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Sample records for tertiary amine oxides

  1. The observed and calculated 1H and 13C chemical shifts of tertiary amines and their N-oxides

    Czech Academy of Sciences Publication Activity Database

    Pohl, Radek; Dračínský, Martin; Slavětínská, Lenka; Buděšínský, Miloš

    2011-01-01

    Roč. 49, č. 6 (2011), s. 320-327 ISSN 0749-1581 R&D Projects: GA ČR GA203/09/1919 Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR * 1H * 13C * in situ oxidation of tertiary amines * calculated chemical shifts * HF * MP2 * DFT Subject RIV: CC - Organic Chemistry Impact factor: 1.437, year: 2011

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

    Directory of Open Access Journals (Sweden)

    Orozco Gustavo A.

    2014-09-01

    Full Text Available 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 (N2O and nitrogen (N2 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.

  3. The genotype dependent presence of pyrrolizidine alkaloids as tertiary amine in Jacobaea vulgaris

    NARCIS (Netherlands)

    Joosten, L.; Chenga, D.; Mulder, P.P.J.; Vrieling, K.; Van Veen, J.A.; Klinkhamer, P.G.L.

    2011-01-01

    Secondary metabolites such as pyrrolizidine alkaloids (PAs) play a crucial part in plant defense. PAs can occur in plants in two forms: tertiary amine (free base) and N-oxide. PA extraction and detection are of great importance for the understanding of the role of PAs as plant defense compounds, as

  4. The genotype dependent presence of pyrrolizidine alkaloids as tertiary amine in jacobaea vulgaris

    NARCIS (Netherlands)

    Joosten, L.; Cheng, D.; Mulder, P.P.J.; Vrieling, K.; Veen, van J.A.; Klinkhamer, P.G.L.

    2011-01-01

    Secondary metabolites such as pyrrolizidine alkaloids (PAs) play a crucial part in plant defense. PAs can occur in plants in two forms: tertiary amine (free base) and N-oxide. PA extraction and detection are of great importance for the understanding of the role of PAs as plant defense compounds, as

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. Graphite Oxide and Aromatic Amines : Size Matters

    NARCIS (Netherlands)

    Spyrou, Konstantinos; Calvaresi, Matteo; Diamanti, Evmorfi A. K.; Tsoufis, Theodoros; Gournis, Dimitrios; Rudolf, Petra; Zerbetto, Francesco

    2015-01-01

    Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline

  10. 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

  11. 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

  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. Expedient protocol for solid-phase synthesis of secondary and tertiary amines

    DEFF Research Database (Denmark)

    Olsen, Christian A; Witt, Matthias; Jaroszewski, Jerzy W

    2004-01-01

    [reaction: see text] An expedient solid-phase synthetic approach to secondary and tertiary amines was developed. The protocol employs conversion of resin-bound amino alcohols to the corresponding iodides, followed by iodide displacement with primary or secondary amines or with unprotected amino a...... alcohols. This two-step procedure, affording products in good to excellent yields, is suitable for solid-phase synthesis of polyamines....

  14. Enthalpy of cooperative hydrogen bonding in complexes of tertiary amines with aliphatic alcohols: Calorimetric study

    International Nuclear Information System (INIS)

    Zaitseva, Ksenia V.; Varfolomeev, Mikhail A.; Novikov, Vladimir B.; Solomonov, Boris N.

    2011-01-01

    Research highlights: → Solution enthalpies of aliphatic alcohols in tertiary amines and vice versa were measured. → The enthalpies of specific interaction of amines in aliphatic alcohols are lower than the enthalpies of hydrogen bonding in 1:1 complexes amine-alcohol determined in base media. → Hydrogen bond cooperativity factors in multi-particle complexes of alcohols with aromatic amines are approximately equal for all alcohols. → Hydrogen bond cooperativity factors in multi-particle complexes of alcohols with trialkylamines decrease with increasing of alkyl radical length in alcohol and amine molecules. - Abstract: The work is devoted to the investigation of thermodynamics of specific interaction of the tertiary aliphatic and aromatic amines with associated solvents as which aliphatic alcohols were taken. Solution enthalpies of aliphatic alcohols in amines (tri-n-propylamine, 2-methylpyridine, 3-methylpyridine, N-methylimidazole) as well as amines in alcohols were measured at infinite dilution. The enthalpies of specific interaction (H-bonding) in systems studied were determined based on experimental data. The enthalpies of specific interaction of amines in aliphatic alcohols significantly lower than the enthalpies of hydrogen bonding in complexes amine-alcohol of 1:1 composition determined in base media due to the reorganization of aliphatic alcohols as solvents. The determination of solvent reorganization contribution makes possible to define the hydrogen bonding enthalpies of amines with clusters of alcohols. Obtained enthalpies of hydrogen bonding in multi-particle complexes are sensitive to the influence of cooperative effect. It was shown, that hydrogen bond cooperativity factors in multi-particle complexes of alcohols with amines are approximately equal for all alcohols when pyridines and N-methylimidazole as solutes are used. At the same time, H-bonding cooperativity factors in complexes of trialkylamines with associative species of alcohols

  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. Extraction and purification of plutonium by a tertiary amine

    International Nuclear Information System (INIS)

    Trentinian, M. de; Chesne, A.; Commissariat a l'Energie Atomique, Saclay

    1960-01-01

    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) [fr

  17. Extraction Equilibrium of Dicarboxylic Acids with Tertiary Amine in Single and Binary Diluents

    Czech Academy of Sciences Publication Activity Database

    Procházka, Jaroslav; Heyberger, Aleš; Volaufová, Eva

    2004-01-01

    Roč. 39, č. 5 (2004), s. 1075-1093 ISSN 0149-6395. [CHISA 2000. Prague, 27.08.2000-31.08.2000] R&D Projects: GA ČR GA104/97/1213 Institutional research plan: CEZ:AV0Z4072921 Keywords : liquid extraction * dicarboxylic acids * tertiary amine Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.896, year: 2004

  18. Primary, secondary, and tertiary amines for CO2 capture: designing for mesoporous CO2 adsorbents.

    Science.gov (United States)

    Ko, Young Gun; Shin, Seung Su; Choi, Ung Su

    2011-09-15

    CO(2) emissions, from fossil-fuel-burning power plants, the breathing, etc., influence the global worming on large scale and the man's work efficiency on small scale. The reversible capture of CO(2) is a prominent feature of CO(2) organic-inorganic hybrid adsorbent to sequester CO(2). Herein, (3-aminopropyl) trimethoxysilane (APTMS), [3-(methylamino)propyl] trimethoxysilane (MAPTMS), and [3-(diethylamino) propyl] trimethoxysilane (DEAPTMS) are immobilized on highly ordered mesoporous silicas (SBA-15) to catch CO(2) as primary, secondary, and tertiary aminosilica adsorbents. X-ray photoelectron spectroscopy was used to analyze the immobilized APTMS, MAPTMS, and DEAPTMS on the SBA-15. We report an interesting discovery that the CO(2) adsorption and desorption on the adsorbent depend on the amine type of the aminosilica adsorbent. The adsorbed CO(2) was easily desorbed from the adsorbent with the low energy consumption in the order of tertiary, secondary, and primary amino-adsorbents while the adsorption amount and the bonding-affinity increased in the reverse order. The effectiveness of amino-functionalized (1(o), 2(o), and 3(o) amines) SBA-15s as a CO(2) capturing agent was investigated in terms of adsorption capacity, adsorption-desorption kinetics, and thermodynamics. This work demonstrates apt amine types to catch CO(2) and regenerate the adsorbent, which may open new avenues to designing "CO(2) basket". Copyright © 2011. Published by Elsevier Inc.

  19. Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates.

    Science.gov (United States)

    Bauer, Johannes Moritz; Frey, Wolfgang; Peters, René

    2016-04-11

    The streamlined catalytic access to enantiopure allylic amines as valuable precursors towards chiral β- and γ-aminoalcohols as well as α- and β-aminoacids is desirable for industrial purposes. In this article an enantioselective method is described that transforms achiral allylic alcohols and N-tosylisocyanate in a single step into highly enantioenriched N-tosyl protected allylic amines via an allylic carbamate intermediate. The latter is likely to undergo a cyclisation-induced [3,3]-rearrangement catalysed by a planar chiral pentaphenylferrocene palladacycle in cooperation with a tertiary amine base. The otherwise often indispensable activation of palladacycle catalysts by a silver salt is not required in the present case and there is also no need for an inert gas atmosphere. To further improve the synthetic value, the rearrangement was used to form dimethylaminosulfonyl-protected allylic amines, which can be deprotected under non-reductive conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Oxidative nucleophilic aromatic amination of nitrobenzenes

    Czech Academy of Sciences Publication Activity Database

    Khutorianskyi, Viktor V.; Sonawane, Manoj R.; Pošta, Martin; Klepetářová, Blanka; Beier, Petr

    2016-01-01

    Roč. 52, č. 45 (2016), s. 7237-7240 ISSN 1359-7345 R&D Projects: GA ČR GAP207/12/0072 Institutional support: RVO:61388963 Keywords : C-H amination * bond formation * substitution Subject RIV: CC - Organic Chemistry Impact factor: 6.319, year: 2016

  1. Decoding nitric oxide release rates of amine-based diazeniumdiolates.

    Science.gov (United States)

    Wang, Yan-Ni; Collins, Jack; Holland, Ryan J; Keefer, Larry K; Ivanic, Joseph

    2013-08-01

    Amine-based diazeniumdiolates (NONOates) have garnered widespread use as nitric oxide (NO) donors, and their potential for nitroxyl (HNO) release has more recently been realized. While NO release rates can vary significantly with the type of amine, half-lives of seconds to days under physiological conditions, there is as yet no way to determine a priori the NO or HNO production rates of a given species, and no discernible trends have manifested other than that secondary amines produce only NO (i.e., no HNO). As a step to understanding these complex systems, here we describe a procedure for modeling amine-based NONOates in water solvent that provides an excellent correlation (R(2) = 0.94) between experimentally measured dissociation rates of seven secondary amine species and their computed NO release activation energies. The significant difference in behavior of NONOates in the gas and solvent phases is also rigorously demonstrated via explicit additions of quantum mechanical water molecules. The presented results suggest that the as-yet unsynthesized simplest amine-based NONOate, the diazeniumdiolated ammonia anion [H2N-N(O)═NO(-)], could serve as an unperturbed HNO donor. These results provide a step forward toward the accurate modeling of general NO and/or HNO donors as well as for the identification of tailored prodrug candidates.

  2. Asymmetric additions of thioglycolates and N-Boc aldimines catalyzed by a bifunctional tertiary-amine squaramide.

    Science.gov (United States)

    Feng, Bo-Xu; Wang, Bin; Li, Xin

    2016-10-21

    A highly enantioselective asymmetric addition reaction of thioglycolates and N-Boc aldimines was promoted by a bifunctional tertiary-amine squaramide catalyst. As a result, a number of chiral N,S-acetal derivatives were efficiently synthesized with good enantioselectivities.

  3. Reduction of amine N-oxides by diboron reagents.

    Science.gov (United States)

    Kokatla, Hari Prasad; Thomson, Paul F; Bae, Suyeal; Doddi, Venkata Ramana; Lakshman, Mahesh K

    2011-10-07

    Facile reduction of alkylamino-, anilino-, and pyridyl-N-oxides can be achieved via the use of diboron reagents, predominantly bis(pinacolato)- and in some cases bis(catecholato)diboron [(pinB)(2) and (catB)(2), respectively]. Reductions occur upon simply mixing the amine N-oxide and the diboron reagent in a suitable solvent, at a suitable temperature. Extremely fast reductions of alkylamino- and anilino-N-oxides occur, whereas pyridyl-N-oxides undergo slower reduction. The reaction is tolerant of a variety of functionalities such as hydroxyl, thiol, and cyano groups, as well as halogens. Notably, a sensitive nucleoside N-oxide has also been reduced efficiently. The different rates with which alkylamino- and pyridyl-N-oxides are reduced has been used to perform stepwise reduction of the N,N'-dioxide of (S)-(-)-nicotine. Because it was observed that (pinB)(2) was unaffected by the water of hydration in amine oxides, the feasibility of using water as solvent was evaluated. These reactions also proceeded exceptionally well, giving high product yields. In constrast to the reactions with (pinB)(2), triethylborane reduced alkylamino-N-oxides, but pyridine N-oxide did not undergo efficient reduction even at elevated temperature. Finally, the mechanism of the reductive process by (pinB)(2) has been probed by (1)H and (11)B NMR.

  4. 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.

  5. Thermodynamic properties of donor–acceptor complexes of tertiary amine with aryl ketones in hexane medium

    International Nuclear Information System (INIS)

    Kumar, R.; Jayakumar, S.; Kannappan, V.

    2012-01-01

    Highlights: ► Ultrasonic scan is carried out on ternary systems of aromatic tertiary amine and three aryl ketones. ► Formation of CT complexes is found between tertiary amine with aryl ketones. ► Stability constant values are computed by ultrasonic and spectral methods are compared. ► The trend in the ‘K’ suggests that substituents in ketones influence the stabilities of these complexes. ► 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 (ΔG), enthalpy (ΔH) and entropy (ΔS) changes for complex formation are computed and discussed.

  6. (GaIn)(NAs) growth using di-tertiary-butyl-arsano-amine (DTBAA)

    Science.gov (United States)

    Sterzer, E.; Ringler, B.; Nattermann, L.; Beyer, A.; von Hänisch, C.; Stolz, W.; Volz, K.

    2017-06-01

    III/V semiconductors containing small amounts of Nitrogen (N) are very interesting for a variety of optoelectronic applications. Unfortunately, the conventionally used N precursor 1,1-dimethylhydrazine (UDMHy) has an extremely low N incorporation efficiency in GaAs when grown using metal organic vapor phase epitaxy. Alloying Ga(NAs) with Indium (In) even leads to an exponential reduction of N incorporation. The huge amount of UDMHy in turn changes drastically the growth conditions. Furthermore, the application of this material is still hampered by the large carbon incorporation, most probably originating from the metal organic precursors. Hence, novel precursors for dilute nitride growth are needed. This paper will show (GaIn)(NAs) growth studies with the novel precursor di-tertiary-butyl-arsano-amine in combination with tri-ethyl-gallium and tri-methyl-indium. We show an extremely high N incorporation efficiency in the In containing (GaIn)(NAs). The (GaIn)(NAs) samples investigated in this study have been examined using high resolution X-Ray diffraction, room temperature photoluminescence and atomic force microscope measurements as well as secondary ion mass spectrometry.

  7. Synthesis of N-Boc-Propargylic and Allylic Amines by Reaction of Organomagnesium Reagents with N-Boc-Aminals and Their Oxidation to N-Boc-Ketimines.

    Science.gov (United States)

    Kano, Taichi; Kobayashi, Ryohei; Maruoka, Keiji

    2016-01-15

    Previously inaccessible N-Boc-protected propargylic and allylic amines were synthesized by the reaction between N-Boc-aminals and organomagnesium reagents through the in situ generated N-Boc-imine intermediates. The obtained N-Boc-propargylic amines could be readily converted into unprecedented N-Boc-ketimines by oxidation with manganese dioxide.

  8. 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.

  9. 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.

  10. 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...

  11. 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.

  12. 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.

  13. 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.

  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

    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...... 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...... investigated using bupivacaine as a model compound. X-ray structure analyses of selected salts were included to investigate the potential existence of correlations between salt solubility and crystal packing modes. Alkyl groups were methyl, ethyl, propyl, and butyl and the derivatives were isolated...

  15. 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.

  16. 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...

  17. 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...

  18. Thermodynamic and Experimental Study of the Energetic Cost Involved in the Capture of Carbon Dioxide by Aqueous Mixtures of Commonly Used Primary and Tertiary Amines.

    Science.gov (United States)

    Arcis, Hugues; Coulier, Yohann; Coxam, Jean-Yves

    2016-01-05

    The capture of carbon dioxide with chemical solvents is one solution to mitigate greenhouse gas emissions from anthropogenic sources and thus tackle climate change. Recent research has been focused on optimizing new kinds of advanced absorbents including aqueous amine blends, but critical downsides such as the large energetic cost involved with the industrial process remain. To address this issue, a better understanding of the energetic interactions existing in solution is necessary. In this paper, we report direct experimental measurements of the energy cost involved in the solvation of CO2 in two aqueous amine blends at different temperatures. The chemical solvents were designed as aqueous mixtures of commonly used primary and tertiary amines to study the influence of the different chemical properties inferred by the amine class. We have also applied a thermodynamic model to represent the energetic effects that take place in solution during CO2 dissolution in these mixtures, where all parameters were taken from previous studies focused on single amine absorbents. The noteworthy agreement observed with the reported experimental heats of absorption and with literature vapor liquid equilibrium properties confirmed the relevance of the underlying molecular mechanisms considered in our model, and suggest that this model would prove useful to investigate CO2 dissolution in other amine blends.

  19. 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.

  20. Theoretical Mechanism Studies on the Enantioselectivity of aza-MBH-type Reaction of Nitroalkene to N-tosylimine Catalyzed by Thiourea-tertiary Amine

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Nan; Wang, Huatian; Wang, Yangping [Shandong Agricultural Univ., Taian (China)

    2013-12-15

    The enantioselective aza-Morita Baylis Hillman reaction of nitroalkene and N-tosylimine catalyzed by thiourea-tertiary amine has been investigated using density functional theory. Enantioselectivity is dominated by the cooperative effect of non-covalent and weak covalent interactions imposed by different units of catalyst. As Lewis base, the tertiary amine unit activates nitroalkene via weak covalent bond. The weak covalent interaction orients the reaction in a major path with smaller variations of this bond. The aromatic ring unit activates N-tosylimine via π-π stacking. The non-covalent interaction selects the major path with smaller changes of the efficient packing areas. Thiourea unit donates more compact H-bonded network for species of the major path. The calculated ee value in xylene solution phase (97.6%) is much higher than that in N,N-Dimethylformamide (27.2%). Our conclusion is also supported by NBO analysis.

  1. 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...

  2. 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.

  3. Unexpected Reduction of Ethyl 3-Phenylquinoxaline-2- carboxylate 1,4-Di-N-oxide Derivatives by Amines

    Directory of Open Access Journals (Sweden)

    Antonio Monge

    2008-01-01

    Full Text Available The unexpected tendency of amines and functionalized hydrazines to reduceethyl 3-phenylquinoxaline-2-carboxylate 1,4-di-N-oxide (1 to afford a quinoxaline 1c andmono-oxide quinoxalines 1a and 1b is described. The experimental conditions werestandardized to the use of two equivalents of amine in ethanol under reflux for two hours,with the aim of studying the distinct reductive profiles of the amines and thechemoselectivity of the process. With the exception of hydrazine hydrate, which reducedcompound 1 to a 3-phenyl-2-quinoxalinecarbohydrazide derivative, the amines only actedas reducing agents.

  4. 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.

  5. 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)

  6. 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...

  7. 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.

  8. 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.

  9. Dual-cloud point extraction and tertiary amine labeling for selective and sensitive capillary electrophoresis-electrochemiluminescent detection of auxins.

    Science.gov (United States)

    Yin, Xue-Bo; Guo, Jun-Min; Wei, Wei

    2010-02-19

    The low concentrations of the auxins in samples of plant tissue necessitate the use of selective and sensitive techniques for their quantification. Herein a selective and sensitive method based on dual-cloud point extraction (dCPE) and tertiary amine labeling for the quantification of indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA) by capillary electrophoresis-electrochemiluminescence (CE-ECL) is proposed. The procedure for dCPE included two cloud point processes with Triton X-114 as the extractant. The two auxins became hydrophobic in an acidic solution and were extracted into surfactant-rich phase after the first cloud point procedure. They were then back-extracted into the alkaline aqueous phase during the second cloud point step. The extracted auxins were reacted with 2-(2-aminoethyl)-1-methylpyrrolidine (AEMP) in acetonitrile that contained N,N'-dicyclohexylcarbodiimide and 3,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine to produce their AEMP-derivatives. The two auxin-AEMP-derivatives were subjected into CE and detected by Ru(bpy)(3)(2+)-based ECL. The preconcentration factors for IAA and IBA with dCPE were 40.5 and 43.4, respectively. The on-capillary detection limits (S/N=3) were 2.5 and 2.8nM for IAA and IBA. This protocol presents a clear advantage in that it reduces the interference from the matrixes extensively and gives a high sensitivity for the detection of auxins. The proposed method was applied successfully to the detection of the two auxins in acacia tender leaves, buds, and bean sprout. Copyright 2009 Elsevier B.V. All rights reserved.

  10. 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.

  11. Reduction of secondary and tertiary phosphine oxides to phosphines.

    Science.gov (United States)

    Hérault, Damien; Nguyen, Duc Hanh; Nuel, Didier; Buono, Gérard

    2015-04-21

    Achiral or chiral phosphines are widely used in two main domains: ligands in organometallic catalysis and organocatalysis. For this reason, the obtention of optically pure phosphine has always been challenging in the development of asymmetric catalysis. The simplest method to obtain phosphines is the reduction of phosphine oxides. The essential difficulty is the strength of the P=O bond which involves new procedures to maintain a high chemio- and stereoselectivity. The reduction can occur with retention or inversion of the stereogenic phosphorus atom depending on the nature of the reducing agent and the presence of additives. In fact, the reactivity of the phosphine oxides and the mechanism of the reduction are not always well understood. Since the first work in the 1950's, numerous studies have been realised in order to develop methodologies with different reagents or to understand the mechanism of the reaction. In the last decade, efficient stereospecific methodologies have been developed to obtain optically pure tertiary phosphines from P-stereogenic phosphine oxides. In this review, we intend to provide a comprehensive and critical overview of these methodologies.

  12. 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.

  13. Rhodium-catalyzed asymmetric arylation of cyclic N-sulfonyl aryl alkyl ketimines: efficient access to highly enantioenriched α-tertiary amines.

    Science.gov (United States)

    Jiang, Tao; Wang, Zheng; Xu, Ming-Hua

    2015-02-06

    A simple catalyst system of Rh(I)/sulfur-olefin with exceptional catalytic performance has been developed for the highly enantioselective arylation of cyclic N-sulfonyl aryl alkyl ketimines with arylboroxines/arylboronic acids. Optically active α-arylalkyl-substituted benzosultams and benzosulfamidates which are generally difficult to obtain were easily prepared with excellent stereocontrol (up to 99.9% ee). The synthetic utility of the approach was demonstrated by the facile construction of NMDA antagonist FR115427 and benzoxazinone derivatives. This protocol offers new opportunities for the efficient synthesis of diverse chiral α-tertiary amines.

  14. Tertiary amine derivatives of chlorochalcone as acetylcholinesterase (AChE) and buthylcholinesterase (BuChE) inhibitors: the influence of chlorine, alkyl amine side chain and α,β-unsaturated ketone group.

    Science.gov (United States)

    Gao, Xiao-Hui; Zhou, Chao; Liu, Hao-Ran; Liu, Lin-Bo; Tang, Jing-Jing; Xia, Xin-Hua

    2017-12-01

    A new series of tertiary amine derivatives of chlorochalcone (4a∼4l) were designed, synthesized and evaluated for the effect on acetylcholinesterase (AChE) and buthylcholinesterase (BuChE). The results indicated that all compounds revealed moderate or potent inhibitory activity against AChE, and some possessed high selectivity for AChE over BuChE. The structure-activity investigation showed that the substituted position of chlorine significantly influenced the activity and selectivity. The alteration of tertiary amine group also leads to obvious change in bioactivity. Among them, IC 50 of compound 4l against AChE was 0.17 ± 0.06 µmol/L, and the selectivity was 667.2 fold for AChE over BuChE. Molecular docking and enzyme kinetic study on compound 4l suggested that it simultaneously binds to the catalytic active site (CAS) and peripheral anionic site (PAS) of AChE. Further study showed that the pyrazoline derivatives synthesized from chlorochalcones had weaker activity and lower selectivity in inhibiting AChE compared to that of chlorochalcone derivatives.

  15. 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.

  16. 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

  17. One-step synthesis of robust amine- and vinyl-capped magnetic iron oxide nanoparticles for polymer grafting, dye adsorption, and catalysis.

    Science.gov (United States)

    Zhou, Li; He, Benzhao; Huang, Jiachang

    2013-09-11

    Magnetic iron oxide nanoparticles (MIONs) bearing amine and vinyl groups are fabricated straightforwardly using vinyl-based tertiary amine molecules as both alkaline source and ligands based on the coprecipitation of iron ions in aqueous solution. The as-prepared MIONs present amphiphilic performance that can be well-dispersed both in aqueous solution and common organic solvents (e.g., ethanol, dichloromethane and tetrahydrofuran). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and vibrating sample magnetometer (VSM) measurements reveal that the MIONs are superparamagnetic Fe3O4 nanoparticles with a mean diameter below 10 nm. The presence of ligands on the surface of MIONs was confirmed by thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) characterizations. Benefiting from the surface vinyl groups, the MIONs are able to graft polyvinyl-based polymers by in situ polymerization of the corresponding vinyl monomers as confirmed by grafting poly(methyl methacrylate) (PMMA) in this paper. On the basis of their surface amine groups, the MIONs show high adsorption capacity (ca. 0.42 mmol/g) for congo red dye and excellent performance for in situ growth of Pt nanocatalyst. Moreover, the MIONs possess high stability and can be reused several times without obvious decrease of their adsorption capacity and catalytic efficiency. Considering the facile fabrication process and versatile performance of the obtained MIONs, this work may open up new opportunities for the large-scale applications of MIONs.

  18. 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

  19. Tandem Brook Rearrangement/Silicon Polonovski Reaction via Oxidative Generation of Ammonium Ylides.

    Science.gov (United States)

    Shibuya, Hiromasa; Nakago, Takahiro; Inoue, Seiichi; Hoshino, Yujiro; Honda, Kiyoshi

    2017-08-01

    A tandem Brook rearrangement/silicon Polonovski reaction has been achieved by in situ generation of ammonium ylides via the oxidation of α-silyl-tertiary amines. Furthermore, we found that the oxidation of N-(1-cyano-1-silyl)methyl-tertiary amines with peracids induced the tandem Brook rearrangement/silicon Polonovski reaction/fragmentation to give formamide derivatives in moderate yields.

  20. Adsorption and oxidation of fluoroquinolone antibacterial agents and structurally related amines with goethite.

    Science.gov (United States)

    Zhang, Huichun; Huang, Ching-Hua

    2007-01-01

    Seven members (ciprofloxacin, enrofloxacin, norfloxacin, ofloxacin, lomefloxacin, pipemidic acid, and flumequine) of the popular fluoroquinolone antibacterial agents (FQs) were found to adsorb strongly to goethite with 50-76% of the added FQ adsorbed under the experimental conditions. The adsorption isotherms fitted well to the Langmuir model. Adsorption was accompanied by slow oxidation of the FQs (except for flumequine) by goethite yielding a range of hydroxylated and dealkylated products. The oxidation kinetics showed different stages in reaction rate, mostly likely caused by accumulation of Fe(II) species on the oxide surface that slowed the reaction. Structurally related amines 1-phenylpiperazine, N-phenylmorpholine, aniline, and N,N-dimethylaniline were found to be oxidized by goethite without significant adsorption. The results strongly indicate that the carboxylic group of FQs is critical for adsorption while the piperazine ring is susceptible to oxidation. A radical mechanism is proposed for the oxidation of FQs by goethite which involves formation of a surface complex between the FQ and surface-bound Fe(III) through adsorption, and initial oxidation at the piperazinyl N1 atom to form radical intermediates that ultimately lead to the final products. This study indicates that Fe oxides in aquatic sediments may well play an important role in the natural attenuation of fluoroquinolone antibacterial agents.

  1. Hydrogenation using iron oxide-based nanocatalysts for the synthesis of amines.

    Science.gov (United States)

    Jagadeesh, Rajenahally V; Stemmler, Tobias; Surkus, Annette-Enrica; Junge, Henrik; Junge, Kathrin; Beller, Matthias

    2015-04-01

    In this protocol, we describe the preparation of nanoscale iron oxide-based materials and their use in the catalysis of different hydrogenation reactions. Pyrolysis of a Fe(OAc)2-phenanthroline complex on carbon at 800 °C under argon atmosphere results in the formation of nanoscale Fe2O3 particles surrounded by nitrogen-doped graphene layers. By applying these catalysts, the hydrogenation of structurally diverse and functionalized nitroarenes to anilines proceeds with excellent selectivity. Furthermore, we have shown that one-pot reductive amination of carbonyl compounds with nitroarenes is also possible in the presence of these iron oxide catalysts. We report herein the synthesis of more than 40 amines, which are important feedstocks and key intermediates for pharmaceuticals, agrochemicals and polymers. The detailed preparation of the catalysts and the procedures for the hydrogenation processes are presented. The overall time required for the catalyst preparation and for the hydrogenation reactions are 35 h and 20-35 h, respectively.

  2. 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.

  3. 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

  4. 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.

  5. 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)

  6. Enantioselective sulfonation of enones with sulfonyl imines by cooperative N-heterocyclic-carbene/thiourea/tertiary-amine multicatalysis.

    Science.gov (United States)

    Jin, Zhichao; Xu, Jianfeng; Yang, Song; Song, Bao-An; Chi, Yonggui Robin

    2013-11-18

    Many hands make light work: In an organocatalytic asymmetric sulfonation of enones, the activation of a sulfonyl imine by an N-heterocyclic carbene (NHC) catalyst led to the release of a sulfinic anion, which underwent nucleophilic addition to the enone. The enantioselectivity of the process was controlled by a chiral thiourea/amine co-catalyst through anion recognition and hydrogen-bonding interactions. Tol=p-tolyl. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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....

  8. 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

  9. 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.

  10. 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

  11. 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

    The formation of imines by aerobic oxidative coupling of mixtures of alcohols and amines was studied using gold nanoparticles supported on titanium dioxide, TiO2, as a heterogeneous catalyst. The reactions were performed at ambient conditions (room temperature and atmospheric pressure) and occurr......-product represents a new green reaction protocol for imine formation.......The formation of imines by aerobic oxidative coupling of mixtures of alcohols and amines was studied using gold nanoparticles supported on titanium dioxide, TiO2, as a heterogeneous catalyst. The reactions were performed at ambient conditions (room temperature and atmospheric pressure) and occurred...... 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...

  12. Cu-BTC/aminated graphite oxide composites as high-efficiency CO2 capture media.

    Science.gov (United States)

    Policicchio, Alfonso; Zhao, Yunxia; Zhong, Qin; Agostino, Raffaele G; Bandosz, Teresa J

    2014-01-08

    CO2 adsorption isotherms on Cu-BTC/aminated graphite oxide composites were measured in the pressure range up to 1.5 MPa at three different temperatures close to ambient. Adsorption capacity, isosteric heat of adsorption, and regenerability were investigated. They are considered as significant factors determining the practical application of materials for CO2 capture. The results indicate a significant improvement in the performance of the composites as CO2 adsorbents in comparison with the parent Cu-BTC MOF. Among all samples analyzed, the composite of Cu-BTC and modified graphite oxide with the highest N content (MOF/GO-U3) is the best performing sample. On its surface 13.41 mmol/g CO2 was adsorbed at room temperature and 1.5 MPa. A high selectivity for CO2 adsorption over that of CH4 was found. The selectivities for CO2 adsorption over N2 are governed by the properties of the MOF phase. A relatively low heat of CO2 adsorption and the high degree of surface homogeneity cause that the composites can be fully regenerated and used in multicycle adsorption with the minimum energy demand.

  13. Sapindus mukorossi mediated green synthesis of some manganese oxide nanoparticles interaction with aromatic amines

    Science.gov (United States)

    Jassal, Vidhisha; Shanker, Uma; Gahlot, Sweta; Kaith, B. S.; Kamaluddin; Iqubal, Md Asif; Samuel, Pankaj

    2016-04-01

    A green route was successfully used to synthesize some manganese oxides (MO) nanoparticles like MnO2, Mn2O3 and Mn3O4 with varied Mn/O ratio. This approach involved utilization of Sapindus mukorossi (raw reetha)-water as a natural surfactant-solvent system. The most important feature of present work was that during the synthesis of nanoparticles, no harmful toxic solvent or chemicals were used in order to follow the principles of green chemistry. The size of nanoparticles was recorded below 100 nm with different shapes and morphologies. MnO2 nanoparticles were found to have needle shape, Mn2O3: spherical and Mn3O4: cubic shape. The synthesized nanoparticles were characterized by powder X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. The synthesized MO nanoparticles were found to act as a solid support cum catalysts for the oxidation and polymerization of some aromatic amines like p-anisidine, p-toluidine, p-chloroaniline and aniline.

  14. 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

  15. Comparison of the efficacy of disinfectants in automated endoscope reprocessors for colonoscopes: tertiary amine compound (Sencron2®) versus ortho-phthalaldehyde (Cidex®OPA).

    Science.gov (United States)

    Seo, Hyun Il; Lee, Dae Sung; Yoon, Eun Mi; Kwon, Min-Jung; Park, Hyosoon; Jung, Yoon Suk; Park, Jung Ho; Sohn, Chong Il; Park, Dong Il

    2016-04-01

    To prevent the transmission of pathogens by endoscopes, following established reprocessing guidelines is critical. An ideal reprocessing step is simple, fast, and inexpensive. Here, we evaluated and compared the efficacy and safety of two disinfectants, a tertiary amine compound (TAC) and ortho-phthalaldehyde (OPA). A total of 100 colonoscopes were randomly reprocessed using two same automated endoscope reprocessors, according to disinfectant. The exposure time was 10 minutes for 0.55% OPA (Cidex® OPA, Johnson & Johnson) and 5 minutes for 4% TAC (Sencron2®, Bab Gencel Pharma & Chemical Ind. Co.). Three culture samples were obtained from each colonoscope after reprocessing. A total of nine samples were positive among the 300 culture samples. The positive culture rate was not statistically different between the two groups (4% for OPA and 2% for TAC, P=0.501). There were no incidents related to safety during the study period. TAC was non-inferior in terms of reprocessing efficacy to OPA and was safe to use. Therefore, TAC seems to be a good alternative disinfectant with a relatively short exposure time and is also less expensive than OPA.

  16. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mercier, D.; Rouchaud, J.-C. [Centre d' Etudes de Chimie Metallurgique, CNRS, 15 rue Georges Urbain, 94407 Vitry Cedex (France); Barthes-Labrousse, M.-G. [Centre d' Etudes de Chimie Metallurgique, CNRS, 15 rue Georges Urbain, 94407 Vitry Cedex (France)], E-mail: marie-genevieve.barthes@u-psud.fr

    2008-08-15

    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{sub x}O{sub y}H{sub 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{sub x}O{sub y}H{sub z}...N bond. Al-OH...N and C{sub x}O{sub y}H{sub 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 {eta}{sup 1}-OH and bridged {mu}{sub 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.

  18. [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.

  19. Sorption studies of chromium(VI) onto new ion exchanger with tertiary amine, quaternary ammonium and ketone groups

    Energy Technology Data Exchange (ETDEWEB)

    Wojcik, Grzegorz [College of Chemistry, University of Maria Curie-Sklodowska, Department of Inorganic Chemistry Pl. M. Curie-Sklodowskiej 2, 20-031 Lublin (Poland); Neagu, Violeta, E-mail: vneagu@icmpp.ro [' Petru Poni' Institute of Macromolecular Chemistry, Gr. Ghica Voda 41A, Iasi 700487 (Romania); Bunia, Ion [' Petru Poni' Institute of Macromolecular Chemistry, Gr. Ghica Voda 41A, Iasi 700487 (Romania)

    2011-06-15

    A new acrylic anion exchanger with both tertiary and quaternary ammonium as well as ketone groups in the structural unit has been prepared by the nucleophilic substitution reaction of aminolyzed vinylacetate:acrylonitrile:divinylbenzene copolymer of porosity structure in the swelling state with 2-chloroacetone as a halogenated compound. The new compound exhibits better qualities of strong base exchange capacity than the weak base anion exchangers. The obtained acrylic anion exchanger was used to remove Cr(VI) from the aqueous solution. Batch adsorption studies have been carried out to determine the effect of contact time, concentration of hexavalent chromium in the solution and pH on the sorption capacity. The kinetic parameters were determined on the basis of the static results. The thermodynamic parameters of Cr(VI) sorption process on the anion exchanger were calculated based on the Langmuir and Freundlich isotherms. Sorption was studied in the pH range of 1.5-7 and it was found that it depends on the solution acidity. At the pH values of 3.5 and 7 the anion exchanger exhibited large values of chromium sorption capacity. The speciation of chromium was investigated in the studied pH range by the Diffuse Reflectance Spectroscopy (DRS) method. Reduction of chromium(VI) to chromium(III) under acidic conditions was observed. The performed acrylic strong base anion exchanger is superior compared to the conventional one based on the styrene:divinylbenzene matrix due to its ability for reposition of the long spacer arm for providing exchange sites, hydrophilic character of matrix, and possible hydrogen bonds provided by carbonyl functional groups.

  20. 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....

  1. Structure and Oxidation of Pyrrole Adducts Formed between Aflatoxin B2aand 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.

  2. Silica Fume Functionalized With Amine-Based Additives as a Modifier to Enhance Asphalt Resistance to Oxidation

    Science.gov (United States)

    Abutalib, Nader Turki

    This dissertation investigates the practical feasibility of functionalizing silica fume particles with the amine groups in Bio-binder and pure APTES chemical to disperse silica fume in asphalt binder matrix to produce silica-fume-modified binder (SFMB). Dispersed silica fume was then introduced to asphalt to reduce oxidative aging. It has been widely reported that asphalt binder oxidation is one of the phenomena that reduces the service life of asphalt pavement by negatively affecting its rheological properties. This in turn can lead to a more brittle pavement, which is more prone to cracks due to thermal stress and traffic loading. It has been shown that the introduction of 4% silica fume to asphalt can reduce asphalt oxidative aging. However, the challenge with a higher percentage of silica fume was found to be the agglomeration of nano- particles to form micro-size clusters, which can reduce the effectiveness of silica fume while making asphalt binder more susceptible to shear. Therefore, this dissertation studies the effectiveness of functionalizing the SFMB to reduce asphalt oxidative aging while alleviating the agglomeration effect. To do so, various percentages of bio-binder (BB) and bio-char (BC) were introduced to SFMB, and the rheological properties and high-temperature performance of each specimen were evaluated by measuring the rotational viscosity and complex shear modulus before and after oxidative aging. It is hypothesized that fine-graded BC and BB with nano- to micro-level particles can be used to reduce asphalt oxidation and create a new generation of low- agglomeration SFMB with higher resistance to oxidative aging. To further study the effects of functionalization on dispersion of silica fume, silica fume particles were produced with different functional groups: amine (APTES) groups and phosphonate (THPMP) groups. Agglomeration studies using a scanning electron microscope and zeta potential analysis indicate that modifying asphalt binder with

  3. 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.

  4. 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.

  5. S-nitroso-N-acetylpenicillamine (SNAP) derivatization of peptide primary amines to create inducible nitric oxide donor biomaterials.

    Science.gov (United States)

    VanWagner, Michael; Rhadigan, Jessica; Lancina, Michael; Lebovsky, Allison; Romanowicz, Genevieve; Holmes, Hal; Brunette, Margaret A; Snyder, Katherine L; Bostwick, Michael; Lee, Bruce P; Frost, Megan C; Rajachar, Rupak M

    2013-09-11

    An S-nitroso-N-acetylpenicillamine (SNAP) derivatization approach was used to modify existing free primary amines found in fibrin (a natural protein-based biomaterial) to generate a controlled nitric oxide (NO) releasing scaffold material. The duration of the derivatization reaction affects the NO release kinetics, the induction of controlled NO-release, hydrophobicity, swelling behavior, elastic moduli, rheometric character, and degradation behavior. These properties were quantified to determine changes in fibrin hydrogels following covalent attachment of SNAP. NO-releasing materials exhibited minimal cytotoxicity when cultured with fibroblasts or osteoblasts. Cells maintained viability and proliferative character on derivatized materials as demonstrated by Live/Dead cell staining and counting. In addition, SNAP-derivatized hydrogels exhibited an antimicrobial character indicative of NO-releasing materials. SNAP derivatization of natural polymeric biomaterials containing free primary amines offers a means to generate inducible NO-releasing biomaterials for use as an antimicrobial and regenerative support for tissue engineering.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. Excess molar volumes and excess molar enthalpies of binary and ternary mixtures of 1-butanol, a tertiary amine (tri-n-butylamine or tri-n-octylamine) and n-hexane: Experimental results and ERAS-model calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kwaterski, Matthias [Applied Thermodynamics, Institute of Physical Chemistry, University of Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg (Germany); Rezanova, Elena N. [Applied Thermodynamics, Institute of Physical Chemistry, University of Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg (Germany); Lichtenthaler, Ruediger N. [Applied Thermodynamics, Institute of Physical Chemistry, University of Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg (Germany)]. E-mail: R.Lichtenthaler@urz.uni-heidelberg.de

    2006-10-15

    Experimental data at T=298.15K and ambient pressure of excess molar volumes V{sub m}{sup E} and excess molar enthalpies H{sub m}{sup E} are reported for two ternary and the corresponding binary mixtures of {l_brace}1-butanol, tri-n-butylamine (TBA), or tri-n-octylamine (TOA), and n-hexane{r_brace}. A vibrating-tube densitometer was used to determine V{sub m}{sup E}. H{sub m}{sup E} was measured using a quasi-isothermal flow calorimeter. The experimental results are used to test the applicability of the ERAS model for describing both thermodynamic excess properties of ternary mixtures containing an alkanol, a tertiary amine and an n-alkane. Qualitative agreement of calculated values with experimental results was achieved using only system-specific parameters determined from binary mixtures. The results are explained in terms of the self-association between alkanol molecules, cross-association between the alkanol and the tertiary amines and structural effects.

  11. 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 (Pbacon (Pbacon (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.

  12. Biogenic amine formation and oxidation by Staphylococcus xylosus strains from artisanal fermented sausages.

    Science.gov (United States)

    Martuscelli, M; Crudele, M A; Gardini, F; Suzzi, G

    2000-09-01

    Fifty strains of Staph. xylosus, isolated from artisanal fermented sausages in Southern Italy (Lucania region) were tested to verify their potential to produce or degrade biogenic amines. Twenty-six strains analysed were not able to form amines, but seven had the potential to produce spermine and/or spermidine and, at lower levels, tryptamine and tyramine. By contrast, about 80% of the strains that did not possess amino acid decarboxylase activity, exhibited an ability to degrade histamine. The greatest histamine-oxidase activity was present in the strains S81 (100% degradation), S206 (93%), S79 (68%) and S90 (53%). The strain S142 exhibited a remarkably high potential to oxidase tyramine and histamine, reducing the initial concentrations by 63 and 47%, respectively.

  13. Pro-Oxidant Activity of Amine-Pyridine-Based Iron Complexes Efficiently Kills Cancer and Cancer Stem-Like Cells.

    Science.gov (United States)

    González-Bártulos, Marta; Aceves-Luquero, Clara; Qualai, Jamal; Cussó, Olaf; Martínez, M Angeles; Fernández de Mattos, Silvia; Menéndez, Javier A; Villalonga, Priam; Costas, Miquel; Ribas, Xavi; Massaguer, Anna

    2015-01-01

    Differential redox homeostasis in normal and malignant cells suggests that pro-oxidant-induced upregulation of cellular reactive oxygen species (ROS) should selectively target cancer cells without compromising the viability of untransformed cells. Consequently, a pro-oxidant deviation well-tolerated by nonmalignant cells might rapidly reach a cell-death threshold in malignant cells already at a high setpoint of constitutive oxidative stress. To test this hypothesis, we took advantage of a selected number of amine-pyridine-based Fe(II) complexes that operate as efficient and robust oxidation catalysts of organic substrates upon reaction with peroxides. Five of these Fe(II)-complexes and the corresponding aminopyridine ligands were selected to evaluate their anticancer properties. We found that the iron complexes failed to display any relevant activity, while the corresponding ligands exhibited significant antiproliferative activity. Among the ligands, none of which were hemolytic, compounds 1, 2 and 5 were cytotoxic in the low micromolar range against a panel of molecularly diverse human cancer cell lines. Importantly, the cytotoxic activity profile of some compounds remained unaltered in epithelial-to-mesenchymal (EMT)-induced stable populations of cancer stem-like cells, which acquired resistance to the well-known ROS inducer doxorubicin. Compounds 1, 2 and 5 inhibited the clonogenicity of cancer cells and induced apoptotic cell death accompanied by caspase 3/7 activation. Flow cytometry analyses indicated that ligands were strong inducers of oxidative stress, leading to a 7-fold increase in intracellular ROS levels. ROS induction was associated with their ability to bind intracellular iron and generate active coordination complexes inside of cells. In contrast, extracellular complexation of iron inhibited the activity of the ligands. Iron complexes showed a high proficiency to cleave DNA through oxidative-dependent mechanisms, suggesting a likely mechanism of

  14. 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.

  15. 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

    2015-11-01

    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. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. One pot in situ growth of gold nanoparticles on amine-modified graphene oxide and their high catalytic properties

    Science.gov (United States)

    Ju, Yuyun; Li, Xi; Feng, Jie; Ma, Yanhua; Hu, Jing; Chen, Xingguo

    2014-10-01

    In this work, one pot strategy was proposed for in situ growth of Au nanoparticles (Au NPs) on the surface of amine-modified graphene oxide (GO@NH2) nanosheets. Au NPs were generated via an in situ reduction of Au3+ by Cu+ which was linked to the surface of GO@NH2 nanosheets through inorganic grafting. The initial Au NPs then served as seed for subsequent particle growth. The as-obtained GO@NH2-Au nanocomposites (GO@NH2-Au NCs) exhibited high catalytic activity for the degradation of 4-nitrophenol, which was a refractory pollutant that occur in industrial waste water. The catalytic efficiency was examined by turnover frequency (TOF). It was calculated to be 595 h-1, which was higher than that of other Au catalysts. Furthermore, the as-prepared catalyst showed high cycle stabilization during the catalytic reduction.

  17. Detection of Guanine and Adenine Using an Aminated Reduced Graphene Oxide Functional Membrane-Modified Glassy Carbon Electrode

    Directory of Open Access Journals (Sweden)

    Di Li

    2017-07-01

    Full Text Available A new electrochemical sensor based on a Nafion, aminated reduced graphene oxide and chitosan functional membrane-modified glassy carbon electrode was proposed for the simultaneous detection of adenine and guanine. Fourier transform-infrared spectrometry (FTIR, transmission electron microscopy (TEM, and electrochemical methods were utilized for the additional characterization of the membrane materials. The prepared electrode was utilized for the detection of guanine (G and adenine (A. The anodic peak currents to G and A were linear in the concentrations ranging from 0.1 to 120 μM and 0.2 to 110 μM, respectively. The detection limits were found to be 0.1 μM and 0.2 μM, respectively. Moreover, the modified electrode could also be used to determine G and A in calf thymus DNA.

  18. Selection of Amine-Oxidizing Dairy Lactic Acid Bacteria and Identification of the Enzyme and Gene Involved in the Decrease of Biogenic Amines

    Science.gov (United States)

    Guarcello, Rosa; De Angelis, Maria; Settanni, Luca; Formiglio, Sabino; Gaglio, Raimondo; Moschetti, Giancarlo; Gobbetti, Marco

    2016-01-01

    ABSTRACT Accumulation of biogenic amines (BAs) in cheese and other foods is a matter of public health concern. The aim of this study was to identify the enzyme activities responsible for BA degradation in lactic acid bacteria which were previously isolated from traditional Sicilian and Apulian cheeses. The selected strains would control the concentration of BAs during cheese manufacture. First, 431 isolates not showing genes encoding the decarboxylases responsible for BA formation were selected using PCR-based methods. Ninety-four out of the 431 isolates degraded BAs (2-phenylethylamine, cadaverine, histamine, putrescine, spermine, spermidine, tyramine, or tryptamine) during cultivation on chemically defined medium. As shown by random amplification of polymorphic DNA-PCR and partial sequencing of the 16S rRNA gene, 78 of the 94 strains were Lactobacillus species (Lactobacillus casei, Lb. fermentum, Lb. parabuchneri, Lb. paracasei, Lb. paraplantarum, and Lb. rhamnosus), Leuconostoc species (Leuconostoc lactis and Ln. mesenteroides), Pediococcus pentosaceus, Lactococcus lactis, Streptococcus species (Streptococcus gallolyticus and S. thermophilus), Enterococcus lactis, and Weissella paramesenteroides. A multicopper oxidase-hydrolyzing BA was purified from the most active strain, Lb. paracasei subsp. paracasei CB9CT. The gene encoding the multicopper oxidase was sequenced and was also detected in other amine-degrading strains of Lb. fermentum, Lb. paraplantarum, and P. pentosaceus. Lb. paracasei subsp. paracasei CB9CT and another strain (CACIO6CT) of the same species that was able to degrade all the BAs were singly used as adjunct starters for decreasing the concentration of histamine and tyramine in industrial Caciocavallo cheese. The results of this study disclose a feasible strategy for increasing the safety of traditional cheeses while maintaining their typical sensorial traits. IMPORTANCE Because high concentrations of the potentially toxic biogenic amines may be

  19. Photocatalytic splitting of CS2 to S8 and a carbon-sulfur polymer catalyzed by a bimetallic ruthenium(II) compound with a tertiary amine binding site: toward photocatalytic splitting of CO2?

    Science.gov (United States)

    Livanov, Konstantin; Madhu, Vedichi; Balaraman, Ekambaram; Shimon, Linda J W; Diskin-Posner, Yael; Neumann, Ronny

    2011-11-21

    The catalytic photocleavage of CS(2) to S(8) and a (C(x)S(y))(n) polymer with visible light using a dinuclear ruthenium(II) compound with a bipyridine units for photoactivity and a vicinal tertiary amine binding site for CS(2) activation was studied. The catalyst was characterized by X-ray diffraction, (1)H NMR, and (13)C NMR, ESI-MS and elemental analysis. CS(2) photocleavage was significant (240 turnovers, 20 h) to yield isolable S(8) and a (C(x)S(y))(n) polymer. A mononuclear catalyst or one without an amine binding site showed significantly less activity. XPS of the (C(x)S(y))(n) polymer showed a carbon/sulfur ratio ∼1.5-1.6 indicating that in part both C-S bonds of CS(2) had been cleaved. Catalyst was also included within the polymer. The absence of peaks in the (1)H NMR verified the (C(x)S(y))(n) nature of the polymer, while (13)C NMR and IR indicated that the polymer had multiple types of C-S and C-C bonds.

  20. 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.

  1. 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.

  2. 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.

  3. Isolation and characterization of the tertiary amine Alamine 304 hydrochioride. Its application on the extraction of Co(II, Au(III and Pt(IV

    Directory of Open Access Journals (Sweden)

    López-Delgado, Aurora

    2000-06-01

    Full Text Available Amine Alamine 304 dissolved in xylene reacts with hydrochloric acid to form the amine chloride (R3NH+Cl- and the amine dichloride (R3NH2Cl2. The former compound was isolated and characterized by chemical analysis, X-ray powder diffraction, infrared spectroscopy and scanning electron microscopy. Lattice parameters of the isolated amine chloride were determined and refined by least-square numerical treatment (monoclinic cell, with a = 29.017(4 Å, b = 14.564(7 Å, c = 5.043(1 Å, b = 95.68(3 ° and V = 2,120 Å3. The amine chloride is a potential anion-exchanger with metals, thus data on the liquid-liquid extraction of Co(II, Au(III and Pt(IV are also reported.

    La amina Alamine 304 disuelta en xileno reacciona con el ácido clorhídrico para formar el cloruro de la amina (R3NH+Cl- y el dicloruro de amina (R3NH2Cl2. El primero de estos compuestos se aisló y caracterizó mediante análisis químico, difracción de rayos X, espectroscopia de IR y microscopía electrónica de barrido. Se determinaron y refinaron los parámetros de red del cloruro de amina (monoclínico, a = 29,017(4 Å, b = 14,564(7 Å, c = 5,043(1 Å, b = 95,68(3 ° y V = 2.120 Å3. El cloruro de amina actúa como un intercambiador aniónico con ciertos metales, por lo que se incluyen datos sobre la extracción líquido-líquido de Co(II, Au(III y Pt(IV.

  4. 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

    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...

  5. Selection of Amine-Oxidizing Dairy Lactic Acid Bacteria and Identification of the Enzyme and Gene Involved in the Decrease of Biogenic Amines.

    Science.gov (United States)

    Guarcello, Rosa; De Angelis, Maria; Settanni, Luca; Formiglio, Sabino; Gaglio, Raimondo; Minervini, Fabio; Moschetti, Giancarlo; Gobbetti, Marco

    2016-12-01

    Accumulation of biogenic amines (BAs) in cheese and other foods is a matter of public health concern. The aim of this study was to identify the enzyme activities responsible for BA degradation in lactic acid bacteria which were previously isolated from traditional Sicilian and Apulian cheeses. The selected strains would control the concentration of BAs during cheese manufacture. First, 431 isolates not showing genes encoding the decarboxylases responsible for BA formation were selected using PCR-based methods. Ninety-four out of the 431 isolates degraded BAs (2-phenylethylamine, cadaverine, histamine, putrescine, spermine, spermidine, tyramine, or tryptamine) during cultivation on chemically defined medium. As shown by random amplification of polymorphic DNA-PCR and partial sequencing of the 16S rRNA gene, 78 of the 94 strains were Lactobacillus species (Lactobacillus casei, Lb. fermentum, Lb. parabuchneri, Lb. paracasei, Lb. paraplantarum, and Lb. rhamnosus), Leuconostoc species (Leuconostoc lactis and Ln. mesenteroides), Pediococcus pentosaceus, Lactococcus lactis, Streptococcus species (Streptococcus gallolyticus and S. thermophilus), Enterococcus lactis, and Weissella paramesenteroides A multicopper oxidase-hydrolyzing BA was purified from the most active strain, Lb. paracasei subsp. paracasei CB9CT. The gene encoding the multicopper oxidase was sequenced and was also detected in other amine-degrading strains of Lb. fermentum, Lb. paraplantarum, and P. pentosaceus Lb. paracasei subsp. paracasei CB9CT and another strain (CACIO6CT) of the same species that was able to degrade all the BAs were singly used as adjunct starters for decreasing the concentration of histamine and tyramine in industrial Caciocavallo cheese. The results of this study disclose a feasible strategy for increasing the safety of traditional cheeses while maintaining their typical sensorial traits. Because high concentrations of the potentially toxic biogenic amines may be found in traditional

  6. 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}.

  7. Solution-Phase Conversion of Bulk Metal Oxides to Metal Chalcogenides Using a Simple Thiol-Amine Solvent Mixture.

    Science.gov (United States)

    McCarthy, Carrie L; Webber, David H; Schueller, Emily C; Brutchey, Richard L

    2015-07-13

    A thiol-amine solvent mixture is used to dissolve ten inexpensive bulk oxides (Cu2O, ZnO, GeO2, As2O3, Ag2O, CdO, SnO, Sb2O3, PbO, and Bi2O3) under ambient conditions. Dissolved oxides can be converted to the corresponding sulfides using the thiol as the sulfur source, while selenides and tellurides can be accessed upon mixing with a stoichiometric amount of dissolved selenium or tellurium. The practicality of this method is illustrated by solution depositing Sb2Se3 thin films from compound inks of dissolved Sb2O3 and selenium that give high photoelectrochemical current response. The direct band gap of the resulting material can be tuned from 1.2-1.6 eV by modulating the ink formulation to give compositionally controlled Sb2Se(3-x)S(x) alloys. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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

  9. 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

  10. 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 authent...... 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....

  11. Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation

    Science.gov (United States)

    Hill, Christopher K.; Hartwig, John F.

    2017-12-01

    Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.

  12. 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

  13. The Oxidative Mannich Reaction Catalyzed by Dirhodium Caprolactamate

    Science.gov (United States)

    Catino, Arthur J.; Nichols, Jason M.; Nettles, Brian J.; Doyle, Michael P.

    2008-01-01

    Dirhodium caprolactamate [Rh2(cap)4] is a highly effective catalyst for the oxidative Mannich reaction. The reaction proceeds via C-H oxidation of a tertiary amine followed by nucleophilic capture. This green transformation is conducted in protic solvent using inexpensive T-HYDRO® (70% t–BuOOH in water). Synthetically valuable γ-aminoalkyl-butenolides are obtained. PMID:16637627

  14. Applications of Flavoprotein Oxidases in Organic Synthesis : Novel Reactivities that Go Beyond Amine and Alcohol Oxidations

    NARCIS (Netherlands)

    Winter, R.T.; Fraaije, M.W.

    2012-01-01

    Oxidases represent a distinct and interesting class of oxidative biocatalysts. A major portion of the known oxidases contain a flavin as cofactor, with glucose oxidase as best known example. While a number of oxidases are well known in the field of biocatalysis, the total number of available

  15. 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

  16. 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

  17. Visible light catalyzed Mannich reaction between tert-amines and silyl diazoenolates.

    Science.gov (United States)

    Pramanik, Mukund M D; Nagode, Savita B; Kant, Ruchir; Rastogi, Namrata

    2017-09-13

    The present work documents the α-C-H functionalization of tertiary amines via the visible light catalyzed Mannich reaction with silyl diazoenolates. The reaction takes place at room temperature with an organic dye, Rose Bengal, as a photocatalyst and oxygen as the oxidant. The resulting multifunctional products bearing an α-diazo-β-keto group undergo Rh-carbenoid mediated cyclization, affording stable ammonium ylides in high yields.

  18. Ion Clusters in Nucleation Experiments in the CERN Cloud Chamber: Sulfuric Acid + Ammonia + Dimethyl Amine + Oxidized Organics

    Science.gov (United States)

    Worsnop, D. R.; Schobesberger, S.; Bianchi, F.; Ehrhart, S.; Junninen, H.; Kulmala, M. T.

    2012-12-01

    Nucleation from gaseous precursors is an important source of aerosol particles in the atmosphere. The CLOUD experiment at CERN provides exceptionally clean and well-defined experimental conditions for studies of atmospheric nucleation and initial growth, in a 26 m3 stainless-steel chamber. In addition, the influence of cosmic rays on nucleation and nanoparticle growth can be simulated by exposing the chamber to a pion beam produced by the CERN Proton Synchrotron. A key to understanding the mechanism by which nucleation proceeds in the CLOUD chamber is the use of state-of-the-art instrumentation, including the Atmospheric Pressure interface Time-Of-Flight (APi-TOF) mass spectrometer. The APi-TOF is developed by Tofwerk AG, and Aerodyne Research, Inc., and typically obtains resolutions between 4000 and 6000 Th/Th and mass accuracies APi-TOF detected ion clusters that could directly be linked to nucleation. The composition of these ion clusters could be determined based on their exact masses and isotopic patterns. Aided by the chamber's cleanliness and the possibility of enhancing ion concentrations by using CERN's pion beam, a remarkably large fraction of the ion spectra could be identified, even for more complex chemical systems studied. For the ammonia-sulfuric acid-water system, for instance, growing clusters containing ammonia (NH3) and sulfuric acid (H2SO4) were observed up to 3300 Th. Adding dimethyl amine and/or pinanediol into the CLOUD chamber, altered the chemical compositions of the observed ion clusters accordingly. Cluster growth then included mixtures of sulfuric acid and dimethyl amine and/or a wide range of pinanediol oxidation products. The initial growth of clusters/particles was studied from smallest clusters upwards, using a range of employed instrumentation. Condensation particle counters (such as the Particle Size Magnifier, PSM, by Airmodus Oy), for instance, were specially modified to obtain aerosol number size distributions down to the size

  19. 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.

  20. 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.

  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. 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

  3. 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.

  4. 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.

  5. 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

  6. 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

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

    Science.gov (United States)

    Garcia-Segura, Sergi; Keller, Jürg; Brillas, Enric; Radjenovic, Jelena

    2015-01-01

    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(-) ions present in the wastewater at the BDD anode gave rise to active chlorine species (Cl2/HClO/ClO(-)), which are competitive oxidizing agents yielding chloramines and organohalogen byproducts, quantified as adsorbable organic halogen. However, further anodic oxidation of HClO/ClO(-) species led to the production of ClO3(-) and ClO4(-) 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Preventive effects of an original combination of grape seed polyphenols with amine fluoride on dental biofilm formation and oxidative damage by oral bacteria.

    Science.gov (United States)

    Furiga, A; Roques, C; Badet, C

    2014-04-01

    To investigate the preventive effects of an original combination of a grape seed extract (GSE) with an amine fluoride (Fluorinol(®) ) on dental plaque formation and oxidative damage caused by oral bacteria. The antibacterial activity of the compounds was assessed using the broth macrodilution method, and their antiplaque activity was evaluated on a multispecies biofilm grown on saliva-coated hydroxyapatite discs. The effect on glucosyltransferases activity was analysed through reductions in the overall reaction and the quantity of insoluble glucan synthesized. The combination of 2000 μg ml(-1) of GSE with 10·2 mg ml(-1) of Fluorinol(®) significantly decreased the biofilm formation (up to 4·76 log10 of reduction) and inhibited by 97·4% the insoluble glucan synthesis by glucosyltransferases. The antioxidant activity of this combination, alone or incorporated into a formulated mouthwash (Eludril daily(®) ), was determined using the Trolox equivalent antioxidant capacity assay (TEAC), and both showed significantly greater antioxidant capacity than vitamin C. The GSE/Fluorinol(®) combination showed both a significant antiplaque activity and an important antioxidant capacity in vitro, without any bactericidal effects. This is, to our knowledge, the first report on the properties of an original combination of a polyphenolic extract with amine fluoride that could be used for the prevention of oral diseases and oxidative damage associated. © 2013 The Society for Applied Microbiology.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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 ...

  14. Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO₄.

    Science.gov (United States)

    Mancuso, Raffaella; Maner, Asif; Ziccarelli, Ida; Pomelli, Christian; Chiappe, Cinzia; Della Ca', Nicola; Veltri, Lucia; Gabriele, Bartolo

    2016-07-08

    A convenient carbonylative approach to 2-oxazolidinone derivatives carried out using an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, EmimEtSO₄) as the solvent is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis): the first cycle corresponds to the oxidative monoaminocarbonylation of the triple bond of propargylic amines to give the corresponding 2-ynamide intermediates, while the second one involves the cyclocarbonylation of the latter to yield 2-(2-oxooxazolidin-5-ylidene)-acetamides. Reactions are carried out using a simple catalytic system consisting of PdI₂ in conjunction with an excess of KI, and the catalyst/solvent system could be recycled several times without appreciable loss of activity after extraction of the organic product with Et₂O.

  15. 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

  16. Amine promiscuity and toxicology analysis.

    Science.gov (United States)

    Lee, Esther C Y; Steeno, Gregory; Wassermann, Anne Mai; Zhang, Liying; Shah, Falgun; Price, David A

    2017-02-01

    Drug discovery programs often face challenges to obtain sufficient duration of action of the drug (i.e. seek longer half-lives). If the pharmacodynamic response is driven by free plasma concentration of the drug then extending the plasma drug concentration is a valid approach. Half-life is dependent on the volume of distribution, which in turn can be dependent upon the ionization state of the molecule. Basic compounds tend to have a higher volume of distribution leading to longer half-lives. However, it has been shown that bases may also have higher promiscuity. In this work, we describe an analysis of in vitro pharmacological profiling and toxicology data investigating the role of primary, secondary, and tertiary amines in imparting promiscuity and thus off-target toxicity. Primary amines are found to be less promiscuous in in vitro assays and have improved profiles in in vivo toxicology studies compared to secondary and tertiary amines. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. 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 phosphatidylethanolamin...

  18. Purification and characterization of amine oxidase from Vigna ...

    African Journals Online (AJOL)

    Amine oxidases (AO) are a group of enzymes that catalyze oxidative deamination of various amines and thus are of potential use in analytical applications. Amine oxidase from five-day-old Vigna mungo L. seedlings (VAO) was purified using ammonium sulfate fractionation and Q-Sepharose chromatography to 544 ...

  19. Effect of antioxidant tertiary butyl hydroquinone on the thermal and oxidative stability of sesame oil (sesamum indicum) by ultrasonic studies.

    Science.gov (United States)

    Prasad, N; Siddaramaiah, Basavarajaiah; Banu, Mujeeda

    2015-04-01

    The aim of the current investigation is to evaluate the efficiency of tertiary butyl hydroquinone (TBHQ) as an antioxidant in sesame oil (sesamum indicum) by density, viscosity and ultrasonic velocity. The effects of varying amounts of TBHQ on the oxidation stability of sesame oil have been investigated. The antioxidant incorporated sesame oil system and control edible oil were subjected to heating at 180 ± 5 °C continuously for a period of 4 h per day for consecutive 4 days. The parameters used to assess the thermal degradation and oxidation properties of the oils include ultrasonic velocity, viscosity, density and peroxide value. The fatty acid compositions of the oils were measured by gas chromatography. Adiabatic compressibility, intermolecular free length, relaxation time and acoustic impedance have been calculated from experimental data. Viscosity, density and ultrasonic velocity change in control oil is from 3.6553 × 10(-2) to 11.1729 × 10(-2) Nsm(-2), 912.59 to 940.31 kg/m(3) and 1,421 to 1,452 m/s respectively and in sesame oil with 200 ppm TBHQ is from 3.6793 × 10(-2) to 6.4842 × 10(-2) Nsm(-2), 913.78 to 922.45 kg/m(3) and 1,421 to 1,431 m/s respectively for 16 h of heat treated oil. The ultrasonic results obtained have shown reduction in thermal degradation and improvement in oxidation stability of antioxidant loaded oil in comparison to base oil. Hence, it can be recommended that sesame oil with 200 ppm TBHQ can be used for frying without adverse effect on physical properties. The ultrasonic velocity can be used for assessment of stability of frying oil.

  20. 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.

  1. 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.

  2. 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.

  3. 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

    , including semiquinone radicals, quinones, and metal ion-DOPA complexes have also been implicated in some cases. Non-radical reactions of DOPA with suitable nucleophiles (e.g. thiol groups) can also result in modification of the target, with this process being particularly prevalent with proteins......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...

  4. Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia.

    Science.gov (United States)

    Cui, Xinjiang; Dai, Xingchao; Deng, Youquan; Shi, Feng

    2013-03-11

    The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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...

  6. Amine Oxidative N-Dealkylation via Cupric Hydroperoxide Cu–OOH Homolytic Cleavage Followed by Site-Specific Fenton Chemistry

    Science.gov (United States)

    Kim, Sunghee; Ginsbach, Jake W.; Lee, Jung Yoon; Peterson, Ryan L.; Liu, Jeffrey J.; Siegler, Maxime A.; Sarjeant, Amy A.; Solomon, Edward I.; Karlin, Kenneth D.

    2015-01-01

    Copper(II)-hydroperoxide species are significant intermediates in processes such as fuel cells and (bio)chemical oxidations, all involving stepwise reduction of molecular oxygen. We previously reported a CuII-OOH species that performs oxidative N-dealkylation on a dibenzylamino group that is appended to the 6-position of a pyridyl donor of a tripodal tetradentate ligand. To obtain insights into the mechanism of this process, reaction kinetics and products were determined employing ligand substrates with various para- substituent dibenzyl pairs (-H,-H; -H,-Cl; -H,-OMe and -Cl,-OMe), or with partially or fully deuterated dibenzyl N-(CH2Ph)2 moieties. A series of ligand-copper(II) bis-perchlorate complexes were synthesized, characterized, and the X-ray structures of the -H, -OMe analog was were determined. The corresponding metastable CuII-OOH species were generated by addition of H2O2/base in acetone at –90 °C. These convert (t1/2 ~ 53 s) to oxidatively N-dealkylated products, producing para-substituted benzaldehydes. Based on the experimental observations and supporting DFT calculations, a reaction mechanism involving dibenzylamine H-atom abstraction or electron-transfer oxidation by the CuII-OOH entity could be ruled out. It is concluded that the chemistry proceeds by rate limiting Cu–O homolytic cleavage of the CuII–(OOH) species, followed by site-specific copper Fenton chemistry. As a process of broad interest in copper as well as iron oxidative (bio)chemistries, a detailed computational analysis was performed, indicating that a CuIOOH species undergoes O–O homolytic cleavage to yield a hydroxyl radical and CuIIOH rather than heterolytic cleavage to yield water and a CuII-O•−. PMID:25706825

  7. Extraction of trace amounts of cerium(III) by oxides of amines and its separation from cerium(IV)

    International Nuclear Information System (INIS)

    Ejaz, M.

    1977-01-01

    The solvent extraction of cerium(III) from nitric, hydr0hydrochloric and sulphuric acid solutions by 4-(5-nonyl)pyridine oxide and triooctylamine oxide in xylene has been studied. Pre-equilibrated volumes of 2 cm 3 each of the phases were added to 15 cm 3 r.lass vials fitted with polythene caps. Aliquots of the radioactivity were added to the solution and the vials sealed and shaken at constant temperature. After centrifugation aliquots of each phase were withdrawn and counted to a counting error of less than 3 percent for gamma ray activity. The influence of the concentration of the solvents and salting-out agents is described. From the results of partition experiments attempts have been made to deduce the nature of the extracted species. The investigation shows that cerium(III) can be separated from cerium(IV) from very dilute solutions of mineral acids and also from moderate nitric acid media. (T.G.)

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

    OpenAIRE

    Ebrahiminezhad, Alireza; Varma, Vikas; Yang, Shuyi; Ghasemi, Younes; Berenjian, Aydin

    2015-01-01

    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 avera...

  9. One-step amine modification of graphene oxide to get a green trifunctional metal-free catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Anwei; Li, Jingjing [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China); Zhang, Chen [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Zhang, Wenqin [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China); Ma, Ning, E-mail: mntju@tju.edu.cn [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

    2015-08-15

    Graphical abstract: Graphene oxide is modified by diethylenetriamine through a one-step route to prepare GO-NH(CH{sub 2}){sub 2}NH(CH{sub 2}){sub 2}NH{sub 2} (GO-DETA), which has primary and secondary amino groups and carboxyl groups. The obtained GO-DETA is used to catalyze Knoevenagel condensation and Michael addition in water and it shows high catalytic activity. - Highlights: • GO-DETA was synthesized through a mild and facile route. • It shows high cooperative catalytic activities for Knoevenagel and Michael reaction. • It has features of simple preparation, recyclability and environmental friendliness. • The solvent of the reactions is water, which is green and nontoxic. - Abstract: Graphene oxide is modified by diethylenetriamine through a one-step route to prepare GO-NH(CH{sub 2}){sub 2}NH(CH{sub 2}){sub 2}NH{sub 2} (GO-DETA), which has primary and secondary amino groups and carboxyl groups. GO-DETA is characterized by Fourier transform-infrared spectrum (FT-IR), X-ray diffraction spectroscopy (XRD), thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The catalytic performance of obtained GO-DETA is investigated in Knoevenagel condensation and Michael addition in water; the results show it can be used as an efficient and stable catalyst. In addition, it has other features, such as simple preparation, good recyclability and environmental friendliness.

  10. One-step amine modification of graphene oxide to get a green trifunctional metal-free catalyst

    Science.gov (United States)

    Yang, Anwei; Li, Jingjing; Zhang, Chen; Zhang, Wenqin; Ma, Ning

    2015-08-01

    Graphene oxide is modified by diethylenetriamine through a one-step route to prepare GO-NH(CH2)2NH(CH2)2NH2 (GO-DETA), which has primary and secondary amino groups and carboxyl groups. GO-DETA is characterized by Fourier transform-infrared spectrum (FT-IR), X-ray diffraction spectroscopy (XRD), thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The catalytic performance of obtained GO-DETA is investigated in Knoevenagel condensation and Michael addition in water; the results show it can be used as an efficient and stable catalyst. In addition, it has other features, such as simple preparation, good recyclability and environmental friendliness.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Preparation of arginine-modified reduced graphene oxide composite filled in an on-line solid-phase extraction disk and its application in the analysis of heterocyclic aromatic amines.

    Science.gov (United States)

    Cai, Lemei; Xu, Na; Xia, Shujun; Wang, Yiru; Chen, Xi

    2017-07-01

    An arginine-modified reduced graphene oxide composite was prepared in an on-line solid-phase extraction disk and coupled to high-performance liquid chromatography for the re-enrichment of heterocyclic aromatic amines. The synthetic composite presented an excellent adsorption capability because of the ultrahigh active surface area of graphene and the abundant alkaline groups of arginine. The adsorption capacity of it was 52.7 mg 2-amino-3-methyl-imidazo[4,5-f]-quinoline per gram, nearly twice that of threonine-modified reduced graphene oxide composite, glutamic acid modified reduced graphene oxide composite, and reduced graphene oxide. This on-line method was successfully applied to the detection of a series of heterocyclic aromatic amines in beef jerky. After clean-up and re-enrichment of the on-line solid-phase extraction disk, the chromatographic background of the sample was low and the shape of chromatographic peaks was sharp. The method detection limit was in the range of 0.30-0.49 ng/g, and the recovery was in the range of 82.0-111.5%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. An Alumino-Mannich Reaction of Organoaluminum Reagents, Silylated Amines, and Aldehydes.

    Science.gov (United States)

    Tarasewicz, Anika; Ensan, Deeba; Batey, Robert A

    2018-03-08

    A multi-component coupling using organoaluminum reagents, silylated amines, and aldehydes results in the formation of tertiary amines. Both alkenyl- and alkylaluminum reagents undergo reaction with iminium ion substrates for which the corresponding Petasis borono-Mannich reactions are unsuccessful. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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

  18. 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...

  19. 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

  20. 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.

  1. Organic ligand-free alkylation of amines, carboxamides, sulfonamides, and ketones by using alcohols catalyzed by heterogeneous Ag/Mo oxides.

    Science.gov (United States)

    Cui, Xinjiang; Zhang, Yan; Shi, Feng; Deng, Youquan

    2011-01-17

    Complicated and expensive organic ligands are normally essential in fine chemical synthesis at preparative or industrial levels. The synthesis of fine chemicals by using heterogeneous catalyst systems without additive organic ligand is highly desirable but severely limited due to their poor generality and rigorous reaction conditions. Here, we show the results of carbon-nitrogen or carbon-carbon bond formation catalyzed by an Ag/Mo hybrid material with specific Ag(6) Mo(10) O(33) crystal structure. 48 nitrogen- or oxygen-containing compounds, that is, amines, carboxamides, sulfonamides, and ketones, were successfully synthesized through a borrowing-hydrogen mechanism. Up to 99 % isolated yields were obtained under relatively mild conditions without additive organic ligand. The catalytic process shows promise for the efficient and economic synthesis of amine, carboxamide, sulfonamide, and ketone derivatives because of the simplicity of the system and ease of operation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Comparison of kinetic properties of amine oxidases from sainfoin and lentil and immunochemical characterization of copper/quinoprotein amine oxidases.

    Science.gov (United States)

    Zajoncová, L; Frébort, I; Luhová, L; Sebela, M; Galuszka, P; Pec, P

    1999-01-01

    Kinetic properties of novel amine oxidase isolated from sainfoin (Onobrychis viciifolia) were compared to those of typical plant amine oxidase (EC 1.4.3.6) from lentil (Lens culinaris). The amine oxidase from sainfoin was active toward substrates, such as 1,5-diaminopentane (cadaverine) with K(m) of 0.09 mM and 1,4-diaminobutane (putrescine) with K(m) of 0.24 mM. The maximum rate of oxidation for cadaverine at saturating concentration was 2.7 fold higher than that of putrescine. The amine oxidase from lentil had the maximum rate for putrescine comparable to the rate of sainfoin amine oxidase with the same substrate. Both amine oxidases, like other plant Cu-amine oxidases, were inhibited by substrate analogs (1,5-diamino-3-pentanone, 1,4-diamino-2-butanone and aminoguanidine), Cu2+ chelating agents (diethyltriamine, 1,10-phenanthroline, 8-hydroxyquinoline, 2,2'-bipyridyl, imidazole, sodium cyanide and sodium azide), some alkaloids (L-lobeline and cinchonine), some lathyrogens (beta-aminopropionitrile and aminoacetonitrile) and other inhibitors (benzamide oxime, acetone oxime, hydroxylamine and pargyline). Tested by Ouchterlony's double diffusion in agarose gel, polyclonal antibodies against the amine oxidase from sainfoin, pea and grass pea cross-reacted with amine oxidases from several other Fabaceae and from barley (Hordeum vulgare) of Poaceae, while amine oxidase from the filamentous fungus Aspergillus niger did not cross-react at all. However, using Western blotting after SDS-PAGE with rabbit polyclonal antibodies against the amine oxidase from Aspergillus niger, some degree of similarity of plant amine oxidases from sainfoin, pea, field pea, grass pea, fenugreek, common melilot, white sweetclover and Vicia panonica with the A. niger amine oxidase was confirmed.

  3. 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.

  4. The interaction of diamines and polyamines with the peroxidase-catalyzed metabolism of aromatic amines: a potential mechanism for the modulation of aniline toxicity.

    Science.gov (United States)

    Michail, Karim; Aljuhani, Naif; Siraki, Arno G

    2013-03-01

    Synthetic and biological amines such as ethylenediamine (EDA), spermine, and spermidine have not been previously investigated in free-radical biochemical systems involving aniline-based drugs or xenobiotics. We aimed to study the influence of polyamines in the modulation of aromatic amine radical metabolites in peroxidase-mediated free radical reactions. The aniline compounds tested caused a relatively low oxidation rate of glutathione in the presence of horseradish peroxidase (HRP), and H2O2; however, they demonstrated marked oxygen consumption when a polyamine molecule was present. Next, we characterized the free-radical products generated by these reactions using spin-trapping and electron paramagnetic resonance (EPR) spectrometry. Primary and secondary but not tertiary polyamines dose-dependently enhanced the N-centered radicals of different aniline compounds catalyzed by either HRP or myeloperoxidase, which we believe occurred via charge transfer intermediates and subsequent stabilization of aniline-derived radical species as suggested by isotopically labeled aniline. Aniline/peroxidase reaction product(s) were monitored at 435 nm by kinetic spectrophotometry in the presence and absence of a polyamine additive. Using gas chromatography-mass spectrometry, the dimerziation product of aniline, azobenzene, was significantly amplified when EDA was present. In conclusion, di- and poly-amines are capable of enhancing the formation of aromatic-amine-derived free radicals, a fact that is expected to have toxicological consequences.

  5. 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)

  6. 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)

  7. Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers.

    Science.gov (United States)

    Sun, Yue; Li, Xiao-Tao; Xu, Chao; Chen, Jin-Long; Li, Ai-Min; Zhang, Quan-Xing

    2005-01-01

    Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.

  8. Investigations of stabilizing additives—III. Antagonistic effect of thioester on hindered amine antioxidants for radiation stability

    Science.gov (United States)

    Williams, J. L.; Williams, E. E.; Dunn, T. S.

    The use of hindered amines as primary antioxidants has been investigated both in a model antioxidant activity system and polypropylene. Also, the effectiveness of hindered amines in the presence of thioester has been evaluated. The antagonistic aspects of thioester on the ability of hindered amine to prevent polymer oxidation is discussed.

  9. Diesel fuel containing polyalkylene amine and Mannich base

    Energy Technology Data Exchange (ETDEWEB)

    Harle, O.L.

    1979-06-21

    The fuel composition for diesel engines is characterized in that it contains a hydrocarbon with a boiling range of 120-455/sup 0/C as main component and as additive 5 to 300 ppm of a polyakylene amine, as well as 5 to 300 ppm of the reaction product of an alkyl phenol, an aldehyde and an amine (Mannich base). This additive composition increases the oxidation and thermal stability of the fuel.

  10. Antidepressant-like effect of 1-(7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinolin-4-YL)-cyclohexanol, a putative trace amine receptor ligand involves l-arginine-nitric oxide-cyclic guanosine monophosphate pathway.

    Science.gov (United States)

    Dhir, Ashish; Kulkarni, S K

    2011-10-03

    1-(7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinolin-4-YL)-cyclohexanol is a novel putative trace amine receptor modulator hypothesized to be useful for treatment-resistant depression. In our previous study, we have demonstrated the antidepressant-like effect of this molecule in mouse forced swim and tail suspension tests and shown to act via modulating the levels of norepinephrine, serotonin and dopamine. The present study attempts to explore the involvement of l-arginine-nitric oxide-cyclic guanosine monophosphate pathway in the antidepressant-like effect of 1-(7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinolin-4-YL)-cyclohexanol in the mouse forced swim test. The antidepressant-like action of 1-(7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinolin-4-YL)-cyclohexanol (8 mg/kg, i.p) was reversed by pretreatment with L-arginine (750 mg/kg, i.p.), a nitric oxide precursor. In contrast, pretreatment with methylene blue (a soluble guanlyate cyclase inhibitor and nitric oxide synthase (NOS) inhibitor) or 7-nitroindazole (a specific neuronal NOS inhibitor) potentiated the antidepressant-like effect of sub-effective dose of 1-(7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinolin-4-YL)-cyclohexanol (2mg/kg, i.p.) in this test model. Furthermore, the antidepressant-like effect of this molecule (8 mg/kg, i.p.) was reversed by sildenafil (5mg/kg, i.p.), a phosphodiesterase inhibitor. In conclusion, the antidepressant-like action of 1-(7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinolin-4-YL)-cyclohexanol involved L-arginine-nitric oxide-cyclic guanosine monophospate signaling pathway. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  11. 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.

  12. 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.

  13. Oxidation of 5'-site guanine at GG and GGG sequences induced by a metabolite of carcinogenic heterocyclic amine PhIP in the presence of Cu(II) and NADH.

    Science.gov (United States)

    Murata, Mariko; Kawanishi, Shosuke

    2002-05-01

    Adduct formation has been considered to be a major causal factor of DNA damage by carcinogenic heterocyclic amines. By means of experiments with an electrochemical detector coupled to a high-performance liquid chromatograph, we revealed that N-hydroxy metabolite of 2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine (PhIP) induced the formation of 8-hydroxy-2'-deoxyguanosine (8-OH-dG) in the presence of Cu(II). Addition of an endogenous reductant NADH enhanced the 8-OH-dG formation. Experiments with (32)P-labeled DNA fragments showed that this metabolite [PhIP(NHOH)] caused 8-hydroxylation of guanines in the presence of Cu(II) and NADH, and subsequent treatment with formamidopyrimidine-DNA glycosylase led to chain cleavages at the 5'-site guanine of GG and GGG sequences. Interestingly, antioxidant enzyme SOD enhanced the intensity of DNA damage, and thymine residues were appended to its guanine-predominant cleavage sites. Catalase and bathocuproine, a Cu(I)-specific chelator, inhibited the DNA damage, suggesting the involvement of H(2)O(2) and Cu(I). A UV-visible spectroscopic study indicated that Cu(II) and SOD catalyze the autoxidation of PhIP(NHOH). These results suggest that Cu(II)-dependent autooxidation of PhIP(NHOH) coupled with NADH-mediated reduction of its oxidized product form redox cycle, resulting in oxidative DNA damage by low concentrations of PhIP(NHOH). We conclude that in addition to DNA adduct formation, oxidative DNA damage may be involved in the carcinogenic process of PhIP.

  14. Oxidative degradation and non-enzymatic browning due to the interaction between oxidised lipids and primary amine groups in different marine PL emulsions

    DEFF Research Database (Denmark)

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

    2012-01-01

    levels of triglycerides in the emulsions. The oxidative and hydrolytic stability of emulsions was investigated through measurement of peroxide value, free fatty acids, and 31P NMR during storage at 2 C for up to 32 days. The oxidative stability of marine PL emulsions during storage was further......Due to the beneficial health effects of marine phospholipids (PL) there is an increasing industrial interest in using them for nutritional applications including emulsified foods. This study was undertaken to investigate both oxidative and hydrolytic stability of marine PL emulsions in relation...... investigated through the measurement of secondary volatile compounds by solid-phase microextraction (SPME) and dynamic headspace (DHS) connected to gas chromatography (GC–MS). Non-enzymatic browning reactions were investigated through the measurement of Strecker derived volatiles, colour changes and pyrrole...

  15. 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.

  16. 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

  17. 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.)

  18. 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.

  19. 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

    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...... sequentially in fed batch–batch mode. Both reactors are interconnected through a semi-permeable membrane, where multicomponent intra-membrane transport takes place by diffusion and viscous flow. The kinetic modeling of both reactions has been carried out and model simulations show that in this way...

  20. 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.

  1. 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

  2. Exposure to heterocyclic amines.

    Science.gov (United States)

    Wakabayashi, K; Ushiyama, H; Takahashi, M; Nukaya, H; Kim, S B; Hirose, M; Ochiai, M; Sugimura, T; Nagao, M

    1993-03-01

    Many mutagenic heterocyclic amines (HAs) have been isolated from cooked foods and pyrolysates of amino acids and proteins, and the carcinogenicity of 10 of these HAs in rodents and of 1 in monkeys has been reported. Quantification of these carcinogenic HAs in various kinds of cooked foods indicated that the level of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) was highest (0.56-69.2 ng/g), that of 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) was second highest (0.64-6.44 ng/g), and those of other HAs were 0.03-2.50 ng/g. Heterocyclic amines were found in urine samples of 10 healthy volunteers consuming a normal diet, but HAs were not detectable in urine samples of three patients receiving parenteral alimentation. These results strongly suggest that humans are continuously exposed to HAs derived from food in the normal diet. Based on quantitative data on the levels of HAs in cooked foods and urine samples, the daily exposures to PhIP and MeIQx were estimated to be 0.1-13.8 micrograms and 0.2-2.6 micrograms per person, respectively. These levels of carcinogenic HAs are in the same range as those of other carcinogens such as N-nitrosodimethylamine and benzo[a]pyrene to which humans are exposed.

  3. 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.

  4. 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.

  5. 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.

  6. 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 ...

  7. Enzymatic treatment of sulfonated aromatic amines generated from reductive degradation of reactive azo dyes.

    Science.gov (United States)

    Biswas, Mousumi Mani; Taylor, Keith E; Bewtra, Jatinder K; Biswas, Nihar

    2007-04-01

    Anaerobic degradation, an effective treatment process of textile industry effluent, generates sulfonated aromatic amines, which are carcinogenic, mutagenic, and resistant to microbial degradation. These aromatic amines can be effectively removed by oxidative polymerization catalyzed by peroxidase enzyme. The amines, generated in this study from the anaerobic reduction by zero-valent iron of two reactive azo dyes (Reactive Red 2 [RR2] and Reactive Black 5 [RB5]), were successfully removed (90%) by Arthromyces ramosus peroxidase (ARP). For better understanding of the process, enzymatic treatment of two model compounds, diphenylamine (DPA) and 2-amino-8-naphthol-3,6-disulfonic acid (ANDSA), were also studied. Diphenylamine has a similar diarylamine bond as RR2. The ANDSA has a similar structure as the dye reduction products. The secondary amine bond in DPA and RR2 were oxidized by ARP. Enzymatic reaction of sulfonated aromatic amines generated soluble colored compounds, which were removed by coagulant. Optimum reaction parameters were also determined.

  8. 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.

  9. Electrochemical C-H Amination by Cobalt Catalysis in a Renewable Solvent.

    Science.gov (United States)

    Sauermann, Nicolas; Mei, Ruhuai; Ackermann, Lutz

    2018-03-06

    Syntheses of substituted anilines primarily rely on palladium-catalyzed coupling chemistry with prefunctionalized aryl electrophiles. While oxidative aminations have emerged as powerful alternatives, they largely produce undesired metal-containing by-products in stoichiometric quantities. In contrast, described herein is the unprecedented electrochemical C-H amination by cobalt-catalyzed C-H activation. The environmentally benign electrocatalysis avoids stoichiometric metal oxidants, can be conducted under ambient air, and employs a biomass-derived, renewable solvent for sustainable aminations in an atom- and step-economical manner with H 2 as the sole byproduct. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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...... 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....

  11. Standard CGIF interoperability in Amine

    OpenAIRE

    Kabbaj, A.; Launders, I.; Polovina, S.

    2009-01-01

    The adoption of standard CGIF by CG tools will enable interoperability between them to be achieved, and in turn lead to the interoperability between CG tools and other tools. The integration of ISO Common Logic’s standard CGIF notation in the Amine platform is presented. It also describes the first steps towards full interoperability between the Amine CG tool (through its Synergy component) and CharGer, a representative CG tool that supports similar interoperability and for process (or ‘activ...

  12. Investigação da cinética de cura por calorimetria diferencial exploratória (DSC de resinas epóxi preparadas a partir de óleo de soja epoxidado com diferentes anidridos e aminas terciárias Investigation of the kinetics of cure by differential scanning calorimetry (DSC of epoxy resins prepared from epoxidized soybean oil with different anhydrides and tertiary amines

    Directory of Open Access Journals (Sweden)

    Ana P. O. Costa

    2011-01-01

    Full Text Available No presente trabalho, utilizou-se a calorimetria diferencial exploratória (DSC para investigar a cinética da reação de cura de resinas epóxi produzidas a partir da reação do óleo de soja epoxidado (ESO, com os anidridos dodecenilsuccínico (DDS, maleico (MAL, ftálico (FTA, succínico (SUC e hexahidroftálico (CH, atuando como agentes de cura, e na presença de aminas terciárias como a trietilamina (TEA, a N,N'-dimetilanilina (ARO e a 1,4- diazobiciclo [2,2,2] octano (DABCO, atuando como catalisadores. A taxa de aquecimento, a natureza química e a estrutura do anidrido e das aminas influenciaram a reação de cura. Os métodos dinâmicos de Kissinger, Ozawa e de Barrett foram utilizados para calcular a energia de ativação dos sistemas onde se variou o anidrido. Observou-se que os anidridos mais reativos foram o DDS e maleico que apresentaram os menores valores de energias de ativação. No estudo da influência do catalisador, utilizou-se o método de Barrett para determinar as energias de ativação das reações com as diferentes aminas. A amina cicloaliafática (DABCO foi a mais reativa obtendo-se o menor valor de energia de ativação (Ea = 51 kJ.mol-1 e fator pré-exponencial (ln A0 = 9 s-1.In the present work, differential scanning calorimetry (DSC was used to investigate the curing reaction kinetics of epoxy resins produced from reaction of epoxidized soybean oil (ESO with cyclic anhydrides dodecenylsuccinic (DDS, maleic (MAL, phthalic (PA, succinic (SUC and hexahydrophthalic (CH, in the presence of tertiary amines such as triethylamine (TEA, N,N-dimethylaniline (ARO and 1,4-diazabicyclo [2,2,2] octane (DABCO. The heating rate, the nature and structure of anhydrides and amines were found to affect the curing reaction. The dynamic methods of Kissinger, Ozawa and Barrett were used to calculate the activation energy of the reactions where different anhydrides were used. DDS and maleic anhydrides were more reactive than the others

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C-H Amination of Arenes with Carbamates, Urea, and N-Heterocycles.

    Science.gov (United States)

    Das, Somnath; Natarajan, Palani; König, Burkhard

    2017-12-22

    The C-H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH 2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Tertiary Education in Poland

    OpenAIRE

    World Bank

    2004-01-01

    The polish tertiary education report was undertaken by the World Bank and the European Investment Bank in consultation with the Ministry of National Education and Sports of Poland (MoNES). The modernization of higher education and other tertiary education services has become an increasing focus of public concern in Poland. A major purpose of the report is to discuss important issues in Pol...

  1. Electrochemical release of amine molecules from carbamate-based, electroactive self-assembled monolayers.

    Science.gov (United States)

    Hong, Daewha; Kang, Kyungtae; Hong, Seok-Pyo; Shon, Hyun Kyong; Son, Jin Gyeong; Lee, Tae Geol; Choi, Insung S

    2012-01-10

    In this paper, carbamate-based self-assembled monolayers (SAMs) of alkanethiolates on gold were suggested as a versatile platform for release of amine-bearing molecules in response to the electrical signal. The designed SAMs underwent the electrochemical oxidation on the gold surface with simultaneous release of the amine molecules. The synthesis of the thiol compounds was achieved by coupling isocyanate-containing compounds with hydroquinone. The electroactive thiol was mixed with 11-mercaptoundecanol [HS(CH(2))(11)OH] to form a mixed monolayer, and cyclic votammetry was used for the characterization of the release behaviors. The mixed SAMs showed a first oxidation peak at +540 mV (versus Ag/AgCl reference electrode), indicating the irreversible conversion from carbamate to hydroquinone groups with simultaneous release of the amine molecules. The analysis of ToF-SIMS further indicated that the electrochemical reaction on the gold surface successfully released amine molecules.

  2. 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...

  3. MOF-derived cobalt nanoparticles catalyze a general synthesis of amines.

    Science.gov (United States)

    Jagadeesh, Rajenahally V; Murugesan, Kathiravan; Alshammari, Ahmad S; Neumann, Helfried; Pohl, Marga-Martina; Radnik, Jörg; Beller, Matthias

    2017-10-20

    The development of base metal catalysts for the synthesis of pharmaceutically relevant compounds remains an important goal of chemical research. Here, we report that cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts. Their convenient and practical preparation entailed template assembly of cobalt-diamine-dicarboxylic acid metal organic frameworks on carbon and subsequent pyrolysis under inert atmosphere. The resulting stable and reusable catalysts were active for synthesis of primary, secondary, tertiary, and N -methylamines (more than 140 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, or nitro compounds, and molecular hydrogen under industrially viable and scalable conditions, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

  4. potential bag filter for volatile organic amines

    Indian Academy of Sciences (India)

    VADDYPALLY SHIVAIAH

    2018-03-22

    Mar 22, 2018 ... be described as a potential bag filter for volatile organic amines. Keywords. Volatile organic amines; hydrogen ..... this bag filter, which can capture volatile amines to form. Figure 8. Thermal ellipsoid plot of ..... huber H, Baumann M and Amann A 2013 Blood and breath levels of selected volatile organic ...

  5. 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...

  6. 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

  7. 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.

  8. Ontogeny in Tertiary Frogs

    Czech Academy of Sciences Publication Activity Database

    Roček, Zbyněk

    2004-01-01

    Roč. 260, č. 3 (2004), s. 322-323 ISSN 0362-2525. [International Congress of Vertebrate Morphology /7./. 27.07.2004-01.08.2004, Boca Raton] Keywords : Anura * Tertiary * Czech Republic Subject RIV: EA - Cell Biology

  9. 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.

  10. 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.)

  11. 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

  12. 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.

  13. Trace Amines and Cocaine Abuse

    OpenAIRE

    Li, Jun-Xu

    2014-01-01

    Cocaine addiction remains a clinical challenge with no effective pharmacotherapy available. Trace amine associated receptor (TAAR) 1 represents a promising drug target for the modulation of dopaminergic system and stimulant abuse. This Viewpoint discusses the emerging data which strongly suggest that TAAR 1 functions as a molecular “brake” that controls the addiction-related effects of cocaine and could be a novel drug target for the development of efficacious pharmacothe...

  14. Resolution of water in crude oil emulsion by some novel aromatic amine polyesters

    Directory of Open Access Journals (Sweden)

    A.M. Al-Sabagh

    2015-09-01

    Full Text Available In this work, three aromatic amines (p-toluidine, p-nitroaniline and p-chloroaniline were chosen as bases for the repatriation of some nonionic polyesters. These amines were ethoxylated with different total number of ethylene oxide units 6, 12, 18. The prepared ethoxylated amine diols were polyesterified with maleic anhydride and polypropylene oxide polyethylene oxide block copolymers in polyesterification reaction. The demulsification efficiency of these demulsifiers was investigated using the bottle test. The effects of the molecular weight, concentration, asphaltene content, water content, Hydrophile Lipophile Balance (HLB and temperature on the demulsification efficiency were investigated. The surface active properties were correlated with their demulsification efficiency. It was found that, NAE18D gave the best result in the demulsification process. The demulsification efficiency was discussed on the light of surface active properties, interfacial tension and the factors affecting the demulsification. The surface-active properties of the prepared demulsifiers were measured at 60 °C.

  15. Michael Addition Polymerization of Trifunctional Amine and Acrylic Monomer: A Versatile Platform for Development of Biomaterials.

    Science.gov (United States)

    Cheng, Weiren; Wu, Decheng; Liu, Ye

    2016-10-10

    Michael addition polymerizations of amines and acrylic monomers are versatile approaches to biomaterials for various applications. A combinatorial library of poly(β-amino ester)s and diverse poly(amido amine)s from diamines and diacrylates or bis(acrylamide)s have been reported, respectively. Furthermore, novel linear and hyperbranched polymers from Michael addition polymerizations of trifunctional amines and acrylic monomers significantly enrich this category of biomaterials. In this Review, we focus on the biomaterials from Michael addition polymerizations of trifunctional amines and acrylic monomers. First we discuss how the polymerization mechanisms, which are determined by the reactivity sequence of the three types of amines of trifunctional amines, i.e., secondary (2°) amines (original), primary (1°) amines, and 2° amines (formed), are affected by the chemistry of monomers, reaction temperature, and solvent. Then we update how to design and synthesize linear and hyperbranched polymers based on the understanding of polymerization mechanisms. Linear polymers containing 2° amines in the backbones can be obtained from polymerizations of diacrylates or bis(acrylamide)s with equimolar trifunctional amine, and several approaches, e.g., 2A 2 +BB'B″, A 3 +2BB'B', A 2 +BB'B″, to hyperbranched polymers are developed. Further through molecular design of monomers, conjugation of functional species to 2° amines in the backbones of linear polymers and the abundant terminal groups of hyperbranched polymers, the amphiphilicity of polymers can be adjusted, and additional stimuli, e.g., thermal, redox, reactive oxidation species (ROS), and light, responses can be integrated with the intrinsic pH response. Finally we discuss the applications of the polymers for gene/drug delivery and bioimaging through exploring their self-assemblies in various motifs, e.g., micelles, polyplexes particles/nanorings and hydrogels. Redox-responsive hyperbranched polymers can display 300

  16. Development of an expression macroarray for amine metabolism-related genes.

    Science.gov (United States)

    Chaves, P; Correa-Fiz, F; Melgarejo, E; Urdiales, J L; Medina, M A; Sánchez-Jiménez, F

    2007-08-01

    Cationic amino acids are the precursors of biogenic amines, histamine from histidine, and putrescine, spermidine and spermine from arginine/ornithine (and methionine), as well as nitric oxide. These amines play important biological roles in inter- and intracellular signaling mechanisms related to inflammation, cell proliferation and neurotransmission. Biochemical and epidemiological relationships between arginine-derived products and histamine have been reported to play important roles in physiopathological problems. In this communication, we describe the construction of an expression macroarray containing more than 30 human probes for most of the key proteins involved in biogenic amines metabolisms, as well as other inflammation- and proliferation-related probes. The array has been validated on human mast HMC-1 cells. On this model, we have got further support for an inverse correlation between polyamine and histamine synthesis previously observed on murine basophilic models. These tools should also be helpful to understand the amine roles in many other inflammatory and neoplastic pathologies.

  17. 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.

  18. Morita-Baylis-Hillman (MBH) Reaction Derived Nitroallylic Alcohols, Acetates and Amines as Synthons in Organocatalysis and Heterocycle Synthesis.

    Science.gov (United States)

    Huang, Wan-Yun; Anwar, Shaik; Chen, Kwunmin

    2017-03-01

    The Morita-Baylis-Hillman (MBH) reaction is one of the most useful and efficient protocols for constructing new carbon-carbon bonds between an activated olefin and electrophiles in the presence of a tertiary amine/phosphine. Herein, we present the use of MBH alcohols, which are obtained from the reaction of nitrostyrenes with aldehydes, as well as acetates and amines derived thereof in several organocatalytic transformations. Densely functionalised MBH adducts can also be used to synthesise substituted heteroaromatic compounds, such as furan, pyrrole, pyrazole and imidazole derivatives. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

  20. 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....

  1. 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.

  2. 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

  3. Surface amination of poly(acrylonitrile)

    NARCIS (Netherlands)

    Hartwig, Andreas; Mulder, M.H.V.; Smolders, C.A.; Smolders, C.A.

    1994-01-01

    The surface amination of poly (acrylonitrile) by ammonia plasma treatment has been studied. Furthermore, two other surface modification techniques have been investigated, the plasma chemical decomposition of an amino group containing chemical (tris-(2-aminoethyl)amine) onto the polymer surface and

  4. 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

  5. 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

  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. Rhodium-catalyzed direct C-H amination of benzamides with aryl azides: a synthetic route to diarylamines.

    Science.gov (United States)

    Ryu, Jaeyune; Shin, Kwangmin; Park, Sae Hume; Kim, Ji Young; Chang, Sukbok

    2012-09-24

    No muss, no fuss: A rhodium-catalyzed direct intermolecular C-H amination of benzamides and ketoximes using aryl azides as the amine source has been developed. The reaction exhibits a broad substrate scope with excellent functional-group tolerance, requires no external oxidants, releases N(2) as the only by-product, and produces diarylamines in high yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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

  9. Studies on the sunthesis of geminal bisphosphono amine derivatives using pentacovalent oxaphospholenes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Mi Young; Jung, Kang Yeoun [Kangnung National Univ., Kangnung (Korea, Republic of)

    1999-06-01

    Geminal bisphosphonates have been well known to be effective inhibitors of various calcium-relates disorders such as Paget's disease, hypercalcemia of malignancy, and osteoporosis. To synthesize bis-phosphonates, we have used the pentacovalent oxaphospholene prepared from methyl vinyl ketone and triethyl-phosphite. {gamma}-Ketobisphosphonates are obtained by bromination, applied Westheimer reaction, and hydrolysis of synthesized oxaphospholene. This compound was converted to the N-alkylated {gamma}-Ketobisphosphonates by the reductive amination. Conversion of the resulting secondary amine to the tertiary one, followed by introduction of the second alkyl group on the nitrogen, was led to the synthesis of new N,N'-dialkylated {gamma}-aminobisphosphonates.

  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. 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.

  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. Incidence of biogenic amines in foods implications for the Gambia ...

    African Journals Online (AJOL)

    Amines are found in food. Biogenic amines are a class of amines, which result from decarboxylation. They are food quality indicators. Health-wise biogenic amines play positive roles and have adverse effects as well; they are a public health concern. Certain conditions make it possible for them to be produced. These could ...

  14. Magnetic graphitic carbon nitride: its applicationin the C-& H-activation of amines.

    Science.gov (United States)

    Magnetic graphitic carbon nitride, Fe@g-C3N4, has been synthesized by adorning graphitic carbon nitride (g-C3N4) support with iron oxide via non-covalent interaction. The magnetically recyclable catalyst showed excellent reactivity for expeditious C-H activation and cyanation of amines.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, H. Changseok, M. Nadagouda , and R. Varma. Magnetic graphitic carbon nitride: its applicationin the C–H activation of amines. CHEMICAL COMMUNICATIONS. Royal Society of Chemistry, Cambridge, UK, 51(85): 15554 - 15557, (2015).

  15. 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.

  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. 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

  18. 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.

  19. Carbon capture and sequestration: an exploratory inhalation toxicity assessment of amine-trapping solvents and their degradation products.

    Science.gov (United States)

    McDonald, Jacob D; Kracko, Dean; Doyle-Eisele, Melanie; Garner, C Edwin; Wegerski, Chris; Senft, Al; Knipping, Eladio; Shaw, Stephanie; Rohr, Annette

    2014-09-16

    Carbon dioxide (CO2) absorption with aqueous amine solvents is a method of carbon capture and sequestration (CCS) from flue gases. One concern is the possible release of amine solvents and degradation products into the atmosphere, warranting evaluation of potential pulmonary effects from inhalation. The CCS amines monoethanolamine (MEA), methyldiethanolamine (MDEA), and piperazine (PIP) underwent oxidative and CO2-mediated degradation for 75 days. C57bl/6N mice were exposed for 7 days by inhalation of 25 ppm neat amine or equivalant concentration in the degraded mixture. The aqueous solutions were nebulized to create the inhalation atmospheres. Pulmonary response was measured by changes in inflammatory cells in bronchoalveolar lavage fluid and cytokine expression in lung tissue. Ames mutagenicity and CHO-K1 micronucleus assays were applied to assess genotoxicity. Chemical analysis of the test atmosphere and liquid revealed complex mixtures, including acids, aldehydes, and other compounds. Exposure to oxidatively degraded MEA increased (p < 0.05) total cells, neutrophils, and lymphocytes compared to control mice and caused inflammatory cytokine expression (statistical increase at p < 0.05). MEA and CO2-degraded MEA were the only atmospheres to show statistical (p < 0.05) increase in oxidative stress. CO2 degradation resulted in a different composition, less degradation, and lower observed toxicity (less magnitude and number of effects) with no genotoxicity. Overall, oxidative degradation of the amines studied resulted in enhanced toxicity (increased magnitude and number of effects) compared to the neat chemicals.

  20. 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.

  1. 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...

  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. 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)

  4. Electrochemical oxidation of substituted benzylamines in aquo ...

    Indian Academy of Sciences (India)

    TECS

    the medium stabilizes such a transition state and consequently makes the oxidation easier, which re- quires less potential. It may be concluded that since amines are very harmful to human health and the environment, the removal of amines from the environment is the ulti- mate goal of research today. For this a deep under-.

  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. 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

  7. PEGylated bioreducible poly(amido amine)s for non-viral gene delivery

    NARCIS (Netherlands)

    Lin, C.; Engbersen, Johannes F.J.

    2011-01-01

    A facile method for PEGylated bioreducible poly(amido amine)s is described by a one-pot Michael-type addition polymerization of N, N′-cystaminebisacrylamide (CBA) with a mixture of 4-amino-1-butanol (ABOL) and mono-tert-butoxycarbonyl (Boc) PEG diamine. By this approach, two Boc-amino-PEGylated

  8. 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

  9. Metabolic Effects of Dietary Proteins, Amino Acids and The Other Amine Consisting Compounds on Cardiovascular System.

    Directory of Open Access Journals (Sweden)

    Elif Uğur

    2017-01-01

    Full Text Available During the prevention and treatment of cardiovascular diseases, first cause of deaths in the world, diet has a vital role. While nutrition programs for the cardiovascular health generally focus on lipids and carbohydrates, effects of proteins are not well concerned. Thus this review is written in order to examine effect of proteins, amino acids, and the other amine consisting compounds on cardiovascular system. Because of that animal or plant derived proteins have different protein composition in different foods such as dairy products, egg, meat, chicken, fish, pulse and grains, their effects on blood pressure and regulation of lipid profile are unlike. In parallel amino acids made up proteins have different effect on cardiovascular system. From this point, sulfur containing amino acids, branched chain amino acids, aromatic amino acids, arginine, ornithine, citrulline, glycine, and glutamine may affect cardiovascular system in different metabolic pathways. In this context, one carbon metabolism, synthesis of hormone, stimulation of signaling pathways and effects of intermediate and final products that formed as a result of amino acids metabolism is determined. Despite the protein and amino acids, some other amine consisting compounds in diet include trimethylamine N-oxide, heterocyclic aromatic amines, polycyclic aromatic hydrocarbons and products of Maillard reaction. These amine consisting compounds generally increase the risk for cardiovascular diseases by stimulating oxidative stress, inflammation, and formation of atherosclerotic plaque.

  10. 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.

  11. Application of chemical oxidation for removal of pharmaceuticals in wastewater effluents

    DEFF Research Database (Denmark)

    Hey, G.; Ledin, A.; la Cour Jansen, J.

    2012-01-01

    ). In effluent 1 (35 mg/L COD), more than half of the APIs were already oxidized at 5 mg/L ClO2 in comparison to effluent 2 (55 mg/L COD) where significant increase in API oxidation was observed after treatment with 8 mg/L ClO2. The antiphlogistic diclofenac and antidiabetic repaglinide can be easily oxidized...... of wastewater effluent, over 90% removal of diclofenac and repaglinide was reached but with much higher ozone dose. On the other hand in effluent 3 (51 mg/L COD), citalopram and trimetoprim can be oxidized effectively by lower O3 dose than ClO2 however, in high COD wastewater (effluent 4, 90 mg/L COD), O3......-rich functional groups in their structure such as aniline (diclofenac) and tertiary amine (repaglinide) are easily removed during oxidation. On the other hand, the presence of electron-withdrawing functional groups such as halogens resulted in slow reactivity of the APIs to oxidation. In addition, the difference...

  12. Biogenic amines in meat and meat products.

    Science.gov (United States)

    Ruiz-Capillas, Claudia; Jiménez-Colmenero, Francisco

    2004-01-01

    It has been recognized for some time that biogenic amines occur in a wide range of foods, among them meat and meat products. Meat is an important component of the diet in developed countries. The presence of these amines in food is of interest for two reasons: firstly, for toxicological reasons, in the sense that high levels of dietary biogenic amines can be toxic for certain consumers, and secondly, for their role as possible quality indicators. Based on these two premises, the present article offers a new analysis on aspects of toxicology and on the use of biogenic amines as a quality control method, as well as on their presence in meat and meat products. The article focuses particularly on factors affecting the production of biogenic amines, with reference to various parameters relating to microorganisms, meat raw materials, and processing conditions. A better understanding of the factors determining their formation (i.e., microorganisms, raw materials used, and technological processes applied) and their effects could lead to ways of controlling their production, limiting their presence in the end product, and hence, rendering them less toxic.

  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. Hypoxia inhibits semicarbazide-sensitive amine oxidase activity in adipocytes.

    Science.gov (United States)

    Repessé, Xavier; Moldes, Marthe; Muscat, Adeline; Vatier, Camille; Chetrite, Gérard; Gille, Thomas; Planes, Carole; Filip, Anna; Mercier, Nathalie; Duranteau, Jacques; Fève, Bruno

    2015-08-15

    Semicarbazide-sensitive amine oxidase (SSAO), an enzyme highly expressed on adipocyte plasma membranes, converts primary amines into aldehydes, ammonium and hydrogen peroxide, and is likely involved in endothelial damage during the course of diabetes and obesity. We investigated whether in vitro, adipocyte SSAO was modulated under hypoxic conditions that is present in adipose tissue from obese or intensive care unit. Physical or pharmacological hypoxia decreased SSAO activity in murine adipocytes and human adipose tissue explants, while enzyme expression was preserved. This effect was time-, dose-dependent and reversible. This down-regulation was confirmed in vivo in subcutaneous adipose tissue from a rat model of hypoxia. Hypoxia-induced suppression in SSAO activity was independent of the HIF-1-α pathway or of oxidative stress, but was partially antagonized by medium acidification. Hypoxia-induced down-regulation of SSAO activity could represent an adaptive mechanism to lower toxic molecules production, and may thus protect from tissue injury during these harmful conditions. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  15. 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.

  16. 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......, 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...... compared to HB fishmeal at this temperature. Higher levels of liver pyruvate and plasma lactate together with high level of betaine and AAs in both liver and plasma were associated with the LB fishmeal diets. The lower concentration of AAs especially in liver of fish fed with HB fishmeal demonstrated...

  17. 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

  18. 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.

  19. An example of regioselective esterification by intramolecular acyl transfer from a tertiary amine

    Energy Technology Data Exchange (ETDEWEB)

    Waddell, T.G.; Rambalakos, T.; Christie, K.R. (Univ. of Tennessee, Chattanooga (United States))

    1990-07-20

    Despite the fact that the famous antimarlarial quinine (1) has been known for 170 years, there is still considerable interest in its chemical and biological properties. Much of the most recent attention is due to the utility of quinine as a chiral resolving agent and catalyst. Important and new chemistry of quinine may yet be discovered. To this point, the authors became interested in constructing quinine derivatives which have built into their structures electrophilic centers which might make covalent bonds with cellular protein or nucleic acid nucleophilic sites. In order to preserve the noncovalent binding properties of quinine, functionalization and derivatization of the remote vinyl group were desired. In an esterification step of the derivatization, a structurally hindered ester was formed, to our surprise. The mechanism for this regioselective reaction are discussed.

  20. Effects of tertiary amine local anesthetics on the assembly and disassembly of brain microtubules in vitro.

    Science.gov (United States)

    Genna, J M; Coffe, G; Pudles, J

    1980-09-01

    From kinetic and electron microscopy studies on the effects of procaine, tetracaine and dibucaine on the polymerization and depolymerization of the microtubules isolated from pig and rat brains the following results were obtained. 1. Procaine or tetracaine, at the concentration range of 0.5--20 mM and of 0.5--5 mM respectively, increases the rate of tubulin polymerization (24 degrees C or 37 degrees C) and of microtubule depolymerization (4 degrees C) as a linear function of the concentration of the anesthetics, while identical amounts of microtubules are formed. In the absence of microtubule-associated proteins the polymerization of tubulin is not induced by 10 mM procaine, furthermore, the critical concentration of microtubule proteins necessary for assembly into microtubules is not affected at this concentration level of the anesthetic. This suggests that procaine affects not the nucleation, but rather the elongation process. 2. Dibucaine, from 0.5 mM to 3 mM increases the lag time of the polymerization reaction, while from 0.5 mM to 2 mM it linearly decreases both tubulin polymerization (24 degrees C) and microtubule depolymerization (4 degrees C) rates. Dibucaine, up to mM concentration, does not affect the extent of tubulin polymerization; however, above this concentration it induces the formation of amorphous aggregates. 3. Procaine or tetracaine enhances the depolymerizing effect of calcium on microtubules. The half-maximal values for the depolymerizing effect of calcium were 0.96, 0.71 and 0.51 mM for the control, in the presence of 10 mM procaine and 5 mM tetracaine respectively.

  1. 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.

  2. 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.

  3. 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.

  4. Amine templated zinc phosphates phases for membrane separations

    Energy Technology Data Exchange (ETDEWEB)

    Nenoff, T.M.; Chavez, A.V.; Thoma, S.G.; Provencio, P. [Sandia National Labs., Albuquerque, NM (United States); Harrison, W.T.A. [Univ. of Western Australia, Nedlands (Australia); Phillips, M.L.F. [Gemfire Corp., Palo Alto, CA (United States)

    1998-08-01

    This research is focused on developing inorganic molecular sieve membranes for light gas separations such as hydrogen recovery and natural gas purification, and organic molecular separations, such as chiral enantiomers. The authors focus on zinc phosphates because of the ease in crystallization of new phases and the wide range of pore sizes and shapes obtained. With hybrid systems of zinc phosphate crystalline phases templated by amine molecules, the authors are interested in better understanding the association of the template molecules to the inorganic phase, and how the organic transfers its size, shape, and (in some cases) chirality to the bulk. Furthermore, the new porous phases can also be synthesized as thin films on metal oxide substrates. These films allow one to make membranes from organic/inorganic hybrid systems, suitable for diffusion experiments. Characterization techniques for both the bulk phases and the thin films include powder X-ray diffraction, TGA, Scanning Electron Micrograph (SEM) and Electron Dispersive Spectrometry (EDS).

  5. 40 CFR 721.640 - Amine substituted metal salts.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amine substituted metal salts. 721.640... Substances § 721.640 Amine substituted metal salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as amine substituted metal salts...

  6. Selective Removal of Nitrosamines from a Model Amine Carbon-Capture Waterwash Using Low-Cost Activated-Carbon Sorbents.

    Science.gov (United States)

    Widger, Leland R; Combs, Megan; Lohe, Amit R; Lippert, Cameron A; Thompson, Jesse G; Liu, Kunlei

    2017-09-19

    Nitrosamines generated in the amine solvent loop of postcombustion carbon capture systems are potent carcinogens, and their emission could pose a serious threat to the environment or human health. Nitrosamine emission control strategies are critical for the success of amine-based carbon capture as the technology approaches industrial-scale deployment. Waterwash systems have been used to control volatile and aerosol emissions, including nitrosamines, from carbon-capture plants, but it is still necessary to remove or destroy nitrosamines in the circulating waterwash to prevent their subsequent emission into the environment. In this study, a cost-effective method for selectively removing nitrosamines from the absorber waterwash effluent with activated-carbon sorbents was developed to reduce the environmental impact associated with amine-based carbon capture. The results show that the commercial activated-carbon sorbents tested have a high capacity and selectivity for nitrosamines over the parent solvent amines, with capacities up to 190 mg/g carbon, under simulated amine waterwash conditions. To further reduce costs, an aerobic thermal sorbent regeneration step was also examined due to the low thermal stability of nitrosamines. To model the effect of oxidation on the sorbent performance, thermal- and acid-oxidized sorbents were also prepared from the commercial sorbents and analyzed. The chemical and physical properties of nitrosamines, the parent amine, and the influence of the physical properties of the carbon sorbents on nitrosamine adsorption was examined. Key sorbent properties included the sorbent hydrophilicity and hydrophobicity, surface pK a of the sorbent, and chemical structure of the parent amine and nitrosamine.

  7. Rh2(II)-catalyzed intramolecular aliphatic C-H bond amination reactions using aryl azides as the N-atom source.

    Science.gov (United States)

    Nguyen, Quyen; Sun, Ke; Driver, Tom G

    2012-05-02

    Rhodium(II) dicarboxylate complexes were discovered to catalyze the intramolecular amination of unactivated primary, secondary, or tertiary aliphatic C-H bonds using aryl azides as the N-atom precursor. While a strong electron-withdrawing group on the nitrogen atom is typically required to achieve this reaction, we found that both electron-rich and electron-poor aryl azides are efficient sources for the metal nitrene reactive intermediate. © 2012 American Chemical Society

  8. Rh2(II)-Catalyzed Intramolecular Aliphatic C–H Bond Amination Reactions Using Aryl Azides as the N-Atom Source

    Science.gov (United States)

    Nguyen, Quyen; Sun, Ke; Driver, Tom G.

    2012-01-01

    Rhodium(II) dicarboxylate complexes were discovered to catalyze the intramolecular amination of unactivated primary-, secondary-, or tertiary aliphatic C–H bonds using aryl azides as the N-atom precursor. While a strong electron-withdrawing group on the nitrogen atom is typically required to achieve this reaction, we found that both electron-rich- and electron-poor aryl azides are efficient sources for the metal nitrene reactive intermediate. PMID:22519742

  9. 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

  10. Tuning the conversion of cyclohexane into cyclohexanol/one by molecular dioxygen, protons and reducing agents at a single non-porphyrinic iron centre and chemical versatility of the tris(2-pyridylmethyl)amine TPAFe(II)Cl2 complex in mild oxidation chemistry.

    Science.gov (United States)

    Jaafar, Hassen; Vileno, Bertrand; Thibon, Aurore; Mandon, Dominique

    2011-01-07

    We report that the oxygen sensitivity of some Fe(II) complexes with tripodal ligands can be used, with benefit, in the oxidation of cyclohexane under mild conditions. Depending on the solvent, two very different reaction pathways are involved, which share the coordination of O(2) to the metal as the common initial step. We have synthesized a series of α-chlorinated tripods in the tris(2-pyridylmethyl)amine series Cl(n)TPA (n = 1-3) and fully characterized the corresponding FeX(2) complexes (X = Cl, CF(3)SO(3)). The single-crystal X-ray structure analyses of the FeCl(2) complexes are reported. In CH(3)CN, the FeCl(2) complexes react smoothly with O(2), whereas the Fe(CF(3)SO(3))(2) complexes are non-sensitive. In CH(3)CN, the reaction of the oxygen-sensitive Cl(n)TPAFeCl(2) (n = 0-3) with O(2), acetic acid and zinc amalgam, in the presence of cyclohexane, affords a mixture of cyclohexanol/one in an ≈ ol/one ratio of 3.1 and a selectivity of the C3°/C2° in the adamantane conversion that is consistent with a metal-oxo based oxidation. Limited efficiency (≈ 2 TON) was observed for the parent TPAFeCl(2) complex and Cl(1)TPAFeCl(2), whereas both other complexes turned out to be poorly active. The TPAFeCl(2) complex was used to address mechanistic questions: when the reaction was carried out in pyridine, the ol/one ratio shifted to 0.15 while efficiency was improved by 7-fold. In pyridine and in the presence of a spin trap (DMPO), the radical-based character of the reaction was definitely established, by contrast with acetonitrile, where no oxygenated radicals were detected. Thus, the reactivity differences arise from involvement of two distinct active species. The dichotomous radical/biomimetic pathway is discussed to interpret these results.

  11. PEMIKIRAN QASIM AMIN TENTANG EMANSIPASI WANITA

    Directory of Open Access Journals (Sweden)

    Eliana Siregar

    2017-02-01

    Full Text Available The aim of this research is to explore the idea belong to Qosim Amin "Tahrir al-Mar'ah" as the main theme  of Qasim Amin reformation is an idea that is based on the spirit of liberation and empowerment of women. This idea emerged as a reflection and manifestation of concern intellectualism against the reality of Egyptian woman, who had reached the threshold of tolerance limits area . By using library research method, this research used book, journal, and others as the data resouces. As the cosequency, content analysis was used to analyse the data. Qasim Amin stresses that Islam should be granted rights of women in proportion tha is the right in education and acquire  same right in tasting educational right between men and women, because Islaic value is full of fairness and required the responsibility to Allah. The resut of this research shows that Qosim Amin concern on vision and educational issues in his Idea. There was an awareness of Egytianson the important position of women on education, chance of women to wear veily the government’s attention on the revision of religions justice. These changes have in fired the Egypt women todays.

  12. Fate and biodegradability of sulfonated aromatic amines

    NARCIS (Netherlands)

    Tan, N.C.G.; Leeuwen, van A.; Voorthuizen, van E.M.; Slenders, P.; Prenafeta, F.X.; Temmink, H.; Lettinga, G.; Field, J.A.

    2005-01-01

    Ten sulfonated aromatic amines were tested for their aerobic and anaerobic biodegradability and toxicity potential in a variety of environmental inocula. Of all the compounds tested, only two aminobenzenesulfonic acid (ABS) isomers, 2- and 4-ABS, were degraded. The observed degradation occurred only

  13. 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 ...

  14. New adducts of Lapachol with primary amines

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Mirelly D.F.; Litivack-Junior, Jose T.; Antunes, Roberto V.; Silva, Tania M.S.; Camara, Celso A., E-mail: ccelso@dq.ufrpe.b [Universidade Federal Rural de Pernambuco (UFRPE), Recife, PE (Brazil). Dept. de Quimica

    2011-07-01

    New adducts of lapachol with neat primary aliphatic amines were obtained in a solvent-free reaction in good to reasonable yields (52 to 88%), at room temperature. The new compounds containing a phenazine moiety were obtained from suitable functionalized aminoalkyl compounds, including ethanolamine, 3-propanolamine, 2-methoxy-ethylamine, 3-methoxy-propylamine, n-butylamine and 2-phenetylamine. (author)

  15. 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)

  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. 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.

  18. 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.

  19. Antibacterial and antioxidative activity of O-amine functionalized chitosan.

    Science.gov (United States)

    Tamer, Tamer M; Hassan, Mohamed A; Omer, Ahmed M; Valachová, Katarína; Eldin, Mohamed S Mohy; Collins, Maurice N; Šoltés, Ladislav

    2017-08-01

    Cinnamaldehyde was immobilized to O-amine functionalized chitosan via a coupling reaction. Fourier transform infrared spectroscopy confirmed N-cinnamyl substitution. Wetting analyses demonstrate more hydrophobicity in the N-cinnamyl substituted O-amine functionalized chitosan compared to chitosan or unsubstituted O-amine functionalized chitosan. Thermal gravimetric analysis and differential scanning calorimetry demonstrates that the prepared N-cinnamyl substituted O-amine functionalized chitosan exhibits higher thermostability than unmodified chitosan at temperatures in which polysaccharides are commonly stored and utilised. The N-cinnamyl substituted O-amine functionalized chitosan, against four different bacteria strains [two gram-positive (Staphylococcus aureus and Bacillus cereus) and two gram-negative (Escherichia coli and Pseudomonas aeruginosa)], displays promotion of inhibition activity against these bacterial strains. Finally, the antioxidative activity of the N-cinnamyl substituted O-amine functionalized chitosan was compared with those activities of chitosan and O-amine functionalized chitosan. This was evaluated by uninhibited and inhibited hyaluronan degradation and ABTS assay. The N-cinnamyl substituted O-amine functionalized chitosan shows a lower activity towards donating a hydrogen radical compared to chitosan or O-amine functionalized chitosan. On the other hand, the N-cinnamyl substituted O-amine functionalized chitosan exhibited a higher ability to scavenge the ABTS + cation radical compared to chitosan and O-amine functionalized chitosan. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. 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.

  1. 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)

  2. 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

  3. 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

  4. 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

  5. Organic chemistry. Strain-release amination.

    Science.gov (United States)

    Gianatassio, Ryan; Lopchuk, Justin M; Wang, Jie; Pan, Chung-Mao; Malins, Lara R; Prieto, Liher; Brandt, Thomas A; Collins, Michael R; Gallego, Gary M; Sach, Neal W; Spangler, Jillian E; Zhu, Huichin; Zhu, Jinjiang; Baran, Phil S

    2016-01-15

    To optimize drug candidates, modern medicinal chemists are increasingly turning to an unconventional structural motif: small, strained ring systems. However, the difficulty of introducing substituents such as bicyclo[1.1.1]pentanes, azetidines, or cyclobutanes often outweighs the challenge of synthesizing the parent scaffold itself. Thus, there is an urgent need for general methods to rapidly and directly append such groups onto core scaffolds. Here we report a general strategy to harness the embedded potential energy of effectively spring-loaded C-C and C-N bonds with the most oft-encountered nucleophiles in pharmaceutical chemistry, amines. Strain-release amination can diversify a range of substrates with a multitude of desirable bioisosteres at both the early and late stages of a synthesis. The technique has also been applied to peptide labeling and bioconjugation. Copyright © 2016, American Association for the Advancement of Science.

  6. Reductive Alkylation of Tertiary Lactams via Addition of Organocopper (RCu) Reagents to Thioiminium Ions.

    Science.gov (United States)

    Mateo, Pierre; Cinqualbre, Joséphine E; Meyer Mojzes, Melinda; Schenk, Kurt; Renaud, Philippe

    2017-12-01

    A simple procedure for the conversion of tertiary lactams to 2-monoalkylated cyclic amines is described. The reaction sequence involves conversion of a lactam to a thioiminium ion followed by reaction with an organocopper (RCu) reagent and final reduction with triacetoxyborohydride. The reaction is high yielding and shows an excellent functional group tolerance. Its utility is demonstrated by a rapid synthesis of indolizidine 167B. The excellent chemoselectivity of the process, where only monoalkylation products are formed, is rationalized by a mechanism involving the formation of a transient enamine.

  7. Catalyst for hydrogen-amine D exchange

    International Nuclear Information System (INIS)

    Holtslander, W.J.; Johnson, R.E.

    1977-01-01

    In a process for enrichment of deuterium by contacting hydrogen with an amine (such as methylamine), an alkali metal amide (such as potassium methylamide) is used as a catalyst. The present improvement is to use a mixture of two metal amides (e.g. lithium methylamide plus potassium methylamide) in order to prevent precipitation of a hydride and to reduce thermal decomposition of the catalyst. (NDH)

  8. Whole cell biotransformation for reductive amination reactions

    OpenAIRE

    Klatte, Stephanie; Lorenz, Elisabeth; Wendisch, Volker F

    2013-01-01

    Whole cell biotransformation systems with enzyme cascading increasingly find application in biocatalysis to complement or replace established chemical synthetic routes for production of, e.g., fine chemicals. Recently, we established an Escherichia coli whole cell biotransformation system for reductive amination by coupling a transaminase and an amino acid dehydrogenase with glucose catabolism for cofactor recycling. Transformation of 2-keto-3-methylvalerate to l-isoleucine by E. coli cells w...

  9. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

    2018-01-01

    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope...... of the reaction. Particularly, a formation of configurationally labile aminal centers with alkyl substituents has been a formidable challenge due to the enamine/imine equilibrium of electrophilic substrates. Herein, we report enantioselective nucleophilic addition reactions of potassium phthalimides to Boc-protected...

  10. 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)

  11. 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.

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

    African Journals Online (AJOL)

    Preferred Customer

    sample with concentrated nitric acid and adjusting the pH to avoid precipitation of silver molybdate [12]. Both bromine and chlorine in tungsten halocarbonyls were determined gravimetrically by weighing as the silver halides after taking the following precautions taken to avoid precipitation of either silver tungstate or tungstic ...

  13. Rett syndrome - Stimulation of endogenous biogenic amines

    Science.gov (United States)

    Pelligra, R.; Norton, R. D.; Wilkinson, R.; Leon, H. A.; Matson, W. R.

    1992-01-01

    Transient hypercapnic hyperoxemia was induced in two Rett syndrome children by the administration of a gaseous mixture of 80 percent O2 and 20 percent CO2. Time course studies of neurotransmitters and their metabolites showed an immediate and marked increase in central biogenic amine turnover following inhalation of the gas mixture. The increased turnover of biogenic amines was associated with improved clinical changes. This suggests a coupled relationship and provides further support for an etiological role of neurotransmitter dysfunction in Rett syndrome. In a complementary study, elevation of pulmonary CO2 by application of a simple rebreathing device resulted in improvement of abnormal blood gases and elimination of the Cheyne-Stokes-like respiratory pattern of the Rett syndrome. Near normalization of the EEG occurred when a normal respiratory pattern was imposed by means of a respirator. Taken together, these results lead to the preliminary conclusion that cerebral hypoxemia secondary to abnormal respiratory function may contribute to diminished production of biogenic amines in Rett syndrome.

  14. 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

  15. Amine promoted, metal enhanced degradation of Mirex under high temperature conditions

    International Nuclear Information System (INIS)

    Jallad, Karim N.; Lynn, Bert C.; Alley, Earl G.

    2006-01-01

    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

  16. 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

  17. 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...

  18. A One-Pot Selective Synthesis of N-Boc Protected Secondary Amines: Tandem Direct Reductive Amination/N-Boc Protection

    OpenAIRE

    Neelarapu, Raghupathi; Petukhov, Pavel A.

    2012-01-01

    A one-pot tandem direct reductive amination of aldehydes with primary amines resulting in N-Boc secondary amines using a (Boc)2O/sodium triacetoxyborohydride (STAB) system is reported. The tandem procedure is efficient, selective, and versatile, giving excellent yields of N-Boc protected secondary amines even in those cases where the products are prone to intramolecular lactamization

  19. A One-Pot Selective Synthesis of N-Boc Protected Secondary Amines: Tandem Direct Reductive Amination/N-Boc Protection.

    Science.gov (United States)

    Neelarapu, Raghupathi; Petukhov, Pavel A

    2012-09-02

    A one-pot tandem direct reductive amination of aldehydes with primary amines resulting in N-Boc secondary amines using a (Boc)(2)O/sodium triacetoxyborohydride (STAB) system is reported. The tandem procedure is efficient, selective, and versatile, giving excellent yields of N-Boc protected secondary amines even in those cases where the products are prone to intramolecular lactamization.

  20. 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.

  1. Thermodynamics of organic 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 [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain); Fuente, Isaias Garcia de la [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain); Cobos, Jose Carlos [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain)

    2006-02-01

    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{sup E}), molar excess enthalpies (H{sup E}), molar excess heat capacities at constant pressure (C{sub P}{sup E}) and the concentration-concentration structure factor (S{sub CC}(0)). It is remarkable that DISQUAC correctly predicts the W-shaped curve of the C{sub P}{sup 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{sup E}(pyridine)>H{sup E}(methylpyridine)

  2. 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)

  3. 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)

  4. Amine-functionalized magnetic nanoparticles as robust support for ...

    Indian Academy of Sciences (India)

    and 2,2 -(ethylenedioxy)bis(ethylamine) (EDBE) as amine precursors. These aminated nanoparticles were used as support for the immobilization of lipase, an important industrial enzyme. Lipase was immobilized via glutaraldehyde coupling agent. These functionalized nanoparticles were characterized by XRD, FTIR, TEM,.

  5. Efficient acetylation of primary amines and amino acids in ...

    Indian Academy of Sciences (India)

    The present methodology illustrates the efficient acetylation of primary amines and amino acids in brine solution by means of acetyl chloride under weakly basic condition in the presence of sodium acetate and/or triethyl amine followed by trituration with aqueous saturated bicarbonate solution. This effort represents the first ...

  6. Linear free energy relationship in reactions between diphenyl amine ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 118; Issue 3. Linear free energy relationship in reactions between diphenyl amine and benzyl bromides. S Ranga Reddy P Manikyamba. Volume ... Keywords. Diphenyl amine; substituent effect; reaction constant; isokinetic temperature; linear free energy relationship.

  7. 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

  8. Amine-functionalized magnetic nanoparticles as robust support for ...

    Indian Academy of Sciences (India)

    surface were prepared through solvothermal method, using poly(ethylene imine) (PEI), ethanolamine (EA), and 2,2 -(ethylenedioxy)bis(ethylamine) (EDBE) as amine precursors. These aminated nanoparticles were used as support for the immobilization of lipase, an important industrial enzyme. Lipase was immobilized via.

  9. Predicting the phospholipophilicity of monoprotic positively charged amines

    NARCIS (Netherlands)

    Droge, S T J; Hermens, J L M; Gutsell, S; Rabone, J; Hodges, G

    2017-01-01

    The sorption affinity of eighty-six charged amine structures to phospholipid monolayers (log KIAM) was determined using immobilized artificial membrane high-performance liquid chromatography (IAM-HPLC). The amine compounds covered the most prevalent types of polar groups, widely ranged in structural

  10. Diesel fuel containing polyalkylene amine and Mannich base

    Energy Technology Data Exchange (ETDEWEB)

    Harle, O.L.

    1979-09-04

    Disclosed is a fuel additive and fuel composition. The additive comprises a mixture of a polyalkylene amine and the reaction product of an alkylphenol, an aldehyde and an amine. The additive provides surprising stability in preventing thermal degradation of fuels, particularly fuels for compression ignition engines.

  11. 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.

  12. 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.

  13. Heterocyclic amines produced in cooked food: unavoidable xenobiotics.

    Science.gov (United States)

    Sugimura, T; Wakabayashi, K; Ohgaki, H; Takayama, S; Nagao, M; Esumi, H

    1990-01-01

    Humans are continuously exposed to naturally occurring and industrial xenobiotics in their daily lives. Heterocyclic amines, which are formed during the cooking of proteinaceous foods, have been categorized as a new class of naturally occurring xenobiotics. They are divided into 2-amino-3-methylimidazo[4,5-f] quinoline (IQ)- and non-IQ-types. The amounts and proportion of total mutagenicity contributed by the IQ-type heterocyclic amines in cooked food are greater than those of the non-IQ-types. Precursors of the IQ-type heterocyclic amines including IQ, 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) are creatinine, amino acids and sugars in meat and fish. Both types of heterocyclic amines are carcinogenic in mice and rats. All heterocyclic amines except PhIP frequently induce cancers in the liver, while PhIP induces lymphomas in mice and carcinomas of the colon and mammary gland in rats. Based on quantitative analysis of heterocyclic amines in cooked food and levels of excretion of unchanged heterocyclic amines in human urine, total heterocyclic amine intake was calculated to be around 0.4-16 micrograms/person per day. As in the case of other naturally occurring xenobiotics, and degree of exposure is small and is presumably insufficient alone to account for the development of human cancer. Nevertheless, a linear relationship has been demonstrated between DNA adduct levels and a wide range of doses of MeIQx in animals. In addition, combined treatment with five heterocyclic amines yielded additive or synergistic effects in the development of glutathione S-transferase placental form (GST-P) positive foci. Taking these results and current observations of multiple genetic alterations in human cancers into consideration together, heterocyclic amines are probably involved in the development of human cancer in the presence of other carcinogens, tumor promoters and factors stimulating cancer progression.

  14. Bioreducible poly(amido amine)s with oligoamine side chains: synthesis, characterization, and structural effects on gene delivery

    NARCIS (Netherlands)

    Lin, C.; Blaauboer, Cees-Jan; Mateos timoneda, Miguel; Lok, Martin C.; Steenbergen, Mies; Hennink, Wim E.; Zhong, Zhiyuan; Feijen, Jan; Engbersen, Johannes F.J.

    2008-01-01

    A group of bioreducible poly(amido amine)s containing multiple disulfide linkages in main chain and oligoamines in side chain (SS–PAOAs) were prepared by Michael-type polyaddition of N-tert-butyloxycarbonyl (N-Boc) protected oligoamine to the disulfide-containing cystaminebisacrylamide, followed by

  15. 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.

  16. Metabolomic profiling of amines in sepsis predicts changes in NOS canonical pathways.

    Directory of Open Access Journals (Sweden)

    Abel Tesfai

    Full Text Available Nitric oxide synthase (NOS is a biomarker/target in sepsis. NOS activity is driven by amino acids, which cycle to regulate the substrate L-arginine in parallel with cycles which regulate the endogenous inhibitors ADMA and L-NMMA. The relationship between amines and the consequence of plasma changes on iNOS activity in early sepsis is not known.Our objective was to apply a metabolomics approach to determine the influence of sepsis on a full array of amines and what consequence these changes may have on predicted iNOS activity.34 amino acids were measured using ultra purification mass spectrometry in the plasma of septic patients (n = 38 taken at the time of diagnosis and 24-72 hours post diagnosis and of healthy volunteers (n = 21. L-arginine and methylarginines were measured using liquid-chromatography mass spectrometry and ELISA. A top down approach was also taken to examine the most changed metabolic pathways by Ingenuity Pathway Analysis. The iNOS supporting capacity of plasma was determined using a mouse macrophage cell-based bioassay.Of all the amines measured 22, including L-arginine and ADMA, displayed significant differences in samples from patients with sepsis. The functional consequence of increased ADMA and decreased L-arginine in context of all cumulative metabolic changes in plasma resulted in reduced iNOS supporting activity associated with sepsis.In early sepsis profound changes in amine levels were defined by dominant changes in the iNOS canonical pathway resulting in functionally meaningful changes in the ability of plasma to regulate iNOS activity ex vivo.

  17. 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.

  18. 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.

  19. Synthesis and characterization of bisimide amines and bisimide amine-cured epoxy resins

    Science.gov (United States)

    Scola, D. A.

    1983-01-01

    An attempt is made to develop tough, moisture resistant, high char yield epoxy resins by means of novel bisimide amine (BIA) hardener curing agents and a state-of-the-art epoxy resin system. The BIAs are isolated as mixtures containing monomer, oligomer, and polymeric species, and then characterized by elemental analysis and high pressure liquid chromatography. The bisimide amine-cured epoxies (IMEs) were characterized with respect to moisture absorption, thermal properties, and physical and mechanical properties, as well as in the role of matrices in Celion 6000/IME composites. The relative toughness characteristics of each IME formulation was measured by the 10 deg off-axis tensile test, measuring the uniaxial tensile strength, shear strength, and shear-strain-to-failure of the composite systems.

  20. 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

  1. Whole cell biotransformation for reductive amination reactions

    Science.gov (United States)

    Klatte, Stephanie; Lorenz, Elisabeth; Wendisch, Volker F

    2014-01-01

    Whole cell biotransformation systems with enzyme cascading increasingly find application in biocatalysis to complement or replace established chemical synthetic routes for production of, e.g., fine chemicals. Recently, we established an Escherichia coli whole cell biotransformation system for reductive amination by coupling a transaminase and an amino acid dehydrogenase with glucose catabolism for cofactor recycling. Transformation of 2-keto-3-methylvalerate to l-isoleucine by E. coli cells was improved by genetic engineering of glucose metabolism for improved cofactor regeneration. Here, we compare this system with different strategies for cofactor regeneration such as cascading with alcohol dehydrogenases, with alternative production hosts such as Pseudomonas species or Corynebacterium glutamicum, and with improving whole cell biotransformation systems by metabolic engineering of NADPH regeneration. PMID:24406456

  2. Biogenic amines in Portuguese traditional foods and wines.

    Science.gov (United States)

    Ferreira, Isabel M P L V O; Pinho, Olívia

    2006-09-01

    The presence of biogenic amines in foodstuffs is an important food safety problem because of the implication of these compounds in food intolerance and intoxication. The separation and quantification of biogenic amines in foods is normally performed by chromatographic techniques. This review contains descriptions of the quantification of biogenic amines in Portuguese traditional fermented and/or ripened foods and wines, including Protected Denomination of Origin cheeses, dry-cured sausages, and Portuguese wines (including Port wines), using different analytical methods based on high-pressure liquid chromatography (UV or diode array and/or fluorometric detectors) and gas chromatography (with a mass spectrometry detector). The evolution of biogenic amines during fermentation, ripening, aging, or storage of those products was also evaluated. Biogenic amine concentrations ranged widely within individual food items, and storage, transport, and handling conditions can influence to some extent the biogenic amines present and their concentrations. Traditional foods are an important part of the Portuguese diet, and a high intake of harmful amounts of biogenic amines from traditional Portuguese fermented foods is possible. However, extensive research is needed to extend the current limited database.

  3. Kinetics and mechanism of the sorption of some aromatic amines onto amberlite IRA-904 anion-exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Zaki, A.B.; El-Sheikh, M.Y.; Evans, J.; El-Safty, S.A.

    2000-01-01

    The kinetics of the sorption of aromatic amines such as o-aminophenol (o-AP), o-phenylenediamine (o-PDA), and p-phenylenediamine (p-PDA) onto Amberlite anion-exchange resin in chloride form was investigated in batch experiments spectrophotometrically at different temperatures. The sorption rate is zero order in all amines sorbed, increasing directly in the order: p-PDA < o-PDA < o-AP, which corresponds to the sequence of the electrostatic contributions to the sorption interactions. The attainments of sorption equilibrium of aromatic amines is seen to be similar. The diffusion coefficients (D) have been calculated by using Fick's equation from the second portions of the sorption/desorption curves; D values ranged from 0.7 to 2.8 x 10{sup {minus}9} cm{sup 2}/s. These results, reflecting the diffusion mechanism, were ascribed to intraparticle diffusion. Arrhenius parameters for the diffusion process and the thermodynamic quantities for the process of equilibrium sorption have been estimated. The effect of a chemical oxidation reaction on intraparticle diffusion was investigated by measuring the intraparticle diffusion of amines during the redox reaction.

  4. Kinetics and Mechanism of the Sorption of Some Aromatic Amines onto Amberlite IRA-904 Anion-Exchange Resin.

    Science.gov (United States)

    Zaki; El-Sheikh; Evans; El-Safty

    2000-01-01

    The kinetics of the sorption of aromatic amines such as o-aminophenol (o-AP), o-phenylenediamine (o-PDA), and p-phenylenediamine (p-PDA) onto Amberlite anion-exchange resin in chloride form was investigated in batch experiments spectrophotometrically at different temperatures. The sorption rate is zero order in all amines sorbed, increasing directly in the order: p-PDAamines is seen to be similar. The diffusion coefficients (D) have been calculated by using Fick's equation from the second portions of the sorption/desorption curves; D values ranged from 0.7 to 2.8x10(-9) cm(2)/s. These results, reflecting the diffusion mechanism, were ascribed to intraparticle diffusion. Arrhenius parameters for the diffusion process and the thermodynamic quantities for the process of equilibrium sorption have been estimated. The effect of a chemical oxidation reaction on intraparticle diffusion was investigated by measuring the intraparticle diffusion of amines during the redox reaction. Copyright 2000 Academic Press.

  5. 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.

  6. Novel phosphorus containing epoxy networks based on trihydrocarbyl phosphine oxides having active substituents

    OpenAIRE

    1990-01-01

    Epoxy resins can be cured or crosslinked with trihydrocarbyl phosphine oxide compounds having epoxy-reactive (active hydrogen) substituents either alone or in combination with amine-terminated polyarylene ethers (e.g., amine-terminated polysulfone oligomers or high polymers.

  7. 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)

  8. Paramagnetic titanium(III) and zirconium(III) metallocene complexes as precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes.

    Science.gov (United States)

    Helten, Holger; Dutta, Barnali; Vance, James R; Sloan, Matthew E; Haddow, Mairi F; Sproules, Stephen; Collison, David; Whittell, George R; Lloyd-Jones, Guy C; Manners, Ian

    2013-01-02

    Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Selective Reductive Elimination at Alkyl Palladium(IV) by Dissociative Ligand Ionization: Catalytic C(sp3)-H Amination to Azetidines.

    Science.gov (United States)

    Nappi, Manuel; He, Chuan; Whitehurst, William G; Chappell, Ben G N; Gaunt, Matthew J

    2018-01-30

    A palladium(II)-catalyzed γ-C-H amination of cyclic alkyl amines to deliver highly substituted azetidines is reported. The use of a benziodoxole tosylate oxidant in combination with AgOAc was found to be crucial for controlling a selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral α-amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Learning Enhancement in Tertiary Institutions Using Mobile ...

    African Journals Online (AJOL)

    2012-12-01

    Dec 1, 2012 ... Abstract. The educational standard in tertiary institutions has witnessed a down turn in the area of teaching and learning. This paper links this down fall to traditional face-to-face educational model that is still by far the dominant mode of education and learning in tertiary institutions. In addition to identifying ...

  11. Tertiary Education Fees Public Opinion Poll, Australia.

    Science.gov (United States)

    McNair Anderson Associates Pty., Ltd., (Australia).

    The public reaction to the proposal that the Australian government should reintroduce fees for tertiary education was surveyed in 1985. The influence of the proposal on the way people would vote in a federal election was also investigated. The fee would be between $900 and $1,500 per year for full-time tertiary education. As part of a McNair…

  12. 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.

  13. 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...

  14. Amine reclaiming technologies in post-combustion carbon dioxide capture.

    Science.gov (United States)

    Wang, Tielin; Hovland, Jon; Jens, Klaus J

    2015-01-01

    Amine scrubbing is the most developed technology for carbon dioxide (CO2) capture. Degradation of amine solvents due to the presence of high levels of oxygen and other impurities in flue gas causes increasing costs and deterioration in long term performance, and therefore purification of the solvents is needed to overcome these problems. This review presents the reclaiming of amine solvents used for post combustion CO2 capture (PCC). Thermal reclaiming, ion exchange, and electrodialysis, although principally developed for sour gas sweetening, have also been tested for CO2 capture from flue gas. The three technologies all have their strengths and weaknesses, and further development is needed to reduce energy usage and costs. An expected future trend for amine reclamation is to focus on process integration of the current reclaiming technologies into the PCC process in order to drive down costs. Copyright © 2014. Published by Elsevier B.V.

  15. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides ...

    Indian Academy of Sciences (India)

    016-1096-y. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides/. Isocyanate leading to Guanidines/Urea derivatives formation. JAYEETA BHATTACHARJEE, MITALI SACHDEVA, INDRANI BANERJEE and. TARUN K PANDA.

  16. Two simple amine hydrochlorides from the soft coral Lobophytum strictum

    Digital Repository Service at National Institute of Oceanography (India)

    Parameswaran, P.S.; Naik, C.G.; Das, B.; Kamat

    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...

  17. Health Problems of Epoxy Resins and Amine-curing Agents

    Science.gov (United States)

    Bourne, L. B.; Milner, F. J. M.; Alberman, K. B.

    1959-01-01

    Epoxy resins were first introduced about 10 years ago. Toxic effects, particularly dermatitis, have been frequently described. An investigation into the possible causes of pathological sequelae following the use of epoxy resin/amine mixtures has been undertaken. The cause of most cases of dermatitis and sensitization appears to be uncombined amine which is present in recent mixtures and persists in hardened resin for long periods. The results of experiments with two of the most commonly used resin/amine mixtures confirm this. Cold-cured resins are more dangerous and remain so even when hardened. A simple theory is suggested for the mechanism of the reaction between epoxy resins, amines, and biological systems. This theory leads logically to the handling precautions outlined. Images PMID:13651551

  18. 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##

  19. 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.

  20. Facile and Green Synthesis of Saturated Cyclic Amines.

    Science.gov (United States)

    Hameed, Arruje; Javed, Sadia; Noreen, Razia; Huma, Tayyaba; Iqbal, Sarosh; Umbreen, Huma; Gulzar, Tahsin; Farooq, Tahir

    2017-10-12

    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.

  1. 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.

  2. Dispersant additives derived from lactone modified amido-amine adducts

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, A.; Lundberg, R.D.

    1990-10-16

    This patent describes a lactone modified dispersant additive. It comprises one adduct of a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.8 (e.g., from about 1 to 4) dicarboxylic acid producing moieties (preferably acid or anhydride moieties) per polyolefin molecule, an amido-amine or thioamido-amine characterized by being a reaction product of at least a polyamine and an alpha, beta-unsaturated compound.

  3. Ability of Kocuria varians LTH 1540 To Degrade Putrescine: Identification and Characterization of a Novel Amine Oxidase.

    Science.gov (United States)

    Callejón, Sara; Sendra, Ramón; Ferrer, Sergi; Pardo, Isabel

    2015-04-29

    This work describes the identification and characterization of an amine oxidase from Kocuria varians LTH 1540 (syn. Micrococcus varians) primarily acting on putrescine. Data from MALDI-TOF MS/MS and the identification of Δ(1)-pyrroline as degradation product from putrescine indicate that the enzyme is a flavin-dependent putrescine oxidase (PuO). Properties of partially purified enzyme have been determined. The enzyme oxidizes diamines, putrescine and cadaverine, and, to a lesser extent, polyamines, such as spermidine, but not monoamines. The kinetic constants (Km and Vmax) for the two major substrates were 94 ± 10 μM and 2.3 ± 0.1 μmol/min·mg for putrescine and 75 ± 5 μM and 0.15 ± 0.02 μmol/min·mg for cadaverine. Optimal temperature and pH were 45 °C and 8.5, respectively. Enzyme was stable until 50 °C. K. varians PuO is sensitive to human flavin-dependent amine oxidase inhibitors and carboxyl-modifying compounds. The new enzyme has been isolated from a bacterial starter used in the manufacture of fermented meat. One of the problems of fermented foods or beverages is the presence of toxic biogenic amines produced by bacteria. The importance of this works lies in the description of a new enzyme able to degrade two of the most abundant biogenic amines (putrescine and cadaverine), the use of which could be envisaged to diminish biogenic amines content in foods in the future.

  4. Brain perfusion imaging with iodinated amines

    International Nuclear Information System (INIS)

    Kung, H.F.

    1989-01-01

    Traditional nuclear medicine brain study using 99m Tc pertechnetate, glucoheptonate or diethlenetriaminepentacetic acid (DTPA) and planar imaging has experienced a significant decline in the past 10 years. This is mainly due to the introduction of X-ray CT and more recently the nuclear magnetic resonance (NMR) imaging, by which detailed morphology of the brain, including the detection of breakdown of the blood-brain barrier, can be obtained. The nuclear medicine brain imaging is only prescribed as a complementary test when X-ray CT is negative or equivocal and clinical suspicion remains. The attention of nuclear medicine brain imaging has been shifted from the detection of the breakdown of the blood-brain barrier to the study of brain function-perfusion, metabolism, and receptor binding, etc. The functional brain imaging provides diagnostic information usually unattainable by other radiological techniques. In this article, the iodinated amines as brain perfusion imaging agents are reviewed. Potential clinical application of these agents is discussed

  5. Development of I-123-labeled amines for brain studies: localization of I-123 iodophenylalkyl amines in rat brain

    International Nuclear Information System (INIS)

    Winchell, H.S.; Baldwin, R.M.; Lin, T.H.

    1980-01-01

    Localization in rat brain of forty iodophenylalkyl amines labeled with I-123 was evaluated in an attempt to develop I-123-labeled amines useful for brain studies. For the amines studied, the highest activity in brain and the brain-to-blood activity ratios ranked p > m > o as related to iodine position on the benzene ring: for alkyl groups the rank order was α-methylethyl > ethyl > methyl > none; for N additions it was single lipophilic group > H > two lipophilic groups. It is suggested that introduction of a halogen into the ring structure of many amines results in greater concentration of the agent in brain than is seen with the nonhalogenated parent compound. The agent N-isopropyl-p-iodoamphetamine was chosen for further study because, in the rat, it showed high brain activity (1.57%/g) and brain-blood ratio (12.6) at 5 min

  6. Fate and transformation products of amine-terminated PAMAM dendrimers under ozonation and irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Santiago-Morales, Javier [Department of Chemical Engineering, University of Alcalá, 28871 Alcalá de Henares, Madrid (Spain); Rosal, Roberto, E-mail: roberto.rosal@uah.es [Department of Chemical Engineering, University of Alcalá, 28871 Alcalá de Henares, Madrid (Spain); Advanced Study Institute of Madrid, IMDEA Agua, Parque Científico Tecnológico, 28805 Alcalá de Henares, Madrid (Spain); Hernando, María D. [Spanish National Institute for Agricultural and Food Research and Technology – INIA, Crta. de la Coruña, km 7.5, 28040 Madrid (Spain); Ulaszewska, Maria M. [Advanced Study Institute of Madrid, IMDEA Agua, Parque Científico Tecnológico, 28805 Alcalá de Henares, Madrid (Spain); García-Calvo, Eloy [Department of Chemical Engineering, University of Alcalá, 28871 Alcalá de Henares, Madrid (Spain); Advanced Study Institute of Madrid, IMDEA Agua, Parque Científico Tecnológico, 28805 Alcalá de Henares, Madrid (Spain); Fernández-Alba, Amadeo R. [Advanced Study Institute of Madrid, IMDEA Agua, Parque Científico Tecnológico, 28805 Alcalá de Henares, Madrid (Spain); Pesticide Residue Research Group, Department of Hydrogeology and Analytical Chemistry, University of Almería, 04120 Almería (Spain)

    2014-02-15

    Highlights: • We detected transformation products from dendrimer under ozonation and irradiation. • Retro-Michael fragmentation pathway with highly oxygenated structures. • High toxicity of G3 PAMAM dendrimer for green algae. • Reactive oxygen species were associated with the toxic damage. • Transformation mixtures could be more toxic than the parent dendrimer. -- Abstract: This article deals with the degradation of a third-generation (G3) poly(amidoamine) (PAMAM) dendrimer under ozonation and irradiation. The identification and quantification of G3 PAMAM dendrimer and its transformation products has been performed by liquid chromatography–electrospray ionization-hybrid quadrupole time-of-flight-mass spectrometry. The dendrimer was completely depleted by ozone in less than 1 min. The effect of ultraviolet irradiation was attributed to hydroxyl-mediated oxidation. The transformation products were attributed to the oxidation of amines, which resulted in highly oxidized structures with abundance of carboxylic acids, which started from the formation of amine oxide and the scission of the C-N bond of the amide group. We studied the toxicity of treated mixtures for six different organisms: the acute toxicity for the bacterium Vibrio fischeri and the microcrustacean Daphnia magna, the multigenerational growth inhibition of the alga Pseudokirchneriella subcapitata, and the seed germination phytotoxicity of Licopersicon esculentum, Lactuca sativa and Lolium perenne. Ozonation and irradiation originated transformation products are more toxic than the parent dendrimer. The toxicity of the dendrimer for the green alga was linked to a strong increase of intracellular reactive oxygen species with intense lipid peroxidation.

  7. Catalytic Ester and Amide to Amine Interconversion: Nickel-Catalyzed Decarbonylative Amination of Esters and Amides by C−O and C−C Bond Activation

    KAUST Repository

    Yue, Huifeng

    2017-03-15

    An efficient nickel-catalyzed decarbonylative amination reaction of aryl and heteroaryl esters has been achieved for the first time. The new amination protocol allows the direct interconversion of esters and amides into the corresponding amines and represents a good alternative to classical rearrangements as well as cross coupling reactions.

  8. Asymmetric synthesis of tertiary alcohols by the use of tricarbonylchromium (O) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Furtado, O.R.; Gomes Costa, M.R.; Marcelo Curto, M.J. [Instituto Nacional de Engenharia e Tecnolgia Industrial, Queluz (Portugal)] [and others

    1995-12-31

    The demand for homochiral compounds by the pharmaceutical and related industries has stimulated great interest in the development of asymmetric methodology for organic synthesis. The authors report herein the stereoselective synthesis of tertiary benzylic alcohols. These homochiral tertiary alcohols could be obtained by stereoselective addition to the carbonyl function of chiral [(aryl)Cr(CO){sub 3}] ketones. The syntheses of these ketones were performed by reaction of lithiated (arene)Cr(CO){sub 3} complexes with acyl halides or aldehydes followed by Swern oxidation of the alcohols obtained.

  9. Study on tertiary in-situ leachable uranium mineralization conditions in South Songliao basin

    International Nuclear Information System (INIS)

    Zhang Zhenqiang; Li Guokuan; Zhao Zonghua; Zhang Jingxun

    2001-01-01

    Tertiary in-situ leachable mineralization in Songliao Basin was analyzed in theory in the past. Since 1998, regional investigation at 1:200000 scale has been done with about 120 holes drilled. Based on drill holes recording, section compiling and sample analysis, the authors investigate into the Tertiary in-situ leachable conditions including rock character, sedimentary facies, rock chemistry, organic substances, uranium content, sandstone porosity, sandstone bodies, interlayer oxidation, and hydro-dynamic value. The study would play important role in prospecting for in-situ leachable uranium in South Songliao basin

  10. Nitric oxide mediates insect cellular immunity via phospholipase A2 activation

    Science.gov (United States)

    After infection or invasion is recognized, biochemical mediators act in signaling insect immune functions. These include biogenic amines, insect cytokines, eicosanoids and nitric oxide (NO). Treating insects or isolated hemocyte populations with different mediators often leads to similar results. Se...

  11. Mutagenic activity and heterocyclic amine content of the human diet

    Energy Technology Data Exchange (ETDEWEB)

    Knize, M.G.; Dolbeare, F.A.; Cunningham, P.L.; Felton, J.S.

    1993-01-15

    The mutagenic activity and the mass amount of heterocyclic amines responsible for the mutagenic activity have been measured in some cooked foods. Cooked meats are the predominant source of mutagenic activity in the diet with values ranging from 0 to 10,000 revertants per gram reported in the Ames/Salmonelia test with strain TA98. Several heterocyclic amines are present and have been quantified using solid-phase extraction followed by HPLC. Frying at higher temperatures and for longer times produces the greatest mutagenic response, and concomitantly, the largest amounts of heterocyclic amines. Most of the mutagenic activity in fried meat samples can be accounted for by MelQx, DiMelQx and IQ, although other heterocylic amines are present and PHIP mutagenic activity becomes significant at higher temperatures. Non-meat products such as baked breads can also form significant mutagenic activity, particularly when overcooked. Commercially prepared hamburgers made from meat substitutes such as tofu, wheat gluten or tempeh and fried at 210{degrees}C have up to 10% of the mutagenic activity of a fried beef patty cooked under the same conditions. When detected, amounts of heterocyclic amines in fried beef patties range from a total of 0.35 ng/g for commercial beef hamburgers to 142 ng/g for a beef patty cooked over a barbecue. Dietary intake is expected to have a large range, from less than one microgram per day to over 50 micrograms per day based on current knowledge of known heterocyclic amine chemicals and heterocyclic amine-containing foods.

  12. Biogenic amines in Italian Pecorino cheese

    Directory of Open Access Journals (Sweden)

    Maria eSchirone

    2012-05-01

    Full Text Available The quality of distinctive artisanal cheeses is closely associated with the territory of production and its traditions. Pedoclimatic characteristics, genetic autochthonous variations and anthropic components create an environment so specific that it would be extremely difficult to reproduce elsewhere. Pecorino cheese is included in this sector of the market and is widely diffused in Italy (approximately 53.727t of production. Pecorino is a common name given to indicate Italian cheeses made exclusively from pure ewes' milk characterized by a high content of fat matter and it is mainly produced in the middle and south of Italy by traditional procedures from raw or thermized milk. The microbiota plays a major role in the development of the organoleptic characteristics of the cheese but it can also be responsible for the accumulation of undesirable substances, such as biogenic amines (BA. Several factors can contribute to the qualitative and quantitative profiles of BA’s in Pecorino cheese such as environmental hygienic conditions, pH, salt concentration, aw, fat content, pasteurization of milk, decarboxylase microorganisms, starter cultures, temperature and time of ripening, storage, part of the cheese (core, edge and the presence of cofactor. Generally, the total content of BA’s can range from about 100-2400 mg/kg, with a prevalence of toxicologically important BA’s, tyramine and histamine. The presence of BA in Pecorino cheeses is becoming increasingly important to consumers and cheese-maker alike, due to the potential threats of toxicity to humans and consequent trade implications.

  13. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  14. Efficiency of SPIONs functionalized with polyethylene glycol bis(amine) for heavy metal removal

    Energy Technology Data Exchange (ETDEWEB)

    Wanna, Yongyuth, E-mail: yongyuth.wanna@gmail.com [College of KMITL Nanotechnology, King Mongkut' s Institute of Technology Ladkrabang, Chalongkrung Rd., Ladkrabang, Bangkok 10520 (Thailand); Nara Machinery Co., Ltd., 2-5-7, Jonan-Jima, Ohta-ku, Tokyo 143-0002 (Japan); Chindaduang, Anon; Tumcharern, Gamolwan [National Nanotechnology Center (NANOTEC), 111 Thailand Science Park, Pahol Yothin Rd, Klong Luang, Pathum Thani 12120 (Thailand); Phromyothin, Darinee [College of KMITL Nanotechnology, King Mongkut' s Institute of Technology Ladkrabang, Chalongkrung Rd., Ladkrabang, Bangkok 10520 (Thailand); Porntheerapat, Supanit [NECTEC, National Science and Technology Development Agency (NSTDA), 112 Thailand Science Park, Phahonyothin Rd., Khlong Nueng, Khlong Luang, Pathum Thani 12120 (Thailand); Nukeaw, Jiti [College of KMITL Nanotechnology, King Mongkut' s Institute of Technology Ladkrabang, Chalongkrung Rd., Ladkrabang, Bangkok 10520 (Thailand); Hofmann, Heirich [Laboratory of Powder Technology, Ecole Polytechnique Fédérale de Lausanne (Switzerland); Pratontep, Sirapat [College of KMITL Nanotechnology, King Mongkut' s Institute of Technology Ladkrabang, Chalongkrung Rd., Ladkrabang, Bangkok 10520 (Thailand)

    2016-09-15

    Hybrid magnetic nanoparticles based on poly(methylmethacrylate) (PMMA) and super-paramagnetic iron oxide nanopaticles (SPIONs) with selective surface modification has been developed for heavy metal removal by applying external magnetic fields. The nanoparticles were prepared by the emulsion polymerization technique in an aqueous suspension of SPIONs. The hydrolysis of carboxyl functional group was then applied for grafting polyethylene glycol bis(amine)(PEG-bis(amine)) onto the PMMA-coated SPIONs. The morphology, the chemical structure and the magnetic properties of the grafted nanoparticles were investigated. The efficiency of the hybrid nanoparticles for heavy metal removal were conducted on Pb(II), Hg(II), Cu(II) and Co(II) in aqueous solutions.The metal concentration in the solutions after separation by the hybrid nanoparticles was determined by inductively coupled plasma optical emission spectrometer (ICP-OES). The results show the heavy metal uptake ratios of 0.08, 0.04, 0.03, and 0.01 mM per gramme of the grafted SPIONs for Pb(II), Hg(II), Cu(II), and Co(II), respectively. A competitive removal of Cu(II), Pb(II), Co(II) and Hg(II) ions in mixed metal salt solutions has also been studied.The heavy metal removal efficiency of the hybrid nanoparitcles was found to depend on the cation radius, in accordance with capture of metal ions by the amine group. - Highlights: • We synthesis hybrid magnetic nanoparticles for heavy metal removal. • The efficiency of hybrid nanoparticles for heavy metal removal is proposed. • We investigated the characteristic of hybrid nanoparticle. • The heavy metal removal efficiency of the hybrid nanoparticle was founded that depend on the heavy metal cation radius.

  15. Oxidative Heck Reaction as a Tool for Para-selective Olefination of Aniline: A DFT Supported Mechanism.

    Science.gov (United States)

    Moghaddam, Firouz Matloubi; Pourkaveh, Raheleh; Karimi, Ashkan

    2017-10-06

    This study describes the first para-selective palladium-catalyzed alkenylation of tertiary amines. This regioselective C-H activation was conducted without any chelation moieties. A series of olefins were reacted under mild reaction conditions at 60 °C, and the corresponding products were obtained in good yields with high selectivity.

  16. Can an amine be a stronger acid than a carboxylic acid? The surprisingly high acidity of amine-borane complexes.

    Science.gov (United States)

    Martín-Sómer, Ana; Lamsabhi, Al Mokhtar; Yáñez, Manuel; Dávalos, Juan Z; González, Javier; Ramos, Rocío; Guillemin, Jean-Claude

    2012-12-03

    The gas-phase acidity of a series of amine-borane complexes has been investigated through the use of electrospray mass spectrometry (ESI-MS), with the application of the extended Cooks kinetic method, and high-level G4 ab initio calculations. The most significant finding is that typical nitrogen bases, such as aniline, react with BH(3) to give amine-borane complexes, which, in the gas phase, have acidities as high as those of either phosphoric, oxalic, or salicylic acid; their acidity is higher than many carboxylic acids, such as formic, acetic, and propanoic acid. Indeed the complexation of different amines with BH(3) leads to a substantial increase (from 167 to 195 kJ mol(-1)) in the intrinsic acidity of the system; in terms of ionization constants, this increase implies an increase as large as fifteen orders of magnitude. Interestingly, this increase in acidity is almost twice as large as that observed for the corresponding phosphine-borane analogues. The agreement between the experimental and the G4-based calculated values is excellent. The analysis of the electron-density rearrangements of the amine and the borane moieties indicates that the dative bond is significantly stronger in the N-deprotonated anion than in the corresponding neutral amine-borane complex, because the deprotonated amine is a much better electron donor than the neutral amine. On the top of that, the newly created lone pair on the nitrogen atom in the deprotonated species, conjugates with the BN bonding pair. The dispersion of the extra electron density into the BH(3) group also contributes to the increased stability of the deprotonated species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis, characterization and photophysical-theoretical analysis of compounds A-π-D. 1. Effect of alkyl-phenyl substituted amines in photophysical properties

    Science.gov (United States)

    Ortega, E.; Montecinos, R.; Cattin, L.; Díaz, F. R.; del Valle, M. A.; Bernède, J. C.

    2017-08-01

    The study of new dipolar A-π-D molecules, which have an acceptor (A) and donor (D) charge joined by a conjugate bridge, have been an attention focus in the recent years due their different properties. In the current work, a molecular system has been modified in order to compare the effect on properties, such as quantum yield. Thus, two series were generated (alkyl- and alkoxy-substituted) to determine if molecules with tertiary asymmetric amines change their optical properties and whether quantum yield is affected. The different products have been characterized by several techniques such as UV-Vis spectrophotometry, elemental analysis, NMR, FT-IR, mass spectroscopy and fluorescence spectroscopy. Furthermore, their behavior in eight organic solvents, dichloromethane, tetrahydrofuran, ethyl acetate, 1,4-dioxane, acetone, acetonitrile, dimethylformamide and dimethylsulfoxide were experimentally and theoretically studied. The quantum yields were higher for the alkyl-substituted series. Theoretically, the dihedral angles formed between the tertiary amine and carbonyl group moieties have a correlation with quantum yield values, helping to explain why they are higher in non-polar solvents. Consequently, the maximum quantum yield was obtained with (E)-2-cyano-3-(5-((E)-2-(9,9-diethyl-7-(methyl(phenyl)amino)-9H-fluoren-2-yl) vinyl)thiophen-2-yl)acrylic acid (M8-1) in 1,4-dioxane, reaching 98.8%.

  18. Choosing amine-based absorbents for CO2 capture.

    Science.gov (United States)

    Gomes, João; Santos, Samuel; Bordado, João

    2015-01-01

    CO2 capture from gaseous effluents is one of the great challenges faced by chemical and environmental engineers, as the increase in CO2 levels in the Earth atmosphere might be responsible for dramatic climate changes. From the existing capture technologies, the only proven and mature technology is chemical absorption using aqueous amine solutions. However, bearing in mind that this process is somewhat expensive, it is important to choose the most efficient and, at the same time, the least expensive solvents. For this purpose, a pilot test facility was assembled and includes an absorption column, as well as a stripping column, a heat exchanger between the two columns, a reboiler for the stripping column, pumping systems, surge tanks and all necessary instrumentation and control systems. Some different aquous amine solutions were tested on this facility and it was found that, from a set of six tested amines, diethanol amine is the one that turned out to be the most economical choice, as it showed a higher CO2 loading capacity (0.982 mol of CO2 per mol of amine) and the lowest price per litre (25.70 €/L), even when compared with monoethanolamine, the benchmark solvent, exhibiting a price per litre of 30.50 €/L.

  19. Chromosomal localization of the human vesicular amine transporter genes

    Energy Technology Data Exchange (ETDEWEB)

    Peter, D.; Finn, P.; Liu, Y.; Roghani, A.; Edwards, R.H.; Klisak, I.; Kojis, T.; Heinzmann, C.; Sparkes, R.S. (UCLA School of Medicine, Los Angeles, CA (United States))

    1993-12-01

    The physiologic and behavioral effects of pharmacologic agents that interfere with the transport of monoamine neurotransmitters into vesicles suggest that vesicular amine transport may contribute to human neuropsychiatric disease. To determine whether an alteration in the genes that encode vesicular amine transport contributes to the inherited component of these disorders, the authors have isolated a human cDNA for the brain transporter and localized the human vesciular amine transporter genes. The human brain synaptic vesicle amine transporter (SVAT) shows unexpected conservation with rat SVAT in the regions that diverge extensively between rat SVAT and the rat adrenal chromaffin granule amine transporter (CGAT). Using the cloned sequences with a panel of mouse-human hybrids and in situ hybridization for regional localization, the adrenal CGAT gene (or VAT1) maps to human chromosome 8p21.3 and the brain SVAT gene (or VAT2) maps to chromosome 10q25. Both of these sites occur very close to if not within previously described deletions that produce severe but viable phenotypes. 26 refs., 3 figs., 1 tab.

  20. In situ infrared study of the effect of amine density on the nature of adsorbed CO2 on amine-functionalized solid sorbents.

    Science.gov (United States)

    Tumuluri, Uma; Isenberg, Mathew; Tan, Chung-Sung; Chuang, Steven S C

    2014-07-01

    In situ Fourier transform infrared spectroscopy was used to determine the nature of adsorbed CO2 on class I (amine-impregnated) and class II (amine-grafted) sorbents with different amine densities. Adsorbed CO2 on amine sorbents exists in the form of carbamate-ammonium ion pairs, carbamate-ammonium zwitterions, and carbamic acid. The adsorbed CO2 on high-amine density sorbents showed that the formation of ammonium ions correlates with the suppression of CH stretching intensities. An HCl probing technique was used to resolve the characteristic infrared bands of ammonium ions, clarifying that the band observed around 1498 cm(-1) is a combination of the deformation vibration of ammonium ion (NH3(+)) at 1508 and 1469 cm(-1) and the deformation vibration of NH in carbamate (NHCOO(-)) at 1480 cm(-1). Carbamate and carbamic acid on sorbents with low amine density desorbed at a rate faster than those on sorbents with high amine density after switching the flow from CO2 to Ar at 55 °C. Evaluation of the desorption temperature profiles showed that the temperature required to achieve the maximal desorption of CO2 (Tmax. des) increases with amine density. The adsorbed CO2 on sorbents with high amine density is stabilized via hydrogen bonding interactions with adjacent amine sites. These sorbents require higher temperature to desorb CO2 than those with low amine density.

  1. Aminodiols via stereocontrolled oxidation of methyleneaziridines.

    Science.gov (United States)

    Rigoli, Jared W; Guzei, Ilia A; Schomaker, Jennifer M

    2014-03-21

    A highly diastereoselective Ru-catalyzed oxidation/reduction sequence of bicyclic methyleneaziridines provides a facile route to complex 1-amino-2,3-diol motifs. The relative anti stereochemistry between the amine and the vicinal alcohol are proposed to result from 1,3-bischelation in the transition state by the C1 and C3 heteroatoms.

  2. Graphene composites containing chemically bonded metal oxides

    Indian Academy of Sciences (India)

    (figure 7). We have also been able to bond Al2O3 to graphene by using AlCl3 as the reactant. The oxide film was amor- phous after calcination at 600. ◦. C. We have prepared chemically bonded magnetic Fe3O4 nanoparticles to graphene by functionalizing Fe3O4 by amine, then reacting it with graphene functionalized with.

  3. Characterization and Oxidative Addition Reactions of Different ...

    African Journals Online (AJOL)

    1HNMRdata and density functional theory calculations illustrate that the coordination of the metal centre in [M(bpt-NH)(cod)] (M = Rh or Ir) occurs via the amine moiety and a nitrogen of a pyridine ring. Keywords: Rhodium(I), Iridium(I), Triazole, Cyclooctadiene, Oxidative Addition, Methyl Iodide, DFT. Attached PDF and ...

  4. Roles of free radicals in type 1 phototherapeutic agents: aromatic amines, sulfenamides, and sulfenates.

    Science.gov (United States)

    Lin, Tien-Sung; Rajagopalan, Raghavan; Shen, Yuefei; Park, Sungho; Poreddy, Amruta R; Asmelash, Bethel; Karwa, Amolkumar S; Taylor, John-Stephen A

    2013-07-03

    Detailed analyses of the electron spin resonance (ESR) spectra, cell viability, and DNA degradation studies are presented for the photolyzed Type I phototherapeutic agents: aromatic amines, sulfenamides, and sulfenates. The ESR studies provided evidence that copious free radicals can be generated from these N-H, N-S, and S-O containing compounds upon photoirradiation with UV/visible light. The analyses of spectral data allowed us to identify the free radical species. The cell viability studies showed that these agents after exposure to light exert cytotoxicity to kill cancer cells (U937 leukemia cell lines HTC11, KB, and HT29 cell lines) in a dosage- and time-dependent manner. We examined a possible pathway of cell death via DNA degradation by a plasmid cleavage assay for several compounds. The effects of photosensitization with benzophenone in the presence of oxygen were examined. The studies indicate that planar tricyclic amines and sulfenamides tend to form π-electron delocalized aminyl radicals, whereas nonplanar ones tend to yield nitroxide radicals resulting from the recombination of aminyl radicals with oxygen. The ESR studies coupled with the results of cell viability measurements and DNA degradation reveal that planar N-centered radicals can provide higher potency in cell death and allow us to provide some insights on the reaction mechanisms. We also found the formation of azatropylium cations possessing high aromaticity derived from azepines can facilitate secondary electron transfer to form toxic O2(•-) radicals, which can further exert oxidative stress and cause cell death.

  5. Role of amine oxidase expression to maintain putrescine homeostasis in Rhodococcus opacus.

    Science.gov (United States)

    Foster, Alexander; Barnes, Nicole; Speight, Robert; Morris, Peter C; Keane, Mark A

    2013-04-10

    While applications of amine oxidases are increasing, few have been characterised and our understanding of their biological role and strategies for bacteria exploitation are limited. By altering the nitrogen source (NH4Cl, putrescine and cadaverine (diamines) and butylamine (monoamine)) and concentration, we have identified a constitutive flavin dependent oxidase (EC 1.4.3.10) within Rhodococcus opacus. The activity of this oxidase can be increased by over two orders of magnitude in the presence of aliphatic diamines. In addition, the expression of a copper dependent diamine oxidase (EC 1.4.3.22) was observed at diamine concentrations>1mM or when cells were grown with butylamine, which acts to inhibit the flavin oxidase. A Michaelis-Menten kinetic treatment of the flavin oxidase delivered a Michaelis constant (KM)=190μM and maximum rate (kcat)=21.8s(-1) for the oxidative deamination of putrescine with a lower KM (=60μM) and comparable kcat (=18.2s(-1)) for the copper oxidase. MALDI-TOF and genomic analyses have indicated a metabolic clustering of functionally related genes. From a consideration of amine oxidase specificity and sequence homology, we propose a putrescine degradation pathway within Rhodococcus that utilises oxidases in tandem with subsequent dehydrogenase and transaminase enzymes. The implications of PUT homeostasis through the action of the two oxidases are discussed with respect to stressors, evolution and application in microbe-assisted phytoremediation or bio-augmentation. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Radioguided parathyroidectomy for tertiary hyperparathyroidism.

    Science.gov (United States)

    Somnay, Yash R; Weinlander, Eric; Alfhefdi, Amal; Schneider, David; Sippel, Rebecca S; Chen, Herbert

    2015-05-15

    Tertiary hyperparathyroidism (3HPT) is defined as the persistent hyperproduction of parathyroid hormone and resulting hypercalcemia after renal transplantation. Here, we examine the utility of radioguided parathyroidectomy (RGP) in patients with 3HPT. We reviewed a prospective surgery database containing 80 3HPT patients who underwent RGP from January 2001-July 2014 at our institution. We evaluated patient demographics, operative management, radioguided neoprobe utilization, and operative outcomes. Data are reported as mean ± standard error of the mean. The mean age of the patients was 52 ± 1 y, and 46% were male. A total of 69 patients had hyperplasia and received subtotal parathyroidectomy, whereas 5 patients had double adenomas and 6 patients had single adenomas. The average calcium level among 3HPT patients was 10.8 ± 0.1 mg/dL preoperatively and 8.7 ± 0.1 mg/dL postoperatively. In vivo radioguided counts normalized to background counts averaged 145 ± 4%, whereas ex vivo counts normalized to background counts averaged 69 ± 5%. All but one ex vivo count was >20%. Ectopically located glands were successfully localized in 38 patients using the gamma probe. Ex vivo percentage did not correlate with parathyroid gland weight, preoperative parathyroid hormone, or preoperative calcium. Our radioguided approach achieved normocalcemia in 96% of 3HPT patients undergoing RGP; two patients developed recurrent disease. In this series, all enlarged parathyroid glands were localized and resected using the gamma probe. Thus, RGP reliably localizes adenomatous, hyperplastic, and ectopically located glands in patients with 3HPT, resulting in high cure rate after resection. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Pharmacological potential of biogenic amine-polyamine interactions beyond neurotransmission.

    Science.gov (United States)

    Sánchez-Jiménez, F; Ruiz-Pérez, M V; Urdiales, J L; Medina, M A

    2013-09-01

    Histamine, serotonin and dopamine are biogenic amines involved in intercellular communication with multiple effects on human pathophysiology. They are products of two highly homologous enzymes, histidine decarboxylase and l-aromatic amino acid decarboxylase, and transmit their signals through different receptors and signal transduction mechanisms. Polyamines derived from ornithine (putrescine, spermidine and spermine) are mainly involved in intracellular effects related to cell proliferation and death mechanisms. This review summarizes structural and functional evidence for interactions between components of all these amine metabolic and signalling networks (decarboxylases, transporters, oxidases, receptors etc.) at cellular and tissue levels, distinct from nervous and neuroendocrine systems, where the crosstalk among these amine-related components can also have important pathophysiological consequences. The discussion highlights aspects that could help to predict and discuss the effects of intervention strategies. © 2013 The Authors. British Journal of Pharmacology © 2013 The British Pharmacological Society.

  8. Ligands of low electronegativity in the VSEPR model: Molecules and ions isoelectronic with primary, secondary and tertiary amines

    Science.gov (United States)

    Cuthbertson, Alastair F.; Glidewell, Christopher

    Equilibrium geometries, skeletal bending force constants, and inversion barriers have been calculated for 15 molecules and ions of type (MH 3) 3YE1 n+ : the results are consistent with interpretations of molecular configurations based upon the second-order Jahn-Teller effect. Molecules and ions of types H 2NMH 3n+ and HN(MH 3) 2n+ are also described.

  9. Acetic acid recovery from fast pyrolysis oil. An exploratory study on liquid-liquid reactive extraction using aliphatic tertiary amines

    NARCIS (Netherlands)

    Mahfud, F. H.; van Geel, F. P.; Venderbosch, R. H.; Heeres, H. J.

    2008-01-01

    Flash pyrolysis oil or Bio-oil (BO), obtained by flash pyrolysis of lignocellulosic biomass, is very acidic in nature. The major component responsible for this acidity is acetic acid, present in levels up to 2-10 wt%. Here, we report an exploratory study on BO upgrading by reactive extraction of

  10. Determination of composition of complexes and calculation of their activity coefficients during extraction of some lanthanides with tertiary amine nitrates

    International Nuclear Information System (INIS)

    Ochkin, A.V.; Lazarevich, V.E.; Zagorets, P.A.; Dmitriev, A.Yu.

    1979-01-01

    Extraction of promethium and europium with trioctylammonium nitrate solutions in toluene and cerium extraction with solution of tridodecylammonium nitrate in CCl 4 has been studied as a function of extragent concentration. The dependence of distribution coefficient logarithm on the extragent concentration logarithm is non-linear. The solutions of tridodecylammonium nitrate in CCl 4 containing cerium or luthecium nitrates have been investigated ebulliometrically. The activity coefficients of the complex have been calculated. The ebulliometric data agree with extraction data for cerium only under assumption of the formation of (R 3 NH) 3 M(NO 3 ) 6 during extraction. Such complexes are weakly associated in CCl 4 and association grows when passing from cerium to lutecium

  11. Efficient CO2 capture by tertiary amine-functionalized ionic liquids through Li+-stabilized zwitterionic adduct formation

    Directory of Open Access Journals (Sweden)

    Zhen-Zhen Yang

    2014-08-01

    Full Text Available Highly efficient CO2 absorption was realized through formation of zwitterionic adducts, combining synthetic strategies to ionic liquids (ILs and coordination. The essence of our strategy is to make use of multidentate cation coordination between Li+ and an organic base. Also PEG-functionalized organic bases were employed to enhance the CO2-philicity. The ILs were reacted with CO2 to form the zwitterionic adduct. Coordination effects between various lithium salts and neutral ligands, as well as the CO2 capacity of the chelated ILs obtained were investigated. For example, the CO2 capacity of PEG150MeBu2N increased steadily from 0.10 to 0.66 (mol CO2 absorbed per mol of base through the formation of zwitterionic adducts being stabilized by Li+.

  12. Tertiary Logistics in the Focus of All Logistics

    OpenAIRE

    Ratko Zelenika; Mirjana Grèiæ; Helga Pavliæ Skender

    2008-01-01

    Trade logistics, traffic logistics, transport logistics and warehouse logistics are just some of the tertiary logistics which enables production processes of all economic sector products and services. Tertiary logistics representing the tertiary economic sector is the most sofisticated and the most important logistics due to the characteristics of the tertiary sector as a service sector that promotes business conditions in all economic sectors. Accordingly, tertiary logistics has a crucial ro...

  13. Amine Metabolism Is Influenced by Dietary Protein Source

    Directory of Open Access Journals (Sweden)

    Soumya K. Kar

    2017-09-01

    Full Text Available Growth in world population will inevitably leads to increased demand for protein for humans and animals. Protein from insects and blood plasma are being considered as possible alternatives, but more research on their nutritional quality and health effects is needed. Here, we studied the effect of dietary protein source on metabolism and metabolic amine profiles in serum and urine of mice. Groups of mice were fed semi-purified diets containing 300 g/kg of soybean meal, casein, partially delactosed whey powder, spray-dried plasma protein, wheat gluten meal, and yellow mealworm. Feed and water intake as well as body weight gain were measured for 28 days. After 14 and 28 days, serum and urine samples were collected for measurement of a large panel of amine metabolites. MetaboAnalyst 3.0 was used for analysis of the raw metabolic data. Out of 68 targeted amine metabolites, we could detect 54 in urine and 41 in blood serum. Dietary protein sources were found to have profound effects on host metabolism, particularly in systemic amine profiles, considered here as an endophenotype. We recommend serum over urine to screen for the amine metabolic endophenotype based on partial least squares discriminant analysis. We concluded that metabolites like alpha-aminobutyric acid and 1-methylhistidine are sensitive indicators of too much or too little availability of specific amino acids in the different protein diets. Furthermore, we concluded that amine metabolic profiles can be useful for assessing the nutritional quality of different protein sources.

  14. Biogenic amines in smear and mould-ripened cheeses

    Directory of Open Access Journals (Sweden)

    Pavel Pleva

    2014-02-01

    Full Text Available The aim of the study was the monitoring of six biogenic amines (histamine, tyramine, phenylethylamine, tryptamine, putrescine, and cadaverine and two polyamines (spermidine and spermine in 30 samples of dairy products purchased in the Czech Republic, namely in 15 samples of mould-ripened cheeses and in 15 samples of smear-ripened cheeses. A further goal was the microbiological analysis of the individual samples of cheeses (total count of microorganisms, number of enterobacteria, enterococci, lactic acid bacteria, yeasts and moulds. The monitored biogenic amines were analyzed by a high performance liquid chromatography equipped with a UV/VIS DAD detector. The amount of enterobacteria in fresh cheese exceeded 105 CFU.g‑1. In smear-ripened cheese flavourless (Romadur type, the amount was >103 CFU.g-1 and 104-105 CFU.g-1 in smear-ripened cheese with flavour. Biogenic amines were observed in two groups of blue cheeses (white veined cheese and blue veined cheese and smear-ripened cheeses. In both groups, there is a possibility of the presence of biogenic amines because the number of microorganisms and concentration of free amino acids increase during ripening. In ten samples of soft smear-ripening acid cheese and in smear-ripened cheese, the total content of biogenic amines were 22-1000 mg.kg-1 and in 5 samples of these cheeses, it was in range 1000-6000 mg.kg-1. The total amount of biogenic amines in the blue cheeses were in range 40-600 mg.kg-1. The presense of the tyramine was observed in the all analysed cheeses. The tyramine producing strains generated more than 900 mg.kg-1 of this biogenic amine. The production of tryptamine in the analysed cheeses was not proved by this study. The results of this study show that biogenic amines and polyamines are common in cheese. However, in some cases, they can pose a significant health danger for consumers. Any legislative control authority does not monitor them, as they are secondary metabolites even

  15. Mesoporous amine-bridged polysilsesquioxane for CO2 capture

    KAUST Repository

    Qi, Genggeng

    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 surface area or pore volume available for CO2 capture, leading to a CO2 capture capacity of 3.2 mmol g−1 under simulated flue gas conditions. The sorbent is readily regenerated at 100°C and exhibits good stability over repetitive adsorption-desorption cycling.

  16. Determination of Biogenic Amines in Different Shrimp Species for Export

    International Nuclear Information System (INIS)

    Myat Myat Thaw; Oo Aung; Aung Myint; Bisswanger, Hans

    2004-06-01

    This study is part of the project on the ''Quality Assurance of Different Shrimp Species for Export''. Local shrimp samples were collected from Ministry of Livestock and Fisheries and various private enterprises. Contents of biogenic amines were determined by using benzoyl chloride derivatization method with HPLC (reverse phase high performance liquid chromatography). Based on the biogenic amines, quality index of shrimps were correlated with freshness index so that the grade of shrimp samples can be classified as excellent, good, and acceptable. All sizes of shrimps such as extra large, large, medium were found to excceptable respectively

  17. Status of application of amines in US PWRs

    Energy Technology Data Exchange (ETDEWEB)

    Millett, P.J. [iSagacity, Half Moon Bay, CA (United States); Fruzzetti, K. [Electric Power Reserch Inst., Palo Alto, CA (United States)

    2005-10-01

    Prior to 1990, the majority of US units with pressurized water reactors (PWRs) were using ammonia as the primary pH control agent in secondary systems. Morpholine was used in one plant that did not employ condensate polishers. With the introduction of ethanolamine and other advanced amines in 1992, US PWRs could now get the benefit of improved pH control and still operate condensate polishers in the H-OH form. In this paper, the current practice with amines in US PWRs is reviewed with consideration for the optimization of pH control in secondary systems. (orig.)

  18. Amine functionalization of carbon nanotubes for the preparation of CNT based polyactide composites - A comparative study

    CSIR Research Space (South Africa)

    Kesavan Pillai, Sreejarani

    2011-11-01

    Full Text Available This work describes a comparison between two chemical functionalization strategies for the amine functionalization of carbon nanotubes (CNTs). In the first procedure, the CNTs are functionalized in direct amination process that avoids the use...

  19. Monomers for thermosetting and toughening epoxy resins. [glycidyl amine derivatives, propargyl-containing amines, and mutagenic testing of aromatic diamines

    Science.gov (United States)

    Pratt, J. R.

    1981-01-01

    Eight glycidyl amines were prepared by alkylating the parent amine with epichlorohydrin to form chlorohydrin, followed by cyclization with aqueous NaOH. Three of these compounds contained propargyl groups with postcuring studies. A procedure for quantitatively estimating the epoxy content of these glycidyl amines was employed for purity determination. Two diamond carbonates and several model propargly compounds were prepared. The synthesis of three new diamines, two which contain propargyloxy groups, and another with a sec-butyl group is in progress. These materials are at the dinitro stage ready for the final hydrogenation step. Four aromatic diamines were synthesized for mutagenic testing purposes. One of these compounds rapidly decomposes on exposure to air.

  20. Stabilization of Phenolic Radicals on Graphene Oxide : An XPS and EPR Study

    NARCIS (Netherlands)

    Stathi, Panagiota; Gournis, Dimitrios; Deligiannakis, Yiannis; Rudolf, Petra

    2015-01-01

    A graphene oxide-gallic acid hybrid material was synthesized by the immobilization of gallic acid (3,4,5-trihydroxobenzoic acid) on graphene oxide. The grafting was achieved via the formation of amide bonds between the amine groups on the organofunctionalized graphite oxide surface and the carboxyl

  1. A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

    DEFF Research Database (Denmark)

    Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth

    2016-01-01

    A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.......A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

  2. The Effect of the Aminic Substituent on the Thermal Decomposition of Cyclic Dithiocarbamates

    Directory of Open Access Journals (Sweden)

    Cavalheiro Éder T.G.

    1999-01-01

    Full Text Available Thermogravimetric and Differential Scanning Calorimetric investigation of the thermal behaviour of NH4+, Na+, Zn2+, Cd2+ e Pb2+ dithiocarbamates obtained from cyclic amines, is described under nitrogen and air atmospheres in order to investigate the effect of a cyclic ring on the mechanism of decomposition. Intermediates were identified by X-ray Diffraction analysis. Zn2+, Cd2+ e Pb2+ oxysulphates were detected under air atmosphere suggesting the thermal decomposition under these conditions as an alternating synthetic route to prepare those compounds. The final decomposition products were the metallic sulphides under N2 atmosphere while transition metal oxides and sodium sulphate were obtained under air. Melting enthalpies are also reported from DSC data.

  3. Electrochemical behaviour of gold modified with contaminated TMP amine adlayers studied by STM, CV, EPR

    Energy Technology Data Exchange (ETDEWEB)

    Krukowski, P. [Division of Physics and Technology of Nanometric Structures, Solid State Physics Department, University of Lodz, Pomorska 149/153, 90-236 Lodz (Poland)], E-mail: pkrukowski@std2.phys.uni.lodz.pl; Kowalczyk, P.J. [Division of Physics and Technology of Nanometric Structures, Solid State Physics Department, University of Lodz, Pomorska 149/153, 90-236 Lodz (Poland); Krzyczmonik, P. [Department of General and Inorganic Chemistry, University of Lodz, Narutowicza 68, 90-136 Lodz (Poland); Olejniczak, W.; Klusek, Z.; Puchalski, M. [Division of Physics and Technology of Nanometric Structures, Solid State Physics Department, University of Lodz, Pomorska 149/153, 90-236 Lodz (Poland); Gwozdzinski, K. [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland)

    2009-01-15

    Scanning tunnelling microscopy (STM), cyclic voltammetry (CV) and electron paramagnetic resonance spectroscopy (EPR) were used to investigate the influence of the TMP amine derivative on Au (1 1 1). The STM results show that the gold surface covered by the adlayer of the TMP derivative is easily modified (holes formation) after increasing the bias voltage to 0.5 V. The CV and EPR results show the electrochemical origin of observed STM topography changes. It is suggested that TMP could be oxidized to the nitroxyl TEMPO radical which adsorbs on Au in the form of an oxoammonium cation. Such an oxoammonium cation at the potential of 0.5 V forms a permanent complex of gold and the nitroxyl radical which could be easily desorbed during STM imaging.

  4. Where is Idi Amin? On violence, ethics and social memory in Africa ...

    African Journals Online (AJOL)

    The former Uganda dictator, Amin Dada, recently died in a Saudi hospital, after spending the last twenty four years of his life in exile. Given Amin's brutal dictatorship and the notoriety of his regime in. Uganda one would have expected that there has been a lot of public discussion about Amin's legacy and his continuing ...

  5. Mechanism of the N-Hydroxylation of Primary and Secondary Amines by Cytochrome P450

    DEFF Research Database (Denmark)

    Seger, Signe T.; Rydberg, Patrik; Olsen, Lars

    2015-01-01

    Cytochrome P450 enzymes (CYPs) metabolize alkyl- and arylamines, generating several different products. For the primary and secondary amines, some of these reactions result in hydroxylated amines, which may be toxic. Thus, when designing new drugs containing amine groups, it is important to be able...

  6. Laboratory evaluation of borate:amine:copper derivatives In wood for fungal decay protection

    Science.gov (United States)

    George Chen

    2011-01-01

    This study aimed to evaluate borate:amine:copper derivatives in wood for fungal decay protection as well as the permanence of copper and boron in wood. Each of four derivatives of borate:amine:copper prevented fungal decay in wood. Disodium tetraborate decahydrate (borax):amine:copper derivatives with 0.61-0.63% retention after water leaching prevented decay by...

  7. Thermal properties of wood reacted with a phosphorus pentoxide–amine system

    Science.gov (United States)

    Hong-Lin Lee; George C. Chen; Roger M. Rowell

    2004-01-01

    The objective of this research was to improve the fire-retardant properties of wood in one treatment using a phosphorus pentoxide–amine system. Phosphorus pentoxide and 16 amines including alkyl, halophenyl, and phenyl amines were compounded in N,N-dimethylformamide and the resulting solutions containing phosphoramides were reacted with wood. The characteristics of...

  8. Preparation and characterization of amine-functionalized sugarcane bagasse for CO2 capture.

    Science.gov (United States)

    Luo, Shihe; Chen, Siyu; Chen, Shuixia; Zhuang, Linzhou; Ma, Nianfang; Xu, Teng; Li, Qihan; Hou, Xunan

    2016-03-01

    A low-cost solid amine adsorbent for CO2 capture was prepared by using sugarcane bagasse (SB), a dominant agro-industrial residue in the sugar and alcohol industry as raw materials. In this preparation process, acrylamide was grafted on SB, and the grafted fiber was then aminated with different type of amine reagents to introduce primary and secondary amine groups onto the surface of SB fibers. The graft and amination conditions were optimized. The prepared solid amine adsorbent showed remarkable CO2 adsorption capacity and the adsorption capacity of the solid amine adsorbent could reach 5.01 mmol CO2/g at room temperature. The comparison of adsorption capacities of amine fibers aminated with various amination agents demonstrated that fibers aminated with triethylenetetramine would obtain higher adsorption capacities and higher amine efficiency. These adsorbents also showed good regeneration performance, the regenerated adsorbent could maintain almost the same adsorption capacity for CO2 after 10 recycles. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Blue Chitin columns for the extraction of heterocyclic amines from urine samples

    DEFF Research Database (Denmark)

    Bang, J.; Frandsen, Henrik Lauritz; Skog, K.

    2004-01-01

    During normal cooking of meat, a class of mutagenic/carcinogenic compounds called heterocyclic amines is formed. Heterocyclic amines are rapidly absorbed and metabolised in the human body, and for estimation of the intake of heterocyclic amines, it is useful to determinate their levels in the uri...

  10. Blue Chitin columns for the extraction of heterocyclic amines from urine samples

    DEFF Research Database (Denmark)

    Bang, J.; Frandsen, Henrik Lauritz; Skog, K.

    2004-01-01

    . Blue Chitin columns were used for the extraction and purification of heterocyclic amines from urine samples spiked with 14 different heterocyclic amines. The samples were analysed using LC-MS. The results show that Blue Chitin columns provide a straightforward and rapid means of extracting heterocyclic...... amines from urine samples, and that Blue Chitin column are also useful in the purification of urinary metabolites....

  11. Super absorbent conjugated microporous polymers: a synergistic structural effect on the exceptional uptake of amines.

    Science.gov (United States)

    Liu, Xiaoming; Xu, Yanhong; Guo, Zhaoqi; Nagai, Atsushi; Jiang, Donglin

    2013-04-21

    Conjugated microporous polymers exhibit a synergistic structural effect on the exceptional uptake of amines, whereas the dense porphyrin units facilitate uptake, the high porosity offers a large interface and the swellability boosts capacity. They are efficient in the uptake of both vapor and liquid amines, are applicable to various types of amines, and are excellent for cycle use.

  12. The effect of antioxidants on oxidative DNA damage induced by visible-light-irradiated camphorquinone/N,N-dimethyl-p-toluidine.

    Science.gov (United States)

    Winter, Kyle; Pagoria, Dustin; Geurtsen, Werner

    2005-09-01

    Previous investigations have found that visible-light (VL)-irradiated camphorquinone (CQ), in the presence of a tertiary amine (e.g., N,N-dimethyl-p-toluidine, DMT), generates reactive oxygen species and causes oxidative DNA damage in vitro. In this study, oxidative DNA damage produced by VL-irradiated CQ/DMT, in the presence and absence of antioxidants (glutathione, N-acetyl-L-cysteine (NAC), mannitol, vitamin C, and vitamin E), was measured by the conversion of PhiX-174 RF I supercoiled (SC) double-stranded plasmid DNA into open and linear forms. VL-irradiated CQ/DMT, lacking antioxidant, damaged 99.4 +/- 1% of the PhiX-174 RF I SC double-stranded plasmid DNA. Our results revealed that glutathione (10.0, 5.0, 2.5, 1.0, and 0.5 mm) and NAC (10.0, 5.0, and 2.5 mm) significantly (p < 0.02) reduced oxidative DNA damage produced by VL-irradiated CQ/DMT. Vitamin E, vitamin C, and mannitol were ineffective at reducing oxidative DNA damage produced by VL-irradiated CQ/DMT. Furthermore, vitamin E (10.0 and 5.0 mm) and vitamin C (10.0, 5.0, 2.5, 1.0, 0.5 mm) treatment significantly (p < 0.02) enhanced VL-irradiated CQ/DMT-induced oxidative DNA damage and caused significant (p < 0.001) DNA damage following VL-irradiation in the absence of CQ/DMT. As a result, future studies should evaluate whether glutathione and NAC effectively reduce or prevent oxidative damage induced by VL-irradiated CQ/DMT in vivo.

  13. Metal mediated amination of aromatic rings following carbon ...

    Indian Academy of Sciences (India)

    Administrator

    Metal-mediated reactions which result in addition of [NR]2– fragments belong to a reaction class of fundamental importance in chemistry in connection with carbon- nitrogen bond formation processes. In this presentation we wish to report our results on aromatic ring amination of a pendant phenyl ring of coordinated ...

  14. INTEGRASI ILMU-ILMU KEISLAMAN DALAM PERSPEKTIF M. AMIN ABDULLAH

    Directory of Open Access Journals (Sweden)

    Parluhutan Siregar

    2014-12-01

    Full Text Available The Integration of Islamic Sciences in the Perspective of M. Amin Abdullah. Criticism on the pattern of Islamic sciences development in Indonesia, especially at the level of Islamic religious higher education, has caught the attension of many critiques. This essay tries to analytically describe M. Amin Abdullah’s thought who promotes the concept of Islamic sciences integration. The writer maintains that Islamic sciences thus far, have still fragmentary in nature and have not yet interconnected with contemporary issues. As such, it is required to build the epistemology of integrated and interconnected science. The writer finds that theo-anthropocentric-integralistic epistemology of science of Amin Abdullah is developed against the backdrop of classification of science. His theory departs from the Qur’an and Sunnah, ‘Ulûm al-Dîn, al-Fikr al-Islâmy, and Dirâsah al-Islâmiyyah. Those categories of Islamic sciences are drawn by Amin Abdullah into four-layered concept mapping of spider web. Such epistemology combines all disciplines of social and religious sciences vis a vis contemporary issues.

  15. Isomerization of metastable amine radical cations by dissociation-recombination

    DEFF Research Database (Denmark)

    Pedersen, Anders Holmen; Nielsen, Christian Benedikt; Bojesen, Gustav

    2015-01-01

    The metastable molecular ions of primary aliphatic amines branched at C2 can isomerize by cleavage-recombination, thereby facilitating fragmentation reactions that require less energy than simple cleavage of the initial molecular ion. This process complements the reactions described by Audier...

  16. The repertoire of trace amine G-protein-coupled receptors

    DEFF Research Database (Denmark)

    Gloriam, David E.; Bjarnadóttir, Thóra K; Yan, Yi-Lin

    2005-01-01

    eukaryotic species for receptors similar to the mammalian trace amine (TA) receptor subfamily. We identified 18 new receptors in rodents that are orthologous to the previously known TA-receptors. Remarkably, we found 57 receptors (and 40 pseudogenes) of this type in the zebrafish (Danio rerio), while fugu...

  17. Metal mediated amination of aromatic rings following carbon ...

    Indian Academy of Sciences (India)

    Administrator

    Metal mediated amination of aromatic rings following carbon-nitrogen bond formation and the coordination chemistry thereof. AMRITA SAHA, AMIT K GHOSH, PARTHA MAJUMDAR and. SREEBRATA GOSWAMI. Department of Inorganic Chemistry, Indian Association for the Cultivation of. Science, Calcutta 700 032, India.

  18. Linear free energy relationship in reactions between diphenyl amine ...

    Indian Academy of Sciences (India)

    Unknown

    Minimal structural effects observed are attributed to the fact that the isokinetic temperature of the reaction is close to the reaction temperature. Keywords. Diphenyl amine; substituent effect; reaction constant; isokinetic temperature; linear free energy relationship. 1. Introduction. Nucleophilic substitution at the benzylic carbon ...

  19. Linear free energy relationship in reactions between diphenyl amine ...

    Indian Academy of Sciences (India)

    Rate of reaction between benzyl bromide and diphenyl amine is retarded by electron-donating groups and enhanced by electron-withdrawing groups present on the benzene ring of the substrate. Hammett's reaction constant of the reaction decreases with increase in temperature according to the equation,. \\rho = -11.92 + ...

  20. Preparation and adsorption property of aminated cross linking ...

    Indian Academy of Sciences (India)

    Administrator

    Preparation and adsorption property of aminated cross linking microbeads of GMA/EGDMA for bilirubin. ZHIPING CHEN, BAOJIAO GAO* and XIAOFENG YANG. Department of Chemical Engineering, North University of China, Taiyuan, 030051, China e-mail: gaobaojiao@126.com. MS received 17 December 2008; revised ...

  1. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides ...

    Indian Academy of Sciences (India)

    ... Journal of Chemical Sciences; Volume 128; Issue 6. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides/ Isocyanate leading to Guanidines/Urea derivatives formation. JAYEETA BHATTACHARJEE MITALI SACHDEVA INDRANI BANERJEE TARUN K PANDA. Regular Article Volume 128 Issue 6 June 2016 ...

  2. Monofunctional primary amine: A new class of organocatalyst for ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 3 ... A new class of organocatalysts involving a primary amine as the only functional group is developed for catalytic asymmetric aldol reaction of cyclohexanone/ cyclopentanone with various aryl aldehydes in thepresence of benzoic acid as an additive at ...

  3. Linear free energy relationship in reactions between diphenyl amine ...

    Indian Academy of Sciences (India)

    Unknown

    close to the reaction temperature. Keywords. Diphenyl amine; substituent effect; reaction constant; isokinetic temperature; linear free energy relationship. 1. Introduction. Nucleophilic substitution at the benzylic carbon is of broad synthetic utility and has received considerably significant attention from organic chemists. Funda ...

  4. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides ...

    Indian Academy of Sciences (India)

    DOI 10.1007/s12039-016-1096-y. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides/ ... A possible mechanism involving penta-coordinated zinc transition state for the catalytic reaction is presented. Keywords. Carbodiimide ... or receptors through hydrogen bonds and electrostatic interactions. They are ...

  5. incidence of biogenic amines in foods implications for the gambia

    African Journals Online (AJOL)

    Temechegn

    Health-wise biogenic amines play positive roles and ... BAs include, fish, fish products, meat products, eggs, cheeses, fermented vegetables, soybean ... The amount of. BAs present in foods, fruits and vegetables provides an index for measuring food quality [3]. In the tropics fish are caught in temperatures more than 200C.

  6. Efficient acetylation of primary amines and amino acids in ...

    Indian Academy of Sciences (India)

    Abstract. Acetyl chloride is one of the most commonly available and cheap acylating agent but its high reactivity and concomitant instability in water precludes its use to carry out acetylation in aqueous medium. The present methodology illustrates the efficient acetylation of primary amines and amino acids in brine solution ...

  7. Monofunctional primary amine: A new class of organocatalyst for ...

    Indian Academy of Sciences (India)

    for catalytic asymmetric aldol reaction of cyclohexanone/cyclopentanone with various aryl aldehydes in the presence of benzoic ... reactions gave excellent yield and good to excellent stereoselectivity, while secondary amines were found to have little or no ...... alytic anti-Mannich and syn-Aldol Reactions J. Am. Chem. Soc.

  8. Hydrothermal synthesis and characterisation of amine-templated ...

    African Journals Online (AJOL)

    Hydrothermal synthesis and characterisation of amine-templated metal phosphate framework. ... The complexes were thermally stable up to 3000C, after which the organic components starts decomposing. The solubility test in a wide spectrum of solvents (at room temperature) showed that the complexes were insoluble in ...

  9. Efficient acetylation of primary amines and amino acids in ...

    Indian Academy of Sciences (India)

    This effort represents the first efficient use of this most reactive but cheap acetylating agent to acetylate amines in excellent yields in aqueous medium. This is a potentially useful green chemical transformation where reaction takes place in environment-friendly brine solution leading to easy work-up and isolation of the ...

  10. METALCOMPLEXES OF TELLURIUM-CONTAINING AMINES AND AZOMETINES

    Directory of Open Access Journals (Sweden)

    G. M. Abakarov

    2014-01-01

    Full Text Available In this article methods of synthesis and reactionary ability of metalcomplexes of tellurium-containing amines, azometines, of a problem of competitive coordination with use of the principle of "soft" and "rigid" acids and the bases (R. Pearson.

  11. Experimental and theoretical investigations into the stability of cyclic aminals

    Directory of Open Access Journals (Sweden)

    Edgar Sawatzky

    2016-10-01

    Full Text Available Background: Cyclic aminals are core features of natural products, drug molecules and important synthetic intermediates. Despite their relevance, systematic investigations into their stability towards hydrolysis depending on the pH value are lacking.Results: A set of cyclic aminals was synthesized and their stability quantified by kinetic measurements. Steric and electronic effects were investigated by choosing appropriate groups. Both molecular mechanics (MM and density functional theory (DFT based studies were applied to support and explain the results obtained. Rapid decomposition is observed in acidic aqueous media for all cyclic aminals which occurs as a reversible reaction. Electronic effects do not seem relevant with regard to stability, but the magnitude of the conformational energy of the ring system and pKa values of the N-3 nitrogen atom.Conclusion: Cyclic aminals are stable compounds when not exposed to acidic media and their stability is mainly dependent on the conformational energy of the ring system. Therefore, for the preparation and work-up of these valuable synthetic intermediates and natural products, appropriate conditions have to be chosen and for application as drug molecules their sensitivity towards hydrolysis has to be taken into account.

  12. Understanding the political economy of contemporary Africa | Amin ...

    African Journals Online (AJOL)

    Further readings, offering a critique of 'post modernist' sociology and cultural studies (see, for instance, Samir Amin, The Liberal Virus, Pluto 2004, pages 19 et seq.) complete the picture of the ongoing intellectual disaster. CODESRIA constitutes an important intellectual locus conducting real open debates with a strong ...

  13. An innovative strategy for secondary side system lay-up using film-forming amines

    Energy Technology Data Exchange (ETDEWEB)

    Ramminger, U.; Drexler, A.; Fandrich, J. [AREVA NP GnbH, Erlangen (Germany)

    2012-07-01

    The major safety function of steam generators (SG) in pressurized reactors is well known as acting as a barrier between the radioactive primary side and the non-radioactive secondary side. The main reason for SG tube failure is known to be the accumulation of deposits contributing to formation of local aggressive conditions. Consequently the SG has to be kept as clean as possible and the corrosion product transport into the SG has to be minimized. In order to reach this target, plant operators are making worldwide huge efforts to protect plant systems against corrosion during standstill and outages. Especially in case of large component replacements campaigns like steam generator or fuel channel replacements which are linked to prolonged outages lay-up strategies become important. The use of surface active agents like film-forming amines (FFA) has become very popular in the fossil power plant sector, showing a decrease of corrosion product generation by improving the surface conditions. The adherent non wettable film built by FFA acts as a shield that limits the access of water and hydrated species to the metal or metal oxide surface. This barrier lowers the corrosion rate by inhibiting the mass transfer between surface and solution. The hydrocarbon chain imparts a hydrophobic character while the amine group bounds to the metal. Advantages of the FFA application for lay-up: Significant reduction of lay-up efforts; Long-term stability of the protective film even in aggressive environmental conditions; No influence on existing oxide layers; No negative influence on plant operation and performance; No environmental hazards of the waste water after system lay-up. Nevertheless application of film-forming amines are applied in fossil fired power plants, the requirement of nuclear power reactors are more ambitious. This paper deals with a possible lay-up application scenario in pressurized heavy water reactors. The proposed lay-up strategy will consider AREVA

  14. The acidity function of diethyl amine and triethyl amine in aqueous solutions; Funcion de acidez de disoluciones de dietilamina y trietilamina

    Energy Technology Data Exchange (ETDEWEB)

    Verdu, J. [Departamento de Quimica Fisica, Universidad de Valladolid (Spain)

    1995-12-31

    The acidity function of diethyl amine (DEA) and triethyl amine (TEA) in aqueous solutions, ethanolic solutions and ethanol-water mixtures has been determined spectrophotometrically, using as indicator butanol 2,4-dinitrophenylhydrazine. The acidity function lies within the range from 12.5 to 14.2. The basicity of solutions increases with the water content, and the order of basicity of the amines is TEA

  15. Transglutaminase-catalyzed amination of pea protein peptides using the biogenic amines histamine and tyramine.

    Science.gov (United States)

    Lu, Xinyao; Hrynets, Yuliya; Betti, Mirko

    2017-06-01

    Biogenic amines (BAs) are produced by the enzymatic decarboxylation of amino acids, and are well-known for their toxicity to humans. This study describes a new method using microbial transglutaminase (MTGase) to covalently link BAs such as histamine (HIS) and tyramine (TYR) to the glutamine residues of alcalase-hydrolyzed pea protein (PPH). The incubation of PPH and HIS and TYR in the presence of MTGase at 37 °C led to the formation of conjugates, as determined by liquid chromatography, after derivatization with dansyl chloride. Seventy-six % of HIS and 65% of TYR were covalently incorporated to PPH by MTGase. The incubation of PPH and TYR in the presence of MTGase exhibited a 52% DPPH radical scavenging activity at 10 mg mL -1 . Conjugation via MTGase improved the antioxidant status by reducing lipid peroxidation. This study emphasizes that the application of MTGase can effectively reduce histamine and tyramine content while simultaneously enhancing antioxidative capacity of PPH. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  16. Poly(amido amine)s as gene delivery vectors: effects of quaternary nicotinamide moieties in the side chains

    NARCIS (Netherlands)

    Mateos timoneda, Miguel; Lok, Martin C.; Hennink, Wim E.; Feijen, Jan; Engbersen, Johannes F.J.

    2008-01-01

    To evaluate the effect of quaternary nicotinamide pendant groups on gene delivery properties, a series of poly(amido amine) (co)polymers were synthesized by Michael addition polymerization of N, N-cystaminebisacrylamide with variable ratios of 1-(4-aminobutyl)-3-carbamoylpyridinium (Nic-BuNH2), and

  17. Analysis of a Buchwald-Hartwig amination: reaction for pharmaceutical production

    DEFF Research Database (Denmark)

    Christensen, Henrik

    is to increase the understanding of the chem­ical reaction mechanisms and kinetics for the Buchwald-Hartwig amination reaction. Also, to develop methods for application of these mechanisms and kinetics to optimize and scale up an organic synthesis to an industrial phar­maceutical production. The Buchwald......The Buchwald-Hartwig amination reaction is widely used in the production of N-arylated amines in the pharmaceutical industry. The reaction is betweenan aryl halogen and a primary or secondary amine in the presence of a base and a homogeneous catalyst giving the desired N-arylated amine. Due to mild...

  18. Analysis of a Buckwald-Hartwig amination: reaction for pharmaceutical production

    DEFF Research Database (Denmark)

    Christensen, Henrik; Kiil, Søren; Dam-Johansen, Kim

    is to increase the understanding of the chem­ical reaction mechanisms and kinetics for the Buchwald-Hartwig amination reaction. Also, to develop methods for application of these mechanisms and kinetics to optimize and scale up an organic synthesis to an industrial phar­maceutical production. The Buchwald......The Buchwald-Hartwig amination reaction is widely used in the production of N-arylated amines in the pharmaceutical industry. The reaction is betweenan aryl halogen and a primary or secondary amine in the presence of a base and a homogeneous catalyst giving the desired N-arylated amine. Due to mild...

  19. Toward rational design of amine solutions for PCC applications: the kinetics of the reaction of CO2(aq) with cyclic and secondary amines in aqueous solution.

    Science.gov (United States)

    Conway, William; Wang, Xiaoguang; Fernandes, Debra; Burns, Robert; Lawrance, Geoffrey; Puxty, Graeme; Maeder, Marcel

    2012-07-03

    The kinetics of the fast reversible carbamate formation reaction of CO(2)(aq) with a series of substituted cyclic secondary amines as well as the noncyclic secondary amine diethanolamine (DEA) has been investigated using the stopped-flow spectrophotometric technique at 25.0 °C. The kinetics of the slow parallel reversible reaction between HCO(3)(-) and amine has also been determined for a number of the amines by (1)H NMR spectroscopy at 25.0 °C. The rate of the reversible reactions and the equilibrium constants for the formation of carbamic acid/carbamate from the reactions of CO(2) and HCO(3)(-) with the amines are reported. In terms of the forward reaction of CO(2)(aq) with amine, the order with increasing rate constants is as follows: diethanolamine (DEA) < morpholine (MORP) ~ thiomorpholine (TMORP) < N-methylpiperazine (N-MPIPZ) < 4-piperidinemethanol (4-PIPDM) ~ piperidine (PIPD) < pyrrolidine (PYR). Both 2-piperidinemethanol (2-PIPDM) and 2-piperidineethanol (2-PIPDE) do not form carbamates. For the carbamate forming amines a Brønsted correlation relating the protonation constant of the amine to the carbamic acid formation rate and equilibrium constants at 25.0 °C has been established. The overall suitability of an amine for PCC in terms of kinetics and energy is discussed.

  20. Alkane oxidation by osmium tetroxide.

    Science.gov (United States)

    Bales, Brian C; Brown, Peter; Dehestani, Ahmad; Mayer, James M

    2005-03-09

    Aqueous alkaline OsO4 at 85 degrees C oxidizes saturated alkanes, including primary, secondary, and tertiary C-H bonds. Isobutane affords tert-butanol in quantitative yield based on consumed OsO4. Cyclohexane is oxidized to a mixture of adipate and succinate. Ethane and propane are oxidized to acetate, which itself is further oxidized under the reaction conditions. A few turnovers of isobutane oxidation have been accomplished using NaIO4 as the terminal oxidant. The alkane oxidation is an example of ligand accelerated catalysis, as hydroxide binding to OsO4 is required for reaction. A concerted mechanism involving [3+2] addition of a C-H bond to two oxo groups of OsO4(OH)- is suggested, analogous to the pathways for dihydroxylation of alkenes by OsO4(L) and for addition of H2 to OsO4(L).

  1. Milestones and recent discoveries on cell death mediated by mitochondria and their interactions with biologically active amines.

    Science.gov (United States)

    Grancara, Silvia; Ohkubo, Shinji; Artico, Marco; Ciccariello, Mauro; Manente, Sabrina; Bragadin, Marcantonio; Toninello, Antonio; Agostinelli, Enzo

    2016-10-01

    Mitochondria represent cell "powerhouses," being involved in energy transduction from the electrochemical gradient to ATP synthesis. The morphology of their cell types may change, according to various metabolic processes or osmotic pressure. A new morphology of the inner membrane and mitochondrial cristae, significantly different from the previous one, has been proposed for the inner membrane and mitochondrial cristae, based on the technique of electron tomography. Mitochondrial Ca(2+) transport (the transporter has been isolated) generates reactive oxygen species and induces the mitochondrial permeability transition of both inner and outer mitochondrial membranes, leading to induction of necrosis and apoptosis. In the mitochondria of several cell types (liver, kidney, and heart), mitochondrial oxidative stress is an essential step in the induction of cell death, although not in brain, in which the phenomenon is caused by a different mechanism. Mitochondrial permeability transition drives both apoptosis and necrosis, whereas mitochondrial outer membrane permeability is characteristic of apoptosis. Adenine nucleotide translocase remains the most important component involved in membrane permeability, with the opening of the transition pore, although other proteins, such as ATP synthase or phosphate carriers, have been proposed. Intrinsic cell death is triggered by the release from mitochondria of proteic factors, such as cytochrome c, apoptosis inducing factor, and Smac/DIABLO, with the activation of caspases upon mitochondrial permeability transition or mitochondrial outer membrane permeability induction. Mitochondrial permeability transition induces the permeability of the inner membrane in sites in contact with the outer membrane; mitochondrial outer membrane permeability forms channels on the outer membrane by means of various stimuli involving Bcl-2 family proteins. The biologically active amines, spermine, and agmatine, have specific functions on mitochondria

  2. Alteration of amine oxidase activity in the adipose tissue of obese subjects.

    Science.gov (United States)

    Visentin, Virgile; Prévot, Danielle; De Saint Front, Véronique Durand; Morin-Cussac, Nathalie; Thalamas, Claire; Galitzky, Jean; Valet, Philippe; Zorzano, Antonio; Carpéné, Christian

    2004-03-01

    To explore the activity of monoamine oxidases (MAOs) and semicarbazide-sensitive amine oxidases (SSAOs) in adipose tissue and blood of lean and moderately obese subjects and to study whether there is a link between these hydrogen peroxide-generating enzymes and blood markers of oxidative stress. Nine obese male subjects (BMI 32.6 +/- 0.4 kg/m(2)) and nine controls (BMI 23.4 +/- 0.5) of 24- to 40-year-old subjects were included in the study. MAO and SSAO activities were measured on microbiopsies of abdominal subcutaneous adipose tissue by quantifying (14)C-tyramine and (14)C-benzylamine oxidation. Levels of soluble SSAO, lipid peroxidation products, and antioxidant agents were measured in plasma, whereas cytoprotective enzymes were determined in blood lysates. The high MAO activity found in adipose tissue was diminished by one-half in obese subjects (maximum initial velocity of 1.2 vs. 2.3 nmol tyramine oxidized/mg protein/min). There was no change in SSAO activity, either under its adipose tissue-bound or plasma-soluble form. Plasma levels of lipid peroxidation products and antioxidant vitamins remained unmodified, as well as erythrocyte antioxidant enzymes, whereas circulating triglycerides, insulin, and leptin were increased. Although they already exhibited several signs of endocrino-metabolic disorders, the obese men did not exhibit the increase in blood markers of oxidative stress or the decrease in antioxidant defenses reported to occur in very obese or diabetic subjects. The reduced MAO and the unchanged SSAO activities found in obesity suggest that these hydrogen peroxide-generating enzymes expressed in adipocytes are probably not involved in the onset of the oxidative stress found in severe obesity and/or in its complications.

  3. Sexual promiscuity among female undergraduates in tertiary ...

    African Journals Online (AJOL)

    The study focused on sexual promiscuity among female undergraduates and the attendant health implications. It was carried out in the tertiary institutions in Imo State using 415 final year degree students drawn from four institutions in the State. Three research questions were formulated to guide the study. The design was a ...

  4. Indigenous Students in the Tertiary Education Sector

    Science.gov (United States)

    Bandias, Susan; Fuller, Don; Larkin, Steven

    2014-01-01

    Important recent objectives of indigenous education policy in Australia have been aimed at redressing indigenous economic and social disadvantage through increasing student retention, progression and completion rates in both compulsory and post-compulsory education. The two sectors of the tertiary education system, vocational education and…

  5. American Tertiary mollusks of the genus Clementia

    Science.gov (United States)

    Woodring, W.P.

    1927-01-01

    Aside from its value as an aid in determining the age of Tertiary beds, the chief interest of the genus Clementia lies in the anomalous features of its present and former distribution. An attempt is made in this paper to trace its geologic history, to point out its paleobiologic significance, and to describe all the known American Tertiary species. The fossils from Colombia used in preparing this report were collected during explorations made under the direction of Dr. 0. B. Hopkins, chief geologist of the Imperial Oil Co. (Ltd.), who kindly donated them to the United States National Museum. Dr. T. Wayland Vaughan, of the Scripps Institution of Oceanography, furnished information relating to specimens collected by him in Mexico. Dr. Bruce L. Clark, of the University of California; Dr. G. Dallas Hanna, of the California Academy of Sciences; Dr. H. A. Pilsbry, of the Philadelphia Academy of Natural Sciences; and Dr. W. D. Matthew, of the American Museum of Natural History, generously loaned type specimens and other material. Doctor Clark and Doctor Hanna also gave information concerning the Tertiary species from California. Mr. Ralph B. Stewart, of the University of California, read the manuscript, and I have taken advantage of his suggestions. I am also indebted to Mr. L. R. Cox, of the British Museum, for information relating to the fossil species from Persia, Zanzibar, and Burma, and to Dr. Axel A. Olsson, of the International Petroleum Co., for data concerning undescribed Tertiary species from Peru.

  6. Misconception of emergency contraception among tertiary school ...

    African Journals Online (AJOL)

    Objective: To assess the degree of awareness and use of emergency contraception among tertiary school students in Akwa Ibom State, Nigeria. Design: A self-administered questionnaire survey. Setting: The Akwa Ibom State Polytechnic, Ikot Osurua, located on the outskirts of Ikot Ekpene local government area between ...

  7. RELIGIOUS EXTREMISM AS A CHALLENGE TO TERTIARY ...

    African Journals Online (AJOL)

    IK

    2016-07-01

    Jul 1, 2016 ... tertiary institutions in Nigeria, through General Studies, should educate the youth to be self- reliant so that they are not lured by religious extremists to achieve their political and economic agenda. Publication of well researched papers and books that contribute to the study of religions and cultures should be ...

  8. Recruitment Of International Students Into Cameroon Tertiary ...

    African Journals Online (AJOL)

    This paper highlights the importance of Cameroon\\'s tertiary institutions\\' cooperation links with other African Universities given the rebirth of Organisation of African Unity as African Union, and the New Partnership for Africa Development (NEPAD). The present system of recruiting international students is haphazardly been ...

  9. Modelling the harmonized tertiary Institutions Salary Structure ...

    African Journals Online (AJOL)

    This paper analyses the Harmonized Tertiary Institution Salary Structure (HATISS IV) used in Nigeria. The irregularities in the structure are highlighted. A model that assumes a polynomial trend for the zero step salary, and exponential trend for the incremental rates, is suggested for the regularization of the structure.

  10. Economics of Tertiary Education - Challenges and dynamics of the public tertiary education in Albania

    Directory of Open Access Journals (Sweden)

    Gledian Llatja

    2016-07-01

    Full Text Available The tertiary education is a critic mechanism for the socio-economic progress, for individuals who aspire a brighter future and it is also considered an important catalyzer of the economic mobility (Department of Treasury and Department of Education, 2012, 2. Based on the positive role and impact that the tertiary education has on the sustainable development, President Obama once stated that it is of damage to treat education as a luxurious public service. In line with the general considerations about the tertiary education in the U.S. the parallel comparison with Albania comes as a direct interpretation of utopia in the education policy-making. As policies are usually drafted based on data and findings, in the case of Albania there is a lack of data on expenses on tertiary education as share of GDP. This stands also for the main limitation of the paper.

  11. Tertiary Education in the Czech Republic: The Pathway to Change

    Science.gov (United States)

    Pesik, Richard; Gounko, Tatiana

    2011-01-01

    This article analyzes recent policy proposals to reform Czech tertiary education. A brief overview of the evolution of Czech tertiary education presents the background against which emerging policy trends in education are examined. We relate the changes in tertiary education to the policy framework and recommendations of the OECD, underpinned by…

  12. Separation of boron isotopes by aminated polystyrene-divinylbenzene resins

    International Nuclear Information System (INIS)

    Choi, Sei Young; Baek, Joong Hyun; Kim, Hee Lake

    1991-01-01

    Separation of boron isotopes was carried out by using nonporous aminated polystyrene-divinylbenzene as ion exchangers. After 0.1 M boric acid containing 10% sucrose solution was passed through the column, the boric acid band formed on the column was eluted with pure water of 50% methyl alchol water solution. The contents of boric acid of the fraction were determined with neutralization titrations. The relative mass of boron isotopes of the fractions was analyzed on a mass spectrometer. From these results, we found that separation factors for porous aminated polystyrene-divinylbenzene ion exchanger is larger than value of non porous ion exchanger, and then separation factors for 50%-methanol as eluting agent is larger than the value of pure water. (Author)

  13. Alpha-(trifluoromethyl)amine derivatives via nucleophilic trifluoromethylation of nitrones.

    Science.gov (United States)

    Nelson, D W; Owens, J; Hiraldo, D

    2001-04-20

    (Trifluoromethyl)trimethylsilane (TMSCF(3)) reacts with nitrones to afford alpha-(trifluoromethyl)hydroxylamines protected as O-trimethylsilyl ethers. Potassium t-butoxide initiates the nucleophilic trifluoromethylation. The reaction works best with alpha,N-diaryl nitrones, and the conditions are compatible with a range of substituents on the aryl groups. Acidic deprotection of the nitrone/TMSCF(3) adducts generates alpha-(trifluoromethyl)hydroxylamines. Catalytic hydrogenation of the adducts produces alpha-(trifluoromethyl)amines. Nitrone/TMSCF(3) adducts with strong electron-withdrawing groups on the alpha-aryl ring or heterocyclic alpha-aryl groups undergo an elimination/addition sequence to generate alpha,alpha-bis(trifluoromethyl)amines. Nitrones with alkyl groups bound directly to the 1,3-dipolar moiety fail to react with TMSCF(3), but trifluoromethylation of beta,gamma-unsaturated nitrones followed by reduction of the double bond can circumvent this limitation.

  14. Optimization of amine-terminated polyacrylonitrile synthesis and characterization

    Directory of Open Access Journals (Sweden)

    Mohamed H. El-Newehy

    2014-04-01

    Full Text Available Amine-terminated PANs were prepared in two steps. The first step includes free radical polymerization of acrylonitrile (AN using initiator pair of ammonium persulfate and sodium thiosulfate as redox system. In the second step, the amino groups were introduced through the reaction of polyacrylonitrile with excess of different diamines (10-fold including ethylenediamine (EDA, hexamethylenediamine (HMDA and octamethylenediamine (OMDA, to yield PAN–EDA, PAN–HMDA and PAN–OMDA, respectively. Optimization of the amine-terminated PANs synthesis was carried out at different temperatures (30–90 °C and different time intervals (4–24 h. In addition, the introduction of the amino group was followed by the piperidine test and recording of the FT-IR spectra. All polymers were characterized by, 1H NMR spectra, thermogravimetric analysis (TGA, and FT-IR spectra.

  15. Asymmetric trienamine catalysis: new opportunities in amine catalysis.

    Science.gov (United States)

    Kumar, Indresh; Ramaraju, Panduga; Mir, Nisar A

    2013-02-07

    Amine catalysis, through HOMO-activating enamine and LUMO-activating iminium-ion formation, is receiving increasing attention among other organocatalytic strategies, for the activation of unmodified carbonyl compounds. Particularly, the HOMO-raising activation concept has been applied to the greatest number of asymmetric transformations through enamine, dienamine, and SOMO-activation strategies. Recently, trienamine catalysis, an extension of amine catalysis, has emerged as a powerful tool for synthetic chemists with a novel activation strategy for polyenals/polyenones. In this review article, we discuss the initial developments of trienamine catalysis for highly asymmetric Diels-Alder reactions with different dienophiles and emerging opportunities for other types of cycloadditions and cascade reactions.

  16. AECL--Sulzer amine process for heavy water

    International Nuclear Information System (INIS)

    Wynn, N.P.

    1978-01-01

    A heavy water process based on isotopic exchange between hydrogen and methylamine and methylamine and water has been developed by Sulzer and Atomic Energy of Canada. Deuterium source is the synthesis gas stream of an ammonia plant. Deuterium enrichment is achieved by bithermal amine-hydrogen exchange; however, preliminary enrichment is made to occur in the reformers of the ammonia plant by using the steam reforming process as the decomposition step of a monothermal enrichment stage. This feature, coupled with the high value of the separation factor achievable with hydrogen-amine exchange, allows a high deuterium yield without the use of hydrogen recycle in the extraction stage. Design work has been based on pilot tests of the key process steps using industrial contacting equipment. 8 figures

  17. Debromination of endo-(+)-3-bromocamphor with primary amines

    Energy Technology Data Exchange (ETDEWEB)

    Markovic, Svetlana; Markovic, Violeta; Joksovic, Milan D.; Joksovic, Ljubinka, E-mail: ljubinka@kg.ac.rs [Department of Chemistry, Faculty of Science, University of Kragujevac (Serbia); Todorovic, Nina [Institute for Chemistry, Technology and Metallurgy, Belgrade (Serbia); Divjakovic, Vladimir [Department of Physics, University of Novi Sad (Serbia); Trifunovic, Snezana [Faculty of Chemistry, University of Belgrade, Belgrade, (Serbia)

    2013-07-15

    Reductive debromination of endo-(+)-3-bromocamphor with different primary amines followed by imine formation was investigated. This reaction requires simple experimental procedure without any organic solvent, metal or conventional reducing agent. A strong influence of amine polarity on the efficacy of debromination process was observed, and ethanolamine and ethylene diamine having sufficiently high boiling points can debrominate 3-bromocamphor giving corresponding camphanimines in good isolated yields. The mechanisms of debromination of 3-bromocamphor with ethanolamine and n-hexylamine were investigated at the B3LYP/6-311+G(d,p) level of theory. The radical mechanism was revealed, and it was shown that the reaction with more polar ethanolamine is energetically more favorable. (author)

  18. Praseodymium and neodymium separation by extraction with amines

    International Nuclear Information System (INIS)

    Benesova, M.; Kuca, L.; Sraier, V.

    1987-01-01

    Steady-state data were obtained for the separation of praseodymium and neodymium by extractions using different types of amines. The best is the system of a 30% solution of quaternary ammonium salt Aliquat 336 in xylene with a >3 M aqueous solution of NH 4 NO 3 where, at unit size of Pr and Nd partition ratios, the values of the Pr/Nd separation coefficient are within the region of 1.7 to 2.0. Pr cannot be separated from Nd by extraction with primary amine Primene-JMT from a sulfate medium. Separation factors in extraction with tri-n-octylamine have values of approx. 1.8 but the partition ratios of the two rare earth elements are less than 1. (author). 5 tabs., 5 refs

  19. Convenient Reductive Methylation of Amines with Carbonates at Room Temperature.

    Science.gov (United States)

    Li, Yuehui; Sorribes, Iván; Vicent, Cristian; Junge, Kathrin; Beller, Matthias

    2015-11-16

    Methylation of amines is a fundamental and commonly used reaction in organic synthesis. Many methods are known including various reductive methylations using formaldehyde, formic acid, or carbon dioxide in the presence of reductants. However, several of these methods suffer from limited substrate scope and chemoselectivity because of the different nucleophilicities of substrates. In this respect, the combination of carbonates and hydrosilanes is a valuable methylation source in the presence of Pt-based catalysts. This highly tunable method allows for methylation of both aromatic and aliphatic amines, and chemoselective methylation of aminoalcohols and diamines. Notably, the in situ-formed catalyst can also be used for the reduction of carbonates to methanol at room temperature. Mechanistic insights on intermediates formed during the reaction pathway were obtained by using ESI mass spectrometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Extraction of beryllium sulfate by a long chain amine

    International Nuclear Information System (INIS)

    Etaix, E.S.

    1968-01-01

    The extraction of sulfuric acid in aqueous solution by a primary amine in benzene solution, 3-9 (diethyl) - 6-amino tri-decane (D.E.T. ) - i.e., with American nomenclature 1-3 (ethyl-pentyl) - 4-ethyl-octyl amine (E.P.O.) - has made it possible to calculate the formation constants of alkyl-ammonium sulfate and acid sulfate. The formula of the beryllium and alkyl-ammonium sulfate complex formed in benzene has next been determined, for various initial acidity of the aqueous solution. Lastly, evidence has been given of negatively charged complexes of beryllium and sulfate in aqueous solution, through the dependence of the aqueous sulfate ions concentration upon beryllium extraction. The formation constant of these anionic complexes has been evaluated. (author) [fr

  1. Amine enriched solid sorbents for carbon dioxide capture

    Science.gov (United States)

    Gray, McMahan L.; Soong, Yee; Champagne, Kenneth J.

    2003-04-15

    A new method for making low-cost CO.sub.2 sorbents that can be used in large-scale gas-solid processes. The new method entails treating a solid substrate with acid or base and simultaneous or subsequent treatment with a substituted amine salt. The method eliminates the need for organic solvents and polymeric materials for the preparation of CO.sub.2 capture systems.

  2. Electrophysiological effects of trace amines on mesencephalic dopaminergic neurons

    Directory of Open Access Journals (Sweden)

    Ada eLedonne

    2011-07-01

    Full Text Available Trace amines (TAs are a class of endogenous compounds strictly related to classic monoamine neurotransmitters with regard to their structure, metabolism and tissue distribution. Although the presence of TAs in mammalian brain has been recognized for decades, until recently they were considered to be by-products of amino acid metabolism or as ‘false’ neurotransmitters. The discovery in 2001 of a new family of G protein-coupled receptors (GPCRs, namely trace amines receptors, has re-ignited interest in TAs. In particular, two members of the family, trace amine receptor 1 (TA1 and trace amine receptor 2 (TA2, were shown to be highly sensitive to these endogenous compounds. Experimental evidence suggests that TAs modulate the activity of catecholaminergic neurons and that TA dysregulation may contribute to neuropsychiatric disorders, including schizophrenia, attention deficit hyperactivity disorder, depression and Parkinson’s disease, all of which are characterised by altered monoaminergic networks. Here we review recent data concerning the electrophysiological effects of TAs on the activity of mesencephalic dopaminergic neurons. In the context of recent data obtained with TA1 receptor knockout mice, we also discuss the mechanisms by which the activation of these receptors modulates the activity of these neurons. Three important new aspects of TAs action have recently emerged: (a inhibition of firing due to increased release of dopamine; (b reduction of D2 and GABAB receptor-mediated inhibitory responses (excitatory effects due to dysinhibition; and (c a direct TA1 receptor-mediated activation of GIRK channels which produce cell membrane hyperpolarization. While the first two effects have been well documented in our laboratory, the direct activation of GIRK channels by TA1 receptors has been reported by others, but has not been seen in our laboratory (Geracitano et al., 2004. Further research is needed to address this point, and to further

  3. Addition of amines to naphthoquinone in water and solid phase

    International Nuclear Information System (INIS)

    Martinez, Sabrina T.; Silva, Barbara V.; Pinto, Angelo C.; Ferreira, Vitor F.; Silva, Fernando de Carvalho da

    2012-01-01

    Considering all the aspects of the principles of green chemistry, we present herein the addition reactions of amines to 1,4-naphthoquinone in water as solvent and also in solid phase. These reactions resulted in very colorful products that were easily monitored by thin layer chromatography and consequently easy to separate. Therefore, they are interesting experiments for experimental organic chemistry in the classrooms or in the laboratories. (author)

  4. Amides derived from heteroaromatic amines and selected steryl hemiesters

    Czech Academy of Sciences Publication Activity Database

    Bildziukevich, Uladzimir; Rárová, L.; Šaman, David; Havlíček, Libor; Drašar, P.; Wimmer, Zdeněk

    2013-01-01

    Roč. 78, č. 14 (2013), s. 1347-1352 ISSN 0039-128X R&D Projects: GA ČR(CZ) GAP503/11/0616 Grant - others:GA MŠk(CZ) ED0007/01/01 Program:ED Institutional support: RVO:61389030 ; RVO:61388963 Keywords : Heteroaromatic amine * Cholesterol * Lanosterol Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 2.716, year: 2013

  5. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    properties to the widely discussed gold catalysts. Literature results were summarized for alcohol oxidation, epoxidation, amine oxidation, phenol hydroxylation, silane and sulfide oxidation, (side-chain) oxidation of alkyl aromatic compounds, hydroquinone oxidation and cyclohexane oxidation. It was found...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...... contact while leaching could be excluded. The silver catalyst was most active when calcined over a short time at 500 °C potentially due to the formation of silver-oxygen species. Removal of these species might be a deactivation mechanism as was suggested by X-ray absorption spectroscopy (XAS) analysis...

  6. Joint effects of nine antidepressants on Raphidocelis subcapitata and Skeletonema marinoi: A matter of amine functional groups.

    Science.gov (United States)

    Minguez, Laetitia; Bureau, Ronan; Halm-Lemeille, Marie-Pierre

    2018-03-01

    Antidepressants are among the most prescribed pharmaceuticals throughout the world. Their presence has already been detected in several aquatic ecosystems worldwide and their effects on non-target organisms justify the growing concern of both the public and regulatory authorities. These emerging pollutants do not occur as isolated compounds but rather as multi-component mixtures, which may lead to increased adverse effects compared to individual compounds. Freshwater and marine algae seem particularly sensitive to pharmaceuticals, including antidepressants. Studies assessing the toxicity of antidepressant mixture to algae focused mainly on binary mixtures of selective serotonin reuptake inhibitors. In the present experiment, the freshwater algae Raphidocelis subcapitata (formerly known as Pseudokirchneriella subcapitata) and the marine diatom Skeletonema marinoi were exposed to equitoxic mixtures of 9 antidepressants (fluvoxamine, fluoxetine, sertraline, duloxetine, venlafaxine, clomipramine, amitriptyline, and citalopram) at different concentrations. The growth inhibition was measured. Results showed that the toxicity of this mixture was higher than the effects of each individual component, highlighting simple additivity or synergistic effects, whereas tested concentrations were below the 10% inhibition concentration (IC 10 ) of each compound. Moreover, the QSAR analysis highlighted that antidepressants would act through narcosis (non-specific mode of action) towards the two species of algae. However, more specific effects can be observed by differentiating compounds with a primary/secondary amine from those with a tertiary amine. These mixture effects on algal species have to be assessed, especially since any impacts on phytoplankton could ultimately impact higher trophic levels (less food, secondary poisoning). Copyright © 2018 Elsevier B.V. All rights reserved.

  7. Metabolism and genotoxicity of aromatic amines in aquatic organisms

    International Nuclear Information System (INIS)

    Knezovich, J.P.; Krauter, P.W.; Lawton, M.P.; Harrison, F.L.

    1987-01-01

    Marine mussels (Mytilus edulis) and bullfrog tadpoles (Rana catesbeiana) were used to investigate the comparative metabolism and genotoxicity of aromatic amines in vivo. These organisms were selected because they possess distinctly different metabolic capabilities: mussels lack an active mixed-function-oxidase enzyme system that is present in most other organisms, including amphibians. Using 14 C-labeled chemical probes (o- and p-toluidine, 2-aminofluorene (2-AF), and 2-acetylaminofluorene (2-AAF)), mussels and tadpoles well dosed with individual compounds by direct immersion in aqueous solutions. The identities of metabolites were then determined by HPLC and GC/MS methods. Results indicate that the N-conjugating pathways used by mussels result primarily in the detoxification of aromatic amines by limiting the amount of primary amine available for activation. The tadpoles excreted a number of 2-AAF metabolites but did form DNA and protein adducts in the liver. Induction of micronuclei in the peripheral red blood cells was also demonstrated. The tadpole was shown to be a sensitive biological indicator of pollution in aquatic ecosystems

  8. Identification of amines in wintertime ambient particulate material using high resolution aerosol mass spectrometry

    Science.gov (United States)

    Bottenus, Courtney L. H.; Massoli, Paola; Sueper, Donna; Canagaratna, Manjula R.; VanderSchelden, Graham; Jobson, B. Thomas; VanReken, Timothy M.

    2018-05-01

    Significant amounts of amines were detected in fine particulate matter (PM) during ambient wintertime conditions in Yakima, WA, using a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Positive matrix factorization (PMF) of the organic aerosol (OA) signal resulted in a six-factor solution that included two previously unreported amine OA factors. The contributions of the amine factors were strongly episodic, but the concentration of the combined amine factors was as high as 10-15 μg m-3 (2-min average) during those episodes. In one occasion, the Amine-II component was 45% of total OA signal. The Amine-I factor was dominated by spectral peaks at m/z 86 (C5H12N+) and m/z 100 (C6H14N+), while the Amine-II factor was dominated by spectral peaks at m/z 58 (C3H8N+ and C2H6N2+) and m/z 72 (C4H10N+ and C3H8N2+). The ions dominating each amine factor showed distinct time traces, suggesting different sources or formation processes. Investigation into the chemistry of the amine factors suggests a correlation with inorganic anions for Amine-I, but no evidence that the Amine-II was being neutralized by the same inorganic ions. We also excluded the presence of organonitrates (ON) in the OA. The presence of C2H4O2+ at m/z 60 (a levoglucosan fragment) in the Amine-I spectrum suggests some influence of biomass burning emissions (more specifically residential wood combustion) in this PMF factor, but wind direction suggested that the most likely sources of these amines were agricultural activities and feedlots to the S-SW of the site.

  9. Photocatalysis as a tertiary treatment for petroleum refinery wastewaters

    Directory of Open Access Journals (Sweden)

    F. V. Santos

    2006-12-01

    Full Text Available Photocatalysis has been used as tertiary treatment for petroleum refinery wastewaters to comply with the regulatory discharge limits and to oxidize persistent compounds that had not been oxidized in the biological treatment. The wastewater is generated by the refinery and directly discharged into the Guanabara Bay (Rio de Janeiro. Although BOD removal is high, a residual and persistent COD, besides a somewhat high phenol content remains. Three photocatalysts were tested - TiO2 (Aldrich, ZnO (Aldrich, and TiO2 (P25, Degussa - the third being the most active. The optimized conditions obtained with an experimental design were 3.0 g L-1 TiO2 and pH 6.3. The use of hydrogen peroxide (H2O2 showed no beneficial effect. Removal of 93% of phenols, 63% of dissolved organic carbon (DOC, and more than 50% of oil and grease (OG were achieved in the photocatalytic process, improving the quality of the treated wastewater.

  10. Laboratory Studies of the Role of Amines in Particle Formation, Growth and Climate

    Energy Technology Data Exchange (ETDEWEB)

    Finlayson-Pitts, Barbara J. [Univ. of California, Irvine, CA (United States)

    2015-02-07

    Organosulfur compounds have a variety of sources, particularly biological processes in the oceans. Their oxidation in air forms sulfur dioxide, which is further oxidized to sulfuric acid, as well as methanesulfonic acid (MSA). While sulfuric acid is a well known precursor to particles in air, MSA had not been regarded as a source of new particle formation. Laboratory studies were carried out under this project that showed MSA forms new particles quite efficiently in the presence of amines and water vapor. The data could be reproduced with a relatively simple kinetics model representing cluster formation and growth, which is promising for representing this chemistry in global climate models. The initial steps in the kinetics scheme are based on quantum chemical calculations of likely clusters. The organosulfur chemistry was introduced into an atmospheric model for southern California and used to predict the impact of going to a fossil-fuel free world in which anthropogenic emissions of SO2 are removed, but the natural processes remain.

  11. Temperature-Dependent Henry's Law Constants of Atmospheric Amines.

    Science.gov (United States)

    Leng, Chunbo; Kish, J Duncan; Roberts, Jason E; Dwebi, Iman; Chon, Nara; Liu, Yong

    2015-08-20

    There has been growing interest in understanding atmospheric amines in the gas phase and their mass transfer to the aqueous phase because of their potential roles in cloud chemistry, secondary organic aerosol formation, and the fate of atmospheric organics. Temperature-dependent Henry's law constants (KH) of atmospheric amines, a key parameter in atmospheric chemical transport models to account for mass transfer, are mostly unavailable. In this work, we investigated gas-liquid equilibria of five prevalent atmospheric amines, namely 1-propylamine, di-n-propylamine, trimethylamine, allylamine, and 4-methylmorpholine using bubble column technique. We reported effective KH, intrinsic KH, and gas phase diffusion coefficients of these species over a range of temperatures relevant to the lower atmosphere for the first time. The measured KH at 298 K and enthalpy of solution for 1-propylamine, di-n-propylamine, trimethylamine, allylamine, and 4-methylmorpholine are 61.4 ± 4.9 mol L(-1) atm(-1) and -49.0 ± 4.8 kJ mol(-1); 14.5 ± 1.2 mol L(-1) atm(-1) and -72.5 ± 6.8 kJ mol(-1); 8.9 ± 0.7 mol L(-1) atm(-1) and -49.6 ± 4.7 kJ mol(-1); 103.5 ± 10.4 mol L(-1) atm(-1) and -42.7 ± 4.3 kJ mol(-1); and 952.2 ± 114.3 mol L(-1) atm(-1) and -82.7 ± 9.7 kJ mol(-1), respectively. In addition, we evaluated amines' characteristic times to achieve gas-liquid equilibrium for partitioning between gas and aqueous phases. Results show gas-liquid equilibrium can be rapidly established at natural cloud droplets surface, but the characteristic times may be extended substantially at lower temperatures and pHs. Moreover, our findings imply that atmospheric amines are more likely to exist in cloud droplets, and ambient temperature, water content, and pH of aerosols play important roles in their partitioning.

  12. Missed injury and the tertiary trauma survey.

    Science.gov (United States)

    Thomson, Charles B; Greaves, Ian

    2008-01-01

    Missed injury in the context of major trauma remains a persistent problem, both from a clinical and medico-legal point-of-view. Estimates of the incidence vary widely, dependent on the precise parameters of the studied population, the definition of missed injury and the extent of follow-up, but may be as high as 38%. The tertiary survey, in which formal repeated examination of the patient is undertaken after initial resuscitation and treatment have taken place, has been suggested as a way of identifying injuries not found at presentation. This paper appraises the concept of the tertiary survey, and also reviews the literature on missed injury in order to identify the risk factors, the types of injury and the reasons for error.

  13. Alcohol consumption in tertiary education students

    Directory of Open Access Journals (Sweden)

    Reavley Nicola J

    2011-07-01

    Full Text Available Abstract Background Heavy alcohol consumption among adolescents and young adults is an issue of significant public concern. With approximately 50% of young people aged 18-24 attending tertiary education, there is an opportunity within these settings to implement programs that target risky drinking. The aim of the current study was to survey students and staff within a tertiary education institution to investigate patterns of alcohol use, alcohol-related problems, knowledge of current National Health and Medical Research Council (NHMRC guidelines for alcohol consumption and intentions to seek help for alcohol problems. Methods Students of an Australian metropolitan university (with staff as a comparison group participated in a telephone interview. Questions related to knowledge of NHMRC guidelines, drinking behaviour, alcohol-related problems and help-seeking intentions for alcohol problems. Level of psychological distress was also assessed. Results Of the completed interviews, 774 (65% were students and 422 (35% were staff. While staff were more likely to drink regularly, students were more likely to drink heavily. Alcohol consumption was significantly higher in students, in males and in those with a history of earlier onset drinking. In most cases, alcohol-related problems were more likely to occur in students. The majority of students and staff had accurate knowledge of the current NHMRC guidelines, but this was not associated with lower levels of risky drinking. Psychological distress was associated with patterns of risky drinking in students. Conclusions Our findings are consistent with previous studies of tertiary student populations, and highlight the disconnect between knowledge of relevant guidelines and actual behaviour. There is a clear need for interventions within tertiary education institutions that promote more effective means of coping with psychological distress and improve help-seeking for alcohol problems, particularly among

  14. Tertiary lymphoid organs in Takayasu Arteritis

    OpenAIRE

    Marc eClement; Marc eClement; Adrien eGaly; Patrick eBruneval; Marion eMorvan; Fabien eHyafil; Fabien eHyafil; Khadija eBenali; Nicoletta ePasi; Lydia eDeschamps; Quentin ePellenc; Quentin ePellenc; Thomas ePapo; Antonino eNicoletti; Antonino eNicoletti

    2016-01-01

    Objective: The role of B cells in the pathogenesis of Takayasu arteritis (TA) is controversial. We aimed to study the presence of tertiary lymphoid organs (TLOs) in the aortic wall of TA patients.Methods: Hematoxylin and eosin–stained sections from aorta specimens from patients with TA were screened for TLOs. The presence of B cell aggregates (CD20), follicular dendritic cells (FDCs, CD21), and high endothelial venules (HEVs, PNAd) was investigated by immunohistochemistry. Immune cells from t...

  15. Tertiary Lymphoid Organs in Takayasu Arteritis

    OpenAIRE

    Clement, Marc; Galy, Adrien; Bruneval, Patrick; Morvan, Marion; Hyafil, Fabien; Benali, Khadija; Pasi, Nicoletta; Deschamps, Lydia; Pellenc, Quentin; Papo, Thomas; Nicoletti, Antonino; Sacre, Karim

    2016-01-01

    Objective The role of B cells in the pathogenesis of Takayasu arteritis (TA) is controversial. We aimed to study the presence of tertiary lymphoid organs (TLOs) in the aortic wall of TA patients. Methods Hematoxylin and eosin-stained sections from aorta specimens from patients with TA were screened for TLOs. The presence of B cell aggregates (CD20), follicular dendritic cells (FDCs, CD21), and high endothelial venules (HEVs, PNAd) was investigated by immunohistochemistry. Immune ce...

  16. Optimising Tertiary Student Accommodation within University Neighbourhoods

    OpenAIRE

    Ike, Nnenna; Baldwin, Claudia; Lathouras, Athena

    2017-01-01

    Tertiary students’ activities within neighbourhoods adjacent to universities engender positive and negative impacts that have consequences for neighbourhood sustainability. This might lead to studentification, a process that triggers physical, economic and socio-cultural transformation of university towns. Where non-student residents perceive negative impacts, it can lead to conflict and resentment towards the student population, mistrust between student and local resident groups and a decrea...

  17. Sponges with covalently tethered amines for high-efficiency carbon capture

    KAUST Repository

    Qi, Genggeng

    2014-12-12

    © 2014 Macmillan Publishers Limited. All rights reserved. Adsorption using solid amine sorbents is an attractive emerging technology for energy-efficient carbon capture. Current syntheses for solid amine sorbents mainly based on physical impregnation or grafting-to methods (for example, aminosilane-grafting) lead to limited sorbent performance in terms of stability and working capacity, respectively. Here we report a family of solid amine sorbents using a grafting-from synthesis approach and synthesized by cationic polymerization of oxazolines on mesoporous silica. The sorbent with high amount of covalently tethered amines shows fast adsorption rate, high amine efficiency and sorbent capacity well exceeding the highest value reported to date for lowerature carbon dioxide sorbents under simulated flue gas conditions. The demonstrated efficiency of the new amine-immobilization chemistry may open up new avenues in the development of advanced carbon dioxide sorbents, as well as other nitrogen-functionalized systems.

  18. Direct α-C-H bond functionalization of unprotected cyclic amines

    Science.gov (United States)

    Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

    2018-02-01

    Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

  19. Evaluating tetracycline degradation pathway and intermediate toxicity during the electrochemical oxidation over a Ti/Ti4O7anode.

    Science.gov (United States)

    Wang, Jianbing; Zhi, Dan; Zhou, Hao; He, Xuwen; Zhang, Dayi

    2018-03-12

    Tetracycline (TC) is one of the most widely used antibiotics with significant impacts on human health and thus it needs appropriate approaches for its removal. In the present study, we evaluated the performance and complete pathway of the TC electrochemical oxidation on a Ti/Ti 4 O 7 anode prepared by plasma spraying. Morphological data and composition analysis indicated a compact coating layer on the anode, which had the characteristic peaks of Ti 4 O 7 as active constituent. The TC electrochemical oxidation on the Ti/Ti 4 O 7 anode followed a pseudo-first-order kinetics, and the TC removal efficiency reached 95.8% in 40 min. The influential factors on TC decay kinetics included current density, anode-cathode distance and initial TC concentration. This anode also had high durability and the TC removal efficiency was maintained over 95% after five times reuse. For the first time, we unraveled the complete pathway of the TC electrochemical oxidation using high-performance liquid chromatograph (HPLC) and gas chromatograph (GC) coupled with mass spectrometer (MS). ·OH radicals produced from electrochemical oxidation attack the double bond, phenolic group and amine group of TC, forming a primary intermediate (m/z = 461), secondary intermediates (m/z = 432, 477 and 509) and tertiary intermediates (m/z = 480, 448 and 525). The latter were further oxidized to the key downstream intermediate (m/z = 496), followed by further downstream intermediates (m/z = 451, 412, 396, 367, 351, 298 and 253) and eventually short-chain carboxylic acids. We also evaluated the toxicity change during the electrochemical oxidation process with bioluminescent bacteria. The bioluminescence inhibition ratio peaked at 10 min (55.41%), likely owing to the high toxicity of intermediates with m/z = 461, 432 and 477 as obtained from quantitative structure activity relationship (QSAR) analysis. The bioluminescence inhibition ratio eventually decreased to 16.78% in 40

  20. Tris{2-[(2,6-dimethylphenylamino]ethyl}amine

    Directory of Open Access Journals (Sweden)

    Yurii S. Moroz

    2011-12-01

    Full Text Available The title compound, C30H42N4, is an arylated tris(aminoethylamine derivative which was obtained by reducing the corresponding tris-amide with AlH3. The asymmetric unit consists of one third of a C3v-symmetric molecule with the tertiary N atom lying on a crystallographic threefold axis.

  1. Amines in the marking fluid and anal sac secretion of the tiger, Panthera tigris.

    Science.gov (United States)

    Banks, G R; Buglass, A J; Waterhouse, J S

    1992-01-01

    Analysis of the marking fluid of two tigers (one Bengal and one Sumatran) by GC using an amine-specific column and a nitrogen-specific detector has shown the presence of the following amines: ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, propylamine, and butane-1,4-diamine (putrescine). In contrast to previously published reports, we were unable to detect 2-phenylethylamine. The anal sac secretion was found to have a similar amine content.

  2. Synthesis of propargylic and allenic carbamates via the C-H amination of alkynes.

    Science.gov (United States)

    Grigg, R David; Rigoli, Jared W; Pearce, Simon D; Schomaker, Jennifer M

    2012-01-06

    Propargylic amines are important intermediates for the synthesis of nitrogen-containing heterocycles. The insertion of a nitrene into a propargylic C-H bond has not been explored, despite the attention directed toward the Rh-catalyzed amination of other types of C-H bonds. In this communication, the conversion of a series of homopropargylic carbamates to propargylic carbamates and aminated allenes is described. © 2011 American Chemical Society

  3. Cross-Linking Amine-Rich Compounds into High Performing Selective CO2 Absorbents

    OpenAIRE

    Andreoli, Enrico; Dillon, Eoghan P.; Cullum, Laurie; Alemany, Lawrence B.; Barron, Andrew R.

    2014-01-01

    Amine-based absorbents play a central role in CO2 sequestration and utilization. Amines react selectively with CO2, but a drawback is the unproductive weight of solvent or support in the absorbent. Efforts have focused on metal organic frameworks (MOFs) reaching extremely high CO2 capacity, but limited selectivity to N2 and CH4, and decreased uptake at higher temperatures. A desirable system would have selectivity (cf. amine) and high capacity (cf. MOF), but also increased adsorption at highe...

  4. Nickel-Catalyzed Amination of Aryl Sulfamates and Carbamates Using an Air-Stable Precatalyst

    Science.gov (United States)

    Hie, Liana; Ramgren, Stephen D.; Mesganaw, Tehetena; Garg, Neil K.

    2012-01-01

    A facile nickel-catalyzed method to achieve the amination of synthetically useful aryl sulfamates and carbamates is reported. Contrary to most Ni-catalyzed amination reactions, this user-friendly approach relies on an air-stable Ni(II) precatalyst, which, when employed with a mild reducing agent, efficiently delivers aminated products in good to excellent yields. The scope of the method is broad with respect to both coupling partners and includes heterocyclic substrates. PMID:22849697

  5. Laboratory evaluation of borate/amine/zinc formulations for fungal decay protection

    Science.gov (United States)

    George C. Chen; Rebecca E. Ibach

    2010-01-01

    The goals of this study were to evaluate borate/amine/zinc formulations in wood for fungal decay protection as well as the permanence of zinc and boron in wood. Wood treated with each of four formulations of borate/amine/zinc prevented or decreased fungal degradation after a 12-week AWPA Standard soil-block test. For non-leached specimens, wood treated with borax/amine...

  6. The toxicity of MEA and amine waste water samples using standardised freshwater bioassays

    OpenAIRE

    Brooks, S.; Heiaas, H.; Lillicrap, A.

    2013-01-01

    Water samples provided by Tel-Tek AS were assessed for their toxicity to freshwater organisms from three trophic groups. The water samples included pure monoethanolamine (MEA) and two amine waste water mixtures described as Amine Reactor Waste (ARW) and treated amine waste water (TW). The toxicity of these three test solutions to the unicellular algae Pseudokirchneriella subcapitata, the freshwater crustacean Daphnia magna, and the embryos of the zebra fish Danio rerio were performed in accor...

  7. Chemical vapor deposition of fluorine-doped zinc oxide

    Science.gov (United States)

    Gordon, Roy G.; Kramer, Keith; Liang, Haifan

    2000-06-06

    Fims of fluorine-doped zinc oxide are deposited from vaporized precursor compounds comprising a chelate of a dialkylzinc, such as an amine chelate, an oxygen source, and a fluorine source. The coatings are highly electrically conductive, transparent to visible light, reflective to infrared radiation, absorbing to ultraviolet light, and free of carbon impurity.

  8. Performance Characterization and Simulation of Amine-Based Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

    Science.gov (United States)

    Swickrath, Michael J.; Watts,Carly; Anderson, Molly; McMillin, Summer; Boerman, Craig; Colunga, Aaron; Vogel, Matthew

    2011-01-01

    Controlling carbon dioxide (CO2) and water (H2O) concentrations in the vapor phase of a space suit is critical to ensuring an astronauts safety, comfortability, and capability to perform extra-vehicular activity (EVA) tasks. Historically, this has been accomplished using lithium hydroxide (LiOH) and metal oxides (MetOx). Lithium hydroxide is a consumable material and requires priming with water before it becomes effective at removing carbon dioxide. MetOx is regenerable through a power-intensive thermal cycle but is significantly heavier on a volume basis than LiOH. As an alternative, amine-based vacuum swing beds are under aggressive development for EVA applications which control atmospheric concentrations of both CO2 and H2O through a fully-regenerative process. The current concept, referred to as the rapid cycle amine (RCA), has resulted in numerous laboratory prototypes. Performance of these prototypes have been assessed and documented from experimental and theoretical perspectives. To support developmental efforts, a first principles model has also been established for the vacuum swing adsorption technology. The efforts documented herein summarize performance characterization and simulation results for several variable metabolic profiles subjected to the RCA. Furthermore, a variety of control methods are explored including timed swing cycles, instantaneous CO2 feedback control, and time-averaged CO2 feedback control. A variety of off-nominal tests are also explored including high/low suit temperatures, increasingly high humidity cases, and dynamic pressure cases simulating the suit pre-breathe protocol. Consequently, this work builds on efforts previous efforts to fully bound the performance of the rapid cycle amine under a variety of nominal and off-nominal conditions.

  9. Ligand-exchange chromatography of aromatic amines on resin-bound cobalt ion

    Energy Technology Data Exchange (ETDEWEB)

    Pehlivan, E.; Vural, U.S.; Ayar, A.; Yildiz, S. [Selcuk Univ., Konya (Turkey)

    1996-06-01

    The use of cobalt metal for the selective separation of aromatic amines is completed with a chemically bonded diamine and glyoxime functional groups onto Lycopodium clavatum. Oximes and amines are excellent complexing agents for transition metal ions. Cobalt(II) metal ions can easily be immobilized on bis-diaminoethyl-glyoximated sporopollenin (bDAEG-sporopollenin). The ligand-exchange behavior of modified Lycopodium clavatum with respect to aromatic amines was investigated. This will permit the evaluation of bDAEG-sporopollenin ligand exchangers for their utilization as sorbents in the recovery, pollution control, and elimination of amines from wastewater.

  10. Targeting polyamines and biogenic amines by green tea epigallocatechin-3-gallate.

    Science.gov (United States)

    Melgarejo, Esther; Urdiales, José Luis; Sánchez-Jiménez, Francisca; Medina, Miguel Angel

    2010-02-01

    Biogenic amines and polyamines are organic polycations derived from aromatic or cationic amino acids. They exert pleiotropic effects, more related to intercellular communication in the case of biogenic amines, and to intracellular signaling in the case of polyamines. The bioactive compound epigallocatechin-3-gallate (EGCG), a major component of green tea, has been shown to target key enzyme of biogenic amine and polyamine metabolic pathways. Herein, we review the specific effects of EGCG on concrete molecular targets of both biogenic amine and polyamine metabolic pathways, and discuss the relevance of these data to support the potential therapeutic interest of this compound.

  11. Control of Biogenic Amines in Fermented Sausages: Role of Starter Cultures

    Science.gov (United States)

    Latorre-Moratalla, M.L.; Bover-Cid, Sara; Veciana-Nogués, M.T.; Vidal-Carou, M.C.

    2012-01-01

    Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed. PMID:22586423

  12. Control of biogenic amines in fermented sausages: role of starter cultures

    Directory of Open Access Journals (Sweden)

    Mariluz eLatorre-Moratalla

    2012-05-01

    Full Text Available Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed.

  13. Synthesis of substituted propargylamines from aminals and phenylacetylen in the presence of Cu(I) halides

    Energy Technology Data Exchange (ETDEWEB)

    Komissarov, V.N.; Ukhin, L.Yu.; Orlova, Zh.I.; Tokarskaya, O.A.

    1987-11-20

    Aminals, the condensation products of carbonyl compounds with secondary amines (1), have been examined within a general scheme for the Mannich reaction (2), as precursors of iminium ions. The authors investigated the behavior of aminals derived from aromatic aldehydes upon heating with phenylacetylene and CuX (X = I, Br, Cl) in acetonitrile. The authors assumed that an aminal, acting as an HX acceptor, would lead to the formation of copper phenylacetylide, and be itself converted via this process to an iminium salt, which could then participate in an aminomethylation reaction of copper phenylacetylide. It was found that propargylamines were formed rapidly upon heating stoichiometric amounts of the reagents in acetonitrile solution.

  14. Method of neutralizing the corrosive surface of amine-cured epoxy resins

    Science.gov (United States)

    Lee, S. Y. (Inventor)

    1982-01-01

    The corrosive alkaline surface layer of an epoxy resin product formed by the curing of the epoxy with an aliphatic amine is eliminated by first applying a non-solvent to remove most or all of the free unreacted amine and then applying a layer of a chemical reagent to neutralize the unused amine or amine functional groups by forming a substituted urea. The surface then may be rinsed with acetone and then with alcohol. The non-solvent may be an alcohol. The neutralizing chemical reagent is a mono-isocyanate or a mono-isothiocyanate. Preferred is an aromatic mono-isocyanate such as phenyl isocyanate, nitrophenyl isocyanate and naplthyl isocyanate.

  15. New polymeric membrane cadmium(II)-selective electrodes using tripodal amine based ionophores

    Energy Technology Data Exchange (ETDEWEB)

    Khamjumphol, Utisawadee [Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand); Watchasit, Sarayut [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Suksai, Chomchai [Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Burapha University, Chonburi 20131 (Thailand); Janrungroatsakul, Wanwisa [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Boonchiangma, Suthasinee [Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand); Tuntulani, Thawatchai [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Ngeontae, Wittaya, E-mail: wittayange@kku.ac.th [Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand); Research Center for Environmental and Hazardous Substance Management, Khon Kaen University, Khon Kaen 40002 (Thailand); National Center of Excellence for Environmental and Hazardous Waste Management, Khon Kaen University, Khon Kaen 40002 (Thailand)

    2011-10-17

    Highlights: {yields} New four ionophores having tripodal amine (TPA) unit on anthracene and calixarene. {yields} Synthesis and characterization data were reported. {yields} Incorporated to the plasticized PVC membranes to prepare Cd-ISEs. {yields} Two TPA units on calixarene showed the best selectivity toward Cd{sup 2+}. {yields} Applied for sensing Cd{sup 2+} from the oxidation of CdS QDs solution. - Abstract: Fabrication of PVC membrane electrodes incorporating selective neutral carriers for Cd{sup 2+} was reported. The ionophores were designed to have different topologies, donor atoms and lipophilicity by attaching tripodal amine (TPA) units to the lipophilic anthracene (ionophore I) and p-tert-butylcalix[4]arene (ionophores II, III and IV). The synthesized ionophores were incorporated to the plasticized PVC membranes to prepare Cd(II) ion selective electrodes (ISEs). The membrane electrodes were optimized by changing types and amounts of ionic sites and plasticizers. The selectivity of the membranes fabricated from the synthesized ionophores was evaluated, the relationship between structures of ionophores and membrane characteristics were explored. The ionophore IV which composed of two opposites TPA units on the calix[4]arene compartment showed the best selectivity toward Cd{sup 2+}. The best membrane electrode was fabricated from ionophore IV (10.2 mmol kg{sup -1}) with KTpClPB (50.1 mol% related to the ionophore) as an ion exchanger incorporated in the DOS plasticized PVC membrane (1:2; PVC:DOS). The Cd-ISE fabricated from ionophore IV exhibited good properties with a Nernstian response of 29.4 {+-} 0.6 mV decade{sup -1} of activity for Cd{sup 2+} ions and a working concentration range of 1.6 x 10{sup -6}-1.0 x 10{sup -2} M. The sensor has a fast response time of 10 s and can be used for at least 1 week without any divergence in potential. The electrode can be used in the pH range of 6.0-9.0. The proposed electrodes using ionophores III and IV were employed

  16. New polymeric membrane cadmium(II)-selective electrodes using tripodal amine based ionophores

    International Nuclear Information System (INIS)

    Khamjumphol, Utisawadee; Watchasit, Sarayut; Suksai, Chomchai; Janrungroatsakul, Wanwisa; Boonchiangma, Suthasinee; Tuntulani, Thawatchai; Ngeontae, Wittaya

    2011-01-01

    Highlights: → New four ionophores having tripodal amine (TPA) unit on anthracene and calixarene. → Synthesis and characterization data were reported. → Incorporated to the plasticized PVC membranes to prepare Cd-ISEs. → Two TPA units on calixarene showed the best selectivity toward Cd 2+ . → Applied for sensing Cd 2+ from the oxidation of CdS QDs solution. - Abstract: Fabrication of PVC membrane electrodes incorporating selective neutral carriers for Cd 2+ was reported. The ionophores were designed to have different topologies, donor atoms and lipophilicity by attaching tripodal amine (TPA) units to the lipophilic anthracene (ionophore I) and p-tert-butylcalix[4]arene (ionophores II, III and IV). The synthesized ionophores were incorporated to the plasticized PVC membranes to prepare Cd(II) ion selective electrodes (ISEs). The membrane electrodes were optimized by changing types and amounts of ionic sites and plasticizers. The selectivity of the membranes fabricated from the synthesized ionophores was evaluated, the relationship between structures of ionophores and membrane characteristics were explored. The ionophore IV which composed of two opposites TPA units on the calix[4]arene compartment showed the best selectivity toward Cd 2+ . The best membrane electrode was fabricated from ionophore IV (10.2 mmol kg -1 ) with KTpClPB (50.1 mol% related to the ionophore) as an ion exchanger incorporated in the DOS plasticized PVC membrane (1:2; PVC:DOS). The Cd-ISE fabricated from ionophore IV exhibited good properties with a Nernstian response of 29.4 ± 0.6 mV decade -1 of activity for Cd 2+ ions and a working concentration range of 1.6 x 10 -6 -1.0 x 10 -2 M. The sensor has a fast response time of 10 s and can be used for at least 1 week without any divergence in potential. The electrode can be used in the pH range of 6.0-9.0. The proposed electrodes using ionophores III and IV were employed as a probe for determining Cd 2+ from the oxidation of CdS QDs

  17. Synthesis and antimicrobial activity of styryl/pyrrolyl/pyrazolyl sulfonylmethyl-1,3,4-oxadiazolyl amines and styryl/pyrrolyl/pyrazolyl sulfonylmethyl-1,3,4-thiadiazolyl amines.

    Science.gov (United States)

    Sravya, G; Yamini, G; Padmavathi, V; Padmaja, A

    2016-10-21

    A new class of mono and bis heterocycles - styryl sulfonylmethyl-1,3,4-oxadiazolyl/1,3,4-thiadiazolyl amines, pyrrolyl sulfonylmethyl-1,3,4-oxadiazolyl/1,3,4-thiadiazolyl amines and pyrazolyl sulfonylmethyl-1,3,4-oxadiazolyl/1,3,4-thiadiazolyl amines were prepared from the synthetic intermediate Z-styrylsulfonylacetic acid adopting simple and well versed synthetic methodologies and studied their antimicrobial activity. Amongst all the tested compounds styryl thiadiazole 5c exhibited promising antimicrobial activity against Pseudomonas aeruginosa and Penicillium chrysogenum. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  18. Amination of oxy acids in aqueous solution by gamma-irradiation

    International Nuclear Information System (INIS)

    Ema, Kimiko; Kato, Taizo; Shinagawa, Mutsuaki

    1978-01-01

    Alanin, β-alanine, glicine, and aspartic, α-amino-n-butyric, and γ-amino-n-butyric acids were obtained by γ-irradiation of aqueous ammonia solutions of lactic, β-oxypropionic, glycolic, malic, α-oxybutyric, and γ-oxybutyric acids, respectively. The yields of amino acids were examined for functions of radiation dose (0.75 - 3.55Mrad), concentrations of oxy acid (0.01 - 0.1M) and ammonia (0.1 - 15M), and substances added as radical (potassium iodide), and hydrated electron (nitrous oxide) scavengers. The maximum G-values were 0.6 for alanine in a solution of 0.1M lactic acid-4M ammonia and some nitrous oxide and 1.14 for β-alanine in a solution of 0.1M β-oxypropionic acid and 0.7M ammonia. The yield of alanine increased with increased concentrations of lactic acid and ammonia due to saturation of nitrous oxide but decreased when potassium iodide (0.03M) was added. The yield of β-alanine showed a maximum increase at ca. 0.7M ammonia and decreased when potassium iodide and nitrous oxide were added. Serine was obtained from G = 0.002 in a solution of β-oxypropionic acid and increased to G = 0.058 due to saturation of nitrous oxide. The manner of chemical amination due to radiation was studied from the above results. In general, oxy acids from which hydrogen has been abstracted by an H or OH radical react with ammonia to form amino acids. The effect of ammonia concentration on the yield of amino acids demonstrates that the NH 2 radical abstracts the α-hydrogen of lactic acid but does not react with the β-hydrogen of β-oxypropionic acid. The effect of nitrous oxide indicates that hydrated electrons interfere with alanine formation, contribute to β-alanine formation, react with the carboxyl group of lactic acids to form lactamide, and abstract the β-hydroxyl group of β-oxypropionic acids to form β-alanine. (Bell, E.)

  19. Differential toxicity of heterocyclic aromatic amines and their mixture in metabolically competent HepaRG cells

    International Nuclear Information System (INIS)

    Dumont, Julie; Josse, Rozenn; Lambert, Carine; Antherieu, Sebastien; Le Hegarat, Ludovic; Aninat, Caroline; Robin, Marie-Anne; Guguen-Guillouzo, Christiane

    2010-01-01

    Human exposure to heterocyclic aromatic amines (HAA) usually occurs through mixtures rather than individual compounds. However, the toxic effects and related mechanisms of co-exposure to HAA in humans remain unknown. We compared the effects of two of the most common HAA, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), individually or in combination, in the metabolically competent human hepatoma HepaRG cells. Various endpoints were measured including cytotoxicity, apoptosis, oxidative stress and DNA damage by the comet assay. Moreover, the effects of PhIP and/or MeIQx on mRNA expression and activities of enzymes involved in their activation and detoxification pathways were evaluated. After a 24 h treatment, PhIP and MeIQx, individually and in combination, exerted differential effects on apoptosis, oxidative stress, DNA damage and cytochrome P450 (CYP) activities. Only PhIP induced DNA damage. It was also a stronger inducer of CYP1A1 and CYP1B1 expression and activity than MeIQx. In contrast, only MeIQx exposure resulted in a significant induction of CYP1A2 activity. The combination of PhIP with MeIQx induced an oxidative stress and showed synergistic effects on apoptosis. However, PhIP-induced genotoxicity was abolished by a co-exposure with MeIQx. Such an inhibitory effect could be explained by a significant decrease in CYP1A2 activity which is responsible for PhIP genotoxicity. Our findings highlight the need to investigate interactions between HAA when assessing risks for human health and provide new insights in the mechanisms of interaction between PhIP and MeIQx.

  20. Theoretical study on perylene derivatives as fluorescent sensors for amines

    Science.gov (United States)

    Lathiotakis, Nektarios N.; Kerkines, Ioannis S. K.; Theodorakopoulos, Giannoula; Petsalakis, Ioannis D.

    2018-01-01

    A theoretical study is presented on perylene diimide (PDI) and perylene monoimide (PMI) and their action as sensors of amines in solution. Density functional theory (DFT) and Time dependent DFT (TDDFT) calculations are carried out on complexes of PDI and PMI with aniline in THF solution. The optimized geometries for the complexes have aniline lying parallel above the perylene at 3.15 Å and with binding energy of 0.53 eV in the ground state. The results on the excited states are consistent with a photoinduced electron transfer (PET) mechanism. The effective aniline-perylene distance resulting from a Mulliken's approach is 3.61 Å.

  1. Economic Considerations for Selecting an Amine Donor in Biocatalytic Transamination

    DEFF Research Database (Denmark)

    Tufvesson, Pär; Nordblad, Mathias; Krühne, Ulrich

    2015-01-01

    the process, in particular the choice of amine donor. This paper discusses these constraints and demonstrates, through simple thermodynamic and economic models, the process targets that need to be set and achieved for a process dependent on allowed process costs and quality targets....... in industry. The technology has been demonstrated in a few selected cases, but widespread implementation and for a broader range of target molecules requires a deeper understanding of the underlying thermodynamic as well as economic constraints for the different choices that can be made in designing...

  2. Binary VLE measurements and modeling for selected amine systems

    OpenAIRE

    Saleem, Fahad

    2011-01-01

    During the course of this work, vapor pressure data of pure water, DEEA and DIPEA was measured. The results give good agreement with literature data. VLE data of DEEA-H2O and DIPEA-H2O systems was then obtained at varying concentration and temperature (50-95oC) range. Experimental activity coefficients were calculated using this VLE data. Moreover, FTIR spectroscopy in conjunction with ?The Unscrambler? was used for amine analyses of the experimental samples and results were compared with ...

  3. Synthesis of 2-aminoBODIPYs by palladium catalysed amination.

    Science.gov (United States)

    Alnoman, Rua B; Stachelek, Patrycja; Knight, Julian G; Harriman, Anthony; Waddell, Paul G

    2017-09-20

    Palladium catalysed coupling of the 2-iodoBODIPY 3 with a range of anilines and a primary alkylamine succeeds in generating the corresponding 2-aminoBODIPYs. These 2-aminoBODIPY derivatives are non-emissive and quantum chemical calculations and electrochemistry are consistent with charge transfer from the amine substituent. Attenuation of this charge transfer pathway by conversion of the 1,2-phenylenediamine derivative 9 into the corresponding benzimidazolone 10 restores the fluorescence and has been used as the basis for a fluorescence sensor for phosgene.

  4. Carbon nanomaterial based electrochemical sensors for biogenic amines

    International Nuclear Information System (INIS)

    Yang, Xiao; He, Xiulan; Li, Fangping; Fei, Junjie; Feng, Bo; Ding, Yonglan

    2013-01-01

    This review describes recent advances in the use of carbon nanomaterials for electroanalytical detection of biogenic amines (BAs). It starts with a short introduction into carbon nanomaterials such as carbon nanotubes, graphene, nanodiamonds, carbon nanofibers, fullerenes, and their composites. Next, electrochemical sensing schemes are discussed for various BAs including dopamine, serotonin, epinephrine, norepinephrine, tyramine, histamine and putrescine. Examples are then given for methods for simultaneous detection of various BAs. Finally, we discuss the current and future challenges of carbon nanomaterial-based electrochemical sensors for BAs. The review contains 175 references. (author)

  5. Hardness of restorative resins: effect of camphorquinone, amine, and inhibitor.

    Science.gov (United States)

    Peutzfeldt, A; Asmussen, E

    1989-08-01

    The influence of the content of camphorquinone (CQ), amine (DABE), and inhibitor (MHQ) on the Wallace indentation hardness of light-curing polymers was investigated. The hardness was measured on disc-shaped specimens made from 50 bisphenol-A-glycidyl-dimethacrylate/triethyleneglycol-dimethacryla te-based monomers with various contents of CQ, DABE, and MHQ. When no MHQ had been added, the hardness number decreased with increasing content of CQ. This was also the case with increasing content of DABE, but to a lesser extent. In the presence of MHQ, the contents of CQ and DABE did not influence the hardness number significantly.

  6. Phenols and aromatic amines as thermal stabilizers in polyolefin processing

    Czech Academy of Sciences Publication Activity Database

    Pospíšil, Jan; Habicher, W. D.; Al-Malaika, S.; Zweifel, H.; Nešpůrek, Stanislav

    2001-01-01

    Roč. 176, - (2001), s. 55-63 ISSN 1022-1360. [International Conference on Polymer Modification, Degradation and Stabilization /1./. Palermo, 03.09.2000-07.09.2000] R&D Projects: GA AV ČR IAA1050901; GA MŠk ME 184; GA MŠk ME 372; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : thermal stabilizers * phenols * aromatic amines Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.634, year: 2001

  7. Pulmonary extraction of biogenic amines during septic shock

    International Nuclear Information System (INIS)

    Kerstein, M.D.; Kohler, J.; Gould, S.; Moseley, P.

    1982-01-01

    The effect of live Escherichia coli on the pulmonary extraction of the biogenic amines 14 C 5-hydroxytryptamine, (5-HT) and 3 H-epinephrine was investigated. The labeled isotopes were injected into a central venous catheter and collected from an aortic catheter. One hundred per cent of the labeled epinephrine was recovered in the control and septic state. Only 32.8 +/- 3.6% SEM of the 5-hydroxytryptamine was recovered before sepsis and 42.5 +/- 4.9% SEM after sepsis. During sepsis, mean arterial pressure fell to 58 mm Hg from 121 mm Hg. Pulmonary shunt increased from .7 +/- .05 SEM to .33 +/- .09 SEM

  8. Effects of ultraviolet light on biogenic amines and other quality indicators of chicken meat during refrigerated storage.

    Science.gov (United States)

    Lázaro, C A; Conte-Júnior, C A; Monteiro, M L G; Canto, A C V S; Costa-Lima, B R C; Mano, S B; Franco, R M

    2014-09-01

    Radiation from UV-C has been demonstrated as a potential surface decontamination method in addition to several advantages over regular sanitation methods. However, UV-C radiation possibly affects the physicochemical properties of meat products. To determine the optimum exposure time for bacterial reduction, 39 chicken breasts, inoculated with a pool of Salmonella spp., were submitted to 3 levels of UV-C intensities (0.62, 1.13, and 1.95 mW/cm²) for up to 120 s. After the optimum exposure time of 90 s was determined, changes in the biogenic amines, total aerobic mesophilic bacteria, Enterobacteriaceae, lipid oxidation, pH, and instrumental color were evaluated in 84 chicken breasts that were irradiated (0.62, 1.13, and 1.95 mW/cm²) and stored at 4°C for 9 d. The groups treated with UV-C radiation exhibited an increase in tyramine, cadaverine, and putrescine contents (P light was demonstrated to be an efficient alternative technology to improve the bacteriological quality of chicken meat without negatively affecting the physical and chemical parameters of chicken breast meat. Nonetheless, the increases on the biogenic amines content should be considered as an effect of the UV processing and not as an indicator of bacterial growth. © 2014 Poultry Science Association Inc.

  9. The effect of N-acetyl-l-cysteine and ascorbic acid on visible-light-irradiated camphorquinone/N,N-dimethyl-p-toluidine-induced oxidative stress in two immortalized cell lines.

    Science.gov (United States)

    Pagoria, D; Geurtsen, W

    2005-11-01

    Recent studies have revealed that visible-light (VL)-irradiated camphorquinone (CQ), in the presence of a tertiary amine (e.g., N,N-dimethyl-p-toluidine, DMT), generates initiating radicals that may indiscriminately react with molecular oxygen forming reactive oxygen species (ROS). In this study, the ability of the antioxidants N-acetyl-l-cysteine (NAC) and ascorbic acid (AA) to reduce intracellular oxidative stress induced by VL-irradiated CQ/DMT or VL-irradiated hydrogen peroxide (H(2)O(2)) was assessed in an immortalized Murine cementoblast cell line (OCCM.30) and an immortalized Murine fibroblast cell line, 3T3-Swiss albino (3T3). Intracellular oxidative stress was measured with the membrane permeable dye, 2',7'-dichlorodihydrofluorescein diacetate (H(2)DCF-DA). VL-irradiated CQ/DMT and VL-irradiated H(2)O(2) each produced significantly (p<0.001) elevated intracellular oxidative levels in both cell types compared to intracellular ROS levels in VL-irradiated untreated cells. OCCM.30 cementoblasts were found to be almost twice as sensitive to VL-irradiated CQ/DMT and VL-irradiated H(2)O(2) treatment compared to 3T3 fibroblasts. Furthermore, 10mm NAC and 10mm AA each eliminated oxidative stress induced by VL-irradiated CQ/DMT and VL-irradiated H(2)O(2) in both cell types. Our results suggest that NAC and AA may effectively reduce or eliminate oxidative stress in cells exposed to VL-irradiated CQ/DMT following polymerization.

  10. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    Energy Technology Data Exchange (ETDEWEB)

    Poole, Loree Joanne [Univ. of California, Berkeley, CA (United States); King, C. Judson [Univ. of California, Berkeley, CA (United States)

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO2 and H2S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The

  11. A Review of Aspects of Oxidative Hair Dye Chemistry with Special Reference toN-Nitrosamine Formation.

    Science.gov (United States)

    Lewis, David; Mama, John; Hawkes, Jamie

    2013-02-13

    This review discusses a new aspect to the safety profile of oxidative hair dyes using data already in the public domain. These dyes contain secondary amines that are capable of forming potentially carcinogenic nitrosamine derivatives when exposed to atmospheric pollution. Numerous scientific articles confirm the existence of secondary amines in hair dyes (and their intermediates), the possibility of nitrosation by atmospheric NO x of secondary amines to give the N- nitrosamines, and the significant safety risks on N -nitrosamines. It is believed that such nitrosamine derivatives should be investigated more fully in the interests of consumer safety.

  12. A Review of Aspects of Oxidative Hair Dye Chemistry with Special Reference to N-Nitrosamine Formation

    Directory of Open Access Journals (Sweden)

    Jamie Hawkes

    2013-02-01

    Full Text Available This review discusses a new aspect to the safety profile of oxidative hair dyes using data already in the public domain. These dyes contain secondary amines that are capable of forming potentially carcinogenic nitrosamine derivatives when exposed to atmospheric pollution. Numerous scientific articles confirm the existence of secondary amines in hair dyes (and their intermediates, the possibility of nitrosation by atmospheric NOx of secondary amines to give the N-nitrosamines, and the significant safety risks on N-nitrosamines. It is believed that such nitrosamine derivatives should be investigated more fully in the interests of consumer safety.

  13. A Review of Aspects of Oxidative Hair Dye Chemistry with Special Reference to N-Nitrosamine Formation

    Science.gov (United States)

    Lewis, David; Mama, John; Hawkes, Jamie

    2013-01-01

    This review discusses a new aspect to the safety profile of oxidative hair dyes using data already in the public domain. These dyes contain secondary amines that are capable of forming potentially carcinogenic nitrosamine derivatives when exposed to atmospheric pollution. Numerous scientific articles confirm the existence of secondary amines in hair dyes (and their intermediates), the possibility of nitrosation by atmospheric NOx of secondary amines to give the N-nitrosamines, and the significant safety risks on N-nitrosamines. It is believed that such nitrosamine derivatives should be investigated more fully in the interests of consumer safety. PMID:28809322

  14. Analysis of irradiated biogenic amines by computational chemistry and spectroscopy

    International Nuclear Information System (INIS)

    Oliveira, Jorge L.S.P.; Borges Junior, Itamar; Cardozo, Monique; Souza, Stefania P.; Lima, Antonio L.S.; Lima, Keila S.C.

    2011-01-01

    Biogenic Amines (B A) are nitrogenous compounds able to cause food poisoning. In this work, we studied the tyramine, one of the most common BA present in foods by combining experimental measured IR (Infrared) and GC/MS (Gas Chromatograph / Mass Spectrometry) spectra and computational quantum chemistry. Density Functional Theory (DFT) and the Deformed Atoms in Molecules (DMA) method was used to compute the partition the electronic densities in a chemically-intuitive way and electrostatic potentials of molecule to identify the acid and basic sites. Trading pattern was irradiated using a Cs 137 radiator, and each sample was identified by IR and GC/MS. Calculated and experimental IR spectra were compared. We observed that ionizing gamma irradiation was very effective in decreasing the population of standard amine, resulting in fragments that could be rationalized through the quantum chemistry calculations. In particular, we could locate the acid and basic sites of both molecules and identify possible sites of structural weaknesses, which allowed to propose mechanistic schemes for the breaking of chemical bonds by the irradiation. Moreover, from this work we hope it will be also possible to properly choose the dose of gamma irradiation which should be provided to eliminate each type of contamination. (author)

  15. Switchable regioselectivity in amine-catalysed asymmetric cycloadditions

    Science.gov (United States)

    Zhou, Zhi; Wang, Zhou-Xiang; Zhou, Yuan-Chun; Xiao, Wei; Ouyang, Qin; Du, Wei; Chen, Ying-Chun

    2017-06-01

    Building small-molecule libraries with structural and stereogenic diversity plays an important role in drug discovery. The development of switchable intermolecular cycloaddition reactions from identical substrates in different regioselective fashions would provide an attractive protocol. However, this also represents a challenge in organic chemistry, because it is difficult to control regioselectivity to afford the products exclusively and at the same time achieve high levels of stereoselectivity. Here, we report the diversified cycloadditions of α‧-alkylidene-2-cyclopentenones catalysed by cinchona-derived primary amines. An asymmetric γ,β‧-regioselective intermolecular [6+2] cycloaddition reaction with 3-olefinic (7-aza)oxindoles is realized through the in situ generation of formal 4-aminofulvenes, while a different β,γ-regioselective [2+2] cycloaddition reaction with maleimides to access fused cyclobutanes is disclosed. In contrast, an intriguing α,γ-regioselective [4+2] cycloaddition reaction is uncovered with the same set of substrates, by employing an unprecedented dual small-molecule catalysis of amines and thiols. All of the cycloaddition reactions exhibit excellent regio- and stereoselectivity, producing a broad spectrum of chiral architectures with high structural diversity and molecular complexity.

  16. Technological factors affecting biogenic amine content in foods: a review

    Directory of Open Access Journals (Sweden)

    Fausto Gardini

    2016-08-01

    Full Text Available Biogenic amines (BAs are molecules which can be present in foods and, due to their toxicity, can cause adverse effects on the consumers. BAs are generally produced by microbial decarboxylation of amino acids in food products. The most significant BAs occurring in foods are histamine, tyramine, putrescine, cadaverine, tryptamine, 2-phenylethylamine, spermine, spermidine and agmatine. The importance of preventing the excessive accumulation of BAs in food is related to their impact on human health and food quality. Quality criteria in connection with the presence of BAs in food and food products are necessary from a toxicological point of view. This is particularly important in fermented foods in which the massive microbial proliferation required for obtaining specific products is often relater with BA accumulation. In this review, up-to-date information and recent discoveries about technological factors affecting biogenic amine content in foods are reviewed. Specifically, BA forming-microorganism and decarboxylation activity, genetic and metabolic organization of decarboxylases, risk associated to BAs (histamine, tyramine toxicity and other BAs, environmental factors influencing BA formation (temperature, salt concentration, pH. In addition, the technological factors for controlling BA production (use of starter culture, technological additives, effects of packaging, other non-thermal treatments, metabolising BA by microorganisms, effects of pressure treatments on BA formation and antimicrobial substances are addressed.

  17. BIODEGRADATION OF AROMATIC AMINE COMPOUNDS USING MOVING BED BIOFILM REACTORS

    Directory of Open Access Journals (Sweden)

    M. Delnavaz ، B. Ayati ، H. Ganjidoust

    2008-10-01

    Full Text Available Three moving bed biofilm reactors were used to treat synthesized wastewater of aromatic amine compounds including aniline, para-diaminobenzene and para-aminophenol that are found in many industrial wastewaters. The reactors with cylindrical shape had an internal diameter and an effective depth of 10 and 60 cm, respectively. The reactors were filled with light expanded clay aggregate as carriers and operated in an aerobic batch and continuous conditions. Evaluation of the reactors' efficiency was done at different retention time of 8, 24, 48 and 72 h with an influent COD from 100 to 3500 mg/L (filling ratio of 50%. The maximum obtained removal efficiencies were 90% (influent COD=2000 mg/L, 87% (influent COD=1000 mg/L and 75% (influent COD=750 mg/L for aniline, para-diaminobenzene and para-aminophenol, respectively. In the study of decrease in filling ratio from 50 to 30 percent, 6% decrease for both para-diaminobenzene and para-aminophenol and 7% increase for aniline degradation were obtained. The removal efficiency was decreased to about 10% after 15 days of continuous loading for each of the above three substrates. In the shock loading test, initially the COD removal rate was decreased in all reactors, but after about 10 days, it has been approached to the previous values. Finally, biodegradability of aromatic amines has been proved by nuclear magnetic resonance system.

  18. Effect of Ionic Liquid on the Determination of Aromatic Amines as Contaminants in Hair Dyes by Liquid Chromatography Coupled to Electrochemical Detection

    Directory of Open Access Journals (Sweden)

    Maria Valnice Boldrin Zanoni

    2012-07-01

    Full Text Available The room temperature ionic liquid (IL 1-butyl-3-methylimidazolium bis-(trifluorometanesulfonylimide BMIm[NTf2] was used as a novel medium for improvement of separation and quantization of 16 aromatic amines typically present as contaminants in consumer products and detected by HPLC coupled to an electrochemical detector. The aromatic amines, namely 4,4'-diaminodiphenylmethane, 4-chloroaniline, 2-methoxy-5-methyl-aniline, 3,3'-dimethylbenzidine, 2,4-diaminotoluidine, 2-chloro-4-nitroaniline, 4,4'-oxydianiline, aniline, 3,3'-dichlorobenzidine, benzidine, 4-aminobiphenyl, o-dianisidine, o-anisidine, o-toluidine, 4,4'-methylene-bis-2-chloroaniline and 2-naphthyl-amine are oxidized in methanol/BMIm[NTf2] at a potential around +0.68V to +0.93V vs. Ag/AgCl at a glassy carbon electrode, which is the base for their determination by HPLC/ED. Using the optimized conditions of methanol/BMIm[NTf2] 70:30 (v/v as mobile phase, flow-rate of 0.8 mL·min−1, column CLC-ODS, Eap = +1.0 V and T = 40 °C analytical curves were constructed for each of the tested amines. Good linearity was obtained in the concentration range of 1.09 mg·L−1 to 217 mg·L−1, with excellent correlation coefficients. The limits of detection reached 0.021 mg·L−1 to 0.246 mg·L−1 and good relative standard deviations (RSD, n = 3 were obtained from the measurements. Satisfactory recovery for each aromatic amine was achieved, ranging from 95 to 103%. The developed method was successfully applied to determine six aromatic amines present as contaminants in commercial hair dye samples.

  19. Sheikh al-Amin Mazrui (1891-1947) and the Dilemma of Islamic Law ...

    African Journals Online (AJOL)

    Sheikh al-Amin Mazrui (1891-1947) and the Dilemma of Islamic Law in the Kenyan Legal System in the 21st Century ... While Sheikh al-Amin was radical in initiating educational and social transformation of the Muslim community in East Africa, his reform schemata in the realm of Islamic law was generally less impressive, ...

  20. Elaboration and characterisation of acids catalyst for the obtention of amines

    International Nuclear Information System (INIS)

    Khemaissia, S.; Zaoui, B.; Nibou, D.

    1997-04-01

    The nuclear energy has shown the interest of aminated substances as solvents for removal and purification. These extractants are generally used in uranium ores treatment processes and several technology fields, specially, in organic and pharmaceutical industries. The present work deals with elaboration and characterization of acidic solid catalyst used in aminated extractants obtaining