different zero-valent metals, in order to optimize the conditions under which complete degradation of mirex takes place. These dehalogenation reactions illustrated the role of zero-valent metals as reductants, whereas the amine solvents acted as proton donors. In this study, we report that mirex was completely degraded with diethyl amine (l) in the presence of copper at 100 deg. C and the hydrogenated products accounted for more than 94 of the degraded mirex.

  1. 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.

  2. Amine functionalized TiO2-carbon nanotube composite: synthesis, characterization and application to glucose biosensing

    Science.gov (United States)

    Tasviri, Mahboubeh; Rafiee-Pour, Hossain-Ali; Ghourchian, Hedayatollah; Gholami, Mohammad Reza

    2011-12-01

    The synthesis of amine functionalized TiO2-coated multiwalled carbon nanotubes (NH2-TiO2-CNTs) using sol-gel method was investigated. The synthesized nanocomposite was characterized with XRD, FTIR spectroscopy, BET test and SEM imaging. The results demonstrated a unique nanostructure with no destruction of the CNTs' shape. In addition, the presence of amine groups on the composite surface was confirmed by FTIR. This nanocomposite was used for one-step immobilization of glucose oxidase (GOx) to sense glucose. The result of cyclic voltammetry showed a pair of well-defined and quasi-reversible peaks for direct electron transfer of GOx in the absence of glucose. Also, the result of electrochemical impedance spectroscopy indicated that GOx was successfully immobilized on the surface of NH2-TiO2-CNTs. Furthermore, good amperometric response showed that immobilized GOx on the NH2-TiO2-CNTs exhibits exceptional bioelectrocatalytic activity toward glucose oxidation.

  3. Role of L-alanine for redox self-sufficient amination of alcohols.

    Science.gov (United States)

    Klatte, Stephanie; Wendisch, Volker F

    2015-01-23

    In white biotechnology biocatalysis represents a key technology for chemical functionalization of non-natural compounds. The plasmid-born overproduction of an alcohol dehydrogenase, an L-alanine-dependent transaminase and an alanine dehydrogenase allows for redox self-sufficient amination of alcohols in whole cell biotransformation. Here, conditions to optimize the whole cell biocatalyst presented in (Bioorg Med Chem 22:5578-5585, 2014), and the role of L-alanine for efficient amine functionalization of 1,10-decanediol to 1,10-diaminodecane were analyzed. The enzymes of the cascade for amine functionalization of alcohols were characterized in vitro to find optimal conditions for an efficient process. Transaminase from Chromobacterium violaceum, TaCv, showed three-fold higher catalytic efficiency than transaminase from Vibrio fluvialis, TaVf, and improved production at 37°C. At 42°C, TaCv was more active, which matched thermostable alcohol dehydrogenase and alanine dehydrogenase and improved the 1,10-diaminodecane production rate four-fold. To study the role of L-alanine in the whole cell biotransformation, the L-alanine concentration was varied and 1,10.diaminodecane formation tested with constant 10 mM 1,10- decanediol and 100 mM NH4Cl. Only 5.6% diamine product were observed without added L-alanine. L-alanine concentrations equimolar to that of the alcohol enabled for 94% product formation but higher L-alanine concentrations allowed for 100% product formation. L-alanine was consumed by the E. coli biocatalyst, presumably due to pyruvate catabolism since up to 16 mM acetate accumulated. Biotransformation employing E. coli strain YYC202/pTrc99a-ald-adh-ta Cv, which is unable to catabolize pyruvate, resulted in conversion with a selectivity of 42 mol-%. Biotransformation with E. coli strains only lacking pyruvate oxidase PoxB showed similar reduced amination of 1,10-decanediol indicating that oxidative decarboxylation of pyruvate to acetate by PoxB is primarily

  4. Methemoglobin Formation and Characterization of Hemoglobin Adducts of Carcinogenic Aromatic Amines and Heterocyclic Aromatic Amines.

    Science.gov (United States)

    Pathak, Khyatiben V; Chiu, Ting-Lan; Amin, Elizabeth Ambrose; Turesky, Robert J

    2016-03-21

    Arylamines (AAs) and heterocyclic aromatic amines (HAAs) are structurally related carcinogens formed during the combustion of tobacco or cooking of meat. They undergo cytochrome P450 mediated N-hydroxylation to form metabolites which bind to DNA and lead to mutations. The N-hydroxylated metabolites of many AAs also can undergo a co-oxidation reaction with oxy-hemolgobin (HbO2) to form methemoglobin (met-Hb) and the arylnitroso intermediates, which react with the β-Cys(93) chain of Hb to form Hb-arylsulfinamide adducts. The biochemistry of arylamine metabolism has been exploited to biomonitor certain AAs through their Hb arylsulfinamide adducts in humans. We examined the reactivity of HbO2 with the N-hydroxylated metabolites of 4-aminobiphenyl (ABP, HONH-ABP), aniline (ANL, HONH-ANL), and the HAAs 2-amino-9H-pyrido[2,3-b]indole (AαC, HONH-AαC), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP, HONH-PhIP), and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx, HONH-MeIQx). HONH-ABP, HO-ANL, and HONH-AαC induced methemoglobinemia and formed Hb sulfinamide adducts. However, HONH-MeIQx and HONH-PhIP did not react with the oxy-heme complex, and met-Hb formation and chemical modification of the β-Cys(93) residue were negligible. Molecular modeling studies showed that the distances between the H-ON-AA or H-ON-HAA substrates and the oxy-heme complex of HbO2 were too far away to induce methemoglobinemia. Different conformational changes in flexible helical and loop regions around the heme pocket induced by the H-ON-AA or H-ON-HAAs may explain the different proclivities of these chemicals to induce methemoglobinemia. Hb-Cys(93β) sulfinamide and sulfonamide adducts of ABP, ANL, and AαC were identified, by Orbitrap MS, following the proteolysis of Hb with trypsin, Glu-C, or Lys-C. Hb sulfinamide and sulfonamide adducts of ABP were identified in the blood of mice exposed to ABP, by Orbitrap MS. This is the first report of the identification of intact Hb

  5. Theoretical investigation of some high-performance novel amine azide propellants

    Energy Technology Data Exchange (ETDEWEB)

    Sengupta, Debasis [Computational Fluid Dynamics Research Corp., Huntsville, AL 35805 (United States); Raman, Sumathi [Department of Chemistry, Oakwood College, 2000 Adventist Blvd., Huntsville, AL 35896 (United States)

    2007-08-15

    Monomethylhydrazine (MMH) is currently the most widely used hypergolic propellant, due to its high performance and low ignition delay. However, its toxicity is a major concern. The present work aims at developing high-performance hypergolic fuels that are based on tertiary amine azide functionality. A number of potential amine azide candidates have been proposed, and some of their physical and chemical properties have been computed using state-of-the-art molecular modeling techniques. Gas-phase heats of formation have been calculated using the CBS-QB3 method, and the first-principle COSMO-RS method has been used to compute heats of vaporization and vapor pressures. A density correlation, based on molecular-volume calculation, has been established to predict the densities of the candidate molecules. Finally, the liquid-phase heats of formation and densities have been used to predict the specific and density impulses of the proposed candidate molecules. The results show that many of the molecules proposed here have much higher density impulse than that of MMH, and may be considered for experimental studies. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  6. Treatment of effluents from ammonia plants--3. Ozonation of amines in an effluent from a reforming plant serving an ammonia complex

    Energy Technology Data Exchange (ETDEWEB)

    Wilde, F G.N.D.

    1977-01-01

    The use of ozone in aqueous solutions was studied in an investigation of the oxidation of methylamines in the process condensate from an ammonia plant. Good conversion of trimethylamine to the nonodorous oxidation product could be achieved with a 1:1.5 ratio of amine to ozone when ozone passed into a packed tower through which an alkaline solution of the amine was flowing. Mono- and dimethylamine did not react as readily. The importance of a high pH value is stressed.

  7. Fluorescence quenching of Rhodamine B base by two amines

    Science.gov (United States)

    Bakkialakshmi, S.; Selvarani, P.; Chenthamarai, S.

    2013-03-01

    Fluorescence quenching of Rhodamine B base (RhB) in DMF solution has been studied at different concentrations of the amine Triethyl amine (TEA) and n-butyl amine (NBA) at room temperature. It has been observed that the fluorescence intensity of RhB decrease with increase in the concentration of the TEA and NBA. It has been observed that the quenching due to amines proceeds via dynamic quenching process. The rate constants for the quenching process have been calculated using Stern-Volmer equation. Time resolved fluorescence study and 1H NMR spectral study have also been carried out and discussed.

  8. Evaluation of amine inhibitors for suitability as crevice buffering agents

    International Nuclear Information System (INIS)

    Jayaweera, P.; Hettiarachchi, S.

    1994-03-01

    This report describes the results of a research effort to evaluate the suitability of some selected amines and amino acids as a crevice-buffering agents in pressurized water reactor (PWR) steam generators. The amines may be useful for buffering acid crevices, and the amino acids, because they contain both acidic and basic groups, may be useful for acidic and caustic crevices. Five commercially available amines and two amino acids were studied during this research. The study involved (1) the hydrolysis of these commercially available amines and amino acids, including measurement of their kinetics of decomposition, in simulated steam generator bulk water at 290 C, and (2) determination of their thermal stability in a simulated crevice environment. The study showed that, although the high-molecular-weight amines undergo hydrothermal decomposition, they have a better buffering capacity than their low-molecular-weight counterparts at 290 C. The amines provide effective crevice buffering by increasing the pH of the crevice solution by as much as 2.84 and to 4.24 units in the experimental setup used in this program. It was concluded that polyamines provide excellent buffering of the simulated crevice environment at 290 C and morpholine remains the best low-molecular-weight amine investigated. However, detailed volatility studies of the amines were not considered in this work. Such data would be needed before in-plant testing to ensure that the amines can concentrate in steam generator crevices to the levels assumed in this study

  9. Evaluation of tertiary treatments for the reduction of refractory micropollutants in wastewater

    OpenAIRE

    Besnault, S.; Martin Ruel, S.; Baig, S.; Heiniger, B.; Esperanza, M.; Budzinski, H.; Miege, C.; Coquery, M.; Dauthuille, P.

    2012-01-01

    Some refractory micropollutants remain in treated wastewater after secondary treatments. In order to reduce their concentration in treated water, tertiary treatments can be used such as advanced oxidation processes and activated carbon. The efficiency of granular activated carbon in a long term is not well known and advanced oxidation processes have mostly been studied at laboratory scale. Advanced oxidation processes and granular activated carbon pilots were studied in two different wastewat...

  10. Enantioselective Direct α-Amination of Aldehydes via a Photoredox Mechanism: A Strategy for Asymmetric Amine Fragment Coupling

    OpenAIRE

    Cecere, Giuseppe; Koenig, Christian M.; Alleva, Jennifer L.; MacMillan, David W. C.

    2013-01-01

    The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated, nitrogen-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Important...

  11. Parathyroid carcinoma in tertiary hyperparathyroidism.

    Science.gov (United States)

    Kim, Byung Seup; Ryu, Han Suk; Kang, Kyung Ho; Park, Sung Jun

    2016-10-01

    Parathyroid carcinoma is a rare disease of unknown etiology. This study presents a case of parathyroid carcinoma in a patient with tertiary hyperparathyroidism. Despite a successful kidney transplantation, the intact parathyroid hormone (iPTH) level of the patient was elevated consistently and could not be controlled by medical therapy. Due to the development of tertiary hyperparathyroidism with bone pain and osteoporosis, subtotal parathyroidectomy was performed 4 months after the kidney transplantation. Histological evaluation revealed that one of four parathyroid lesions was a parathyroid carcinoma, while the others were diffuse hyperplasia. Postoperative laboratory studies indicated a decreased level of iPTH. A positron emission tomography-computed tomography performed 6 months after the operation revealed no evidence of local recurrence or distant metastasis. Copyright © 2013. Published by Elsevier Taiwan.

  12. Poly(Amido Amine)s containing agmatine and butanol side chains as efficient gene carriers

    NARCIS (Netherlands)

    Won, Young-Wook; Ankone, Martinus J.K.; Engbersen, Johannes F.J.; Feijen, Jan; Kim, S.W.

    2016-01-01

    A new type of bioreducible poly(amido amine) copolymer is synthesized by the Michael addition polymerization of cystamine bisacrylamide (CBA) with 4-aminobutylguanidine (agmatine, AGM) and 4-aminobutanol (ABOL). Since the positively charged guanidinium groups of AGM and the hydroxybutyl groups of

  13. Amine reactivity with charged sulfuric acid clusters

    Directory of Open Access Journals (Sweden)

    B. R. Bzdek

    2011-08-01

    Full Text Available The distribution of charged species produced by electrospray of an ammonium sulfate solution in both positive and negative polarities is examined using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS. Positively-charged ammonium bisulfate cluster composition differs significantly from negatively-charged cluster composition. For positively-charged clusters all sulfuric acid is neutralized to bisulfate, whereas for negatively-charged clusters the degree of sulfuric acid neutralization is cluster size-dependent. With increasing cluster size (and, therefore, a decreasing role of charge, both positively- and negatively-charged cluster compositions converge toward ammonium bisulfate. The reactivity of negatively-charged sulfuric acid-ammonia clusters with dimethylamine and ammonia is also investigated by FTICR-MS. Two series of negatively-charged clusters are investigated: [(HSO4(H2SO4x] and [(NH4x(HSO4x+1(H2SO43]. Dimethylamine substitution for ammonia in [(NH4 x(HSO4 x+1(H2SO43] clusters is nearly collision-limited, and subsequent addition of dimethylamine to neutralize H2SO4 to bisulfate is within one order of magnitude of the substitution rate. Dimethylamine addition to [(HSO4 (H2SO4 x] clusters is either not observed or very slow. The results of this study indicate that amine chemistry will be evident and important only in large ambient negative ions (>m/z 400, whereas amine chemistry may be evident in small ambient positive ions. Addition of ammonia to unneutralized clusters occurs at a rate that is ~2–3 orders of magnitude slower than incorporation of dimethylamine either by substitution or addition

  14. Trace Amines and the Trace Amine-Associated Receptor 1: Pharmacology, Neurochemistry and Clinical Implications

    Directory of Open Access Journals (Sweden)

    Yue ePei

    2016-04-01

    Full Text Available Biogenic amines are a collection of endogenous molecules that play pivotal roles as neurotransmitters and hormones. In addition to the classical biogenic amines resulting from decarboxylation of aromatic acids, including dopamine (DA, norepinephrine, epinephrine, serotonin (5-HT and histamine, other biogenic amines, present at much lower concentrations in the central nervous system (CNS, and hence referred to as trace amines (TAs, are now recognized to play significant neurophysiological and behavioural functions. At the turn of the century, the discovery of the trace amine-associated receptor 1 (TAAR1, a phylogenetically conserved G protein-coupled receptor that is responsive to both TAs, such as β-phenylethylamine, octopamine and tyramine, and structurally-related amphetamines, unveiled mechanisms of action for TAs other than interference with aminergic pathways, laying the foundations for deciphering the functional significance of TAs and its mammalian CNS receptor, TAAR1. Although its molecular interactions and downstream targets have not been fully elucidated, TAAR1 activation triggers accumulation of intracellular cAMP, modulates PKA and PKC signalling and interferes with the β-arrestin2-dependent pathway via G protein-independent mechanisms. TAAR1 is uniquely positioned to exert direct control over DA and 5-HT neuronal firing and release, which has profound implications for understanding the pathophysiology of, and therefore designing more efficacious therapeutic interventions for, a range of neuropsychiatric disorders that involve aminergic dysregulation, including Parkinson’s disease, schizophrenia, mood disorders and addiction. Indeed, the recent development of novel pharmacological tools targeting TAAR1 has uncovered the remarkable potential of TAAR1-based medications as new generation pharmacotherapies in neuropsychiatry. This review summarizes recent developments in the study of TAs and TAAR1, their intricate neurochemistry and

  15. Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination

    KAUST Repository

    Moulin, Solenne; Dentel, Hé lè ne; Pagnoux-Ozherelyeva, Anastassiya; Gaillard, Sylvain; Poater, Albert; Cavallo, Luigi; Lohier, Jean Franç ois; Renaud, Jean Luc

    2013-01-01

    . Festival of amination: Two series of modified Knölker's complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight

  16. Poly(ethylene oxide) surfactant polymers

    OpenAIRE

    VACHEETHASANEE, KATANCHALEE; WANG, SHUWU; QIU, YONGXING; MARCHANT, ROGER E.

    2004-01-01

    We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly (ethyleneoxide) (PEO) were simultaneously att...

  17. Thermodynamics of organic mixtures containing amines

    International Nuclear Information System (INIS)

    Gonzalez, Juan Antonio; Mozo, Ismael; Fuente, Isaias Garcia de la; Cobos, Jose Carlos

    2006-01-01

    Binary mixtures containing pyridine (PY), or 2-methylpyridine (2MPY) or 3-methylpyridine (3MPY) or 4-methylpyridine (4MPY) and an organic solvent as benzene, toluene, alkane, or 1-alkanol are investigated in the framework of DISQUAC. The corresponding interaction parameters are reported. The model describes accurately a whole set of thermodynamic properties: vapor-liquid equilibria (VLE), liquid-liquid equilibria (LLE), solid-liquid equilibria (SLE), molar excess Gibbs energies (G E ), molar excess enthalpies (H E ), molar excess heat capacities at constant pressure (C P E ) and the concentration-concentration structure factor (S CC (0)). It is remarkable that DISQUAC correctly predicts the W-shaped curve of the C P E of the pyridine + n-hexadecane system. The model can be applied successfully to mixtures with strong positive or negative deviations from the Raoult's law. DISQUAC improves the theoretical results from UNIFAC (Dortmund version). The replacement of pyridine by a methylpyridine leads to a weakening of the amine-amine interactions, ascribed to the steric effect caused by the methyl group attached to the aromatic ring. This explains that for a given solvent (alkane, 1-alkanol) H E (pyridine)>H E (methylpyridine)

  18. Reducing tube bundle deposition with alternative amines

    International Nuclear Information System (INIS)

    Turner, C.W.; Klimas, S.J.; Frattini, P.L.

    1998-01-01

    Particle deposition rates have been measured in a high-temperature loop for magnetite and hematite depositing onto Inconel-600 under flow-boiling conditions with pH controlled using one of the following amines: morpholine, ammonia, ethanolamine, or dimethylamine. Hematite particles deposited at rates an order of magnitude greater than those measured for magnetite, although the hematite deposition rate dropped when the loop was operated under reducing conditions. The magnetite deposition rate was influenced by the amine used to control the pH, with the relative rate decreasing in the following series: morpholine (1) : ethanolamine (0.72) ammonia (0.51) : dimethylamine (0.25). These trends in deposition rate are discussed in terms of the surface chemistry of the corrosion products. Deposition rates for both magnetite and hematite increased significantly once the mixture quality exceeded about 0.3, which may be related to a change in the heat transfer mechanism from nucleate boiling to two-phase forced convection through a thin film. (author)

  19. Reducing tube bundle deposition using alternative amines

    International Nuclear Information System (INIS)

    Turner, C.W.; Klimas, S.J.; Frattini, P.L.

    1999-07-01

    Particle deposition rates were measured in a high-temperature loop for magnetite and hematite depositing onto Inconel-600 under flow-boiling conditions with pH controlled, using one of the following amines: morpholine, ammonia, ethanolamine, or dimethylamine. Hematite particles deposited at rates 10 times greater than those measured for magnetite although the hematite deposition rate dropped when the loop was operated under reducing conditions. The magnetite deposition rate was influenced by the amine used to control the pH, with the relative rate decreasing in the following series: morpholine (1) : ethanolamine (0.72) : ammonia (0.51) dimethylamine (0.25). These trends in deposition rate are discussed in terms of the surface chemistry of the corrosion products. Deposition rates for both magnetite and hematite increased significantly once the mixture quality exceeded about 0.3, which may be related to a change in the heat-transfer mechanism from nucleate boiling to 2-phase forced-convection through a thin film. (author)

  20. Conditions allowing the formation of biogenic amines in cheese

    NARCIS (Netherlands)

    Joosten, H.M.L.J.

    1988-01-01

    A study was undertaken to reveal the conditions that allow the formation of biogenic amines in cheese.

    The starters most commonly used in the Dutch cheese industry do not have decarboxylative properties. Only if the milk or curd is contaminated with non-starter bacteria, amine

  1. Amine-selective bioconjugation using arene diazonium salts.

    Science.gov (United States)

    Diethelm, Stefan; Schafroth, Michael A; Carreira, Erick M

    2014-08-01

    A novel bioconjugation strategy is presented that relies on the coupling of diazonium terephthalates with amines in proteins. The diazonium captures the amine while the vicinal ester locks it through cyclization, ensuring no reversibility. The reaction is highly efficient and proceeds under mild conditions and short reaction times. Densely functionalized, complex natural products were directly coupled to proteins using low concentrations of coupling partners.

  2. Effects of dietary amines on the gut and its vasculature.

    Science.gov (United States)

    Broadley, Kenneth J; Akhtar Anwar, M; Herbert, Amy A; Fehler, Martina; Jones, Elen M; Davies, Wyn E; Kidd, Emma J; Ford, William R

    2009-06-01

    Trace amines, including tyramine and beta-phenylethylamine (beta-PEA), are constituents of many foods including chocolate, cheeses and wines and are generated by so-called 'friendly' bacteria such as Lactobacillus, Lactococcus and Enterococcus species, which are found in probiotics. We therefore examined whether these dietary amines could exert pharmacological effects on the gut and its vasculature. In the present study we examined the effects of tyramine and beta-PEA on the contractile activity of guinea-pig and rat ileum and upon the isolated mesenteric vasculature and other blood vessels. Traditionally, these amines are regarded as sympathomimetic amines, exerting effects through the release of noradrenaline from sympathetic nerve endings, which should relax the gut. A secondary aim was therefore to confirm this mechanism of action. However, contractile effects were observed in the gut and these were independent of noradrenaline, acetylcholine, histamine and serotonin receptors. They were therefore probably due to the recently described trace amine-associated receptors. These amines relaxed the mesenteric vasculature. In contrast, the aorta and coronary arteries were constricted, a response that was also independent of a sympathomimetic action. From these results, we propose that after ingestion, trace amines could stimulate the gut and improve intestinal blood flow. Restriction of blood flow elsewhere diverts blood to the gut to aid digestion. Thus, trace amines in the diet may promote the digestive process through stimulation of the gut and improved gastrointestinal circulation.

  3. Mesoporous amine-bridged polysilsesquioxane for CO2 capture

    KAUST Repository

    Qi, Genggeng; Fu, Liling; Duan, Xiaonan; Choi, Brian Hyun; Abraham, Michael; Giannelis, Emmanuel P.

    2011-01-01

    A novel class of amine-supported sorbents based on amine-bridged mesoporous polysilsesquioxane was developed via a simple one-pot sol-gel process. The new sorbent allows the incorporation of a large amount of active groups without sacrificing

  4. Astramol polypropyleneimine dendrimers as Norrish Type II amine synergists

    NARCIS (Netherlands)

    Jansen, J.F.G.A.; Dias, A.A.; Hartwig, H.; Janssen, R.A.J.

    2000-01-01

    UV-curable coatings for various applications . In most of these applications they serve a dual role ie as initiator and as oxygen scavenger. Dimethylethanolamine is one of the more frequently employed aliphatic amines. However, this amine is a highly volatile . AstramolTM polypropyleneimine

  5. Bioconversion of Airborne Methylamine by Immobilized Recombinant Amine Oxidase from the Thermotolerant Yeast Hansenula polymorpha

    Directory of Open Access Journals (Sweden)

    Sasi Sigawi

    2014-01-01

    Full Text Available Aliphatic amines, including methylamine, are air-pollutants, due to their intensive use in industry and the natural degradation of proteins, amino acids, and other nitrogen-containing compounds in biological samples. It is necessary to develop systems for removal of methylamine from the air, since airborne methylamine has a negative effect on human health. The primary amine oxidase (primary amine : oxygen oxidoreductase (deaminating or amine oxidase, AMO; EC 1.4.3.21, a copper-containing enzyme from the thermotolerant yeast Hansenula polymorpha which was overexpressed in baker’s yeast Saccharomyces cerevisiae, was tested for its ability to oxidize airborne methylamine. A continuous fluidized bed bioreactor (CFBR was designed to enable bioconversion of airborne methylamine by AMO immobilized in calcium alginate (CA beads. The results demonstrated that the bioreactor with immobilized AMO eliminates nearly 97% of the airborne methylamine. However, the enzymatic activity of AMO causes formation of formaldehyde. A two-step bioconversion process was therefore proposed. In the first step, airborne methylamine was fed into a CFBR which contained immobilized AMO. In the second step, the gas flow was passed through another CFBR, with alcohol oxidase from the yeast H. polymorpha immobilized in CA, in order to decompose the formaldehyde formed in the first step. The proposed system provided almost total elimination of the airborne methylamine and the formaldehyde.

  6. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Directory of Open Access Journals (Sweden)

    P. J. Silva

    2009-03-01

    Full Text Available 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 (<1% for all amines 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.

  7. Engineering an enantioselective amine oxidase for the synthesis of pharmaceutical building blocks and alkaloid natural products.

    Science.gov (United States)

    Ghislieri, Diego; Green, Anthony P; Pontini, Marta; Willies, Simon C; Rowles, Ian; Frank, Annika; Grogan, Gideon; Turner, Nicholas J

    2013-07-24

    The development of cost-effective and sustainable catalytic methods for the production of enantiomerically pure chiral amines is a key challenge facing the pharmaceutical and fine chemical industries. This challenge is highlighted by the estimate that 40-45% of drug candidates contain a chiral amine, fueling a demand for broadly applicable synthetic methods that deliver target structures in high yield and enantiomeric excess. Herein we describe the development and application of a "toolbox" of monoamine oxidase variants from Aspergillus niger (MAO-N) which display remarkable substrate scope and tolerance for sterically demanding motifs, including a new variant, which exhibits high activity and enantioselectivity toward substrates containing the aminodiphenylmethane (benzhydrylamine) template. By combining rational structure-guided engineering with high-throughput screening, it has been possible to expand the substrate scope of MAO-N to accommodate amine substrates containing bulky aryl substituents. These engineered MAO-N biocatalysts have been applied in deracemization reactions for the efficient asymmetric synthesis of the generic active pharmaceutical ingredients Solifenacin and Levocetirizine as well as the natural products (R)-coniine, (R)-eleagnine, and (R)-leptaflorine. We also report a novel MAO-N mediated asymmetric oxidative Pictet-Spengler approach to the synthesis of (R)-harmicine.

  8. Biogenic amines degradation by microorganisms isolated from cheese

    Directory of Open Access Journals (Sweden)

    Irena Butor

    2017-01-01

    Full Text Available The aim of this study was the isolation and characterization of microorganisms able to degrade biogenic amines and their identification. Individual microorganisms were obtained by isolation from commercially available foodstuffs and food produced in the technological laboratories of Faculty of Technology, Tomas Bata University in Zlín and subsequently identified by MALDI-TOF MS. The results of MALDI-TOF MS identification were verified by 16S rRNA sequenation. In this work was studied the ability of 5 bacterial strains positive to biogenic amines degradation isolated from dairy products to decrease biogenic amines content in vitro and quantified reduction in the concentration of biogenic amines tryptamine, β-phenylethylamine, putrescine, cadaverine, histamine and tyramine. The level of degradation (decrease of biogenic amines was determined on the base of the ability to grow in media with biogenic amines as the sole source carbon and nitrogen. The isolated strains with the ability of degradation of one or more biogenic amines were cultured in medium supplemented with relevant biogenic amines, the media derivatized with dansyl chloride and these amines separated by HPLC at a wavelength of 254 nm. From five tested strains identified as Bacillus subtilis, Bacillus pumilus, Enterobacter cloacae, Rhizobium radiobacter and Acinetobacter pitii, isolated from gouda type cheese, the greatest ability of degradation was observed in Bacillus subtilis, which was capable to degrade almost all amount of histamine, cadaverine and putrescine. Other four strains showed a lower rate of degradation than Bacillus subtilis, but the ability to degrade biogenic amines with these microorganisms was still significant.

  9. Strong cation exchange-type chiral stationary phase for enantioseparation of chiral amines in subcritical fluid chromatography.

    Science.gov (United States)

    Wolrab, Denise; Kohout, Michal; Boras, Mario; Lindner, Wolfgang

    2013-05-10

    A new strong cation exchange type chiral stationary phase (SCX CSP) based on a syringic acid amide derivative of trans-(R, R)-2-aminocyclohexanesulfonic acid was applied to subcritical fluid chromatography (SFC) for separation of various chiral basic drugs and their analogues. Mobile phase systems consisting of aliphatic alcohols as polar modifiers and a broad range of amines with different substitution patterns and lipophilicity were employed to evaluate the impact on the SFC retention and selectivity characteristics. The observed results point to the existence of carbonic and carbamic acid salts formed as a consequence of reactions occurring between carbon dioxide, the alcoholic modifiers and the amine species present in the sub/supercritical fluid medium, respectively. Evidence is provided that these species are essential for affecting ion exchange between the strongly acidic chiral selector units and the basic analytes, following the well-established stoichiometric displacement mechanisms. Specific trends were observed when different types of amines were used as basic additives. While ammonia gave rise to the formation of the most strongly eluting carbonic and carbamic salt species, simple tertiary amines consistently provided superior levels of enantioselectivity. Furthermore, trends in the chiral SFC separation characteristics were investigated by the systematic variation of the modifier content and temperature. Different effects of additives are interpreted in terms of changes in the relative concentration of the transient ionic species contributing to analyte elution, with ammonia-derived carbamic salts being depleted at elevated temperatures by decomposition. Additionally, in an effort to optimize SFC enantiomer separation conditions for selected analytes, the impact of the type of the organic modifier, temperature, flow rate and active back pressure were also investigated. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Protonation of Ferrous Dinitrogen Complexes Containing a Diphosphine Ligand with a Pendant Amine

    Energy Technology Data Exchange (ETDEWEB)

    Heiden, Zachariah M.; Chen, Shentan; Mock, Michael T.; Dougherty, William G.; Kassel, W. S.; Rousseau, Roger J.; Bullock, R. Morris

    2013-04-01

    The addition of protons to pendant amine containing ferrous dinitrogen complexes, of the type [FeX(N2)(PEtNMePEt)(dmpm)]+ (X = H, Cl, or Br; PEtNMePEt = Et2PCH2N(Me)CH2PEt2 and dmpm = Me2PCH2PMe2), was found to protonate at the pendant amine as opposed to the dinitrogen ligand. This protonation increased the νN2 of the complex by about 25 cm-1, shifting the Fe(II/I) couple 330 mV to a more positive potential. A similar shift was observed in the case of [FeX(CO)(PEtNMePEt)(dmpm)]+ (X = H, Cl, or Br). Computational analysis verified these experimental results and showed the coordination of N2 to Fe(II) centers increases the basicity of N2 (vs. free N2) by 13 and 20 pKa units for the trans halides and hydrides, respectively. Although the iron center was found to increase the basicity of the bound N2 ligand, coordinated N2 is not sufficiently basic to be protonated. In the case of ferrous dinitrogen complexes containing a basic pendant methylamine, the amine site was determined to be the most basic site by 30 pKa units compared to protonation at the N2 ligand. To increase the basicity of the N2 ligand in order to promote proton transfer from the pendant amine to the N2 ligand, chemical reduction of these ferrous dinitrogen complexes was performed and found to result in oxidative addition of the methylene C-H bond of the PEtNMePEt ligand to Fe, preventing isolation of a reduced Fe(0) N2 complex. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences.

  11. Rapid Temperature Swing Adsorption using Polymeric/Supported Amine Hollow Fibers

    Energy Technology Data Exchange (ETDEWEB)

    Chance, Ronald [Georgia Tech Research Corporation, Atlanta, GA (United States); Chen, Grace [Georgia Tech Research Corporation, Atlanta, GA (United States); Dai, Ying [Georgia Tech Research Corporation, Atlanta, GA (United States); Fan, Yanfang [Georgia Tech Research Corporation, Atlanta, GA (United States); Jones, Christopher [Georgia Tech Research Corporation, Atlanta, GA (United States); Kalyanaraman, Jayashree [Georgia Tech Research Corporation, Atlanta, GA (United States); Kawajiri, Yoshiaki [Georgia Tech Research Corporation, Atlanta, GA (United States); Koros, William [Georgia Tech Research Corporation, Atlanta, GA (United States); Lively, Ryan [Georgia Tech Research Corporation, Atlanta, GA (United States); McCool, Benjamin [Georgia Tech Research Corporation, Atlanta, GA (United States); Pang, Simon [Georgia Tech Research Corporation, Atlanta, GA (United States); Realff, Matthew [Georgia Tech Research Corporation, Atlanta, GA (United States); Rezaei, Fateme [Georgia Tech Research Corporation, Atlanta, GA (United States); Searcy, Katherine [Georgia Tech Research Corporation, Atlanta, GA (United States); Sholl, David [Georgia Tech Research Corporation, Atlanta, GA (United States); Subramanian, Swernath [Georgia Tech Research Corporation, Atlanta, GA (United States); Pang, Simon [Georgia Tech Research Corporation, Atlanta, GA (United States)

    2015-03-31

    This project is a bench-scale, post-combustion capture project carried out at Georgia Tech (GT) with support and collaboration with GE, Algenol Biofuels, Southern Company and subcontract to Trimeric Corporation. The focus of the project is to develop a process based on composite amine-functionalized oxide / polymer hollow fibers for use as contactors in a rapid temperature swing adsorption post-combustion carbon dioxide capture process. The hollow fiber morphology allows coupling of efficient heat transfer with effective gas contacting, potentially giving lower parasitic loads on the power plant compared to traditional contacting strategies using solid sorbents.

  12. Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones.

    Science.gov (United States)

    Liang, Guanfeng; Wang, Aiqin; Li, Lin; Xu, Gang; Yan, Ning; Zhang, Tao

    2017-03-06

    Transformation of biomass into valuable nitrogen-containing compounds is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO 2 , which could catalyze the reductive amination of a variety of biomass-derived aldehydes/ketones in aqueous ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two-step approach for production of ethanolamine, a large-market nitrogen-containing chemical, from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO 2 -containing multivalence Ru association species worked as a bifunctional catalyst, with RuO 2 as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Elaboration of y-fanjasite catalysts containing radioactive elements such as uranyl ion in order to obtain aromatic solvents and heavy amines

    International Nuclear Information System (INIS)

    Nibou, D.

    1990-06-01

    The present work has shown the possibility of ammonia alkylation by n-octanol-l in gaseous phase, in presence of zeolitic catalysts. These catalysts are Y faujasitic types being used in waste water demineralization containing radioactive elements such as uranyl ion. This ion gives to the Y faujasite similar activity and selectivity as those of catalysts containing rare earths or transition metals. Toluene disproportionation has permitted to test beforehand catalysts destined to ammonia alkylation and to compare their mechanism. We have also proved the possibility to produce heavy amines such as tertiary amines which are used as uranium extractant agent. Some zeolites such as ZSM-5, beta, X, A, analcime, HS and Y faujasite type are prepared by hydrothermal synthesis method and characterized by some analysis techniques

  14. Electrochemical characterization of aminated acrylic conducting polymer

    International Nuclear Information System (INIS)

    Rashid, Norma Mohammad; Heng, Lee Yook; Ling, Tan Ling

    2015-01-01

    New attempt has been made to synthesize aminated acrylic conducting polymer (AACP) using precursor of phenylvinylsulfoxide (PVS). The process was conducted via the integration of microemulsion and photopolymerization techniques. It has been utilized for covalent immobilization of amino groups by the adding of N-achryiloxisuccinimide (NAS). Thermal eliminating of benzene sulfenic acids from PVS has been done at 250 °C to form electroactive polyacetylene (PA) segment. Characterization of AACP has been conducted using fourier transform infrared (FTIR), scanning electron microscopy (SEM) and linear sweep cyclic voltammetry (CV). A range of 0.3-1.25μm particle size obtained from SEM characterization. A quasi-reversible system performed as shown in electrochemical study

  15. Electrochemical characterization of aminated acrylic conducting polymer

    Energy Technology Data Exchange (ETDEWEB)

    Rashid, Norma Mohammad [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Lestari Universiti Kebangsaan Malaysia (UKM), 43600 Bangi, Selangor Darul Ehsan (Malaysia); Heng, Lee Yook [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Lestari Universiti Kebangsaan Malaysia (UKM), 43600 Bangi, Selangor Darul Ehsan (Malaysia); Southeast Asia Disaster Prevention Research Initiative, Lestari Universiti Kebangsaan Malaysia (UKM), 43600 Bangi, Selangor Darul Ehsan (Malaysia); Ling, Tan Ling [Southeast Asia Disaster Prevention Research Initiative, Lestari Universiti Kebangsaan Malaysia (UKM), 43600 Bangi, Selangor Darul Ehsan (Malaysia)

    2015-09-25

    New attempt has been made to synthesize aminated acrylic conducting polymer (AACP) using precursor of phenylvinylsulfoxide (PVS). The process was conducted via the integration of microemulsion and photopolymerization techniques. It has been utilized for covalent immobilization of amino groups by the adding of N-achryiloxisuccinimide (NAS). Thermal eliminating of benzene sulfenic acids from PVS has been done at 250 °C to form electroactive polyacetylene (PA) segment. Characterization of AACP has been conducted using fourier transform infrared (FTIR), scanning electron microscopy (SEM) and linear sweep cyclic voltammetry (CV). A range of 0.3-1.25μm particle size obtained from SEM characterization. A quasi-reversible system performed as shown in electrochemical study.

  16. Regulation of adipose branched-chain amin acid catabolism enzyme expression and cross-adipose amino acid flux in human obesity

    Science.gov (United States)

    Elevated blood branched-chain amin acids (BCAA)are often assoicated with insulin resistance and type2 diabetes, which might result from a reduced cellular utilization and/or incomplete BCAA oxidation. White adipose tissue (WAT) has become appreciated as a potential player in whole body BCAA metaboli...

  17. Poly(Amido Amine)s Containing Agmatine and Butanol Side Chains as Efficient Gene Carriers.

    Science.gov (United States)

    Won, Young-Wook; Ankoné, Marc; Engbersen, Johan F J; Feijen, Jan; Kim, Sung Wan

    2016-04-01

    A new type of bioreducible poly(amido amine) copolymer is synthesized by the Michael addition polymerization of cystamine bisacrylamide (CBA) with 4-aminobutylguanidine (agmatine, AGM) and 4-aminobutanol (ABOL). Since the positively charged guanidinium groups of AGM and the hydroxybutyl groups of ABOL in the side chains have shown to improve the overall transfection efficiency of poly(amido amine)s, it is hypothesized that poly(CBA-ABOL/AGM) synthesized at the optimal ratio of both components would result in high transfection efficiency and minimal toxicity. In this study, a series of the poly(CBA-ABOL/AGM) copolymers is synthesized as gene carriers. The polymers are characterized and luciferase transfection efficiencies of the polymers in various cell lines are investigated to select the ideal ratio between AGM and ABOL. The poly(CBA-ABOL/AGM) containing 80% AGM and 20% ABOL has shown the best transfection efficiency with the lowest cytotoxicity, indicating that this polymer is very promising as a potent and nontoxic gene carrier. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Non-traditional Oxidants in Preparative Coordination Chemistry

    Science.gov (United States)

    Kukushkin, Vadim Yu; Kukushkin, Yurii N.

    1986-10-01

    The application of nitrosonium and arenediazonium salts, carbenium, silver(I), and mercury(II) ions, protic acids, and amine oxides as oxidants in preparative coordination chemistry is examined. Specific examples illustrate which problems in the field of the synthesis and reactions of coordination compounds can be solved with the aid of these oxidants. The bibliography includes 158 references.

  19. Amine functionalized nanodiamond promotes cellular adhesion, proliferation and neurite outgrowth

    International Nuclear Information System (INIS)

    Hopper, A P; Dugan, J M; Gill, A A; Haycock, J W; Claeyssens, F; Fox, O J L; May, P W

    2014-01-01

    In this study, we report the production of amine functionalized nanodiamond. The amine functionalized nanodiamond forms a conformal monolayer on a negatively charged surface produced via plasma polymerization of acrylic acid. Nanodiamond terminated surfaces were studied as substrates for neuronal cell culture. NG108-15 neuroblastoma-glyoma hybrid cells were successfully cultured upon amine functionalized nanodiamond coated surfaces for between 1 and 7 d. Additionally, primary dorsal root ganglion (DRG) neurons and Schwann cells isolated from Wistar rats were also successfully cultured over a period of 21 d illustrating the potential of the coating for applications in the treatment of peripheral nerve injury. (paper)

  20. BIOGENIC AMINES CONTENT IN SELECTED WINES DURING WINEMAKING

    Directory of Open Access Journals (Sweden)

    Radka Flasarová

    2012-02-01

    Full Text Available The aim of this study was to describe the development of selected biogenic amines (histamine; tyramine; phenylethylamine; putrescine; agmatine; and cadaverine during the winemaking in 10 selected species grown in Central Europe in 2008. The analysis was performed using ion-exchange chromatography by the sodium-citrate buffers with the post-column ninhydrin derivatization and photometric detection. A comparison of the content of biogenic amines in red and wine varieties showed that red wines have higher concentrations of biogenic amines.

  1. CYP-450 isoenzymes catalyze the generation of hazardous aromatic amines after reaction with the azo dye Sudan III.

    Science.gov (United States)

    Zanoni, Thalita Boldrin; Lizier, Thiago M; Assis, Marilda das Dores; Zanoni, Maria Valnice B; de Oliveira, Danielle Palma

    2013-07-01

    This work describes the mutagenic response of Sudan III, an adulterant food dye, using Salmonella typhimurium assay and the generation of hazardous aromatic amines after different oxidation methods of this azo dye. For that, we used metabolic activation by S9, catalytic oxidation by ironporphyrin and electrochemistry oxidation in order to simulate endogenous oxidation conditions. The oxidation reactions promoted discoloration from 65% to 95% of Sudan III at 1 × 10(-4)molL(-1) and generation of 7.6 × 10(-7)molL(-1) to 0.31 × 10(-4)molL(-1) of aniline, o-anisidine, 2-methoxi-5-methylaniline, 4-aminobiphenyl, 4,4'-oxydianiline; 4,4'-diaminodiphenylmethane and 2,6-dimethylaniline. The results were confirmed by LC-MS-MS experiments. We also correlate the mutagenic effects of Sudan III using S. typhimurium with the strain TA1535 in the presence of exogenous metabolic activation (S9) with the metabolization products of this compound. Our findings clearly indicate that aromatic amines are formed due to oxidative reactions that can be promoted by hepatic cells, after the ingestion of Sudan III. Considering that, the use of azo compounds as food dyestuffs should be carefully controlled. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Atmospheric chemistry and environmental impact of the use of amines in carbon capture and storage (CCS).

    Science.gov (United States)

    Nielsen, Claus J; Herrmann, Hartmut; Weller, Christian

    2012-10-07

    This critical review addresses the atmospheric gas phase and aqueous phase amine chemistry that is relevant to potential emissions from amine-based carbon capture and storage (CCS). The focus is on amine, nitrosamine and nitramine degradation, and nitrosamine and nitramine formation processes. A comparison between the relative importance of the various atmospheric sinks for amines, nitrosamines and nitramines is presented.

  3. Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected beta-Amino Aldehydes

    NARCIS (Netherlands)

    Dong, Jiajia; Harvey, Emma C.; Fananas-Mastral, Martin; Browne, Wesley R.; Feringa, Bernard

    2014-01-01

    A general method for the preparation of N-protected beta-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward

  4. Efficient acetylation of primary amines and amino acids in ...

    Indian Academy of Sciences (India)

    bDepartment of Clinical and Experimental Pharmacology, School of Tropical Medicine ... As a result ... methods of acetylation of amines are known using ace- ... vents we report here, environmentally benign, eco- ... It was filtered under suction,.

  5. Preparation and adsorption property of aminated cross linking ...

    Indian Academy of Sciences (India)

    Administrator

    city and blood compatible and biocompatible. The preliminary study on the ... der reduced pressure before being used. Polyvinyl .... above, the difference of the amount of amine groups ... varying of connecting arm in length. Bilirubin mole-.

  6. Two simple amine hydrochlorides from the soft coral Lobophytum strictum

    Digital Repository Service at National Institute of Oceanography (India)

    Parameswaran, P.S.; Naik; Das, B.; Kamat, S.Y.

    Two simple amine hydrochlorides, viz., 1-amino-1, 1-dimethyl-3-oxo-butane hydrochloride (1) (Diacetonamine) and 2, 2, 6, 6-tetramethylpiperidone hydrochloride (2) have been isolated from the fraction of the methanolic extract of the soft coral...

  7. Next Generation Life Support (NGLS): Rapid Cycle Amine Swing Bed

    Data.gov (United States)

    National Aeronautics and Space Administration — The Rapid Cycle Amine (RCA) swingbed has been identified as a technology with high potential to meet the stringent requirements for the next generation spacesuit's...

  8. Silver-catalyzed synthesis of amides from amines and aldehydes

    Science.gov (United States)

    Madix, Robert J; Zhou, Ling; Xu, Bingjun; Friend, Cynthia M; Freyschlag, Cassandra G

    2014-11-18

    The invention provides a method for producing amides via the reaction of aldehydes and amines with oxygen adsorbed on a metallic silver or silver alloy catalyst. An exemplary reaction is shown in Scheme 1: (I), (II), (III). ##STR00001##

  9. Cell Wall Amine Oxidases: New Players in Root Xylem Differentiation under Stress Conditions

    Directory of Open Access Journals (Sweden)

    Sandip A. Ghuge

    2015-07-01

    Full Text Available Polyamines (PAs are aliphatic polycations present in all living organisms. A growing body of evidence reveals their involvement as regulators in a variety of physiological and pathological events. They are oxidatively deaminated by amine oxidases (AOs, including copper amine oxidases (CuAOs and flavin adenine dinucleotide (FAD-dependent polyamine oxidases (PAOs. The biologically-active hydrogen peroxide (H2O2 is a shared compound in all of the AO-catalyzed reactions, and it has been reported to play important roles in PA-mediated developmental and stress-induced processes. In particular, the AO-driven H2O2 biosynthesis in the cell wall is well known to be involved in plant wound healing and pathogen attack responses by both triggering peroxidase-mediated wall-stiffening events and signaling modulation of defense gene expression. Extensive investigation by a variety of methodological approaches revealed high levels of expression of cell wall-localized AOs in root xylem tissues and vascular parenchyma of different plant species. Here, the recent progresses in understanding the role of cell wall-localized AOs as mediators of root xylem differentiation during development and/or under stress conditions are reviewed. A number of experimental pieces of evidence supports the involvement of apoplastic H2O2 derived from PA oxidation in xylem tissue maturation under stress-simulated conditions.

  10. Solvent extraction of cerium (III) with high molecular weight amines

    International Nuclear Information System (INIS)

    Chatterjee, A.; Basu, S.

    1992-01-01

    The use of high molecular weight amines in the extraction of cerium (III) as EDTA complex from neutral aqueous medium is reported. The extraction condition was optimised from the study of effects of several variables like concentration of amine and EDTA pH nature of diluents etc. The method has been applied for the determination of cerium in few mineral samples. (author). 7 refs., 5 tabs

  11. Effects of dietary amines on the gut and its vasculature

    OpenAIRE

    Broadley, Kenneth John; Anwar, Mohammad Akhtar; Herbert, Amy Angharad; Fehler, Martina; Jones, Elen M.; Davies, W. E.; Kidd, Emma Jane; Ford, William Richard

    2009-01-01

    Trace amines, including tyramine and β-phenylethylamine (β-PEA), are constituents of many foods including chocolate, cheeses and wines and are generated by so-called ‘friendly’ bacteria such as Lactobacillus, Lactococcus and Enterococcus species, which are found in probiotics. We therefore examined whether these dietary amines could exert pharmacological effects on the gut and its vasculature. In the present study we examined the effects of tyramine and β-PEA on the contractile activity of gu...

  12. Biogenic amines in dry fermented sausages: a review.

    Science.gov (United States)

    Suzzi, Giovanna; Gardini, Fausto

    2003-11-15

    Biogenic amines are compounds commonly present in living organisms in which they are responsible for many essential functions. They can be naturally present in many foods such as fruits and vegetables, meat, fish, chocolate and milk, but they can also be produced in high amounts by microorganisms through the activity of amino acid decarboxylases. Excessive consumption of these amines can be of health concern because their not equilibrate assumption in human organism can generate different degrees of diseases determined by their action on nervous, gastric and intestinal systems and blood pressure. High microbial counts, which characterise fermented foods, often unavoidably lead to considerable accumulation of biogenic amines, especially tyramine, 2-phenylethylamine, tryptamine, cadaverine, putrescine and histamine. However, great fluctuations of amine content are reported in the same type of product. These differences depend on many variables: the quali-quantitative composition of microbial microflora, the chemico-physical variables, the hygienic procedure adopted during production, and the availability of precursors. Dry fermented sausages are worldwide diffused fermented meat products that can be a source of biogenic amines. Even in the absence of specific rules and regulations regarding the presence of these compounds in sausages and other fermented products, an increasing attention is given to biogenic amines, especially in relation to the higher number of consumers with enhanced sensitivity to biogenic amines determined by the inhibition of the action of amino oxidases, the enzymes involved in the detoxification of these substances. The aim of this paper is to give an overview on the presence of these compounds in dry fermented sausages and to discuss the most important factors influencing their accumulation. These include process and implicit factors as well as the role of starter and nonstarter microflora growing in the different steps of sausage production

  13. Facile and Green Synthesis of Saturated Cyclic Amines

    Directory of Open Access Journals (Sweden)

    Arruje Hameed

    2017-10-01

    Full Text Available Single-nitrogen containing saturated cyclic amines are an important part of both natural and synthetic bioactive compounds. A number of methodologies have been developed for the synthesis of aziridines, azetidines, pyrrolidines, piperidines, azepanes and azocanes. This review highlights some facile and green synthetic routes for the synthesis of unsubstituted, multisubstituted and highly functionalized saturated cyclic amines including one-pot, microwave assisted, metal-free, solvent-free and in aqueous media.

  14. Calcium(ii)-catalyzed enantioselective conjugate additions of amines.

    Science.gov (United States)

    Uno, Brice E; Dicken, Rachel D; Redfern, Louis R; Stern, Charlotte M; Krzywicki, Greg G; Scheidt, Karl A

    2018-02-14

    The direct enantioselective chiral calcium(ii)·phosphate complex (Ca[CPA] 2 )-catalyzed conjugate addition of unprotected alkyl amines to maleimides was developed. This mild catalytic system represents a significant advance towards the general convergent asymmetric amination of α,β-unsaturated electrophiles, providing medicinally relevant chiral aminosuccinimide products in high yields and enantioselectivities. Furthermore, the catalyst can be reused directly from a previously chromatographed reaction and still maintain both high yield and selectivity.

  15. Detection of atmospheric gaseous amines and amides by a high-resolution time-of-flight chemical ionization mass spectrometer with protonated ethanol reagent ions

    Directory of Open Access Journals (Sweden)

    L. Yao

    2016-11-01

    Full Text Available Amines and amides are important atmospheric organic-nitrogen compounds but high time resolution, highly sensitive, and simultaneous ambient measurements of these species are rather sparse. Here, we present the development of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS method, utilizing protonated ethanol as reagent ions to simultaneously detect atmospheric gaseous amines (C1 to C6 and amides (C1 to C6. This method possesses sensitivities of 5.6–19.4 Hz pptv−1 for amines and 3.8–38.0 Hz pptv−1 for amides under total reagent ion signals of  ∼  0.32 MHz. Meanwhile, the detection limits were 0.10–0.50 pptv for amines and 0.29–1.95 pptv for amides at 3σ of the background signal for a 1 min integration time. Controlled characterization in the laboratory indicates that relative humidity has significant influences on the detection of amines and amides, whereas the presence of organics has no obvious effects. Ambient measurements of amines and amides utilizing this method were conducted from 25 July to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few parts per trillion by volume to hundreds of parts per trillion by volume, concentrations of amides varied from tens of parts per trillion by volume to a few parts per billion by volume. Among the C1- to C6-amines, the C2-amines were the dominant species with concentrations up to 130 pptv. For amides, the C3-amides (up to 8.7 ppb were the most abundant species. The diurnal and backward trajectory analysis profiles of amides suggest that in addition to the secondary formation of amides in the atmosphere, industrial emissions could be important sources of amides in urban Shanghai. During the campaign, photo-oxidation of amines and amides might be a main loss pathway for them in daytime, and wet deposition was also an important sink.

  16. Production of biogenic amines in "Salamini italiani alla cacciatora PDO".

    Science.gov (United States)

    Coı X0308 Sson, Jean Daniel; Cerutti, Caterina; Travaglia, Fabiano; Arlorio, Marco

    2004-06-01

    Various fermented and seasoned foods such as cheese, sauerkraut, wine, beer and meat products may contain biogenic amines. The aim of this paper was to describe the presence of some biogenic amines (histamine, tyramine, tryptamine, 2-phenylethylamine) in "Salamini italiani alla cacciatora PDO", a typical fermented-ripened dry sausage widely consumed in Italy. Total level of biogenic amines in commercial samples ranged from 71 to 586 mg kg(-1). The amine recovered in higher concentrations was tyramine (372 mg kg(-1)) followed by histamine (165 mg kg(-1)). The second aim of this work was the quality control of the production in order to determine the parameters influencing the presence of biogenic amines in ripened salami. Sausages sampled for analysis during production, manipulation and ripening showed the presence of tyramine (64.4 mg kg(-1)) only after 15 days of fermentation. All investigated biogenic amines were detected in "Salamini" after 21 days of fermentation. We suggest the control of biogenic as important tool to establish the better condition of preservation of "Salamini italiani alla cacciatore PDO" during their shelf-life.

  17. STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; ZHANG Jingyi; FENG Xinde(S. T. Voong)

    1983-01-01

    Two main types of amine-containing initiation systems were studied in this work. In the case of MMA polymerization initiated by BPO-amine (DMT, DHET, DMA) redox systems, it was found that the polymerization rate and colour stability of the polymer for different amine systems were in the following order: DMT≈DHET>DMA. Accordingly, BPO-DMT and BPO-DHET are effective initiators. In the case of MEMA polymerization by amine (DMT, DHET, DMA) alone, it was found that the polymerization rate and the percentage of conversion for these different amine systems were in the following order: DMT≥DHET>DMA. The polymerization rate and the percentage of conversion also increased with the increase of DMT concentration. From the kinetic investigation the rate equation of Rp=K [DMT]1/2 [MEMA]3/2 was obtained, and the overall activation energy of polymerization was calculated to be 34.3 KJ/mol (8.2 Kcal/mol). Moreover, the polymerization of MEMA in the presence of DMT was strongly inhibited by hydroquinone, indicating the polymerization being free radical in nature. From these results, the mechanism of MEMA polymerization initiated by amine was proposed.

  18. Biogenic amine formation and bacterial contribution in Natto products.

    Science.gov (United States)

    Kim, Bitna; Byun, Bo Young; Mah, Jae-Hyung

    2012-12-01

    Twenty-one Natto products currently distributed in Korea were analysed for biogenic amine contents and tested to determine physicochemical and bacterial contributions to biogenic amine formation. Among them, nine products (about 43%) had β-phenylethylamine or tyramine contents greater than the toxic dose (30mg/kg and 100mg/kg, respectively) of each amine, although no products showed total amounts of biogenic amines above the harmful level (1000mg/kg), which indicates that the amounts of biogenic amines in some Natto products are not within the safe level for human health. From four different Natto products, that contained noticeable levels of β-phenylethylamine and tyramine, 80 bacterial strains were isolated. All the strains were identified to be Bacillus subtilis and highly capable of producing β-phenylethylamine and tyramine. Therefore, it seems likely that the remarkable contents of β-phenylethylamine and tyramine in Natto predominantly resulted from the strains highly capable of producing those amines present in the food. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Mechanism of the oxidation of diphenylamine compounds

    International Nuclear Information System (INIS)

    Pankratov, A.N.; Shmakov, S.L.; Mushtakova, S.P.; Gribov, L.A.

    1986-01-01

    A spectrophotometric, radiospectroscopic, and quantum chemical study of the oxidation of compounds of the diphenylamine series in acid medium has made it possible to establish a common reaction scheme for amines with different types of substituents and to determine certain details of the reaction mechanism: the participation of protonated amine molecules in the interaction with the oxidizing agent; intermediate formation of radical cations of the type of diphenylamine and N,N'-diarylbenzidine; the concrete directions of the dimerization of radical cations of diarylamines with the participation of the para-carbon atoms of the aromatic rings

  20. Heterocyclic amines in meat and meat products

    Directory of Open Access Journals (Sweden)

    Aliye BULGAN

    2013-06-01

    Full Text Available Heterocyclic amines (HA are the mutagenic/carcinogenic compounds which generate as a result of cooking of red meat, poultry meat and fish fillets at high temperatures. Up to 20 different HAs were detected and classified in the researches that conducted on these types of meats cooked at high temperatures. HAs are the products of Maillard reactions and the Strecker degredation of main precursors such as creatine/creatinine, aminoacid and the polysaccharides. Many physical and chemical factors effect the formation of HAs. Thus, it was reported by many researchers that utilizing coating and marination processes in addition to using natural and synthetic antioxidants and seasonings-plant extracts were effective on inhibiting/decreasing the formation of HAs. Additionally, boiling/steaming and microwave cooking methodologies were recommended instead of barbecuing, grilling or frying to inhibit/decrease the formation of HAs. The HAs formed in meat and meat products and the factors which have effects on the formation of HAs are presented in this review.