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Sample records for regioselective copper-catalyzed c-n

  1. Synthesis of ketene N,N-acetals by copper-catalyzed double-amidation of 1,1-dibromo-1-alkenes.

    Science.gov (United States)

    Coste, Alexis; Couty, François; Evano, Gwilherm

    2009-10-01

    An efficient procedure for the preparation of ketene N,N-acetals by copper-catalyzed double amidation of 1,1-dibromo-1-alkenes is reported. The reaction was found to be general, and ketene aminals could be obtained in good yields when potassium phosphate in toluene was used at 80 degrees C. The reaction was found to proceed through a regioselective monocoupling reaction followed by dehydrobromination and hydroamidation.

  2. Solvent effect on copper-catalyzed azide-alkyne cycloaddition (CuAAC): synthesis of novel triazolyl substituted quinolines as potential anticancer agents.

    Science.gov (United States)

    Ellanki, Amarender Reddy; Islam, Aminul; Rama, Veera Swamy; Pulipati, Ranga Prasad; Rambabu, D; Krishna, G Rama; Reddy, C Malla; Mukkanti, K; Vanaja, G R; Kalle, Arunasree M; Kumar, K Shiva; Pal, Manojit

    2012-05-15

    A regioselective route to novel mono triazolyl substituted quinolines has been developed via copper-catalyzed azide-alkyne cycloaddition (CuAAC) of 2,4-diazidoquinoline with terminal alkynes in DMF. The reaction provided bis triazolyl substituted quinolines when performed in water in the presence of Et(3)N. A number of the compounds synthesized showed promising anti-proliferative properties when tested in vitro especially against breast cancer cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    International Nuclear Information System (INIS)

    Paik, Seung Uk; Jung, Myoung Geun

    2012-01-01

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions

  4. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Energy Technology Data Exchange (ETDEWEB)

    Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

    2012-02-15

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

  5. Copper-catalyzed transformation of ketones to amides via C(CO)-C(alkyl) bond cleavage directed by picolinamide.

    Science.gov (United States)

    Ma, Haojie; Zhou, Xiaoqiang; Zhan, Zhenzhen; Wei, Daidong; Shi, Chong; Liu, Xingxing; Huang, Guosheng

    2017-09-13

    Copper catalyzed chemoselective cleavage of the C(CO)-C(alkyl) bond leading to C-N bond formation with chelation assistance of N-containing directing groups is described. Inexpensive Cu(ii)-acetate serves as a convenient catalyst for this transformation. This method highlights the emerging strategy to transform unactivated alkyl ketones into amides in organic synthesis and provides a new strategy for C-C bond cleavage.

  6. Remote C−H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling

    KAUST Repository

    Xu, Jun

    2016-01-12

    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    Science.gov (United States)

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Copper-catalyzed decarboxylative trifluoromethylation of allylic bromodifluoroacetates.

    Science.gov (United States)

    Ambler, Brett R; Altman, Ryan A

    2013-11-01

    The development of new synthetic fluorination reactions has important implications in medicinal, agricultural, and materials chemistries. Given the prevalence and accessibility of alcohols, methods to convert alcohols to trifluoromethanes are desirable. However, this transformation typically requires four-step processes, specialty chemicals, and/or stoichiometric metals to access the trifluoromethyl-containing product. A two-step copper-catalyzed decarboxylative protocol for converting allylic alcohols to trifluoromethanes is reported. Preliminary mechanistic studies distinguish this reaction from previously reported Cu-mediated reactions.

  9. Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

    Science.gov (United States)

    Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

    2014-01-01

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

  10. Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

    Science.gov (United States)

    Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

    2014-06-16

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

    Science.gov (United States)

    Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

    2014-02-05

    The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

  12. In situ generation of nitrilium from nitrile ylide and the subsequent Mumm rearrangement: copper-catalyzed synthesis of unsymmetrical diacylglycine esters.

    Science.gov (United States)

    Chen, Jijun; Shao, Ying; Ma, Liang; Ma, Meihua; Wan, Xiaobing

    2016-12-07

    A novel in situ generation of nitrilium from a nitrile ylide and the subsequent Mumm rearrangement of carboxylic acid, nitrile, and diazo compounds gave various unsymmetrical diacylglycine esters in moderate to high yields. This copper-catalyzed cascade reaction enables one-pot generation of two C-N bonds, one C[double bond, length as m-dash]O bond, and one C-H bond, with nitrogen as the only byproduct. The reaction has a broad functional-group tolerance, is rapid, easily scales up to the 100 mmol scale, and is insensitive to air and moisture.

  13. Synthesis of trifluoromethylated acetylenes via copper-catalyzed trifluoromethylation of alkynyltrifluoroborates

    KAUST Repository

    Zheng, Huidong

    2012-12-01

    A new method for the synthesis of trifluoromethylated acetylenes is developed which involves the copper-catalyzed trifluoromethylation of alkynyltrifluoroborates with an electrophilic trifluoromethylating reagent. This method offers significant advantages such as efficiency and mild and base-free reaction conditions. A plausible mechanism is proposed. © 2012 Elsevier Ltd. All rights reserved.

  14. Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O-Benzoyl Hydroxylamines.

    Science.gov (United States)

    Zhou, Shuangliu; Yang, Zhiyong; Chen, Xu; Li, Yimei; Zhang, Lijun; Fang, Hong; Wang, Wei; Zhu, Xiancui; Wang, Shaowu

    2015-06-19

    A copper-catalyzed electrophilic amination of aryl and heteroaryl aluminums with N,N-dialkyl-O-benzoyl hydroxylamines that affords the corresponding anilines in good yields has been developed. The catalytic reaction proceeds very smoothly under mild conditions and exhibits good substrate scope. Moreover, the developed catalytic system is also well suited for heteroaryl aluminum nucleophiles, providing facile access to heteroaryl amines.

  15. Room-temperature base-free copper-catalyzed trifluoromethylation of organotrifluoroborates to trifluoromethylarenes

    KAUST Repository

    Huang, Yuanyuan; Fang, Xin; Lin, Xiaoxi; Li, Huaifeng; He, Weiming; Huang, Kuo-Wei; Yuan, Yaofeng; Weng, Zhiqiang

    2012-01-01

    An efficient room temperature copper-catalyzed trifluoromethylation of organotrifluoroborates under the base free condition using an electrophilic trifluoromethylating reagent is demonstrated. The corresponding trifluoromethylarenes were obtained in good to excellent yields and the reaction tolerates a wide range of functional groups. © 2012 Elsevier Ltd. All rights reserved.

  16. Copper-catalyzed trifluoromethylation of arylsulfinate salts using an electrophilic trifluoromethylation reagent

    KAUST Repository

    Lin, Xiaoxi

    2013-03-01

    A copper-catalyzed method for the trifluoromethylation of arylsulfinates with Togni\\'s reagent has been developed, affording aryltrifluoromethylsulfones in moderate to good yields. A wide range of functional groups in arylsulfinates are compatible with the reaction conditions. © 2013 Elsevier Ltd. All rights reserved.

  17. Room-temperature base-free copper-catalyzed trifluoromethylation of organotrifluoroborates to trifluoromethylarenes

    KAUST Repository

    Huang, Yuanyuan

    2012-12-01

    An efficient room temperature copper-catalyzed trifluoromethylation of organotrifluoroborates under the base free condition using an electrophilic trifluoromethylating reagent is demonstrated. The corresponding trifluoromethylarenes were obtained in good to excellent yields and the reaction tolerates a wide range of functional groups. © 2012 Elsevier Ltd. All rights reserved.

  18. Synthesis of trifluoromethylated acetylenes via copper-catalyzed trifluoromethylation of alkynyltrifluoroborates

    KAUST Repository

    Zheng, Huidong; Huang, Yuanyuan; Wang, Zhiwei; Li, Huaifeng; Huang, Kuo-Wei; Yuan, Yaofeng; Weng, Zhiqiang

    2012-01-01

    A new method for the synthesis of trifluoromethylated acetylenes is developed which involves the copper-catalyzed trifluoromethylation of alkynyltrifluoroborates with an electrophilic trifluoromethylating reagent. This method offers significant advantages such as efficiency and mild and base-free reaction conditions. A plausible mechanism is proposed. © 2012 Elsevier Ltd. All rights reserved.

  19. Copper-catalyzed azide alkyne cycloaddition polymer networks

    Science.gov (United States)

    Alzahrani, Abeer Ahmed

    The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo

  20. Copper-Catalyzed Trifluoromethylazidation of Alkynes: Efficient Access to CF3-Substituted Azirines and Aziridines.

    Science.gov (United States)

    Wang, Fei; Zhu, Na; Chen, Pinhong; Ye, Jinxing; Liu, Guosheng

    2015-08-03

    A novel method for convenient access to CF3-containing azirines has been developed, and involves a copper-catalyzed trifluoromethylazidation of alkynes and a photocatalyzed rearrangement. Both terminal and internal alkynes are compatible with the mild reaction conditions, thus delivering the CF3-containing azirines in moderate to good yields. The azirines can be converted into various CF3-substituted aziridines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation.

    Science.gov (United States)

    Sequeira, Fatima C; Bovino, Michael T; Chipre, Anthony J; Chemler, Sherry R

    2012-05-01

    (S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure.

  2. Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

    Directory of Open Access Journals (Sweden)

    Zachary L. Palchak

    2015-08-01

    Full Text Available Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this uncommon class of hindered triazoles will accelerate exploration of their therapeutic potential. The superior activity of copper(II triflate in the formation of triazoles from sensitive alkyne substrates extends to simple terminal alkynes.

  3. A new approach to ferrocene derived alkenes via copper-catalyzed olefination

    Directory of Open Access Journals (Sweden)

    Vasily M. Muzalevskiy

    2015-11-01

    Full Text Available A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

  4. A new approach to ferrocene derived alkenes via copper-catalyzed olefination.

    Science.gov (United States)

    Muzalevskiy, Vasily M; Shastin, Aleksei V; Demidovich, Alexandra D; Shikhaliev, Namiq G; Magerramov, Abel M; Khrustalev, Victor N; Rakhimov, Rustem D; Vatsadze, Sergey Z; Nenajdenko, Valentine G

    2015-01-01

    A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

  5. Copper-Catalyzed Sulfonyl Azide-Alkyne Cycloaddition Reactions: Simultaneous Generation and Trapping of Copper-Triazoles and -Ketenimines for the Synthesis of Triazolopyrimidines.

    Science.gov (United States)

    Nallagangula, Madhu; Namitharan, Kayambu

    2017-07-07

    First simultaneous generation and utilization of both copper-triazole and -ketenimine intermediates in copper-catalyzed sulfonyl azide-alkyne cycloaddition reactions is achieved for the one-pot synthesis of triazolopyrimidines via a novel copper-catalyzed multicomponent cascade of sulfonyl azides, alkynes, and azirines. Significantly, the reaction proceeds under very mild conditions in good yields.

  6. Copper-Catalyzed N-Arylation of Amides Using (S-N-Methylpyrrolidine-2-carboxylate as the Ligand

    Directory of Open Access Journals (Sweden)

    Dong-Sheng Ma

    2010-03-01

    Full Text Available (S-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields.

  7. Bis(trialkylsilyl) peroxides as alkylating agents in the copper-catalyzed selective mono-N-alkylation of primary amides.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-06-13

    The copper-catalyzed selective mono-N-alkylation of primary amides with bis(trialkylsilyl) peroxides as alkylating agents was reported. The results of a mechanistic study suggest that this reaction should proceed via a free radical process that includes the generation of alkyl radicals from bis(trialkylsilyl) peroxides.

  8. Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents.

    Science.gov (United States)

    Hari, Durga Prasad; Waser, Jerome

    2016-02-24

    Alkynes have found widespread applications in synthetic chemistry, biology, and materials sciences. In recent years, methods based on electrophilic alkynylation with hypervalent iodine reagents have made acetylene synthesis more flexible and efficient, but they lead to the formation of one equivalent of an iodoarene as side-product. Herein, a more efficient strategy involving a copper-catalyzed oxy-alkynylation of diazo compounds with ethynylbenziodoxol(on)e (EBX) reagents is described, which proceeds with generation of nitrogen gas as the only waste. This reaction is remarkable for its broad scope in both EBX reagents and diazo compounds. In addition, vinyl diazo compounds gave enynes selectively as single geometric isomers. The functional groups introduced during the transformation served as easy handles to access useful building blocks for synthetic and medicinal chemistry.

  9. Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

    Science.gov (United States)

    Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

    2013-12-02

    A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Relative Performance of Alkynes in Copper-Catalyzed Azide-Alkyne Cycloaddition

    Science.gov (United States)

    Kislukhin, Alexander A.; Hong, Vu P.; Breitenkamp, Kurt E.; Finn, M.G.

    2013-01-01

    Copper-catalyzed azide–alkyne cycloaddition (CuAAC) has found numerous applications in a variety of fields. We report here only modest differences in the reactivity of various classes of terminal alkynes under typical bioconjugative and preparative organic conditions. Propargyl compounds represent an excellent combination of azide reactivity, ease of installation, and cost. Electronically activated propiolamides are slightly more reactive, at the expense of increased propensity for Michael addition. Certain alkynes, including tertiary propargyl carbamates, are not suitable for bioconjugation due to copper-induced fragmentation. A fluorogenic probe based on such reactivity is available in one step from rhodamine 110 and can be useful for optimization of CuAAC conditions. PMID:23566039

  11. Synthesis of Arylthiopyrimidines by Copper-catalyzed Aerobic Oxidative C-S Cross-coupling

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ok Suk; Kim, Hyeji; Sohn, Jeong-Hun [Chungnam National University, Daejeon (Korea, Republic of); Lee, Hee-Seung [KAIST, Daejeon (Korea, Republic of); Shin, Hyunik [Yonsung Fine Chemicals R and D Center, Suwon (Korea, Republic of)

    2016-02-15

    Copper-catalyzed C–S cross-coupling reactions have been considered as powerful tools in synthetic chemistry and utilized for diverse heterocycle syntheses. In the reactions, the aspects of no need of ligands has been particular advantage over other metal catalysis. We have developed a Cu-catalyzed cascade reaction for the synthesis of fully substituted 2-arylthiopyrimidines from 3,4-dihydropyrimidine-2(1H)-thiones (DHPMs) under aerobic conditions. This cascade reaction of DHPM with aryl iodide proceeds presumably via sequential tautomerization, C–S cross-coupling, and oxidative dehydrogenation (oxidation followed by elimination). Considering that DHPM substrates were easily synthesized by Biginelli three component coupling reaction of aryl aldehyde, β-ketoester, and thiourea, the present method provides a direct access toward diverse 2-arylthiopyrimidines which have been used as a prominent substructure of drug molecules.

  12. A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.

    Science.gov (United States)

    Xu, Boran; Lumb, Jean-Philip; Arndtsen, Bruce A

    2015-03-27

    The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides

    Science.gov (United States)

    Strieter, Eric R.; Bhayana, Brijesh; Buchwald, Stephen L.

    2009-01-01

    The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggest that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation. PMID:19072233

  14. Facile synthesis of benzofurans via copper-catalyzed aerobic oxidative cyclization of phenols and alkynes.

    Science.gov (United States)

    Zeng, Wei; Wu, Wanqing; Jiang, Huanfeng; Huang, Liangbin; Sun, Yadong; Chen, Zhengwang; Li, Xianwei

    2013-07-28

    Regioselective synthesis of polysubstituted benzofurans using a copper catalyst and molecular oxygen from phenols and alkynes in a one-pot procedure has been reported. The transformation consists of a sequential nucleophilic addition of phenols to alkynes and oxidative cyclization. A wide variety of phenols and alkynes can be used in the same manner.

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

    Science.gov (United States)

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

    2015-02-06

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

  16. Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(i) acetylides†

    OpenAIRE

    Hein, Jason E.; Fokin, Valery V.

    2010-01-01

    Copper-catalyzed azide–alkyne cycloaddition (CuAAC) is a widely utilized, reliable, and straightforward way for making covalent connections between building blocks containing various functional groups. It has been used in organic synthesis, medicinal chemistry, surface and polymer chemistry, and bioconjugation applications. Despite the apparent simplicity of the reaction, its mechanism involves multiple reversible steps involving coordination complexes of copper(i) acetylides of varying nucle...

  17. Selective Formation of Secondary Amides via the Copper-Catalyzed Cross-Coupling of Alkylboronic Acids with Primary Amides

    Science.gov (United States)

    Rossi, Steven A.; Shimkin, Kirk W.; Xu, Qun; Mori-Quiroz, Luis M.; Watson, Donald A.

    2014-01-01

    For the first time, a general catalytic procedure for the cross coupling of primary amides and alkylboronic acids is demonstrated. The key to the success of this reaction was the identification of a mild base (NaOSiMe3) and oxidant (di-tert-butyl peroxide) to promote the copper-catalyzed reaction in high yield. This transformation provides a facile, high-yielding method for the mono-alkylation of amides. PMID:23611591

  18. Structural Determinants of Alkyne Reactivity in Copper-Catalyzed Azide-Alkyne Cycloadditions

    Directory of Open Access Journals (Sweden)

    Xiaoguang Zhang

    2016-12-01

    Full Text Available This work represents our initial effort in identifying azide/alkyne pairs for optimal reactivity in copper-catalyzed azide-alkyne cycloaddition (CuAAC reactions. In previous works, we have identified chelating azides, in particular 2-picolyl azide, as “privileged” azide substrates with high CuAAC reactivity. In the current work, two types of alkynes are shown to undergo rapid CuAAC reactions under both copper(II- (via an induction period and copper(I-catalyzed conditions. The first type of the alkynes bears relatively acidic ethynyl C-H bonds, while the second type contains an N-(triazolylmethylpropargylic moiety that produces a self-accelerating effect. The rankings of reactivity under both copper(II- and copper(I-catalyzed conditions are provided. The observations on how other reaction parameters such as accelerating ligand, reducing agent, or identity of azide alter the relative reactivity of alkynes are described and, to the best of our ability, explained.

  19. RESULTS OF COPPER CATALYZED PEROXIDE OXIDATION (CCPO) OF TANK 48H SIMULANTS

    Energy Technology Data Exchange (ETDEWEB)

    Peters, T.; Pareizs, J.; Newell, J.; Fondeur, F.; Nash, C.; White, T.; Fink, S.

    2012-08-14

    Savannah River National Laboratory (SRNL) performed a series of laboratory-scale experiments that examined copper-catalyzed hydrogen peroxide (H{sub 2}O{sub 2}) aided destruction of organic components, most notably tetraphenylborate (TPB), in Tank 48H simulant slurries. The experiments were designed with an expectation of conducting the process within existing vessels of Building 241-96H with minimal modifications to the existing equipment. Results of the experiments indicate that TPB destruction levels exceeding 99.9% are achievable, dependent on the reaction conditions. The following observations were made with respect to the major processing variables investigated. A lower reaction pH provides faster reaction rates (pH 7 > pH 9 > pH 11); however, pH 9 reactions provide the least quantity of organic residual compounds within the limits of species analyzed. Higher temperatures lead to faster reaction rates and smaller quantities of organic residual compounds. Higher concentrations of the copper catalyst provide faster reaction rates, but the highest copper concentration (500 mg/L) also resulted in the second highest quantity of organic residual compounds. Faster rates of H{sub 2}O{sub 2} addition lead to faster reaction rates and lower quantities of organic residual compounds. Testing with simulated slurries continues. Current testing is examining lower copper concentrations, refined peroxide addition rates, and alternate acidification methods. A revision of this report will provide updated findings with emphasis on defining recommended conditions for similar tests with actual waste samples.

  20. Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-07-06

    The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Kinetics and mechanism of auto- and copper-catalyzed oxidation of 1,4-naphthohydroquinone.

    Science.gov (United States)

    Yuan, Xiu; Miller, Christopher J; Pham, A Ninh; Waite, T David

    2014-06-01

    H indicated good agreement between thermodynamic and kinetic considerations for various key reactions involved, further validating the proposed mechanisms involved in both the autoxidation and the copper-catalyzed oxidation of NH2Q in circumneutral pH solutions. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. Results Of Copper Catalyzed Peroxide Oxidation (CCPO) Of Tank 48H Simulants

    Energy Technology Data Exchange (ETDEWEB)

    Peters, T. B.; Pareizs, J. M.; Newell, J. D.; Fondeur, F. F.; Nash, C. A.; White, T. L.; Fink, S. D.

    2012-12-13

    Savannah River National Laboratory (SRNL) performed a series of laboratory-scale experiments that examined copper-catalyzed hydrogen peroxide (H{sub 2}O{sub 2}) aided destruction of organic components, most notably tetraphenylborate (TPB), in Tank 48H simulant slurries. The experiments were designed with an expectation of conducting the process within existing vessels of Building 241-96H with minimal modifications to the existing equipment. Results of the experiments indicate that TPB destruction levels exceeding 99.9% are achievable, dependent on the reaction conditions. A lower reaction pH provides faster reaction rates (pH 7 > pH 9 > pH 11); however, pH 9 reactions provide the least quantity of organic residual compounds within the limits of species analyzed. Higher temperatures lead to faster reaction rates and smaller quantities of organic residual compounds. A processing temperature of 50°C as part of an overall set of conditions appears to provide a viable TPB destruction time on the order of 4 days. Higher concentrations of the copper catalyst provide faster reaction rates, but the highest copper concentration (500 mg/L) also resulted in the second highest quantity of organic residual compounds. The data in this report suggests 100-250 mg/L as a minimum. Faster rates of H{sub 2}O{sub 2} addition lead to faster reaction rates and lower quantities of organic residual compounds. An addition rate of 0.4 mL/hour, scaled to the full vessel, is suggested for the process. SRNL recommends that for pH adjustment, an acid addition rate 42 mL/hour, scaled to the full vessel, is used. This is the same addition rate used in the testing. Even though the TPB and phenylborates can be destroyed in a relative short time period, the residual organics will take longer to degrade to <10 mg/L. Low level leaching on titanium occurred, however, the typical concentrations of released titanium are very low (~40 mg/L or less). A small amount of leaching under these conditions is not

  3. Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: an efficient method for the preparation of oxygen isotopically labeled carbonyl compounds.

    Science.gov (United States)

    Shibahara, Fumitoshi; Suenami, Aiko; Yoshida, Atsunori; Murai, Toshiaki

    2007-06-21

    A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative.

  4. Synthesis of phenanthrenes through copper-catalyzed cross-coupling of N-tosylhydrazones with terminal alkynes.

    Science.gov (United States)

    Hossain, Mohammad Lokman; Ye, Fei; Liu, Zhenxing; Xia, Ying; Shi, Yi; Zhou, Lei; Zhang, Yan; Wang, Jianbo

    2014-09-19

    A novel protocol for the synthesis of phenanthrenes through the copper-catalyzed reaction of aromatic tosylhydrazones with terminal alkynes is explored. The reaction proceeds via the formation of an allene intermediate and subsequent six-π-electron cyclization-isomerization, affording phenanthrene derivatives in good yields. The transformation can be performed in two ways: (1) with N-tosylhydrazones derived from [1,1'-biphenyl]-2-carbaldehydes and terminal alkynes as the starting materials and (2) with N-tosylhydrazones derived from aromatic aldehydes and 2-alkynyl biphenyls as the starting materials. This new phenanthrene synthesis uses readily available starting materials and a cheap copper catalyst and has a wide range of functional group compatibility.

  5. A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries

    International Nuclear Information System (INIS)

    Zeng, Guisheng; Deng, Xiaorong; Luo, Shenglian; Luo, Xubiao; Zou, Jianping

    2012-01-01

    Highlights: ► Catalytic ion was first applied to the bioleaching process of spent lithium-ion batteries. ► The bioleaching efficiency was great improved from 43.1% to 99.9% in the presence of copper ion. ► A new reaction model was proposed to explain the catalytic mechanism. - Abstract: A copper-catalyzed bioleaching process was developed to recycle cobalt from spent lithium-ion batteries (mainly LiCoO 2 ) in this paper. The influence of copper ions on bioleaching of LiCoO 2 by Acidithiobacillus ferrooxidans (A.f) was investigated. It was shown that almost all cobalt (99.9%) went into solution after being bioleached for 6 days in the presence of 0.75 g/L copper ions, while only 43.1% of cobalt dissolution was obtained after 10 days without copper ions. EDX, XRD and SEM analyses additionally confirmed that the cobalt dissolution from spent lithium-ion batteries could be improved in the presence of copper ions. The catalytic mechanism was investigated to explain the enhancement of cobalt dissolution by copper ions, in which LiCoO 2 underwent a cationic interchange reaction with copper ions to form CuCo 2 O 4 on the surface of the sample, which could be easily dissolved by Fe 3+ .

  6. A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guisheng, E-mail: zengguisheng@hotmail.com [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Deng, Xiaorong [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Luo, Shenglian, E-mail: sllou@hnu.edu.cn [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Luo, Xubiao; Zou, Jianping [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China)

    2012-01-15

    Highlights: Black-Right-Pointing-Pointer Catalytic ion was first applied to the bioleaching process of spent lithium-ion batteries. Black-Right-Pointing-Pointer The bioleaching efficiency was great improved from 43.1% to 99.9% in the presence of copper ion. Black-Right-Pointing-Pointer A new reaction model was proposed to explain the catalytic mechanism. - Abstract: A copper-catalyzed bioleaching process was developed to recycle cobalt from spent lithium-ion batteries (mainly LiCoO{sub 2}) in this paper. The influence of copper ions on bioleaching of LiCoO{sub 2} by Acidithiobacillus ferrooxidans (A.f) was investigated. It was shown that almost all cobalt (99.9%) went into solution after being bioleached for 6 days in the presence of 0.75 g/L copper ions, while only 43.1% of cobalt dissolution was obtained after 10 days without copper ions. EDX, XRD and SEM analyses additionally confirmed that the cobalt dissolution from spent lithium-ion batteries could be improved in the presence of copper ions. The catalytic mechanism was investigated to explain the enhancement of cobalt dissolution by copper ions, in which LiCoO{sub 2} underwent a cationic interchange reaction with copper ions to form CuCo{sub 2}O{sub 4} on the surface of the sample, which could be easily dissolved by Fe{sup 3+}.

  7. Synthesis of [methyl-[sup 14]C]-N-methylputrescine

    Energy Technology Data Exchange (ETDEWEB)

    Secor, H.V.; Izac, R.R.; Hassam, S.B.; Frisch, A.F. (Philip Morris Research Center, Richmond, VA (United States))

    1994-05-01

    [Methyl-[sup 14]C]-N-methylputrescine was prepared from [[sup 14]C]methylamine hydrochloride in five steps. Reaction of benzaldehyde and [[sup 14]C]methylamine (10 mCi) followed by catalytic hydrogenation yielded [methyl-[sup 14]C]-N-methylbenzylamine. The key step in this process is the alkylation of [methyl-[sup 14]C]-N-methylbenzylamine in aqueous medium with 4-bromobutyronitrile. The radiochemical purity of the final product after two successive catalytic hydrogenations was in excess of 97%. The radiochemical yields in two successive runs were 26 and 38%, based on starting [[sup 14]C]methylamine, with specific activities of 22 and 23 mCi/mmol, respectively. This sequence provides a convenient and efficient regioselective radiosynthesis of [methyl-[sup 14]C]-N-methylputrescine. (author).

  8. Copper-catalyzed difunctionalization of activated alkynes by radical oxidation-tandem cyclization/dearomatization to synthesize 3-trifluoromethyl spiro[4.5]trienones.

    Science.gov (United States)

    Hua, Hui-Liang; He, Yu-Tao; Qiu, Yi-Feng; Li, Ying-Xiu; Song, Bo; Gao, Pin; Song, Xian-Rong; Guo, Dong-Hui; Liu, Xue-Yuan; Liang, Yong-Min

    2015-01-19

    A copper-catalyzed difunctionalizing trifluoromethylation of activated alkynes with the cheap reagent sodium trifluoromethanesulfinate (NaSO2CF3 or Langlois' reagent) has been developed incorporating a tandem cyclization/dearomatization process. This strategy affords a straightforward route to synthesis of 3-(trifluoromethyl)-spiro[4.5]trienones, and presents an example of difunctionalization of alkynes for simultaneous formation of two carbon-carbon single bonds and one carbon-oxygen double bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Development of Copper-Catalyzed Electrophilic Trifluoromethylation and Exploiting Cu/Cu2O Nanowires with Novel Catalytic Reactivity

    KAUST Repository

    Li, Huaifeng

    2014-06-01

    This thesis is based on research in Cu-catalyzed electrophilic trifluoromethylation and exploiting Cu/Cu2O nanowires with novel catalytic reactivity for developing of catalytic and greener synthetic methods. A large number of biological active pharmaceuticals and agrochemicals contain fluorine substituents (-F) or trifluoromethyl groups (-CF3) because these moieties often result in profound changes of their physical, chemical, and biological properties, such as metabolic stability and lipophilicity. For this reason, the introduction of fluorine or trifluoromethyl groups into organic molecules has attracted intensive attention. Among them, transition metal-catalyzed trifluoromethylation reactions has proved to be an efficient and reliable strategy to construct carbon-fluorine (C-F) and carbontrifluoromethyl (C-CF3) bond. We have developed a catalytic process for the first time for trifluoromethylation of terminal alkynes with Togni’s reagent, affording trifluoromethylated acetylenes in good to excellent yields. The reaction is conducted at room temperature and exhibits tolerance to a range of functional groups. Derived from this discovery, the extension of work of copper catalyzed electrophilic trifluoromethylation were investigated which include the electrophilic trifluoromethylation of arylsulfinate salts and electrophilic trifluoromethylation of organotrifluoroborates. Because of growing environmental concern, the development of greener synthetic methods has drawn much attention. Nano-sized catalysts are environment-friendly and an attractive green alternative to the conventional homogeneous catalysts. The nano-sized catalysts can be easily separated from the reaction mixture due to their insolubility and thus they can be used recycled. Notably, because of the high reactivities of nano-sized metal catalysts, the use of ligands can be avoided and the catalysts loadings can be reduced greatly. Moreover, the nano-sized catalysts can increase the exposed surface

  10. C N Sundaresan

    Indian Academy of Sciences (India)

    Fascinating Organic Molecules from Nature - Colours in Flight - Pigments from Bird Feathers and Butterfly Wings · N R Krishnaswamy C N Sundaresan · More Details Fulltext PDF. Volume 18 Issue 3 March 2013 pp 218-225 Series Article. Fascinating Organic Molecules from Nature - Hunting with Poisoned Arrows: Story of ...

  11. Nonafluorobutanesulfonyl azide as a shelf-stable highly reactive oxidant for the copper-catalyzed synthesis of 1,3-diynes from terminal alkynes.

    Science.gov (United States)

    Suárez, José Ramón; Collado-Sanz, Daniel; Cárdenas, Diego J; Chiara, Jose Luis

    2015-01-16

    Nonafluorobutanesulfonyl azide is a highly efficient reagent for the copper-catalyzed coupling of terminal alkynes to give symmetrical and unsymmetrical 1,3-diynes in good to excellent yields and with good functional group compatibility. The reaction is extremely fast (<10 min), even at low temperature (−78 °C), and requires substoichiometric amounts of a simple copper(I) or copper(II) salt (2–5 mol %) and an organic base (0.6 mol %). A possible mechanistic pathway is briefly discussed on the basis of model DFT theoretical calculations. The quantitative assessment of the safety of use and shelf stability of nonafluorobutanesulfonyl azide has confirmed that this reagent is a superior and safe alternative to other electrophilic azide reagents in use today.

  12. Copper-Catalyzed Domino Three-Component Approach for the Assembly of 2-Aminated Benzimidazoles and Quinazolines.

    Science.gov (United States)

    Tran, Lam Quang; Li, Jihui; Neuville, Luc

    2015-06-19

    A copper-promoted three-component synthesis of 2-aminobenzimidazoles (1) or of 2-aminoquinazolines (2) involving cyanamides, arylboronic acids, and amines has been developed. The operationally simple oxidative process, performed in the presence of K2CO3, a catalytic amount of CuCl2·2H2O, 2,2'-bipyridine, and an O2 atmosphere (1 atm), allows the rapid assembly of either benzimidazoles or quinazolines starting from aryl- or benzyl-substituted cyanamides, respectively. In this process, the copper promotes the formation of three bonds, two C-N bonds, and an additional bond resulting from C-H functionalization event.

  13. Solvent-free copper-catalyzed click chemistry for the synthesis of N-heterocyclic hybrids based on quinoline and 1,2,3-triazole

    Directory of Open Access Journals (Sweden)

    Martina Tireli

    2017-11-01

    Full Text Available Copper-catalyzed mechanochemical click reactions using Cu(II, Cu(I and Cu(0 catalysts have been successfully implemented to provide novel 6-phenyl-2-(trifluoromethylquinolines with a phenyl-1,2,3-triazole moiety at O-4 of the quinoline core. Milling procedures proved to be significantly more efficient than the corresponding solution reactions, with up to a 15-fold gain in yield. Efficiency of both solution and milling procedures depended on the p-substituent in the azide reactant, resulting in H < Cl < Br < I reactivity bias. Solid-state catalysis using Cu(II and Cu(I catalysts entailed the direct involvement of the copper species in the reaction and generation of highly luminescent compounds which hindered in situ monitoring by Raman spectroscopy. However, in situ monitoring of the milling processes was enabled by using Cu(0 catalysts in the form of brass milling media which offered a direct insight into the reaction pathway of mechanochemical CuAAC reactions, indicating that the catalysis is most likely conducted on the surface of milling balls. Electron spin resonance spectroscopy was used to determine the oxidation and spin states of the respective copper catalysts in bulk products obtained by milling procedures.

  14. Regioselective Synthesis of Cellulose Ester Homopolymers

    Science.gov (United States)

    Daiqiang Xu; Kristen Voiges; Thomas Elder; Petra Mischnick; Kevin J. Edgar

    2012-01-01

    Regioselective synthesis of cellulose esters is extremely difficult due to the small reactivity differences between cellulose hydroxyl groups, small differences in steric demand between acyl moieties of interest, and the difficulty of attaching and detaching many protecting groups in the presence of cellulose ester moieties without removing the ester groups. Yet the...

  15. Lewis acid controlled regioselectivity in styrene hydrocyanation

    NARCIS (Netherlands)

    Bini, L.; Pidko, E.A.; Müller, C.; Santen, van R.A.; Vogt, D.

    2009-01-01

    According to present knowledge, the Ni-catalyzed hydrocyanation of styrene leads predominantly to the branched product 2-phenylpropionitrile (98%). We observed a dramatic inversion of the regioselectivity upon addition of a Lewis acid. Up to 83 % of the linear product 3-phenylpropionitrile was

  16. Fully recoverable rigid shape memory foam based on copper-catalyzed azide-alkyne cycloaddition (CuAAC) using a salt leaching technique.

    Science.gov (United States)

    Alzahrani, Abeer A; Saed, Mohand; Yakacki, Christopher M; Song, Han Byul; Sowan, Nancy; Walston, Joshua J; Shah, Parag K; McBride, Matthew K; Stansbury, Jeffrey W; Bowman, Christopher N

    2018-01-07

    This study is the first to employ the use of the copper-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization to form a tough and stiff, porous material from a well-defined network possessing a high glass transition temperature. The effect of the network linkages formed as a product of the CuAAC reaction, i.e., the triazoles, on the mechanical behavior at high strain was evaluated by comparing the CuAAC foam to an epoxy-amine-based foam, which consisted of monomers with similar backbone structures and mechanical properties (i.e., T g of 115 °C and a rubbery modulus of 1.0 MPa for the CuAAC foam, T g of 125 °C and a rubbery modulus of 1.2 MPa for the epoxy-amine foam). When each foam was compressed uniformly to 80% strain at ambient temperature, the epoxy-amine foam was severely damaged after only reaching 70% strain in the first compression cycle with a toughness of 300 MJ/m 3 . In contrast, the CuAAC foam exhibited pronounced ductile behavior in the glassy state with three times higher toughness of 850 MJ/m 3 after the first cycle of compression to 80% strain. Additionally, when the CuAAC foam was heated above T g after each of five compression cycles to 80% strain at ambient temperature, the foam completely recovered its original shape while exhibiting a gradual decrease in mechanical performance over the multiple compression cycles. The foam demonstrated almost complete shape fixity and recovery ratios even through five successive cycles, indicative of "reversible plasticity", making it highly desirable as a glassy shape memory foams.

  17. Designing new catalytic C-C and C-N bond formations promoted by organoactinides

    International Nuclear Information System (INIS)

    Eisen, M.S.; Straub, T.; Haskel, A.

    1998-01-01

    Organoactinides of the type Cp 2 * AcMe 2 (Cp * =C 5 Me 5 ; Ac=Th; U) are active catalytic precursors for the oligomerization of terminal alkynes HC≡CR (R=alkyl, aryl, SiMe 3 ). The regioselectivity and the extent of oligomerization depend strongly on the alkyne substituent R, whereas the catalytic reactivity is similar for both organoactinides. Reaction with tert-butylacetylene yields regioselectively the E-2,4-disubstituted 1-buten-3-yne dimer whereas trimethylsilylacetylene is regioselective trimerized to the E,E-1,4,6-tris(trimethylsilyl)-1,3-hexa diene-5-yne, with small amounts (3-5%) of the corresponding E-2,4-disubstituted 1-buten-3-yne dimer. Oligomerization with less bulky alkyl and aryl substituted alkynes produces a mixture of higher oligomers with no regioselectivity. Using the Cp 2 * ThMe 2 catalyst, we have recently developed a strategic method to control the extent and in some cases the regioselectivity of the catalyzed oligomerization of nonbulky terminal alkynes to dimers and/or trimers. The metallocene catalytic precursors ensure the selective synthesis of small oligomers by the addition of specific amines. Catalytic ''tailoring'' to dimer and trimers can be achieved by using small or bulky amines, respectively. Kinetic and mechanistic data for the controlling experiments argue that the turnover-limiting step involves the acetylide actinide complex formation with the rapid insertion of the alkyne and protonolysis by the amine. The analog Cp 2 * UMe 2 in the presence of primary amines induce the selective C-N bond formation, producing enamines which are tautomerized to the corresponding imines. (orig.)

  18. Synthesis and characterization of cyclic polystyrene using copper-catalyzed alkyne-azide cycloaddition coupling - evaluation of physical properties and optimization of cyclization conditions

    Science.gov (United States)

    Elupula, Ravinder

    Polymers with a cyclic topology exhibit a range of unique and potentially useful physical properties, including reduced rates of degradation and increased rates of diffusion in bulk relative to linear analogs. However the synthesis of high purity cyclic polymers, and verification of their structural purity remains challenging. The copper-catalyzed azide-alkyne "click" cyclization route toward cyclic polymers has been used widely, due to its synthetic ease and its compatibility with diverse polymer backbones. Yet unoptimized click cyclization conditions have been observed to generate oligomeric byproducts. In order to optimize these cyclization conditions, and to better understand the structure of the higher molecular weight oligomers, these impurities have been isolated by size exclusion chromatography (SEC) and characterized by mass spectrometry (MS). Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-ToF) MS is a particularly valuable characterization tool and was used to determine that the high molecular weight impurities are predominantly cyclic oligomers. It should also be noted that the rapid analysis and small analyte requirements of this MS technique make it particularly attractive as a general tool for elucidating polymer architecture. Ability to tailor the physical properties of polymers by changing the architecture alone has garnered a lot of attention over the past few decades. Compared to their linear analogues, these novel polymer architectures behave completely different in nanoscale regime. Cyclic polymers are especially intriguing since we can compare the differences in the physical properties with that of the linear chains. One of the major physical property changes are T g-confinement effect. Using ATRP and "click chemistry" we have produced highly pure cyclic PS (c-PS) with number-average molecular weight (MW) of 3.4 kg/mol and 9.1 kg/mol. Bulk glass transition temperatures for c-PS were weakly depended on MWs

  19. Direct, Regioselective N-Alkylation of 1,3-Azoles.

    Science.gov (United States)

    Chen, Shuai; Graceffa, Russell F; Boezio, Alessandro A

    2016-01-04

    Regioselective N-alkylation of 1,3-azoles is a valuable transformation. Organomagnesium reagents were discovered to be competent bases to affect regioselective alkylation of various 1,3-azoles. Counterintuitively, substitution selectively occurred at the more sterically hindered nitrogen atom. Numerous examples are provided, on varying 1,3-azole scaffolds, with yields ranging from 25 to 95%.

  20. Regioselectivity of conjugate additions to monoalkyl-1,4-benzoquinones

    Directory of Open Access Journals (Sweden)

    SNEZANA TRIFUNOVIC

    2002-09-01

    Full Text Available The regioselectivity of the reaction of conjugate addition of thiols, amines, methanol and hydrogen chloride with the monoalkyl-1,4-benzoquinones avarone and 2-tert-butyl-1,4-benzoquinone was investigated. It was shown that the regioselectivity of the reaction is influenced by the electrophilicity of position 5 in unprotonated 2-alkylquinones, the increased electrophilicity of position 6 in acidic medium, and by the acidity of the intermediate hydroquinones.

  1. High regioselective acetylation of vitamin A precursors using lipase ...

    African Journals Online (AJOL)

    Administrator

    2011-09-26

    Sep 26, 2011 ... High regioselective acetylation of vitamin A precursors using lipase B from Candida antarctica in organic media. Jingpeng Sun, Keju Jing* and Yinghua Lu. Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen. University, Xiamen 361005, P. R. ...

  2. Method Development in the Regioselective Glycosylation of Unprotected Carbohydrates

    DEFF Research Database (Denmark)

    Niedbal, Dominika Alina

    and the glycosylations were promoted by tetrabutylammonium bromide. The couplings were completely selective and gave rise to a number of 1,6-linked disaccharides with 1,2- cis-linked orientation. Project 2: Boron-mediated glycosylation of unprotected carbohydrates Boron-mediated regioselective Koenigs...

  3. Regioselective iodoazidation of alkynes: synthesis of α,α-diazidoketones.

    Science.gov (United States)

    Okamoto, Noriko; Sueda, Takuya; Minami, Hideki; Miwa, Yoshihisa; Yanada, Reiko

    2015-03-06

    Aryl alkyl alkynes reacted with N-iodosuccinimide (NIS) and trimethylsilyl azide (TMSN3), leading to α,α-diazidoketones via the regioselective addition of IN3 to alkynes. Huisgen cyclization of α,α-diazidoketones generated bis-triazole compounds.

  4. Mechanism and regioselectivity of 1,3-dipolar cycloaddition ...

    Indian Academy of Sciences (India)

    1,3-Dipolar cycloaddition; sulphur-centred 1,3-dipoles; regioselectivity; DFT reactivity indices;. FMO theory. 1. Introduction. Five-membered heterocyclic compounds can be gene- rated by addition of a 1,3-dipole to a dipolarophile under a 1,3-dipolar cycloaddition (1,3-DC) reaction which is well known as pericyclic reaction.

  5. Exploring Cooperative Effects in Oxidative NHC Catalysis: Regioselective Acylation of Carbohydrates.

    Science.gov (United States)

    Cramer, David L; Bera, Srikrishna; Studer, Armido

    2016-05-23

    The utility of oxidative NHC catalysis for both the regioselective and chemoselective functionalization of carbohydrates is explored. Chiral NHCs allow for the highly regioselective oxidative esterification of various carbohydrates using aldehydes as acylation precursors. The transformation was also shown to be amenable to both cis/trans diol isomers, free amino groups, and selective for specific sugar epimers in competition experiments. Efficiency and regioselectivity of the acylation can be improved upon using two different NHC catalysts that act cooperatively. The potential of the method is documented by the regioselective acylation of an amino-linked neodisaccharide. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Electronic and steric effects in regioselective tritiation of anilides

    Energy Technology Data Exchange (ETDEWEB)

    OOhashi, Kunio; Udo, Masato (Chiba Univ. (Japan). Coll. of Arts and Sciences)

    1992-07-01

    Acetanilide, propionanilide and isobutyranilide were tritiated at the ortho positions with very high regioselectivity by heating with HTO in the presence of RhCl[sub 3][center dot]3H[sub 2]O in N, N-dimethylformamide (DMF). In this reaction for pivalanilide the specific activity alone was determined, because attempts to establish the regioselectivity were unsuccessful. The extent of tritium incorporation decreased with increasing bulkiness of the alkyl groups. Only slight tritium was introduced by the same reaction for trifluoroacetanilide, which would probably be attributed to a strong electron-attracting property of the trifluoromethyl group. The above findings give support to the previous suggestion that the present isotope exchange reaction proceeds via an initial coordination of the nitrogen atom of anilides to the rhodium (III) chloride trihydrate catalyst. (author).

  7. Role of ligands in controlling the regioselectivity in ruthenium ...

    Indian Academy of Sciences (India)

    of Hay and Wadt (LANL2DZ)11 for ruthenium atom and 6-31G(d)12 for other .... C2 atom in 3x/3′ x. To understand the wider role of lig- ands in modulating the regio-selectivity of product for- mation, we have studied the benzoic acid addition to the selected .... at C1 and the localization of electron density in the. M=C double ...

  8. Rhodium-Catalyzed Regioselective C7-Olefination of Indazoles Using an N-Amide Directing Group.

    Science.gov (United States)

    Guo, Lei; Chen, Yanyu; Zhang, Rong; Peng, Qiujun; Xu, Lanting; Pan, Xianhua

    2017-02-01

    A rhodium-catalyzed regioselective C-H olefination of indazole is described. This protocol relies on the use of an efficient and removable N,N-diisopropylcarbamoyl directing group, which offers facile access to C7-olefinated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Regioselective Acylation of Diols and Triols: The Cyanide Effect.

    Science.gov (United States)

    Peng, Peng; Linseis, Michael; Winter, Rainer F; Schmidt, Richard R

    2016-05-11

    Central topics of carbohydrate chemistry embrace structural modifications of carbohydrates and oligosaccharide synthesis. Both require regioselectively protected building blocks that are mainly available via indirect multistep procedures. Hence, direct protection methods targeting a specific hydroxy group are demanded. Dual hydrogen bonding will eventually differentiate between differently positioned hydroxy groups. As cyanide is capable of various kinds of hydrogen bonding and as it is a quite strong sterically nondemanding base, regioselective O-acylations should be possible at low temperatures even at sterically congested positions, thus permitting formation and also isolation of the kinetic product. Indeed, 1,2-cis-diols, having an equatorial and an axial hydroxy group, benzoyl cyanide or acetyl cyanide as an acylating agent, and DMAP as a catalyst yield at -78 °C the thermodynamically unfavorable axial O-acylation product; acyl migration is not observed under these conditions. This phenomenon was substantiated with 3,4-O-unproteced galacto- and fucopyranosides and 2,3-O-unprotected mannopyranosides. Even for 3,4,6-O-unprotected galactopyranosides as triols, axial 4-O-acylation is appreciably faster than O-acylation of the primary 6-hydroxy group. The importance of hydrogen bonding for this unusual regioselectivity could be confirmed by NMR studies and DFT calculations, which indicate favorable hydrogen bonding of cyanide to the most acidic axial hydroxy group supported by hydrogen bonding of the equatorial hydroxy group to the axial oxygen. Thus, the "cyanide effect" is due to dual hydrogen bonding of the axial hydroxy group which enhances the nucleophilicity of the respective oxygen atom, permitting an even faster reaction for diols than for mono-ols. In contrast, fluoride as a counterion favors dual hydrogen bonding to both hydroxy groups leading to equatorial O-acylation.

  10. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    Science.gov (United States)

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  11. Iridium-Catalyzed Regioselective Borylation of Substituted Biaryls

    KAUST Repository

    Chotana, Ghayoor

    2018-03-28

    Biarylboronic esters are generally prepared by directed ortho­ -metalation or by Miyaura borylation and hence rely on the presence of a directing group or pre-functionalization. In this paper, the preparation of biarylboronic esters by direct C–H borylation of biaryl substrates is reported. Sterically governed regioselectivities were observed in the borylation of appropriately substituted biaryls by using [Ir(OMe)(COD)] precatalyst and di- tert -butylbipyridyl ligand. The resulting biarylboronic esters were isolated in 38–98% yields. The synthesized biarylboronic esters were further successfully employed in C–O, C–Br, and C–C coupling reactions.

  12. Regioselective synthesis of C3 alkylated and arylated benzothiophenes

    Science.gov (United States)

    Shrives, Harry J.; Fernández-Salas, José A.; Hedtke, Christin; Pulis, Alexander P.; Procter, David J.

    2017-03-01

    Benzothiophenes are heterocyclic constituents of important molecules relevant to society, including those with the potential to meet modern medical challenges. The construction of molecules would be vastly more efficient if carbon-hydrogen bonds, found in all organic molecules, can be directly converted into carbon-carbon bonds. In the case of elaborating benzothiophenes, functionalization of carbon-hydrogen bonds at carbon-number 3 (C3) is markedly more demanding than at C2 due to issues of regioselectivity (C3 versus C2), and the requirement of high temperatures, precious metals and the installation of superfluous directing groups. Herein, we demonstrate that synthetically unexplored but readily accessible benzothiophene S-oxides serve as novel precursors for C3-functionalized benzothiophenes. Employing an interrupted Pummerer reaction to capture and then deliver phenol and silane coupling partners, we have discovered a directing group-free method that delivers C3-arylated and -alkylated benzothiophenes with complete regioselectivity, under metal-free and mild conditions.

  13. Highly efficient and enzymatic regioselective undecylenoylation of gastrodin in 2-methyltetrahydrofuran-containing systems.

    Directory of Open Access Journals (Sweden)

    Rongling Yang

    Full Text Available Highly efficient and regioselective acylation of pharmacologically interesting gastrodin with vinyl undecylenic acid has been firstly performed through an enzymatic approach. The highest catalytic activity and regioselectivity towards the acylation of 7'-hydroxyl of gastrodin was obtained with Pseudomonas cepacia lipase. In addition, it was observed the lipase displayed higher activity in the eco-friendly solvent 2-methyltetrahydrofuran-containing systems than in other organic solvents. In the co-solvent mixture of tetrahydrofuran and 2-methyltetrahydrofuran (3/1, v/v, the reaction rate was 60.6 mM/h, substrate conversion exceeded 99%, and 7'-regioselectivity was 93%. It was also interesting that the lipase-catalyzed acylation couldn't be influenced by the benzylic alcohol in gastrodin. However, pseudomonas cepacia lipase displayed different regioselectivity towards gastrodin and arbutin.

  14. Regioselective alkali metal reduction of dibenzocyclooctadiene lignan derivatives, demethoxylation followed by dehalogenation.

    Science.gov (United States)

    Wang, Qing-Yao; Fang, Jia-Qi; Deng, Lu-Lu; Hao, Xiao-Jiang; Mu, Shu-Zhen

    2017-12-27

    The regioselective demethoxylation and dehalogenation of dihalogenated dibenzocyclooctadiene lignans derivatives were realized in a one-step reaction with excellent yields in the sodium and t-butanol reaction system.

  15. Highly efficient and enzymatic regioselective undecylenoylation of gastrodin in 2-methyltetrahydrofuran-containing systems.

    Science.gov (United States)

    Yang, Rongling; Liu, Xueming; Chen, Zhiyi; Yang, Chunying; Lin, Yaosheng; Wang, Siyuan

    2014-01-01

    Highly efficient and regioselective acylation of pharmacologically interesting gastrodin with vinyl undecylenic acid has been firstly performed through an enzymatic approach. The highest catalytic activity and regioselectivity towards the acylation of 7'-hydroxyl of gastrodin was obtained with Pseudomonas cepacia lipase. In addition, it was observed the lipase displayed higher activity in the eco-friendly solvent 2-methyltetrahydrofuran-containing systems than in other organic solvents. In the co-solvent mixture of tetrahydrofuran and 2-methyltetrahydrofuran (3/1, v/v), the reaction rate was 60.6 mM/h, substrate conversion exceeded 99%, and 7'-regioselectivity was 93%. It was also interesting that the lipase-catalyzed acylation couldn't be influenced by the benzylic alcohol in gastrodin. However, pseudomonas cepacia lipase displayed different regioselectivity towards gastrodin and arbutin.

  16. Rhodium-catalyzed Chemo- and Regioselective Cross-dimerization of Two Terminal Alkynes

    Science.gov (United States)

    Xu, Hua-Dong; Zhang, Ren-Wei; Li, Xiaoxun; Huang, Suyu; Tang, Weiping; Hu, Wen-Hao

    2013-01-01

    Cross-dimerization of terminal arylacetylenes and terminal propargylic alcohols/amides has been achieved in the effect of a rhodium catalyst. This method features high chemo- and regioselectivities rendering convenient and atom economical access to functionalized enynes. PMID:23356993

  17. Regioselective Alcoholysis of Silychristin Acetates Catalyzed by Lipases

    Directory of Open Access Journals (Sweden)

    Eva Vavříková

    2015-05-01

    Full Text Available A panel of lipases was screened for the selective acetylation and alcoholysis of silychristin and silychristin peracetate, respectively. Acetylation at primary alcoholic group (C-22 of silychristin was accomplished by lipase PS (Pseudomonas cepacia immobilized on diatomite using vinyl acetate as an acetyl donor, whereas selective deacetylation of 22-O-acetyl silychristin was accomplished by Novozym 435 in methyl tert-butyl ether/ n-butanol. Both of these reactions occurred without diastereomeric discrimination of silychristin A and B. Both of these enzymes were found to be capable to regioselective deacetylation of hexaacetyl silychristin to afford penta-, tetra- and tri-acetyl derivatives, which could be obtained as pure synthons for further selective modifications of the parent molecule.

  18. Regioselective Alcoholysis of Silychristin Acetates Catalyzed by Lipases ‡

    Science.gov (United States)

    Vavříková, Eva; Gavezzotti, Paolo; Purchartová, Kateřina; Fuksová, Kateřina; Biedermann, David; Kuzma, Marek; Riva, Sergio; Křen, Vladimír

    2015-01-01

    A panel of lipases was screened for the selective acetylation and alcoholysis of silychristin and silychristin peracetate, respectively. Acetylation at primary alcoholic group (C-22) of silychristin was accomplished by lipase PS (Pseudomonas cepacia) immobilized on diatomite using vinyl acetate as an acetyl donor, whereas selective deacetylation of 22-O-acetyl silychristin was accomplished by Novozym 435 in methyl tert-butyl ether/n-butanol. Both of these reactions occurred without diastereomeric discrimination of silychristin A and B. Both of these enzymes were found to be capable to regioselective deacetylation of hexaacetyl silychristin to afford penta-, tetra- and tri-acetyl derivatives, which could be obtained as pure synthons for further selective modifications of the parent molecule. PMID:26016503

  19. The first organocatalytic, ortho-regioselective inverse-electron-demand hetero-Diels-Alder reaction.

    Science.gov (United States)

    Hejmanowska, Joanna; Jasiński, Marcin; Wojciechowski, Jakub; Mlostoń, Grzegorz; Albrecht, Łukasz

    2017-10-17

    The development of the unprecedented ortho-regioselective inverse-electron-demand hetero-Diels-Alder (IEDHDA) reaction is described. It has been demonstrated that by proper choice of reactants and reaction conditions the inverse-electron-demand hetero-Diels-Alder cycloaddition can be realized with unprecedented regioselectivity arising from the reaction between the terminal carbon atom of the dienophile and the heteroatom of the heterodiene.

  20. Enzyme-Catalyzed Regioselective Modification of Starch Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Soma [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Sahoo, Bishwabhusan [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Teraoka, Iwao [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Miller, Lisa M. [Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source (NSLS); Gross, Richard A. [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering

    2004-12-13

    The selective esterification of starch nanoparticles was performed using as catalyst Candida antartica Lipase B (CAL-B) in its immobilized (Novozym 435) and free (SP-525) forms. The starch nanoparticles were made accessible for acylation reactions by formation of Aerosol-OT (AOT, bis(2-ethylhexyl)sodium sulfosuccinate) stabilized microemulsions. Starch nanoparticles in microemulsions were reacted with vinyl stearate, ε-caprolactone, and maleic anhydride at 40 °C for 48 h to give starch esters with degrees of substitution (DS) of 0.8, 0.6, and 0.4, respectively. Substitution occurred regioselectively at the C-6 position of the glucose repeat units. Infrared microspectroscopy (IRMS) revealed that AOT-coated starch nanoparticles diffuse into the outer 50 μm shell of catalyst beads. Thus, even though CAL-B is immobilized within a macroporous resin, CAL-B is sufficiently accessible to the starch nanoparticles. When free CAL-B was incorporated along with starch within AOT-coated reversed micelles, CAL-B was also active and catalyzed the acylation with vinyl stearate (24 h, 40 °C) to give DS = 0.5. After removal of surfactant from the modified starch nanoparticles, they were dispersed in DMSO or water and were shown to retain their nanodimensions.

  1. Regioselective hydroxylation of isoflavones by Streptomyces avermitilis MA-4680.

    Science.gov (United States)

    Roh, Changhyun; Seo, Su-Hyun; Choi, Kwon-Young; Cha, Minho; Pandey, Bishnu Prasad; Kim, June-Hyung; Park, Jun-Seong; Kim, Duck Hee; Chang, Ih Seop; Kim, Byung-Gee

    2009-07-01

    Screening of bacterial whole cells was performed for regioselective hydroxylation of daidzein and genistein. Among the strains examined, Streptomyces avermitilis MA-4680 showed high ortho-dihydroxylation activity to produce 3',4',7-trihydroxyisoflavone and 3',4',5,7-tetrahydroxyisoflavone from daidzein (4',7-dihydroxyisoflavone) and genistein (4',5,7-trihydroxyisoflavone), respectively. Using 100 mg cells (wet wt.) and 1% (v/v) Triton X100 in 1 ml of total reaction volume, where 100 microl of the substrate solution (0.5 mM in 10% (v/v) mixed solvent of DMSO:MeOH = 3:7) was added to 900 microl of potassium phosphate buffer (100 mM, pH 7.2), a 16% molar conversion yield of 3',4',7-trihydroxyisoflavone was obtained from 0.5 mM daidzein after 24 h of reaction time at 28 degrees C and 200 rpm. Ketoconazole significantly (ca. 90%) inhibited the ortho-hydroxylation activity of daidzein, suggesting that cytochrome P450 enzymes putatively play roles in regiospecific daidzein hydroxylation. The analysis of the reaction products was determined by gas chromatography/mass spectrometry (GC/MS) and (1)H NMR.

  2. Highly regioselective synthesis of undecylenic acid esters of purine nucleosides catalyzed by Candida antarctica lipase B.

    Science.gov (United States)

    Gao, Wen-Li; Li, Ning; Zong, Min-Hua

    2011-11-01

    Regioselective undecylenoylation of purine nucleosides as potential dual prodrugs was achieved by Candida antarctica lipase B using adenosine as a model reactant. The optimum organic solvent, molar ratio of vinyl ester to nucleoside, enzyme dosage, reaction temperature and molecular sieve amount were anhydrous THF, 5:1, 20 U/ml, 45°C and 75 mg/ml, respectively. Under the optimum conditions, the initial reaction rate, yield and 5'-regioselectivity were 1.1 mM/h, 90% and >99%, respectively. The enzymatic acylation of various nucleosides furnished the desired 5'-ester derivatives with the yields of 60-95% and 5'-regioselectivities of >99%. In addition, the lipase displayed excellent operational stability in THF, and retained 96% of its initial activity after reused for five batches.

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

    Science.gov (United States)

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

    2015-04-20

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

  4. short communication regioselective iodination of aryl amines using 1

    African Journals Online (AJOL)

    B. S. Chandravanshi

    Reddy, S.K.K.; Narender, N.; Rohitha, C.N.; Kulkarni, S.I. Synth. Commun. 2008, 38, 3894. 15. Adimurthy, S.; Ramachandraiah, G.; Ghosh, P.K.; Bedekar, A.V. Tetrahedron Lett. 2003,. 44, 5099. 16. Sathiyapriya, R.; Karunakaran, R.J. Synth. Commun. 2006, 36, 1915. 17. Yamamoto, T.; Toyota, K.; Morita, N. Tetrahedron Lett.

  5. Regioselective Benzoylation of Diols and Carbohydrates by Catalytic Amounts of Organobase.

    Science.gov (United States)

    Lu, Yuchao; Hou, Chenxi; Ren, Jingli; Xin, Xiaoting; Xu, Hengfu; Pei, Yuxin; Dong, Hai; Pei, Zhichao

    2016-05-17

    A novel metal-free organobase-catalyzed regioselective benzoylation of diols and carbohydrates has been developed. Treatment of diol and carbohydrate substrates with 1.1 equiv. of 1-benzoylimidazole and 0.2 equiv. of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in MeCN under mild conditions resulted in highly regioselective benzoylation for the primary hydroxyl group. Importantly, compared to most commonly used protecting bulky groups for primary hydroxyl groups, the benzoyl protective group offers a new protection strategy.

  6. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    Science.gov (United States)

    Koch, Daniel J.; Arnold, Frances H.

    2013-01-29

    Cytochrome P450 CYP153A6 from Myobacterium sp. strain HXN1500 was engineered using in-vivo directed evolution to hydroxylate small-chain alkanes regioselectively. Mutant CYP153A6-BMO1 selectively hydroxylates butane and pentane at the terminal carbon to form 1-butanol and 1-pentanol, respectively, at rates greater than wild-type CYP153A6 enzymes. This biocatalyst is highly active for small-chain alkane substrates and the regioselectivity is retained in whole-cell biotransformations.

  7. Regioselectivity of tributyltin ether mediated alkylations. A 119Sn and 13C NMR study

    International Nuclear Information System (INIS)

    Cruzado, C.; Bernabe, M.; Martin-Lomas, M.

    1989-01-01

    The 119 Sn and 13 C NMR spectra of the stannylated species resulting from the treatment of conformationally rigid polyhydroxylated compounds with bis(tributyltin) oxide have been determined and the effect of N-methylimidazole, added as catalyst in tributyltin ether mediated regioselective alkylations, has been investigated. The observed signal intensity changes, upfield shifts, signal broadenings, and the results of variable temperature experiments have been interpreted as indicative of the selective formation of pentacoordinated tin species, involving conveniently disposed adjacent hydroxyl groups, on addition of the catalyst. On these bases, a mechanistic hypothesis for the observed regioselectivity of N-methylimidazole-catalyzed tributyltin ether mediated benzylations is proposed. 13 references, 5 tables

  8. Regioselectivity and Enantioselectivity in Nickel-Catalysed Reductive Coupling Reactions of Alkynes

    Science.gov (United States)

    Moslin, Ryan M.; Miller-Moslin, Karen; Jamison, Timothy F.

    2011-01-01

    Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included. PMID:17971951

  9. Activated N-nitrosocarbamates for regioselective synthesis of N-nitrosoureas.

    Science.gov (United States)

    Martinez, J; Oiry, J; Imbach, J L; Winternitz, F

    1982-02-01

    A practical and convenient method for synthesizing antitumor compounds, N-alkyl-N-nitrosoureas, regioselectively nitrosated on the nitrogen atom bearing the alkyl group is proposed. N-Alkyl-N-nitrosocarbamates are interesting intermediates in these syntheses and yield, by reaction with amino compounds, the regioselectively nitrosated N-alkyl-N-nitrosoureas. As an interesting example, N,N'-bis[(2-chloroethyl)nitrosocarbamoyl]cystamine, a new attractive oncostatic derivative, has been prepared. The cytotoxic activity of these various compounds were tested on L1210 leukemia.

  10. Regioselectivity in lithiation of 1-methylpyrazole: experimental, density functional theory and multinuclear NMR study

    DEFF Research Database (Denmark)

    Balle, Thomas; Begtrup, Mikael; Jaroszewski, Jerzy W.

    2006-01-01

    -position. The observed regioselectivity can be correctly predicted, at least qualitatively, using density functional B3LYP/6-31+G(d,p) calculations only when solvation effects (IEFPCM) are taken into account. The 1H,6Li HOESY and NOESY NMR spectra of the thermodynamic product 5-lithio-1-methylpyrazole (5...

  11. 1,5-Anhydro-D-fructose: regioselective acylation with fatty acids

    DEFF Research Database (Denmark)

    Lundt, Inge; Andersen, Søren Møller; Marcussen, Jan

    1999-01-01

    Regioselective acylation of 1,5-anhydro-D-fructose was performed with dodecanoic acid to give 1,5-anhydro-6-O-dodecanoyl-D-fructose, chemically in 50% yield and enzymatically in quantitative yield. Quantitative conversions were also obtained using hexadecanoic and octadecanoic acids as acyl donors...

  12. Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes.

    Science.gov (United States)

    Li, Changkun; Grugel, Christian P; Breit, Bernhard

    2016-04-30

    A highly efficient rhodium-catalyzed chemo- and regioselective addition of β-ketoacids to alkynes is reported. Applying a Rh(i)/(S,S)-DIOP catalyst system, γ,δ-unsaturated ketones were prepared with exclusively branched selectivity under mild conditions. This demonstrates that readily available alkynes can be an alternative entry to allyl electrophiles in transition-metal catalyzed allylic alkylation reactions.

  13. Regioselective annulation of nitrosopyridine with alkynes: straightforward synthesis of N-oxide-imidazopyridines.

    Science.gov (United States)

    Manna, Srimanta; Narayan, Rishikesh; Golz, Christopher; Strohmann, Carsten; Antonchick, Andrey P

    2015-04-11

    We have developed a novel method for the regioselective annulation of 2-nitrosopyridines with variably substituted alkynes under mild reaction conditions. This approach allows the annulation of alkynes with 2-nitrosopyridines under reagent- and catalyst-free reaction conditions. The developed method shows excellent functional group tolerance and provides easy access to N-oxide-imidazo[1,2-a]pyridines.

  14. Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

    KAUST Repository

    Morandi, Bill

    2013-07-26

    Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  15. The regioselectivity of glutathione adduct formation with flavonoid quinone methides is pH-dependent

    NARCIS (Netherlands)

    Awad, H.M.; Boersma, M.G.; Boeren, S.; Vervoort, J.; Bladeren, van P.J.; Rietjens, I.M.C.M.

    2002-01-01

    In the present study, the formation of glutathionyl adducts from a series of 3',4'-dihydroxy flavonoid o-quinone/p-quinone methides was investigated with special emphasis on the regioselectivity of the glutathione addition as a function of pH. The flavonoid o-quinones were generated using

  16. Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

    KAUST Repository

    Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

    2013-01-01

    Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  17. A simple, effective, green method for regioselective 3-acylation of unprotected indoles

    DEFF Research Database (Denmark)

    Tran, Phuong Huong; Tran, Hai N.; Hansen, Poul Erik

    2015-01-01

    A fast and green method is developed for regioselective acylation of indoles in the 3-position without the need for protection of the NH position. The method is based on Friedel-Crafts acylation using acid anhydrides. The method has been optimized, and Y(OTf)3 in catalytic amounts is found...

  18. Regioselective desymmetrization of diaryltetrahydrofurans via directed ortho-lithiation: an unexpected help from green chemistry.

    Science.gov (United States)

    Mallardo, Valentina; Rizzi, Ruggiero; Sassone, Francesca C; Mansueto, Rosmara; Perna, Filippo M; Salomone, Antonio; Capriati, Vito

    2014-08-14

    An efficient functionalization of diaryltetrahydrofurans via a regioselective THF-directed ortho-lithiation is first described. This reaction can be successfully carried out in cyclopentyl methyl ether as a "greener" alternative to Et2O, with better results in terms of yield and selectivity and, surprisingly, also in protic eutectic mixtures competitively with protonolysis.

  19. Solvent-dependent regioselective oxidation of trans-chalcones using aqueous hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Wang; Jiabin, Yang; Lushen, Li, E-mail: jimin@seu.edu.cn [Southeast University, Nanjing (China). School of Biological Science and Medical Engineering; Jin, Cai; Chunlong, Sun; Min, Ji [Southeast University, Nanjing (China). School of Chemistry and Chemical Engineering

    2013-03-15

    A novel method for regioselective oxidation of trans-chalcones with hydrogen peroxide in acetonitrile to afford cinnamic acids is reported. Only trans-b-arylacrylic acids were observed. A wide range of functionalized products can be effectively produced from various chalcones in good to excellent yields. (author)

  20. Regioselective conversion of primary alcohols into iodides in unprotected methyl furanosides and pyranosides

    DEFF Research Database (Denmark)

    Skaanderup, Philip Robert; Poulsen, Carina Storm; Hyldtoft, Lene

    2002-01-01

    Two methods are described for the regioselective displacement of the primary hydroxy group in methyl glycosides with iodide. The first method is a modification of a literature procedure employing triphenylphosphine and iodine, where purification has been carried out on a reverse phase column in o...

  1. Reactivity and Regioselectivity in the Heck Reaction - A Hammett Study of 4-Substituted Styrenes

    DEFF Research Database (Denmark)

    Fristrup, Peter; Le Quement, Sebastian; Tanner, David Ackland

    2004-01-01

    The regioselectivity in the cationic Heck reaction of 4-substituted styrenes was addressed by a Hammett study. In this branching reaction, plots based on the substrate reactivity did not give meaningful data, whereas the product distribution was variable due to differing preferences for further...

  2. Regioselective synthesis of isoxazole-mercaptobenzimidazole hybrids and their in vivo analgesic and anti-inflammatory activity studies

    DEFF Research Database (Denmark)

    Kankala, Shravankumar; Kankala, Ranjith Kumar; Gundepaka, Prasad

    2013-01-01

    Regioselective synthesis of isoxazole-mercaptobenzimidazole hybrids and their efficiency in in vivo analgesic and anti-inflammatory activity was described. A comparison of structure-activity relationship for there compounds was also emphasized....

  3. MULTICOMPONENT AND REGIOSELECTIVE SYNTHESIS OF DIHYDROPYRAZOLO[1,5-a]PYRIMIDINES FROM AROMATIC ALDEHYDES, MELDRUM'S ACID AND AMINOPYRAZOLE CAN508

    OpenAIRE

    Jedinák, L.; Kryštof, V. (Vladimír); Trávníček, Z.; Cankař, P.

    2014-01-01

    A regioselective synthesis of dihydropyrazolo[1,5-a]pyrimidines is reported. The multicomponent reaction of readily available arylaldehydes, Meldrum's acid, and aminopyrazole CAN508 afforded fused pyrazolopyrimidines in high yields. The reaction proceeded regioselectively via initial Michael addition of the exocyclic amino group to arylidene Meldrum's acid intermediate followed by a ring closure at the endocyclic nitrogen of aminopyrazole. The regioselectivity of the reaction was determined b...

  4. Delocalization model of regioselectivity and reactivity of free radicals in reactions of addition to olefins

    International Nuclear Information System (INIS)

    Volovik, S.V.; Dyadyusha, G.G.; Staninets, V.I.

    1987-01-01

    On the basis of the concept of polarity (philicity) of free radicals as proposed by the authors, within the framework of methods of qualitative surfaces of potential energy (linear combinations of configurations of fragments) and stabilization energy, an effective model has been developed for the regioselectivity and reactivity of radicals in processes of addition. A critical examination is made of certain key aspects of the change in regiochemistry and reactivity with changes in the electronic structure of the free radical and substrate. The dominant trends in regioselectivity and reactivity in processes of free-radical addition to olefins are controlled by electronic effects and can be predicted by analyzing interactions of diabatic potential energy surfaces or orbital interactions for a system consisting of a free radical and an unsaturated substrate

  5. A Novel and Highly Regioselective Synthesis of New Carbamoylcarboxylic Acids from Dianhydrides

    Directory of Open Access Journals (Sweden)

    Adrián Ochoa-Terán

    2014-01-01

    Full Text Available A regioselective synthesis has been developed for the preparation of a series of N,N′-disubstituted 4,4′-carbonylbis(carbamoylbenzoic acids and N,N′-disubstituted bis(carbamoyl terephthalic acids by treatment of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (1 and 1,2,4,5-benzenetetracarboxylic dianhydride (2 with arylalkyl primary amines (A-N. The carbamoylcarboxylic acid derivatives were synthesized with good yield and high purity. The specific reaction conditions were established to obtain carbamoyl and carboxylic acid functionalities over the thermodynamically most favored imide group. Products derived from both anhydrides 1 and 2 were isolated as pure regioisomeric compounds under innovative experimental conditions. The chemo- and regioselectivity of products derived from dianhydrides were determined by NMR spectroscopy and confirmed by density functional theory (DFT. All products were characterized by NMR, FTIR, and MS.

  6. Regioselective Galactofuranosylation for the Synthesis of Disaccharide Patterns Found in Pathogenic Microorganisms.

    Science.gov (United States)

    Legentil, Laurent; Cabezas, Yari; Tasseau, Olivier; Tellier, Charles; Daligault, Franck; Ferrières, Vincent

    2017-07-21

    Koenigs-Knorr glycosylation of acceptors with more than one free hydroxyl group by 2,3,5,6-tetrabenzoyl galactofuranosyl bromide was performed using diphenylborinic acid 2-aminoethyl ester (DPBA) as inducer of regioselectivity. High regioselectivity for the glycosylation on the equatorial hydroxyl group of the acceptor was obtained thanks to the transient formation of a borinate adduct of the corresponding 1,2-cis diol. Nevertheless formation of orthoester byproducts hampered the efficiency of the method. Interestingly electron-withdrawing groups on O-6 or on C-1 of the acceptor displaced the reaction in favor of the desired galactofuranosyl containing disaccharide. The best yield was obtained for the furanosylation of p-nitrophenyl 6-O-acetyl mannopyranoside. Precursors of other disaccharides, found in the glycocalix of some pathogens, were synthesized according to the same protocol with yields ranging from 45 to 86%. This is a good alternative for the synthesis of biologically relevant glycoconjugates.

  7. A facile regioselective synthesis of novel spiroacenaphthene pyrroloisoquinolines through 1,3-dipolar cycloaddition reactions

    International Nuclear Information System (INIS)

    Sarrafi, Yaghoub; Asghari, Asieh; Sadatshahabi, Marzieh; Hamzehloueian, Mahshid; Alimohammadi, Kamal

    2013-01-01

    An efficient one-pot three-component procedure for the synthesis of novel spiroacenaphthene pyrroloisoquinolines with high regioselectivity is described. These compounds were prepared from 1,3-dipolar cycloaddition of an azomethine ylide generated from acenaphthenequinone and 1,2,3,4-tetrahydroisoquinoline via [1,5]-H shift, with chalcone and nitrostyrene derivatives as dipolarophiles. The structure and stereochemistry of the cycloadducts have been established by single crystal X-ray structure and spectroscopic techniques. (author)

  8. Regioselective syntheses of 1,2-benzothiazines by rhodium-catalyzed annulation reactions.

    Science.gov (United States)

    Cheng, Ying; Bolm, Carsten

    2015-10-12

    Rhodium-catalyzed directed carbene insertions into aromatic CH bonds of S-aryl sulfoximines lead to intermediates, which upon dehydration provide 1,2-benzothiazines in excellent yields. The domino-type process is regioselective and shows a high functional-group tolerance. It is scalable, and the only by-products are dinitrogen and water. Three illustrative transformations underscore the synthetic value of the products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A facile regioselective synthesis of novel spiroacenaphthene pyrroloisoquinolines through 1,3-dipolar cycloaddition reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sarrafi, Yaghoub; Asghari, Asieh; Sadatshahabi, Marzieh, E-mail: ysarrafi@umz.ac.ir [Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran (Iran, Islamic Republic of); Hamzehloueian, Mahshid [Department of Chemistry, Jouybar Branch, Islamic Azad University, Jouybar (Iran, Islamic Republic of); Alimohammadi, Kamal [Department of Chemistry, Dr. Shariati Branch, University of Farhangian, Sari (Iran, Islamic Republic of)

    2013-12-01

    An efficient one-pot three-component procedure for the synthesis of novel spiroacenaphthene pyrroloisoquinolines with high regioselectivity is described. These compounds were prepared from 1,3-dipolar cycloaddition of an azomethine ylide generated from acenaphthenequinone and 1,2,3,4-tetrahydroisoquinoline via [1,5]-H shift, with chalcone and nitrostyrene derivatives as dipolarophiles. The structure and stereochemistry of the cycloadducts have been established by single crystal X-ray structure and spectroscopic techniques. (author)

  10. A Scalable Method for Regioselective 3-Acylation of 2-Substituted Indoles under Basic Conditions

    DEFF Research Database (Denmark)

    Johansson, Karl Henrik; Urruticoechea, Andoni; Larsen, Inna

    2015-01-01

    Privileged structures such as 2-arylindoles are recurrent molecular scaffolds in bioactive molecules. We here present an operationally simple, high yielding and scalable method for regioselective 3-acylation of 2-substituted indoles under basic conditions using functionalized acid chlorides. The ....... The method shows good tolerance to both electron-withdrawing and donating substituents on the indole scaffold and gives ready access to a variety of functionalized 3-acylindole building blocks suited for further derivatization....

  11. Regioselective oxyalkylation of vinylarenes catalyzed by diatomite-supported manganese oxide nanoparticles.

    Science.gov (United States)

    Sun, Huayin; Zhang, Yonghui; Guo, Fengfeng; Zha, Zhenggen; Wang, Zhiyong

    2012-04-06

    A regioselective oxyalkylation reaction of vinylarenes with cyclic ethers was developed under the catalysis of a new heterogeneous catalyst, the diatomite-supported Mn(3)O(4) nanoparticles (SMONP-1). The use of this heterogeneous catalyst provided a novel approach for the synthesis of α-carbonyled β-alkylated aryl derivatives via a sp(3) C-H bond functionalization under mild aerobic conditions.

  12. Breaking the regioselectivity rule for acrylate insertion in the Mizoroki-Heck reaction.

    Science.gov (United States)

    Wucher, Philipp; Caporaso, Lucia; Roesle, Philipp; Ragone, Francesco; Cavallo, Luigi; Mecking, Stefan; Göttker-Schnetmann, Inigo

    2011-05-31

    In modern methods for the preparation of small molecules and polymers, the insertion of substrate carbon-carbon double bonds into metal-carbon bonds is a fundamental step of paramount importance. This issue is illustrated by Mizoroki-Heck coupling as the most prominent example in organic synthesis and also by catalytic insertion polymerization. For unsymmetric substrates H(2)C = CHX the regioselectivity of insertion is decisive for the nature of the product formed. Electron-deficient olefins insert selectively in a 2,1-fashion for electronic reasons. A means for controlling this regioselectivity is lacking to date. In a combined experimental and theoretical study, we now report that, by destabilizing the transition state of 2,1-insertion via steric interactions, the regioselectivity of methyl acrylate insertion into palladium-methyl and phenyl bonds can be inverted entirely to yield the opposite "regioirregular" products in stoichiometric reactions. Insights from these experiments will aid the rational design of complexes which enable a catalytic and regioirregular Mizoroki-Heck reaction of electron-deficient olefins.

  13. Structural basis for hyperactivity of cN-II mutants

    Czech Academy of Sciences Publication Activity Database

    Hnízda, Aleš; Škerlová, Jana; Šinalová, Martina; Pachl, Petr; Man, Petr; Novák, Petr; Fábry, Milan; Řezáčová, Pavlína; Veverka, Václav

    2015-01-01

    Roč. 22, č. 1 (2015), s. 4 ISSN 1211-5894. [Discussions in Structural Molecular Biology. Annual Meeting of the Czech Society for Structural Biology /13./. 19.03.2015-21.03.2015, Nové Hrady] Institutional support: RVO:61388963 ; RVO:68378050 ; RVO:61388971 Keywords : cN-II mutants * enzyme hyperactivity Subject RIV: CE - Biochemistry

  14. Preparation of bulk superhard B-C-N nanocomposite compact

    Science.gov (United States)

    Zhao, Yusheng [Los Alamos, NM; He, Duanwei [Sichuan, CN

    2011-05-10

    Bulk, superhard, B--C--N nanocomposite compacts were prepared by ball milling a mixture of graphite and hexagonal boron nitride, encapsulating the ball-milled mixture at a pressure in a range of from about 15 GPa to about 25 GPa, and sintering the pressurized encapsulated ball-milled mixture at a temperature in a range of from about 1800-2500 K. The product bulk, superhard, nanocomposite compacts were well sintered compacts with nanocrystalline grains of at least one high-pressure phase of B--C--N surrounded by amorphous diamond-like carbon grain boundaries. The bulk compacts had a measured Vicker's hardness in a range of from about 41 GPa to about 68 GPa.

  15. Plasma-deposited a-C(N) H films

    CERN Document Server

    Franceschini, D E

    2000-01-01

    The growth behaviour, film structure and mechanical properties of plasma-deposited amorphous hydrogenated carbon-nitrogen films are shortly reviewed. The effect of nitrogen-containing gas addition to the deposition to the hydrocarbon atmospheres used is discussed, considering the modifications observed in the chemical composition growth kinetics, carbon atom hybridisation and chemical bonding arrangements of a-C(N):H films. The overall structure behaviour is correlated to the variation of the mechanical properties.

  16. Room-temperature Pd-catalyzed C-H chlorination by weak coordination: one-pot synthesis of 2-chlorophenols with excellent regioselectivity.

    Science.gov (United States)

    Sun, Xiuyun; Sun, Yonghui; Zhang, Chao; Rao, Yu

    2014-02-07

    A room-temperature Pd(II)-catalyzed regioselective chlorination reaction has been developed for a facile one-pot synthesis of a broad range of 2-chlorophenols. The reaction demonstrates an excellent regioselectivity and reactivity for C-H chlorination. This reaction represents one of the rare examples of mild C-H functionalization at ambient temperature.

  17. Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds.

    Science.gov (United States)

    Hari, Durga Prasad; Waser, Jerome

    2017-06-28

    Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks, which are difficult to synthesize in enantiopure form using other methods. The obtained products could be efficiently transformed into vicinal diols and α-hydroxy propargylic esters without loss in enantiopurity.

  18. Copper-Catalyzed Decarboxylative Trifluoromethylation of Propargyl Bromodifluoroacetates.

    Science.gov (United States)

    Ambler, Brett R; Peddi, Santosh; Altman, Ryan A

    2014-07-15

    The development of efficient methods for accessing fluorinated functional groups is desirable. Herein, we report a two-step method that utilizes catalytic Cu for the decarboxylative trifluoromethylation of propargyl bromodifluoroacetates. This protocol affords a mixture of propargyl trifluoromethanes and trifluoromethyl allenes.

  19. Copper-Catalyzed Synthesis of Trifluoroethylarenes from Benzylic Bromodifluoroacetates.

    Science.gov (United States)

    Ambler, Brett R; Zhu, Lingui; Altman, Ryan A

    2015-08-21

    Trifluoroethylarenes are found in a variety of biologically active molecules, and strategies for accessing this substructure are important for developing therapeutic candidates and biological probes. Trifluoroethylarenes can be directly accessed via nucleophilic trifluoromethylation of benzylic electrophiles; however, current catalytic methods do not effectively transform electron-deficient substrates and heterocycles. To address this gap, we report a Cu-catalyzed decarboxylative trifluoromethylation of benzylic bromodifluoroacetates. To account for the tolerance of sensitive functional groups, we propose an inner-sphere mechanism of decarboxylation.

  20. Dimethylglyoxime as an efficient ligand for copper-catalyzed ...

    Indian Academy of Sciences (India)

    SURESH S SHENDAGE

    2018-02-07

    Feb 7, 2018 ... Phenols play key role in production of natural products, pharmaceutical and ... than 90% of the world's phenol requirement is satisfied by the Hock process, ... thesis the development of a mild, general and highly efficient method for .... will attract much attention in research because of their wide applications ...

  1. Copper-catalyzed selective hydroamination reactions of alkynes

    Science.gov (United States)

    Shi, Shi-Liang; Buchwald, Stephen L.

    2014-01-01

    The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a longstanding goal of chemical research. Despite the centrality of amines in a number of important research areas, including medicinal chemistry, total synthesis and materials science, a general, selective, and step-efficient synthesis of amines is still needed. In this work we describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct preparation of three distinct and important amine classes (enamines, α-chiral branched alkylamines, and linear alkylamines) from readily available alkyne starting materials with high levels of chemo-, regio-, and stereoselectivity. This methodology was applied to the asymmetric synthesis of rivastigmine and the formal synthesis of several other pharmaceutical agents, including duloxetine, atomoxetine, fluoxetine, and tolterodine. PMID:25515888

  2. Copper-Catalyzed Synthesis of Mixed Alkyl Aryl Phosphonates

    NARCIS (Netherlands)

    Fañanás-Mastral, Martín; Feringa, Ben L

    2014-01-01

    Copper-catalysis allows the direct oxygenarylation of dialkyl phosphonates with diaryliodonium salts. This novel methodology proceeds with a wide range of phosphonates and phosphoramidates under mild conditions and gives straightforward access to valuable mixed alkyl aryl phosphonates in very good

  3. Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

    Directory of Open Access Journals (Sweden)

    Lucie Brulíková

    2016-09-01

    Full Text Available The hetero-Diels–Alder reaction between a nitroso dienophile and a conjugated diene to give the 3,6-dihydro-2H-1,2-oxazine scaffold is useful for the synthesis of many biologically interesting molecules due to the diverse opportunities created by subsequent transformations of the resulting 1,2-oxazine ring. This review discusses the rationale for the observed regio- and stereoselectivity and the methods developed in recent years used to control and improve the stereo- and regioselectivity for the synthesis of 1,2-oxazine scaffolds.

  4. Stereo- and regioselectivity of the hetero-Diels-Alder reaction of nitroso derivatives with conjugated dienes.

    Science.gov (United States)

    Brulíková, Lucie; Harrison, Aidan; Miller, Marvin J; Hlaváč, Jan

    2016-01-01

    The hetero-Diels-Alder reaction between a nitroso dienophile and a conjugated diene to give the 3,6-dihydro-2 H -1,2-oxazine scaffold is useful for the synthesis of many biologically interesting molecules due to the diverse opportunities created by subsequent transformations of the resulting 1,2-oxazine ring. This review discusses the rationale for the observed regio- and stereoselectivity and the methods developed in recent years used to control and improve the stereo- and regioselectivity for the synthesis of 1,2-oxazine scaffolds.

  5. Predictable and Regioselective Insertion of Internal Unsymmetrical Alkynes in Rhodium-Catalyzed Cycloadditions with Alkenyl Isocyanates

    Science.gov (United States)

    Friedman, Rebecca Keller; Rovis, Tomislav

    2009-01-01

    A regioselective, rhodium-catalyzed cycloaddition between a variety of internal, unsymmetrical alkynes is described. We document the impact of both steric and electronic properties of the alkyne on reaction course, efficiency and enantioselectivity. The substituent that better stabilizes a positive charge or the larger group, all else being equal, inserts distal to the carbonyl moiety in a predictable and controllable fashion. The reaction scope is broad and the enantioselectivities are high, providing an ‘instruction manual’ for substrate choice when utilizing this reaction as a synthetic tool. PMID:19569692

  6. Combining Eosin Y with Selectfluor: A Regioselective Brominating System for Para-Bromination of Aniline Derivatives.

    Science.gov (United States)

    Huang, Binbin; Zhao, Yating; Yang, Chao; Gao, Yuan; Xia, Wujiong

    2017-07-21

    A mild, metal-free, and absolutely para-selective bromination of aniline derivatives has been developed in excellent yields, wherein the organic dye Eosin Y is employed as the bromine source in company with Selectfluor. Neither air nor moisture sensitive, this facile reaction proceeds smoothly at room temperature and completes within a short time. Mechanistic studies indicate a radical pathway; therefore, the existence of an in situ generated brominating reagent, "Selectbrom", is postulated, which may reasonably account for the unique regioselectivity for the para-bromination of N-acyl- as well as N-sulfonylanilines.

  7. The synthesis of 2-14C-N-nitrosothiazolidine

    International Nuclear Information System (INIS)

    Cragin, D.W.; Shibamoto, Takayuki

    1989-01-01

    2- 14 C-N-Nitrosothiazolidine was synthesized with a chemical purity of 99.6%, a radio chemical purity of 99.4%, and an overall yield of 30.7%. Unlabelled N-nitrosothiazolidine, synthesized using the same method, resulted in a purity of 99.85% by capillary GC and 99.7% by HPLC. Analysis of N-nitrosothiazolidine by GC was found to require a low injection port temperature of 160 0 C to prevent denitrosation in the injection port. During the nitrosation of thiazolidine, if the pH was reduced below 4 with hydrochloric acid, ring hydrolysis occurred, and chlorinated disulfide compounds formed. (author)

  8. Bioactivation and Regioselectivity of Pig Cytochrome P450 3A29 towards Aflatoxin B1

    Directory of Open Access Journals (Sweden)

    Jun Wu

    2016-09-01

    Full Text Available Due to unavoidable contaminations in feedstuff, pigs are easily exposed to aflatoxin B1 (AFB1 and suffer from poisoning, thus the poisoned products potentially affect human health. Heretofore, the metabolic process of AFB1 in pigs remains to be clarified, especially the principal cytochrome P450 oxidases responsible for its activation. In this study, we cloned CYP3A29 from pig liver and expressed it in Escherichia coli, and its activity has been confirmed with the typical P450 CO-reduced spectral characteristic and nifedipine-oxidizing activity. The reconstituted membrane incubation proved that the recombinant CYP3A29 was able to oxidize AFB1 to form AFB1-exo-8,9-epoxide in vitro. The structural basis for the regioselective epoxidation of AFB1 by CYP3A29 was further addressed. The T309A mutation significantly decreased the production of AFBO, whereas F304A exhibited an enhanced activation towards AFB1. In agreement with the mutagenesis study, the molecular docking simulation suggested that Thr309 played a significant role in stabilization of AFB1 binding in the active center through a hydrogen bond. In addition, the bulk phenyl group of Phe304 potentially imposed steric hindrance on the binding of AFB1. Our study demonstrates the bioactivation of pig CYP3A29 towards AFB1 in vitro, and provides the insight for understanding regioselectivity of CYP3A29 to AFB1.

  9. Regioselective Nucleophilic Ring Opening of Epoxides and Aziridines derived from Homoallylic Alcohols

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Groth, Thomas

    1997-01-01

    The regioselectivity of nucleophilic ring opening of some 3,4-epoxy and 3,4-aziridino alcohols has been studied. The nucleophiles chosen were complex hydrides (LiAlH4, Red-Al and DIBAL) and Lipshutz- or Gilman-type organocuprate reagents. The C-4 substituent in the substrates was varied in order...... to study steric and electronic effects on the ring opening reactions. For alkyl substituents at C-4, most of the results can be explained on the basis of intramolecular delivery of the nucleophile to C-3 via a six-membered transition state, leading to 1,4-diols or 1,4-amino alcohol derivatives. In general......, the epoxy alcohols gave poorer regioselectivity than the N-tosyl aziridino alcohols, for which selectivities of >95:5 were routinely obtained. The activating effect of a phenyl group at C-4 led to a switch in regiochemistry, with the 1,3-diol or 1,3-amino alcohol derivative as the major product. (C) 1997...

  10. Electronic forces as descriptors of nucleophilic and electrophilic regioselectivity and stereoselectivity.

    Science.gov (United States)

    Liu, Shubin; Rong, Chunying; Lu, Tian

    2017-01-04

    One of the main tasks of theoretical chemistry is to rationalize computational results with chemical insights. Key concepts of such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While computational tools are available to predict barrier heights and other reactivity properties with acceptable accuracy, a conceptual framework to appreciate above quantities is still lacking. In this work, we introduce the electronic force as the fundamental driving force of chemical processes to understand and predict molecular reactivity. It has three components but only two are independent. These forces, electrostatic and steric, can be employed as reliable descriptors for nucleophilic and electrophilic regioselectivity and stereoselectivity. The advantages of using these forces to evaluate molecular reactivity are that electrophilic and nucleophilic attacks are featured by distinct characteristics in the electrostatic force and no knowledge of quantum effects included in the kinetic and exchange-correlation energies is required. Examples are provided to highlight the validity and general applicability of these reactivity descriptors. Possible applications in ambident reactivity, σ and π holes, frustrated Lewis pairs, and stereoselective reactions are also included in this work.

  11. Regioselective Rh-Catalyzed Hydroformylation of 1,1,3-Trisubstituted Allenes Using BisDiazaPhos Ligand.

    Science.gov (United States)

    Eshon, Josephine; Landis, Clark R; Schomaker, Jennifer M

    2017-09-15

    The efficient hydroformylation of 1,1,3-trisubstituted allenes is accomplished with low loadings of a Rh catalyst supported by a BisDiazaPhos (BDP) ligand. The ligand identity is key to achieving high regioselectivity, while the mild reaction conditions minimize competing isomerization and hydrogenation to produce β,γ-unsaturated aldehydes and their derivatives in excellent yields.

  12. Stereo- and regio-selective one-pot synthesis of triazole-based unnatural amino acids and β- amino triazoles

    Science.gov (United States)

    Synthesis of triazole based unnatural amino acids and β-amino triazole has been described via stereo and regioselective one-pot multi-component reaction of sulfamidates, sodium azide, and alkynes under MW conditions. The developed method is applicable to a broad substrate scope a...

  13. A facile and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles using click chemistry

    Science.gov (United States)

    The reaction of α-tosyloxy ketones, sodium azide and terminal alkynes in presence of copper(I) in aqueous polyethylene glycol afforded regioselectively 1,4-disubstituted 1,2,3-triazoles in good yield at ambient temperature. The one-pot exclusive formation of 1,4-disubstituted 1,2...

  14. Regioselective Palmitoylation of 9-(2,3-Dihydroxy-propyl)adenine Catalyzed by a Glycopolymer-enzyme Conjugate

    Czech Academy of Sciences Publication Activity Database

    Brabcová, Jana; Blažek, Jiří; Krečmerová, Marcela; Vondrášek, Jiří; Palomo, J. M.; Zarevúcka, Marie

    2016-01-01

    Roč. 21, č. 5 (2016), č. článku 648. ISSN 1420-3049 Grant - others:AV ČR(CZ) M200551203 Institutional support: RVO:61388963 Keywords : regioselectivity * palmitoylation * glycosylation * chemical modification Subject RIV: CE - Biochemistry Impact factor: 2.861, year: 2016 http://www.mdpi.com/1420-3049/21/5/648/htm

  15. Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyldiphenylsulfonium salts/copper system

    Directory of Open Access Journals (Sweden)

    Satoshi Okusu

    2013-10-01

    Full Text Available Regioselective conjugate 1,4-trifluoromethylation of α,β-unsaturated ketones by the use of shelf-stable electrophilic trifluoromethylating reagents, S-(trifluoromethyldiphenylsulfonium salts and copper under mild conditions is described. A wide range of acyclic aryl–aryl–enones and aryl–alkyl–enones were converted into β-trifluoromethylated ketones in low to moderate yields.

  16. Olefination of Electron-Deficient Alkenes with Allyl Acetate: Stereo- and Regioselective Access to (2Z,4E)-Dienamides.

    Science.gov (United States)

    Li, Feifei; Yu, Chunbing; Zhang, Jian; Zhong, Guofu

    2016-09-16

    A Ru-catalyzed direct olefination of electron-deficient alkenes with allyl acetate via C-H bond activation is disclosed. By using N,N-disubstituted aminocarbonyl as the directing group, this external oxidant-free protocol resulted in high reaction efficiency and good stereo- and regioselectivities, which opens a novel synthetic passway for access to (Z,E)-butadiene skeletons.

  17. Anhydrous ZnCl2: A Highly Efficient Reagent for Facile and Regioselective Conversion of Epoxides to β-Chlorohydrins

    Directory of Open Access Journals (Sweden)

    Ronak Eisavi

    2016-01-01

    Full Text Available Facile conversion of structurally different epoxides to the corresponding β-chlorohydrins was carried out successfully with anhydrous ZnCl2 in CH3CN. The reactions were carried out within 10-50 min to give β-chlorohydrins with perfect regioselectivity and high yields (80-97%.

  18. Tribological Properties of PVD Ti/C-N Nanocoatnigs

    Science.gov (United States)

    Leitans, A.; Lungevics, J.; Rudzitis, J.; Filipovs, A.

    2017-04-01

    The present paper discusses and analyses tribological properties of various coatings that increase surface wear resistance. Four Ti/C-N nanocoatings with different coating deposition settings are analysed. Tribological and metrological tests on the samples are performed: 2D and 3D parameters of the surface roughness are measured with modern profilometer, and friction coefficient is measured with CSM Instruments equipment. Roughness parameters Ra, Sa, Sz, Str, Sds, Vmp, Vmc and friction coefficient at 6N load are determined during the experiment. The examined samples have many pores, which is the main reason for relatively large values of roughness parameter. A slight wear is identified in all four samples as well; its friction coefficient values range from 0,.21 to 0.29. Wear rate values are not calculated for the investigated coatings, as no expressed tribotracks are detected on the coating surface.

  19. Mechanistic Basis for Regioselection and Regiodivergence in Nickel-Catalyzed Reductive Couplings

    Science.gov (United States)

    Jackson, Evan P.; Malik, Hasnain A.; Sormunen, Grant J.; Baxter, Ryan D.; Liu, Peng; Wang, Hengbin; Shareef, Abdur-Rafay; Montgomery, John

    2015-01-01

    CONSPECTUS The control of regiochemistry is a considerable challenge in the development of a wide array of catalytic processes. Simple π-components such as alkenes, alkynes, 1,3-dienes, and allenes are among the many classes of substrates that present complexities in regioselective catalysis. Considering an internal alkyne as a representative example, when steric and electronic differences between the two substituents are minimal, differentiating among the two termini of the alkyne presents a great challenge. In cases where the differences between the alkyne substituents are substantial, overcoming those biases to access the regioisomer opposite that favored by substrate biases often presents an even greater challenge. Nickel-catalyzed reductive couplings of unsymmetrical π-components make up a group of reactions where control of regiochemistry presents a challenging but important objective. In the course of our studies of aldehyde-alkyne reductive couplings, complementary solutions to challenges in regiocontrol have been developed. Through careful selection of the ligand and reductant, as well as the more subtle reaction variables such as temperature and concentration, effective protocols have been established that allow highly selective access to either regiosiomer of the the allylic alcohol products using a wide range of unsymmetrical alkynes. Computational studies and an evaluation of reaction kinetics have provided an understanding of the origin of the regioselectivity control. Throughout the various procedures described, the development of ligand-substrate interactions play a key role, and the overall kinetic descriptions were found to differ between protocols. Rational alteration of the rate-determining step plays a key role in the regiochemistry reversal strategy, and in one instance, the two possible regioisomeric outcomes in a single reaction were found to operate by different kinetic descriptions. With this mechanistic information in hand, the

  20. Preparation and sintering of Zr(C,N,O) phases

    International Nuclear Information System (INIS)

    Tamborenea, S.; Mazzoni, A.D.; Aglietti, E.F.

    2003-01-01

    The Zr(C,O,N) compounds form a great mono-phase zone belonging to the pseudoternary ZrO-ZrN-ZrC system.Theses phases have cubic crystalline structure with a o parameter depending on the C, O 2 and N 2 content.These phases have many potential applications in the manufacture of ceramic pieces utilizable as electronic conductors.The Zr (C,O,N) phases can be obtained from ZrO 2 by carbonitriding reactions: that is carbothermal reduction and simultaneous nitriding.In this work a series of experiences of carbonitriding of zirconia under different conditions (temperatures between 1400 and 1600degC, times of 120 min, carbon content between 20 and 40%) in order to obtain suitable powders to be sintered.The XRD analysis shows the Zr(C,O,N) as the main products and β -ZrON as the only secondary product in proportions depending on the obtaining conditions.The variables employed were the C content and the reaction temperature.The Zr(C,O,N) content varies between 40 and 90% and tends to increase with the temperature and the carbon content whereas the β -ZrON phase varies between the 40 and 10 % decreasing its proportion with temperature and the carbon content.The oxidation resistance of these phases was studied by DTA-TG tests in air.Results show complete oxidation reaction at ∼500degC in air.The sintering of these materials was made on disks obtained by pressing of powders of Zr(C,N,O) contents higher than 90%.Sintering was performed in nitrogen atmosphere and temperatures between 1450 and 1620degC.Disks were characterized by pycnometry and Hg volumeter.The densities obtained were between 5 and 6,6g/cm 3 with a tendency to increase with the Zr(C,N,O) phase content, the temperature and the sintering time.Sintered disks were characterized by dilatometry in N 2

  1. Modulating the regioselectivity of a Pasteurella multocida sialyltransferase for biocatalytic production of 3'- and 6'-sialyllactose

    DEFF Research Database (Denmark)

    Guo, Yao; Jers, Carsten; Meyer, Anne S.

    2015-01-01

    Several bacterial sialyltransferases have been reported to be multifunctional also catalysing sialidase and trans-sialidase reactions. In this study, we examined the trans-sialylation efficacy and regioselectivity of mutants of the multifunctional Pasteurella multocida sialyltransferase (Pm...... activity was abolished. Histidine in this position is conserved in α-2,6-sialyltransferases and has been suggested, and recently confirmed, to be the determinant for strict regiospecificity in the sialyltransferase reaction. Our data verified this theorem. In trans-sialidase reactions, the P34H mutant...... displayed a distinct preference for 6'-sialyllactose synthesis but low levels of 3'-sialyllactose were also produced. The sialyllactose yield was however lower than when using PmSTWT under optimal conditions for 6'-sialyllactose formation. The discrepancy in regiospecificity between the two reactions could...

  2. Regioselective Acetylation of C21 Hydroxysteroids by the Bacterial Chloramphenicol Acetyltransferase I.

    Science.gov (United States)

    Mosa, Azzam; Hutter, Michael C; Zapp, Josef; Bernhardt, Rita; Hannemann, Frank

    2015-07-27

    Chloramphenicol acetyltransferase I (CATI) detoxifies the antibiotic chloramphenicol and confers a corresponding resistance to bacteria. In this study we identified this enzyme as a steroid acetyltransferase and designed a new and efficient Escherichia-coli-based biocatalyst for the regioselective acetylation of C21 hydroxy groups in steroids of pharmaceutical interest. The cells carried a recombinant catI gene controlled by a constitutive promoter. The capacity of the whole-cell system to modify different hydroxysteroids was investigated, and NMR spectroscopy revealed that all substrates were selectively transformed into the corresponding 21-acetoxy derivatives. The biotransformation was optimized, and the reaction mechanism is discussed on the basis of a computationally modeled substrate docking into the crystal structure of CATI. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis of chitosan-PEO hydrogels via mesylation and regioselective Cu(I)-catalyzed cycloaddition.

    Science.gov (United States)

    Tirino, Pasquale; Laurino, Rosaria; Maglio, Giovanni; Malinconico, Mario; d'Ayala, Giovanna Gomez; Laurienzo, Paola

    2014-11-04

    In this work, a well-defined hydrogel was developed by coupling chitosan with PEO through "click chemistry". Azide functionalities were introduced onto chitosan, through mesylation of C-6 hydroxyl groups, and reacted with a di-alkyne PEO by a regioselective Cu(I)-catalyzed cycloaddition. This synthetic approach allowed us to obtain a hydrogel with a controlled crosslinking degree. In fact, the extent of coupling is strictly dependent on the amount of azido groups on chitosan, which in turn can be easily modulated. The obtained hydrogel, with a crosslinking degree of around 90%, showed interesting swelling properties. With respect to chitosan hydrogels reported in literature, a considerably higher equilibrium uptake was reached (940%). The possibility to control the crosslinking degree of hydrogel and its capability to rapidly absorb high amounts of water make this material suitable for several applications, such as controlled drug release and wound healing. Copyright © 2014. Published by Elsevier Ltd.

  4. Thiophene fused azacoronenes: regioselective synthesis, self organization, charge transport, and its incorporation in conjugated polymers

    Science.gov (United States)

    Liu, Yi; He, Bo

    2015-09-15

    A regioselective synthesis of an azacoronene fused with two peripheral thiophene groups has been realized through a concise synthetic route. The resulting thienoazacoronene (TAC) derivatives show high degree of self-organization in solution, in single crystals, in the bulk, and in spuncast thin films. Spuncast thin film field-effect transistors of the TACs exhibited mobilities up to 0.028 cm.sup.2V.sup.-1 S.sup.-1, which is among the top field effect mobilities for solution processed discotic materials. Organic photovoltaic devices using TAC-containing conjugated polymers as the donor material exhibited a high open-circuit voltage of 0.89 V, which was ascribable to TAC's low-lying highest occupied molecular orbital energy level.

  5. Remote control of regioselectivity in acyl-acyl carrier protein-desaturases.

    Science.gov (United States)

    Guy, Jodie E; Whittle, Edward; Moche, Martin; Lengqvist, Johan; Lindqvist, Ylva; Shanklin, John

    2011-10-04

    Regiospecific desaturation of long-chain saturated fatty acids has been described as approaching the limits of the discriminatory power of enzymes because the substrate entirely lacks distinguishing features close to the site of dehydrogenation. To identify the elusive mechanism underlying regioselectivity, we have determined two crystal structures of the archetypal Δ9 desaturase from castor in complex with acyl carrier protein (ACP), which show the bound ACP ideally situated to position C9 and C10 of the acyl chain adjacent to the diiron active site for Δ9 desaturation. Analysis of the structures and modeling of the complex between the highly homologous ivy Δ4 desaturase and ACP, identified a residue located at the entrance to the binding cavity, Asp280 in the castor desaturase (Lys275 in the ivy desaturase), which is strictly conserved within Δ9 and Δ4 enzymes but differs between them. We hypothesized that interaction between Lys275 and the phosphate of the pantetheine, seen in the ivy model, is key to positioning C4 and C5 adjacent to the diiron center for Δ4 desaturation. Mutating castor Asp280 to Lys resulted in a major shift from Δ9 to Δ4 desaturation. Thus, interaction between desaturase side-chain 280 and phospho-serine 38 of ACP, approximately 27 Å from the site of double-bond formation, predisposes ACP binding that favors either Δ9 or Δ4 desaturation via repulsion (acidic side chain) or attraction (positively charged side chain), respectively. Understanding the mechanism underlying remote control of regioselectivity provides the foundation for reengineering desaturase enzymes to create designer chemical feedstocks that would provide alternatives to those currently obtained from petrochemicals.

  6. The synthesis of amphipathic prodrugs of 1,2-diol drugs with saccharide conjugates by high regioselective enzymatic protocol.

    Science.gov (United States)

    Quan, Jing; Chen, Zhichun; Han, Chengyou; Lin, Xianfu

    2007-02-15

    A facile, high regioselective enzymatic synthesis approach for the preparation of amphipathic prodrugs with saccharides of mephenesin and chlorphenesin was developed. Firstly, transesterification of two drugs with divinyl dicarboxylates with different carbon chain length was performed under the catalysis of Candida antarctica lipase acrylic resin and Lipozyme in anhydrous acetone at 50 degrees C, respectively. A series of lipophilic derivatives with vinyl groups of mephenesin and chlorphenesin were prepared. The influences of different organic solvents, enzyme sources, reaction time, and the acylation reagents on the synthesis of vinyl esters were investigated. And then, protease-catalyzed high regioselective acylation of D-glucose and D-mannose with vinyl esters of mephenesin and chlorphenesin gave drug-saccharide derivatives in good yields. The studies of lipophilicity and hydrolysis in vitro of prodrugs verified that drug-saccharide derivatives had amphipathic properties, and both lipophilic and amphipathic drug derivatives had obvious controlled release characteristics.

  7. Relayed Regioselective Alkynylation/Olefination of Unsymmetrical Cyclic Diaryliodonium Species Catalyzed by Cu and Pd: Affording Fluorescent Cytotoxic Benzoxazoles.

    Science.gov (United States)

    Zhu, Daqian; Liu, Panpan; Lu, Wenhua; Wang, Haiwen; Luo, Bingling; Hu, Yumin; Huang, Peng; Wen, Shijun

    2015-12-21

    Although cyclic diaryliodonium species have the potential to act as valuable synthons for cascade transformations, they still remain largely unexplored. The regioselectivity associated with unsymmetrical cyclic diaryliodonium species has previously been known to pose a challenge. A regioselective relayed alkynylation and olefination of unsymmetrical cyclic diaryliodonium species has been achieved by installation of a directing amido group. These relayed transformations were delayed until an oxazole ring had formed, delivering a series of unique fluorescent benzoxazoles. Moreover, some of these synthetic benzoxazoles showed apparent inhibitory activity against malignant cancer cells. Further confocal visualization revealed that benzoxazoles targeted cell nuclei. These findings might provide a novel structural scaffold to develop desirable anticancer agents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Structural analysis of isomeric chondroitin sulfate oligosaccharides using regioselective 6-O-desulfation method and tandem mass spectrometry.

    Science.gov (United States)

    Chen, Shu-Ting; Her, Guor-Rong

    2014-09-16

    A strategy based on a regioselective 6-O-desulfation reaction and negative ion electrospray ionization tandem mass spectrometry (ESI-MS(n)) was developed for the structural delineation of isomeric chondroitin sulfate oligosaccharides. Product ions resulting from the glycosidic cleavage provided information about the number of sulfate groups in each sugar residue. After the regioselective 6-O-desulfation reaction, the number of sulfate groups on each residue was obtained using a tandem mass spectrometry analysis of the reaction product. The sulfation pattern could be obtained based on the product ions of analytes before and after the desulfation reaction. The strategy was demonstrated using a series of tetrasaccharides prepared from shark cartilage chondroitin sulfate D. Among the 12 identified tetrasaccharides, six structures had not been reported before. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Designer HF-Based Fluorination Reagent: Highly Regioselective Synthesis of Fluoroalkenes and gem-Difluoromethylene Compounds from Alkynes

    Science.gov (United States)

    2015-01-01

    Hydrogen fluoride (HF) and selected nonbasic and weakly coordinating (toward cationic metal) hydrogen-bond acceptors (e.g., DMPU) can form stable complexes through hydrogen bonding. The DMPU/HF complex is a new nucleophilic fluorination reagent that has high acidity and is compatible with cationic metal catalysts. The gold-catalyzed mono- and dihydrofluorination of alkynes using the DMPU/HF complex yields synthetically important fluoroalkenes and gem-difluoromethlylene compounds regioselectively. PMID:25260170

  10. Copper Nitrate Mediated Regioselective [2+2+1] Cyclization of Alkynes with Alkenes: A Cascade Approach to Δ(2)-Isoxazolines.

    Science.gov (United States)

    Gao, Mingchun; Li, Yingying; Gan, Yuansheng; Xu, Bin

    2015-07-20

    An efficient method for the regioselective synthesis of pharmacologically relevant polysubstituted Δ(2)-isoxazolines is based on the copper-mediated direct transformation of simple terminal alkynes and alkenes. The overall process involves the formation of four chemical bonds with inexpensive and readily available copper nitrate trihydrate as a novel precursor of nitrile oxides. The reaction can be easily handled and proceeds under mild conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Chen, Ming Z.; Micalizio, Glenn C.

    2009-01-01

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

  12. Regioselective C-H imidation of five-membered heterocyclic compounds through a metal catalytic or organocatalytic approach.

    Science.gov (United States)

    Wang, Xin; Sun, Kai; Lv, Yunhe; Ma, Fengji; Li, Gang; Li, Donghui; Zhu, Zhonghong; Jiang, Yongqing; Zhao, Feng

    2014-12-01

    An efficient method for the synthesis of 2-amino and β-amino five-membered heterocyclic derivatives that are closely related to a variety of biologically active natural products is described. Regioselectivity was achieved through a metal catalytic or organocatalytic approach. Preliminary studies on the reaction mechanism suggest a radical imidation pathway; however, further studies are needed to verify the mechanism. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Asymmetric synthesis of allylic sulfonic acids: enantio- and regioselective iridium-catalyzed allylations of Na2SO3.

    Science.gov (United States)

    Liu, Wei; Zhao, Xiao-ming; Zhang, Hong-bo; Zhang, Liang; Zhao, Ming-zhu

    2014-12-15

    An enantioselective allylation reaction of allylic carbonates with sodium sulfite (Na2 SO3 ) catalyzed by Ir complex was accomplished, providing allylic sulfonic acids in good to excellent yields with a high level of enantio- and regioselectivities. (R)-2-Phenyl-2-sulfoacetic acid, a key intermediate for the synthesis of Cefsulodin and Sulbenicillin, was synthesized as well. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Orthogonal protection of saccharide polyols through solvent-free one-pot sequences based on regioselective silylations

    Directory of Open Access Journals (Sweden)

    Serena Traboni

    2016-12-01

    Full Text Available tert-Butyldimethylsilyl (TBDMS and tert-butyldiphenylsilyl (TBDPS are alcohol protecting groups widely employed in organic synthesis in view of their compatibility with a wide range of conditions. Their regioselective installation on polyols generally requires lengthy reactions and the use of high boiling solvents. In the first part of this paper we demonstrate that regioselective silylation of sugar polyols can be conducted in short times with the requisite silyl chloride and a very limited excess of pyridine (2–3 equivalents. Under these conditions, that can be regarded as solvent-free conditions in view of the insolubility of the polyol substrates, the reactions are faster than in most examples reported in the literature, and can even be further accelerated with a catalytic amount of tetrabutylammonium bromide (TBAB. The strategy proved also useful for either the selective TBDMS protection of secondary alcohols or the fast per-O-trimethylsilylation of saccharide polyols. In the second part of the paper the scope of the silylation approach was significantly extended with the development of unprecedented “one-pot” and “solvent-free” sequences allowing the regioselective silylation/alkylation (or the reverse sequence of saccharide polyols in short times. The developed methodologies represent a very useful and experimentally simple tool for the straightforward access to saccharide building-blocks useful in organic synthesis.

  15. Rhodium(III)-catalyzed regioselective C2-amidation of indoles with N-(2,4,6-trichlorobenzoyloxy)amides and its synthetic application to the development of a novel potential PPARγ modulator.

    Science.gov (United States)

    Shi, Jingjing; Zhao, Guanguan; Wang, Xiaowei; Xu, H Eric; Yi, Wei

    2014-09-21

    A new and efficient method for the direct regioselective C2-amidation of various functionalized indoles with several N-(2,4,6-trichlorobenzoyloxy)amides via Rh(iii)-catalyzed C-H activation/N-O cleavage/C-N formation using the pyrimidyl group as a readily installable and removable directing group has been developed. With this method, a variety of valuable 2-amido indoles can be easily prepared under mild conditions with broad functional group tolerance and excellent region-/site-specificities. Application of this strategy to the synthesis of target compound as a novel PPARγ modulator was also demonstrated. The results from biological evaluation showed that compound had a partial PPARγ agonistic activity and a strong PPARγ binding affinity with an IC50 value of 120.0 nM, along with a less pronounced adipocyte differentiation ability compared to the currently marketed anti-diabetic drug rosiglitazone, suggesting that further development of such a compound might be of great interest.

  16. Tree species is the major factor explaining C:N ratios in European forest soils

    DEFF Research Database (Denmark)

    Cools, Nathalie; Vesterdal, Lars; De Vos, Bruno

    2014-01-01

    The C:N ratio is considered as an indicator of nitrate leaching in response to high atmospheric nitrogen (N) deposition. However, the C:N ratio is influenced by a multitude of other site-related factors. This study aimed to unravel the factors determining C:N ratios of forest floor, mineral soil...... mineral soil layers it was the humus type. Deposition and climatic variables were of minor importance at the European scale. Further analysis for eight main forest tree species individually, showed that the influence of environmental variables on C:N ratios was tree species dependent. For Aleppo pine...... and peat top soils in more than 4000 plots of the ICP Forests large-scale monitoring network. The first objective was to quantify forest floor, mineral and peat soil C:N ratios across European forests. Secondly we determined the main factors explaining this C:N ratio using a boosted regression tree...

  17. Organomolybdenum (VI) and lithium Organomolybdate (VI) and (V) Complexes with C,N-Chelating Aminoaryl Ligands

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Leur, M. de; Gossage, R.A.; Spek, A.L.

    1999-01-01

    The synthesis and characterization of new, five-coordinate molybdenum bis(imidoaryl) complexes [Mo(NAr)2(C-N)X] (Ar = C6H3i-Pr2-2,6; C-N = [C6H4(CH2NMe2)-2]-; X = Cl (1), Me (2), Et (3), Bu (4), CH2SiMe3 (5), (p-tolyl) (6), (C-N) (7)) is reported. The solid-state structure of 2 has been elucidated

  18. Insights into regioselective metabolism of mefenamic acid by cytochrome P450 BM3 mutants through crystallography, docking, molecular dynamics, and free energy calculations

    DEFF Research Database (Denmark)

    Capoferri, Luigi; Leth, Rasmus; Ter Haar, Ernst

    2016-01-01

    of the protein mutant M11 was expressed, purified, and crystallized, and its X-ray structure was used as template for modeling. A multistep approach was used that combines molecular docking, molecular dynamics (MD) simulation, and binding free-energy calculations to address protein flexibility. In this way...... active-site mutations such as V87I were reported to invert regioselectivity in NSAID hydroxylation. In this work, we combine crystallography and molecular simulation to study the effect of single mutations on binding and regioselective metabolism of mefenamic acid by M11 mutants. The heme domain...... of mefenamic acid by M11 and its mutants by including protein flexibility and dynamics in free-energy computation. In addition, we could obtain structural insights into the change in regioselectivity of mefenamic acid hydroxylation due to single active-site mutations. Our findings confirm that use of MD...

  19. Near-surface microstructural modification of (Ti,W)(C,N)-based compacts with nitrogen

    International Nuclear Information System (INIS)

    Ucakar, V.; Kral, C.; Lengauer, W.

    2001-01-01

    For developing of functional-gradient hardmetals the interaction of nitrogen with (Ti,W)(C,N)-based compacts was investigated. Hot-pressed (Ti,W)(C,N) compacts as well as sintered compacts of (Ti,W)(C,N)+Co were subjected to sintering and heat treatment at 1200-1500 o C and up to 30 bar N 2 . In (Ti,W)(C,N) compacts four microstructure types were obtained upon reaction with nitrogen. A uniform single-phase (Ti,W)(C,N) forms in samples with a low WC and high TiN content. If medium WC and high TiN/TiC ratio is present a core-rim type structure forms during Ar annealing which remains the same when nitrogen in-diffusion occurs. The third type of microstructure shows sub-micron lamellae of nitrogen-rich fcc phase and WC. This structure forms at increased WC and/or TiC content. If the WC content is increased again a WC layer forms at the outermost surface. Compressive stresses introduced by phase formation/decomposition were obtained for the nitrogen in-diffusion. Sintered (Ti,W)(C,N)+Co compacts were heat treated above and below the eutectic temperature. Above the eutectic temperature compact Ti(C,N) top-layers independent an sample composition were observed. Below the eutectic temperature the microstructure formation is mainly influenced by the sample composition. A Ti(C,N) top-layer forms in materials with a high Ti(C,N) content. Contrary, interaction zones without a layer were obtained in compacts with high WC/Ti(C,N) ratio. Some of these surface modified compacts show surfaces and particle sizes favorable for a cutting tool. (author)

  20. Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives.

    Science.gov (United States)

    Larksarp, C; Sellier, O; Alper, H

    2001-05-18

    The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.

  1. Theoretical Study on Regioselectivity of the Diels-Alder Reaction between 1,8-Dichloroanthracene and Acrolein.

    Science.gov (United States)

    Sultan, Mujeeb A; Karama, Usama; Almansour, Abdulrahman I; Soliman, Saied M

    2016-09-23

    A theoretical study of the regioselectivity of the Diels-Alder reaction between 1,8-dichloroanthracene and acrolein is performed using DFT at the B3LYP/6-31G(d,p) level of theory. The FMO analysis, global and local reactivity indices confirmed the reported experimental results. Potential energy surface analysis showed that the cycloadditions (CAs) favor the formation of the anti product. These results are in good agreement with the reported results obtained experimentally where the anti is the major product.

  2. The Inverse Demand Oxa-Diels-Alder Reaction of Resorcinarenes: An Experimental and Theoretical Analysis of Regioselectivity and Diastereoselectivity.

    Science.gov (United States)

    Stefańska, Karolina; Jędrzejewska, Hanna; Wierzbicki, Michał; Szumna, Agnieszka; Iwanek, Waldemar

    2016-07-15

    The Diels-Alder reaction enables introduction of new functionalities onto the resorcinarene skeleton with simultaneous generation of new stereogenic centers and expansion of the internal cavity. We present highly regio- and diastereoselective inverse electron demand oxa-Diels-Alder reactions of resorcinarene ortho-quinone methide with benzofuran and indene, each generating 12 new stereogenic centers. The mechanism and reasons for regioselectivity and diastereoselectivity were analyzed using theoretical calculations (NBO charges, Fukui functions, transition state energies, and thermodynamic stability of the products). Enantiomers were separated, and their configurations were determined by comparison of experimental and theoretical electronic circular dichroism spectra.

  3. Theoretical Study on Regioselectivity of the Diels-Alder Reaction between 1,8-Dichloroanthracene and Acrolein

    Directory of Open Access Journals (Sweden)

    Mujeeb A. Sultan

    2016-09-01

    Full Text Available A theoretical study of the regioselectivity of the Diels-Alder reaction between 1,8-dichloroanthracene and acrolein is performed using DFT at the B3LYP/6-31G(d,p level of theory. The FMO analysis, global and local reactivity indices confirmed the reported experimental results. Potential energy surface analysis showed that the cycloadditions (CAs favor the formation of the anti product. These results are in good agreement with the reported results obtained experimentally where the anti is the major product.

  4. Rhodium catalyzed regioselective arene homologation of aryl urea via double C-H bond activation and migratory insertion of alkyne

    Institute of Scientific and Technical Information of China (English)

    Yan Wang; Hao Zhou; Ke Xu; Mei-Hua Shen; Hua-Dong Xu

    2017-01-01

    A convenient rhodium catalyzed oxidative arene homologation of aniline derivatives with symmetrical or unsymmetrical alkynes using Cu(OAc)2 as oxidant is described.Urea group is shown to be effective as a directing group for initial ortho C-H activation.Two migratory insertion events of alkyne into Rh-C bond occur successively,both with complete regioselectivity.This method is particularly useful for synthesis of polyarenes with different substituents,which has not been reported with conventional protocol.A mechanism has been proposed to explain the observed data.

  5. Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

    Energy Technology Data Exchange (ETDEWEB)

    Pham, Tien Q.; Pyne, Stephen G.; Skelton, Brian W.; White, Allan H. (UWA); (Wollongong)

    2010-07-20

    The phosphine-catalyzed [3 + 2]-cycloaddition of 5-methylenehydantoins 4 with the ylides 5, derived from addition of tributylphosphine to the 2-butynoic acid derivatives, 6a-d, gives spiro-heterocyclic products. The camphor sultam derivative 6b gives optically active products. Noteable was that the ylides derived from ethyl 2-butynoate and the 3-(2-butynoyl)-1,3-oxazolidin-2-one derivatives 6c and 6d gave spiro-heterocyclic products with reverse regioselectivities. The N,N-dibenzylprotected cycloadduct has been converted to carbocyclic hydantocidin and 6,7-diepi-carbocyclic hydantocidin.

  6. Synthesis of 6-[18F] and 4-[18F]fluoro-L-m-tyrosines via regioselective radiofluorodestannylation

    International Nuclear Information System (INIS)

    Namavari, Mohammad; Satyamurthy, N.; Phelps, M.E.; Barrio, J.R.; California Univ., Los Angeles, CA

    1993-01-01

    The regioselective radiofluorodestannylation of 6-trimethylstannyl-L-m-tyrosine derivative with [ 18 F]F 2 and [ 18 F]acetyl hypofluorite afforded, after acid hydrolysis, 6-[ 18 F]fluoro-L-m-tyrosine in radiochemical yields of 23 and 17%, respectively. Similarly, 4-[ 18 F]fluoro-L-m-tyrosine was synthesized in 11% radiochemical yield from the corresponding 4-trimethylstannyl-L-m-tyrosine derivative using [ 18 F]F 2 . The structural analyses of precursors, intermediates, and the final products (after 18 F decay), were carried out by 1 H, 13 C, 19 F, 119 Sn-NMR and high resolution mass spectroscopy. (author)

  7. Chemo- and regioselective homogeneous rhodium-catalyzed hydroamidomethylation of terminal alkenes to N-alkylamides.

    Science.gov (United States)

    Raoufmoghaddam, Saeed; Drent, Eite; Bouwman, Elisabeth

    2013-09-01

    A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through catalytic hydroamidomethylation with 1-pentene and acetamide as model substrates. For appropriate catalyst performance, it appears to be essential that catalytic amounts of a strong acid promoter, such as p-toluenesulfonic acid (HOTs), as well as larger amounts of a weakly acidic protic promoter, particularly hexafluoroisopropyl alcohol (HOR(F) ) are applied. Apart from the product N-1-hexylacetamide, the isomeric unsaturated intermediates, hexanol and higher mass byproducts, as well as the corresponding isomeric branched products, can be formed. Under optimized conditions, almost full alkene conversion can be achieved with more than 80% selectivity to the product N-1-hexylamide. Interestingly, in the presence of a relatively high concentration of HOR(F) , the same catalyst system shows a remarkably high selectivity for the formation of hexanol from 1-pentene with syngas, thus presenting a unique example of a selective rhodium-catalyzed hydroformylation-hydrogenation tandem reaction under mild conditions. Time-dependent product formation during hydroamidomethylation batch experiments provides evidence for aldehyde and unsaturated intermediates; this clearly indicates the three-step hydroformylation/condensation/hydrogenation reaction sequence that takes place in hydroamidomethylation. One likely role of the weakly acidic protic promoter, HOR(F) , in combination with the strong acid HOTs, is to establish a dual-functionality rhodium catalyst system comprised of a neutral rhodium(I) hydroformylation catalyst species and a cationic rhodium(III) complex capable of selectively reducing the imide and/or ene-amide intermediates that are in a dynamic, acid-catalyzed condensation equilibrium with the aldehyde and amide in a syngas environment. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Hydrolysis of Some C,N-Chelated Organotin(IV) Species Used in Catalysis

    OpenAIRE

    Švec, P.

    2012-01-01

    This work deals with the reactivity of the selected C, N-chelated organotin (IV) species towards cyclohexene oxide, ethylene carbonate, and CO2. Structure of organotin(IV) hydrolytic products isolated from respective reaction mixtures was described.

  9. Highly efficient and regioselective acylation of pharmacologically interesting cordycepin catalyzed by lipase in the eco-friendly solvent 2-methyltetrahydrofuran.

    Science.gov (United States)

    Chen, Zhi-Gang; Zhang, Dan-Ni; Cao, Lin; Han, Yong-Bin

    2013-04-01

    A total of nine lipases and three proteases were tested for enzymatic regioselective acylation(s) of cordycepin with vinyl acetate in organic media. The highest conversion with better initial reaction rate was achieved with immobilized Candida antarctica lipase B (Novozym 435). An eco-friendly solvent 2-methyltetrahydrofuran (MeTHF) was thought to be the most suitable reaction medium. Novozym 435 was found to be a useful biocatalyst for the 25-g scale syntheses of cordycepin acetate (96.2% isolated yield), and the biocatalyst displayed excellent regioselectivity and high operational stability during the transformation. The 5'-substituted cordycepin derivative was the sole detectable product from each acylation reaction. Novozym 435 could be recycled for the synthesis of cordycepin derivative on a 25-g scale and 63% of its original activity was maintained after being reused for 7 batches. MeTHF could be considered as an eco-friendly solvent for the large scale use in biotransformation. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. [Hydrogen production and enzyme activity of acidophilic strain X-29 at different C/N ratio].

    Science.gov (United States)

    Li, Qiu-bo; Xing, De-feng; Ren, Nan-qi; Zhao, Li-hua; Song, Ye-ying

    2006-04-01

    Some fermentative bacteria can produce hydrogen by utilizing carbohydrate and other kinds of organic compounds as substrates. Hydrogen production was also determined by both the limiting of growth and related enzyme activity in energy metabolism. Carbon and nitrogen are needed for the growth and metabolism of microorganisms. In addition, the carbon/nitrogen (C/N) ratio can influence the material metabolized and the energy produced. In order to improve the hydrogen production efficiency of the bacteria, we analyzed the effect of different C/N ratios on hydrogen production and the related enzyme activities in the acidophilic strain X-29 using batch test. The results indicate that the differences in the metabolism level and enzyme activity are obvious at different C/N ratios. Although the difference in liquid fermentative products produced per unit of biomass is not obvious, hydrogen production is enhanced at a specifically determined ratio. At a C/N ratio of 14 the accumulative hydrogen yield of strain X-29 reaches the maximum, 2210.9 mL/g. At different C/N ratios, the expression of hydrogenase activity vary; the activity of hydrogenase decrease quickly after reaching a maximum along with the fermentation process, but the time of expression is short. The activity of alcohol dehydrogenase (ADH) tend to stabilize after reaching a peak along with the fermentation process, the difference in expression activity is little, and the expression period is long at different C/N ratios. At a C/N ratio of 14 hydrogenase and ADH reach the maximum 2.88 micromol x (min x mg)(-1) and 33.2 micromol x (min x mg)(-1), respectively. It is shown that the C/N ratio has an important effect on enhancing hydrogen production and enzyme activity.

  11. Some Congruence Properties of a Restricted Bipartition Function cN(n

    Directory of Open Access Journals (Sweden)

    Nipen Saikia

    2016-01-01

    Full Text Available Let cN(n denote the number of bipartitions (λ,μ of a positive integer n subject to the restriction that each part of μ is divisible by N. In this paper, we prove some congruence properties of the function cN(n for N=7, 11, and 5l, for any integer l≥1, by employing Ramanujan’s theta-function identities.

  12. Preparation and characterization of B-C-N hybrid thin films

    International Nuclear Information System (INIS)

    Uddin, Md. Nizam; Shimoyama, Iwao; Sekiguchi, Tetsuhiro; Baba, Yuji; Nath, Krishna G.; Nagano, Masamitsu

    2006-06-01

    Two dimensional thin films composed of boron, carbon and nitrogen (B-C-N hybrid) were synthesized by ion beam deposition, and their electronic and geometrical structures were characterized by core-level spectroscopy using synchrotron radiation. B-C-N hybrid thin films were grown from ion beam plasma of borazine on highly oriented pyrolitic graphite (HOPG) at various temperatures. The films were characterized in-situ by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS). XPS study suggested that B, N and C atoms in the deposited films were in a wide variety of chemical bonds e.g., B-C, B-N, N-C, and B-C-N. It was found that B-C-N hybrid formation was enhanced at high temperature, and that the B-C-N component was dominantly synthesized at low boron content. In the NEXAFS spectra, the resonance peaks from B 1s to unoccupied π * -like orbitals were clearly observed. The polarization dependence of the B 1s → π * resonance peaks confirmed that the highly oriented graphite-like B-C-N hybrids surely exist at low boron content. (author)

  13. Soil microbial C:N ratio is a robust indicator of soil productivity for paddy fields

    Science.gov (United States)

    Li, Yong; Wu, Jinshui; Shen, Jianlin; Liu, Shoulong; Wang, Cong; Chen, Dan; Huang, Tieping; Zhang, Jiabao

    2016-10-01

    Maintaining good soil productivity in rice paddies is important for global food security. Numerous methods have been developed to evaluate paddy soil productivity (PSP), most based on soil physiochemical properties and relatively few on biological indices. Here, we used a long-term dataset from experiments on paddy fields at eight county sites and a short-term dataset from a single field experiment in southern China, and aimed at quantifying relationships between PSP and the ratios of carbon (C) to nutrients (N and P) in soil microbial biomass (SMB). In the long-term dataset, SMB variables generally showed stronger correlations with the relative PSP (rPSP) compared to soil chemical properties. Both correlation and variation partitioning analyses suggested that SMB N, P and C:N ratio were good predictors of rPSP. In the short-term dataset, we found a significant, negative correlation of annual rice yield with SMB C:N (r = -0.99), confirming SMB C:N as a robust indicator for PSP. In treatments of the short-term experiment, soil amendment with biochar lowered SMB C:N and improved PSP, while incorporation of rice straw increased SMB C:N and reduced PSP. We conclude that SMB C:N ratio does not only indicate PSP but also helps to identify management practices that improve PSP.

  14. Microwave-Enhanced Sulphated Zirconia and SZ/MCM-41 Catalyzed Regioselective Synthesis of β-Amino Alcohols Under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Eduardo González-Zamora

    2008-04-01

    Full Text Available A solvent-free approach for the regioselective synthesis of β-amino alcohols inshorter reaction times and higher yields, compared to conventional heating is described. Itinvolves microwave (MW exposure of undiluted reactants in the presence of sulphatedzirconia (SZ or sulphated zirconia over MCM-41 (SZM as catalyst. Both acid materialscan be easily recovered and reused.

  15. Synthesis of unnatural amino acids via microwave-assisted regio-selective one-pot multi-component reactions of sulfamidates

    Science.gov (United States)

    Synthesis of triazole-based unnatural amino acids, triazole bisaminoacids and β-amino triazole has been described via stereo and regioselective one-pot multi-component reaction of sulfamidates, sodium azide, and alkynes under MW irradiation conditions. The developed method is app...

  16. Controlled acrylate insertion regioselectivity in diazaphospholidine- sulfonato palladium(II) complexes

    KAUST Repository

    Wucher, Philipp

    2012-12-24

    Diazaphospholidine-sulfonato Pd(II) complexes [{κ2-P,O-(N- Ar2C2H4N2P)C6H 4SO3}PdMe(L)] 1-L (L = dmso, pyridine, lutidine, or μ-LiCl(solvent); 1a: Ar = Ph, 1b: Ar = 2-MeC6H4, 1c: Ar = 2-MeOC6H4, 1d: Ar = 2,4,6-Me3C 6H2, 1e: Ar = 2,6-iPr2C6H 3, 1f: Ar = 2,6-(p-tolyl)2C6H3) were prepared and structurally characterized. The regioselectivity of methyl acrylate (MA) insertion into the Pd-Me bond is entirely inverted from >93% 1,2-insertion for bulky substituents (1d-f, yielding the insertion products [(P̂O)Pd{κ2-C,O-CH2CHMeC(O)OMe], 12) to the usual electronically controlled 2,1-insertion (>95%) for the less bulky Ar = Ph (1a, yielding the insertion product [(P̂O)Pd{κ2-C,O- CHEtC(O)OMe], 11, and β-H elimination product methyl crotonate). DFT studies underline that this is due to a more favorable insertion transition state (2,1- favored by 12 kJ mol-1 over 1,2- for 1a) vs destabilization of the 2,1-insertion transition state in 1d,e. By contrast, MA insertion into the novel isolated and structurally characterized hydride and deuteride complexes [{κ2-P,O-(N-Ar2C 2H4N2P)C6H4SO 3}PdR(lutidine)] (Ar = 2,6-iPr2C6H3; 9e: R = H, 10e: R = D) occurs 2,1-selectively. This is due to the insertion occurring from the isomer with the P-donor and the olefin in trans arrangement, rather than the insertion into the alkyl from the cis isomer in which the olefin is in proximity to the bulky diazaphospholidine. 1a-f are precursors to active catalysts for ethylene polymerization to highly linear polyethylene with M n up to 35 000 g mol-1. In copolymerization experiments, norbornene was incorporated in up to 6.1 mol % into the polyethylene backbone. © 2012 American Chemical Society.

  17. Engineered biosynthesis of regioselectively modified aromatic polyketides using bimodular polyketide synthases.

    Directory of Open Access Journals (Sweden)

    Yi Tang

    2004-02-01

    Full Text Available Bacterial aromatic polyketides such as tetracycline and doxorubicin are a medicinally important class of natural products produced as secondary metabolites by actinomyces bacteria. Their backbones are derived from malonyl-CoA units by polyketide synthases (PKSs. The nascent polyketide chain is synthesized by the minimal PKS, a module consisting of four dissociated enzymes. Although the biosynthesis of most aromatic polyketide backbones is initiated through decarboxylation of a malonyl building block (which results in an acetate group, some polyketides, such as the estrogen receptor antagonist R1128, are derived from nonacetate primers. Understanding the mechanism of nonacetate priming can lead to biosynthesis of novel polyketides that have improved pharmacological properties. Recent biochemical analysis has shown that nonacetate priming is the result of stepwise activity of two dissociated PKS modules with orthogonal molecular recognition features. In these PKSs, an initiation module that synthesizes a starter unit is present in addition to the minimal PKS module. Here we describe a general method for the engineered biosynthesis of regioselectively modified aromatic polyketides. When coexpressed with the R1128 initiation module, the actinorhodin minimal PKS produced novel hexaketides with propionyl and isobutyryl primer units. Analogous octaketides could be synthesized by combining the tetracenomycin minimal PKS with the R1128 initiation module. Tailoring enzymes such as ketoreductases and cyclases were able to process the unnatural polyketides efficiently. Based upon these findings, hybrid PKSs were engineered to synthesize new anthraquinone antibiotics with predictable functional group modifications. Our results demonstrate that (i bimodular aromatic PKSs present a general mechanism for priming aromatic polyketide backbones with nonacetate precursors; (ii the minimal PKS controls polyketide chain length by counting the number of atoms

  18. Ecological stoichiometry of C, N and P on different time enclosed in desertification steppe soil

    Science.gov (United States)

    Yang, W. Z.; Jiao, Y.; Jia, Y. Q.

    2017-08-01

    It is the research object for the ecological stoichiometry of C, N and P on the different time of desertification grasslands enclosed and grazing grassland in Taibusi country of the Inner Mongolia, China. Through the measurement and analysis on ecological stoichiometric ratio of C, N and P in soil, the time of desertification grassland enclosed is determined. There are 13 soil of desertification grassland with different en-closure time, and 1 soil of grazing grassland. They are analyzed for the soil organic carbon, total nitro-gen, total phosphorus content and their density. The C/N of soil were increased with the extension of the time of desertification grassland enclosed. To 22 years enclosed, the C/N of grassland desertification soil enclosed is greater than the soil of grazing grassland that is 17. After the desertification grassland is en-closed, the C/N of soil is 13, and it is accumulated to maximum for C and N, and The grazing period is the best.

  19. Effects of three global change drivers on terrestrial C:N:P stoichiometry

    DEFF Research Database (Denmark)

    Yue, Kai; Fornara, Dario A; Yang, Wanqin

    2017-01-01

    more common than synergistic or antagonistic interactions, (4) C:N:P stoichiometry of soil and soil microbial biomass shows high homeostasis under global change manipulations, and (5) C:N:P responses to global change are strongly affected by ecosystem type, local climate and experimental conditions......Over the last few decades there has been an increasing number of controlled-manipulative experiments to investigate how plants and soils might respond to global change. These experiments typically examined the effects of each of three global change drivers (i.e. nitrogen (N) deposition, warming...... of plants, soils and soil microbial biomass might respond to individual vs. combined effects of the three global change drivers. Our results show that (1) individual effects of N addition and elevated CO2 on C:N:P stoichiometry are stronger than warming, (2) combined effects of pairs of global change...

  20. Novel precursor-derived Si-C-N ceramic material for purification application.

    Science.gov (United States)

    Roh, Changhyun; Lee, Sea-Hoon; Francois, Villatte

    2008-02-01

    Metagenomic DNA (gDNA) is an important research topic because uncultivated microorganisms represent an interesting reservoir of genes with potential biotechnological applications. Here we describe a novel Si-C-N chromatography approach of gDNA extraction from environmental samples. Amorphous Si-C-N ceramic was obtained by the pyrolysis of a polymer precursor (polycarbosilazane) at 1350 degrees C in Ar. The purified gDNA fragments were at least 12 kilo base pairs in size and were sufficiently free of contaminants, thus were applicable to both restriction enzyme digestion using five different enzymes and polymerase chain reaction amplification for detecting phylogenetic groups of native microorganisms in environmental samples. This Si-C-N material produces pure gDNA that can be utilized in some of the most common molecular biological procedures applied in the purification step.

  1. Co-composting of green waste and food waste at low C/N ratio

    International Nuclear Information System (INIS)

    Kumar, Mathava; Ou, Y.-L.; Lin, J.-G.

    2010-01-01

    In this study, co-composting of food waste and green waste at low initial carbon to nitrogen (C/N) ratios was investigated using an in-vessel lab-scale composting reactor. The central composite design (CCD) and response surface method (RSM) were applied to obtain the optimal operating conditions over a range of preselected moisture contents (45-75%) and C/N ratios (13.9-19.6). The results indicate that the optimal moisture content for co-composting of food waste and green waste is 60%, and the substrate at a C/N ratio of 19.6 can be decomposed effectively to reduce 33% of total volatile solids (TVS) in 12 days. The TVS reduction can be modeled by using a second-order equation with a good fit. In addition, the compost passes the standard germination index of white radish seed indicating that it can be used as soil amendment.

  2. Contribution to the study of the (U,Pu)C,N system; Contribution a l'etude du systeme (U,Pu)C,N

    Energy Technology Data Exchange (ETDEWEB)

    Lorenzelli, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1968-07-01

    The reactions of UC, PuC, (U,Pu)C, UC{sub 2} and U(C{sub 1-x}O{sub x}) with nitrogen at moderate temperatures (room temperature to 400 C) are described. The influence of the uptake of nitrogen by the powders necessary to sinter the carbides upon the nature of the final product has been investigated; it has been shown that the sintered carbides are hyper-stoichiometric. The reactions of carbon with UN, PuN and (U,Pu)N has also been studied. Under vacuum, carbon reacts on the nitrides at temperatures as low as 1100 C; nitrogen is replaced by carbon and the final product is a carbonitride. The reaction is: MN + x C {yields} MN{sub 1-x}C{sub x} + x/2N{sub 2}. The reaction is limited and the carbonitrides have a fixed composition in presence of M{sub 2}C{sub 3} or MC{sub 2}; hence it is impossible to produce pure MC using the reaction. The ternary diagram U-C-N, Pu-C-N and (U,Pu)C-N have been drawn. They show clearly that it is possible to obtain single phase carbonitrides in a wide domain of compositions. (author) [French] On decrit les reactions avec l'azote de UC, PuC,(U,Pu)C,UC{sub 2} et U(C{sub 1-x}O{sub x}), par action directe de l'azote a temperature moderee (de l'ambiante a 450 C). On a etudie l'influence de la contamination par l'azote des poudres de carbures necessaires au frittage sur la nature des produits frittes; on a montre que les carbures frittes obtenus sont hyperstoechiometriques. On a etudie parallelement les reactions du carbone avec UN, PuN et (U,Pu)N. Sous vide le carbone reagit sur les nitrures des 1100 C: le carbone se substitue a l'azote; l'azote libere est elimine et le produit final est un carbonitrure. La reaction s'ecrit: MN + x C {yields} MN{sub 1-x}C{sub x} + x/2N{sub 2}. La reaction est limitee et les carbonitrures obtenus ont une composition limite fixe en presence des carbures superieurs M{sub 2}C{sub 3} et MC{sub 2}; il est donc impossible d'obtenir MC pur par cette reaction. Les diagrammes d'equilibre U-C-N, Pu-C-N et (U,Pu) C-N, ont

  3. Contribution to the study of the (U,Pu)C,N system; Contribution a l'etude du systeme (U,Pu)C,N

    Energy Technology Data Exchange (ETDEWEB)

    Lorenzelli, R. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1968-07-01

    The reactions of UC, PuC, (U,Pu)C, UC{sub 2} and U(C{sub 1-x}O{sub x}) with nitrogen at moderate temperatures (room temperature to 400 C) are described. The influence of the uptake of nitrogen by the powders necessary to sinter the carbides upon the nature of the final product has been investigated; it has been shown that the sintered carbides are hyper-stoichiometric. The reactions of carbon with UN, PuN and (U,Pu)N has also been studied. Under vacuum, carbon reacts on the nitrides at temperatures as low as 1100 C; nitrogen is replaced by carbon and the final product is a carbonitride. The reaction is: MN + x C {yields} MN{sub 1-x}C{sub x} + x/2N{sub 2}. The reaction is limited and the carbonitrides have a fixed composition in presence of M{sub 2}C{sub 3} or MC{sub 2}; hence it is impossible to produce pure MC using the reaction. The ternary diagram U-C-N, Pu-C-N and (U,Pu)C-N have been drawn. They show clearly that it is possible to obtain single phase carbonitrides in a wide domain of compositions. (author) [French] On decrit les reactions avec l'azote de UC, PuC,(U,Pu)C,UC{sub 2} et U(C{sub 1-x}O{sub x}), par action directe de l'azote a temperature moderee (de l'ambiante a 450 C). On a etudie l'influence de la contamination par l'azote des poudres de carbures necessaires au frittage sur la nature des produits frittes; on a montre que les carbures frittes obtenus sont hyperstoechiometriques. On a etudie parallelement les reactions du carbone avec UN, PuN et (U,Pu)N. Sous vide le carbone reagit sur les nitrures des 1100 C: le carbone se substitue a l'azote; l'azote libere est elimine et le produit final est un carbonitrure. La reaction s'ecrit: MN + x C {yields} MN{sub 1-x}C{sub x} + x/2N{sub 2}. La reaction est limitee et les carbonitrures obtenus ont une composition limite fixe en presence des carbures superieurs M{sub 2}C{sub 3} et MC{sub 2}; il est donc impossible d'obtenir MC pur par cette reaction. Les diagrammes

  4. A new approach to construct a fused 2-ylidene chromene ring: highly regioselective synthesis of novel chromeno quinoxalines.

    Science.gov (United States)

    Kumar, K Shiva; Rambabu, D; Prasad, Bagineni; Mujahid, Mohammad; Krishna, G Rama; Rao, M V Basaveswara; Reddy, C Malla; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

    2012-06-28

    Regioselective construction of a fused 2-ylidene chromene ring was achieved for the first time by using AlCl(3)-induced C-C bond formation followed by Pd/C-Cu mediate coupling-cyclization strategy. A number of chromeno[4,3-b]quinoxaline derivatives were prepared by using this strategy. Single crystal X-ray diffraction study of a representative compound e.g. 6-(2,2-dimethylpropylidene)-4-methyl-6H-chromeno[4,3-b]quinoxalin-3-ol confirmed the presence of an exocyclic C-C double bond with Z-geometry. The crystal structure analysis and hydrogen bonding patterns of the same compound along with its structure elaboration via propargylation followed by Sonogashira coupling of the resulting terminal alkyne is presented. A probable mechanism for the formation of 2-ylidene chromene ring is discussed. Some of the compounds synthesized showed anticancer properties when tested in vitro.

  5. Isolation and characterisation of an unexpected byproduct in the regioselective butane diacetal protection of α-methyl galactopyranoside.

    Science.gov (United States)

    Fontenelle, Clément Q; Kuppala, Ramakrishna; Light, Mark; Linclau, Bruno

    2018-01-02

    The regioselective protection of both methyl galactopyranoside anomers at the 2 and 3-positions as the butane diacetal (BDA) is well known. Here we describe the formation of an unexpected byproduct, which mainly occurs when α-methyl galactopyranoside is reacted with 2,3-butanedione under BF 3 •OEt 2 catalysis. The structure of the byproduct, which did not arise from anomerisation to the β-anomer or from BDA formation at the galactopyranoside 3,4-positions, was elucidated by NMR and X-ray crystallographic analysis, and proved to be the expected BDA protected galactopyranoside, but in which the stereochemistry of both its BDA acetal centres are inverted. Interestingly, the conformation of the resulting six-membered BDA ring was distorted to a skew boat conformation in order to maintain anomeric stabilisation. Copyright © 2017. Published by Elsevier Ltd.

  6. Microwave promoted simple, efficient and regioselective synthesis of trisubstituted imidazo[1,2-a]benzimidazoles on soluble support.

    Science.gov (United States)

    Chen, Li-Hsun; Hsiao, Ya-Shan; Yellol, Gorakh S; Sun, Chung-Ming

    2011-03-14

    An efficient microwave-assisted and soluble polymer-supported synthesis of medicinally important imidazole-fused benzimidazoles has been developed. The protocol involves the rapid condensation of polymer-bound amino benzimidazoles with various α-bromoketones and subsequent in situ intramolecular cyclization under microwave irradiation resulting in a one pot synthesis of imidazole interlacing benzimidazole polymer conjugates. The condensed product was obtained with excellent regioselectivity. The biologically interesting imidazo[1,2-a]benzimidazoles was released from polymer support at ambient temperature. Diversity in the triheterocyclic nucleus was achieved by the different substitutions at its 2, 3, and 9 positions. The new protocol has the advantages of short reaction time, easy workup process, excellent yields, reduced environmental impact, wide substrate scope and convenient procedure.

  7. Bulk superhard B-C-N nanocomposite compact and method for preparing thereof

    Science.gov (United States)

    Zhao, Yusheng; He, Duanwei

    2004-07-06

    Bulk, superhard, B-C-N nanocomposite compact and method for preparing thereof. The bulk, superhard, nanocomposite compact is a well-sintered compact and includes nanocrystalline grains of at least one high-pressure phase of B-C-N surrounded by amorphous diamond-like carbon grain boundaries. The bulk compact has a Vicker's hardness of about 41-68 GPa. It is prepared by ball milling a mixture of graphite and hexagonal boron nitride, encapsulating the ball-milled mixture, and sintering the encapsulated ball-milled mixture at a pressure of about 5-25 GPa and at a temperature of about 1000-2500 K.

  8. DARC PLURIDATA system: the /sup 13/C-N. M. R. data bank

    Energy Technology Data Exchange (ETDEWEB)

    Dubois, J E; Bonnet, J C [Paris-7 Univ., 75 (France)

    1979-09-15

    The capabilities of the DARC system are discussed and illustrated by the storage and retrieval functions of the /sup 13/C-N.M.R. data bank of the DARC PLURIDATA system. The data covered by the bank, as well as the input stream to the bank and validation of the spectra, are described. Particular stress is laid on the DARC structural retrieval system, which illustrates the interactive interrogration of a chemical bank by means of the structural diagram of a molecule, i.e. the universal language in chemistry. The potential of the /sup 13/C-N.M.R. data bank in computer-aided structural elucidation is outlined.

  9. Thermal properties of black phosphorene and doped phosphorene (C, N & O): A DFT study

    Science.gov (United States)

    Devi, Anjna; Singh, Amarjeet

    2018-04-01

    In this work, we present the results from a DFT based computational study of pristine phosphorene and doped (C, N & O) phosphorene. We systematically investigated the lattice thermal properties of black phosphorene and the effect of doping on its thermal properties. We first determined the vibrational properties of pristine and doped phosphorene and from these results we calculated their thermal properties. We doped the phosphorene with C, N and O and observed that the structural stability of doped phosphorene decreases, while the thermal stability is increased as compared to pristine phosphorene. The presence of finite temperature effects in the doped system can contribute to acceleration of progress in future nano-scale technology.

  10. Mechanism of copper(I)-catalyzed allylic alkylation of phosphorothioate esters: influence of the leaving group on α regioselectivity.

    Science.gov (United States)

    Sheng, Wenhao; Wang, Mian; Lein, Matthias; Jiang, Linbin; Wei, Wanxing; Wang, Jianyi

    2013-10-11

    The mechanism of Cu(I) -catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)2 ; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)2 Cu](-) prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α- or γ-selective product. If OPiv, SPiv, Cl, or SPO(OiPr)2 groups are present, the optimal route for the formation of both α- and γ-substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α- and γ-substituted products are 2.75 kcal mol(-1) with SPO(OiPr)2 , 2.44 kcal mol(-1) with SPiv, 2.33 kcal mol(-1) with OPiv, and 1.98 kcal mol(-1) with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)2 >SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)2 , SPiv, OPiv, and Cl groups on the Cu group. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Thermally Oxidized C, N Co-Doped ANATASE-TiO2 Coatings on Stainless Steel for Tribological Properties

    Science.gov (United States)

    Wang, Hefeng; Shu, Xuefeng; Li, Xiuyan; Tang, Bin; Lin, Naiming

    2013-07-01

    Ti(C, N) coatings were prepared on stainless steel (SS) substrates by plasma surface alloying technique. Carbon-nitrogen co-doped titanium dioxide (C-N-TiO2) coatings were fabricated by oxidative of the Ti(C, N) coatings in air. The prepared C-N-TiO2 coatings were characterized by SEM, XPS and XRD. Results reveal that the SS substrates were entirely shielded by the C-N-TiO2 coatings. The C-N-TiO2 coatings are anatase in structure as characterized by X-ray diffraction. The tribological behavior of the coatings was tested with ball-on-disc sliding wear and compared with substrate. Such a C-N-TiO2 coatings showed good adhesion with the substrate and tribological properties of the SS in terms of much reduced friction coefficient and increased wear resistance.

  12. Aggregation behavior of gemini pyrrolidine-based ionic liquids 1,1'-(butane-1,4-diyl)bis(1-alkylpyrrolidinium) bromide ([C(n)py-4-C(n)py][Br2]) in aqueous solution.

    Science.gov (United States)

    Zhang, Shaohua; Yan, Han; Zhao, Mingwei; Zheng, Liqiang

    2012-04-15

    Three gemini pyrrolidine-based ionic liquids, 1,1'-(butane-1,4-diyl)bis(1-alkylpyrrolidinium) bromide ([C(n)py-4-C(n)py][Br(2)], n=10, 12, 14), were synthesized. Their aggregation behavior in aqueous solution was systematically investigated by surface tension, electrical conductivity, and steady-state fluorescence. Compared with their corresponding monomers, N-alkyl-N-methylpyrrolidinium bromide (C(n)MPB), [C(n)py-4-C(n)py][Br(2)], have higher surface activity. The special structure of [C(n)py-4-C(n)py][Br(2)] that has a spacer in their hydrophilic head groups results in a lower surface excess concentration (Γ(max)) and a larger molecular cross-sectional area (A(min)). Electrical conductivity studies show a lower degree of counter-ion binding to the aggregates. A smaller aggregation number (N(agg)) is observed by the pyrene fluorescence quenching method. A series of thermodynamic parameters (ΔG(agg)(0),ΔH(agg)(0),-TΔS(agg)(0)) of aggregation derived from electrical conductivity indicate that the aggregation of [C(n)py-4-C(n)py][Br(2)] is enthalpy-driven, while aggregation of C(n)MPB is entropy-driven at low temperatures but enthalpy-driven at high temperatures. Copyright © 2012 Elsevier Inc. All rights reserved.

  13. Low-energy electron scattering by C, N, and O atoms

    Energy Technology Data Exchange (ETDEWEB)

    Nesbet, R K [International Business Machines Corp., San Jose, Calif. (USA). Research Lab.

    1977-07-01

    Recent theoretical studies of low-energy electron scattering by C, N, and O atoms are reviewed and results are compared with available experimental data. A critical comparison is made of the two principal methods used in this work-polarized pseudostate expansion with R-matrix computations or direct integration, and Bethe-Goldstone expansion with matrix variational computations. 31 references.

  14. Preparation of Ta(C)N films by pulsed high energy density plasma

    Energy Technology Data Exchange (ETDEWEB)

    Feng Wenran [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China); Chen Guangliang [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China); Zhang Yan [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China); Gu Weichao [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China); Zhang Guling [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China); Niu Erwu [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China); Liu Chizi [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China); Yang Size [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100080 Beijing (China)

    2007-04-07

    The pulsed high energy density plasma (PHEDP) is generated in the working gas due to a high-voltage high-current discharge, within a coaxial gun. In PHEDP surface modification, discharge is applied for preparing the amorphous and nanostructured high-melting materials as thin films deposited on various substrates. In this investigation, Ta(C)N films were deposited using PHEDP on stainless steel. Pure tantalum and graphite were used as the inner and outer electrodes of the PHEDP coaxial gun, respectively. Nitrogen was used as the working gas and also one of the reactants. Preliminary study on the films prepared under different conditions shows that the formation of Ta(C)N is drastically voltage dependent. At lower gun voltage, no Ta(C)N was detected in the films; when the gun voltage reaches or exceeds 3.0 kV, Ta(C)N occurred. The films are composed of densely stacked nanocrystallines with diameter less than 30 nm, and some grains are within 10 nm in diameter.

  15. Optical features of C, N, Mn implanted MgO films

    International Nuclear Information System (INIS)

    Dorosinets, V.A.; Dobrinets, I.A.; Wieck, A.

    2013-01-01

    Optical absorption and Raman spectra investigations of C/ N/ Mn implanted MgO films have been investigated. The spectra reveal a surface modification and a dependence of the defect formation mechanism on the ion type and the annealing regime. (authors)

  16. Forest wildfire increases soil microbial biomass C:N:P stoichiometry in long-term effects

    Science.gov (United States)

    Zhou, Xuan

    2017-04-01

    Boreal forest fire strongly influences carbon (C) stock in permafrost soil by thawing permafrost table which accelerated microbe decomposition process. We studied soil microbial biomass stoichiometry in a gradient of four (3 yr, 25 yr, 46 yr and more than 100 yr) ages since fire in Canada boreal forest. Soil microbial biomass (MB) in long-term after fire is significantly higher than in short-term. MB C and nitrogen (N) were mainly dominated by corresponding soil element concentration and inorganic P, while MB phosphorus (P) changes were fully explained by soil N. Fire ages and soil temperature positively increased MB N and P, indicating the negative impact by fire. Microbial C:N:P gradually increased with fire ages from 15:2:1 to 76:6:1 and then drop down to 17:2:1 in the oldest fire ages. The degree of homeostasis of microbial C, N and P are close to 1 indicates non-homoeostasis within microbial elements, while it of C:N:P is close to 8 shows a strong homeostasis within element ratios and proved microbial stoichiometric ratio is not driven by soil element ratios. In conclusion, i) microbial biomass elements highly depends on soil nutrient supply rather than fire ages; ii) wildfire decreased microbial stoichiometry immediate after fire but increased with years after fire (YF) which at least 3 times higher than > 100 fire ages; iii) microbial biomass C, N and P deviated from strict homeostasis but C:N:P ratio reflects stronger homeostasis.

  17. Research Update: A hafnium-based metal-organic framework as a catalyst for regioselective ring-opening of epoxides with a mild hydride source

    International Nuclear Information System (INIS)

    Stephenson, Casey J.; Hassan Beyzavi, M.; Klet, Rachel C.; Hupp, Joseph T.; Farha, Omar K.

    2014-01-01

    Reaction of styrene oxide with sodium cyanoborohydride and a catalytic amount of Hf-NU-1000 yields the anti-Markovnikov product, 2-phenylethanol, with over 98% regioselectivity. On the other hand, propylene oxide is ring opened in a Markovnikov fashion to form 2-propanol with 95% regioselectivity. Both styrene oxide and propylene oxide failed to react with sodium cyanoborohydride without the addition of Hf-NU-1000 indicative of the crucial role of Hf-NU-1000 as a catalyst in this reaction. To the best of our knowledge, this is the first report of the use of a metal-organic framework material as a catalyst for ring-opening of epoxides with hydrides

  18. Regioselective 1,4- and 1,6-Conjugate Additions of Grignard Reagent-Derived Organozinc(II)ates to Polyconjugated Esters.

    Science.gov (United States)

    Hatano, Manabu; Mizuno, Mai; Ishihara, Kazuaki

    2016-09-16

    Regioselective synthetic methods were developed for 1,4- and 1,6-conjugate additions of Grignard reagent-derived organozinc(II)ates to malonate-derived polyconjugated esters. By taking advantage of the tight ion-pair control of organozinc(II)ates, it was possible to switch between 1,4- and 1,6-conjugate additions by introducing a terminal ethoxy moiety in the conjugation.

  19. Regioselectivity in the Thermal Rearrangement of Unsymmetrical 4-Methyl-4H-1,2,4-triazoles to 1-Methyl-1H-1,2,4-triazoles

    Directory of Open Access Journals (Sweden)

    Per H.J. Carlsen

    2001-11-01

    Full Text Available The rearrangement of 4-methyl-3,5-diaryl-4H-1,2,4-triazoles to the corresponding 1-methyl-3,5-diaryl-1H-1,2,4-triazoles showed regioselectivity comparable to that observed for the alkylation of 3,5-diaryl-1H-1,2,4-triazoles. This lends support to a proposed mechanism for the rearrangement that involves consecutive nucleophilic displacements steps.

  20. A Mild and Green Route for Regio-selective Amination of Oxiranes Using Nanomagnetic Supported Ferrous Ion as a Solid Lewis Acid Catalyst in Water

    Directory of Open Access Journals (Sweden)

    Fariborz Mansouri

    2016-07-01

    Full Text Available A mild, green and highly efficient route for regio-selective amination of oxiranes was developed via incorporation of Mn(II, Fe(II, Co(II, Ni(II, Cu(II and Zn(II cations onto the surface of hydroxyapatite-encapsulated γ-Fe2O3 nanoparticles (γ-Fe2O3@HAp. Among six magnetically recoverable catalytic systems denoted as [γ-Fe2O3@HAp-MII], the catalyst in which M designated as Fe(II showed the best efficiency as well as regio-selectivity in amination of oxiranes under an ambient reaction condition. A wide variety of aromatic and aliphatic amines were reacted with epoxides using magnetically separable iron catalyst to give the corresponding amino alcohols in excellent yields and selectivities in water as solvent at room temperature. In addition, recovery of the catalyst was successfully carried out in subsequent runs without any decrease in activity even after 5 runs. High regio-selectivity toward terminal ring-opening, efficient catalyst reusability using simple magnetic separation, high yields, simplicity in operation and diversity for various substrates are of advantages of this study.

  1. Unveiling of novel regio-selective fatty acid double bond hydratases from Lactobacillus acidophilus involved in the selective oxyfunctionalization of mono- and di-hydroxy fatty acids.

    Science.gov (United States)

    Kim, Kyoung-Rok; Oh, Hye-Jin; Park, Chul-Soon; Hong, Seung-Hye; Park, Ji-Young; Oh, Deok-Kun

    2015-11-01

    The aim of this study is the first time demonstration of cis-12 regio-selective linoleate double-bond hydratase. Hydroxylation of fatty acids, abundant feedstock in nature, is an emerging alternative route for many petroleum replaceable products thorough hydroxy fatty acids, carboxylic acids, and lactones. However, chemical route for selective hydroxylation is still quite challenging owing to low selectivity and many environmental concerns. Hydroxylation of fatty acids by hydroxy fatty acid forming enzymes is an important route for selective biocatalytic oxyfunctionalization of fatty acids. Therefore, novel fatty acid hydroxylation enzymes should be discovered. The two hydratase genes of Lactobacillus acidophilus were identified by genomic analysis, and the expressed two recombinant hydratases were identified as cis-9 and cis-12 double-bond selective linoleate hydratases by in vitro functional validation, including the identification of products and the determination of regio-selectivity, substrate specificity, and kinetic parameters. The two different linoleate hydratases were the involved enzymes in the 10,13-dihydroxyoctadecanoic acid biosynthesis. Linoleate 13-hydratase (LHT-13) selectively converted 10 mM linoleic acid to 13S-hydroxy-9(Z)-octadecenoic acid with high titer (8.1 mM) and yield (81%). Our study will expand knowledge for microbial fatty acid-hydroxylation enzymes and facilitate the designed production of the regio-selective hydroxy fatty acids for useful chemicals from polyunsaturated fatty acid feedstocks. © 2015 Wiley Periodicals, Inc.

  2. Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions.

    Science.gov (United States)

    Ruiz-Castillo, Paula; Buchwald, Stephen L

    2016-10-12

    Pd-catalyzed cross-coupling reactions that form C-N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C-N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts.

  3. The Beckman-Quarles theorem for continuous mappings from R^n to C^n

    OpenAIRE

    Tyszka, Apoloniusz

    2002-01-01

    Let \\phi((x_1,...,x_n),(y_1,...,y_n))=(x_1-y_1)^2+...+(x_n-y_n)^2. We say that f:R^n -> C^n preserves distance d>=0 if for each x,y \\in R^n \\phi(x,y)=d^2 implies \\phi(f(x),f(y))=d^2. We prove that if x,y \\in R^n (n>=3) and |x-y|=(\\sqrt{2+2/n})^k \\cdot (2/n)^l (k,l are non-negative integers) then there exists a finite set {x,y} \\subseteq S(x,y) \\subseteq R^n such that each unit-distance preserving mapping from S(x,y) to C^n preserves the distance between x and y. It implies that each continuou...

  4. The Main Path to C, N, O Elements in Big Bang Nucleosynthesis

    International Nuclear Information System (INIS)

    Su-Qing, Hou; Kai-Su, Wu; Yong-Shou, Chen; Neng-Chuan, Shu; Zhi-Hong, Li

    2010-01-01

    The production of C, N, O elements in a standard big bang nucleosynthesis scenario is investigated. Using the up-to-date data of nuclear reactions in BBN, in particular the 8 Li (n,γ) 9 Li which has been measured in China Institute of Atomic Energy, a full nucleosynthesis network calculation of BBN is carried out. Our calculation results show that the abundance of 12 C is increased for an order of magnitude after addition of the reaction chain 8 Li(n,γ) 9 Li(α,n) 12 B(β) 12 C, which was neglected in previous studies. We find that this sequence provides the main channel to convert the light elements into C, N, O in standard BBN. (nuclear physics)

  5. Synthesis and purification of /sup 14/C N-2-hydroxyethyl-N-nitrosourea

    Energy Technology Data Exchange (ETDEWEB)

    Perez, G.; Possagno, E.; Caponecchi, G.; Lilla, E.; Polcaro, C.

    1986-04-01

    /sup 14/C N-2-hydroxyethyl-N-nitrosourea was prepared at a specific activity of 30 mCi/mmol and 1.29 mCi/mmol by a two-step synthetic sequence using /sup 14/C ethanolamine as the labelled precursor. Its purification was performed by HPLC using a Lichrosorb-DIOL column eluted by ethyl ether. The overall radiochemical yield was 10%.

  6. Synthesis and purification of 14C N-2-hydroxyethyl-N-nitrosourea

    International Nuclear Information System (INIS)

    Perez, G.; Possagno, E.; Caponecchi, G.; Lilla, E.

    1986-01-01

    14 C N-2-hydroxyethyl-N-nitrosourea was prepared at a specific activity of 30 mCi/mmol and 1.29 mCi/mmol by a two-step synthetic sequence using 14 C ethanolamine as the labelled precursor. Its purification was performed by HPLC using a Lichrosorb-DIOL column eluted by ethyl ether. The overall radiochemical yield was 10%. (author)

  7. C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

    Science.gov (United States)

    Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

    2013-04-17

    We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

  8. Optimal C:N ratio for the production of red pigments by Monascus ruber.

    Science.gov (United States)

    Said, Farhan M; Brooks, John; Chisti, Yusuf

    2014-09-01

    The carbon-to-nitrogen (C:N) ratio in the biomass of microfungi tends to be quite different (e.g. 10-15) compared with the C:N ratio in the red pigments (e.g. >20) of the fungus Monascus ruber. Therefore, determining an optimal C:N ratio in the culture medium for maximizing the production of the pigments is important. A culture medium composition is established for maximizing the production of the red pigment by the fungus M. ruber ICMP 15220 in submerged culture. The highest volumetric productivity of the red pigment was 0.023 AU L(-1) h(-1) in a batch culture (30 °C, initial pH of 6.5) with a defined medium of the following composition (g L(-1)): glucose (10), monosodium glutamate (MSG) (10), MgSO4·7H2O (0.5), KH2PO4 (5), K2HPO4 (5), ZnSO4·7H2O (0.01), FeSO4·7H2O (0.01), CaCl2 (0.1), MnSO4·H2O (0.03). This medium formulation had a C:N mole ratio of 9:1. Under these conditions, the specific growth rate of the fungus was 0.043 h(-1) and the peak biomass concentration was 6.7 g L(-1) in a 7-day culture. The biomass specific productivity of the red pigment was 1.06 AU g(-1) h(-1). The best nitrogen source proved to be MSG although four other inorganic nitrogen sources were evaluated.

  9. Effects of extrinsic point defects in phosphorene: B, C, N, O and F Adatoms

    OpenAIRE

    Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P.

    2015-01-01

    Phosphorene is emerging as a promising 2D semiconducting material with a direct band gap and high carrier mobility. In this paper, we examine the role of the extrinsic point defects including surface adatoms in modifying the electronic properties of phosphorene using density functional theory. The surface adatoms considered are B, C, N, O and F with a [He] core electronic configuration. Our calculations show that B and C, with electronegativity close to P, prefer to break the sp3 bonds of pho...

  10. Oxidation resistance of quintuple Ti-Al-Si-C-N coatings and associated mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Wu Guizhi; Ma Shengli; Xu Kewei; Ji, Vincent; Chu, Paul K. [State Key Laboratory for Mechanical Behavior of Materials, Xi' an Jiaotong University, Xi' an 710049 (China); ICMMO/LEMHE, Universite Paris-Sud 11, 91405 Orsay Cedex (France); Department of Physics and Materials Science, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon (Hong Kong)

    2012-07-15

    The oxidation behavior of Ti-Al-Si-C-N hard coatings with different Al contents deposited on high-speed steel and Si substrates by hybrid arc-enhanced magnetron sputtering is investigated in the temperature range of 500 Degree-Sign C-1000 Degree-Sign C. The coating hardness is maintained at around 35 GPa, and the parabolic oxidation rate constant K{sub p} at 1000 Degree-Sign C decreases to 3.36 Multiplication-Sign 10{sup -10} kg{sup 2} m{sup -4} s{sup -1} when the Al concentration is increased to 30 at. %, indicating that Ti-Al-Si-C-N coatings with larger Al concentrations have better oxidation resistance. X-ray diffraction, cross-sectional scanning electron microscopy, and x-ray photoelectron spectroscopy reveal a protective surface layer consisting of Al{sub 2}O{sub 3}, TiO{sub 2}, and SiO{sub 2} that retards inward oxygen diffusion. A mechanism is proposed to elucidate the oxide formation. As a consequence of the good oxidation resistance, the Ti-Al-Si-C-N coatings have a large potential in high-speed dry cutting as well as other high temperature applications.

  11. The chemical composition and band gap of amorphous Si:C:N:H layers

    Energy Technology Data Exchange (ETDEWEB)

    Swatowska, Barbara, E-mail: swatow@agh.edu.pl [AGH University of Science and Technology, Department of Electronics, Mickiewicza Av. 30, 30-059 Krakow (Poland); Kluska, Stanislawa; Jurzecka-Szymacha, Maria [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Mickiewicza Av. 30, 30-059 Krakow (Poland); Stapinski, Tomasz [AGH University of Science and Technology, Department of Electronics, Mickiewicza Av. 30, 30-059 Krakow (Poland); Tkacz-Smiech, Katarzyna [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Mickiewicza Av. 30, 30-059 Krakow (Poland)

    2016-05-15

    Highlights: • Six type of amorphous hydrogenated films were obtained and analysed. • Investigated chemical bondings strongly influenced energy gap values. • Analysed layers could be applied as semiconductors and also as dielectrics. - Abstract: In this work we presented the correlation between the chemical composition of amorphous Si:C:N:H layers of various content of silicon, carbon and nitrogen, and their band gap. The series of amorphous Si:C:N:H layers were obtained by plasma assisted chemical vapour deposition method in which plasma was generated by RF (13.56 MHz, 300 W) and MW (2.45 GHz, 2 kW) onto monocrystalline silicon Si(001) and borosilicate glass. Structural studies were based on FTIR transmission spectrum registered within wavenumbers 400–4000 cm{sup −1}. The presence of Si−C, Si−N, C−N, C=N, C=C, C≡N, Si−H and C−H bonds was shown. The values band gap of the layers have been determined from spectrophotometric and ellipsometric measurements. The respective values are contained in the range between 1.64 eV – characteristic for typical semiconductor and 4.21 eV – for good dielectric, depending on the chemical composition and atomic structure of the layers.

  12. Ti-Al-Si-C-N hard coatings synthesized by hybrid arc enhanced magnetron sputtering

    International Nuclear Information System (INIS)

    Wu, Guizhi; Liu, Sitao; Ma, Shengli; Xu, Kewei; Vincent, Ji; Chu, Paul K.

    2010-01-01

    Ti-Al-Si-C-N coatings are deposited by hybrid arc-enhanced magnetic sputtering and characterized by various micro- and macro-tools. X-ray diffraction, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy reveal that the coatings are nanocomposites consisting of nanocrystallites and amorphous phases. They are generally in the form of nc-(Ti,Al)(C,N)/a-Si_3N_4/a-C depending on the composition of the coatings. With increasing Al concentrations, the X-ray diffraction peaks shift to a lower angle indicating compressive stress in the coatings. The measured hardness also diminishes implying reduced contributions from the self-organized stable nanostructure. The dry friction coefficients of the Ti-Al-Si-C-N coatings are found to be about 0.3 which is lower than that of conventional Ti-Si-N coatings. These coatings can find potential applications requiring high temperature with heavy contact loading. (author)

  13. Contribution to the study of the (U,Pu)C,N system

    International Nuclear Information System (INIS)

    Lorenzelli, R.

    1968-01-01

    The reactions of UC, PuC, (U,Pu)C, UC 2 and U(C 1-x O x ) with nitrogen at moderate temperatures (room temperature to 400 C) are described. The influence of the uptake of nitrogen by the powders necessary to sinter the carbides upon the nature of the final product has been investigated; it has been shown that the sintered carbides are hyper-stoichiometric. The reactions of carbon with UN, PuN and (U,Pu)N has also been studied. Under vacuum, carbon reacts on the nitrides at temperatures as low as 1100 C; nitrogen is replaced by carbon and the final product is a carbonitride. The reaction is: MN + x C → MN 1-x C x + x/2N 2 . The reaction is limited and the carbonitrides have a fixed composition in presence of M 2 C 3 or MC 2 ; hence it is impossible to produce pure MC using the reaction. The ternary diagram U-C-N, Pu-C-N and (U,Pu)C-N have been drawn. They show clearly that it is possible to obtain single phase carbonitrides in a wide domain of compositions. (author) [fr

  14. Crystallization behavior and controlling mechanism of iron-containing Si-C-N ceramics.

    Science.gov (United States)

    Francis, Adel; Ionescu, Emanuel; Fasel, Claudia; Riedel, Ralf

    2009-11-02

    The crystallization behavior and controlling mechanism of the Si-Fe-C-N system based on polymer-derived SiCN ceramic filled with iron metal powder has been studied. The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer matrix volume for the Si-C-N system. Pyrolysis of the composite material at 1100 degrees C indicates the presence of one crystalline phase Fe(3)Si. While the sample pyrolyzed at 1200 degrees C reveals the formation of both Fe(3)Si and Fe(5)Si(3) phases, a crystallization of beta-SiC is additionally observed by increasing the temperature up to 1300 degrees C. The propensity for the formation of SiC is due to the presence of Fe(5)Si(3), where a solid-liquid-solid (SLS) growth mechanism was suggested to occur. X-ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis (DTA), and thermal gravimetric analysis with mass spectroscopic detection (TGA-MS) were employed to investigate the crystallization behavior of the Si-Fe-C-N system.

  15. A thermodynamic model for C-(N-)A-S-H gel: CNASHss. Derivation and validation

    International Nuclear Information System (INIS)

    Myers, Rupert J.; Bernal, Susan A.; Provis, John L.

    2014-01-01

    The main reaction product in Ca-rich alkali-activated cements and hybrid Portland cement (PC)-based materials is a calcium (alkali) aluminosilicate hydrate (C-(N-)A-S-H) gel. Thermodynamic models without explicit definitions of structurally-incorporated Al species have been used in numerous past studies to describe this gel, but offer limited ability to simulate the chemistry of blended PC materials and alkali-activated cements. Here, a thermodynamic model for C-(N-)A-S-H gel is derived and parameterised to describe solubility data for the CaO–(Na 2 O,Al 2 O 3 )–SiO 2 –H 2 O systems and alkali-activated slag (AAS) cements, and chemical composition data for C-A-S-H gels. Simulated C-(N-)A-S-H gel densities and molar volumes are consistent with the corresponding values reported for AAS cements, meaning that the model can be used to describe chemical shrinkage in these materials. Therefore, this model can provide insight into the chemistry of AAS cements at advanced ages, which is important for understanding the long-term durability of these materials

  16. Ab Initio Predictions of Hexagonal Zr(B,C,N) Polymorphs for Coherent Interface Design

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Chongze [Univ. of Minnesota-Twin Cities, Minneapolis, MN (United States); Huang, Jingsong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sumpter, Bobby G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Meletis, Efstathios [Univ. of Texas at Arlington, Arlington, TX (United States); Dumitrica, Traian [Univ. of Minnesota-Twin Cities, Minneapolis, MN (United States)

    2017-10-27

    Density functional theory calculations are used to explore hexagonal (HX) NiAs-like polymorphs of Zr(B,C,N) and compare with corresponding Zr(B,C,N) Hagg-like face-centered cubic rocksalt (B1) phases. While all predicted compounds are mechanically stable according to the Born-Huang criteria, only HX Zr(C,N) are found dynamically stable from ab initio molecular dynamics simulations and lattice dynamics calculations. HX ZrN emerges as a candidate structure with ground state energy, elastic constants, and extrinsic mechanical parameters comparable with those of B1 ZrN. Ab initio band structure and semi-classical Boltzmann transport calculations predict a metallic character and a monotonic increase in electrical conductivity with the number of valence electrons. Electronic structure calculations indicate that the HX phases gain their stability and mechanical attributes by Zr d- non-metal p hybridization and by broadening of Zr d bands. Furthermore, it is shown that the HX ZrN phase provides a low-energy coherent interface model for connecting B1 ZrN domains, with significant energetic advantage over an atomistic interface model derived from high resolution transmission electron microscopy images. The ab initio characterizations provided herein should aid the experimental identification of non-Hagg-like hard phases. Furthermore, the results can also enrich the variety of crystalline phases potentially available for designing coherent interfaces in superhard nanostructured materials and in materials with multilayer characteristics.

  17. Synthesis of nanostructured multiphase Ti(C,N)/a-C films by a plasma focus device

    International Nuclear Information System (INIS)

    Ghareshabani, E.; Rawat, R.S.; Sobhanian, S.; Verma, R.; Karamat, S.; Pan, Z.Y.

    2010-01-01

    Nanostructured multiphase Ti(C,N)/a-C films were deposited using a 3.3 kJ pulsed plasma focus device onto silicon (1 0 0) substrates at room temperature. The plasma focus device, fitted with solid titanium anode instead of usual hollow copper anode, was operated with nitrogen and Ar/CH 4 as the filling gas. Films were deposited with different number of shots, at 80 mm from top of the anode and at zero angular position with respect to anode axis. X-ray diffraction results show the diffraction peaks related to different compounds such as TiC 2 , TiN, Ti 2 CN, Ti and TiC 0.62 confirming the deposition of multiphase titanium carbo-nitride composite films on silicon. X-ray photoelectron spectroscopy confirms the formation of Ti-C, C-N, Ti-N, Ti-O and C-C bonds in the films. Scanning electron microscopy reveals that the nanostructure grains are agglomerates of smaller nanoparticles about 10-20 nm in size. Raman studies verify the formation of multiphase Ti(C,N) and also of amorphous graphite in the films. The maximum microhardness value of the composite film is 14.8 ± 1.3 GPa for 30 shots.

  18. Microstructural differences between two Zr(C,N) coatings revealed by analytical transmission electron microscopy

    International Nuclear Information System (INIS)

    Dörfel, Ilona; Rooch, Heidemarie; Österle, Werner

    2012-01-01

    The microstructures of two samples of a Zr(C,N) coating on steel, which unexpectedly differed in their tribological properties, were investigated by analytical transmission electron microscopy. The samples were produced by a cathodic arc evaporation process in two commercial coating devices under similar coating conditions with the exception of the number of Zr targets. The source of the differing tribological properties of the samples was detected by analytical transmission electron microscopy (TEM) methods energy-dispersive X-ray spectroscopy (EDX), energy filtering TEM (EFTEM), electron diffraction, high resolution electron microscopy, and high angel annular dark field. The TEM preparation and the results of the TEM investigations are shown in detail. The origin of the unexpected behavior was determined to be a nano-scale multilayer structure that existed only in the tribologically superior specimen. EDX and EFTEM investigations indicated enrichment in oxygen at the interface between coating and steel substrate in the tribologically inferior sample. Findings of the microstructural configuration were obtained by taking a closer look at the structure and comparing the results of the several analytical TEM techniques. This allows the allocation of the concentration fluctuations in N, C, and Zr to the two thickness fractions of the nano multilayers and a local correlation of the identified minority phase Zr 3 (C,N) 4 to the higher N content in the narrower type of the multilayer fraction of the sample with the excellent tribological properties. The minority phase Zr 3 (C,N) 4 is randomly distributed in the sample with the defective tribological properties. Coating conditions are not topic of this work, but after discussion of the TEM results, the fact that one of the coating devices worked with one Zr target and the other one with two, could be identified as cause for the formation of the nano multilayer structure in the sample with the superior tribological

  19. Degradation of Paracetamol by Photolysis Using C-N-codoped TiO2

    OpenAIRE

    Vanny Yulia Safitri; Adlis Santoni; Diana Vanda Wellia; Khoiriah Khoiriah; Safni Safni

    2017-01-01

    Paracetamol is generally used as analgesic and antipyretic drugs. Contamination paracetamol in the environment can occur because of waste material disposal from production site and immediate disposal of household that cause water pollution. Paracetamol is degraded by photolysis method under irradiation 10 watt UV-light (λ=365 nm), visible-light (Philips LED 13 watt 1400 lux) and solar-light with and without addition C-N-codoped TiO2catalyst. The solution is analyzed by UV-Vis spectrophotomete...

  20. Asymmetric Hydrogenation of Seven-Membered C=N-containing Heterocycles and Rationalization of the Enantioselectivity.

    Science.gov (United States)

    Balakrishna, Bugga; Bauzá, Antonio; Frontera, Antonio; Vidal-Ferran, Anton

    2016-07-18

    Iridium(I) complexes with phosphine-phosphite ligands efficiently catalyze the enantioselective hydrogenation of diverse seven-membered C=N-containing heterocyclic compounds (eleven examples; up to 97 % ee). The P-OP ligand L3, which incorporates an ortho-diphenyl substituted octahydrobinol phosphite fragment, provided the highest enantioselectivities in the hydrogenation of most of the heterocyclic compounds studied. The observed stereoselection was rationalized by means of DFT calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Plutonium diffusion in advanced fuels (U,Pu)(C,O) and (U,Pu)(C,N)

    International Nuclear Information System (INIS)

    Bradbury, M.H.; Matzke, H.

    1983-01-01

    The self-diffusion of 238 Pu was measured in an oxicarbide (U,Pu)(C,O) and a carbonitride (U,Pu) (C,N). The activation enthalpies were 447 and 347 kJ mol -1 , respectively. The carbonitrides were confirmed to fall into three classes: carbide-like compositions with less than 30% nitrogen in the metalloid lattice, nitride-like composition with more than 70% nitrogen and with reduced atomic mobilities, and carbonitrides with about 50% nitrogen showing an intermediate behavior. The oxicarbide showed diffusion coefficients slightly larger than those of pure carbides

  2. C/N and other Elemental Ratios of Chondritic Porous IDPS and a Fluffy Concordia Micrometeorite

    Science.gov (United States)

    Smith, T.; Nakamura-Messenger, K.; Messenger, S.; Keller, L. P.; Khodja, H.; Raepsaet, C.; Wirick, S.; Flynn, G. J.; Taylor, S.; Engrand, C.; hide

    2013-01-01

    Chondritic porous interplanetary dust particles (CP-IDPs) may be cometary in origin [1], as may ultracarbona-ceous (UCAMMs) [2] and 'fluffy' [3] micrometeorites from the Concordia collection. They are all rich in organics, which can rim grains and may have helped glue grains together during accretion [4]. The organics also contain nitrogen the input of which to Earth has potential biological importance. We report C/N ratios, and other properties of CP-IDPs and a Concordia fluffy microme-teorite.

  3. ΛcN interaction from lattice QCD and its application to Λc hypernuclei

    Science.gov (United States)

    Miyamoto, Takaya; Aoki, Sinya; Doi, Takumi; Gongyo, Shinya; Hatsuda, Tetsuo; Ikeda, Yoichi; Inoue, Takashi; Iritani, Takumi; Ishii, Noriyoshi; Kawai, Daisuke; Murano, Keiko; Nemura, Hidekatsu; Sasaki, Kenji

    2018-03-01

    The interaction between Λc and a nucleon (N) is investigated by employing the HAL QCD method in the (2 + 1)-flavor lattice QCD on a (2.9fm) 3 volume at mπ ≃ 410 , 570 , 700 MeV. We study the central potential in S10 channel as well as central and tensor potentials in S31-3D1 channel, and find that the tensor potential for Λc N is negligibly weak and central potentials in both S10 and S31-3D1 channels are almost identical with each other except at short distances. Phase shifts and scattering lengths calculated with these potentials show that the interaction of Λc N system is attractive and has a similar strength in S10 and S31 channels at low energies (i.e. the kinetic energy less than about 40 MeV). While the attractions are not strong enough to form two-body bound states, our results lead to a possibility to form Λc hypernuclei for sufficiently large atomic numbers (A). To demonstrate this, we derive a single-folding potential for Λc hypernuclei from the Λc-nucleon potential obtained in lattice QCD, and find that Λc hypernuclei can exist for A ≥ 12 with the binding energies of a few MeV. We also estimate the Coulomb effect for the Λc hypernuclei.

  4. Degradation of Paracetamol by Photolysis Using C-N-codoped TiO2

    Directory of Open Access Journals (Sweden)

    Vanny Yulia Safitri

    2017-11-01

    Full Text Available Paracetamol is generally used as analgesic and antipyretic drugs. Contamination paracetamol in the environment can occur because of waste material disposal from production site and immediate disposal of household that cause water pollution. Paracetamol is degraded by photolysis method under irradiation 10 watt UV-light (λ=365 nm, visible-light (Philips LED 13 watt 1400 lux and solar-light with and without addition C-N-codoped TiO2catalyst. The solution is analyzed by UV-Vis spectrophotometer at λ 200-400 nm. Optimum weight of C-N-codoped TiO2 catalyst obtained is 20 mg under UV-light photolysis. Paracetamol 4 mg/L is degraded 45.48% after 120 minutes under UV-light irradiation without catalyst, and increases to be 69.31% by using 20 mg catalyst. While degradation percentage of paracetamol is 16.96 % without catalyst, the percentage increases to be 34.29% after using 20 mg catalyst for 120 minutes photolysis under visible-light. Degradation of paracetamol by solar light achieves only 12.27% in absance of catalyst for 120 minutes irradiation, but it increases significantly until 70.39% in presence of 20 mg catalyst.

  5. Pasarela metálica sobre la C. N. III, Madrid-Valencia

    Directory of Open Access Journals (Sweden)

    Rodríguez-Borlado Olavarrieta, Ramiro

    1967-03-01

    Full Text Available The footbridge over the C. N. Ill , Madrid-Valencia road, near Madrid, enables pedestrians to cross the motor road where the latter runs between Moratalaz and Vallecas, without impeding the road traffic. The adoption of an elevated pass is convenient, since at this section the road runs along a deep trench. The structure of the footpath is a continuous metallic box girder, resting on five rectangular metal supports, and two end concrete abutments. The total length of the bridge is 100 m, and the width of the platform is 2.40 m. The project took one month to complete.La pasarela sobre la C. N. III, Madrid-Valencia, en la autopista de acceso a Madrid, permite el paso de peatones entre los barrios de Moratalaz y Vallecas sin interferir el tráfico rodado. La solución de paso superior resulta conveniente, ya que la autopista discurre en trinchera en el lugar de ubicación de esta obra. La estructura está formada por una viga metálica continua de sección en cajón, apoyada sobre cinco soportes rectangulares metálicos y dos estribos de hormigón armado. La obra tiene una longitud total de aproximadamente 100 m y el ancho de la plataforma es de 2,40 metros. El plazo de realización de la obra ha sido de un mes aproximadamente.

  6. Distinct features of C/N balance regulation in Prochlorococcus sp. strain MIT9313.

    Science.gov (United States)

    Domínguez-Martín, María Agustina; López-Lozano, Antonio; Rangel-Zúñiga, Oriol Alberto; Díez, Jesús; García-Fernández, José Manuel

    2018-02-01

    The abundance and significant contribution to global primary production of the marine cyanobacterium Prochlorococcus have made it one of the main models in marine ecology. Several conditions known to cause strong effects on the regulation of N-related enzymes in other cyanobacteria lacked such effect in Prochlorococcus. Prochlorococcus sp. strain MIT9313 is one of the most early-branching strains among the members of this genus. In order to further understand the C/N control system in this cyanobacterium, we studied the effect of the absence of three key elements in the ocean, namely N, P and Fe, as well as the effect of inhibitors of the N assimilation or photosynthesis on the N metabolism of this strain. Furthermore, we focused our work in the effect of ageing, as the age of cultures has clear effects on the regulation of some enzymes in Prochlorococcus. To reach this goal, expression of the main three regulators involved in N assimilation in cyanobacteria, namely ntcA, glnB and pipX, as well as that of icd (encoding for isocitrate dehydrogenase) were analysed. Our results show that the control of the main proteins involved in the C/N balance in strain MIT9313 differs from other model Prochlorococcus strains. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  7. AUTOBA: automation of backbone assignment from HN(C)N suite of experiments.

    Science.gov (United States)

    Borkar, Aditi; Kumar, Dinesh; Hosur, Ramakrishna V

    2011-07-01

    Development of efficient strategies and automation represent important milestones of progress in rapid structure determination efforts in proteomics research. In this context, we present here an efficient algorithm named as AUTOBA (Automatic Backbone Assignment) designed to automate the assignment protocol based on HN(C)N suite of experiments. Depending upon the spectral dispersion, the user can record 2D or 3D versions of the experiments for assignment. The algorithm uses as inputs: (i) protein primary sequence and (ii) peak-lists from user defined HN(C)N suite of experiments. In the end, one gets H(N), (15)N, C(α) and C' assignments (in common BMRB format) for the individual residues along the polypeptide chain. The success of the algorithm has been demonstrated, not only with experimental spectra recorded on two small globular proteins: ubiquitin (76 aa) and M-crystallin (85 aa), but also with simulated spectra of 27 other proteins using assignment data from the BMRB.

  8. Global biodiversity, stoichiometry and ecosystem function responses to human-induced C-N-P imbalances.

    Science.gov (United States)

    Carnicer, Jofre; Sardans, Jordi; Stefanescu, Constantí; Ubach, Andreu; Bartrons, Mireia; Asensio, Dolores; Peñuelas, Josep

    2015-01-01

    Global change analyses usually consider biodiversity as a global asset that needs to be preserved. Biodiversity is frequently analysed mainly as a response variable affected by diverse environmental drivers. However, recent studies highlight that gradients of biodiversity are associated with gradual changes in the distribution of key dominant functional groups characterized by distinctive traits and stoichiometry, which in turn often define the rates of ecosystem processes and nutrient cycling. Moreover, pervasive links have been reported between biodiversity, food web structure, ecosystem function and species stoichiometry. Here we review current global stoichiometric gradients and how future distributional shifts in key functional groups may in turn influence basic ecosystem functions (production, nutrient cycling, decomposition) and therefore could exert a feedback effect on stoichiometric gradients. The C-N-P stoichiometry of most primary producers (phytoplankton, algae, plants) has been linked to functional trait continua (i.e. to major axes of phenotypic variation observed in inter-specific analyses of multiple traits). In contrast, the C-N-P stoichiometry of higher-level consumers remains less precisely quantified in many taxonomic groups. We show that significant links are observed between trait continua across trophic levels. In spite of recent advances, the future reciprocal feedbacks between key functional groups, biodiversity and ecosystem functions remain largely uncertain. The reported evidence, however, highlights the key role of stoichiometric traits and suggests the need of a progressive shift towards an ecosystemic and stoichiometric perspective in global biodiversity analyses. Copyright © 2014 Elsevier GmbH. All rights reserved.

  9. Formation of Si-C-N ceramics from melamine-carbosilazane single source precursors

    International Nuclear Information System (INIS)

    Shatnawi, Mazin; Al-Mansi, Wafaa; Arafa, Isam

    2008-01-01

    A series of melamine-carbosilazane pre-ceramic macromolecules (Mel-CSZs) were prepared by the condensation of melamine with different organochlorosilanes (R x SiCl 4-x where R is CH 3 /C 6 H 5 and x is 1, 2 or 3) using pyridine as a solvent under nitrogen atmosphere. These melamine-based carbosilazane macromolecules (Mel-CSZs) were characterized by infrared spectroscopy (FT-IR), mass spectrometry (MS), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The backbone of the resulting Mel-CSZs consists of melamine and carbosilazane building blocks. Pyrolysis of these Mel-CSZs at 600 deg. C under nitrogen and vacuum afforded the corresponding silicon-based nonoxide carbonitride ceramics (Si-C-N). The microstructure and textural morphology of the resulting fine ceramic materials were examined using FT-IR, powder X-ray diffraction (XRD), and scanning electron microscopy (SEM). - Graphical abstract: Pyrolysis of the prepared melamine-organosilane macromolecules afforded Si-C-N ceramics with different textural morphology

  10. Structure of small TiC n clusters: A theoretical study

    International Nuclear Information System (INIS)

    Largo, Laura; Cimas, Alvaro; Redondo, Pilar; Rayon, Victor M.; Barrientos, Carmen

    2006-01-01

    A theoretical study of the TiC n (n = 1-8) clusters has been carried out at the B3LYP/6-311+G(d) level. Molecular properties for three different isomers, namely linear, cyclic, and fan species, have been determined. The fan isomers, where the titanium atom is essentially side-bonded to the entire C n unit, are predicted to be more stable than both linear and cyclic isomers. Only for the largest studied species, TiC 8 , the cyclic isomer is located lower in energy. An even-odd parity effect in the incremental binding energies is observed for the three isomers, n-even species being in general more stable for linear and fan isomers, whereas for the cyclic species n-odd clusters are favoured. A topological analysis of the electronic charge density shows that all cyclic isomers correspond to true monocyclic rings, whereas for the fan species a variety of different connectivities has been observed

  11. Effects of extrinsic point defects in phosphorene: B, C, N, O, and F adatoms

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gaoxue, E-mail: gaoxuew@mtu.edu, E-mail: pandey@mtu.edu, E-mail: shashi.p.karna.civ@mail.mil; Pandey, Ravindra, E-mail: gaoxuew@mtu.edu, E-mail: pandey@mtu.edu, E-mail: shashi.p.karna.civ@mail.mil [Department of Physics, Michigan Technological University, Houghton, Michigan 49931 (United States); Karna, Shashi P., E-mail: gaoxuew@mtu.edu, E-mail: pandey@mtu.edu, E-mail: shashi.p.karna.civ@mail.mil [U.S. Army Research Laboratory, Weapons and Materials Research Directorate, ATTN: RDRL-WM, Aberdeen Proving Ground, Maryland 21005-5069 (United States)

    2015-04-27

    Phosphorene is emerging as a promising 2D semiconducting material with a direct band gap and high carrier mobility. In this paper, we examine the role of the extrinsic point defects including surface adatoms in modifying the electronic properties of phosphorene using density functional theory. The surface adatoms considered are B, C, N, O, and F with a [He] core electronic configuration. Our calculations show that B and C, with electronegativity close to P, prefer to break the sp{sup 3} bonds of phosphorene and reside at the interstitial sites in the 2D lattice by forming sp{sup 2} like bonds with the native atoms. On the other hand, N, O, and F, which are more electronegative than P, prefer the surface sites by attracting the lone pairs of phosphorene. B, N, and F adsorption will also introduce local magnetic moment to the lattice. Moreover, B, C, N, and F adatoms will modify the band gap of phosphorene, yielding metallic transverse tunneling characters. Oxygen does not modify the band gap of phosphorene, and a diode like tunneling behavior is observed. Our results therefore offer a possible route to tailor the electronic and magnetic properties of phosphorene by the adatom functionalization and provide the physical insights of the environmental sensitivity of phosphorene, which will be helpful to experimentalists in evaluating the performance and aging effects of phosphorene-based electronic devices.

  12. Oxidation and Tribological Behavior of Ti-B-C-N-Si Nanocomposite Films Deposited by Pulsed Unbalanced Magnetron Sputtering.

    Science.gov (United States)

    Jang, Jaeho; Heo, Sungbo; Kim, Wang Ryeol; Kim, Jun-Ho; Nam, Dae-Geun; Kim, Kwang Ho; Park, Ikmin; Park, In-Wook

    2018-03-01

    Quinary Ti-B-C-N-Si nanocomposite films were deposited onto AISI 304 substrates using a pulsed d.c. magnetron sputtering system. The quinary Ti-B-C-N-Si (5 at.%) film showed excellent tribological and wear properties compared with those of the Ti-B-C-N films. The steady friction coefficient of 0.151 and a wear rate of 2 × 10-6 mm3N-1m-1 were measured for the Ti-B-C-N-Si films. The oxidation behavior of Ti-B-C-N-Si nanocomposite films was systematically investigated using X-ray diffraction (XRD), and thermal analyzer with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). It is concluded that the addition of Si into the Ti-B-C-N film improved the tribological properties and oxidation resistance of the Ti-B-C-N-Si films. The improvements are due to the formation of an amorphous SiOx phase, which plays a major role in the self-lubricant tribo-layers and oxidation barrier on the film surface or in the grain boundaries, respectively.

  13. Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates

    Science.gov (United States)

    Rannulu, Nalaka S.; Cole, Richard B.

    2012-09-01

    The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

  14. Molecular dynamics investigations of regioselectivity of anionic/aromatic substrates by a family of enzymes: a case study of diclofenac binding in CYP2C isoforms.

    Science.gov (United States)

    Cui, Ying-Lu; Xu, Fang; Wu, Rongling

    2016-06-29

    The CYP2C subfamily is of particular importance in the metabolism of drugs, food toxins, and procarcinogens. Like other P450 subfamilies, 2C enzymes share a high sequence identity, but significantly contribute in different ways to hepatic capacity to metabolize drugs. They often metabolize the same substrate to more than one product with different catalytic sites. Because it is challenging to characterize experimentally, much still remains unknown about the reason for why the substrate regioselectivity of these closely related subfamily members is different. Here, we have investigated the structural features of CYP2C8, CYP2C9, and CYP2C19 bound with their shared substrate diclofenac to elucidate the underlying molecular mechanism for the substrate regioselectivity of CYP2C subfamily enzymes. The obtained results demonstrate how a sequence divergence for the active site residues causes heterogeneous variations in the secondary structures and in major tunnel selections, and further affects the shape and chemical properties of the substrate-binding site. Structural analysis and free energy calculations showed that the most important determinants of regioselectivity among the CYP2C isoforms are the geometrical features of the active sites, as well as the hydrogen bonds and the hydrophobic interactions, mainly presenting as the various locations of Arg108 and substitutions of Phe205 for Ile205 in CYP2C8. The MM-GB/SA calculations combined with PMF results accord well with the experimental KM values, bridging the gap between the theory and the experimentally observed results of binding affinity differences. The present study provides important insights into the structure-function relationships of CYP2C subfamily enzymes, the knowledge of ligand binding characteristics and key residue contributions could guide future experimental and computational work on the synthesis of drugs with better pharmacokinetic properties so that CYP interactions could be avoided.

  15. Nb(C,N) precipitation kinetics in the bainite region of a low-carbon Nb-microalloyed steel

    International Nuclear Information System (INIS)

    Park, J.S.; Lee, Y.K.

    2007-01-01

    Nb(C,N) precipitation in the bainite region (580-660 deg. C) of a low-carbon Nb-microalloyed steel was investigated by electrical resistivity and transmission electron microscopy. Nb(C,N) particles started precipitating after 100-200 s at isothermal temperatures after bainite transformation and cementite formation, and precipitation finished in 1000-2000 s. The precipitation-time-temperature diagram of Nb(C,N) in the bainite region of a low-carbon microalloyed steel was a type of C-curve, with a nose temperature of about 615 deg. C

  16. Si-Imidazole-HSO4 Functionalized Magnetic Fe3O4 Nanoparticles as an Efficient and Reusable Catalyst for the Regioselective Ring Opening of Epoxides in Water

    Directory of Open Access Journals (Sweden)

    Eshagh Rezaee Nezhad

    2016-01-01

    Full Text Available An efficient and simple method for the preparation of Si-Imidazole-HSO4 functionalized magnetic Fe3O4 nanoparticles (Si-Im-HSO4 MNPs and used as an efficient and reusable magnetic catalysts for the regioselective ring opening of epoxides under green conditions in water. This catalyst was used for the ring opening of epoxide corresponding to the thiocyanohydrins and azidohydrines. Compared to the classical ring opening of epoxides, this new method consistently has the advantage of excellent yields, short reaction times, and methodological simplicity.

  17. Substituent Effects on Regioselectivity of the Diels-Alder Reactions: Reactions of 10-Allyl-1,8-dichloroanthracene with 2-Chloroacrylonitrile, 1-Cyanovinyl Acetate and Phenyl Vinyl Sulfone

    Directory of Open Access Journals (Sweden)

    Mujeeb A. Sultan

    2016-01-01

    Full Text Available Diels-Alder reaction of 10-allyl-1,8-dichloroanthracene (3 with 2-chloroacrylonitrile (4 and 1-cyanovinyl acetate (5 gives exclusively the ortho isomer while its reaction with phenyl vinyl sulfone (10 yields a mixture of two isomeric adducts with priority to ortho isomer. The reactions proceeded under microwave condition in xylene. Configurations of these isomers have been assigned with the help of NMR spectra. The results indicated that the steric effect is dominating toward the isomer regioselectivity in the Diels-Alder reaction of the present compounds.

  18. Cross-conjugated Trienamine Catalysis with α'-Alkylidene 2-Cyclohexenones: Application in β,γ-Regioselective Aza-Diels-Alder Reaction.

    Science.gov (United States)

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

    2017-02-24

    Endo-type cross-conjugated trienamines between highly congested α'-alkylidene 2-cyclohexenones and a chiral primary amine catalyst serve as HOMO-raised dienophiles in inverse-electron-demand aza-Diels-Alder cycloadditions with a number of 1-azadiene substrates. The reactions exhibit exclusive β,γ-regioselectivity, and multifunctional products with high molecular complexity are efficiently constructed in excellent diastereo- and enantioselectivity (>19:1 d.r., up to 99 % ee). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Theoretical Study of 1,3-Dipolar Cycloadditions Regioselectivity of Benzyl Azide with Glycosyl-O Acetylene Using Density Functional Theory (DFT

    Directory of Open Access Journals (Sweden)

    Adib Ghaleb

    2017-12-01

    Full Text Available A theoretical study of 1,3-cycloaddition has been carried out using density functional theory (DFT methods at the B3LYP/6-31G* level. The regioselectivity of the reaction have been clarified through different theoretical approaches: Case of a Two-Center Process (Domingo approach, HSAB principle (Gazquez and Mendez approach, and the activation energy calculations. The analysis of results shows that the reaction takes place along concerted asynchronous mechanism and the isomer meta is favored, in agreement with the experiment results. DOI: http://dx.doi.org/10.17807/orbital.v9i5.1017 

  20. Hydrogen-Bond Directed Regioselective Pd-Catalyzed Asymmetric Allylic Alkylation: The Construction of Chiral α-Amino Acids with Vicinal Tertiary and Quaternary Stereocenters.

    Science.gov (United States)

    Wei, Xuan; Liu, Delong; An, Qianjin; Zhang, Wanbin

    2015-12-04

    A Pd-catalyzed asymmetric allylic alkylation of azlactones with 4-arylvinyl-1,3-dioxolan-2-ones was developed, providing "branched" chiral α-amino acids with vicinal tertiary and quaternary stereocenters, in high yields and with excellent selectivities. Mechanistic studies revealed that the formation of a hydrogen bond between the Pd-allylic complex and azlactone isomer is responsible for the excellent regioselectivities. This asymmetric alkylation can be carried out on a gram scale without a loss of catalytic efficiency, and the resulting product can be further transformed to a chiral azetidine in two simple steps.

  1. Highly efficient regioselective synthesis, spectroscopic characterizations and DFT calculations of novel hydroxymethylated 1,4-disubstituted-1,2,3-triazole-based sulfonamides

    Science.gov (United States)

    Taheri, Elmira; Mirjafary, Zohreh; Saeidian, Hamid

    2018-04-01

    The novel hydroxymethylated 1,4-disubstituted-1,2,3-triazole-based sulfonamides were synthesized in excellent yields and high regioselectivity via a one-pot, two-step, three-component reaction of N-propargylsulfonamides, sodium azide, and epoxide derivatives under green conditions. Green and mild reaction condition, commercially readily available and inexpensive starting materials, wide scope and easy work-up are the key features of the present method. The Li+ and Na+ ion affinities of the model structure have been also investigated by density functional theory (DFT) studies to find the applicability of these products as ligand in coordination chemistry.

  2. Evaluation of single amino acid chelate derivatives and regioselective radiolabelling of a cyclic peptide for the urokinase plasminogen activator receptor

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, Andrea F.; Lemon, Jennifer A. [McMaster Institute for Applied Radiation Sciences, McMaster University, ON, L8S 4M1 (Canada); Czorny, Shannon K. [McMaster Institute for Applied Radiation Sciences, McMaster University, ON, L8S 4M1 (Canada); Juravinski Cancer Centre, Hamilton, ON, L8V 5C2 (Canada); Singh, Gurmit [Juravinski Cancer Centre, Hamilton, ON, L8V 5C2 (Canada); Valliant, John F. [Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1 (Canada); Department of Medical Physics and Applied Radiation Sciences, McMaster University, Hamilton, ON, L8S 4M1 (Canada)], E-mail: valliant@mcmaster.ca

    2009-11-15

    Introduction: The aim of this work was to investigate the relative radiolabelling kinetics and affinity of a series of ligands for the [{sup 99m}Tc(CO){sub 3}]{sup +} core, both in the absence and in the presence of competing donors. This information was used to select a suitable ligand for radiolabelling complex peptide-based targeting vectors in high yield under mild conditions. Methods: A series of {alpha}-N-Fmoc-protected lysine derivatives bearing two heterocyclic donor groups at the {epsilon}-amine (, 2-pyridyl; , quinolyl; , 6-methoxy-2-pyridyl; 1d, 2-thiazolyl; 1e, N-methylimidazolyl; , 3-pyridyl) were synthesized and labelled with {sup 99m}Tc. A resin-capture purification strategy for the separation of residual ligand from the radiolabelled product was also developed. The binding affinities of targeted peptides 4, 5a and 5b for uPAR were determined using flow cytometry. Results: Variable temperature radiolabelling reactions using - and [{sup 99m}Tc(CO){sub 3}]{sup +} revealed optimal kinetics and good selectivity for compounds and 1d; in the case of , 1d, and 1e, the labelling can be conducted at ambient temperature. The utility of this class of ligands was further demonstrated by the radiolabelling of a cyclic peptide that is known to target the serine protease receptor uPAR; essentially quantitative incorporation of {sup 99m}Tc occurred exclusively at the SAAC site, despite the presence of a His residue, and without disruption of the disulfide bond. Conclusion: A series of single amino acid chelate (SAAC) ligands have been evaluated for their ability to incorporate {sup 99m}Tc into peptides. The lead agent to emerge from this work is the thiazole SAAC derivative 1d which has demonstrated the ability to regioselectively label the widest range of peptides.

  3. Anomalous regioselective four-member multicomponent Biginelli reaction II: one-pot parallel synthesis of spiro heterobicyclic aliphatic rings.

    Science.gov (United States)

    Byk, Gerardo; Kabha, Eihab

    2004-01-01

    In a previous preliminary study, we found that a cyclic five-member ring beta-keto ester (lactone) reacts with one molecule of urea and two of aldehyde to give a new family of spiro heterobicyclic aliphatic rings in good yields with no traces of the expected dihydropyrimidine (Biginelli) products. The reaction is driven by a regiospecific condensation of two molecules of aldehyde with urea and beta-keto-gamma-lactone to afford only products harboring substitutions exclusively in a syn configuration (Byk, G.; Gottlieb, H. E.; Herscovici, J.; Mirkin, F. J. Comb. Chem. 2000, 2, 732-735). In the present work ((a) Presented in part at ISCT Combitech, October 15, 2002, Israel, and Eurocombi-2, Copenhagen 2003 (oral and poster presentation). (b) Also in American Peptide Society Symposium, Boston, 2003 (poster presentation). (c) Abstract in Biopolymers 2003, 71 (3), 354-355), we report a large and exciting extension of this new reaction utilizing parallel organic synthesis arrays, as demonstrated by the use of chiral beta-keto-gamma-lactams, derived from natural amino acids, instead of tetronic acid (beta-keto-gamma-lactone) and the potential of the spirobicyclic products for generating "libraries from libraries". Interestingly, we note an unusual and important anisotropy effect induced by perpendicular interactions between rigid pi systems and different groups placed at the alpha position of the obtained spirobicyclic system. Stereo/regioselectivity of the aldehyde condensation is driven by the nature of the substitutions on the starting beta-keto-gamma-lactam. Aromatic aldehydes can be used as starting reagents with good yields; however, when aliphatic aldehydes are used, the desired products are obtained in poor yields, as observed in the classical Biginelli reaction. The possible reasons for these poor yields are addressed and clarify, to some extent, the complexity of the Biginelli multicomponent reaction mechanism and, in particular, the mechanism of the present

  4. Effects of wildfires on ash Carbon, Nitrogen and C/N ratio in Mediterranean forests

    Science.gov (United States)

    Pereira, P.; Ubeda, X.; Martin, D. A.

    2009-04-01

    Carbon (C) and Nitrogen(N) are key nutrients in ecosystems health and the more affected by fire temperatures, because of their low temperatures of volatilization. After a wildfire, due higher temperatures reached, a great amount of C and N can be evacuated from the ecosystems and the percentage of C and N not vaporized is concentrated in ashes. Hence, the study of ash C and N is of major importance because will be linked with the capacity of ecosystem recuperation. The aim of this work is study the C, and C/N of three wildfires occurred in Mediterranean forests dominated by Quercus suber and Pinus pinea in Portugal. In the first wildfire, named "Quinta do Conde", we collected 30 samples, in the second, "Quinta da Areia", 32 samples and the third, "Casal do Sapo" 40 samples To estimate the consequences of wildfires in the parameters in study, we collected several samples of unburned litter near burned areas, composed by the same vegetation. The results showed that wildfires induced in % of Total Carbon (%TC) ashes content a non significantly reduction in Quinta do Conde plot (at a pPinus pinaster samples decreasing thereafter especially after the 400°C. In %TN we identified a rise in both species reducing abruptly at 450°C. C/N ratio decrease importantly after the 150°C. Theses results showed us that wildfires can have different effects C and N litter resources, depending on the severity and temperature reached. Crossing the results obtained in laboratory simulations with the samples collected in wildfires we will have an idea about the severity and temperature occurred in each wildfire. Overall, the lower severity were observed in Quinta do Conde plot and the higher in Casal do Sapo plot, being Quinta da Areia in a middle position. The C and N levels after a wildfire will determine the capacity of landscape recuperation and according the data obtained this will be higher in Quinta do Conde plot and lesser in Casal do Sapo plot. These hypothesis will be confirmed

  5. High-frequency fire alters C : N : P stoichiometry in forest litter.

    Science.gov (United States)

    Toberman, Hannah; Chen, Chengrong; Lewis, Tom; Elser, James J

    2014-07-01

    Fire is a major driver of ecosystem change and can disproportionately affect the cycling of different nutrients. Thus, a stoichiometric approach to investigate the relationships between nutrient availability and microbial resource use during decomposition is likely to provide insight into the effects of fire on ecosystem functioning. We conducted a field litter bag experiment to investigate the long-term impact of repeated fire on the stoichiometry of leaf litter C, N and P pools, and nutrient-acquiring enzyme activities during decomposition in a wet sclerophyll eucalypt forest in Queensland, Australia. Fire frequency treatments have been maintained since 1972, including burning every 2 years (2yrB), burning every 4 years (4 yrB) and no burning (NB). C : N ratios in freshly fallen litter were 29-42% higher and C : P ratios were 6-25% lower for 2 yrB than NB during decomposition, with correspondingly lower 2yrB N : P ratios (27-32) than for NB (34-49). Trends in litter soluble and microbial N : P ratios were similar to the overall litter N : P ratios across fire treatments. Consistent with these, the ratio of activities for N-acquiring to P-acquiring enzymes in litter was higher for 2 yrB than NB, whereas 4 yrB was generally intermediate between 2 yrB and NB. Decomposition rates of freshly fallen litter were significantly lower for 2 yrB (72 ± 2% mass remaining at the end of experiment) than for 4 yrB (59 ± 3%) and NB (62 ± 3%), a difference that may be related to effects of N limitation, lower moisture content, and/or litter C quality. Results for older mixed-age litter were similar to those for freshly fallen litter although treatment differences were less pronounced. Overall, these findings show that frequent fire (2 yrB) decoupled N and P cycling, as manifested in litter C : N : P stoichiometry and in microbial biomass N : P ratio and enzymatic activities. Furthermore, these data indicate that fire induced a transient shift to N-limited ecosystem conditions

  6. Mild copper-catalyzed trifluoromethylation of terminal alkynes using an electrophilic trifluoromethylating reagent

    KAUST Repository

    Weng, Zhiqiang

    2012-03-01

    A catalytic process for trifluoromethylation of terminal alkynes with Togni\\'s reagent has been developed, affording trifluoromethylated acetylenes in good to excellent yields. The reaction is conducted at room temperature and exhibits tolerance to a range of functional groups. © 2012 Elsevier Ltd. All rights reserved.

  7. Copper-catalyzed asymmetric ring opening of oxabicyclic alkenes with organolithium reagents

    NARCIS (Netherlands)

    Bos, Pieter H.; Rudolph, Alena; Pérez, Manuel; Fañanás-Mastral, Martín; Harutyunyan, Syuzanna R.; Feringa, Bernard

    2012-01-01

    A highly efficient method is reported for the asymmetric ring opening of oxabicyclic alkenes with organolithium reagents. Using a copper/chiral phosphoramidite complex together with a Lewis acid (BF3·OEt2), full selectivity for the anti isomer and excellent enantioselectivities were obtained for the

  8. Copper-Catalyzed Heteroarylboration of 1,3-Dienes with 3-Bromopyridines: A cine Substitution.

    Science.gov (United States)

    Smith, Kevin B; Huang, Yuan; Brown, M Kevin

    2018-04-26

    A method for the heteroarylboration of 1,3-dienes is presented. The process involves an unusual cine substitution of 3-bromopyridine derivatives to deliver highly functionalized heterocyclic products. Mechanistic studies are included that clarify the details of this unusual process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

    Science.gov (United States)

    Liwosz, Timothy W; Chemler, Sherry R

    2013-06-21

    We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

  10. Diversification of indoles via microwave-assisted ligand-free copper-catalyzed N-arylation

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Jae Kwan; Lee, Jin Hee; Kim, Tae Sung; Yum, Eul Kgun [Dept. of Chemistry, Chu ngnam National University, Daejon (Korea, Republic of); Park, Jee Jung [Western Seoul Center Korea Basic Science Institute, Seoul (Korea, Republic of)

    2016-12-15

    A simple, efficient Cu{sub 2}O catalyst system under microwave irradiation was developed for N-arylation of various indoles without ligands and additives. Diverse N-heteroarylated indoles were prepared by coupling indoles with various heteroaryl halides within 1 h. The selective reactivity of bromoindole with aryl iodide provided N-aryl bromoindoles, which could be useful intermediates for palladium-catalyzed Heck and Suzuki coupling reactions.

  11. Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

    Science.gov (United States)

    Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

    2012-10-03

    A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

  12. Copper-catalyzed 1,2-addition of α-carbonyl iodides to alkynes.

    Science.gov (United States)

    Xu, Tao; Hu, Xile

    2015-01-19

    β,γ-Unsaturated ketones are an important class of organic molecules. Herein, copper catalysis has been developed for the synthesis of β-γ-unsaturated ketones through 1,2-addition of α-carbonyl iodides to alkynes. The reactions exhibit wide substrate scope and high functional group tolerance. The reaction products are versatile synthetic intermediates to complex small molecules. The method was applied for the formal synthesis of (±)-trichostatin A, a histone deacetylase inhibitor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Copper-Catalyzed Eglinton Oxidative Homocoupling of Terminal Alkynes: A Computational Study

    Directory of Open Access Journals (Sweden)

    Jesús Jover

    2015-01-01

    Full Text Available The copper(II acetate mediated oxidative homocoupling of terminal alkynes, namely, the Eglinton coupling, has been studied with DFT methods. The mechanism of the whole reaction has been modeled using phenylacetylene as substrate. The obtained results indicate that, in contrast to some classical proposals, the reaction does not involve the formation of free alkynyl radicals and proceeds by the dimerization of copper(II alkynyl complexes followed by a bimetallic reductive elimination. The calculations demonstrate that the rate limiting-step of the reaction is the alkyne deprotonation and that more acidic substrates provide faster reactions, in agreement with the experimental observations.

  14. Copper-Catalyzed Asymmetric Allylic Alkylation of Halocrotonates : Efficient Synthesis of Versatile Chiral Multifunctional Building Blocks

    NARCIS (Netherlands)

    Hartog, Tim den; Maciá, Beatriz; Minnaard, Adriaan J.; Feringa, Bernard

    2010-01-01

    The highly enantioselective synthesis of α-methyl-substituted esters is reported in up to 90% yield and up to 99% ee using copper-TaniaPhos as chiral catalyst. The transformation proved scalable to at least 6.6 mmol (1.7 g scale). The products of this transformation have been further elaborated to

  15. The control of graphene double-layer formation in copper-catalyzed chemical vapor deposition

    Czech Academy of Sciences Publication Activity Database

    Kalbáč, Martin; Frank, Otakar; Kavan, Ladislav

    2012-01-01

    Roč. 50, č. 10 (2012), s. 3682-3687 ISSN 0008-6223 R&D Projects: GA ČR(CZ) GAP208/12/1062 Institutional support: RVO:61388955 Keywords : graphene * electrochemistry * spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 5.868, year: 2012

  16. Gas-phase studies of copper catalyzed aerobic cross coupling of thiol esters and arylboronic acids

    Czech Academy of Sciences Publication Activity Database

    Tsybizová, A.; Schröder, Detlef; Roithová, J.; Henke, A.; Šrogl, Jiří

    2014-01-01

    Roč. 27, č. 3 (2014), s. 198-203 ISSN 0894-3230 R&D Projects: GA ČR GAP207/12/0846 Grant - others:GA ČR(CZ) GAP207/11/0338 Institutional support: RVO:61388963 Keywords : boronic acids * catalysis * copper * cross coupling * electrospray ionization * mass spectrometry * kinetic studies Subject RIV: CC - Organic Chemistry Impact factor: 1.380, year: 2014

  17. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels

    DEFF Research Database (Denmark)

    Peterson, Andrew; Abild-Pedersen, Frank; Studt, Felix

    2010-01-01

    Density functional theory calculations explain copper's unique ability to convert CO2 into hydrocarbons, which may open up (photo-)electrochemical routes to fuels.......Density functional theory calculations explain copper's unique ability to convert CO2 into hydrocarbons, which may open up (photo-)electrochemical routes to fuels....

  18. Concise copper-catalyzed synthesis of tricyclic biaryl ether-linked aza-heterocyclic ring systems.

    Science.gov (United States)

    Mestichelli, Paola; Scott, Matthew J; Galloway, Warren R J D; Selwyn, Jamie; Parker, Jeremy S; Spring, David R

    2013-11-01

    A new method for the synthesis of tricyclic biaryl ether-linked ring systems incorporating seven-, eight-, and nine-membered ring amines is presented. In the presence of catalytic quantities of copper(I), readily accessible acyclic precursors undergo an intramolecular carbon-oxygen bond-forming reaction facilitated by a "templating" chelating nitrogen atom. The methodology displays a broad substrate scope, is practical, and generates rare and biologically interesting tricyclic heteroaromatic products that are difficult to access by other means.

  19. Indirect photopatterning of functionalized organic monolayers via copper-catalyzed "click chemistry"

    Science.gov (United States)

    Williams, Mackenzie G.; Teplyakov, Andrew V.

    2018-07-01

    Solution-based lithographic surface modification of an organic monolayer on a solid substrate is attained based on selective area photo-reduction of copper (II) to copper (I) to catalyze the azide-alkyne dipolar cycloaddition "click" reaction. X-ray photoelectron spectroscopy is used to confirm patterning, and spectroscopic results are analyzed and supplemented with computational models to confirm the surface chemistry. It is determined that this surface modification approach requires irradiation of the solid substrate with all necessary components present in solution. This method requires only minutes of irradiation to result in spatial and temporal control of the covalent surface functionalization of a monolayer and offers the potential for wavelength tunability that may be desirable in many applications utilizing organic monolayers.

  20. Copper-catalyzed activation of disulfides as a key step in the synthesis of benzothiazole moieties

    Czech Academy of Sciences Publication Activity Database

    Hývl, Jakub; Šrogl, Jiří

    -, č. 15 (2010), s. 2849-2851 ISSN 1434-193X R&D Projects: GA ČR GA203/08/1318 Institutional research plan: CEZ:AV0Z40550506 Keywords : oxidation * copper * benzothiazole synthesis Subject RIV: CC - Organic Chemistry Impact factor: 3.206, year: 2010

  1. On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

    2013-01-01

    The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

  2. Remote C−H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling

    KAUST Repository

    Xu, Jun; Shen, Chao; Zhu, Xiaolei; Zhang, Pengfei; Ajitha, Manjaly John; Huang, Kuo-Wei; An, Zhongfu; Liu, Xiaogang

    2016-01-01

    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper

  3. Copper-Catalyzed Chan-Lam Cyclopropylation of Phenols and Azaheterocycles.

    Science.gov (United States)

    Derosa, Joseph; O'Duill, Miriam L; Holcomb, Matthew; Boulous, Mark N; Patman, Ryan L; Wang, Fen; Tran-Dubé, Michelle; McAlpine, Indrawan; Engle, Keary M

    2018-04-06

    Small molecules containing cyclopropane-heteroatom linkages are commonly needed in medicinal chemistry campaigns yet are problematic to prepare using existing methods. To address this issue, a scalable Chan-Lam cyclopropylation reaction using potassium cyclopropyl trifluoroborate has been developed. With phenol nucleophiles, the reaction effects O-cyclopropylation, whereas with 2-pyridones, 2-hydroxybenzimidazoles, and 2-aminopyridines the reaction brings about N-cyclopropylation. The transformation is catalyzed by Cu(OAc) 2 and 1,10-phenanthroline and employs 1 atm of O 2 as the terminal oxidant. This method is operationally convenient to perform and provides a simple, strategic disconnection toward the synthesis of cyclopropyl aryl ethers and cyclopropyl amine derivatives bearing an array of functional groups.

  4. Dopamine receptors in pituitary adenomas: PET visualization with 11C-N-methylspiperone

    International Nuclear Information System (INIS)

    Muhr, C.; Bergstroem, M.L.; Lundberg, P.O.; Bergstroem, K.H.; Hartvig, P.; Lundqvist, H.; Antoni, G.; Langstroem, B.

    1986-01-01

    Two patients with pituitary tumors were examined with positron emission tomography (PET) after intravenous administration of 11C-N-methylspiperone. In repeat studies the patients were given 1 mg of intravenous haloperidol prior to the administration of the radioligand to block the dopamine receptors. High uptakes of the radiolabeled ligand were seen in one of the tumors. With haloperidol pretreatment the uptake was lower, probably mainly showing the remaining unspecific binding. The most marked uptake and the largest effect of haloperidol pretreatment was seen in a patient with a hormonally active prolactinoma. Dopamine receptor binding in pituitary tumors can be demonstrated in vivo with PET, and quantification of this binding is possible using a compartmental model. This technique may be useful in improving our understanding of the variable response to medical treatment of prolactinomas with dopamine agonists as well as in the prediction of the effect of such treatment

  5. Room-temperature ferromagnetism observed in C-/N-/O-implanted MgO single crystals

    Science.gov (United States)

    Li, Qiang; Ye, Bonian; Hao, Yingping; Liu, Jiandang; Zhang, Jie; Zhang, Lijuan; Kong, Wei; Weng, Huimin; Ye, Bangjiao

    2013-01-01

    MgO single crystals were implanted with 70 keV C/N/O ions at room temperature with respective doses of 2 × 1016 and 2 × 1017 ions/cm2. All samples with high-dose implantation showed room temperature hysteresis in magnetization loops. Magnetization and slow positron annihilation measurements confirmed that room temperature ferromagnetism in O-implanted samples was attributed to the presence of Mg vacancies. Furthermore, the introduction of C or N played more effective role in ferromagnetic performance than Mg vacancies. Moreover, the magnetic moment possibly occurred from the localized wave function of unpaired electrons and the exchange interaction formed a long-range magnetic order.

  6. Magnetic resonance in the diagnosis of C.N.S. disorders

    International Nuclear Information System (INIS)

    Antunovic, V.; Samardzic, M.; Levic, Z.; Dragutinovic, G.

    2001-01-01

    An introduction of CT and MRI methods resulted in revolutionary changes in the imaging of central nervous systems diseases. The reliability of the use of MRI in the diagnosis of neurological disorders enabled accurate localization, visualization, and anatomical relation and determination of the nature of different pathological processes in the brain and spinal cord. In the past, it had been very difficult to make such precise diagnosis. A result of this fact is a great improvement of treatment of the patients with C.N.S. disorders. The other advantages are excellent possibilities for an assessment of the results of the therapeutical procedures and accurate follow-up of the cases. This was the reason that the authors wanted to make a review of the MRI and clinical characteristic of different neurological and neurosurgical conditions from their wide clinical practice and to determine and illustrate the importance of MRI in the diseases of the brain and spinal cord. (orig.)

  7. Interaction between fullerene halves C_n (n ≤ 40) and single wall carbon nanotube

    International Nuclear Information System (INIS)

    Sharma, Amrish; Kaur, Sandeep; Mudahar, Isha

    2016-01-01

    We have investigated the structural and electronic properties of carbon nanotube with small fullerene halves C_n (n ≤ 40) which are covalently bonded to the side wall of an armchair single wall carbon nanotube (SWCNT) using first principle method based on density functional theory. The fullerene size results in weak bonding between fullerene halves and carbon nanotube (CNT). Further, it was found that the C-C bond distance that attaches the fullerene half and CNT is of the order of 1.60 Å. The calculated binding energies indicate the stability of the complexes formed. The HOMO-LUMO gaps and electron density of state plots points towards the metallicity of the complex formed. Our calculations on charge transfer reveal that very small amount of charge is transferred from CNT to fullerene halves.

  8. Humic acid batteries derived from vermicomposts at different C/N ratios

    Science.gov (United States)

    Shamsuddin, R. M.; Borhan, A.; Lim, W. K.

    2017-06-01

    Humic acid is a known fertilizer derived from decomposed organic matters. Organic wastes are normally landfilled for disposal which had contributed negatively to the environment. From waste-to-wealth perspective, such wastes are potential precursors for compost fertilizers. When worms are added into a composting process, the process is termed as vermicomposting. In this work, humic acid from vermicompost derived from campus green wastes was developed into a battery. This adds value proposition to compost instead of being traditionally used solely as soil improver. This research work aimed to study the correlation between electrical potential generated by humic acid at different Carbon to Nitrogen (C/N) ratios of vermicompost at 20, 25, 30 and 35. The temperature and pH profiles of composting revealed that the compost was ready after 55 days. The humic acid was extracted from compost via alkaline extraction followed by precipitation in a strong acid. The extracted humic acid together with other additives were packed into a compartment and termed as vermibattery. Another set of battery running only on the additives was also prepared as a control. The net voltage produced by a single vermibattery cell with Zn and PbO electrodes was in the range of 0.31 to 0.44 V with compost at C/N ratio of 30 gave the highest voltage. The battery can be connected in series to increase the voltage generation. Quality assessment on the compost revealed that the final carbon content is between 16 to 23 wt%, nitrogen content of 0.4 to 0.5 wt%, humic acid yield of 0.7 to 1.5 wt% and final compost mass reduction of 10 to 35 wt%. Composting campus green wastes carries multi-fold benefits of reducing labour requirement, generating fertilizer for campus greenery and green battery construction.

  9. Land-use induced dynamics of C, N and P in mountain soils of South Ecuador

    Science.gov (United States)

    Hamer, U.; Potthast, K.; Makeschin, F.

    2009-04-01

    The mountain rainforest region in South Ecuador is characterised by sites subjected to forest clearing by slash burn for pasture production. Repeated burning of pastures is a common management practice in South Ecuador. With ongoing pasture age bracken (Pteridium arachnoideum) outcompetes the pasture grass (Setaria sphacelata), pastures are abandoned and a vegetation succession develops. Along a land-use gradient (natural forest, young and old pasture, abandoned pasture with successional vegetation) the dynamics of C, N and P in the mountain soils were investigated. The study sites were located close to the "Estacion Científica San Francisco", about halfway between the province capitals Loja and Zamora, in the Cordillera Real, an eastern range of the South Ecuadorian Andes at about 2000 m above sea level. The mean annual air temperature is 15.3°C with an average annual rainfall of 2176 mm. The land-use change induced an increase of total P in the top soil (0-30 cm) of young and old pastures. An increase in SOC stocks in the top soil of the old pasture was combined with an increase in the proportion of NaOH extractable organic P. In the young pasture soil the mineralization of SOC and the amounts of microbial biomass C, N and P were highest. In 0-5 cm depth gross N mineralization and gross NH4 consumption rates were significantly higher in the young pasture compared to forest and abandoned pasture. Thus, the initial increase in microbial activity after forest to pasture conversion seems to slow down with increasing pasture age. Burning on the abandoned pasture site induced a short-term and short-lived increase in gross N mineralization rates. First results indicate that the land-use induced changes in mineralization rates were connected with changes in the microbial community structure.

  10. Synthesis and structural characterization of a new aluminum oxycarbonitride, Al5(O, C, N)4

    International Nuclear Information System (INIS)

    Inuzuka, Haruya; Kaga, Motoaki; Urushihara, Daisuke; Nakano, Hiromi; Asaka, Toru; Fukuda, Koichiro

    2010-01-01

    A new aluminum oxycarbonitride, Al 5 (O x C y N 4-x-y ) (x∼1.4 and y∼2.1), has been synthesized and characterized by X-ray powder diffraction, transmission electron microscopy and electron energy loss spectroscopy (EELS). The title compound was found to be hexagonal with space group P6 3 /mmc, Z=2, and unit-cell dimensions a=0.328455(6) nm, c=2.15998(3) nm and V=0.201805(6) nm 3 . The atom ratios O:C:N were determined by EELS. The final structural model, which is isomorphous with that of (Al 4.4 Si 0.6 )(O 1.0 C 3.0 ), showed the positional disordering of one of the three types of Al sites. The maximum-entropy method-based pattern fitting (MPF) method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The reliability indices calculated from the MPF were R wp =6.94% (S=1.22), R p =5.34%, R B =1.35% and R F =0.76%. The crystal was an inversion twin. Each twin-related individual was isostructural with Al 5 C 3 N (space group P6 3 mc, Z=2). - Graphical abstract: A new oxycarbonitride discovered in the Al-O-C-N system, Al 5 (O 1.4 C 2.1 N 0.5 ). The crystal is an inversion twin, and hence the structure is represented by a split-atom model. The three-dimensional electron density distributions are determined by the maximum-entropy methods-based pattern fitting, being consistent with the disordered structural model. Display Omitted

  11. C,N-2-[(Dimethylamino)methyl]phenylplatinum Complexes Functionalized with C60 as Macromolecular Building Blocks

    NARCIS (Netherlands)

    Koten, G. van; Meijer, M.D.; Wolf, E. de; Lutz, M.H.; Spek, A.L.; Klink, G.P.M. van

    2001-01-01

    The application of platinum(II) complexes based on the N,N-dimethylbenzylamine ligand (abbreviated as H-C,N) in macromolecular synthesis was demonstrated. Two cationic C,N-platinum moieties were linked with a 4,4'-bipyridine bridge, giving [{C6H4(CH2NMe2)-2-Pt(PPh3)}2(4,4'-bpy)](BF4)2 (2), the

  12. Control of regioselectivity over gold nanocrystals of different surfaces for the synthesis of 1,4-disubstituted triazole through the click reaction.

    Science.gov (United States)

    Rej, Sourav; Chanda, Kaushik; Chiu, Chun-Ya; Huang, Michael H

    2014-11-24

    Gold nanocubes, octahedra, and rhombic dodecahedra were examined for facet-dependent catalytic activity in the formation of triazoles. Rhombic dodecahedra gave 100% regioselective 1,4-triazoles. The product yield was increased by decreasing the particle size. However, a mixture of 1,4- and 1,5-triazoles was obtained in lower yields when cubes and octahedra of similar sizes were used. The lowest Au-atom density on the {110} surface and largest unsaturated coordination number of surface Au atoms may explain their best catalytic efficiency and product regioselectivity. Various spectroscopic techniques were employed to verify the formation of the Au-acetylide intermediate and establish the reaction mechanism, in which phenylacetylene binds to the Au {110} surface through the terminal-binding mode to result in the exclusive formation of 1,4-triazoles. The smallest rhombic dodecahedra can give diverse 1,4-disubstituted triazoles in good yields by coupling a wide variety of alkynes and organic halides. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Building blocks for the solution phase synthesis of oligonucleotides: regioselective hydrolysis of 3',5'-Di-O-levulinylnucleosides using an enzymatic approach.

    Science.gov (United States)

    García, Javier; Fernández, Susana; Ferrero, Miguel; Sanghvi, Yogesh S; Gotor, Vicente

    2002-06-28

    A short and convenient synthesis of 3'- and 5'-O-levulinyl-2'-deoxynucleosides has been developed from the corresponding 3',5'-di-O-levulinyl derivatives by regioselective enzymatic hydrolysis, avoiding several tedious chemical protection/deprotection steps. Thus, Candida antartica lipase B (CAL-B) was found to selectively hydrolyze the 5'-levulinate esters, furnishing 3'-O-levulinyl-2'-deoxynucleosides 3 in >80% isolated yields. On the other hand, immobilized Pseudomonas cepacia lipase (PSL-C) and Candida antarctica lipase A (CAL-A) exhibit the opposite selectivity toward the hydrolysis at the 3'-position, affording 5'-O-levulinyl derivatives 4 in >70% yields. A similar hydrolysis procedure was successfully extended to the synthesis of 3'- and 5'-O-levulinyl-protected 2'-O-alkylribonucleosides 7 and 8. This work demonstrates for the first time application of commercial CAL-B and PSL-C toward regioselective hydrolysis of levulinyl esters with excellent selectivity and yields. It is noteworthy that protected cytidine and adenosine base derivatives were not adequate substrates for the enzymatic hydrolysis with CAL-B, whereas PSL-C was able to accommodate protected bases during selective hydrolysis. In addition, we report an improved synthesis of dilevulinyl esters using a polymer-bound carbodiimide as a replacement for dicyclohexylcarbodiimide (DCC), thus considerably simplifying the workup for esterification reactions.

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

    Science.gov (United States)

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

    2013-01-02

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

  15. Changes in organic matter (C, N and P) of soils under subsistence agriculture; Mudancas na materia organica (C, N e P) de solos sob agricultura de subsistencia

    Energy Technology Data Exchange (ETDEWEB)

    Fraga, Vania da Silva

    2002-10-01

    Productivities under low input or subsistence agriculture are strongly dependent on nutrient supply from soil organic matter mineralization (SOM). Few results are available and they indicate declines in soil fertility under this agricultural system, particularly in SOM levels. In an attempt to understand the nature and extent of these declines we selected ten sites having cultivated areas adjacent with areas under native vegetation at the same slope position, in the states of Pernambuco and Paraiba. Based on the management history, in situ observations and {sup 137} Cs concentrations to evaluate soil erosion, the areas were divided in four groups having different levels of soil use intensity: Undisturbed Dry Forest (UDF), Disturbed Dry Forest (DDF), Preserved-Cultivated (PC) and Degraded-Cultivated (DC). In the first part of this work we quantified total organic C, N and P, in addition to {sup 137} Cs concentrations, under the assumption that changes in organic nutrient contents among land use groups would be greater than the within group variability, thus enabling inferences at a regional scale. Concentrations of C and N in DC were 50% smaller (P<0.05) than those in UDF. Of these losses, 43% were attributed to erosion processes while 57% were related to SOM mineralization. The Po/Pi ratio under UDF was 1.47 and decreased to o.82 in PC and DC (P<0.05). The effects of changes in land use were greater when considering the 0-7.5 cm layer rather than the 0-15 cm layer. Interrelationships between C and P in the dry forest areas suggested that P availability and water controlled C accumulation in these soils. In the second part of this work two experiments were conducted. The first one included a preliminary phase, comparing four methods in their capacity to detect changes in soil organic matter quality. Eighty samples that maximized the variability in C content of the whole set (n=160), were analyzed for: C in the light SOM fraction (density < 1 kg dm{sup -3}) (C-lf); C

  16. The spatial relationship between human activities and C, N, P, S in soil based on landscape geochemical interpretation.

    Science.gov (United States)

    Yu, Huan; He, Zheng-Wei; Kong, Bo; Weng, Zhong-Yin; Shi, Ze-Ming

    2016-04-01

    The development and formation of chemical elements in soil are affected not only by parent material, climate, biology, and topology factors, but also by human activities. As the main elements supporting life on earth system, the C, N, P, S cycles in soil have been altered by human activity through land-use change, agricultural intensification, and use of fossil fuels. The present study attempts to analyze whether and how a connection can be made between macroscopical control and microcosmic analysis, to estimate the impacts of human activities on C, N, P, S elements in soil, and to determine a way to describe the spatial relationship between C, N, P, S in soil and human activities, by means of landscape geochemical theories and methods. In addition, the disturbances of human activities on C, N, P, S are explored through the analysis of the spatial relationship between human disturbed landscapes and element anomalies, thereby determining the diversified rules of the effects. The study results show that the rules of different landscapes influencing C, N, P, S elements are diversified, and that the C element is closely related to city landscapes; furthermore, the elements N, P, and S are shown to be closely related to river landscapes; the relationships between mine landscapes and the elements C, N, P, S are apparent; the relationships between the elements C, N, P, S and road landscapes are quite close, which shows that road landscapes have significant effects on these elements. Therefore, the conclusion is drawn that the response mechanism analysis of human disturbance and soil chemical element aggregation is feasible, based on the landscape geochemical theories and methods. The spatial information techniques, such as remote sensing and geographic information systems, are effective for research on soil element migration.

  17. Savanna Vegetation Dynamics and their Influence on Landscape-Scale C, N, and P Biogeochemistry

    Science.gov (United States)

    Boutton, T. W.; Zhou, Y.; Wu, X. B.; Hyodo, A.

    2017-12-01

    Soil carbon (C), nitrogen (N) and phosphorus (P) cycles are strongly interlinked and controlled through biological processes, and the P cycle is further controlled through geochemical processes. In grasslands, savannas, and other dryland ecosystems throughout the world, woody plant encroachment often modifies soil C, N, and P stores, although it remains unknown if these three elements change proportionally in response to this vegetation change. We evaluated proportional changes and spatial patterns of soil organic C (SOC), total N (TN), and total P (TP) following woody encroachment by taking spatially-explicit soil cores to a depth of 1.2 m across a subtropical savanna landscape which has undergone encroachment by trees and shrubs during the past century in the Rio Grande Plains, USA. SOC and TN were coupled with respect to increasing magnitudes and spatial patterns along the soil profile following woody encroachment. In contrast, TP increased slower than SOC and TN in surface soils, but faster in subsurface soils. Spatial patterns of TP strongly resembled those of vegetation cover throughout the soil profile, but differed from those of SOC and TN, especially in deeper portions of the profile. The encroachment of woody plants into this P-limited ecosystem resulted in the accumulation of proportionally less soil P compared to C and N in surface soils; however, proportionally more P accrued in deeper portions of the profile beneath woody patches where alkaline soil pH and high carbonate concentrations would favor precipitation of P as relatively insoluble calcium phosphates. Structural equation models (SEM) showed that fine root density explained the greatest proportion of variation in SOC, TN, and TP in the surface soil. In deeper portions of the profile, SEM showed that silt and clay explained much of the variation in SOC and TN, while soil pH strongly controlled TP. This imbalanced relationship highlights that the relative importance of biotic vs. abiotic

  18. Kinetics of high-temperature oxidation of (Ti,Ta)(C,N)-based cermets

    International Nuclear Information System (INIS)

    Chicardi, E.; Córdoba, J.M.; Gotor, F.J.

    2016-01-01

    Highlights: • The kinetic of high-temperature oxidation of (Ti,Ta)(C,N)-Co cermets was studied. • A parabolic oxidation kinetic was determined in cermets between 700 °C and 1200 °C. • This parabolic kinetic behaviour is due to the existence of a protective layer. • The protective layer formed was a complex Ti_xTa_1_−_xO_2 oxide with rutile structure. • The oxidation rate is controlled by the Ti and O_2 diffusion through the Ti_xTa_1_−_xO_2. - Abstract: The kinetics of the high-temperature oxidation of titanium–tantalum carbonitride-based cermets with different Ti/Ta ratios was studied. Isothermal oxidation tests were conducted under static air for 48 h at temperatures between 700 °C and 1200 °C. The oxidation satisfied the parabolic kinetics, characteristic of the existence of a protective oxide layer. The apparent activation energy suggests the rate-controlling process during oxidation is the simultaneous inward and outward diffusion of oxygen and titanium, respectively, through the formed protective layer, consisting mainly of a rutile phase. A higher Ta(V) content in the rutile decreased the oxygen diffusivity due to the reduction of oxygen vacancy concentration.

  19. High temperature oxidation resistance of (Ti,Ta)(C,N)-based cermets

    International Nuclear Information System (INIS)

    Chicardi, E.; Córdoba, J.M.; Gotor, F.J.

    2016-01-01

    Highlights: • Cermets based on (Ti,Ta)(C,N) were oxidized in air between 800 and 1100 °C for 48 h. • The substitution of Ti by Ta resulted in a high resistance to oxidation. • A protective layer of cobalt titanates at the surface of cermets was observed. • A rutile phase in which some Ti"4"+ are replaced by Ta"5"+ was detected. • This replacement decelerated the oxygen diffusion into the cermets. - Abstract: Cermets based on titanium–tantalum carbonitride were oxidized in static air between 800 °C and 1100 °C for 48 h. The thermogravimetric and microstructural study showed an outstanding reduction in the oxidation of more than 90% when the Ta content was increased. In cermets with low Ta content, the formation of a thin CoO/Co_3O_4 outer layer tends to disappear by reacting with the underlying rutile phase, which emerges at the surface. However, in cermets with higher Ta content, the formation of an external titanate layer, observed even at a low temperature, appears to prevent the oxygen diffusion and the oxidation progression.

  20. The C-N-cycle additional channels through the combinative resonances phenomenon (CIRs)

    International Nuclear Information System (INIS)

    Gafarov, A.A.; Khugaev, A.V.; Koblik, Yu.N.

    2000-01-01

    The Combinative Isobar Resonances are shown as new channels of the C-N-cycle. In 1994 we had firstly used our new developed approach - the M ethod of Spectra Superposition p roviding measurement of d σ (E) /d ω at every accelerator (including colliders ) with highest energy-resolution depending (for thin targets) only on energy-resolution of detectors [1-5]. Rarely one can read about this[6].That time the Excitation Function (EF) of the l2 C(p,p o ) elastic scattering with energy-resolution ∼10 keV for E p =16 ∼ 19.5 MeV of cyclotron protons by using the multi angular magnetic spectrograph as detector was measured.It was wonderful when after data processing so surprised curve with a saturated structure of overlapped resonances - fluctuations of cross-section (Fig.1) was obtained (in contrary to EF obtained by M.J. LeVine and P.D.Parker in 60 Th at the tandem generator [7]). The precise agreement between well known thresholds and nuclear levels with the brightest anomalies in our curve and not disappearing fine structures in full-events curve (stat.err. 3%) - all this, only, had satisfied me that these structures are not just a joke of statistics. Fig.l shows a comparison of our obtained EF with thresholds and levels of well known product-nuclei

  1. Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

    Science.gov (United States)

    Schuler, Thomas; Nastar, Maylise

    2016-06-01

    We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

  2. Rapid top-down regulation of plant C:N:P stoichiometry by grasshoppers in an Inner Mongolia grassland ecosystem.

    Science.gov (United States)

    Zhang, Guangming; Han, Xingguo; Elser, James J

    2011-05-01

    Understanding how food web interactions alter the processing of limiting nutrient elements is an important goal of ecosystem ecology. An experiment manipulating densities of the grasshopper Oedaleus asiaticus was performed to assess top-down effects of grasshoppers on C:N:P stoichiometry of plants and soil in a grassland ecosystem in Inner Mongolia (China). With increased grasshopper feeding, plant biomass declined fourfold, litter abundance increased 30%, and the plant community became dominated by non-host plant taxa. Plant stoichiometric response depended on whether or not the plant was a grasshopper host food species: C:N and C:P ratios increased with increasing grasshopper density (GD) for host plants but decreased in non-host plants. These data suggest either a direct transfer of grasshopper-recycled nutrients from host to non-host plants or a release of non-host plants from nutrient competition with heavily grazed host plants. Litterfall C:N and C:P decreased across moderate levels of grasshopper density but no effects on C:N:P stoichiometry in the surface soil were observed, possibly due to the short experimental period. Our observations of divergent C:N:P stoichiometric response among plant species highlight the important role of grasshopper herbivory in regulating plant community structure and nutrient cycling in grassland ecosystems.

  3. Simulating the Refractive Index Structure Constant ({C}_{n}^{2}) in the Surface Layer at Antarctica with a Mesoscale Model

    Science.gov (United States)

    Qing, Chun; Wu, Xiaoqing; Li, Xuebin; Tian, Qiguo; Liu, Dong; Rao, Ruizhong; Zhu, Wenyue

    2018-01-01

    In this paper, we introduce an approach wherein the Weather Research and Forecasting (WRF) model is coupled with the bulk aerodynamic method to estimate the surface layer refractive index structure constant (C n 2) above Taishan Station in Antarctica. First, we use the measured meteorological parameters to estimate C n 2 using the bulk aerodynamic method, and second, we use the WRF model output parameters to estimate C n 2 using the bulk aerodynamic method. Finally, the corresponding C n 2 values from the micro-thermometer are compared with the C n 2 values estimated using the WRF model coupled with the bulk aerodynamic method. We analyzed the statistical operators—the bias, root mean square error (RMSE), bias-corrected RMSE (σ), and correlation coefficient (R xy )—in a 20 day data set to assess how this approach performs. In addition, we employ contingency tables to investigate the estimation quality of this approach, which provides complementary key information with respect to the bias, RMSE, σ, and R xy . The quantitative results are encouraging and permit us to confirm the fine performance of this approach. The main conclusions of this study tell us that this approach provides a positive impact on optimizing the observing time in astronomical applications and provides complementary key information for potential astronomical sites.

  4. [The Consiglio Nazionale delle Ricerche (National Research Council - C. N. R.) and the Italian medicine during fascism].

    Science.gov (United States)

    Canali, S

    2001-01-01

    The foundation of C. N. R. in 1923 created in Italy a new public system of research, different from the university one. During fascism, the contribution of C. N. R. to the development of medical research in Italy was very poor. This was mainly due to insufficient means: structures and money. Moreover, the scientists who carried on medical research within the C. N. R. were the same who already held strong university positions, which mean a complete dependence on the academic system. The ideology of fascism also contribute to the weakness of the Italian medical research promoted by the C. N. R.. According to fascist view, science, and for its nature and aims above all medicine, had to addressed to technical, practical, or much better, social achievements. Consequently, the policy of medical research at the C.N.R. was to improve social or political medicine, mainly hygiene. This was in harmony with the demographic policy, which means the policy of reinforcement of "Italian race", and positive eugenics that fascism tried to pursue.

  5. Cryptococcus neoformans in the koala (Phascolarctos cinereus): colonization by C n. var. gattii and investigation of environmental sources.

    Science.gov (United States)

    Krockenberger, M B; Canfield, P J; Malik, R

    2002-06-01

    This study is the one in a series looking at the relationship among Cryptococcus neoformans var. gattii, koalas and the environment. The koala was used as a natural biological sampler in an attempt to understand the dynamics of C. neoformans var. gattii in Australian environments. Evidence of asymptomatic nasal and skin colonization for extended periods by large numbers of C. n. var. gattii was obtained and geographical factors assessed. The key finding was the ability of koalas to amplify numbers of C. n. var. gattii in certain environments. Koalas were not found to be obligatory for the survival of the organism in all environments. Geographical factors alone could not explain differing rates of nasal and skin colonization in koalas in different environments. A strong association between healthy koalas and C. n. var. gattii was confirmed and C n. var. gattii was isolated from novel sources, including the turpentine gum tree (Syncarpia glomulifera), tallowwood (Eucalyptus microcorys) and flooded gum (E. grandis). It seems likely that as yet undiscovered environmental sources of C. n. var. gattii exist in eastern Australia. Further investigation of host, environmental and organism factors integral to the hostpathogen relationship will assist an understanding of the progression from colonization to tissue invasion and cryptococcosis in all species.

  6. Search for {theta}(1540){sup +} in the exclusive proton-induced reaction p+C(N){yields}{theta}{sup +} anti K{sup 0}+C(N) at the energy of 70 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Antipov, Yu.M.; Artamonov, A.V.; Batarin, V.A.; Eroshin, O.V. [Inst. for High Energy Physics, Protvino (Russian Federation); Kolgamov, V.Z. [Inst. of Theoretical and Experimental Physics, Moscow (RU)] [and others

    2004-09-01

    A search for narrow {theta}(1540){sup +}, a candidate for pentaquark baryon with positive strangeness, has been performed in an exclusive proton-induced reaction p+C(N){yields}{theta}{sup +} anti K{sup 0}+C(N) on carbon nuclei or quasifree nucleons at E{sub beam}=70 GeV ({radical}(s)=11.5 GeV) studying nK{sup +}, pK{sub S}{sup 0} and pK{sub L}{sup 0} decay channels of {theta}(1540){sup +} in four different final states of the {theta}{sup +} anti K{sup 0} system. In order to assess the quality of the identification of the final states with neutron or K {sup 0} {sub L}, we reconstructed {lambda}(1520){yields}nK{sup 0}{sub S} and {phi}{yields}K{sup 0}{sub L}K{sup 0}{sub S} decays in the calibration reactions p+C(N){yields}{lambda}(1520)K{sup +}+C(N) and p+C(N){yields}p{phi}+C(N). We found no evidence for narrow pentaquark peak in any of the studied final states and decay channels. Assuming that the production characteristics of the {theta}{sup +} anti K{sup 0} system are not drastically different from those of the {lambda}(1520)K{sup +} and p{phi} systems, we established upper limits on the cross-section ratios {sigma}({theta}{sup +} anti K{sup 0})/{sigma}({lambda}(1520)K{sup +})< 0.02 and {sigma}({theta}{sup +} anti K{sup 0})/{sigma}(p{phi})< 0.15 at 90% CL and a preliminary upper limit for the forward hemisphere cross-section {sigma}({theta}{sup +} anti K{sup 0})< 30 nb/nucleon. (orig.)

  7. Biogas Improvement by Adding Australian Zeolite During the Anaerobic Digestion of C:N Ratio Adjusted Swine Manure

    DEFF Research Database (Denmark)

    Wijesinghe, D. Thushari N.; Dassanayake, Kithsiri B.; Sommer, Sven G.

    2018-01-01

    Abstract: Maintenance of the ideal carbon: nitrogen (C:N) ratio with a minimum level of TAN is a key challenge for achieving maximum potential CH4 production through the anaerobic digestion process of agricultural waste such as swine manure. Biogas production can be enhanced by adding zeolite...... into the anaerobic digestion medium. However, the effects of zeolite addition to C:N ratio adjusted feedstock, on the digester performance is unknown. The objectives of this study were to investigate the effect of Australian zeolite on anaerobic digestion of swine manure with a C:N ratio adjusted to 30...... and to determine the optimal zeolite application rate to achieve the best performance. The Australian zeolite significantly enhanced CH4 production and reduced the lag phase of anaerobic digestion in batch production. The optimal addition rate of zeolite was appeared to be around 40 g/L. The better digester...

  8. 15C-15F Charge Symmetry and the 14C(n,γ)15C Reaction Puzzle

    International Nuclear Information System (INIS)

    Timofeyuk, N.K.; Thompson, I.J.; Baye, D.; Descouvemont, P.; Kamouni, R.

    2006-01-01

    The low-energy reaction 14 C(n,γ) 15 C provides a rare opportunity to test indirect methods for the determination of neutron capture cross sections by radioactive isotopes versus direct measurements. It is also important for various astrophysical scenarios. Currently, puzzling disagreements exist between the 14 C(n,γ) 15 C cross sections measured directly, determined indirectly, and calculated theoretically. To solve this puzzle, we offer a strong test based on a novel idea that the amplitudes for the virtual 15 C→ 14 C+n and the real 15 F→ 14 O+p decays are related. Our study of this relation, performed in a microscopic model, shows that existing direct and some indirect measurements strongly contradict charge symmetry in the 15 C and 15 F mirror pair. This brings into question the experimental determinations of the astrophysically important (n,γ) cross sections for short-lived radioactive targets

  9. Effect of molybdenum content on the microstructure and mechanical properties of ultra-fine Ti(C, N) based cermets

    International Nuclear Information System (INIS)

    Zhang Xiaobo; Liu Ning; Rong Chunlan

    2008-01-01

    Effect of molybdenum as a sintering aid on the microstructure and mechanical properties of Ti(C, N)-20WC-15Co-Mo-2.5C system cermets was studied in this work. Ti(C, N)-based cermets with variable Mo content were fabricated by conventional powder metallurgy techniques. The microstructure was investigated by means of X-ray diffractometer, scanning electron microscopy in combination with an energy dispersive spectrometer. Mechanical properties such as transverse rupture strength, fracture toughness and hardness were also measured, respectively. Results revealed that finer grains, as well as larger amount of bright core/grey shell structures could be obtained by increasing the molybdenum content. Transverse rupture strength and hardness were also improved. Fracture toughness, however, was decreased with the increase of Mo content. The optimized content of Mo was chosen as 15 wt.% for Ti(C, N)-20WC-15Co-Mo-2.5C system cermets

  10. Annealing temperature effects on the magnetic properties and induced defects in C/N/O implanted MgO

    Science.gov (United States)

    Li, Qiang; Ye, Bonian; Hao, Yingping; Liu, Jiandang; Kong, Wei; Ye, Bangjiao

    2013-02-01

    Virgin MgO single crystals were implanted with 70 keV C/N/O ions at room temperature to a dose of 2 × 1017/cm2. After implantation the samples showed room temperature hysteresis in magnetization loops. The annealing effects on the magnetic properties and induced defects of these samples were determined by vibrating sample magnetometer and positron annihilation spectroscopy, respectively. The experimental results indicate that ferromagnetism can be introduced to MgO single crystals by doping with C, N or introduction of Mg related vacancy defects. However, the Mg vacancies coexistence with C or N ions in the C-/N-implanted samples may play a negative role in magnetic performance in these MgO samples. The rapid increase of magnetic moment in O-implanted sample is attributed to the formation of new type of vacancy defects.

  11. Effective Biological Nitrogen Removal Treatment Processes for Domestic Wastewaters with Low C/N Ratios: A Review

    DEFF Research Database (Denmark)

    Sun, Sheng-Peng; Pellicer i Nàcher, Carles; Merkey, Brian

    2010-01-01

    with high efficiency and relative low costs. However, the removal of nitrogen from domestic wastewater with a low carbon/nitrogen (C/N) ratio can often be limited in municipal wastewater plants (WWTPs) because organic carbon is a limiting factor for denitrification. The present work reviews innovative....... They can effectively be used for nitrogen removal from low C/N domestic wastewater without external carbon addition. In addition, conventional and alternative carbon sources for enhanced biological nitrogen removal were also reviewed. We conclude that alternative carbon sources such as wine distillery...... at large scale for nitrogen removal from low C/N domestic wastewater, (2) further method logic are explored to introduce the Anammox pathway into domestic wastewater treatment, and (3) alternative carbon sources are explored and optimized for supporting the denitrification. With these efforts, cost...

  12. Nursery Culture Performance of Litopenaeus vannamei with Probiotics Addition and Different C/N Ratio Under Laboratory Condition

    Directory of Open Access Journals (Sweden)

    WIDANARNI

    2010-09-01

    Full Text Available Application of bioflocs technology and probiotics has improved water quality and production of Pacific white shrimp (Litopenaeus vannamei culture. This experiment was to verify the effect of probiotic bacteria addition and different carbon:nitrogen (C:N ratio on water quality and performance of Pacific white shrimp nursery culture. Nursery culture was carried out for 25 days in an aquarium under laboratory condition with stock density of one Post-Larvae (PL (poslarval per liter (24 PL/aquarium of PL16 shrimp. Different C:N ratio resulted a significant difference on shrimp production performance. Treatment of 10 C:N ratio demonstrated the best shrimp growth (20.37 + 0.48% per day in weight and 6.05 + 0.41% per day in length, harvesting yield (1180 + 62 g/m3 and feed efficiency (121 + 6%. There was however no significant difference observed between treatments in water quality.

  13. Nursery Culture Performance of Litopenaeus vannamei with Probiotics Addition and Different C/N Ratio Under Laboratory Condition

    Directory of Open Access Journals (Sweden)

    WIDANARNI

    2010-09-01

    Full Text Available Application of bioflocs technology and probiotics has improved water quality and production of Pacific white shrimp (Litopenaeus vannamei culture. This experiment was to verify the effect of probiotic bacteria addition and different carbon:nitrogen (C:N ratio on water quality and performance of Pacific white shrimp nursery culture. Nursery culture was carried out for 25 days in an aquarium under laboratory condition with stock density of one Post-Larvae (PL (poslarval per liter (24 PL/aquarium of PL16 shrimp. Different C:N ratio resulted a significant difference on shrimp production performance. Treatment of 10 C:N ratio demonstrated the best shrimp growth (20.37 ± 0.48% per day in weight and 6.05 ± 0.41% per day in length, harvesting yield (1180 ± 62 g/m3 and feed efficiency (121 ± 6%. There was however no significant difference observed between treatments in water quality.

  14. Quantitative effects of composting state variables on C/N ratio through GA-aided multivariate analysis

    International Nuclear Information System (INIS)

    Sun Wei; Huang, Guo H.; Zeng Guangming; Qin Xiaosheng; Yu Hui

    2011-01-01

    It is widely known that variation of the C/N ratio is dependent on many state variables during composting processes. This study attempted to develop a genetic algorithm aided stepwise cluster analysis (GASCA) method to describe the nonlinear relationships between the selected state variables and the C/N ratio in food waste composting. The experimental data from six bench-scale composting reactors were used to demonstrate the applicability of GASCA. Within the GASCA framework, GA searched optimal sets of both specified state variables and SCA's internal parameters; SCA established statistical nonlinear relationships between state variables and the C/N ratio; to avoid unnecessary and time-consuming calculation, a proxy table was introduced to save around 70% computational efforts. The obtained GASCA cluster trees had smaller sizes and higher prediction accuracy than the conventional SCA trees. Based on the optimal GASCA tree, the effects of the GA-selected state variables on the C/N ratio were ranged in a descending order as: NH 4 + -N concentration > Moisture content > Ash Content > Mean Temperature > Mesophilic bacteria biomass. Such a rank implied that the variation of ammonium nitrogen concentration, the associated temperature and the moisture conditions, the total loss of both organic matters and available mineral constituents, and the mesophilic bacteria activity, were critical factors affecting the C/N ratio during the investigated food waste composting. This first application of GASCA to composting modelling indicated that more direct search algorithms could be coupled with SCA or other multivariate analysis methods to analyze complicated relationships during composting and many other environmental processes. - Research Highlights: → A genetic algorithm aided stepwise cluster analysis method in food waste composting. → Nonlinear relationships between the selected state variables and the C/N ratio. → Introduced proxy tables save around 70% computational

  15. Quantitative effects of composting state variables on C/N ratio through GA-aided multivariate analysis

    Energy Technology Data Exchange (ETDEWEB)

    Sun Wei [Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2 (Canada); Huang, Guo H., E-mail: huangg@iseis.org [Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2 (Canada); MOE Key Laboratory of Regional Energy Systems Optimization, Sino-Canada Energy and Environmental Research Academy, North China Electric Power University, Beijing, 102206 (China); Zeng Guangming [MOE Key Laboratory of Environmental Biology and Pollution Control, College of Environmental Science and Engineering, Hunan University, Changsha, Hunan, 410082 (China); Qin Xiaosheng [School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Yu Hui [Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2 (Canada)

    2011-03-01

    It is widely known that variation of the C/N ratio is dependent on many state variables during composting processes. This study attempted to develop a genetic algorithm aided stepwise cluster analysis (GASCA) method to describe the nonlinear relationships between the selected state variables and the C/N ratio in food waste composting. The experimental data from six bench-scale composting reactors were used to demonstrate the applicability of GASCA. Within the GASCA framework, GA searched optimal sets of both specified state variables and SCA's internal parameters; SCA established statistical nonlinear relationships between state variables and the C/N ratio; to avoid unnecessary and time-consuming calculation, a proxy table was introduced to save around 70% computational efforts. The obtained GASCA cluster trees had smaller sizes and higher prediction accuracy than the conventional SCA trees. Based on the optimal GASCA tree, the effects of the GA-selected state variables on the C/N ratio were ranged in a descending order as: NH{sub 4}{sup +}-N concentration > Moisture content > Ash Content > Mean Temperature > Mesophilic bacteria biomass. Such a rank implied that the variation of ammonium nitrogen concentration, the associated temperature and the moisture conditions, the total loss of both organic matters and available mineral constituents, and the mesophilic bacteria activity, were critical factors affecting the C/N ratio during the investigated food waste composting. This first application of GASCA to composting modelling indicated that more direct search algorithms could be coupled with SCA or other multivariate analysis methods to analyze complicated relationships during composting and many other environmental processes. - Research Highlights: {yields} A genetic algorithm aided stepwise cluster analysis method in food waste composting. {yields} Nonlinear relationships between the selected state variables and the C/N ratio. {yields} Introduced proxy tables

  16. Ti2Al(C, N) Solid Solution Reinforcing TiAl-Based Composites: Evolution of a Core-Shell Structure, Interfaces, and Mechanical Properties.

    Science.gov (United States)

    Song, Xiaojie; Cui, Hongzhi; Han, Ye; Ding, Lei; Song, Qiang

    2018-05-16

    In this work, Ti 2 Al(C, N) solid solution with lamellar structure-enhanced TiAl matrix composites was synthesized by vacuum arc melting, using bulk g-C 3 N 4 , Ti, and Al powders as raw materials. The phases, microstructures, interfaces, and mechanical properties were investigated. MAX phase of Ti 2 Al(C, N) solid solution with lamellar structure was formed. During the melting process, first, C 3 N 4 reacted with Ti to form Ti(C, N) by Ti + C 3 N 4 → Ti(C, N). Then Ti 2 Al(C, N) was formed by a peritectic reaction of TiAl(l) + Ti(C, N)(s) → Ti 2 Al(C, N). C 3 N 4 is the single reactant that provides C and N simultaneously to final product of Ti 2 Al(C, N). The interfaces of TiAl//Ti 2 Al(C, N) and Ti 2 Al(C, N)//Ti(C, N) display perfect orientation relationships with low misfit values. The microhardness, compressive strength, and strain of best-performing TiAl-10 mol % Ti 2 Al(C, N) composite were improved by 45%, 55.7%, and 50% compared with the TiAl alloy, respectively. Uniformly distributed Ti 2 Al(C, N) and unreacted Ti(C, N) particles contributed to the grain refinement and reinforcement of the TiAl matrix. Laminated tearing, particle pull-out, and the crack-arresting of Ti 2 Al(C, N) are crucial for the improvement in compressive strength and plasticity of the composites.

  17. Effects of Land Use Change on C-N cycling: Microbes Matter.

    Science.gov (United States)

    Hofmockel, K.

    2012-12-01

    Large swaths of the terrestrial landscape have been altered by human actions on Earth's biophysical systems, resulting in the homogenization of Earth's biota, while simultaneously increasing greenhouse gases and reactive nitrogen (N). This is especially poignant in grasslands that have been largely replaced by managed agricultural systems with substantial N inputs, or by unmanaged grasslands that are dominated by exotic species. Impacted ecosystems may be important for global C models, because they comprise a major portion of the global land area, terrestrial NPP and the world's soil C stocks. This research investigates how anthropogenic changes in plant community composition and agricultural management systems influence the composition and function of microbial communities that mediate key aspects of belowground C and N cycling and storage. Data from agroecology and grassland climate change experiments are used to illustrate how microbial responses can have important implications for large scale coupling of C and N cycles. In this study exotic plant species significantly decreased root inputs, causing shifts in microbial community composition, including both specific taxa and functional guilds of bacteria. By contrast, climate change (precipitation manipulation) caused functional responses (increased carbon and phosphorus cycling) that were not detected in the microbial community composition. Mycorrhizal fungi in managed systems were responsive to both root biomass and nitrogen inputs, significantly altering hydrolytic enzyme activity and aggregate turnover. Collectively small-scale processes can alter the ecosystem biogeochemical cycles. Together theses results suggest that linking microbial communities to coupled C-N cycles may have important implications for terrestrial C cycling feedbacks that are an integral part of the anthropocene era.

  18. Physical properties of layered homologous RE-B-C(N) compounds

    International Nuclear Information System (INIS)

    Mori, Takao; Zhang Fuxiang; Leithe-Jasper, Andreas

    2004-01-01

    Physical properties of a series of homologous RE-B-C(N) B 12 cluster compounds REB 17 CN, REB 22 C 2 N, and REB 28.5 C 4 (RE=Er,Ho) were investigated. The structures of the compounds are layer-like along the c-axis, with rare earth and B 6 octahedral layers separated by B 12 icosahedral and C-B-C chain layers whose number increases successively from two B 12 layers for the REB 17 CN compound to four for the REB 28.5 C 4 compound. The rare earth atoms are configured in two triangular flat layers which are stacked on top of one another in AB stacking where the nearest-neighbor rare earth directions are the three atoms forming a triangle in the adjacent layer. The series of homologous compounds exhibit a spin glass transition with T f shifting in correspondence with variations of the basal plane lattice constants, consistent with the magnetic interaction being effective in the basal planes. The isothermal remanent magnetization shows a stretched exponential decay I m (t)∝ exp[-Ct -(1-n) ]. Exponents determined for the different homologous compounds were scaled as a function of T r =T/T f and found to follow the empirical dependency determined for typical spin glasses. It is indicated that a mixture of disorder originating from the partial occupancy of the rare earth sites and frustration of interactions due to the unique configuration is responsible for the manifestation of spin glass transitions in these homologous systems

  19. Synthesis of [14C]-62514, a radiolabelled derivative of erythromycin A, via [2-14C]N,N-dimethylethylenediamine

    International Nuclear Information System (INIS)

    Surber, B.W.; Baker, W.R.; Seif, L.

    1991-01-01

    The synthesis of [ 14 C]A-62514, 11-deoxy-11[carboxy(2-dimethylamino-[1- 14 C]ethyl)amino]-6-0-methyl-e rythromycin A 11,12-(cyclic ester), was performed in five steps. The key intermediate, [2- 14 C]N,N-dimethylethyl-enediamine, was obtained in 80% yield by reacting Eschenmoser's salt with K 14 CN and reducing the resulting [1- 14 C]N,N-dimethylglycinonitrile with H 2 and Raney Ni in methanol and ammonium hydroxide. The final product was obtained 97% radiochemically pure in an overall radiochemical yield of 14%, with a specific activity of 39 mCi/mmol. (author)

  20. Microwave electromagnetic properties of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coating

    International Nuclear Information System (INIS)

    Qing Yuchang; Zhou Wancheng; Luo Fa; Zhu Dongmei

    2010-01-01

    The electromagnetic characteristics of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coatings were studied. The reflection loss of the coatings exceeds -10 dB at 8-18 GHz and -9 dB at 2-18 GHz when the coating thickness is 1 and 3 mm, respectively. The dielectric and magnetic absorbers filled coatings possess excellent microwave absorption, which could be attributed to the proper incorporate of the multi-polarization mechanisms as well as strong natural resonance. It is feasible to develop the thin and wideband microwave absorbing coatings using carbonyl iron particles and Si/C/N nano-powder.

  1. Microwave electromagnetic properties of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coating

    Science.gov (United States)

    Qing, Yuchang; Zhou, Wancheng; Luo, Fa; Zhu, Dongmei

    2010-02-01

    The electromagnetic characteristics of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coatings were studied. The reflection loss of the coatings exceeds -10 dB at 8-18 GHz and -9 dB at 2-18 GHz when the coating thickness is 1 and 3 mm, respectively. The dielectric and magnetic absorbers filled coatings possess excellent microwave absorption, which could be attributed to the proper incorporate of the multi-polarization mechanisms as well as strong natural resonance. It is feasible to develop the thin and wideband microwave absorbing coatings using carbonyl iron particles and Si/C/N nano-powder.

  2. Sequential Dy(OTf)3 -Catalyzed Solvent-Free Per-O-Acetylation and Regioselective Anomeric De-O-Acetylation of Carbohydrates.

    Science.gov (United States)

    Yan, Yi-Ling; Guo, Jiun-Rung; Liang, Chien-Fu

    2017-09-19

    Dysprosium(III) trifluoromethanesulfonate-catalyzed per-O-acetylation and regioselective anomeric de-O-acetylation of carbohydrates can be tuned by adjusting the reaction medium. In this study, the per-O-acetylation of unprotected sugars by using a near-stoichiometric amount of acetic anhydride under solvent-free conditions resulted in the exclusive formation of acetylated saccharides as anomeric mixtures, whereas anomeric de-O-acetylation in methanol resulted in a moderate-to-excellent yield. Reactions with various unprotected monosaccharides or disaccharides followed by a semi-one-pot sequential conversion into the corresponding acetylated glycosyl hemiacetal also resulted in high yields. Furthermore, the obtained hemiacetals could be successfully transformed into trichloroimidates after Dy(OTf) 3 -catalyzed glycosylation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. KH 2PO4 as a novel catalyst for regioselective monobromination of aralkyl ketones using N-bromosuccinimide: a green methodology

    Directory of Open Access Journals (Sweden)

    P. Md. Khaja Mohinuddin

    2015-08-01

    Full Text Available A simple, regioselective and green method has been developed for the preparation of monobrominated ketones from various aralkyl ketones by using N-bromosuccinimide in presence of KH 2PO 4 in EtOH at reflux temperature. The present method is of short reaction time and simple with excellent isolated yields of products. The use of eco-friendly solvent, reuse of organic waste (succinimide and recyclable catalyst used for 4 times without loss of activity are advantageous. This is the first example of the use of KH 2PO 4 as a useful catalyst in organohalogen chemistry and the present method meets reduce-reuse-recycle (RRR principle towards development of green protocol.

  4. Rh-Catalyzed (5+2) Cycloadditions of 3-Acyloxy-1,4-enynes and Alkynes: Computational Study of Mechanism, Reactivity, and Regioselectivity

    Science.gov (United States)

    Xu, Xiufang; Liu, Peng; Shu, Xing-zhong; Tang, Weiping; Houk, K. N.

    2013-01-01

    The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast to the (5+2) cycloadditions with vinylcyclopropanes (VCP), in which alkyne inserts into a rhodium-allyl bond, alkyne insertion into a Rh–C(sp2) bond is preferred. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity. In the regioselectivity-determining alkyne insertion step, the alkyne substituent prefers to be distal to the forming C–C bond and thus distal to the OAc group in the product. PMID:23725341

  5. Diels-Alder reactions using 4,7-dioxygenated indanones as dienophiles for regioselective construction of oxygenated 2,3-dihydrobenz[f]indenone skeleton

    Directory of Open Access Journals (Sweden)

    2008-05-01

    Full Text Available Regioselective construction of 4,8,9-trioxygenated 2,3-dihydrobenz[f]indenones, key intermediates for the synthesis of kinamycin antibiotics, was achieved via Diels-Alder reactions (DAR using 4,7-dioxygenated indanone-type compounds as dienophiles. Reaction of indanetrione with 1-methoxybutadiene gave a 1 : 1 mixture of undesired 4,5,9-trioxygenated 2,3-dihydrobenz[f]indenone and [4.4.3]propellane. The addition of Lewis acid did not affect the product ratio, whereas the use of the 6-bromoindanetrione exclusively afforded the latter propellane. On the other hand, DAR of benzyne derived from bromoindan and furan gave 5,8-epoxy-2,3-dihydrobenz[f]indene, which was subjected to acid-induced ring opening to give 2,3-dihydrobenz[f]indenone with undesired 4,5,9-trioxy functions.

  6. Bisindeno-annulated pentacenes with exceptionally high photo-stability and ordered molecular packing: Simple synthesis by a regio-selective Scholl reaction

    KAUST Repository

    Naibi Lakshminarayana, Arun; Chang, Jingjing; Luo, Jie; Zheng, Bin; Huang, Kuo-Wei; Chi, Chunyan

    2015-01-01

    Bisindeno-annulated pentacenes 3a and 3b were synthesized by a simple regio-selective, FeCl3-mediated Scholl reaction from the corresponding 6,13-diaryl pentacene precursors. The fusion of two indeno-units dramatically changes the electronic properties and chemical reactivity of pentacene and the obtained compounds exhibited exceptionally high photo-stability in the solution, with a half-life time of 11.2 (3a) and 32.0 (3b) days under ambient light and air conditions. Ordered molecular packing with a small π-π stacking distance was observed in the single crystals of 3a and 3b. Our research provides a promising strategy to access stable higher order acenes with controlled molecular order. This journal is

  7. Convergent Synthesis of the Potent P2Y Receptor Antagonist MG 50-3-1 Based on a Regioselective Ullmann Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Christa E. Müller

    2012-03-01

    Full Text Available MG 50-3-1 (3, trisodium 1-amino-4-{4-[4-chloro-6-(2-sulfophenylamino-1,3,5-triazin-2-ylamino]-2-sulfophenylamino}-9,10-dioxo-9,10-dihydroanthracene 2-sulfonate is the most potent and selective antagonist (IC50 4.6 nM for “P2Y1-like” nucleotide-activated membrane receptors in guinea-pig taenia coli responsible for smooth muscle relaxation. Full characterization of the compound, however, e.g., at the human P2Y1 receptor, which is a novel potential target for antithrombotic drugs, as well as other P2 receptor subtypes, has been hampered due to difficulties in synthesizing the compound in sufficient quantity. MG 50-3-1 would be highly useful as a biological tool for detailed investigation of signal transduction in the gut. We have now developed a convenient, fast, mild, and efficient convergent synthesis of 3 based on retrosynthetic analysis. A new, regioselective Ullmann coupling reaction under microwave irradiation was successfully developed to obtain 1-amino-4-(4-amino-2-sulfophenylamino-9,10-dioxo-9,10-dihydro­anthracene 2-sulfonate (8. Four different copper catalysts (Cu, CuCl, CuCl2, and CuSO4 were investigated at different pH values of sodium phosphate buffer, and in water in the absence or presence of base. Results showed that CuSO4 in water in the presence of triethylamine provided the best conditions for the regioselective Ullmann coupling reaction yielding the key intermediate compound 8. A new synthon (sodium 2-(4,6-dichloro-1,3,5-triazin-2-ylaminobenzenesulfonate, 13 which can easily be obtained on a gram scale was prepared, and 13 was successfully coupled with 8 yielding the target compound 3.

  8. properties of Cr(C,N) hard coatings deposited in Ar-C2H2-N2 plasma

    International Nuclear Information System (INIS)

    Macek, M.; Cekada, M.; Kek, D.; Panjan, P.

    2002-01-01

    Mechanical properties, microstructure and the average chemical composition of Cr(C,N) hard coatings deposited in Ar-C 2 H 2 -N 2 plasma strongly depends on the partial pressure of the reactive gases (N 2 , C 2 H 2 ) and on the type of the deposition equipment. In this study we report on the properties of Cr(C,N) hard coatings deposited by means of the triode ion plating in the BAI 730 apparatus and those prepared by sputter deposition in Balzers Sputron in the pressure range from 0.12 Pa (pure Ar) up to 0.35 Pa with different ratios (0-100%) between C 2 H 2 and N 2 . At first mechanical properties (microhardness and adhesion) of coatings were analyzed on the common way. Internal stress was measured by the radius of substrate curvature. Chemical composition of coatings was analyzed by means of AES while the Raman and XPS spectroscopy was used to determined the nature of carbon bonding in the Cr(C,N) films. Microstructure was determined by XRD as well as by means of TEM and TED. Chemical state of various elements in the coating has been studied by XPS. The ratio of the carbide bond (C-Cr) against the C-C and C-H bonds was calculated. The existence of the graphite phase in some Cr(C,N) coatings was confirmed by Raman spectroscopy. (Authors)

  9. Analyses of antibacterial activity and cell compatibility of titanium coated with a Zr-C-N film.

    Directory of Open Access Journals (Sweden)

    Yin-Yu Chang

    Full Text Available The purpose of this study was to verify the antibacterial performance and cell proliferation activity of zirconium (Zr-carbon (C-nitride (N coatings on commercially pure titanium (Ti with different C contents.Reactive nitrogen gas (N(2 with and without acetylene (C(2H(2 was activated by Zr plasma in a cathodic-arc evaporation system to deposit either a zirconium nitride (ZrN or a Zr-C-N coating onto Ti plates. The bacterial activity of the coatings was evaluated against Staphylococcus aureus with the aid of SYTO9 nucleic acid staining and scanning electron microscopy (SEM. Cell compatibility, mRNA expression, and morphology related to human gingival fibroblasts (HGFs on the coated samples were also determined by using the MTT assay, reverse transcriptase-polymerase chain reaction, and SEM.The Zr-C-N coating with the highest C content (21.7 at% exhibited the lowest bacterial preservation (P<0.001. Biological responses including proliferation, gene expression, and attachment of HGF cells to ZrN and Zr-C-N coatings were comparable to those of the uncoated Ti plate.High-C-content Zr-C-N coatings not only provide short-term antibacterial activity against S. aureus but are also biocompatible with HGF cells.

  10. Effects of C/N controlled periphyton based organic farming of freshwater prawn on water quality parameters and biotic factors

    Directory of Open Access Journals (Sweden)

    Md. Rezoanul Haque

    2014-08-01

    Full Text Available The effects of C:N controlled periphyton based organic farming of freshwater prawn on water quality parameters and biotic factors were investigated. The experiment had two treatments: T1 and T2 each with three replications. Stocking density was maintained at 20,000 juveniles ha-1. In T1, only commercially available prawn feed was applied and in T2, a locally formulated and prepared feed containing 24% crude protein with C:N ratio close to 20 was used, and maize flour and bamboo side shoots were provided for maintaining C:N ratio 20.Mean values of water quality parameters did not vary significantly (P>0.05 between treatments. Periphytic biomass in terms of dry matter, ash free dry matter (AFDM and chlorophyll a showed significant difference (P<0.05 among different sampling months. Individual harvesting weight, individual weight gain, specific growth rates, gross and net yields of prawn were significantly higher (P<0.05 in T2 than T1. Therefore, it was concluded that freshwater prawn might consume periphyton biomass in C:N controlled periphyton based organic farming practices resulted a significantly (P<0.05 higher production of freshwater prawn than traditional farming.

  11. Palladium-catalyzed domino C,N-coupling/carbonylation/Suzuki coupling reaction: an efficient synthesis of 2-aroyl-/heteroaroylindoles.

    Science.gov (United States)

    Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

    2009-10-15

    A convenient one-pot synthesis of 2-aroylindoles using a domino palladium-catalyzed C,N-coupling/carbonylation/C,C-coupling sequence is described. The reaction involved easily prepared 2-gem-dibromovinylanilines and boronic acids under carbon monoxide. Optimized reaction conditions allowed the construction of a wide variety of highly functionalized 2-aroyl-/heteroaroylindoles in satisfactory yields.

  12. Short-term changes in soil C, N, and biota following harvesting and regeneration of loblolly pine (Pinus taeda L.)

    Science.gov (United States)

    Mason C. Carter; Thomas J. Dean; Minyi Zhou; Michael G. Messina; Ziyin Wang

    2002-01-01

    In affiliation with the USDA-FS long-term soil productivity program, a series of studies have been established in the US gulf coast region to monitor the effects of intensive silviculture on site productivity. This report presents early results of a study of the interactive effects of harvest intensity and cultural treatments on soil C, N, and biological processes...

  13. Effects of C/N ratio and substrate addition on natural food communities in freshwater prawn monoculture ponds

    NARCIS (Netherlands)

    Asaduzzaman, M.; Rahman, M.M.; Azim, M.E.; Islam, M.A.; Wahab, M.A.; Verdegem, M.C.J.; Verreth, J.A.J.

    2010-01-01

    An on-station trial was conducted to investigate the effects of three C/N ratios (10/1, 15/1 and 20/1) along with substrate presence or absence on natural food communities in freshwater prawn culture ponds. An experiment was carried out in 40 m2 ponds stocked with a stocking density of 2 prawn

  14. Franklin Medal and Bower prize awarded to C.N. Yang. On the Yang-Mills gauge field theory

    International Nuclear Information System (INIS)

    Ma Zhongqi

    1995-01-01

    C.N. Yang was awarded the Benjamin Franklin Medal and 1995 Bower Prize mainly for his fundamental work on nonabelian gauge field theory. A brief introduction to this theory and its important role in the development of physics is given

  15. Experimental soil warming effects on C, N, and major element cycling in a low elevation spruce-fir forest soil

    Science.gov (United States)

    Lindsey E. Rustad; Ivan J. Fernandez; Stephanie Arnold

    1996-01-01

    The effect of global warming on north temperate and boreal forest soils has been the subject of much recent debate. These soils serve as major reservoirs for C, N, and other nutrients necessary for forest growth and productivity. Given the uncertainties in estimates of organic matter turnover rates and storage, it is unclear whether these soils will serve as short or...

  16. C/N-controlled periphyton-based freshwater prawn farming system: a sustainable approach to increase pond productivity

    NARCIS (Netherlands)

    Asaduzzaman, M.

    2012-01-01

    Three technologies showed to improve productivity and sustainability of pond production: (1) C/N ratio control, (2) providing substrates for periphyton development, and (3) fish driven re-suspension. The novelty of this PhD research is to combine these technologies, with the goal to raise pond

  17. Changes in organic matter (C, N and P) of soils under subsistence agriculture

    International Nuclear Information System (INIS)

    Fraga, Vania da Silva

    2002-10-01

    Productivities under low input or subsistence agriculture are strongly dependent on nutrient supply from soil organic matter mineralization (SOM). Few results are available and they indicate declines in soil fertility under this agricultural system, particularly in SOM levels. In an attempt to understand the nature and extent of these declines we selected ten sites having cultivated areas adjacent with areas under native vegetation at the same slope position, in the states of Pernambuco and Paraiba. Based on the management history, in situ observations and 137 Cs concentrations to evaluate soil erosion, the areas were divided in four groups having different levels of soil use intensity: Undisturbed Dry Forest (UDF), Disturbed Dry Forest (DDF), Preserved-Cultivated (PC) and Degraded-Cultivated (DC). In the first part of this work we quantified total organic C, N and P, in addition to 137 Cs concentrations, under the assumption that changes in organic nutrient contents among land use groups would be greater than the within group variability, thus enabling inferences at a regional scale. Concentrations of C and N in DC were 50% smaller (P -3 ) (C-lf); C-CO 2 produced during three days of incubation (C-min3d); C oxidized with 333 mM (C-ox 333) and 16,5 mM (C-ox16) KMnO 4 . The only fraction that did not correlate with total C was C-fl. Average proportions of total C extracted by C-mins3d, C-ox 16 were 1.5%, 24% and 7.2 %, respectively. In the second phase, the whole sample set (n=160) was analyzed for C-ox16. This C fraction decreased from 1.65 g kg -1 under UDF to 0.70 in DC (P -1 , in a pot experiment. Total C correlated significantly with N mineralized in 60 d (N-min60d) (r=0.79***) while N-min60 and P-Mehlich-1 explained 80% of the variation in dry matter production by buffel grass (Cenchrus ciliaris). Low P availability, C and N losses, limited water availability and sometimes-inappropriate land management techniques, are considered strong limiting conditions for

  18. Integrated survey of elemental stoichiometry (C, N, P from the western to eastern Mediterranean Sea

    Directory of Open Access Journals (Sweden)

    M. Pujo-Pay

    2011-04-01

    Full Text Available This paper provides an extensive vertical and longitudinal description of the biogeochemistry along an East-West transect of 3000 km across the Mediterranean Sea during summer 2008 (BOUM cruise. During this period of strong stratification, the distribution of nutrients, particulate and dissolved organic carbon (DOC, nitrogen (DON and phosphorus (DOP were examined to produce a detailed spatial and vertically extended description of the elemental stoichiometry of the Mediterranean Sea. Surface waters were depleted in nutrients and the thickness of this depleted layer increased towards the East from about 10 m in the Gulf of Lion to more than 100 m in the Levantine basin, with the phosphacline deepening to a greater extent than that for corresponding nitracline and thermocline depths. We used the minimum oxygen concentration through the water column in combination with 2 fixed concentrations of dissolved oxygen to distinguish an intermediate layer (Mineralization Layer; ML from surface (Biogenic Layer; BL, and deep layers (DL. Whilst each layer was represented by different water masses, this approach allowed us to propose a schematic box-plot representation of the biogeochemical functioning of the two Mediterranean basins. Despite the increasing oligotrophic nature and the degree of P-depletion along the West to East gradient strong similarities were encountered between eastern and western ecosystems. Within the BL, the C:N:P ratios in all pools largely exceeded the Redfield ratios, but surprisingly, the nitrate vs. phosphate ratios in the ML and DL tended towards the canonical Redfield values in both basins. A change in particulate matter composition has been identified by a C increase relative to N and P along the whole water column in the western basin and between BL and ML in the eastern one. Our data showed a noticeable stability of the DOC:DON ratio (12–13 throughout the Mediterranean Sea. This is in good agreement with a P-limitation of

  19. Preparation, properties, and application characteristics of metastable layers of the Ti-Si-C-N system

    International Nuclear Information System (INIS)

    Fella, R.

    1992-10-01

    In the Ti-Si-C and Ti-Si-C-N systems, metastable layers were precipitated by means of non-reactive magnetron sputtering of hot-pressed two-phase TiC/SiC and TiN/SiC targets with 20 mole% and 50 mole% SiC. The preparation parameters were varied as follows: ion bombardment during precipitation (bias sputtering), substrate temperature, and annealing times when annealing amorphous 50%:50% TiC/SiC and 50%:50% TiN/SiC layers. Sputtering of targets containing 20% SiC was found to result in monophase fcc layers (NaCl structure). This was documented on the basis of X-ray and electron diffraction patterns. Direct precipitation of targets with 50 mole% SiC resulted in amorphous layers. Increasing the ion bombardment during accretion, raising the substrate temperature, and annealing amorphous 50%:50% TiC/SiC and 50%:50% TiN/SiC (layers precipitated directly) resulted in the crystallization of TiC and TiN nanocrystallites, respectively, imbedded in an amorphous SiC matrix. These crystallites were detected both by X-ray and by electron diffractions and by XPS studies. The XPS measurements of crystalline TiC and amorphous SiC reference layers demonstrated the existence of new kinds of carbon interface phases ('pseudocarbide layers') around TiC and amorphous SiC regions, respectively, which have a positive impact on the mechanical properties of the layers. The hardness of the layers can be correlated with the degrees of crystallization and texture. Adhesion and toughness are worse in SiC-bearing layers than PVD TiC and TiN layers, respectively. The application characteristics of the layers were determined by model wear tests relative to 100Cr6 by means of a pin/disk tribometer. N-bearing layers were found to have clearly higher friction coefficients and greater wear than layers without N. (orig.)

  20. Quantitative effects of composting state variables on C/N ratio through GA-aided multivariate analysis.

    Science.gov (United States)

    Sun, Wei; Huang, Guo H; Zeng, Guangming; Qin, Xiaosheng; Yu, Hui

    2011-03-01

    It is widely known that variation of the C/N ratio is dependent on many state variables during composting processes. This study attempted to develop a genetic algorithm aided stepwise cluster analysis (GASCA) method to describe the nonlinear relationships between the selected state variables and the C/N ratio in food waste composting. The experimental data from six bench-scale composting reactors were used to demonstrate the applicability of GASCA. Within the GASCA framework, GA searched optimal sets of both specified state variables and SCA's internal parameters; SCA established statistical nonlinear relationships between state variables and the C/N ratio; to avoid unnecessary and time-consuming calculation, a proxy table was introduced to save around 70% computational efforts. The obtained GASCA cluster trees had smaller sizes and higher prediction accuracy than the conventional SCA trees. Based on the optimal GASCA tree, the effects of the GA-selected state variables on the C/N ratio were ranged in a descending order as: NH₄+-N concentration>Moisture content>Ash Content>Mean Temperature>Mesophilic bacteria biomass. Such a rank implied that the variation of ammonium nitrogen concentration, the associated temperature and the moisture conditions, the total loss of both organic matters and available mineral constituents, and the mesophilic bacteria activity, were critical factors affecting the C/N ratio during the investigated food waste composting. This first application of GASCA to composting modelling indicated that more direct search algorithms could be coupled with SCA or other multivariate analysis methods to analyze complicated relationships during composting and many other environmental processes. Copyright © 2010 Elsevier B.V. All rights reserved.

  1. Shrub type dominates the vertical distribution of leaf C : N : P stoichiometry across an extensive altitudinal gradient

    Science.gov (United States)

    Zhao, Wenqiang; Reich, Peter B.; Yu, Qiannan; Zhao, Ning; Yin, Chunying; Zhao, Chunzhang; Li, Dandan; Hu, Jun; Li, Ting; Yin, Huajun; Liu, Qing

    2018-04-01

    Understanding leaf stoichiometric patterns is crucial for improving predictions of plant responses to environmental changes. Leaf stoichiometry of terrestrial ecosystems has been widely investigated along latitudinal and longitudinal gradients. However, very little is known about the vertical distribution of leaf C : N : P and the relative effects of environmental parameters, especially for shrubs. Here, we analyzed the shrub leaf C, N and P patterns in 125 mountainous sites over an extensive altitudinal gradient (523-4685 m) on the Tibetan Plateau. Results showed that the shrub leaf C and C : N were 7.3-47.5 % higher than those of other regional and global flora, whereas the leaf N and N : P were 10.2-75.8 % lower. Leaf C increased with rising altitude and decreasing temperature, supporting the physiological acclimation mechanism that high leaf C (e.g., alpine or evergreen shrub) could balance the cell osmotic pressure and resist freezing. The largest leaf N and high leaf P occurred in valley region (altitude 1500 m), likely due to the large nutrient leaching from higher elevations, faster litter decomposition and nutrient resorption ability of deciduous broadleaf shrub. Leaf N : P ratio further indicated increasing N limitation at higher altitudes. Interestingly, drought severity was the only climatic factor positively correlated with leaf N and P, which was more appropriate for evaluating the impact of water status than precipitation. Among the shrub ecosystem and functional types (alpine, subalpine, montane, valley, evergreen, deciduous, broadleaf, and conifer), their leaf element contents and responses to environments were remarkably different. Shrub type was the largest contributor to the total variations in leaf stoichiometry, while climate indirectly affected the leaf C : N : P via its interactive effects on shrub type or soil. Collectively, the large heterogeneity in shrub type was the most important factor explaining the overall leaf C : N : P variations

  2. Effect of heating rate on the mechanical properties and microstructure of Ti(C,N)-based cermets

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Qingzhong; Ai, Xing, E-mail: aixingsdu@163.com; Zhao, Jun; Zhang, Hongshan; Qin, Wenzhen; Gong, Feng

    2015-03-25

    An appropriate heating rate in the sintering process is crucial to obtain the Ti(C,N)-based cermets with superior properties. In this paper, Ti(C,N)-based cermets were sintered to investigate the influence of heating rate on the mechanical properties and microstructure of the cermet materials. The transverse rupture strength (TRS), Vickers hardness (HV) and fracture toughness (K{sub IC}) were tested. The microstructure, indention crack, fracture morphology and phase composition of the cermets were also studied by scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The results reveal that the heating rate has a great influence on the mechanical properties and microstructure of Ti(C,N)-based cermets. The cermets sintered at the heating rate of 3 °C/min between 1300 °C and 1430 °C have the optimum comprehensive mechanical properties with a transverse rupture strength of 1605±107 MPa, a hardness of 12.02±0.25 GPa and a fracture toughness of 10.73±0.40 MPa m{sup 1/2}. The heating rate can affect the reaction among the constituents of Ti(C,N)-based cermets and then influence the elements distribution in the core–rim microstructures and the lattice parameter of Ti(C,N) phase. When the heating rate is between 2 °C/min and 5 °C/min, the lower the heating rate is, the coarser the Ti(C,N) grains become. A higher heating rate is detrimental to the formation of core–rim microstructures, and a lower heating rate can result in grain coarsening and inhomogeneous microstructure. The observation of indention cracks and fracture surfaces show that the intergranular cracks and intergranular fractures mainly occur in the cermets with larger binder mean free path and medium grains. While the cleavage fractures appear more in the cermets with grain coarsening, and the transgranular fractures exist more in the cermets with non-fully developed fine grains.

  3. Synthesis of (Cr,V){sub 2}(C,N) solid solution powders by thermal processing precursors

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Anrui [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China); Liu, Ying [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China); Key Laboratory of Advanced Special Material & Technology, Ministry of Education, Chengdu, 610065 (China); Ma, Shiqing; Qiu, Yuchong; Rong, Pengcheng; Ye, Jinwen [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China)

    2017-06-01

    The single-phase (Cr,V){sub 2}(C,N) solid solution powders were fabricated via carbothermal reduction-nitridation (CRN) processing technique. The effects of heat treatment temperature, nitrogen pressure and carbon proportion were experimentally studied in detail by X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and thermal analysis. The chemical transformations of vanadium and chromium compounds were as follows: precursors → V{sub 2}O{sub 3}, Cr{sub 2}O{sub 3} → Cr{sub 3}C{sub 2}, Cr{sub 2}O{sub 3}, (Cr,V){sub 2}(C,N) → (Cr,V){sub 2}(C,N). When the heat-treated temperature was below 1200 °C, chromium oxides didn’t completely react. However, higher temperature ∼1300 °C could not only lead to the segregation of some nitrides and carbon black, but also to the occurrence of fiber-bridged particles. The system nitrogen pressure over 0.03 MPa would cause a subtle transformation of (Cr,V){sub 2}(C,N) to VCrN{sub 2}. When the carbon proportion was below 15 wt%, the oxides could not be completely reduced, while when the carbon proportion was above 15.5 wt%, some undesired carbides, like Cr{sub 23}C{sub 6} and Cr{sub 3}C{sub 2}, would form. Ultimately, the homogeneously distributed pure-phase (Cr,V){sub 2}(C,N) spherical particles with the average size of ∼1.5 μm were obtained at the optimal conditions of the treatment of precursors at 1200 °C for 1 h with the nitrogen pressure of 0.03 MPa and carbon content of 15.5 wt%. The chemical composition of the solid solution with the optimal process could be drawn as (Cr{sub 0.85}V{sub 0.15}){sub 2}(C{sub 0.57}N{sub 0.43}). Thermal processing precursors method shows the advantages of lower synthesis temperature, shorter period and finer particles when comparing with the conventional preparations. - Highlights: • Single phase of (Cr,V){sub 2}(C,N) powders were synthesized for the first time. • Precursors were used to prepared the powders by carbothermal

  4. Influence of bulky substituents on the regioselective group-transfer reactions of diorganozinc compounds with N,N'-bis(2,6-di-isopropylphenyl)-1,4-diaza-1,3-butadiene

    NARCIS (Netherlands)

    Koten, G. van; Wissing, E.; Gorp, K. van; Boersma, J.

    1994-01-01

    Diorganozinc compounds R{2}Zn (R=alkyl or aryl) react with N, N'-bis(2,6-di-isopropylphenyl)-1,4-diaza-1,3-butadiene, (i-Pr{2}Ph)N@?CHCHp@?N(i-Pr{2}Ph) (i-Pr{2}Ph-DAB) to give thermally unstable 1:1 coordination complexes R{2}Zn(i-Pr2Ph-DAB), which subsequently undergo a slow regioselective alkyl or

  5. Distribution of C, N, P in aquatic plants of some lakes in the middle of Yangtze river

    International Nuclear Information System (INIS)

    Huang Liang; Wu Ying; Zhou Juzhen; Zhang Jing; Li Wei

    2003-01-01

    By analyzing three elements (C, N, P, 13 C) in the ten aquatic plants of nine lakes in the middle of Yangtze River, the concentrations of C, N and δ 13 C in leaves of aquatic macrophytes depend on the environment where they live in. The concentration of C and N in leaves of submerged macrophytes is significantly lower than that of leaves of floating and emergent macrophytes because of limitation of inorganic carbon; And at the same time, because δ 13 C of inorganic carbon in water is higher than that of CO 2 in air, δ 13 C of leaves of submerged macrophytes is higher than that of leaves of floating and emergent macrophytes. (authors)

  6. Crystallization of an amorphous B-C-N precursor with a Li-B-N catalyst at high pressures and temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Li Dongxu; Yu Dongli; Wang Peng; Li Yingmei; He Julong; Xu Bo; Liu Zhongyuan [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, Hebei Province (China); Tian Yongjun, E-mail: fhcl@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, Hebei Province (China)

    2009-11-15

    An orthorhombic B-C-N compound was synthesized using an amorphous B-C-N precursor and a Li-B-N catalyst at 6 GPa and 1773 K. The results of energy dispersive spectrometry and electronic energy loss spectrometry suggest a stoichiometry of B:C:N = 1:3.3:1. In addition, the Li-B-N catalyst improves the crystallizations of the B-C-N compound, graphite and BN and therefore might be a profitable catalyst in ultrahigh pressure experiments.

  7. Crystallization of an amorphous B-C-N precursor with a Li-B-N catalyst at high pressures and temperatures

    International Nuclear Information System (INIS)

    Li Dongxu; Yu Dongli; Wang Peng; Li Yingmei; He Julong; Xu Bo; Liu Zhongyuan; Tian Yongjun

    2009-01-01

    An orthorhombic B-C-N compound was synthesized using an amorphous B-C-N precursor and a Li-B-N catalyst at 6 GPa and 1773 K. The results of energy dispersive spectrometry and electronic energy loss spectrometry suggest a stoichiometry of B:C:N = 1:3.3:1. In addition, the Li-B-N catalyst improves the crystallizations of the B-C-N compound, graphite and BN and therefore might be a profitable catalyst in ultrahigh pressure experiments.

  8. Comparison of Ti(C,N)-based cermets processed by hot-pressing sintering and conventional pressureless sintering

    International Nuclear Information System (INIS)

    Xu, Qingzhong; Ai, Xing; Zhao, Jun; Qin, Weizhen; Wang, Yintao; Gong, Feng

    2015-01-01

    Highlights: • The HP sintered Ti(C,N)-based cermets exhibit high hardness with fine grain size. • The PLS sintered cermets possess high mechanical properties with low porosity. • The applied pressure can rearrange particles and contribute to grain refinement. • The heating rate can greatly affect the solid and liquid phase sintering of cermets. - Abstract: A suitable sintering method is important to obtain the Ti(C,N)-based cermets with superior properties. In this paper, Ti(C,N)-based cermets were fabricated by hot-pressing sintering (HP) and conventional pressureless sintering (PLS) technology, respectively, to investigate the influence of different sintering methods on the microstructure and mechanical properties of cermets materials. The microstructure, fracture morphology, indention cracks and phase composition were observed and detected using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The transverse rupture strength (TRS), Vickers hardness (HV) and fracture toughness (K IC ) were also measured. The results reveal that all of the Ti(C,N)-based cermets exhibit core–rim microstructures with black cores, white cores and grey rims embedded into metal binder phases. The grain size of the samples fabricated by HP is much finer and the structure is more compact than those fabricated by PLS, while there exist pores in the HP sintered samples. The sintering process has no influence on the phase composition of cermets, but affects the phase content and crystallinity. The samples fabricated by PLS present higher transverse rupture strength, fracture toughness and density than samples fabricated by HP. However, the HP sintered samples possess a higher hardness

  9. The Effects of Fiddler Crabs (Uca sp on C/N Ratio and Redox Potential of Soil in Mangrove Ecosystems

    Directory of Open Access Journals (Sweden)

    Mulyanto Mulyanto

    2017-08-01

    Full Text Available Research has been done in Ketapang mangrove area of  Probolinggo city in months of September-November 2015. The objectives are to observe the fiddler crab community stucture and to analyze the effects of fiddler crabs on C/N ratio and redox potential of soil in mangrove ecosystems. The samples of fiddler crabs were taken during the low tides at 4 station (20 transects with sizes of 1 m2. Data of the fiddler crabs were measured from the soil digging insides the transect. The soil samples were taken from these crab holes wall (at the surface and at the depth of 20 cm, under the holes at the depth of 40 cm as well as from the locations that undwells by these animals at the same depth. The fiddler crab identified are U. Triangularis between 2 – 6 ind/m2, U paradussumieri 1 – 3 ind/m2, U perplexa 14 – 32 ind/m2, U dussumieri 12 – 27 ind/m2 and U. Tetragonon 3 – 6 ind/m2. The diversity is moderate (H = 1.7 and the dominance index was low (C = 0.37. C/N ratio soil were inhabited by fiddler crab between 6 – 14, the undwelled area were 14 – 20. Soil C/N ratio was inhabited by the fiddler crab at the surface and depth of 20 cm in average of 9 cm while at 40 cm in avergae of 12. The low of C/N ratio at surface and depth of 20 cm causing the organic matter turnover faster because the high nitorgen content. Soil potential redox (Eh the undwelled areas was found –0.647 mV, meanwhile the soil Eh in the dwelled areas was positive (0.68 till 0.87 mV. This mean, the decpmposition was occured during aerobic condition and will produce untoxic subtances.

  10. Striatal [[sup 11]C]-N-methyl-spiperone binding in patients with focal dystonia (torticollis) using positron emission tomography

    Energy Technology Data Exchange (ETDEWEB)

    Leenders, K [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Hartvig, P [Hospital Pharmacy, Univ. Hospital, Uppsala (Sweden); Forsgren, L; Holmgren, G; Almay, B [Dept. of Neurology, Umeaa Univ., Umeaa (Sweden); Eckernaes, S A [Dept. of Neurology, Univ. Hospital, Uppsala (Sweden); Lundqvist, H; Laangstroem, B [Uppsala Univ. PET-Center, Uppsala (Sweden)

    1993-01-01

    Specific binding of [[sup 11]C]-N-methyl-spiperone to striatal dopamine D2 receptors was assessed using positron emission tomography (PET) in 6 patients with adult-onset focal dystonia (predominantly spasmodic torticollis) and in 5 healthy subjects. No significant difference in average specific striatal tracer uptake between patients and healthy subjects was found. However, in the 5 patients showing lateralisation of clinical signs a trend to higher striatal tracer uptake in the contralateral hemisphere was observed. (authors).

  11. R-matrix calculations for electron-impact excitation of C(+), N(2+), and O(3+) including fine structure

    Science.gov (United States)

    Luo, D.; Pradhan, A. K.

    1990-01-01

    The new R-matrix package for comprehensive close-coupling calculations for electron scattering with the first three ions in the boron isoelectronic sequence, the astrophysically significant C(+), N(2+), and O(3+), is presented. The collision strengths are calculated in the LS coupling approximation, as well as in pair-coupling scheme, for the transitions among the fine-structure sublevels. Calculations are carried out at a large number of energies in order to study the detailed effects of autoionizing resonances.

  12. Refractive properties of imidazolium ionic liquids with alanine anion [C n mim][Ala] ( n = 2, 3, 4, 5, 6)

    Science.gov (United States)

    Zhou, Cai-bin; Li, Jing; Yi, Zhe; Ai, Hong-jun

    2017-10-01

    Imidazolium ionic liquids with alanine anion, [C n mim][Ala] ( n = 2, 3, 4, 5, 6), were prepared and characterized. The standard addition method was used to measure refractivity of the synthesized ionic liquids in order to eliminate the effect of water traces in the ionic liquids. The molar refraction and molecular polarizability were also calculated by Lorentz-Lorenz's method. Using liner extrapolation, the semiempirical estimation method for optical properties of other ionic liquids with amino acid anions was established.

  13. Mechanism of generation of large (Ti,Nb,V)(C,N)-type precipitates in H13 + Nb tool steel

    Science.gov (United States)

    Xie, You; Cheng, Guo-guang; Chen, Lie; Zhang, Yan-dong; Yan, Qing-zhong

    2016-11-01

    The characteristics and generation mechanism of (Ti,Nb,V)(C,N) precipitates larger than 2 μm in Nb-containing H13 bar steel were studied. The results show that two types of (Ti,Nb,V)(C,N) phases exist—a Ti-V-rich one and an Nb-rich one—in the form of single or complex precipitates. The sizes of the single Ti-V-rich (Ti,Nb,V)(C,N) precipitates are mostly within 5 to 10 μm, whereas the sizes of the single Nb-rich precipitates are mostly 2-5 μm. The complex precipitates are larger and contain an inner Ti-V-rich layer and an outer Nb-rich layer. The compositional distribution of (Ti,Nb,V)(C,N) is concentrated. The average composition of the single Ti-V-rich phase is (Ti0.511V0.356Nb0.133)(C x N y ), whereas that for the single Nb-rich phase is (Ti0.061V0.263Nb0.676)(C x N y ). The calculation results based on the Scheil-Gulliver model in the Thermo-Calc software combining with the thermal stability experiments show that the large phases precipitate during the solidification process. With the development of solidification, the Ti-V-rich phase precipitates first and becomes homogeneous during the subsequent temperature reduction and heat treatment processes. The Nb-rich phase appears later.

  14. Effect of C/N ratio, aeration rate and moisture content on ammonia and greenhouse gas emission during the composting.

    Science.gov (United States)

    Jiang, Tao; Schuchardt, Frank; Li, Guoxue; Guo, Rui; Zhao, Yuanqiu

    2011-01-01

    Gaseous emission (N2O, CH4 and NH3) from composting can be an important source of anthropogenic greenhouse gas and air pollution. A laboratory scale orthogonal experiment was conducted to estimate the effects of C/N ratio, aeration rate and initial moisture content on gaseous emission during the composting of pig faeces from Chinese Ganqinfen system. The results showed that about 23.9% to 45.6% of total organic carbon (TOC) was lost in the form of CO2 and 0.8% to 7.5% of TOC emitted as CH4. Most of the nitrogen was lost in the form of NH3, which account for 9.6% to 32.4% of initial nitrogen. N2O was also an important way of nitrogen losses and 1.5% to 7.3% of initial total nitrogen was lost as it. Statistic analysis showed that the aeration rate is the most important factor which could affect the NH3 (p = 0.0189), CH4 (p = 0.0113) and N2O (p = 0.0493) emissions significantly. Higher aeration rates reduce the CH4 emission but increase the NH3 and N2O losses. C/N ratio could affect the NH3 (p = 0.0442) and CH4 (p = 0.0246) emissions significantly, but not the N2O. Lower C/N ratio caused higher NH3 and CH4 emissions. The initial moisture content can not influence the gaseous emission significantly. Most treatments were matured after 37 days, except a trial with high moisture content and a low C/N ratio.

  15. Effect of carbon content on the microstructure and mechanical properties of superfine Ti(C, N)-based cermets

    International Nuclear Information System (INIS)

    Liu Ning; Liu Xuesong; Zhang Xiaobo; Zhu Longwei

    2008-01-01

    As a new kind of tool materials which appeared in the seventies last century, the Ti (C, N)-based cermets have been widely used in recent years due to many of its good properties. The microstructure of Ti(C, N)-based cermets with various carbon content were studied using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). Vickers hardness and transverse rupture strength (TRS) were also measured. An increased carbon content resulted in the finer grain size, decreased solution strength of tungsten and molybdenum in the binder phase, and a higher volume fraction of heavy (Ti, Mo, W)(C,N) cores. If the addition of carbon content is too little or too much, the phase composition of material will deviate from the normal dual phase section and lead to the formation of the third phase: η-phase if the carbon content is too low or dissociative carbon if the carbon content is too high. And the formation of the third phase will remarkably deteriorate the mechanical properties of cermets

  16. Ash content, carbon and C/N ratio in paricá in function of NPK fertilization

    Directory of Open Access Journals (Sweden)

    CRISTIANE R. VIEIRA

    2018-02-01

    Full Text Available ABSTRACT Fertilization in areas of forest plantations is needed to supplement plants´ nutritional needs until harvest. An experiment was performed to check the influence of fertilization on levels of ash, carbon and C/N relation in Schizolobium amazonicum. Soil liming was performed and fertilization occurred after 15 days of incubation. S. amazonicum seedlings were produced and submitted to fertilization with N, P and K: N = 0, 40, 80 and 120 kg ha-1; P2O5 = 0, 50, 100 and 200 kg ha-1; K2O = 0, 50, 100 and 200 kg ha-1. The plants were measured after 180 days. The seedlings of 20 treatments with the highest increase in height and diameter were transplanted to the field. Soil was fertilized and limestone was spread; seedlings were distributed into randomized blocks, with six replications. After 12 months, the plants were removed to determine ash, organic carbon, C/N relation contents. The ashes were submitted to digestion to determine nutrient concentrations. Fertilization influenced the levels of ash and organic carbon and C/N relation in S. amazonicum. Results indicate that the species has a potential for energy production.

  17. Ash content, carbon and C/N ratio in paricá in function of NPK fertilization.

    Science.gov (United States)

    Vieira, Cristiane R; Weber, Oscarlina L S; Scaramuzza, José Fernando

    2018-01-01

    Fertilization in areas of forest plantations is needed to supplement plants´ nutritional needs until harvest. An experiment was performed to check the influence of fertilization on levels of ash, carbon and C/N relation in Schizolobium amazonicum. Soil liming was performed and fertilization occurred after 15 days of incubation. S. amazonicum seedlings were produced and submitted to fertilization with N, P and K: N = 0, 40, 80 and 120 kg ha-1; P2O5 = 0, 50, 100 and 200 kg ha-1; K2O = 0, 50, 100 and 200 kg ha-1. The plants were measured after 180 days. The seedlings of 20 treatments with the highest increase in height and diameter were transplanted to the field. Soil was fertilized and limestone was spread; seedlings were distributed into randomized blocks, with six replications. After 12 months, the plants were removed to determine ash, organic carbon, C/N relation contents. The ashes were submitted to digestion to determine nutrient concentrations. Fertilization influenced the levels of ash and organic carbon and C/N relation in S. amazonicum. Results indicate that the species has a potential for energy production.

  18. Age-related decrease of 11C-N-methylspiperone in vivo binding to human striatum detected by PET

    International Nuclear Information System (INIS)

    Iyo, Masaomi; Yamasaki, Toshiro; Fukuda, Hiroshi

    1989-01-01

    The effect of aging on 11 C-N-methylspiperone binding to living human striatum was demonstrated using positron emission tomography. The ll normal volunteers (22 to 72 years old) participated in this study. The uptake of 11 C-N-methylspiperone in the brain following intravenous injection was highest in the striatum in individual subject. And the uptake in the striatum only gradually increased until the end of the study. The uptake of 11 C-N-methylspiperone in cerebellum peaked within 10 minutes following injection and then rapidly dropped. The association rate constant 'k 3 ' was calculated from the slope of the radioactivity-ratio of striatum to cerebellum versus the equivalent time. The equivalent time was calculated from the radioactivity of cerebellum as an input function. The exponential decrease of the k 3 value with aging was observed. The k 3 value of the youngest subject (22 years old, male) was 0.035/min, while that of the oldest one (72 years old, male) was found to be 0.020/min. These data suggested that the dopaminergic activity through D2 dopamine receptors reduces with aging in human striatum. (author)

  19. A thermodynamic model for C-(N-)A-S-H gel: CNASH{sub s}s. Derivation and validation

    Energy Technology Data Exchange (ETDEWEB)

    Myers, Rupert J.; Bernal, Susan A.; Provis, John L., E-mail: j.provis@sheffield.ac.uk

    2014-12-15

    The main reaction product in Ca-rich alkali-activated cements and hybrid Portland cement (PC)-based materials is a calcium (alkali) aluminosilicate hydrate (C-(N-)A-S-H) gel. Thermodynamic models without explicit definitions of structurally-incorporated Al species have been used in numerous past studies to describe this gel, but offer limited ability to simulate the chemistry of blended PC materials and alkali-activated cements. Here, a thermodynamic model for C-(N-)A-S-H gel is derived and parameterised to describe solubility data for the CaO–(Na{sub 2}O,Al{sub 2}O{sub 3})–SiO{sub 2}–H{sub 2}O systems and alkali-activated slag (AAS) cements, and chemical composition data for C-A-S-H gels. Simulated C-(N-)A-S-H gel densities and molar volumes are consistent with the corresponding values reported for AAS cements, meaning that the model can be used to describe chemical shrinkage in these materials. Therefore, this model can provide insight into the chemistry of AAS cements at advanced ages, which is important for understanding the long-term durability of these materials.

  20. A New Design of In Situ Ti(C,N) Reinforced Composite Coatings and Their Microstructures, Interfaces, and Wear Resistances.

    Science.gov (United States)

    Wang, Mingliang; Cui, Hongzhi; Wei, Na; Ding, Lei; Zhang, Xinjie; Zhao, Yong; Wang, Canming; Song, Qiang

    2018-01-31

    Here, a unique combination of a novel carbon-nitrogen source (g-C 3 N 4 ) with different mole ratios of Ti/g-C 3 N 4 has been utilized to fabricate iron matrix composite coatings by a synchronized powder feeding plasma transferred arc (PTA) cladding technology. The results show that submicron Ti(C,N) particles are successfully fabricated in situ on a Q235 low carbon steel substrate to reinforce the iron matrix composite coatings and exhibit dense microstructures and good metallurgical bonding between the coating and the substrate. The microstructure of the coating consists of an α-Fe matrix and Ti(C,N) particles when the mole ratio of Ti/g-C 3 N 4 is no more than 5:1. The microhardness and wear resistance of the coating gradually improve with increasing abundance of the in-situ-synthesized Ti(C,N) particles. Interestingly, for a Ti/g-C 3 N 4 mole ratio of 6:1, a fine lamellar eutectic Laves phase (Fe 2 Ti) appears, and this phase further improves the microhardness and wear resistance of the coating. The microhardness of the coating is 3.5 times greater than that of the Q235 substrate, and the wear resistance is enhanced 7.66 times over that of the substrate. The Ti(C,N)/Fe 2 Ti and Fe 2 Ti/α-Fe interfaces are very clean, and the crystallographic orientation relationships between the phases are analyzed by high-resolution transmission electron microscopy (HRTEM) and an edge-to-edge matching model. The theoretical predictions and the experimental results are in good agreement. Furthermore, based on the present study, for the solidification process near equilibrium, smaller interatomic spacing misfits and interplanar spacing d-value mismatches contribute to the formation of crystallographic orientation relationships between phases during the PTA cladding process. The existence of orientation relationships is beneficial for improving the properties of the coatings. This work not only expands the application fields of g-C 3 N 4 but also provides a new idea for the

  1. Tracking Water, C, N, and P by Linking Local Scale Soil Hydrologic and Biogeochemical Features to Watershed Scale

    Science.gov (United States)

    Sedaghatdoost, A.; Mohanty, B.; Huang, Y.

    2017-12-01

    The biogeochemical cycles of carbon (C), nitrogen (N), and phosphorus (P) have many contemporary significance due to their critical roles in determining the structure and function of ecosystems. The objectives of our study is to find out temporal dynamics and spatial distribution of soil physical, chemical, and biological properties and their interaction with C, N, and P cycles in the soil for different land covers and weather conditions. The study is being conducted at three locations within Texas Water Observatory (TWO), including Riesel (USDA-ARS experimental watersheds), Texas A&M Agrilife Research Farm, and Danciger forest in Texas. Soil physical, hydraulic, chemical (total C, total N, total P, pH, EC, redox potential, N-NO3-, N-NH4+, PO42-, K, Ca, Mg, Na, Mn, and Alox and Feox), and microbiological (Microbial biomass C, N, and P, PLFA analysis, enzymatic activity) properties are being measured in the top 30 cm of the soil profile. Our preliminary data shows that biogeochemical processes would be more profound in the areas with higher temperature and precipitation as these factors stimulate microbial activity and thus influence C, N, and P cycles. Also concentrations of C and N are greater in woodlands relative to remnant grasslands as a consequence of the greater above- and below-ground productivity of woodlands relative to remnant grasslands. We hypothesize that finer soil textures have more organic matter, microbial population, and reactive surfaces for chemicals than coarse soils, as described in some recent literature. However, the microbial activity may not be active in fine textured soils as organic materials may be sorbed to clay surfaces or protected from decomposing organisms. We also expect reduced condition in saturated soils which will decrease carbon mineralization while increase denitrification and alkalinity in the soil. Spatio-temporal data with initial evaluation of biogeochemical factors/processes for different land covers will be presented.

  2. C:N:P Molar Ratios, Sources and 14C Dating of Surficial Sediments from the NW Slope of Cuba.

    Directory of Open Access Journals (Sweden)

    Guadalupe de la Lanza Espino

    Full Text Available The surficial sediments recovered from 12 sites located near the channel axis of the Florida Straits and the lower slope off NW Cuba were analyzed for total organic carbon (TOC, nitrogen (TN, phosphorus (TP, elemental C:N:P ratios, C and N isotopic values, and 14C dating. The depth profiles of TOC, TN, and TP (0-18 cm displayed a downcore trend and a significant variation. The TOC values were low (0.15 to 0.62%; 66 to 516 µmol g(-1. Sites near the island's lower slope had lower TOC average concentrations (158-333 µmol g(-1 than those closer to the channel axis (averaging 341-516 µmol g(-1; p <0.05. The TN concentrations near the lower slope attained 0.11% (80 µmol g(-1, whereas, towards the channel axis, they decreased to 0.07% (55 µmol g(-1; p<0.05. The C:N ratios ranged from 1.9 to 10.2. The mean molar C:N ratio (5.4 indicated a marine hemipelagic deposition. The TP was lower at sites near the lower slope (38.4 to 50.0 µmol gv; 0.12% to 0.16% than those near the channel axis (50.0 to 66 µmol g(-1; 0.15 to 0.21%. C:P fluctuated from 7.7 to 14.1 in the surficial sediment layer. The bulk organic δ13Corg and δ15N values confirmed pelagic organic sources, and the 14C dating revealed that the sediments were deposited during the Holocene (1000-5000 yr BP. We suggest that the hydrodynamic conditions in the Straits influence vertical and advective fluxes of particulate organic material trapped in the mixed-layer, which reduces the particulate matter flux to the seabed.

  3. Effects of metal binder on the microstructure and mechanical properties of Ti(C,N)-based cermets

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Qingzhong; Ai, Xing, E-mail: aixingsdu@163.com; Zhao, Jun; Gong, Feng; Pang, Jiming; Wang, Yintao

    2015-09-25

    Highlights: • Ni–Co binder improves the solid solution reaction and the wetting of hard phases. • Cermets with 25 wt.% binder have evenly distributed grains with moderate rims. • Co/(Ni + Co) ratios influence the grain sizes and microstructure features of cermets. • The cermets with pure Co as binder exhibit optimal mechanical properties. - Abstract: To optimize the mechanical properties of Ti(C,N)-based cermets used as tool materials, the cermets with different Ni–Co binder contents and Co/(Ni + Co) weight ratios were prepared. The effects of metal binder content and Co/(Ni + Co) ratio on the microstructure and mechanical properties of Ti(C,N)-based cermets were investigated by scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and measuring the transverse rupture strength (TRS), Vickers hardness (HV) and fracture toughness (K{sub IC}). The experimental results reveal that increasing Ni–Co binder content can increase the thickness of rim phases by improving the solid solution reaction and the wetting of hard phases. The cermets with 25 wt.% binder addition present good comprehensive mechanical properties, which is attributed to the moderate rim phases and uniformly distributed Ti(C,N) grains. The Co/(Ni + Co) weight ratios in binder have a great influence on the grain sizes and microstructure features of Ti(C,N)-based cermets, in virtue of the synergic effects between the wettability of Co and the solubilizing capacity of Ni on hard phases. The cermets with pure Co as binder exhibit optimal mechanical properties with a TRS of 1767 ± 81 MPa, a hardness of 12.26 ± 0.10 GPa and a K{sub IC} of 8.40 ± 0.47 MPa m{sup 1/2}, which meet the requirements for tool materials. And the cermets with a Co/(Ni + Co) ratio of 0.2 have the second best mechanical properties with a TRS of 1848 ± 201 MPa, a hardness of 11.12 ± 0.40 GPa and a K{sub IC} of 9.43 ± 0.54 MPa m{sup 1/2}, in which the lower hardness can

  4. Hard nanocrystalline Zr-B-C-N films with high electrical conductivity prepared by pulsed magnetron sputtering

    Czech Academy of Sciences Publication Activity Database

    Vlček, J.; Steidl, P.; Kohout, J.; Čerstvý, R.; Zeman, P.; Prokšová, S.; Peřina, Vratislav

    2013-01-01

    Roč. 215, JAN 25 (2013), s. 186-191 ISSN 0257-8972. [39th International Conference on Metallurgical Coatings and Thin Films (ICMTF). San Diego, California, 23.04.2012-27.04.2012] Institutional support: RVO:61389005 Keywords : Zr-B-C-N films * nanocomposite materials * pulsed magnetron sputtering * hard ness * high electrical conductivity * osidation resistance Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 2.199, year: 2013 http://www.sciencedirect.com/science/article/pii/S0257897212010584

  5. Paths and Tableaux Descriptions of Jacobi-Trudi Determinant Associated with Quantum Affine Algebra of Type $C_n$

    Directory of Open Access Journals (Sweden)

    Wakako Nakai

    2007-07-01

    Full Text Available We study the Jacobi-Trudi-type determinant which is conjectured to be the $q$-character of a certain, in many cases irreducible, finite-dimensional representation of the quantum affine algebra of type $C_n$. Like the $D_n$ case studied by the authors recently, applying the Gessel-Viennot path method with an additional involution and a deformation of paths, we obtain an expression by a positive sum over a set of tuples of paths, which is naturally translated into the one over a set of tableaux on a skew diagram.

  6. Tableau Formulas for One-Row Macdonald Polynomials of Types C_n and D_n

    Science.gov (United States)

    Feigin, Boris; Hoshino, Ayumu; Noumi, Masatoshi; Shibahara, Jun; Shiraishi, Jun'ichi

    2015-12-01

    We present explicit formulas for the Macdonald polynomials of types C_n and D_n in the one-row case. In view of the combinatorial structure, we call them ''tableau formulas''. For the construction of the tableau formulas, we apply some transformation formulas for the basic hypergeometric series involving very well-poised balanced {}_{12}W_{11} series. We remark that the correlation functions of the deformed W algebra generators automatically give rise to the tableau formulas when we principally specialize the coordinate variables.

  7. Slip-rolling resistance of novel Zr(C,N) thin film coatings under high Hertzian contact pressures

    Energy Technology Data Exchange (ETDEWEB)

    Manier, Charles-Alix

    2010-08-24

    Today, coatings are used in many applications ranging from the decoration purposes to the improvement of efficiency such as in machining tools, medical tools, computer devices (hard disks) and many more. Especially the automotive industry anticipates a benefit in using coatings for example in powertrains and gears where the mechanical components are stressed under slip-rolling motion. A cost effective option to increase efficiency is based on the increase of the load carrying capacity by thin film coatings. It would also represent a way towards downsizing. In the work presented here, a small review concerning rolling contact fatigue of coatings was performed. Experimentally it is then shown, that crystalline Zr(C,N) coatings can be slip-rolling resistant at 120 C in factory fill engine oil up to ten million cycles under average Hertzian contact pressures up to P{sub 0mean} = 1.94 GPa (P{sub 0max} = 2.91 GPa). Basically, it represents here the doubling of the normal force acting on the surface compared to uncoated steel traditionally lubricated with fully formulated oil. Typically, the coated substrates are made of the quenched and tempered bearing steel Cronidur 30. The Zr(C,N) coatings were fully characterized using different characterisation techniques in order to understand the difference in slip-rolling resistance under those high tribological demands. Effectively, the slip-rolling resistance of different batches of the Zr(C,N) coatings is evaluated using a defined and powerful testing procedure. Different results of lifetime were achieved without fundamental changes of the deposition procedure. The characterisation achieved permits the identification of microstructural disparities which should affect the load carrying capacity of the coating. Moreover, the efficiency of the high slip-rolling resistant Zr(C,N) coating was considered not only with respect to the improvement of the load carrying capacity of the substrate but also in terms of tribological

  8. The truncated Hyper-Poisson queues: Hk/Ma,b/C/N with balking, reneging and general bulk service rule

    Directory of Open Access Journals (Sweden)

    Shawky A.I.

    2008-01-01

    Full Text Available The aim of this paper is to derive the analytical solution of the queue: Hk/Ma,b/C/N with balking and reneging in which (I units arrive according to a hyper-Poisson distribution with k independent branches, (II the queue discipline is FIFO; and (III the units are served in batches according to a general bulk service rule. The steady-state probabilities, recurrence relations connecting various probabilities introduced are found and the expected number of units in the queue is derived in an explicit form. Also, some special cases are obtained. .

  9. Covalent Immobilization of Candida rugosa Lipase at Alkaline pH and Their Application in the Regioselective Deprotection of Per-O-acetylated Thymidine

    Directory of Open Access Journals (Sweden)

    Cintia W. Rivero

    2016-08-01

    Full Text Available Lipase from Candida rugosa (CRL was stabilized at alkaline pH to overcome the inactivation problem and was immobilized for the first time by multipoint covalent attachment on different aldehyde-activated matrices. PEG was used as a stabilizing agent on the activity of CRL. At these conditions, CRL maintained 50% activity at pH 10 after 17 h incubation in the presence of 40% (w/v of PEG, whereas the enzyme without additive was instantaneously inactive after incubation at pH 10. Thus, this enzyme was covalently immobilized at alkaline pH on three aldehyde-activated supports: aldehyde-activated Sepharose, aldehyde-activated Lewatit105 and heterofunctional aldehyde-activated EDA-Sepharose in high overall yields. Heterogeneous stable CRL catalysts at high temperature and solvent were obtained. The aldehyde-activated Sepharose-CRL preparation maintained 70% activity at 50 °C or 30% (v/v acetonitrile after 22 h and exhibited high regioselectivity in the deprotection process of per-O-acetylated thymidine, producing the 3′-OH-5′-OAc-thymidine in 91% yield at pH 5.

  10. A Set of Regioselective O-Methyltransferases Gives Rise to the Complex Pattern of Methoxylated Flavones in Sweet Basil1[C][W][OA

    Science.gov (United States)

    Berim, Anna; Hyatt, David C.; Gang, David R.

    2012-01-01

    Polymethoxylated flavonoids occur in a number of plant families, including the Lamiaceae. To date, the metabolic pathways giving rise to the diversity of these compounds have not been studied. Analysis of our expressed sequence tag database for four sweet basil (Ocimum basilicum) lines afforded identification of candidate flavonoid O-methyltransferase genes. Recombinant proteins displayed distinct substrate preferences and product specificities that can account for all detected 7-/6-/4′-methylated, 8-unsubstituted flavones. Their biochemical specialization revealed only certain metabolic routes to be highly favorable and therefore likely in vivo. Flavonoid O-methyltransferases catalyzing 4′- and 6-O-methylations shared high identity (approximately 90%), indicating that subtle sequence changes led to functional differentiation. Structure homology modeling suggested the involvement of several amino acid residues in defining the proteins’ stringent regioselectivities. The roles of these individual residues were confirmed by site-directed mutagenesis, revealing two discrete mechanisms as a basis for the switch between 6- and 4′-O-methylation of two different substrates. These findings delineate major pathways in a large segment of the flavone metabolic network and provide a foundation for its further elucidation. PMID:22923679

  11. Ni@Ru and NiCo@Ru Core-Shell Hexagonal Nanosandwiches with a Compositionally Tunable Core and a Regioselectively Grown Shell.

    Science.gov (United States)

    Hwang, Hyeyoun; Kwon, Taehyun; Kim, Ho Young; Park, Jongsik; Oh, Aram; Kim, Byeongyoon; Baik, Hionsuck; Joo, Sang Hoon; Lee, Kwangyeol

    2018-01-01

    The development of highly active electrocatalysts is crucial for the advancement of renewable energy conversion devices. The design of core-shell nanoparticle catalysts represents a promising approach to boost catalytic activity as well as save the use of expensive precious metals. Here, a simple, one-step synthetic route is reported to prepare hexagonal nanosandwich-shaped Ni@Ru core-shell nanoparticles (Ni@Ru HNS), in which Ru shell layers are overgrown in a regioselective manner on the top and bottom, and around the center section of a hexagonal Ni nanoplate core. Notably, the synthesis can be extended to NiCo@Ru core-shell nanoparticles with tunable core compositions (Ni 3 Co x @Ru HNS). Core-shell HNS structures show superior electrocatalytic activity for the oxygen evolution reaction (OER) to a commercial RuO 2 black catalyst, with their OER activity being dependent on their core compositions. The observed trend in OER activity is correlated to the population of Ru oxide (Ru 4+ ) species, which can be modulated by the core compositions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Studies on 16α-Hydroxylation of Steroid Molecules and Regioselective Binding Mode in Homology-Modeled Cytochrome P450-2C11

    Directory of Open Access Journals (Sweden)

    Hamed I. Ali

    2011-01-01

    Full Text Available We investigated the 16α-hydroxylation of steroid molecules and regioselective binding mode in homology-modeled cytochrome P450-2C11 to correlate the biological study with the computational molecular modeling. It revealed that there was a positive relationship between the observed inhibitory potencies and the binding free energies. Docking of steroid molecules into this homology-modeled CYP2C11 indicated that 16α-hydroxylation is favored with steroidal molecules possessing the following components, (1 a bent A-B ring configuration (5β-reduced, (2 C-3 α-hydroxyl group, (3 C-17β-acetyl group, and (4 methyl group at both the C-18 and C-19. These respective steroid components requirements were defined as the inhibitory contribution factor. Overall studies of the male rat CYP2C11 metabolism revealed that the above-mentioned steroid components requirements were essential to induce an effective inhibition of [3H]progesterone 16α-hydroxylation. As far as docking of homology-modeled CYP2C11 against investigated steroids is concerned, they are docked at the active site superimposed with flurbiprofen. It was also found that the distance between heme iron and C16α-H was between 4 to 6 Å and that the related angle was in the range of 180±45∘.

  13. A Metal-Free Regioselective Multicomponent Approach for the Synthesis of Free Radical Scavenging Pyrimido-Fused Indazoles and Their Fluorescence Studies

    Directory of Open Access Journals (Sweden)

    Jeyakannu Palaniraja

    2016-11-01

    Full Text Available This study deals with a new and efficient metal-free regioselective synthesis of pyrimido-fused indazoles with nitrogen ring junction motifs. We have developed a metal-free domino type reaction between 3-aminoindazole, aryl aldehydes and aceotophenones in the presence of KOH/DMF that leads to pyrimido[1,2-b]indazole analogues. Response Surface Methodology (RSM coupled with a Box-Behnken design (BBD were utilized for exploring the effect of base used (A, temperature of reaction (B and (C, reaction time. This approach can allow access to a variety of pyrimidoindazole fluorophores and related compounds. The compound N,N-dimethyl-4-(2-phenylpyrimido[1,2-b]indazol-4-ylaniline (4e displays the maximum fluorescence intensity at 518 nm and shows a fluorescence quantum yield of 0.068. The synthesized pyramido-fused indazoles have been evaluated for their free radical scavenging activity and compound 4f showed good antioxidant activity.

  14. Regioselectively nucleus and/or side-chain fluorinated 2-(Phenanthryl)propionic acids by an effective combination of radical and organometallic chemistry.

    Science.gov (United States)

    Ricci, Giacomo; Ruzziconi, Renzo

    2005-01-21

    Regioselectively nucleus and/or side-chain fluorinated 2-(phenanthr-1-yl)- and 2-(phenanthr-2-yl)propionic acids 1-5 were prepared using phenanthren-1(2H)-ones 6a-c as key intermediates. Thus, ethyl 2-(fluorophenanthryl)propionates 11 were obtained in good yields by Reformatsky reaction of 6a-c with ethyl 2-bromopropionate followed by dehydratation and DDQ-promoted aromatization of the resulting beta-hydroxyesters. Side-chain alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 14 were obtained by bromine/lithium permutation of dihydrophenanthryl bromides 12a-c with butyllithium followed by quenching of the lithiated intermediates with methyl pyruvate or ethyl 3,3,3-trifluoropyruvate and subsequent DDQ-promoted aromatization. The alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 25 were prepared by reacting 8-bromo-1,3-difluorophenanthrene 24 with butyllithium for 10 seconds at -110 degrees C and subsequent addition of the suitable pyruvate to the lithiated intermediates. Alkyl 2-hydroxy-2-(phenanthr-2-yl)propionates 26 and 29 were suitably obtained by site-selective metalation of 1,3-difluorophenanthrene 28 and the bromophenanthrene 24, respectively, with LDA followed by quenching of the metalated intermediates with the suitable alkyl pyruvate. Fluorination of the above alpha-hydroxypropionates with DAST, followed by the alkaline hydrolysis, allowed the expected 2-(phenanthryl)propionic acids 1-5 to be obtained in satisfactory overall yields.

  15. C,N-bipyrazole receptor grafted onto a porous silica surface as a novel adsorbent based polymer hybrid.

    Science.gov (United States)

    Radi, Smaail; Attayibat, Ahmed; El-Massaoudi, Mohamed; Bacquet, Maryse; Jodeh, Shehdeh; Warad, Ismail; Al-Showiman, Salim S; Mabkhot, Yahia N

    2015-10-01

    A simple heterogeneous synthesis of pure adsorbent based polymer hybrid made by condensing a functionalized C,N-bipyrazole with a 3-glycidoxypropyl-trimethoxysilane silylant agent, previously anchored on a silica surface was developed. The formed material (SG2P) was characterized through elemental analysis, FT-IR spectroscopy, (13)C NMR of solid state, scanning electron microscope (SEM), and was studied and evaluated by determination of the surface area using the BET equation, the adsorption and desorption capability using the isotherm of nitrogen and B.J.H. pore sizes. The new material exhibits good thermal stability determined by thermogravimetry curves and good chemical stability was examined in various acidic and buffer solutions (pH 1-7). The binding and adsorption abilities of SG2P were investigated for Hg(2+), Cd(2+), Pb(2+), Zn(2+), K(+), Na(+) and Li(+) cations and compared to the results of classical liquid-liquid extraction with the unbound C,N-bipyrazole compound. The grafting at the surface of silica does not affect complexing properties of the ligand and the SG2P exhibits a high selectivity toward Hg(2+) ion with no complexation being observed towards zinc and alkali metals. The extracted and the complexing cation percentages were determined by atomic absorption measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Climatic variability and its role in regulating C, N and P retention in the James River Estuary

    Science.gov (United States)

    Bukaveckas, Paul A.; Beck, Michael; Devore, Dana; Lee, William M.

    2018-05-01

    Transformations and retention of C, N and P inputs to estuaries are subject to external factors such as discharge-driven variation in loading rates, and internal processes regulating biogeochemical cycles. We used an 8-year time series of finely resolved (monthly) mass balances for the tidal freshwater segment of the James River Estuary to assess the influence of discharge and temperature on C, N and P retention. Peak export and retention of organic, likely particulate, fractions occurred in months of highest discharge. With increasing discharge we observed higher mass retention, greater proportional retention (in relation to inputs) and more selective retention (with P retained preferentially over N and C). DIN retention was strongly influenced by water temperature with 10-fold high retention occurring at high (>20 °C) vs. low (estuaries is in dissolved inorganic form, and therefore subject to temperature dependent rates of biological assimilation and denitrification. By contrast, the bulk of the P load was in particulate form, which is retained via sediment trapping, and not appreciably affected by water temperature. The tidal freshwater estuary was an important site for nutrient removal where the accumulation of N- and P- rich materials may delay recovery in response to nutrient load reductions.

  17. Fate of nutrient enrichment on continental shelves as indicated by the C/N content of bottom sediments

    Energy Technology Data Exchange (ETDEWEB)

    Walsh, J.J.; Premuzic, E.T.; Whitledge, T.E.

    1980-01-01

    The trajectory and fate of particulate matter are poorly understood processes in a spatially heterogeneous coastal ocean. Parameterization of appropriate hydrodynamics for a quantitative description of these loss processes must thus await definition of the important biological time and space scales. Since the bottom sands tend to record the history of the water column, we have selected the C/N content of shelf sediments as a possible tracer of (1) sites of nutrient introduction to the shelf by various physical mechanisms, of (2) areas of subsequent downstream utilization by the phytoplankton, and of (3) where loss of particulate matter might occur from the water column. An analysis is made of the C/N patterns of bottom surface sediments in relation to the nitrogen sources from upwelling, river runoff, and tidal mixing on the Peruvian, west African, Amazonian, Gulf of Mexico, eastern US, Bering, and North Sea shelves in an initial attempt to proscribe the particle trajectories of organic matter on the continental shelf.

  18. Impact of partial nitritation degree and C/N ratio on simultaneous Sludge Fermentation, Denitrification and Anammox process.

    Science.gov (United States)

    Wang, Bo; Peng, Yongzhen; Guo, Yuanyuan; Yuan, Yue; Zhao, Mengyue; Wang, Shuying

    2016-11-01

    This study presents a novel process (i.e. PN/SFDA) to remove nitrogen from low C/N domestic wastewater. The process mainly involves two reactors, a pre-Sequencing Batch Reactor for partial nitritation (termed as PN-SBR) and an anoxic reactor for integrated Denitrification and Anammox with carbon sources produced from Sludge Fermentation (termed as SFDA). During long-term Runs, NO2(-)/NH4(+) ratio (i.e. NO2(-)-N/NH4(+)-N calculated by mole) in the PN-SBR effluent was gradually increased from 0.2 to 37 by extending aerobic duration, meaning that partial nitritation turning to full nitritation could be achieved. Impact of partial nitritation degree on SFDA process was investigated and the result showed that, NO2(-)/NH4(+) ratios between 2 and 10 were appropriate for the co-existence of denitrification and anammox together in the SFDA reactor, and denitrification instead of anammox contributed greater for nitrogen removal. Further batch tests indicated that anammox collaborated well with denitrification at low C/N (1.0 in this study). Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Verification of the dose in the inspection modules of Co-60 from Mexicali, B.C.N. through thermoluminescent dosimetry

    International Nuclear Information System (INIS)

    Cruz C, D.; Azorin, J.; Rivera, T.

    2005-01-01

    On the February and April 2005 months, there entered in operation two inspection modules, in the mexican border city of Mexicali. B.C.N., those which they work based on gamma rays, emitted by sources of 60 Co; this fact generate a concern, on the part of the population of this city. Soon after these events, a group of personages of the local politics, they began a campaign, in favor of closing these modules, based on the supposition, of that the emitted radiation by these sources, represents a danger for health of people that uses the international crossing located to a side of the porter lodge 1, as well as of the population in general. As service to the community border of Mexico specifically to the population of Mexicali, B.C.N. city, inhabitants of this city, municipal, state and federal authorities and, the outstanding preoccupation of the Republic Senate (Commission of Border Affairs), the National Commission of Nuclear Security and Safeguards (CNSNS) they requested the support of the Metropolitan Autonomous University (UAM) and of the National Polytechnic Institute (IPN) to verify the radiation levels in the facilities of the sources of 60 Co of the porter lodges of Mexicali-Calexico proceeding to the monitoring of this facilities in the period of 14-17 June 2005, 17 using thermoluminescent dosemeters elaborated in Mexico. (Author)

  20. Fate of nutrient enrichment on continental shelves as indicated by the C/N content of bottom sediments

    International Nuclear Information System (INIS)

    Walsh, J.J.; Premuzic, E.T.; Whitledge, T.E.

    1980-01-01

    The trajectory and fate of particulate matter are poorly understood processes in a spatially heterogeneous coastal ocean. Parameterization of appropriate hydrodynamics for a quantitative description of these loss processes must thus await definition of the important biological time and space scales. Since the bottom sands tend to record the history of the water column, we have selected the C/N content of shelf sediments as a possible tracer of (1) sites of nutrient introduction to the shelf by various physical mechanisms, of (2) areas of subsequent downstream utilization by the phytoplankton, and of (3) where loss of particulate matter might occur from the water column. An analysis is made of the C/N patterns of bottom surface sediments in relation to the nitrogen sources from upwelling, river runoff, and tidal mixing on the Peruvian, west African, Amazonian, Gulf of Mexico, eastern US, Bering, and North Sea shelves in an initial attempt to proscribe the particle trajectories of organic matter on the continental shelf

  1. Influence of the deposition geometry on the microstructure of sputter-deposited V-Al-C-N coatings

    Energy Technology Data Exchange (ETDEWEB)

    Darma, Susan; Krause, Baerbel; Doyle, Stephen; Mangold, Stefan; Baumbach, Tilo [ISS, Karlsruher Institut fuer Technologie (Germany); Ulrich, Sven; Stueber, Michael [IAM-AWP, Karlsruher Institut fuer Technologie (Germany)

    2012-07-01

    Multi-element hard coating materials such as V-Al-C-N are of great interest for many technological applications. Their mechanical properties depend on the composition and microstructure of the coating. In order to determine the optimum composition and deposition conditions of these complex materials, many samples are required. One powerful tool for reducing the number of experiments is based on the so-called combinatorial approach for thin film deposition: many different thin film samples can be realized simultaneously, exploiting the deposition gradient resulting from codeposition of several materials. We will present an X-ray diffraction study of the influence of the deposition geometry on the microstructure of V-Al-C-N coatings. The films were deposited by reactive RF magnetron sputtering from a segmented target composed of AlN and VC. Synchrotron radiation measurements where performed at the beamline PDIFF at ANKA. Significant texture changes were observed which can be attributed to the deposition geometry, as verified by calculations of the flux distribution. We conclude that codeposition can accelerate significantly the screening of new materials, under the condition that the desired property is not significantly influenced by the microstructural changes due to the deposition geometry.

  2. Integral measurement of the $^{12}$C(n,p)$^{12}$B reaction up to 10 GeV

    CERN Document Server

    Žugec, P; Bosnar, D; Ventura, A; Mengoni, A; Altstadt, S; Andrzejewski, J; Audouin, L; Barbagallo, M; Bécares, V; Bečvář, F; Belloni, F; Berthoumieux, E; Billowes, J; Boccone, V; Brugger, M; Calviani, M; Calviño, F; Cano-Ott, D; Carrapiço, C; Cerutti, F; Chiaveri, E; Chin, M; Cortés, G; Cortés-Giraldo, M.A; Cosentino, L; Diakaki, M; Domingo-Pardo, C; Dressler, R; Duran, I; Eleftheriadis, C; Ferrari, A; Finocchiaro, P; Fraval, K; Ganesan, S; García, A R; Giubrone, G; Gómez-Hornillos, M B; Gonçalves, I F; González-Romero, E; Griesmayer, E; Guerrero, C; Gunsing, F; Gurusamy, P; Heinitz, S; Jenkins, D G; Jericha, E; Käppeler, F; Karadimos, D; Kivel, N; Kokkoris, M; Krtička, M; Kroll, J; Langer, C; Lederer, C; Leeb, H; Leong, L S; Meo, S Lo; Losito, R; Manousos, A; Marganiec, J; Martínez, T; Massimi, C; Mastinu, P; Mastromarco, M; Mendoza, E; Milazzo, P M; Mingrone, F; Mirea, M; Mondalaers, W; Musumarra, A; Paradela, C; Pavlik, A; Perkowski, J; Plompen, A; Praena, J; Quesada, J; Rauscher, T; Reifarth, R; Riego, A; Roman, F; Rubbia, C; Sarmento, R; Saxena, A; Schillebeeckx, P; Schmidt, S; Schumann, D; Tagliente, G; Tain, J L; Tarrío, D; Tassan-Got, L; Tsinganis, A; Valenta, S; Vannini, G; Variale, V; Vaz, P; Versaci, R; Vermeulen, M J; Vlachoudis, V; Vlastou, R; Wallner, A; Ware, T; Weigand, M; Weiß, C; Wright, T

    2016-01-01

    The integral measurement of the $^{12}$C(n,p)$^{12}$B reaction was performed at the neutron time of flight facility n_TOF at CERN. The total number of $^{12}$B nuclei produced per neutron pulse of the n_TOF beam was determined using the activation technique in combination with a time of flight technique. The cross section is integrated over the n_TOF neutron energy spectrum from reaction threshold at 13.6 MeV to 10 GeV. Having been measured up to 1 GeV on basis of the $^{235}$U(n,f) reaction, the neutron energy spectrum above 200 MeV has been reevaluated due to the recent extension of the cross section reference for this particular reaction, which is otherwise considered a standard up to 200 MeV. The results from the dedicated GEANT4 simulations have been used to evaluate the neutron flux from 1 GeV up to 10 GeV. The experimental results related to the $^{12}$C(n,p)$^{12}$B reaction are compared with the evaluated cross sections from major libraries and with the predictions of different GEANT4 models, which m...

  3. Effects of C/N ratio on nitrate removal and floc morphology of autohydrogenotrophic bacteria in a nitrate-containing wastewater treatment process.

    Science.gov (United States)

    Nguyen, Tran Ngoc Phu; Chao, Shu-Ju; Chen, Pei-Chung; Huang, Chihpin

    2018-07-01

    The effects of C/N ratio of a nitrate-containing wastewater on nitrate removal performed by autohydrogenotrophic bacteria as well as on the morphological parameters of floc such as floc morphology, floc number distribution, mean particle size (MPS), aspect ratio and transparency were examined in this study. The results showed that the nitrate reduction rate increased with increasing C/N ratio from 0.5 to 10 and that the nitrogen removal of up to 95% was found at the C/N ratios of higher than 5 (between 0.5-10). Besides, high C/N ratio values reflected a corresponding high nitrite accumulation after 12-hr operation, and a fast decreasing rate of nitrite in the rest of operational time. The final pH values increased with the C/N ratio increasing from 0.5 to 2.5, but decreased with the C/N ratio increasing from 2.5 to 10. There were no significant changes in floc morphology with the MPSs ranging from 35 to 40μm. Small and medium-sized flocs were dominant in the sludge suspension, and the number of flocs increased with the increasing C/N ratios. Furthermore, the highest apparent frequency of 10% was observed at aspect ratios of 0.5 and 0.6, while the transparency of flocs changed from 0.1 to 0.7. Copyright © 2017. Published by Elsevier B.V.

  4. Seasonal variation in marine C:N:P stoichiometry: can the composition of seston explain stable Redfield ratios?

    Directory of Open Access Journals (Sweden)

    H. Frigstad

    2011-10-01

    Full Text Available Seston is suspended particulate organic matter, comprising a mixture of autotrophic, heterotrophic and detrital material. Despite variable proportions of these components, marine seston often exhibits relatively small deviations from the Redfield ratio (C:N:P = 106:16:1. Two time-series from the Norwegian shelf in Skagerrak are used to identify drivers of the seasonal variation in seston elemental ratios. An ordination identified water mass characteristics and bloom dynamics as the most important drivers for determining C:N, while changes in nutrient concentrations and biomass were most important for the C:P and N:P relationships. There is no standardized method for determining the functional composition of seston and the fractions of POC, PON and PP associated with phytoplankton, therefore any such information has to be obtained by indirect means. In this study, a generalized linear model was used to differentiate between the live autotrophic and non-autotrophic sestonic fractions, and for both stations the non-autotrophic fractions dominated with respective annual means of 76 and 55%. This regression model approach builds on assumptions (e.g. constant POC:Chl-a ratio and the robustness of the estimates were explored with a bootstrap analysis. In addition the autotrophic percentage calculated from the statistical model was compared with estimated phytoplankton carbon, and the two independent estimates of autotrophic percentage were comparable with similar seasonal cycles. The estimated C:nutrient ratios of live autotrophs were, in general, lower than Redfield, while the non-autotrophic C:nutrient ratios were higher than the live autotrophic ratios and above, or close to, the Redfield ratio. This is due to preferential remineralization of nutrients, and the P content mainly governed the difference between the sestonic fractions. Despite the seasonal variability in seston composition and the generally low contribution of autotrophic

  5. [Evaluation of central lymph node dissection for papillary thyroid carcinoma in cN0 T1/T2].

    Science.gov (United States)

    Zhao, S Y; Ma, Y H; Yin, Z; Zhan, X X; Cheng, R C; Qian, J

    2018-02-07

    Objective: To evaluate the application of the central lymph node dissection (CLND) for papillary thyroid carcinoma (PTC) in cN0 T1/T2. Methods: Retrospective analysis of 532 cases with PTC in cN0 T1/T2 who underwent CLND between October 2014 and September 2016 in the Department of Thyroid Surgery, the First Affiliated Hospital of the Kunming Medical University. The incidence of central lymph node (CLN) metastasis and risk factors were analyzed. Results: CLN metastasis rates: 41.2% (42/102) in males vs 34.9% (150/430) in females, P =0.252; 33.9% (116/342) in single focal carcinoma vs 40.4% (74/183) in multifocal carcinoma, P =0.157; 44.0% (125/284) in patients with 45 years old or less vs 27.0% (67/248) in patients more than 45 years old, P =0.000; 30.3% (113/373) in microcarcinoma vs 50.9% (81/159) in non-microcarcinoma, P =0.000.In unilateral lesions, ipsilateral CLN metastasis was correlated with the tumor diameter ( P =0.012), but not with the number of lesions ( P =0.653). also contralateral CLN metastasis was correlated with the tumor diameter ( P =0.000), but not with the number of lesions ( P =0.815). For the left or right unilateral single focal lesion, the tumor diameter was not correlated with the metastasis of the posterior to right recurrent laryngeal nerve central lymph nodes (LN-prRLN-CLN) ( P =0.652, P =0.088). But in bilateral multifocal carcinoma the tumor diameter was correlated with metastasis of LN-prRLN-CLN ( P =0.039). Conclusions: Prophylactic CLND is reasonable for PTC in cN0 T1/T2. A bilateral CLND should be conducted for patients with bilateral multi-focus cancer and unilateral or bilateral non-microcarcinoma, especially in patients more than 45 years old. For unilateral single focal microcarcinoma on the right, the content of CLND should be from laryngeal nerve on right center to posterior branche; for unilateral single focal microcarcinoma on the left side, the left CLND should be conducted. An ipsilateral CLND can be considered in

  6. 13C n.m.r. study of solvation mechanisms in the radiation-induced polymerization of vinyl ethers

    International Nuclear Information System (INIS)

    Deffieux, A.; Subira, F.; Stannett, V.T.

    1984-01-01

    A 13 C n.m.r. study of the microstructure of ethyl vinyl ether (EVE) and isopropyl vinyl ether (IPVE) polymers prepared under various experimental conditions and using chemical or γ-ray initiation has been made. Long stereo-sequence assignments were conducted for poly EVE allowing determination of the configurational statistics of propagation in the radiation-induced polymerization of EVE in low polar solvents. Stereo-sequence intensities are found in good agreement with the Markovian model. The results are considered as further support for the occurrence of a specific interaction between the growing active centres and the polymer chains. In the case of IPVE polymers much more important overlappings of the resonance patterns are observed thus preventing any similar detailed study. (author)

  7. 12C(n , 2 n )11C cross section from threshold to 26.5 MeV

    Science.gov (United States)

    Yuly, M.; Eckert, T.; Hartshaw, G.; Padalino, S. J.; Polsin, D. N.; Russ, M.; Simone, A. T.; Brune, C. R.; Massey, T. N.; Parker, C. E.; Fitzgerald, R.; Sangster, T. C.; Regan, S. P.

    2018-02-01

    The 12C(n ,2 n )11C cross section was measured from just below threshold to 26.5 MeV using the Pelletron accelerator at Ohio University. Monoenergetic neutrons, produced via the 3H(d ,n )4He reaction, were allowed to strike targets of polyethylene and graphite. Activation of both targets was measured by counting positron annihilations resulting from the β+ decay of 11C. Annihilation gamma rays were detected, both in coincidence and singly, using back-to-back NaI detectors. The incident neutron flux was determined indirectly via 1H(n ,p ) protons elastically scattered from the polyethylene target. Previous measurements fall into upper and lower bands; the results of the present measurement are consistent with the upper band.

  8. The 12C(n, 2n)11C cross section from threshold to 26.5 MeV.

    Science.gov (United States)

    Yuly, M; Eckert, T; Hartshaw, G; Padalino, S J; Polsin, D N; Russ, M; Simone, A T; Brune, C R; Massey, T N; Parker, C E; Fitzgerald, R; Sangster, T C; Regan, S P

    2018-02-01

    The 12 C(n, 2n) 11 C cross section was measured from just below threshold to 26.5 MeV using the Pelletron accelerator at Ohio University. Monoenergetic neutrons, produced via the 3 H(d,n) 4 He reaction, were allowed to strike targets of polyethylene and graphite. Activation of both targets was measured by counting positron annihilations resulting from the β + decay of 11 C. Annihilation gamma rays were detected, both in coincidence and singly, using back-to-back NaI detectors. The incident neutron flux was determined indirectly via 1 H(n,p) protons elastically scattered from the polyethylene target. Previous measurements fall into upper and lower bands; the results of the present measurement are consistent with the upper band.

  9. The Precipitation Products Generation Chain for the EUMETSAT Hydrological Satellite Application Facility at C.N.M.C.A.

    Science.gov (United States)

    Zauli, Francesco; Biron, Daniele; Melfi, Davide

    2009-11-01

    The EUMETSA T Satellite Application Facility in support to Hydrology (H-SAF) focuses on the development of new geophysical products on precipitation, soil moisture and snow parameters and the utilisation of these parameters in hydrological models, NWP models and water management. The development phase of the H-SAF started in September 2005 under the leadership of Italian Meteorological Service.The Centro Nazionale di Meteorologia e Climatologia Aeronautica (C.N.M.C.A.), the Italian National Weather Centre, that physically hosts the generation chain of precipitation products, developed activities to reach the final target: development of algorithms, validation of results, implementation of operative procedure to supply the service and to monitor the service performances.The paper shows the recent architectural review of H- SAF precipitation group, stressing components of operation for high sustainability, full redundancy, absolute continuity of service.

  10. C.N. Cofrentes power up-rate up to 110 %. A challenge for cycle 14 core design

    International Nuclear Information System (INIS)

    Gomez Bernal, M.I.; Lopez Carbonell, M.T.; Garcia Delgado, L.

    2001-01-01

    C.N.Cofrentes is a GE design BWR reactor with 624 bundles in the core, a rated power of 2894 MWt and it is currently operating Cycle 13 at 104.2 % power. Commercial operation started in 1984 with 12-month cycles at rated power. Both cycle length and thermal power have been increased since then. Power has been up-rated in two steps, first at 102 % in Cycle 4 and later in Cycle 11 at 104.2%. Cycle length has been extended from the original 12-month to the currently 18-month cycles. Next cycle, Cycle 14, will be an 18-month cycle operating at 110 % power. This goal is a challenge for the in-house nuclear design team. Start up for Cycle 14 is planned for the first quarter of 2002. (author)

  11. Regioselective synthesis of 7,8-dihydroimidazo[5,1-c][1,2,4]triazine-3,6(2H,4H-dione derivatives: A new drug-like heterocyclic scaffold

    Directory of Open Access Journals (Sweden)

    Nikolay T. Tzvetkov

    2012-09-01

    Full Text Available Dihydroimidazo[5,1-c][1,2,4]triazine-3,6(2H,4H-dione derivatives were prepared by successive N3- and N1-alkylation of hydantoins, followed by regioselective thionation and subsequent cyclization under mild conditions. In a final alkylation step a further substituent may be introduced. The synthetic strategy allows broad structural variation of this new drug-like heterobicyclic scaffold. In addition to extensive NMR and MS analyses, the structure of one derivative was confirmed by X-ray crystallography.

  12. Gold(III) chloride catalyzed regioselective synthesis of pyrano[3,4-b]indol-1(9H)-ones and evaluation of anticancer potential towards human cervix adenocarcinoma.

    Science.gov (United States)

    Praveen, Chandrasekaran; Ayyanar, Asairajan; Perumal, Paramasivan Thirumalai

    2011-07-15

    A highly regioselective synthesis of pyrano[3,4-b]indol-1(9H)-ones via gold(III) chloride catalyzed cycloisomerization of 3-ethynyl-indole-2-carboxylic acid was achieved in good to excellent yields. These compounds were screened for their in vitro cytotoxicity against human cervical (HeLa) cell lines. Out of ten compounds, three compounds (7d, 7e and 7j) showed comparable proliferation inhibitory activity against the standard drug cisplatin. Compound 7d was found to be the most efficacious with IC(50) value of 0.22μM. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Synthesis and characterization of Ti-Si-C-N nanocomposite coatings prepared by a filtered vacuum arc method

    Energy Technology Data Exchange (ETDEWEB)

    Thangavel, Elangovan, E-mail: t.elangophy@gmail.com [Advanced Thin Film Research Group, Materials Processing Division, Korea Institute of Materials Science, Changwon 641-831 (Korea, Republic of); Center for Nano-Wear, Yonsei University, Seoul 120-749 (Korea, Republic of); Lee, Seunghun; Nam, Kee-Seok; Kim, Jong-Kuk [Advanced Thin Film Research Group, Materials Processing Division, Korea Institute of Materials Science, Changwon 641-831 (Korea, Republic of); Kim, Do-Geun, E-mail: dogeunkim@kims.re.kr [Advanced Thin Film Research Group, Materials Processing Division, Korea Institute of Materials Science, Changwon 641-831 (Korea, Republic of)

    2013-01-15

    Highlights: Black-Right-Pointing-Pointer Preparation method was used as filtered vacuum arc (FVA) deposition. Black-Right-Pointing-Pointer Ternary coating obtained by using single carbon source with TMS gas. Black-Right-Pointing-Pointer Detailed discussion of chemical nature for these coating by using XPS. - Abstract: Ti-Si-C-N nanocomposite coatings were synthesized by a filtered vacuum arc (FVA) technique. A metal organic precursor, tetramethylsilane (TMS), was used as a source for silicon and carbon to deposit the Ti-Si-C-N nanocomposite coating with a Ti cathode source. The chemical and microstructural properties of the as-deposited coatings were systematically investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Nanoindentation and scratch tests were carried out to evaluate the mechanical and adhesion properties of the coatings. From the XPS analysis, it was found that the Si content in the coating increased from 2 to 16 at.% as the TMS flow rate was increased from 5 to 20 sccm. The TEM analysis clearly demonstrated that the coatings were composed of crystalline TiCN along with amorphous Si{sub 3}N{sub 4} as a secondary phase. From the XRD results, it was found that the crystallite size of TiCN increased with increasing Si content. The microstructure and mechanical properties of the TiSiCN coatings prepared by this method exhibited strong dependencies on the silicon content. A maximum hardness of 49 GPa and a coefficient of friction of 0.17 were obtained for the film with a silicon content of 3 at.%.

  14. Theoretical study of the regioselectivity of the interaction of 3-methyl-4-pyrimidone and 1-methyl-2-pyrimidone with Lewis acids.

    Science.gov (United States)

    Kasende, Okuma Emile; Muya, Jules Tshishimbi; Broeckaert, Lies; Maes, Guido; Geerlings, Paul

    2012-08-23

    A density functional theory (DFT) study is performed to determine the stability of the complexes formed between either the N or O site of 3-methyl-4-pyrimidone and 1-methyl-2-pyrimidone molecules and different ligands. The studied ligands are boron and alkali Lewis acids, namely, B(CH(3))(3), HB(CH(3))(2), H(2)B(CH(3)), BH(3), H(2)BF, HBF(2), BF(3), Li(+), Na(+), and K(+). The acids are divided into two groups according to their hardness. The reactivity predictions, according to the molecular electrostatic potential (MEP) map and the natural bond orbital (NBO) analysis, are in agreement with the calculated relative stabilities. Our findings reveal a strong regioselectivity with borane and its derivatives preferring the nitrogen site in both pyrimidone isomers, while a preference for oxygen is observed for the alkali acids in the 3-methyl-4-pyrimidone molecule. The complexation of 1-methyl-2-pyrimidone with these hard alkali acids does not show any discrimination between the two sites due to the presence of a continuous delocalized density region between the nitrogen and the oxygen atoms. The preference of boron Lewis acids toward the N site is due to the stronger B-N bond as compared to the B-O bond. The influence of fluorine or methyl substitution on the boron atom is discussed through natural orbital analysis (NBO) concentrating on the overlap of the boron empty p-orbital with the F lone pairs and methyl hyperconjugation, respectively. The electrophilicity of the boron acids gives a good overall picture of the interaction capabilities with the Lewis base.

  15. Regioselective biooxidation of (+-valencene by recombinant E. coli expressing CYP109B1 from Bacillus subtilis in a two-liquid-phase system

    Directory of Open Access Journals (Sweden)

    Schmid Rolf D

    2009-07-01

    Full Text Available Abstract Background (+-Nootkatone (4 is a high added-value compound found in grapefruit juice. Allylic oxidation of the sesquiterpene (+-valencene (1 provides an attractive route to this sought-after flavoring. So far, chemical methods to produce (+-nootkatone (4 from (+-valencene (1 involve unsafe toxic compounds, whereas several biotechnological approaches applied yield large amounts of undesirable byproducts. In the present work 125 cytochrome P450 enzymes from bacteria were tested for regioselective oxidation of (+-valencene (1 at allylic C2-position to produce (+-nootkatone (4 via cis- (2 or trans-nootkatol (3. The P450 activity was supported by the co-expression of putidaredoxin reductase (PdR and putidaredoxin (Pdx from Pseudomonas putida in Escherichia coli. Results Addressing the whole-cell system, the cytochrome CYP109B1 from Bacillus subtilis was found to catalyze the oxidation of (+-valencene (1 yielding nootkatol (2 and 3 and (+-nootkatone (4. However, when the in vivo biooxidation of (+-valencene (1 with CYP109B1 was carried out in an aqueous milieu, a number of undesired multi-oxygenated products has also been observed accounting for approximately 35% of the total product. The formation of these byproducts was significantly reduced when aqueous-organic two-liquid-phase systems with four water immiscible organic solvents – isooctane, n-octane, dodecane or hexadecane – were set up, resulting in accumulation of nootkatol (2 and 3 and (+-nootkatone (4 of up to 97% of the total product. The best productivity of 120 mg l-1 of desired products was achieved within 8 h in the system comprising 10% dodecane. Conclusion This study demonstrates that the identification of new P450s capable of producing valuable compounds can basically be achieved by screening of recombinant P450 libraries. The biphasic reaction system described in this work presents an attractive way for the production of (+-nootkatone (4, as it is safe and can easily be

  16. Regioselective biooxidation of (+)-valencene by recombinant E. coli expressing CYP109B1 from Bacillus subtilis in a two-liquid-phase system.

    Science.gov (United States)

    Girhard, Marco; Machida, Kazuhiro; Itoh, Masashi; Schmid, Rolf D; Arisawa, Akira; Urlacher, Vlada B

    2009-07-10

    (+)-Nootkatone (4) is a high added-value compound found in grapefruit juice. Allylic oxidation of the sesquiterpene (+)-valencene (1) provides an attractive route to this sought-after flavoring. So far, chemical methods to produce (+)-nootkatone (4) from (+)-valencene (1) involve unsafe toxic compounds, whereas several biotechnological approaches applied yield large amounts of undesirable byproducts. In the present work 125 cytochrome P450 enzymes from bacteria were tested for regioselective oxidation of (+)-valencene (1) at allylic C2-position to produce (+)-nootkatone (4) via cis- (2) or trans-nootkatol (3). The P450 activity was supported by the co-expression of putidaredoxin reductase (PdR) and putidaredoxin (Pdx) from Pseudomonas putida in Escherichia coli. Addressing the whole-cell system, the cytochrome CYP109B1 from Bacillus subtilis was found to catalyze the oxidation of (+)-valencene (1) yielding nootkatol (2 and 3) and (+)-nootkatone (4). However, when the in vivo biooxidation of (+)-valencene (1) with CYP109B1 was carried out in an aqueous milieu, a number of undesired multi-oxygenated products has also been observed accounting for approximately 35% of the total product. The formation of these byproducts was significantly reduced when aqueous-organic two-liquid-phase systems with four water immiscible organic solvents - isooctane, n-octane, dodecane or hexadecane - were set up, resulting in accumulation of nootkatol (2 and 3) and (+)-nootkatone (4) of up to 97% of the total product. The best productivity of 120 mg l-1 of desired products was achieved within 8 h in the system comprising 10% dodecane. This study demonstrates that the identification of new P450s capable of producing valuable compounds can basically be achieved by screening of recombinant P450 libraries. The biphasic reaction system described in this work presents an attractive way for the production of (+)-nootkatone (4), as it is safe and can easily be controlled and scaled up.

  17. Biochemical Characterization and Structural Basis of Reactivity and Regioselectivity Differences between Burkholderia thailandensis and Burkholderia glumae 1,6-Didesmethyltoxoflavin N-Methyltransferase.

    Science.gov (United States)

    Fenwick, Michael K; Almabruk, Khaled H; Ealick, Steven E; Begley, Tadhg P; Philmus, Benjamin

    2017-08-01

    Burkholderia glumae converts the guanine base of guanosine triphosphate into an azapteridine and methylates both the pyrimidine and triazine rings to make toxoflavin. Strains of Burkholderia thailandensis and Burkholderia pseudomallei have a gene cluster encoding seven putative biosynthetic enzymes that resembles the toxoflavin gene cluster. Four of the enzymes are similar in sequence to BgToxBCDE, which have been proposed to make 1,6-didesmethyltoxoflavin (1,6-DDMT). One of the remaining enzymes, BthII1283 in B. thailandensis E264, is a predicted S-adenosylmethionine (SAM)-dependent N-methyltransferase that shows a low level of sequence identity to BgToxA, which sequentially methylates N6 and N1 of 1,6-DDMT to form toxoflavin. Here we show that, unlike BgToxA, BthII1283 catalyzes a single methyl transfer to N1 of 1,6-DDMT in vitro. In addition, we investigated the differences in reactivity and regioselectivity by determining crystal structures of BthII1283 with bound S-adenosylhomocysteine (SAH) or 1,6-DDMT and SAH. BthII1283 contains a class I methyltransferase fold and three unique extensions used for 1,6-DDMT recognition. The active site structure suggests that 1,6-DDMT is bound in a reduced form. The plane of the azapteridine ring system is orthogonal to its orientation in BgToxA. In BthII1283, the modeled SAM methyl group is directed toward the p orbital of N1, whereas in BgToxA, it is first directed toward an sp 2 orbital of N6 and then toward an sp 2 orbital of N1 after planar rotation of the azapteridine ring system. Furthermore, in BthII1283, N1 is hydrogen bonded to a histidine residue whereas BgToxA does not supply an obvious basic residue for either N6 or N1 methylation.

  18. Fretting wear behaviour of TiC/Ti(C,N)/TiN multi-layer coatings at elevated temperature in gross slip regime

    International Nuclear Information System (INIS)

    Liu Hanwei; Huang Kunpeng; Zhu Minhao; Zhou Zhongrong

    2005-01-01

    Tic/Ti(C,N)/TiN multi-layer coatings are prepared on the 1Cr13 stainless steel substrate by the technique of Chemical Vapour Deposition, and the fretting wear behaviour of 1Cr13 stainless steel and TiC/Ti(C,N)/TiN coatings are investigated and studied controversially from 25 degree C to 400 degree C in the gross slip regime. It shows that the temperature has great influence on the fretting wear in the gross slip regime for the 1Cr13 stainless steel but little for Ti/C/Ti(C,N)/TiN multi-layer coatings. With the temperature increasing, the friction coefficient and the wear volume of the 1Cr13 alloy decreases and the wear volume of TiC/Ti(C, N)/TiN multi-layer coatings is invariant. TiC/Ti(C,N)/TiN multi-layer coatings have better wear-resistant capability than the 1Cr13 stainless steel, but the wear volume of the substrate increases greatly because of the grain-abrasion resulted from hard debris when TiC/Ti(C,N)/TiN multi-layer coatings are ground off. (authors)

  19. Recent Advances in Recoverable Systems for the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction (CuAAC

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli

    2016-09-01

    Full Text Available The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition reaction between organic azides and alkynes (CuAAC have stimulated an impressive number of reports, in the last years, focusing on recoverable variants of the homogeneous or quasi-homogeneous catalysts. Recent advances in the field are reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports.

  20. Development of Copper-Catalyzed Electrophilic Trifluoromethylation and Exploiting Cu/Cu2O Nanowires with Novel Catalytic Reactivity

    KAUST Repository

    Li, Huaifeng

    2014-01-01

    pharmaceuticals and agrochemicals contain fluorine substituents (-F) or trifluoromethyl groups (-CF3) because these moieties often result in profound changes of their physical, chemical, and biological properties, such as metabolic stability and lipophilicity

  1. Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides

    KAUST Repository

    Srimontree, Watchara

    2017-06-05

    A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

  2. Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides.

    Science.gov (United States)

    Srimontree, Watchara; Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Rueping, Magnus

    2017-06-16

    A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

  3. Cooperative effect of silver in copper-catalyzed trifluoromethylation of aryl iodides using Me3SiCF3

    KAUST Repository

    Weng, Zhiqiang

    2011-06-13

    An effective model of cooperative effect of silver for the coppercatalyzed trifluoromethylation of activated and unactivated aryl iodides to trifluoromethylated arenes using Me3SiCF3 was achieved with a broad substrate scope. © 2011 American Chemical Society.

  4. Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides

    KAUST Repository

    Srimontree, Watchara; Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Rueping, Magnus

    2017-01-01

    A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

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

    Science.gov (United States)

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

    2013-08-21

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

  6. Continuous metal scavenging and coupling to one-pot copper-catalyzed azide-alkyne cycloaddition click reaction in flow

    NARCIS (Netherlands)

    Vural - Gursel, Dr. Iris; Aldiansyah, Ferry; Wang, Qi; Noël, Timothy; Hessel, Volker

    2015-01-01

    Increasing usage of catalytic chemistry calls for efficient removal of metal traces. This paper describes the development and optimization of a scavenger-based extraction in flow to remove metal catalysts. It enables liquid-liquid extraction with slug flow and phase separation with a porous

  7. Variation in the C/N-quotient of peat in relation to decomposition rate and age determination with 210Pb

    International Nuclear Information System (INIS)

    Malmer, N.; Holm, E.

    1984-01-01

    Peat profiles ca. 0.5 m in depth through bog hummocks with Sphagnum spp. have been studied on a subarctic mire in northern Sweden and on some bogs in southern Sweden. The C/N-quotient in the peat decreases with depth due to losses in C during the decay processes. As a result of decay and compaction, the annual peat volume increment at the bottom of the profiles is 4-15% of the increment in the upper parts. On the central bog areas in southern Sweden the decay processes during periods are interrupted at earlier stages which gives rise to a more rapid volumetric peat increment than in the marginal bog areas and in the north. Datings from 210 Pb activity have proved to be reliable only in the lower parts of the profiles (age>50 yr) as lead might be mobile in the upper parts. At the deposition in the catotelm layer after a period of at least 150 yr the organic matter has lost up to 80% of its original carbon. The accumulation of 210 Pb and N shows that the supply of these elements is higher in southern Sweden than in the north. (author)

  8. Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis.

    Science.gov (United States)

    Horwitz, Rael; Borell, Esther M; Yam, Ruth; Shemesh, Aldo; Fine, Maoz

    2015-03-05

    Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. δ(13)C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significantly lighter with increasing seawater pCO2. Together with a decrease in the difference between δ(13)C values of both fractions at the higher pCO2 sites, these results indicate there is a greater net autotrophic input to the A. viridis carbon budget under high pCO2 conditions. δ(15)N values and C/N ratios did not change in Symbiodinium and host tissue along the pCO2 gradient. Additional physiological parameters revealed anemone protein and Symbiodinium chlorophyll a remained unaltered among sites. Symbiodinium density was similar among sites yet their mitotic index increased in anemones under elevated pCO2. Overall, our findings show that A. viridis is characterized by a higher autotrophic/heterotrophic ratio as pCO2 increases. The unique trophic flexibility of this species may give it a competitive advantage and enable its potential acclimation and ecological success in the future under increased ocean acidification.

  9. A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation.

    Science.gov (United States)

    Li, Cheng-An; Ji, Wei; Qu, Jian; Jing, Su; Gao, Fei; Zhu, Dun-Ru

    2018-05-22

    The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.

  10. Effect of TaC addition on the microstructures and mechanical properties of Ti(C, N)-based cermets

    International Nuclear Information System (INIS)

    Wu, Peng; Zheng, Yong; Zhao, Yongle; Yu, Haizhou

    2010-01-01

    The microstructures of the prepared Ti(C, N)-based cermets with various TaC additions were studied using X-ray diffractometry (XRD) and scanning electron microscopy (SEM). Mechanical properties such as transverse rupture strength (TRS), fracture toughness (K 1C ) and hardness (HRA) were also measured. The results showed that the grain size of the cermets decreased with increasing TaC addition, but too high TaC addition resulted in agglomeration of the grains. An increasing TaC addition increased the dissolution of tungsten, titanium, molybdenum and tantalum in the binder phase. The hardness of the cermets decreased slightly with increasing TaC addition. The transverse rupture strength was the highest for the cermets with 5 wt.% TaC addition, which was characterized by fine grains, homogeneous microstructure and the moderate thickness of rim phase in the binder. The fracture toughness of the cermets with TaC addition from 0 to 5 wt.% decreased obviously, which resulting from decreased grain size. The further decreasing of fracture toughness for the cermets with 7 wt.% TaC addition was due to increased porosity and interfacial tensile stress.

  11. Influence of C, N and Ti concentration on the intergranular corrosion resistance of AISI 316 Ti stainless steel

    International Nuclear Information System (INIS)

    Pardo, A.; Merino, M.C.; Carboneras, M.; Coy, A.E.; Viejo, F.; Arrabal, R.; Munoz, J.A.

    2004-01-01

    The influence of Ti, C, and N concentration on the intergranular corrosion resistance of AISI 316 Ti stainless steel has been studied. A kinetic study of the corrosion process has been carried out using gravimetric tests according to ASTM A-262 practices B and C (Streicher and Huey, respectively). The TTS diagrams were drawn as a function of alloying elements concentration (C, N and Ti). Materials characterization under several test conditions was carried out using Scanning Electron Microscopy (SEM) analysing microstructural characteristics and the attack microstructure. The chemical resistance of these steels to intergranular test was function of N, C and Ti concentration. High Ti and N concentration favoured the precipitation of TiN during the material manufacture process. N forms TiN very stable, causing the removal of Ti from the matrix and, indirectly, favouring the Cr 23 C 6 precipitation during the sensitization process and increasing the corrosion rate. In order to inhibit the intergranular corrosion in these materials the N and Ti concentrations must be optimised. (authors)

  12. Influence of C, N and Ti concentration on the intergranular corrosion resistance of AISI 316 Ti stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Pardo, A.; Merino, M.C.; Carboneras, M.; Coy, A.E.; Viejo, F.; Arrabal, R.; Munoz, J.A. [Departamento de Ciencia de Materiales, Facultad de Quimica, Universidad Complutense, 28040, Madrid (Spain)

    2004-07-01

    The influence of Ti, C, and N concentration on the intergranular corrosion resistance of AISI 316 Ti stainless steel has been studied. A kinetic study of the corrosion process has been carried out using gravimetric tests according to ASTM A-262 practices B and C (Streicher and Huey, respectively). The TTS diagrams were drawn as a function of alloying elements concentration (C, N and Ti). Materials characterization under several test conditions was carried out using Scanning Electron Microscopy (SEM) analysing microstructural characteristics and the attack microstructure. The chemical resistance of these steels to intergranular test was function of N, C and Ti concentration. High Ti and N concentration favoured the precipitation of TiN during the material manufacture process. N forms TiN very stable, causing the removal of Ti from the matrix and, indirectly, favouring the Cr{sub 23}C{sub 6} precipitation during the sensitization process and increasing the corrosion rate. In order to inhibit the intergranular corrosion in these materials the N and Ti concentrations must be optimised. (authors)

  13. Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds.

    Science.gov (United States)

    Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric

    2015-05-13

    Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

  14. Macroinvertebrate diet in intertidal seagrass and sandflat communities : a study using C, N, and S stable isotopes

    International Nuclear Information System (INIS)

    Leduc, D.; Probert, P.K.; Frew, R.D.; Hurd, C.L.

    2006-01-01

    Most seagrass community food-web studies using stable isotopes have been carried out in subtidal habitats during one sampling event. We used C, N, and S stable isotopes to characterise the diet of the dominant macroinvertebrates found in intertidal Zostera capricorni and sandflat communities of southern New Zealand in late summer and winter. The range of δ 13 C and δ 34 S values for Z. capricorni was wide (>5 permille), which highlights the importance of accounting for spatial and temporal variability in primary producer isotopic signatures. The range of δ 15 N values for Z. capricorni was comparatively small ( 13 C and δ 15 N signatures suggested that Z. capricorni was a potentially important contributor (24-99%) to the diet of most consumers sampled at the seagrass site, whereas microphytobenthos dominated the diet of the same consumers at the sandflat site. The main exception was the bivalve Austrovenus stutchburyi, which had a diet consisting mostly (up to 85%) of Ulva and Polysiphonia spp. at both sites. S isotopes proved to be of limited use owing to the difficulty of sampling microphytobenthos and to potential non-dietary sources of 34 S-depleted sulfur to consumers. Mixing models also suggested that Z. capricorni contributed more to the diet of deposit feeders in August (late winter) than in March (late summer). (author). 75 refs., 3 figs., 3 tabs

  15. Aluminium EN AW-2124 alloy matrix composites reinforced with Ti(C,N), BN and Al2O3 particles

    International Nuclear Information System (INIS)

    Dobrzanski, L.A.; Wlodarczyk, A.; Adamiak, M.

    2003-01-01

    Investigation results of the aluminium alloy EN AW-2124 matrix composite materials with particles of the powders Ti(C,N), BN and Al 2 O 3 (15 wt.%) are presented in the paper. In order to obtain uniform distribution of reinforcement particles in aluminium alloy matrix powders of composite components have been milled in the rotary ball-bearing pulverizer. The composites have been pressed in laboratory vertical press at room temperature under the pressure of 500 kN. Obtained die samplings have been heated to the temperature 520-550 o C and extruded. Bars of diameter 8 mm have been received as a final product. Metallographic examination of the composites materials' structure shows non-uniform distribution of reinforced powders in the aluminium alloy matrix banding of reinforcements particles corresponds to the extrusion direction. Particles of reinforcement distribution in aluminium alloy matrix is irregular, some agglomerations of powder of aluminium oxide and porosity of different size have been noticed. Investigations of hardness and ultimate compressive strength show that the particles of reinforcement improve mechanical properties of composite materials. Investigations of compressive strength, carried out at room temperature, enable to compare mechanical properties of matrix and composite. (author)

  16. Facile preparation of C, N co-modified Nb2O5 nanoneedles with enhanced visible light photocatalytic activity

    KAUST Repository

    Xue, Jiao

    2016-09-28

    C, N co-modified niobium pentoxide (Nb2O5) nanoneedles have been successfully synthesized via a facile hydrothermal method with Niobium Chloride (NbCl5) as a precursor and triethylamine as both the carbon and nitrogen source. The formation process of Nb2O5 nanoneedles has been presented in detail by investigating the effect of the crystallization temperature, the amount of triethylamine and the calcination temperature. The as-prepared Nb2O5 nanoneedles exhibit more efficient photocatalytic activity than commercial Degussa P25 and commercial Nb2O5 towards photodegradation of Rhodamine B (RhB) at a concentration of 10 mg L−1 under visible light. Special chemical species, such as carbonate species and NOX species, that exist on the surface of the as-prepared catalyst could extend the absorption into the visible region and thus enhance the photocatalytic activity of the Nb2O5 nanoneedles. At the same time, the obtained Nb2O5 nanoneedles exhibit excellent stability even after three successive cycles. A possible photodegradation mechanism was proposed and the corresponding photodecomposition process of RhB over the Nb2O5 nanoneedles was elucidated by a reactive species trapping experiment, suggesting that h+ and O2˙− play a major role in the photodegradation of RhB in aqueous solution.

  17. Thermodynamic investigations of the Mn-Ni-C-N quarternary alloys by solid-state galvanic cell technique

    International Nuclear Information System (INIS)

    Teng Lidong; Aune, Ragnhild; Seetharaman, Seshadri

    2005-01-01

    In view of the important applications of carbides and nitrides of transition metals in the hard materials industries, the thermodynamic activities of manganese in Mn-Ni-C-N alloys have been studied by solid-state galvanic cell technique with CaF 2 as the solid electrolyte. The phase compositions and microstructure of various alloys have been analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Nitrogen was introduced into the alloy by equilibrating with N 2 gas. It was established during the experiments that the solubility of nitrogen in the alloys was affected by the carbon content. A (Mn,Ni) 4 (N,C) nitride was formed during the nitriding procedure in the alloys. The electromotive force (EMF) measurements were carried out in the temperature range 940-1127 K in order to determine the activities of Mn in the alloys. The activities of manganese were calculated and compared with those of the corresponding Mn-Ni-C ternary alloys

  18. Effects of C/N ratio on nitrous oxide production from nitrification in a laboratory-scale biological aerated filter reactor.

    Science.gov (United States)

    He, Qiang; Zhu, Yinying; Fan, Leilei; Ai, Hainan; Huangfu, Xiaoliu; Chen, Mei

    2017-03-01

    Emission of nitrous oxide (N 2 O) during biological wastewater treatment is of growing concern. This paper reports findings of the effects of carbon/nitrogen (C/N) ratio on N 2 O production rates in a laboratory-scale biological aerated filter (BAF) reactor, focusing on the biofilm during nitrification. Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and microelectrode technology were utilized to evaluate the mechanisms associated with N 2 O production during wastewater treatment using BAF. Results indicated that the ability of N 2 O emission in biofilm at C/N ratio of 2 was much stronger than at C/N ratios of 5 and 8. PCR-DGGE analysis showed that the microbial community structures differed completely after the acclimatization at tested C/N ratios (i.e., 2, 5, and 8). Measurements of critical parameters including dissolved oxygen, oxidation reduction potential, NH 4 + -N, NO 3 - -N, and NO 2 - -N also demonstrated that the internal micro-environment of the biofilm benefit N 2 O production. DNA analysis showed that Proteobacteria comprised the majority of the bacteria, which might mainly result in N 2 O emission. Based on these results, C/N ratio is one of the parameters that play an important role in the N 2 O emission from the BAF reactors during nitrification.

  19. Determination of the enthalpy of vaporization and prediction of surface tension for ionic liquid 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6).

    Science.gov (United States)

    Tong, Jing; Yang, Hong-Xu; Liu, Ru-Jing; Li, Chi; Xia, Li-Xin; Yang, Jia-Zhen

    2014-11-13

    With the use of isothermogravimetrical analysis, the enthalpies of vaporization, Δ(g)lH(o)m(T(av)), at the average temperature, T(av) = 445.65 K, for the ionic liquids (ILs) 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6) were determined. Using Verevkin's method, the difference of heat capacities between the vapor phase and the liquid phase, Δ(g)lC(p)(o)m, for [C(n)mim][Pro](n = 2, 3, 4, 5, 6), were calculated based on the statistical thermodynamics. Therefore, with the use of Δ(g)lC(p)(o)m, the values of Δ(g)lH(o)m(T(av)) were transformed into Δ(g)lH(o)m(298), 126.8, 130.3, and 136.5 for [C(n)mim][Pro](n = 4, 5, 6), respectively. In terms of the new scale of polarity for ILs, the order of the polarity of [C(n)mim][Pro](n = 2, 3, 4, 5, 6) was predicted, that is, the polarity decreases with increasing methylene. A new model of the relationship between the surface tension and the enthalpy of vaporization for aprotic ILs was put forward and used to predict the surface tension for [C(n)mim][Pro](n = 2, 3, 4, 5, 6) and others. The predicted surface tension for the ILs is in good agreement with the experimental one.

  20. Effects of carbohydrate source for maintaining a high C:N ratio and fish driven re-suspension on pond ecology and production in periphyton-based freshwater prawn culture systems

    NARCIS (Netherlands)

    Asaduzzaman, M.; Wahab, M.A.; Verdegem, M.C.J.; Adhikary, R.K.; Rahman, S.M.S.; Azim, M.E.; Verreth, J.A.J.

    2010-01-01

    The present research investigated the effect of carbohydrate (CH) source for maintaining a high C:N ratio, and tilapia driven bioturbation on pond ecology, production and economical performances in C/N controlled periphyton-based (C/N-CP) freshwater prawn ponds. Two carbohydrate sources (high-cost

  1. Regioselective Sequential Modification of Chitosan via Azide-Alkyne Click Reaction: Synthesis, Characterization, and Antimicrobial Activity of Chitosan Derivatives and Nanoparticles

    Science.gov (United States)

    Sarwar, Atif; Katas, Haliza; Samsudin, Siti Noradila; Zin, Noraziah Mohamad

    2015-01-01

    Recently, the attention of researchers has been drawn toward the synthesis of chitosan derivatives and their nanoparticles with enhanced antimicrobial activities. In this study, chitosan derivatives with different azides and alkyne groups were synthesized using click chemistry, and these were further transformed into nanoparticles by using the ionotropic gelation method. A series of chitosan derivatives was successfully synthesized by regioselective modification of chitosan via an azide-alkyne click reaction. The amino moieties of chitosan were protected during derivatization by pthaloylation and subsequently unblocked at the end to restore their functionality. Nanoparticles of synthesized derivatives were fabricated by ionic gelation to form complexes of polyanionic penta-sodium tripolyphosphate (TPP) and cationic chitosan derivatives. Particle size analysis showed that nanoparticle size ranged from 181.03 ± 12.73 nm to 236.50 ± 14.32 nm and had narrow polydispersity index and positive surface charge. The derivatives and corresponding nanoparticles were evaluated in vitro for antibacterial and antifungal activities against three gram-positive and gram-negative bacteria and three fungal strains, respectively. The minimum inhibitory concentration (MIC) of all derivatives ranged from 31.3 to 250 µg/mL for bacteria and 188 to1500 µg/mL for fungi and was lower than that of native chitosan. The nanoparticles with MIC ranging from 1.56 to 25 µg/mLfor bacteria and 94 to 750 µg/mL for fungi exhibited higher activity than the chitosan derivatives. Chitosan O-(1-methylbenzene) triazolyl carbamate and chitosan O-(1-methyl phenyl sulfide) triazolyl carbamate were the most active against the tested bacterial and fungal strains. The hemolytic assay on erythrocytes and cell viability test on two different cell lines (Chinese hamster lung fibroblast cells V79 and Human hepatic cell line WRL68) demonstrated the safety; suggesting that these derivatives could be used in future

  2. Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

    Science.gov (United States)

    Schimmelmann, A.; Mastalerz, Maria; Gao, L.; Sauer, P.E.; Topalov, K.

    2009-01-01

    Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ??13Ckerogen vs. ??15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back

  3. Formation of halogenated C-, N-DBPs from chlor(am)ination and UV irradiation of tyrosine in drinking water

    International Nuclear Information System (INIS)

    Chu Wenhai; Gao Naiyun; Krasner, Stuart W.; Templeton, Michael R.; Yin Daqiang

    2012-01-01

    The formation of regulated and emerging halogenated carbonaceous (C-) and nitrogenous disinfection by-products (N-DBPs) from the chlor(am)ination and UV irradiation of tyrosine (Tyr) was investigated. Increased chlorine contact time and/or Cl 2 /Tyr ratio increased the formation of most C-DBPs, with the exception of 4-chlorophenol, dichloroacetonitrile, and dichloroacetamideChloroform and dichloroacetic acid increased with increasing pH, dichloroacetonitrile first increased and then decreased, and other DBPs had maximum yields at pH 7 or 8. The addition of ammonia significantly reduced the formation of most C-DBPs but increased 4-chlorophenol, dichloroacetonitrile, dichloroacetamide, and trichloroacetonitrile yields for short prechlorination contact times before dosing ammonia. When UV irradiation and chlorination were performed simultaneously, the concentrations of the relatively stable C-DBPs increased, and the concentrations of dichloroacetonitrile, dichloroacetamide, and 4-chlorophenol decreased with increasing UV dose. This information was used to develop a mechanistic model for the formation of intermediate DBPs and end products from the interaction of disinfectants with tyrosine. Highlights: ► Increased contact time and/or Cl 2 /Tyr decreased the formation of some N-DBPs. ► Changing the pH of disinfection decreases the formation of some N-DBPs. ► N-DBP yields increased for short prechlorination contact time before dosing ammonia. ► Low pressure UV before chlorination did not impact the formation of DBPs from Tyr. ► A novel integrated formation pathway of halogenated C-, N-DBPs is proposed. - Exploring the integrated formation mechanism of regulated and emerging highly toxic DBPs, which is expected to preferably reduce their occurrence in drinking water.

  4. A generic individual-based model to simulate morphogenesis, C-N acquisition and population dynamics in contrasting forage legumes.

    Science.gov (United States)

    Louarn, Gaëtan; Faverjon, Lucas

    2018-04-18

    Individual-based models (IBMs) are promising tools to disentangle plant interactions in multi-species grasslands and foster innovative species mixtures. This study describes an IBM dealing with the morphogenesis, growth and C-N acquisition of forage legumes that integrates plastic responses from functional-structural plant models. A generic model was developed to account for herbaceous legume species with contrasting above- and below-ground morphogenetic syndromes and to integrate the responses of plants to light, water and N. Through coupling with a radiative transfer model and a three-dimensional virtual soil, the model allows dynamic resolution of competition for multiple resources at individual plant level within a plant community. The behaviour of the model was assessed on a range of monospecific stands grown along gradients of light, water and N availability. The model proved able to capture the diversity of morphologies encountered among the forage legumes. The main density-dependent features known about even-age plant populations were correctly anticipated. The model predicted (1) the 'reciprocal yield' law relating average plant mass to density, (2) a self-thinning pattern close to that measured for herbaceous species and (3) consistent changes in the size structure of plant populations with time and pedo-climatic conditions. In addition, plastic changes in the partitioning of dry matter, the N acquisition mode and in the architecture of shoots and roots emerged from the integration of plant responses to their local environment. This resulted in taller plants and thinner roots when competition was dominated by light, and shorter plants with relatively more developed root systems when competition was dominated by soil resources. A population dynamic model considering growth and morphogenesis responses to multiple resources heterogeneously distributed in the environment was presented. It should allow scaling plant-plant interactions from individual to

  5. Visible light-responded C, N and S co-doped anatase TiO{sub 2} for photocatalytic reduction of Cr(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Lei, X.F., E-mail: leixuefei69@163.com [School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004 (China); Institute of Metallurgical Resource and Environmental Engineering, Northeastern University, Shenyang 110819 (China); Liaoning Key Laboratory of Metallurgical Resource Recycling Science, Shenyang 110819 (China); Liaoning Engineering and Technology Research Center of Boron Resource, Comprehensive, Utilization, Shenyang 110819 (China); Liaoning Provincial Universities Key Laboratory of Boron Resource Ecological, Utilization, Technology and Boron Materials, Shenyang 110819 (China); Xue, X.X.; Yang, H. [Institute of Metallurgical Resource and Environmental Engineering, Northeastern University, Shenyang 110819 (China); Liaoning Key Laboratory of Metallurgical Resource Recycling Science, Shenyang 110819 (China); Liaoning Engineering and Technology Research Center of Boron Resource, Comprehensive, Utilization, Shenyang 110819 (China); Liaoning Provincial Universities Key Laboratory of Boron Resource Ecological, Utilization, Technology and Boron Materials, Shenyang 110819 (China); Chen, C.; Li, X.; Pei, J.X.; Niu, M.C.; Yang, Y.T.; Gao, X.Y. [School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004 (China)

    2015-10-15

    The (C, N and S) co-doped TiO{sub 2} (TH-TiO{sub 2}) samples were synthesized by a sol-gel method calcined at 500 °C, employing butyl titanate as the titanium source and thiourea as the dopant. The structures of TH-TiO{sub 2} samples were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectra (DRS), photoluminescence (PL) spectroscopy, Thermo gravimetry and differential thermal analysis (TG-DTA), Scanning electron microscopy (SEM) and nitrogen adsorption–desorption isotherms. The photocatalytic activities were checked through the photocatalytic reduction of Cr(VI) as a model compound under visible light irradiation. The results showed that the thiourea content played an important role on the microstructure and photocatalytic activity of the samples. According to XPS results, (C, N and S) atoms were successfully co-doped into the nanostructures of TH-TiO{sub 2} samples. TH-TiO{sub 2} samples with thiourea: Ti molar ratio of 1.5 exhibits higher photocatalytic activity than that of the other samples under visible light irradiation, which can be attributed to the synergic effect of the pure anatase structure, the higher light absorption characteristics in visible regions, separation efficiency of electron–hole pairs, the specific surface area and the optimum (C, N and S) content. - Graphical abstract: (C, N and S) co-doped TiO{sub 2} samples show good photocatalytic activity for Cr (VI) reduction under visible light irradiation. - Highlights: • (C, N and S) co-doping in TH-TiO{sub 2} samples can promote the formation of the pure anatase structure. • (C, N and S) atoms were successfully co-doped into the nanostructures of TH-TiO{sub 2} samples. • The band gap energy of TH-TiO{sub 2} samples reduced after (C, N and S) co-doping. • (C, N and S) co-doped TiO{sub 2} samples were effective for the photocatalytic reduction of Cr(VI) under visible light

  6. Effect of Mo on Microstructures and Wear Properties of In Situ Synthesized Ti(C,N)/Ni-Based Composite Coatings by Laser Cladding.

    Science.gov (United States)

    Wu, Fan; Chen, Tao; Wang, Haojun; Liu, Defu

    2017-09-06

    Using Ni60 alloy, C, TiN and Mo mixed powders as the precursor materials, in situ synthesized Ti(C,N) particles reinforcing Ni-based composite coatings are produced on Ti6Al4V alloys by laser cladding. Phase constituents, microstructures and wear properties of the composite coatings with 0 wt % Mo, 4 wt % Mo and 8 wt % Mo additions are studied comparatively. Results indicate that Ti(C,N) is formed by the in situ metallurgical reaction, the (Ti,Mo)(C,N) rim phase surrounding the Ti(C,N) ceramic particle is synthesized with the addition of Mo, and the increase of Mo content is beneficial to improve the wear properties of the cladding coatings. Because of the effect of Mo, the grains are remarkably refined and a unique core-rim structure that is uniformly dispersed in the matrix appears; meanwhile, the composite coatings with Mo addition exhibit high hardness and excellent wear resistance due to the comprehensive action of dispersion strengthening, fine grain strengthening and solid solution strengthening.

  7. Organic carbon source and C/N ratio affect inorganic nitrogen profile in the biofloc-based culture media of Pacific white shrimp (Litopenaeus vannamei

    Directory of Open Access Journals (Sweden)

    Muhammad Hanif Azhar

    2016-03-01

    Full Text Available Organic carbon source and C/N ratio play an important role in aquaculture system with biofloc technology application. Nitrogen control by adding carbohydrates to the water to stimulate heterotrophic bacterial growth by converting nitrogen into bacterial biomass. The study investigated the effect molasses, tapioca, tapioca by product and rice bran as carbon sources in a biofloc media at three different C/N ratios i.e. 10, 15, and 20 on total ammonia reduction in biofloc media. Five liters of biofloc media in a conical tank was prepared for each replicate, which consisted of 500 mL of biofloc suspension collected from a shrimp culture unit with biofloc technology application and 4.5 L seawater. Pacific white shrimp culture was performed in 40L glass aquaria at a shrimp density of 30/aquarium. There was a significant interaction between carbon source and the C/N ratio applied (P<0.05. The use of molasses resulted in the highest reduction rate irrespective to the C/N ratio. Keywords: molasses, tapioca, tapioca by product, rice bran, biofloc, total ammonia nitrogen

  8. Study of C/N Ratio Effect on Biogas Production of Carica Solid Waste by SS-AD Method And LS-AD

    Directory of Open Access Journals (Sweden)

    Jos Bakti

    2018-01-01

    Full Text Available Biogas is a renewable energy which can be used as an alternative source to replace fossil fuels. Recently, the use of energy has become an important issue because the oil sources and natural gas are depleting. Utilization of carica waste to produce biogas can reduce the consumption of commercial energy sources such as kerosene as well as the use of firewood. Biogas is produced by the process of organic material digestion by certain anaerobic bacterial activity in anaerobic digester. In this study we studied the influence of LS-AD and SS-AD methods, the effect of C / N ratio on biogas yield obtained and kinetics of biogas production reaction. The study was conducted by making a total solid variation of 7%, 9%, 11%, 13%, 19%, 21%, 23% and C/N ratio 25 and 30. The study started with carica waste collection process and examination of the total composition of solids and water content. Thereafter, calculation and determination of variation of C / N ratio by mixing the substrate with inoculum and urea into the reactor. Observe the volume of biogas produced every two-day intervals. The highest biogas production rate of 1.7825 ml/g TS day was obtained from carica solid waste variable by liquid state anaerobic disgestion and C/N 25.

  9. Nitrogen removal and nitrous oxide emission in surface flow constructed wetlands for treating sewage treatment plant effluent: Effect of C/N ratios.

    Science.gov (United States)

    Li, Ming; Wu, Haiming; Zhang, Jian; Ngo, Huu Hao; Guo, Wenshan; Kong, Qiang

    2017-09-01

    In order to design treatment wetlands with maximal nitrogen removal and minimal nitrous oxide (N 2 O) emission, the effect of influent C/N ratios on nitrogen removal and N 2 O emission in surface flow constructed wetlands (SF CWs) for sewage treatment plant effluent treatment was investigated in this study. The results showed that nitrogen removal and N 2 O emission in CWs were significantly affected by C/N ratio of influent. Much higher removal efficiency of NH 4 + -N (98%) and TN (90%) was obtained simultaneously in SF CWs at C/N ratios of 12:1, and low N 2 O emission (8.2mg/m 2 /d) and the percentage of N 2 O-N emission in TN removal (1.44%) were also observed. These results obtained in this study would be utilized to determine how N 2 O fluxes respond to variations in C/N ratios and to improve the sustainability of CWs for wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. A novel enantiopure proline-based organickel(III) halide monocation with a pentadentate C, N2, O2-bonded bis(ortho-chelating) aryldiamine ligand

    NARCIS (Netherlands)

    Koten, G. van; Kuil, L.A. van de; Veldhuizen, Y.S.J.; Grove, D.M.; Zwikker, J.W.; Jenneskens, L.W.; Drenth, W.; Smeets, W.J.J.

    1995-01-01

    An attempt was made to use the enantiopure arylnickel(II) complex [Ni(L*-N, C, N)Br], 1, (L* is the monoanionic ligand, 2, 6-bis[(2-(S)-2-isopropoxycarbonyl-1-pyrrolidinyl)methyl]phenyl) as a catalyst for the Kharasch addition reaction of CCl4 to alkenes which led instead to a new ionic

  11. Transition Metal Free C-N Bond Forming Dearomatizations and Aryl C-H Aminations by in Situ Release of a Hydroxylamine-Based Aminating Agent.

    Science.gov (United States)

    Farndon, Joshua J; Ma, Xiaofeng; Bower, John F

    2017-10-11

    We outline a simple protocol that accesses directly unprotected secondary amines by intramolecular C-N bond forming dearomatization or aryl C-H amination. The method is dependent on the generation of a potent electrophilic aminating agent released by in situ deprotection of O-Ts activated N-Boc hydroxylamines.

  12. Combined Stable Carbon Isotope and C/N Ratios as Indicators of Source and Fate of Organic Matter in the Bang Pa kong River Estuary, Thailand

    International Nuclear Information System (INIS)

    Boonphakdee, Thanomsak; Kasai, Akihide; Fujiwara, Tateki; Sawangwong, Pichan; Cheevaporn, Voravit

    2007-08-01

    Full text: Stable carbon isotopes and C/N ratios of particulate organic matter (POM) in suspended solids and surficial sediment were used to define the spatial and temporal variability in an anthropogenic tropical river estuary, the Bang Pa kong River Estuary. Samples were taken along salinity gradients during the four different river discharges in the beginning, high river discharge and at the end of the wet season, and low river discharge during the dry season. The values of [C/N]a ratio and d13C in the river estuary revealed significant differences from those of the offshore station. Conservative behaviors of [C/N]a and d13C in the estuary during the wet season indicated major contribution of terrigenous C3 plants derived OM. By contrast, during the dry season, marine input mainly dominated OM contribution with an evidence of anthropogenic input to the estuary. These compositions of the bulk sedimentary OM were dominated by paddy rice soils and marine derived OM during the wet and dry seasons, respectively. These results show that the combined stable carbon isotopes and C/N ratios can be used to identify the source and fate of OM even in a river estuary. This tool will be useful to achieve sustainable management in coastal zone

  13. Searching for stable Si(n)C(n) clusters: combination of stochastic potential surface search and pseudopotential plane-wave Car-Parinello simulated annealing simulations.

    Science.gov (United States)

    Duan, Xiaofeng F; Burggraf, Larry W; Huang, Lingyu

    2013-07-22

    To find low energy Si(n)C(n) structures out of hundreds to thousands of isomers we have developed a general method to search for stable isomeric structures that combines Stochastic Potential Surface Search and Pseudopotential Plane-Wave Density Functional Theory Car-Parinello Molecular Dynamics simulated annealing (PSPW-CPMD-SA). We enhanced the Sunders stochastic search method to generate random cluster structures used as seed structures for PSPW-CPMD-SA simulations. This method ensures that each SA simulation samples a different potential surface region to find the regional minimum structure. By iterations of this automated, parallel process on a high performance computer we located hundreds to more than a thousand stable isomers for each Si(n)C(n) cluster. Among these, five to 10 of the lowest energy isomers were further optimized using B3LYP/cc-pVTZ method. We applied this method to Si(n)C(n) (n = 4-12) clusters and found the lowest energy structures, most not previously reported. By analyzing the bonding patterns of low energy structures of each Si(n)C(n) cluster, we observed that carbon segregations tend to form condensed conjugated rings while Si connects to unsaturated bonds at the periphery of the carbon segregation as single atoms or clusters when n is small and when n is large a silicon network spans over the carbon segregation region.

  14. Effects of stocking density of freshwater prawn Macrobrachium rosenbergii and addition of different levels of tilapia Oreochromis niloticus on production in C/N controlled periphyton based system

    NARCIS (Netherlands)

    Asaduzzaman, M.; Wahab, M.A.; Verdegem, M.C.J.; Mondal, M.N.; Azim, M.E.

    2009-01-01

    An on-station trial was conducted to evaluate the effect of stocking density of freshwater prawn and addition of different levels of tilapia on production in carbon/nitrogen (C/N) controlled periphyton based system. The experiment had a 2 × 3 factorial design, in which two levels of prawn stocking

  15. Effects of addition of tilapia Oreochromis niloticus and substrates for periphyton developments on pond ecology and production in C/N-controlled freshwater prawn Macrobrachium rosenbergii farming systems

    NARCIS (Netherlands)

    Asaduzzaman, M.; Wahab, M.A.; Verdegem, M.C.J.; Benerjee, S.; Akter, T.; Hasan, M.M.; Azim, M.E.

    2009-01-01

    The present research investigated the effect of addition of tilapia and substrates for periphyton development on pond ecology, production and economic performances in C/N controlled freshwater prawn farming system. The absence and presence (0 and 0.5 individual m- 2) of tilapia were investigated in

  16. Diamond ages from Victor (Superior Craton): Intra-mantle cycling of volatiles (C, N, S) during supercontinent reorganisation

    Science.gov (United States)

    Aulbach, S.; Creaser, Robert A.; Stachel, Thomas; Heaman, Larry M.; Chinn, Ingrid L.; Kong, Julie

    2018-05-01

    The central Superior Craton hosts both the diamondiferous 1.1 Ga Kyle Lake and Jurassic Attawapiskat kimberlites. A major thermal event related to the Midcontinent Rift at ca. 1.1 Ga induced an elevated geothermal gradient that largely destroyed an older generation of diamonds, raising the question of when, and how, the diamond inventory beneath Attawapiskat was formed. We determined Re-Os isotope systematics of sulphides included in diamonds from Victor by isotope dilution negative thermal ionisation mass spectrometry in order to obtain insights into the age and nature of the diamond source in the context of regional tectonothermal evolution. Regression of the peridotitic inclusion data (n = 14 of 16) yields a 718 ± 49 Ma age, with an initial 187Os/188Os ratio of 0.1177 ± 0.0016, i.e. depleted at the time of formation (γOs -3.7 ± 1.3). Consequently, Re depletion model ages calculated for these samples are systematically overestimated. Given that reported 187Os/188Os in olivine from Attawapiskat xenoliths varies strongly (0.1012-0.1821), the low and nearly identical initial Os of sulphide inclusions combined with their high 187Re/188Os (median 0.34) suggest metasomatic formation from a mixed source. This was likely facilitated by percolation of amounts of melt sufficient to homogenise Os, (re)crystallise sulphide and (co)precipitate diamond; that is, the sulphide inclusions and their diamond host are synchronous if not syngenetic. The ∼720 Ma age corresponds to rifting beyond the northern craton margin during Rodinia break-up. This suggests mobilisation of volatiles (C, N, S) and Os due to attendant mantle stretching and metasomatism by initially oxidising and S-undersaturated melts, which ultimately produced lherzolitic diamonds with high N contents compared to older Kyle Lake diamonds. Thus, some rift-influenced settings are prospective with respect to diamond formation. They are also important sites of hidden, intra-lithospheric volatile redistribution

  17. Evidence of amino acid precursors: C-N bond coupling in simulated interstellar CO2/NH3 ices

    Science.gov (United States)

    Esmaili, Sasan

    2015-08-01

    Low energy secondary electrons are abundantly produced in astrophysical or planetary ices by the numerous ionizing radiation fields typically encountered in space environments and may thus play a role in the radiation processing of such ices [1]. One approach to determine their chemical effect is to irradiate nanometer thick molecular solids of simple molecular constituents, with energy selected electron beams and to monitor changes in film chemistry with the surface analytical techniques [2].Of particular interest is the formation of HCN, which is a signature of dense gases in interstellar clouds, and is ubiquitous in the ISM. Moreover, the chemistry of HCN radiolysis products such as CN- may be essential to understand of the formation of amino acids [3] and purine DNA bases. Here we present new results on the irradiation of multilayer films of CO2 and NH3 with 70 eV electrons, leading to CN bond formations. The electron stimulated desorption (ESD) yields of cations and anions are recorded as a function of electron fluence. The prompt desorption of cationic reaction/scattering products [4], is observed at low fluence (~4x1013 electrons/cm2). Detected ions include C2+, C2O2+, C2O+, CO3+, C2O3+ or CO4+ from pure CO2, and N+, NH+, NH2+, NH3+, NH4+, N2+, N2H+ from pure NH3, and NO+, NOH+ from CO2/NH3 mixtures. Most saliently, increasing signals of negative ion products desorbing during prolonged irradiation of CO2/NH3 films included C2-, C2H-, C2H2-, as well as CN-, HCN- and H2CN-. The identification of particular product ions was accomplished by using 13CO2 and 15NH3 isotopes. The chemistry induced by electrons in pure films of CO2 and NH3 and mixtures with composition ratios (3:1), (1:1), and (1:3), was also studied by X-ray photoelectron spectroscopy (XPS). Irradiation of CO2/NH3 mixed films at 22 K produces species containing the following bonds/functional groups identified by XPS: C=O, O-H, C-C, C-O, C=N and N=O. (This work has been funded by NSERC).

  18. Volatiles (H, C, N, O, noble gases) in comets as tracers of early solar system events (Invited)

    Science.gov (United States)

    Marty, B.

    2013-12-01

    Volatiles (H, C, N, O, noble gases) present the largest variations in their relative abundances and, importantly, in their isotopic ratios, among solar system elements. The original composition of the protosolar nebula has been investigated through the measurements of primitive meteorites and of in-situ (e.g. Galileo probe analysis of the Jupiter's atmosphere) and sample-return (Genesis, recovery and analysis of solar wind) missions. The protosolar gas was poor in deuterium, in 15N and in 17,18O. Variations among solar system reservoir reach several hundreds of percents for the D/H and 15N/14N ratios. These variations are possibly : (i) due to interactions between XUV photons of the proto-Sun and the-dust, (ii) result from low temperature ion-molecule reactions, or (iii) constitute an heritage on interstellar volatiles trapped in dust (e.g., organics). Likewise, noble gases are elementally and isotopically (1% per amu for xenon) fractionated with respect to the composition of the solar wind (our best proxy for the protosolar nebula composition). Cometary matter directly measured on coma, or in Stardust material, or in IDPs, seems to present among the largest heterogeneities in their stable isotope compositions but knowledge on their precise compositions of the different phases and species is partial and mosty lacking. Among the several important issues requiring a better knowledge of cometary volatiles are the origin(s) of volatile elements on Earth and Moon, on Mars and on Venus, understanding large scale circulation of matter between hot and frozen zones, and the possibility of interstellar heritage for organics. Critical measurements to be made by the next cometary missions include the value of the D/H ratio in water ice, in NH3 and organics. Nitrogen is particularly interesting as cometary HCN and CN are rich in 15N, but an isotoppe mass balance will require to measure the main host species (N2 ?). Noble gases are excellent tracers of physical processes

  19. Carbon, nitrogen and phosphorus accumulation and partitioning, and C:N:P stoichiometry in late-season rice under different water and nitrogen managements.

    Directory of Open Access Journals (Sweden)

    Yushi Ye

    Full Text Available Water and nitrogen availability plays an important role in the biogeochemical cycles of essential elements, such as carbon (C, nitrogen (N and phosphorus (P, in agricultural ecosystems. In this study, we investigated the seasonal changes of C, N and P concentrations, accumulation, partitioning, and C:N:P stoichiometric ratios in different plant tissues (root, stem-leaf, and panicle of late-season rice under two irrigation regimes (continuous flooding, CF; alternate wetting and drying, AWD and four N managements (control, N0; conventional urea at 240 kg N ha(-1, UREA; controlled-release bulk blending fertilizer at 240 kg N ha(-1, BBF; polymer-coated urea at 240 kg N ha(-1, PCU. We found that water and N treatments had remarkable effects on the measured parameters in different plant tissues after transplanting, but the water and N interactions had insignificant effects. Tissue C:N, N:P and C:P ratios ranged from 14.6 to 52.1, 3.1 to 7.8, and 76.9 to 254.3 over the rice growing seasons, respectively. The root and stem-leaf C:N:P and panicle C:N ratios showed overall uptrends with a peak at harvest whereas the panicle N:P and C:P ratios decreased from filling to harvest. The AWD treatment did not affect the concentrations and accumulation of tissue C and N, but greatly decreased those of P, resulting in enhanced N:P and C:P ratios. N fertilization significantly increased tissue N concentration, slightly enhanced tissue P concentration, but did not affect tissue C concentration, leading to a significant increase in tissue N:P ratio but a decrease in C:N and C:P ratios. Our results suggested that the growth of rice in the Taihu Lake region was co-limited by N and P. These findings broadened our understanding of the responses of plant C:N:P stoichiometry to simultaneous water and N managements in subtropical high-yielding rice systems.

  20. Carbon, Nitrogen and Phosphorus Accumulation and Partitioning, and C:N:P Stoichiometry in Late-Season Rice under Different Water and Nitrogen Managements

    Science.gov (United States)

    Ye, Yushi; Liang, Xinqiang; Chen, Yingxu; Li, Liang; Ji, Yuanjing; Zhu, Chunyan

    2014-01-01

    Water and nitrogen availability plays an important role in the biogeochemical cycles of essential elements, such as carbon (C), nitrogen (N) and phosphorus (P), in agricultural ecosystems. In this study, we investigated the seasonal changes of C, N and P concentrations, accumulation, partitioning, and C:N:P stoichiometric ratios in different plant tissues (root, stem-leaf, and panicle) of late-season rice under two irrigation regimes (continuous flooding, CF; alternate wetting and drying, AWD) and four N managements (control, N0; conventional urea at 240 kg N ha−1, UREA; controlled-release bulk blending fertilizer at 240 kg N ha−1, BBF; polymer-coated urea at 240 kg N ha−1, PCU). We found that water and N treatments had remarkable effects on the measured parameters in different plant tissues after transplanting, but the water and N interactions had insignificant effects. Tissue C:N, N:P and C:P ratios ranged from 14.6 to 52.1, 3.1 to 7.8, and 76.9 to 254.3 over the rice growing seasons, respectively. The root and stem-leaf C:N:P and panicle C:N ratios showed overall uptrends with a peak at harvest whereas the panicle N:P and C:P ratios decreased from filling to harvest. The AWD treatment did not affect the concentrations and accumulation of tissue C and N, but greatly decreased those of P, resulting in enhanced N:P and C:P ratios. N fertilization significantly increased tissue N concentration, slightly enhanced tissue P concentration, but did not affect tissue C concentration, leading to a significant increase in tissue N:P ratio but a decrease in C:N and C:P ratios. Our results suggested that the growth of rice in the Taihu Lake region was co-limited by N and P. These findings broadened our understanding of the responses of plant C:N:P stoichiometry to simultaneous water and N managements in subtropical high-yielding rice systems. PMID:24992006

  1. Bonding structure and mechanical properties of B-C-N thin films synthesized by pulsed laser deposition at different laser fluences

    International Nuclear Information System (INIS)

    Wang, C.B.; Xiao, J.L.; Shen, Q.; Zhang, L.M.

    2016-01-01

    Boron carbon nitride (B-C-N) thin films have been grown by pulsed laser deposition under different laser fluences changing from 1.0 to 3.0 J/cm"2. The influence of laser fluence on microstructure, bonding structure, and mechanical properties of the films was studied, so as to explore the possibility of improving their mechanical properties by controlling bonding structure. The bonding structure identified by FT-IR and XPS indicated the coexistence of B-N, B-C, N-C and N=C bonds in the films, suggesting the formation of a ternary B-C-N hybridization. There is a clear evolution of bonding structure in the B-C-N films with the increasing of laser fluence. The variation of the mechanical properties as a function of laser fluence was also in accordance with the evolution of B-C and sp"3 N-C bonds whereas contrary to that of sp"2 B-N and N=C bonds. The hardness and modulus reached the maximum value of 33.7 GPa and 256 GPa, respectively, at a laser fluence of 3.0 J/cm"2, where the B-C-N thin films synthesized by pulsed laser deposition possessed the highest intensity of B-C and N-C bonds and the lowest fraction of B-N and N=C bonds. - Highlights: • Improvement of mechanical property by controlling bonding structure is explored. • A clear evolution of bonding structure with the increasing of laser fluence • Variation of property is in accordance with the evolution of B−C and N−C bonds.

  2. Syntheses of super-hard boron-rich solids in the B-C-N-O system

    Science.gov (United States)

    Hubert, Herve Pierre

    Alpha-rhombohedral (alpha-rh.) B-rich materials belonging to the B-C-N-O system were prepared using high-pressure, high-temperature techniques. The samples were synthesized using a multianvil device and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and parallel electron energy-loss spectroscopy (PEELS). In the B-O system, the formation of BsbxO materials produced from mixtures of B and Bsb2Osb3 between 1 to 10 GPa and 1000 to 1800sp°C was investigated. Graphitic and diamond-like Bsb2O, reported in previous studies, were not detected. The refractory boron suboxide, nominally Bsb6O, which has the alpha-rh. B structure, is the dominant suboxide in the P and T range of our investigation. High-pressure techniques were used successfully to synthesize boron suboxide of improved purity and crystallinity, and less oxygen-deficient (i.e., closer to the nominal Bsb6O composition) in comparison to room-pressure syntheses. Quantitative analyses indicate compositions of Bsb6Osb{0.95} and Bsb6Osb{0.77} for high-pressure and room-pressure samples, respectively. The first preparation, between 4 to 5.5 GPa, of Bsb6O in which the preferred form of the material is as macroscopic near-perfect regular icosahedra (to 30 mum in diameter) is reported. The Bsb6O icosahedra are similar to the multiply-twinned particles observed in some cubic materials. However, a major difference is that Bsb6O has a rhombohedral structure that closely fits the geometrical requirements for obtaining icosahedral twins. The Bsb6O grains are neither 3D-periodic nor quasicrystalline. Their formation can be described as a Mackay packing of icosahedral Bsb{12} units and provides an alternative to crystal formation by propagation of translational symmetry. Icosahedral twins ranging from 20 nm to 30 mum in diameter, as well as micron-sized euhedral crystals (to 40 mum) were prepared. The structural similarity of compounds with the alpha

  3. The comparison of 18C(n; γ)19C and 18C(α; n)21O reaction rates: consequences for the r-process

    International Nuclear Information System (INIS)

    Dan, M.; Singh, G.; Chatterjee, R.; Shubhchintak

    2017-01-01

    Neutron rich light and medium mass nuclei play a major role in determining the reaction flow towards the r-process seed nuclei production. In this text, we calculate the neutron capture rate of 18 C and compare it with that of α-capture by the same nucleus in the temperature range T 9 = 0:1 - 10. This temperature range roughly equals to an energy range of 1 keV to 1 MeV in centre of mass frame, where it is very difficult to perform direct reaction experiments. Further, the theoretical construction of 18 C-n continuum state for the 18 C(n; γ) 19 C direct reaction is a tedious job

  4. Photocatalytic Degradation of 4-Nitrophenol by C, N-TiO2: Degradation Efficiency vs. Embryonic Toxicity of the Resulting Compounds

    Science.gov (United States)

    Osin, Oluwatomiwa A.; Yu, Tianyu; Cai, Xiaoming; Jiang, Yue; Peng, Guotao; Cheng, Xiaomei; Li, Ruibin; Qin, Yao; Lin, Sijie

    2018-06-01

    The photocatalytic activity of TiO2 based photocatalysts can be improved by structural modification and elemental doping. In this study, through rational design, one type of carbon and nitrogen co-doped TiO2 (C, N-TiO2) photocatalyst with mesoporous structure was synthesized with improved photocatalytic activity in degrading 4-nitrophenol under simulated sunlight irradiation. The photocatalytic degradation efficiency of the C, N-TiO2 was much higher than the anatase TiO2 (A-TiO2) based on absorbance and HPLC analyses. Moreover, using zebrafish embryos, we showed that the intermediate degradation compounds generated by photocatalytic degradation of 4-nitrophenol had higher toxicity than the parent compound. A repeated degradation process was necessary to render complete degradation and non-toxicity to the zebrafish embryos. Our results demonstrated the importance of evaluating the photocatalytic degradation efficiency in conjunction with the toxicity assessment of the degradation compounds.

  5. Measurements of Ay(θ) for 12C(n,n)12C from En=2.2 to 8.5 MeV

    International Nuclear Information System (INIS)

    Roper, C.D.; Tornow, W.; Braun, R.T.; Chen, Q.; Crowell, A.; Trotter, D. Gonzalez; Howell, C.R.; Salinas, F.; Setze, R.; Walter, R.L.; Chen Zemin; Tang Hongqing; Zhou Zuying

    2005-01-01

    The analyzing power A y (θ) for neutron elastic scattering from 12 C has been measured for 33 neutron energies between E n =2.2 and 8.5 MeV in the angular range from 25 deg. to 145 deg. in the laboratory system. The primary motivation for these measurements is the need for an accurate knowledge of A y (θ) for 12 C(n,n) 12 C elastic scattering to enable corrections to high-precision neutron-proton and neutron-deuteron A y (θ) data in the neutron-energy range below E n =30 MeV. In their own right, 12 C(n,n) 12 C A y (θ) data are of crucial importance for improving both the parametrization of n- 12 C scattering and our knowledge of the level scheme of 13 C. The present A y (θ) data are compared with published data and previous phase-shift-analysis results

  6. C-N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation.

    Science.gov (United States)

    Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

    2017-06-01

    Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me 3 C 6 H 2 )CH 2 } 2 ]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH 2 SiMe 3 ) 2 and Al(TMP)iBu 2 ), key intermediates in this process have been isolated and structurally defined. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Linking annual N2O emission in organic soils to mineral nitrogen input as estimated by heterotrophic respiration and soil C/N ratio.

    Science.gov (United States)

    Mu, Zhijian; Huang, Aiying; Ni, Jiupai; Xie, Deti

    2014-01-01

    Organic soils are an important source of N2O, but global estimates of these fluxes remain uncertain because measurements are sparse. We tested the hypothesis that N2O fluxes can be predicted from estimates of mineral nitrogen input, calculated from readily-available measurements of CO2 flux and soil C/N ratio. From studies of organic soils throughout the world, we compiled a data set of annual CO2 and N2O fluxes which were measured concurrently. The input of soil mineral nitrogen in these studies was estimated from applied fertilizer nitrogen and organic nitrogen mineralization. The latter was calculated by dividing the rate of soil heterotrophic respiration by soil C/N ratio. This index of mineral nitrogen input explained up to 69% of the overall variability of N2O fluxes, whereas CO2 flux or soil C/N ratio alone explained only 49% and 36% of the variability, respectively. Including water table level in the model, along with mineral nitrogen input, further improved the model with the explanatory proportion of variability in N2O flux increasing to 75%. Unlike grassland or cropland soils, forest soils were evidently nitrogen-limited, so water table level had no significant effect on N2O flux. Our proposed approach, which uses the product of soil-derived CO2 flux and the inverse of soil C/N ratio as a proxy for nitrogen mineralization, shows promise for estimating regional or global N2O fluxes from organic soils, although some further enhancements may be warranted.

  8. The role of C:N:P stoichiometry in affecting denitrification in sediments from agricultural surface and tile-water wetlands.

    Science.gov (United States)

    Grebliunas, Brian D; Perry, William L

    2016-01-01

    Nutrient stoichiometry within a wetland is affected by the surrounding land use, and may play a significant role in the removal of nitrate (NO3-N). Tile-drained, agricultural watersheds experience high seasonal inputs of NO3-N, but low phosphorus (PO4-P) and dissolved organic carbon (DOC) loads relative to surface water dominated systems. This difference may present stoichiometric conditions that limit denitrification within receiving waterways. We investigated how C:N:P ratios affected denitrification rates of sediments from tile-drained mitigation wetlands incubated for: 0, 5, 10, and 20 days. We then tested whether denitrification rates of sediments from surface-water and tile-drained wetlands responded differently to C:N ratios of 2:1 versus 4:1. Ratios of C:N:P (P tile-drained wetland sediments. Carbon limitation of denitrification became evident at elevated NO3-N concentrations (20 mg L(-1)). Denitrification measured from tile water and surface water wetland sediments increased significantly (P < 0.05) at the 2:1 and 4:1 C:N treatments. The results from both experiments suggest wetland sediments provide a limiting pool of labile DOC to maintain prolonged NO3-N removal. Also, DOC limitation became more evident at elevated NO3-N concentrations (20 mg L(-1)). Irrespective of NO3-N concentrations, P did not limit denitrification rates. In addition to wetting period, residence time, and maintenance of anaerobic conditions, the availability of labile DOC is playing an important limiting role in sediment denitrification within mitigation wetlands.

  9. Mechanical and tribological properties of polymer-derived Si/C/N sub-millimetre thick miniaturized components fabricated by direct casting

    OpenAIRE

    Bakumov Vadym; Blugan Gurdial; Roos Sigfried; Graule Thomas J.; Fakhfouri Vahid; Grossenbacher Jonas; Gullo Maurizio Rosario; Kiefer Thomas C.; Brugger Juergen; Parlinska Magdalena; Kuebler Jakob

    2012-01-01

    The utilization of silicon based polymers as a source of amorphous non oxide ceramics obtained upon pyrolytic treatment of them is increasingly gaining attention in research and is currently expanding into the field of commercial products. This work is focused on the near net shaped fabrication mechanical and tribological properties of a polymer derived Si/C/N system. Small sub millimetre thick ceramic test discs and bars were fabricated by casting of polysilazane and/or polycarbosilane precu...

  10. Influences of micro-geomorphology on the stoichiometry of C, N and P in Chenier Island soils and plants in the Yellow River Delta, China.

    Science.gov (United States)

    Qu, Fanzhu; Meng, Ling; Yu, Junbao; Liu, Jingtao; Sun, Jingkuan; Yang, Hongjun; Dong, Linshui

    2017-01-01

    Studies have indicated that consistent or well-constrained (relatively low variability) carbon:nitrogen:phosphorus (C:N:P) ratios exist in large-scale ecosystems, including both marine and terrestrial ecosystems. Little is known about the C, N and P stoichiometric ratios that exist in the soils and plants of Chenier Island in the Yellow River Delta (YRD). We examined the distribution patterns and relationships of C, N and P stoichiometry in the soils and plants of Chenier Island, as well as the potential influences of the island's micro-geomorphology. Based on a study of four soil profile categories and Phragmites australis and Suaeda heteroptera plant tissues, our results showed that micro-geomorphology could leave a distinct imprint on the soil and plant elemental stoichiometry of Chenier Island; significant variation in the atomic C:N:P ratios (RCNP) existed in soils and plants, indicating that the RCNP values in both the soil and plants are not well constrained at the Chenier Island scale. RCN and RCP in Chenier Island soils were high, whereas the RNP values were comparatively low, indicating that the ecosystems of Chenier Island are nutrient-limited by N and P. However, the RNP values in P. australis and S. heteroptera plant tissues were high, suggesting that the plants of Chenier Island are nutrient-limited by P. Finally, we suggest that soil and plant N:P ratios may be good indicators of the soil and plant nutrient status during soil development and plant growth, which could be a useful reference for restoring the degraded soils of Chenier Island.

  11. Magnetron sputtered Hf-B-Si-C-N films with controlled electrical conductivity and optical transparency, and with ultrahigh oxidation resistance

    Czech Academy of Sciences Publication Activity Database

    Šímová, V.; Vlček, J.; Zuzjaková, Š.; Houška, J.; Shen, Y.; Jiang, J. C.; Meletis, E. I.; Peřina, Vratislav

    2018-01-01

    Roč. 653, č. 5 (2018), s. 333-340 ISSN 0040-6090 R&D Projects: GA MŠk LM2015056 Institutional support: RVO:61389005 Keywords : Hf-B-Si-C-N films * pulsed reactive magnetron sputtering * electrical conductivitiy * optical transparency * high-temperature oxidation resistance Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders OBOR OECD: Nuclear physics Impact factor: 1.879, year: 2016

  12. Metal-organic framework derived Fe/Fe3C@N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions.

    Science.gov (United States)

    Song, Chunsen; Wu, Shikui; Shen, Xiaoping; Miao, Xuli; Ji, Zhenyuan; Yuan, Aihua; Xu, Keqiang; Liu, Miaomiao; Xie, Xulan; Kong, Lirong; Zhu, Guoxing; Ali Shah, Sayyar

    2018-08-15

    The development of simple and cost-effective synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is critical to renewable energy technologies. Herein, we report an interesting bifunctional HER and ORR electrocatalyst of Fe/Fe 3 C@N-doped-carbon porous hierarchical polyhedrons (Fe/Fe 3 C@N-C) by a simple metal-organic framework precursor route. The Fe/Fe 3 C@N-C polyhedrons consisting of Fe and Fe 3 C nanocrystals enveloped by N-doped carbon shells and accompanying with some carbon nanotubes on the surface were prepared by thermal annealing of Zn 3 [Fe(CN) 6 ] 2 ·xH 2 O polyhedral particles in nitrogen atmosphere. This material exhibits a large specific surface area of 182.5 m 2  g -1 and excellent ferromagnetic property. Electrochemical tests indicate that the Fe/Fe 3 C@N-C hybrid has apparent HER activity with a relatively low overpotential of 236 mV at the current density of 10 mA cm -2 and a small Tafel slope of 59.6 mV decade -1 . Meanwhile, this material exhibits excellent catalytic activity toward ORR with an onset potential (0.936 V vs. RHE) and half-wave potential (0.804 V vs. RHE) in 0.1 M KOH, which is comparable to commercial 20 wt% Pt/C (0.975 V and 0.820 V), and shows even better stability than the Pt/C. This work provides a new insight to developing multi-functional materials for renewable energy application. Copyright © 2018 Elsevier Inc. All rights reserved.

  13. Measurement of the /sup 12/C(n,γ0)/sup 13/C cross section in the giant dipole resonance region

    International Nuclear Information System (INIS)

    August, R.A.; Weller, H.R.; Tilley, D.R.

    1987-01-01

    The /sup 12/C(n,γ 0 ) /sup 13/C excitation function at 90 0 has been measured for neutron energies from 6.5 to 18.5 MeV. Whereas previous measurements disagreed at the lower energies with a direct-semidirect capture calculation based on /sup 12/C(p,γ 0 ) /sup 13/N data, the present results, especially when the uncertainty in absolute cross section is considered, indicate reasonable qualitative agreement with the calculation

  14. Synthesis and characterization of a new material based on porous silica-Chemically immobilized C,N-pyridylpyrazole for heavy metals adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Radi, Smaail [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Departement de Chimie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco)], E-mail: radi_smaail@yahoo.fr; Attayibat, Ahmed [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Departement de Chimie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco); Lekchiri, Yahya [Laboratoire de Biochimie, Departement de Biologie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco); Ramdani, Abdelkrim [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Departement de Chimie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco); Bacquet, Maryse [Laboratoire de Chimie Macromoleculaire, Universite des Sciences et Technologies de Lille, 59655 Villeneuve d' Ascq (France)

    2008-10-15

    The immobilization of C,N-pyridylpyrazole on the surface of epoxy group containing silica gel phase for the formation of a newly synthesized material based on porous silica-bound C,N-pyridylpyrazole (SGPP) is described. The surface modification was characterized by {sup 13}C NMR of solid sample, elemental analysis and infrared spectra and was studied and evaluated by determination of the surface area using the BET equation, the adsorption and desorption capability using the isotherm of nitrogen and BJH pore sizes, respectively. The new material exhibits good thermal stability determined by thermogravimetry curves. The synthesized material was utilised in column and batch methods for separation and trace extraction of (Hg{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, Cu{sup 2+}, Zn{sup 2+}, K{sup +}, Na{sup +} and Li{sup +}) and compared to results of classical liquid-liquid extraction with the unbound C,N-pyridylpyrazole compound. The grafting at the surface of silica does not affect complexing properties of the ligand and the material exhibits a high selectivity toward Hg(II)

  15. Carbon Nanotubes Filled with Different Ferromagnetic Alloys Affect the Growth and Development of Rice Seedlings by Changing the C:N Ratio and Plant Hormones Concentrations.

    Science.gov (United States)

    Hao, Yi; Yu, Feifan; Lv, Ruitao; Ma, Chuanxin; Zhang, Zetian; Rui, Yukui; Liu, Liming; Cao, Weidong; Xing, Baoshan

    2016-01-01

    The aim of this study was to investigate the phytotoxicity of thin-walled carbon nanotubes (CNTs) to rice (Oryza sativa L.) seedlings. Three different CNTs, including hollow multi-walled carbon nanotubes (MWCNTs), Fe-filled carbon nanotubes (Fe-CNTs), and Fe-Co-filled carbon nanotubes (FeCo-CNTs), were evaluated. The CNTs significantly inhibited rice growth by decreasing the concentrations of endogenous plant hormones. The carbon to nitrogen ratio (C:N ratio) significantly increased in rice roots after treatments with CNTs, and all three types of CNTs had the same effects on the C:N ratio. Interestingly, the increase in the C:N ratio in roots was largely because of decreased N content, indicating that the CNTs significantly decreased N assimilation. Analyses of the Fe and Co contents in plant tissues, transmission electron microscope (TEM) observations and energy dispersive X-ray spectroscopy (EDS) analysis proved that the CNTs could penetrate the cell wall and the cell membrane, and then enter the root cells. According to the author's knowledge, this is the first time to study the relationship between carbon nanotubes and carbon nitrogen ratio and plant hormones.

  16. Experimental and theoretical investigation of the production of cations containing C-N bonds in the reaction of benzene with atomic nitrogen ions

    International Nuclear Information System (INIS)

    Di Stefano, Marco; Rosi, Marzio; Sgamellotti, Antonio; Ascenzi, Daniela; Bassi, Davide; Franceschi, Pietro; Tosi, Paolo

    2003-01-01

    In the last few years, astronomical spectra have revealed the presence of aromatic and polyaromatic molecules in extraterrestrial environments, near carbon stars, in molecular clouds and meteorites. Moreover, the recent observation of benzene in interstellar space has noticeably increased the interest in the entire class of molecules and in their chemical behavior. In this work, we have investigated the reaction between the benzene molecule and the atomic nitrogen cation and, in particular, the mechanisms by which the reactants are converted into cationic products containing at least one C-N bond, according to the general scheme C 6 H 6 +N + →H m C n N + +C x H y . We have measured the energy dependence of the cross section in a guided ion beam tandem mass spectrometer. Relevant stationary points of the potential energy surface have been studied by using the density functional theory hybrid functional B3LYP with the 6-31G* basis set. Thermochemical calculations, and the comparison with experimental results, allow us to distinguish between exoergic and endoergic processes and to obtain a detailed description of the reaction mechanisms. We show that aromatic hydrocarbons may be converted into organic-nitrogen compounds via the insertion of N + into the benzene ring and the formation of C-N bonds from C-C ring reactants

  17. First principles prediction of the magnetic properties of Fe-X6 (X = S, C, N, O, F) doped monolayer MoS2

    KAUST Repository

    Feng, Nan

    2014-02-05

    Using first-principles calculations, we have investigated the electronic structure and magnetic properties of Fe-X 6 clusters (X = S, C, N, O, and F) incorporated in 4 4 monolayer MoS 2, where a Mo atom is substituted by Fe and its nearest S atoms are substituted by C, N, O, and F. Single Fe and Fe-F 6 substituions make the system display half-metallic properties, Fe-C 6 and Fe-N 6 substitutions lead to a spin gapless semiconducting behavior, and Fe-O 6 doped monolayer MoS 2 is semiconducting. Magnetic moments of 1.93, 1.45, 3.18, 2.08, and 2.21...? B are obtained for X = S, C, N, O, and F, respectively. The different electronic and magnetic characters originate from hybridization between the X and Fe/Mo atoms. Our results suggest that cluster doping can be an efficient strategy for exploring two-dimensional diluted magnetic semiconductors.

  18. Effects of taxonomy, sediment, and water column on C:N:P stoichiometry of submerged macrophytes in Yangtze floodplain shallow lakes, China.

    Science.gov (United States)

    Su, Haojie; Wu, Yao; Xie, Ping; Chen, Jun; Cao, Te; Xia, Wulai

    2016-11-01

    Carbon (C), nitrogen (N) and phosphorus (P) are the three most important essential elements limiting growth of primary producers. Submerged macrophytes generally absorb nutrients from sediments by root uptake. However, the C:N:P stoichiometric signatures of plant tissue are affected by many additional factors such as taxonomy, nutrient availability, and light availability. We first revealed the relative importance of taxonomy, sediment, and water column on plant C:N:P stoichiometry using variance partitioning based on partial redundancy analyses. Results showed that taxonomy was the most important factor in determining C:N:P stoichiometry, then the water column and finally the sediment. In this study, a significant positive relationship was found between community C concentration and macrophyte community biomass, indicating that the local low C availability in macrophytes probably was the main reason why submerged macrophytes declined in Yangtze floodplain shallow lakes. Based on our study, it is suggested that submerged macrophytes in Yangtze floodplain shallow lakes are primarily limited by low light levels rather than nutrient availability.

  19. First principles prediction of the magnetic properties of Fe-X6 (X = S, C, N, O, F) doped monolayer MoS2

    KAUST Repository

    Feng, Nan; Mi, Wenbo; Cheng, Yingchun; Guo, Zaibing; Schwingenschlö gl, Udo; Bai, Haili

    2014-01-01

    Using first-principles calculations, we have investigated the electronic structure and magnetic properties of Fe-X 6 clusters (X = S, C, N, O, and F) incorporated in 4 4 monolayer MoS 2, where a Mo atom is substituted by Fe and its nearest S atoms are substituted by C, N, O, and F. Single Fe and Fe-F 6 substituions make the system display half-metallic properties, Fe-C 6 and Fe-N 6 substitutions lead to a spin gapless semiconducting behavior, and Fe-O 6 doped monolayer MoS 2 is semiconducting. Magnetic moments of 1.93, 1.45, 3.18, 2.08, and 2.21...? B are obtained for X = S, C, N, O, and F, respectively. The different electronic and magnetic characters originate from hybridization between the X and Fe/Mo atoms. Our results suggest that cluster doping can be an efficient strategy for exploring two-dimensional diluted magnetic semiconductors.

  20. Toward structural dynamics: protein motions viewed by chemical shift modulations and direct detection of C'N multiple-quantum relaxation.

    Science.gov (United States)

    Mori, Mirko; Kateb, Fatiha; Bodenhausen, Geoffrey; Piccioli, Mario; Abergel, Daniel

    2010-03-17

    Multiple quantum relaxation in proteins reveals unexpected relationships between correlated or anti-correlated conformational backbone dynamics in alpha-helices or beta-sheets. The contributions of conformational exchange to the relaxation rates of C'N coherences (i.e., double- and zero-quantum coherences involving backbone carbonyl (13)C' and neighboring amide (15)N nuclei) depend on the kinetics of slow exchange processes, as well as on the populations of the conformations and chemical shift differences of (13)C' and (15)N nuclei. The relaxation rates of C'N coherences, which reflect concerted fluctuations due to slow chemical shift modulations (CSMs), were determined by direct (13)C detection in diamagnetic and paramagnetic proteins. In well-folded proteins such as lanthanide-substituted calbindin (CaLnCb), copper,zinc superoxide dismutase (Cu,Zn SOD), and matrix metalloproteinase (MMP12), slow conformational exchange occurs along the entire backbone. Our observations demonstrate that relaxation rates of C'N coherences arising from slow backbone dynamics have positive signs (characteristic of correlated fluctuations) in beta-sheets and negative signs (characteristic of anti-correlated fluctuations) in alpha-helices. This extends the prospects of structure-dynamics relationships to slow time scales that are relevant for protein function and enzymatic activity.

  1. DETAILED ABUNDANCES OF RED GIANTS IN THE GLOBULAR CLUSTER NGC 1851: C+N+O AND THE ORIGIN OF MULTIPLE POPULATIONS

    International Nuclear Information System (INIS)

    Villanova, S.; Geisler, D.; Piotto, G.

    2010-01-01

    We present chemical abundance analysis of a sample of 15 red giant branch (RGB) stars of the globular cluster NGC 1851 distributed along the two RGBs of the (v, v-y) color-magnitude diagram. We determined abundances for C+N+O, Na, α, iron-peak, and s-elements. We found that the two RGB populations significantly differ in their light (N, O, Na) and s-element content. On the other hand, they do not show any significant difference in their α and iron-peak element content. More importantly, the two RGB populations do not show any significant difference in their total C+N+O content. Our results do not support previous hypotheses suggesting that the origins of the two RGBs and the two subgiant branches of the cluster are related to different content of either α (including Ca) or iron-peak elements, or C+N+O abundance, due to a second generation polluted by Type II supernovae.

  2. DFT study of small fullerene dimer complexes C_2_0-N_m@C_n (m = 1-6 and n = 24, 28, 32, 36 and 40)

    International Nuclear Information System (INIS)

    Kaur, Sandeep; Sharma, Amrish; Mudahar, Isha

    2016-01-01

    First principle calculations based on density functional theory were performed to calculate the structural and electronic properties of C_2_0-N_m@C_n dimer complexes. The calculated binding energies of the complexes formed are comparable to C_6_0 dimer which ensures their stability. The bond lengths of these dimer complexes were found to be nearly same as pure complexes C_2_0-C_n. Further, nitrogen (N) atoms were encapsulated inside the secondary cage (C_n) of dimer complexes and the number of N atoms depends on diameter of the cage. The HOMO-LUMO gaps of new proposed complexes indicate the increase in gap as compared to pure complexes. Mulliken charge analysis of these complexes has been studied which shows the significant charge transfer from the N atoms to the secondary cage of these complexes. The study propose the formation of the new dimer complexes which are stable and are able to encapsulate atoms which are otherwise reactive in free space.

  3. corrosion and wear resistant ternary Cr-C-N coatings deposited by the ARC PVD process for machining tools and machining parts

    International Nuclear Information System (INIS)

    Knotek, O.; Lugscheider, E.; Zimmermann, H.; Bobzin, K.

    1997-01-01

    With the deposition of PVD hard coatings on the tools applied in machining operations it is possible to achieve significant improvements in the performance and quality of the machining processes. Depending on the machined material and the operating principle, e.g. turning, milling or drilling, not only different machining parameters but also different coating materials are necessary. In interrupted cut machining of tempered steel, for example, the life time of Ti-C-N coated inserts is several times greater than the Ti-C-N coated ones. This is a result of the favourable thermophysical and tribological properties of Ti-N-C. The potential for tool protection by CrN coatings is a result of the high ductility and low internal stress of this coating materials. CrN films can be deposited with greater film thickness, still maintaining very good adhesion. This paper presents the development of new arc PVD coatings in the system Cr-C-N. Owing to the carbon content in the coating an increased hardness and a better wear behavior in comparison to CrN was expected. The effects of various carbon carrier gases on the coating properties were examined. The coating properties were investigated by mechanical tests. X-ray diffraction, SEM analysis and corrosion tests. Some of the coatings were tested in machining tests. The results of these tests are presented in this paper. (author)

  4. Cauliflower-like MnO@C/N composites with multiscale, expanded hierarchical ordered structures as electrode materials for Lithium- and Sodium-ion batteries

    International Nuclear Information System (INIS)

    Chen, Ting; Wu, Zhenguo; Xiang, Wei; Wang, Enhui; Chen, Tingru; Guo, Xiaodong; Chen, Yanxiao; Zhong, Benhe

    2017-01-01

    MnO@C/N composite with expanded cauliflower-like morphology was prepared via one-pot L-tryptophan assisted hydrothermal method following by annealing in Ar atmosphere. The cauliflower structure was assembled by porous nanowires that composed of MnO nanoparticles wrapped by continuous N-doped amorphous carbon matrix. Superior electrochemical performances were obtained in both lithium/sodium ion batteries. And the reaction kinetics of MnO@C/N in lithium/sodium ion batteries were analyzed and compared. More than 837 mAh g −1 could be retained after 300 cycles at 500 mA g −1 . And a high reversible capacity of 336 mAh g −1 at 5000 mA g −1 also demonstrate the excellent rate performance of MnO@C/N for LIBs. As to SIBs, 123 mAh g −1 could be maintained after 200 cycles at 100 mA g −1 . The superior performances could be attributed to the peculiar porous micro-nano structure and N-doped amorphous carbon coating. The reaction kinetics results revealed that the capacitive-controlled capacity would dominate of the electrochemical performance in SIBs and the diffusion-controlled capacity could play a more important role in LIBs, due to the atom weight and size of Na + is larger than Li + .

  5. REGIOSELECTIVE REACTIONS OF 3-ALKYL-1-PHENYL-2-PYRAZOLIN-5-ONES WITH ACYL HALIDES IN THE PRECENCE OF NONOSIZED MAGNESIUM HYDROXIDE AS A HIGHLY EFFECTIVE HETEROGENOUS BASE CATALYST Regioselektive Reaktionen von 3-Alkyl-1-PHENYL-2-pyrazolin-5-ONES Mit Acylhalogeniden IN DER PRECENCE DER NONOSIZED MAGNESIUM HYDROXIDE als hochwirksame heterogene BASE CATALYST

    OpenAIRE

    Hassan Sheibani and Bahman Massomi Nejad

    2012-01-01

    4-Acyl-3-alkyl-1-phenyl-2-pyrazolin-5-one derivatives were prepared by the regioselective acylation of 3-alkyl-1-phenyl-2-pyrazolin-5-ones in the presence of base catalysts such as calcium hydroxide [Ca(OH)2], magnesium hydroxide [Mg(OH)2] and nanosized magnesium hydroxide. In the presence of nanosized magnesium hydroxide, excellent yields of products were obtained and reaction times were significantly reduced.

  6. Leaf non-structural carbohydrate allocation and C:N:P stoichiometry in response to light acclimation in seedlings of two subtropical shade-tolerant tree species.

    Science.gov (United States)

    Xie, Hongtao; Yu, Mukui; Cheng, Xiangrong

    2018-03-01

    Light availability greatly affects plant growth and development. In shaded environments, plants must respond to reduced light intensity to ensure a regular rate of photosynthesis to maintain the dynamic balance of nutrients, such as leaf non-structural carbohydrates (NSCs), carbon (C), nitrogen (N) and phosphorus (P). To improve our understanding of the nutrient utilization strategies of understory shade-tolerant plants, we compared the variations in leaf NSCs, C, N and P in response to heterogeneous controlled light conditions between two subtropical evergreen broadleaf shade-tolerant species, Elaeocarpus sylvestris (E. sylvestris) and Illicium henryi (I. henryi). Light intensity treatments were applied at five levels (100%, 52%, 33%, 15% and 6% full sunlight) for 30 weeks to identify the effects of reduced light intensity on leaf NSC allocation patterns and leaf C:N:P stoichiometry characteristics. We found that leaf soluble sugar, starch and NSC concentrations in E. sylvestris showed decreasing trends with reduced light intensity, whereas I. henryi presented slightly increasing trends from 100% to 15% full sunlight and then significant decreases at extremely low light intensity (6% full sunlight). The soluble sugar/starch ratio of E. sylvestris decreased with decreasing light intensity, whereas that of I. henryi remained stable. Moreover, both species exhibited increasing trends in leaf N and P concentrations but limited leaf N:P and C:P ratio fluctuations with decreasing light intensity, revealing their adaptive strategies for poor light environments and their growth strategies under ideal light environments. There were highly significant correlations between leaf NSC variables and C:N:P stoichiometric variables in both species, revealing a trade-off in photosynthesis production between leaf NSC and carbon allocation. Thus, shade-tolerant plants readjusted their allocation of leaf NSCs, C, N and P in response to light acclimation. Redundancy analysis showed

  7. OPTIMASI KONSENTRASI INOKULUM, RASIO C:N:P DAN pH PADA PROSES BIOREMEDIASI LIMBAH PENGILANGAN MINYAK BUMI MENGGUNAKAN KULTUR CAMPURAN

    Directory of Open Access Journals (Sweden)

    Syukria Ikhsan Zam

    2010-03-01

    Full Text Available The purposes of this research were to obtain the best inoculum concentration, C:N:P ratio, and pH, and also to identify the ability of mixed culture of hydrocarbonoclastic bacteria in oil waste degradation. The isolats were used are Acinetobacter baumanni, Alcaligenes eutrophus, Bacillus sp1., Methylococcus capsulatus, Bacillus sp2., Morococcus sp., Pseudomonas diminuta, Xanthomonas albilineans, Bacillus cereus and Flavobacterium branchiophiia. Variation of inoculum concentrations were 10%, 15%, and 20% (v/v, C:N:P ratios were 100:10:1, 100:10:0,5, 100:5:1, and 100:5:0,5, and pH were 6,5, 7,0, 7,5. Observed parameters in optimization were Total Plate Count (TPC the culture every 24 hours, Total Petroleum Hydrocarbon (TPH and Chemical Oxygen Demand (COD examined at the end of the bioremediation period. Best optimization result then analyzed with GC/MS. Optimization result indicated the best inoculum concentration was 10% with TPH degradation 61,79% and COD slope 61,75%. It is assumed that the low value of TPH degradation and COD slope at 15% and 20% inoculum concentration were caused by competition inside the bacterial population at that high inoculum concentration. The competition result in low growth and degradation. C:N:P ratio was 100:5:1 with TPH degradation 66,55% and COD slope 85,18%. It is assumed that the C:N:P ratio is equal, so it can enhance the bioremediation procces. The best pH was 7,5 with TPH degradation 73,24% and COD slope 86,28%. The process at the optimum conditions using inoculum as a mixed culture enhanced the bioremediation process with the result as follows, TPH degradation 93,06%, COD 90,73% for treatment. The chromatogram indicated that total hydrocarbon compound from nC9 – nC32 have been degraded by 43,413% – 63,117%. A good result of bioremediation was obtained from mixed culture inoculum at 10% concentration, C:N:P ratio of 100:5:1, and pH 7,5.

  8. One-pot synthesis of Au@SiO2 catalysts: A click chemistry approach

    KAUST Repository

    Solovyeva, Vera A.

    2014-10-13

    Using the copper-catalyzed azide-alkyne cycloaddition "click" reaction, a library of triazole amphiphiles with a variety of functional polar "heads" and hydrophobic or superhydrophobic "tails" was synthesized. The amphiphiles were evaluated for their ability to stabilize small Au nanoparticles, and, at the same time, serve as templates for nanocasting porous SiO2. One of the Au@SiO2 materials thus prepared was found to be a highly active catalyst for the Au nanoparticle-catalyzed regioselective hydroamination of alkynes.

  9. One-pot synthesis of Au@SiO2 catalysts: A click chemistry approach

    KAUST Repository

    Solovyeva, Vera A.; Vu, Khanh B.; Merican, Zulkifli; Sougrat, Rachid; Rodionov, Valentin O.

    2014-01-01

    Using the copper-catalyzed azide-alkyne cycloaddition "click" reaction, a library of triazole amphiphiles with a variety of functional polar "heads" and hydrophobic or superhydrophobic "tails" was synthesized. The amphiphiles were evaluated for their ability to stabilize small Au nanoparticles, and, at the same time, serve as templates for nanocasting porous SiO2. One of the Au@SiO2 materials thus prepared was found to be a highly active catalyst for the Au nanoparticle-catalyzed regioselective hydroamination of alkynes.

  10. Directly transport of suspended matter from the Yangtze River to the Okinawa trough post-major flood '98: evidence from stable isotopes and C/N ratios

    International Nuclear Information System (INIS)

    Cai Deling; Shi Xuefa; Song Xiaohong

    2007-01-01

    Water column concentrations of total suspended matter (TSM), particulate organic carbon (POC), particulate nitrogen (PN) and their stable isotopic compositions (δ 13 C and δ 15 N) are measured at two to five different depths in the Yellow Sea and East China Seas and Yangtze Estuary to clarify the effect of '98 Yangtze great flood on the transport of suspended matter in the Yellow Sea and East China Sea. Suspended matters are collected to analyze the distributions of TSM, POC, PN and salinity throughout the Yellow Sea and East China Sea in the autumn of 1998. There are marked positive correlations (r=0.89-0.98) among TSM, POC and PN, but negative relationships (r=-0.29 - -0.59) between TSM and salinity. These results conclude that the POC and PN were controlled primarily by the concentrations of TSM. The C/N ratios of particulate organic matter have a negative linear correlation with PN% (r=-0.44 - -0.71), but no correlation with POC%, which suggests C/N ratios are mainly controlled by PN%. There are distinct positive correlations between δ 15 N and POC% or PN% in surface water (r=0.36 and 0.24, p<0.01, respectively), however, the correlation do not exist in more deeper depths. In indicates that δ 15 N PN could be changed by a lot of factors, such as nutrient availability, nitrification, denitrification, different material sources and so on, except decomposition of organic matter. The distributions of C/N ratios and δ 13 C values of the particulate organic matter suggest that suspended matters from Yangtze River could be transported directly into the Okinawa Trough under the condition of '98 Yangtze major flood, which break through the foregone knowledge obtained under the normal hydrological condition. (authors)

  11. Coupled C, N and P controls on photosynthesis, primary production and decomposition across a land use intensification gradient and implications for land atmosphere C exchange

    Science.gov (United States)

    Reinsch, Sabine; Glanville, Helen; Smart, Simon; Jones, Davey; Mercado, Lina; Blanes-Alberola, Mamen; Cosby, Jack; Emmett, Bridget

    2016-04-01

    The coupling of C, N and P cycles has rarely been studied through the air- land-water continuum. This is essential if we are to enhance land-atmosphere models to account for N and P limitations. It is also important for developing integrated catchment management solutions to deliver improved water quality combined with a wide range of other ecosystem functions and services. We present results from a project which is part of the interdisciplinary pan-UK NERC Macronutrient Cycles Programme (macronutrient-cycles.ouce.ox.ac.uk/). Our aim is to quantify how coupled C, N & P cycles change across a land use intensification gradient from arable to grass, woodland and bog ecosystems and identify the implications for land-atmosphere C exchange. We focus on three key processes; photosynthesis, annual net primary productivity and decomposition and explore their consequences for biodiversity. Other aspects of the project track delivery to, and transformations within, the freshwater and coastal systems. When we explore relationships between C, N and P, results indicate all habitat types fall on a single land use intensification gradient. Stoichiometry suggests plant productivity is primarily N limited. P limitation occurs rarely but at all levels of intensification. Soil priming shows our soils are primarily C limited and, surprisingly, soil acidity provides one of the most powerful single predictors of processes and ecosystem services perhaps as it is a good integrator of many soil properties. Incorporating this knowledge into the UK land-atmosphere model JULES will improve aNPP projections. These are then being used as inputs into a plant species model called MULTIMOVE to enable future scenarios of climate change, land use and air pollution on habitat suitability for > 1400 plant species to be explored. The enhanced Jules model will ensure both N and P limitations on C fluxes from above and below-ground are incorporated into future UK scenario applications.

  12. Characteristics of water obtained by dewatering cyanobacteria-containing sludge formed during drinking water treatment, including C-, N-disinfection byproduct formation.

    Science.gov (United States)

    Xu, Hangzhou; Pei, Haiyan; Jin, Yan; Xiao, Hongdi; Ma, Chunxia; Sun, Jiongming; Li, Hongmin

    2017-03-15

    This is the first study to systematically investigate the characteristics of the water obtained by dewatering cyanobacteria-containing sludge generated in the drinking water treatment plant, including formation of C- and N-disinfection by-products (DBPs). Results showed that this 'dewatering water' (DW) had different properties when the sludge was stored at different times. The content of dissolved organic matter (DOM) and microcystins (MCs) in the DW were low when the sludge was treated or disposed of within 4 days; correspondingly, the C-, N-DBP production was also low. However, due to the damage of algal cells to some extent, the DOM and MC levels increased significantly for storage time longer than 4 days; the production of C-, N-DBPs also increased. There were also obvious differences in the characteristics of the DW from sludges generated with different coagulant species. Due to the better protective effect of FeCl 3 and polymeric aluminium ferric chloride (PAFC) flocs, the DOM and MC levels and the production of C-, N-DBPs in the DW with FeCl 3 and PAFC coagulation were lower than those with AlCl 3 coagulation, even though the sludges were stored for the same amount of time. Furthermore, because of the formation of Al and Fe hydroxides, precipitated onto the surface of flocs, the soluble Al and Fe in the DW decreased with increased storage time, especially in the first four days. Overall, this study revealed the trends in variation of DW quality for cyanobacteria-containing sludges formed with different coagulants, then FeCl 3 and PAFC coagulants are recommended and sludge should be treated or disposed of within 4 days. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Effect of Mo2C/(Mo2C + WC) weight ratio on the microstructure and mechanical properties of Ti(C,N)-based cermet tool materials

    International Nuclear Information System (INIS)

    Xu, Qingzhong; Zhao, Jun; Ai, Xing; Qin, Wenzhen; Wang, Dawei; Huang, Weimin

    2015-01-01

    To optimize the Mo 2 C content in Ti(C,N)-based cermet tool materials used for cutting the high-strength steel of 42CrMo (AISI 4140/4142 steel), the cermets with different Mo 2 C/(Mo 2 C + WC) weight ratios were prepared. And the microstructure and mechanical properties of cermets were investigated by scanning electron microscope (SEM), X-ray diffraction (XRD) and measurements of transverse rupture strength (TRS), Vickers hardness (HV) and fracture toughness (K IC ). The results indicate that the Mo 2 C/(Mo 2 C + WC) ratios have great influences on the microstructure features and mechanical properties of Ti(C,N)-based cermets. When the Mo 2 C/(Mo 2 C + WC) ratio increases, the Ti(C,N) grains become finer with smaller black cores surrounded by thinner rims, and the structure of cermets tends to be more compact with smaller binder mean free path. Owing to the medium grains and moderate rims, the cermets with a Mo 2 C/(Mo 2 C + WC) ratio of 0.4 exhibit better mechanical properties, and can be chosen as the tool material for machining 42CrMo steel due to the lower Mo content. - Highlights: • Mo 2 C/(Mo 2 C + WC) ratios affect microstructure and mechanical properties of cermets. • Grains become fine and structure of cermets tends to be compact with raised Mo 2 C. • The cermets with a Mo 2 C/(Mo 2 C + WC) ratio of 0.4 can be used to machine 42CrMo steel

  14. Probing the impact of magnetic interactions on the lattice dynamics of two-dimensional Ti2X (X = C, N) MXenes.

    Science.gov (United States)

    Sternik, Małgorzata; Wdowik, Urszula D

    2018-03-14

    Dynamical properties of the two-dimensional Ti 2 C and Ti 2 N MXenes were investigated using density functional theory and discussed in connection with their structures and electronic properties. To elucidate the influence of magnetic interactions on the fundamental properties of these systems, the nonmagnetic, ferromagnetic and three distinct antiferromagnetic spin arrangements on titanium sublattice were considered. Each magnetic configuration was also studied at two directions of the spin magnetic moment with respect to the MXene layer. The zero-point energy motion, following from the phonon calculations, was taken into account while analyzing the energetic stability of the magnetic phases against the nonmagnetic solution. This contribution was found not to change a sequence of the energetic stability of the considered magnetic structures of Ti 2 X (X = C, N) MXenes. Both Ti 2 X (X = C, N) systems are shown to prefer antiferromagnetic arrangement of spins between Ti layers and the ferromagnetic order within each layer. This energetically privileged phase is semiconducting for Ti 2 C and metallic for Ti 2 N. The type of magnetic order as well as the in-plane or out-of-plane spin polarizations have a relatively small impact on the structural parameters, Ti-X bonding length, force constants and phonon spectra of both Ti 2 X systems, leading to observable differences only between the nonmagnetic and any other magnetic configurations. Nonetheless, a noticeable effect of the spin orientation on degeneracy of the Ti-3d orbitals is encountered. The magnetic interactions affect to a great extent the positions and intensities of the Raman-active modes, and hence one could exploit this effect for experimental verification of the theoretically predicted magnetic state of Ti 2 X monolayers. Theoretical phonon spectra of Ti 2 X (X = C, N) MXenes exhibit a linear dependence on energy in the long-wavelength limit, which is typical for a 2D system.

  15. Biomolecule-controlled hydrothermal synthesis of C-N-S-tridoped TiO2 nanocrystalline photocatalysts for NO removal under simulated solar light irradiation.

    Science.gov (United States)

    Wang, Yawen; Huang, Yu; Ho, Wingkei; Zhang, Lizhi; Zou, Zhigang; Lee, Shuncheng

    2009-09-30

    In this study, C-N-S-tridoped titanium dioxide (TiO(2)) nanocrystals were synthesized by using a facile hydrothermal method in the presence of a biomolecule l-cysteine. This biomolecule could not only serve as the common source for the carbon, sulfur and nitrogen tridoping, but also could control the final crystal phases and morphology. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and UV-vis diffuse reflectance spectroscopy. XPS analysis revealed that S was incorporated into the lattice of TiO(2) through substituting oxygen atoms, N might coexist in the forms of N-Ti-O and Ti-O-N in tridoped TiO(2) and most C could form a mixed layer of carbonate species deposited on the surface of TiO(2) nanoparticles. The photocatalytic activities of the samples were tested on the removal of NO at typical indoor air level in a flow system under simulated solar light irradiation. The tridoped TiO(2) samples showed much higher removal efficiency than commercial P25 and the undoped counterpart photocatalyst. The enhanced visible light photocatalytic activity of C-N-S-tridoped TiO(2) nanocrystals was explained on the basis of characterizations. The possible formation process of the monodispersed C-N-S-tridoped anatase TiO(2) nanocrystals was also proposed. This study provides a new method to prepare visible light active TiO(2) photocatalyst.

  16. Biomolecule-controlled hydrothermal synthesis of C-N-S-tridoped TiO2 nanocrystalline photocatalysts for NO removal under simulated solar light irradiation

    International Nuclear Information System (INIS)

    Wang Yawen; Huang Yu; Ho Wingkei; Zhang Lizhi; Zou Zhigang; Lee Shuncheng

    2009-01-01

    In this study, C-N-S-tridoped titanium dioxide (TiO 2 ) nanocrystals were synthesized by using a facile hydrothermal method in the presence of a biomolecule L-cysteine. This biomolecule could not only serve as the common source for the carbon, sulfur and nitrogen tridoping, but also could control the final crystal phases and morphology. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and UV-vis diffuse reflectance spectroscopy. XPS analysis revealed that S was incorporated into the lattice of TiO 2 through substituting oxygen atoms, N might coexist in the forms of N-Ti-O and Ti-O-N in tridoped TiO 2 and most C could form a mixed layer of carbonate species deposited on the surface of TiO 2 nanoparticles. The photocatalytic activities of the samples were tested on the removal of NO at typical indoor air level in a flow system under simulated solar light irradiation. The tridoped TiO 2 samples showed much higher removal efficiency than commercial P25 and the undoped counterpart photocatalyst. The enhanced visible light photocatalytic activity of C-N-S-tridoped TiO 2 nanocrystals was explained on the basis of characterizations. The possible formation process of the monodispersed C-N-S-tridoped anatase TiO 2 nanocrystals was also proposed. This study provides a new method to prepare visible light active TiO 2 photocatalyst.

  17. Effect of adding low-concentration of rhamnolipid on reactor performances and microbial community evolution in MBBRs for low C/N ratio and antibiotic wastewater treatment.

    Science.gov (United States)

    Peng, Pengcheng; Huang, Hui; Ren, Hongqiang

    2018-05-01

    This study aims to explore the potential of low-concentration of rhamnolipid in efficient treatment of wastewater with poor biodegradability. Six lab-scale moving bed biofilm reactors (MBBRs) were applied to investigate the effect of rhamnolipid concentration (0, 20, 50 mg/L) on pollutants removal, biomass accumulation, microbial morphology and community evolution in synthetic low C/N ratio (3:1) and antibiotic (50 μg/L tetracycline) wastewater. 20 mg/L rhamnolipid treated groups exhibited significant increase (p poorly biodegradable wastewater by biofilm process with moderate amount of rhamnolipid. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Analysis of the effect of interface state charges on threshold voltage and transconductance of 6H-SiC N-channel MOSFET

    International Nuclear Information System (INIS)

    Tang Xiaoyan; Zhang Yimen; Zhang Yuming

    2002-01-01

    The effect of interface state charges on the threshold voltage and transconductance of 6H-SiC N-channel metal-oxide semiconductor field-effect transistor (MOSFET) is analyzed based on the non-uniformly distributed interface state density in the band gap and incomplete impurity ionization in silicon carbide. The results show that the nonuniform distribution of interface state density cause not only the increment of the threshold voltage but also the degradation of the transconductance of MOSFET so that it is one of the important factors to influence the characteristics of SiC MOSFET

  19. El control numérico computarizado en el desarrollo industrial Parte 2: desarrollo y aplicaciones del C.N.C.

    OpenAIRE

    Ruiz, Lino

    2016-01-01

    En la edición anterior nuestro principal énfasis fue el de presentar el control numérico computarizado (C.N.C.) como una alternativa tecnológica que pueda potenciar nuestro desarrollo industrial, por lo que describimos sus características principales y su incidencia en el trabajador. En el presente articulo nos enfocaremos, más al manejo de la información en las máquinas CNC, las tendencias actuales del desarrollo de las MHCNC y las tendencias industriales de nuestra época.

  20. Measurement of the $^{12}$C($n,p$)$^{12}$B cross section at n_TOF (CERN) by in-beam activation analysis

    CERN Document Server

    Žugec, P.; Bosnar, D.; Mengoni, A.; Altstadt, S.; Andrzejewski, J.; Audouin, L.; Barbagallo, M.; Bécares, V.; Bečvář, F.; Belloni, F.; Berthoumieux, E.; Billowes, J.; Boccone, V.; Brugger, M.; Calviani, M.; Calviño, F.; Cano-Ott, D.; Carrapiço, C.; Cerutti, F.; Chiaveri, E.; Chin, M.; Cortés, G.; Cortés-Giraldo, M.A.; Cosentino, L.; Diakaki, M.; Domingo-Pardo, C.; Dressler, R.; Duran, I.; Eleftheriadis, C.; Ferrari, A.; Finocchiaro, P.; Fraval, K.; Ganesan, S.; García, A.R.; Giubrone, G.; Gómez-Hornillos, M.B.; Gonçalves, I.F.; González-Romero, E.; Griesmayer, E.; Guerrero, C.; Gunsing, F.; Gurusamy, P.; Heinitz, S.; Jenkins, D.G.; Jericha, E.; Käppeler, F.; Karadimos, D.; Kivel, N.; Kokkoris, M.; Krtička, M.; Kroll, J.; Langer, C.; Lederer, C.; Leeb, H.; Leong, L.S.; Lo Meo, S.; Losito, R.; Manousos, A.; Marganiec, J.; Martínez, T.; Massimi, C.; Mastinu, P.; Mastromarco, M.; Mendoza, E.; Milazzo, P.M.; Mingrone, F.; Mirea, M.; Mondalaers, W.; Musumarra, A.; Paradela, C.; Pavlik, A.; Perkowski, J.; Plompen, A.; Praena, J.; Quesada, J.; Rauscher, T.; Reifarth, R.; Riego, A.; Roman, F.; Rubbia, C.; Sarmento, R.; Saxena, A.; Schillebeeckx, P.; Schmidt, S.; Schumann, D.; Tagliente, G.; Tain, J.L.; Tarrío, D.; Tassan-Got, L.; Tsinganis, A.; Valenta, S.; Vannini, G.; Variale, V.; Vaz, P.; Ventura, A.; Versaci, R.; Vermeulen, M.J.; Vlachoudis, V.; Vlastou, R.; Wallner, A.; Ware, T.; Weigand, M.; Weiß, C.; Wright, T.

    2014-01-01

    The integral cross section of the $^{12}$C($n,p$)$^{12}$B reaction has been determined for the first time in the neutron energy range from threshold to several GeV at the n_TOF facility at CERN. The measurement relies on the activation technique, with the $\\beta$-decay of $^{12}$B measured over a period of four half-lives within the same neutron bunch in which the reaction occurs. The results indicate that model predictions, used in a variety of applications, are mostly inadequate. The value of the integral cross section reported here can be used as a benchmark for verifying or tuning model calculations.

  1. Integral measurement of the {sup 12}C(n, p){sup 12}B reaction up to 10 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Zugec, P.; Bosnar, D. [University of Zagreb, Department of Physics, Faculty of Science, Zagreb (Croatia); Colonna, N.; Barbagallo, M.; Mastromarco, M.; Tagliente, G.; Variale, V. [Istituto Nazionale di Fisica Nucleare, Bari (Italy); Ventura, A. [Istituto Nazionale di Fisica Nucleare, Bologna (Italy); Mengoni, A. [ENEA, Bologna (Italy); Altstadt, S.; Langer, C.; Lederer, C.; Reifarth, R.; Schmidt, S.; Weigand, M. [Johann-Wolfgang-Goethe Universitaet, Frankfurt (Germany); Andrzejewski, J.; Marganiec, J.; Perkowski, J. [Uniwersytet Lodzki, Lodz (Poland); Audouin, L.; Leong, L.S.; Tassan-Got, L. [Centre National de la Recherche Scientifique/IN2P3 - IPN, Orsay (France); Becares, V.; Cano-Ott, D.; Garcia, A.R.; Gonzalez-Romero, E.; Martinez, T.; Mendoza, E. [Centro de Investigaciones Energeticas Medioambientales y Tecnologicas (CIEMAT), Madrid (Spain); Becvar, F.; Krticka, M.; Kroll, J.; Valenta, S. [Charles University, Prague (Czech Republic); Belloni, F.; Mondalaers, W.; Plompen, A.; Schillebeeckx, P. [European Commission JRC, Institute for Reference Materials and Measurements, Geel (Belgium); Berthoumieux, E.; Fraval, K.; Gunsing, F. [CEA/Saclay - IRFU, Gif-sur-Yvette (France); Billowes, J.; Ware, T.; Wright, T. [University of Manchester, Manchester (United Kingdom); Boccone, V.; Brugger, M.; Calviani, M.; Cerutti, F.; Chiaveri, E.; Chin, M.; Ferrari, A.; Guerrero, C.; Losito, R.; Roman, F.; Rubbia, C.; Tsinganis, A.; Versaci, R.; Vlachoudis, V.; Weiss, C. [CERN, Geneva (Switzerland); Calvino, F.; Cortes, G.; Gomez-Hornillos, M.B.; Riego, A. [Universitat Politecnica de Catalunya, Barcelona (Spain); Carrapico, C.; Goncalves, I.F.; Sarmento, R.; Vaz, P. [Universidade de Lisboa, C2TN-Instituto Superior Tecnico, Lisboa (Portugal); Cortes-Giraldo, M.A.; Praena, J.; Quesada, J. [Universidad de Sevilla, Sevilla (Spain); Cosentino, L.; Finocchiaro, P. [INFN - Laboratori Nazionali del Sud, Catania (Italy); Diakaki, M.; Karadimos, D.; Kokkoris, M.; Vlastou, R. [National Technical University of Athens (NTUA), Athens (Greece); Domingo-Pardo, C.; Giubrone, G.; Tain, J.L. [CSIC-Universidad de Valencia, Instituto de Fisica Corpuscular, Valencia (Spain); Dressler, R.; Heinitz, S.; Kivel, N.; Schumann, D. [Paul Scherrer Institut, Villigen (Switzerland); Duran, I.; Tarrio, D. [Universidade de Santiago de Compostela, Santiago de Compostela (Spain); Eleftheriadis, C.; Manousos, A. [Aristotle University of Thessaloniki, Thessaloniki (Greece); Ganesan, S.; Gurusamy, P.; Saxena, A. [Bhabha Atomic Research Centre (BARC), Mumbai (India); Griesmayer, E.; Jericha, E.; Leeb, H. [Atominstitut der Oesterreichischen Universitaeten, Technische Universitaet Wien, Wien (Austria); Jenkins, D.G.; Vermeulen, M.J. [University of York, York, Heslington (United Kingdom); Kaeppeler, F. [Karlsruhe Institute of Technology (KIT), Institut fuer Kernphysik, Karlsruhe (Germany); Lo Meo, S. [Istituto Nazionale di Fisica Nucleare, Bologna (Italy); ENEA, Bologna (Italy); Massimi, C.; Mingrone, F.; Vannini, G. [Dipartimento di Fisica, Universita di Bologna (IT); INFN, Bologna (IT); Mastinu, P. [Laboratori Nazionali di Legnaro, Istituto Nazionale di Fisica Nucleare, Legnaro (IT); Milazzo, P.M. [Istituto Nazionale di Fisica Nucleare, Trieste (IT); Mirea, M. [Horia Hulubei National Institute of Physics and Nuclear Engineering - IFIN HH, Magurele (RO); Musumarra, A. [Universita di Catania, Dipartimento di Fisica e Astronomia DFA, Catania (IT); INFN-Laboratori Nazionali del Sud, Catania (IT); Paradela, C. [European Commission JRC, Institute for Reference Materials and Measurements, Geel (BE); Universidade de Santiago de Compostela, Santiago de Compostela (ES); Pavlik, A. [Faculty of Physics, University of Vienna, Wien (AT); Rauscher, T. [University of Hertfordshire, Centre for Astrophysics Research, School of Physics, Astronomy and Mathematics, Hatfield (GB); University of Basel, Department of Physics, Basel (CH); Wallner, A. [Faculty of Physics, University of Vienna, Wien (AT); Australian National University, Research School of Physics and Engineering, Canberra (AU)

    2016-04-15

    The integral measurement of the {sup 12}C(n, p){sup 12}B reaction was performed at the neutron time-of-flight facility nTOF at CERN. The total number of {sup 12}B nuclei produced per neutron pulse of the nTOF beam was determined using the activation technique in combination with a time-of-flight technique. The cross section is integrated over the nTOF neutron energy spectrum from reaction threshold at 13.6 MeV to 10 GeV. Having been measured up to 1GeV on basis of the {sup 235}U(n, f) reaction, the neutron energy spectrum above 200 MeV has been re-evaluated due to the recent extension of the cross section reference for this particular reaction, which is otherwise considered a standard up to 200 MeV. The results from the dedicated GEANT4 simulations have been used to evaluate the neutron flux from 1 GeV up to 10 GeV. The experimental results related to the {sup 12}C(n, p){sup 12}B reaction are compared with the evaluated cross sections from major libraries and with the predictions of different GEANT4 models, which mostly underestimate the {sup 12}B production. On the contrary, a good reproduction of the integral cross section derived from measurements is obtained with TALYS-1.6 calculations, with optimized parameters. (orig.)

  2. Thermophilic co-digestion feasibility of distillers grains and swine manure: effect of C/N ratio and organic loading rate during high solid anaerobic digestion (HSAD).

    Science.gov (United States)

    Sensai, P; Thangamani, A; Visvanathan, C

    2014-01-01

    Anaerobic co-digestion of high solids containing distillers grains and swine manure (total solids, 27 +/- 2% and 18 +/- 2%, respectively) was evaluated in this study to assess the effect of C/N ratio and organic loading rate (OLR). Feed mixture was balanced to achieve a C/N ratio of 30/1 by mixing distillers grains and swine manure. Pilot-scale co-digestion of distillers grains and swine manure was carried out under thermophilic conditions in the continuous mode for seven different OLRs from R1 to R7 (3.5, 5, 6, 8, 10, 12 and 14 kg VS/m3 day) under high solid anaerobic digestion. The methane yield and volatile solid (VS) removal were consistent; ranging from 0.33 to 0.34 m3CH4/kg VS day and 50-53%, respectively, until OLR 8 kg VS/m3 day. After which methane yield and VS removal significantly decreased to 0.26 m3 CH4/kg VS day and 42%, respectively, when OLR was increased to 14 kg VS/m3 day. However, during operation, at OLR of 10 kg VS/m3 day, the methane yield and VS removal increased after the 19th day to 0.33 m3 CH4/kg VS day and 46%, respectively, indicating that a longer acclimatization period is required by methanogens at a higher loading rate.

  3. The radiation effects of aspergillus oryzae spores with soft x-rays near the K shell absorption edges of C, N, O elements from synchrotron radiation

    International Nuclear Information System (INIS)

    Chen Liang; Jiang Shiping; Wan Libiao; Ma Xiaodong; Li Meifang

    2007-01-01

    The dose deposition of different parts of Aspergillus oryzae spores were analyzed with soft X-ray energies near the K-shell absorption edges of C, N, O elements (4.4nm, 3.2nm and 2.3nm), respectively. At the same time, the spores were irradiated with the three wavelengths of soft X-rays on the soft X-ray microscopy from synchrotron radiation at NSRL, and the survivals were compared. The theoretical analyses showed that the deposition doses of different parts of the spore were varying with X-ray energies because of the effects of C, N, O K-shell absorption edges and elemental contents of the different parts of spore. The experimental studies proved three wavelengths of soft X-rays all had high killing abilities. Among these, 2.3nm wavelength X-rays had higher radiation damage to spore than that of 3.2nm, 4.4nm. (authors)

  4. Is Tree Species Diversity or Species Identity the More Important Driver of Soil Carbon Stocks, C/N Ratio, and pH?

    DEFF Research Database (Denmark)

    Dawud, Seid Muhie; Raulund-Rasmussen, Karsten; Domisch, Timo

    2016-01-01

    We explored tree species diversity effects on soil C stock, C/N ratio, and pH as compared with effects of tree species identity. We sampled forest floors and mineral soil (0–40 cm) in a diversity gradient of 1–5 tree species composed of conifers and broadleaves in Białowieża Forest, Poland...... mechanism for higher root carbon input and in turn a deeper distribution of C in diverse forests. Diversity and identity affected soil pH in topsoil with positive and negative impacts, respectively. More diverse forests would lead to higher soil nutrient status as reflected by higher topsoil p......H, but there was a slight negative effect on N status as indicated by higher C/N ratios in the deeper layers. We conclude that tree species diversity increases soil C stocks and nutrient status to some extent, but tree species identity is a stronger driver of the studied soil properties, particularly in the topsoil....

  5. Regioselective aromatic substitution reactions of cyclometalated Ir(III) complexes: synthesis and photochemical properties of substituted Ir(III) complexes that exhibit blue, green, and red color luminescence emission.

    Science.gov (United States)

    Aoki, Shin; Matsuo, Yasuki; Ogura, Shiori; Ohwada, Hiroki; Hisamatsu, Yosuke; Moromizato, Shinsuke; Shiro, Motoo; Kitamura, Masanori

    2011-02-07

    In this manuscript, the regioselective halogenation, nitration, formylation, and acylation of Ir(tpy)(3) and Ir(ppy)(3) (tpy = 2-(4'-tolyl)pyridine and ppy = 2-phenylpyridine) and the subsequent conversions are described. During attempted bromination of the three methyl groups in fac-Ir(tpy)(3) using N-bromosuccinimide (NBS) and benzoyl peroxide (BPO), three protons at the 5'-position (p-position with respect to the C-Ir bond) of phenyl rings in tpy units were substituted by Br, as confirmed by (1)H NMR spectra, mass spectra, and X-ray crystal structure analysis. It is suggested that such substitution reactions of Ir complexes proceed via an ionic mechanism rather than a radical mechanism. UV-vis and luminescence spectra of the substituted Ir(III) complexes are reported. The introduction of electron-withdrawing groups such as CN and CHO groups at the 5'-position of tpy induces a blue shift of luminescence emission to about 480 nm, and the introduction of electron-donating groups such as an amino group results in a red shift to about 600 nm. A reversible change of emission for the 5'-amino derivative of Ir(tpy)(3), Ir(atpy)(3), between red and green occurs upon protonation and deprotonation.

  6. Effective atomic numbers and electron densities of some biologically important compounds containing H, C, N and O in the energy range 145-1330 keV

    International Nuclear Information System (INIS)

    Manjunathaguru, V; Umesh, T K

    2006-01-01

    A semi-empirical relation which can be used to determine the total attenuation cross sections of samples containing H, C, N and O in the energy range 145-1332 keV has been derived based on the total attenuation cross sections of several sugars, amino acids and fatty acids. The cross sections have been measured by performing transmission experiments in a narrow beam good geometry set-up by employing a high-resolution hyperpure germanium detector at seven energies of biological importance such as 145.4 keV, 279.2 keV, 514 keV, 661.6 keV, 1115.5 keV, 1173.2 keV and 1332.1 keV. The semi-empirical relation can reproduce the experimental values within 1-2%. The total attenuation cross sections of five elements carbon, aluminium, titanium, copper and zirconium measured in the same experimental set-up at the energies mentioned above have been used in a new matrix method to evaluate the effective atomic numbers and the effective electron densities of samples such as cholesterol, fatty acids, sugars and amino acids containing H, C, N and O atoms from their effective atomic cross sections. The effective atomic cross sections are the total attenuation cross sections divided by the total number of atoms of all types in a particular sample. Further, a quantity called the effective atomic weight was defined as the ratio of the molecular weight of a sample to the total number of atoms of all types in it. The variation of the effective atomic number was systematically studied with respect to the effective atomic weight and a new semi-empirical relation for Z eff has been evolved. It is felt that this relation can be very useful to determine the effective atomic number of any sample having H, C, N and O atoms in the energy range 145-1332 keV irrespective of its chemical structure

  7. In silico insight into ammonia adsorption on pristine and X-doped phosphorene (X = B, C, N, O, Si, and Ni)

    Energy Technology Data Exchange (ETDEWEB)

    Arabieh, Masoud, E-mail: marabieh@aeoi.org.ir [NSTRI, P. O. Box 11365-8488, Tehran (Iran, Islamic Republic of); Azar, Yavar Taghipour [Theoretical and Computational Physics Group, Physics and accelerators school, NSTRI, AEOI, P. O. Box 11365-8486, Tehran (Iran, Islamic Republic of)

    2017-02-28

    Highlights: • Ammonia adsorption on pristine and doped single layer black phosphorous (SBP) has been investigated theoretically. • Doping heteroatoms increase/decrease internal distortion and E{sub g} values in all systems. • The highest and lowest adsorption energy of ammonia on modified BPS system were found to be −43.3 and −6.79 kcal/mol for B-BPS and O-BPS, respectively. • Ammonia adsorption on B-doped BPS, leaded to the remarkable change in DOS, accompanied by fading of a small peak in the gap region. - Abstract: In this study the details of ammonia adsorption on pristine and doped single layered black phosphorous (SBP) have been investigated based on density functional theory. Geometry optimization were carried using different density functional such as B3LYP, PBE and B97D in conjugate with 6–31 + G* basis set. From geometrical point of view, doping heteroatoms causes internal distortion in SBP which was found large for B-, C-, N- and O-doped BP sheet(s). Doping heteroatom also decreases the Eg values in all of the studied SBP systems. Calculation showed that the largest adsorption energies for ammonia on SBP belong to B-, Si, and Ni-doped system(s) with the energy values of −43.3, −35.3 and −17.05 kcal/mol, respectively. It was found that the adsorption energies for pristine and C-, N- and O-doped SBP are not significant (E{sub ad} < 8.6 kcal/mol). We suggested that metal dopants (B, Ni and Si) improve the reactivity of SBP to ammonia molecule in contrast to pristine and non-metal doped-SBP (C, N and O). Our results showed that whereas the substitution of most dopants has a significant effect on the gap width of the doped system, nitrogen doping has no important influence on gap width and overall shape of DOS curve. Adsorption of ammonia on the N-, C-, and O-doped systems had no significant effect on the electronic structure of these systems, whereas it changed the DOS curves of Si-, and Ni-doped systems slightly. In the case of B

  8. Modelling the response of yields and tissue C : N to changes in atmospheric CO2 and N management in the main wheat regions of western Europe

    DEFF Research Database (Denmark)

    Olin, S.; Schurgers, Guy; Lindeskog, M.

    2015-01-01

    increase the model performance compared to an earlier version of the model that does not account for these interactions. For these simulations, we also demonstrate an implementation of N fertilisation timing for areas where this information is not available. This feature is crucial when accounting...... (DVMs) aim to accurately represent both natural vegetation and managed land, not only from a carbon cycle perspective but increasingly so also for a wider range of processes including crop yields. We present here the extended version of the DVM LPJ-GUESS that accounts for N limitation in crops...... production, tissue C to N ratios (C: N) and phenology. To test the model’s applicability for larger regions, simulations are subsequently performed that cover the wheatdominated regions of western Europe. When compared to regional yield statistics, the inclusion of C–N dynamics in the model substantially...

  9. Interactions between Al₁₂X (X = Al, C, N and P) nanoparticles and DNA nucleobases/base pairs: implications for nanotoxicity.

    Science.gov (United States)

    Jin, Peng; Chen, Yongsheng; Zhang, Shengbai B; Chen, Zhongfang

    2012-02-01

    The interactions between neutral Al(12)X(I ( h )) (X = Al, C, N and P) nanoparticles and DNA nucleobases, namely adenine (A), thymine (T), guanine (G) and cytosine (C), as well as the Watson-Crick base pairs (BPs) AT and GC, were investigated by means of density functional theory computations. The Al(12)X clusters can tightly bind to DNA bases and BPs to form stable complexes with negative binding Gibbs free energies at room temperature, and considerable charge transfers occur between the bases/BPs and the Al(12)X clusters. These strong interactions, which are also expected for larger Al nanoparticles, may have potentially adverse impacts on the structure and stability of DNA and thus cause its dysfunction.

  10. Measured, calculated and predicted Stark widths of the singly ionized C, N, O, F, Ne, Si, P, S, Cl and Ar spectral lines

    Directory of Open Access Journals (Sweden)

    Djeniže S.

    2000-01-01

    Full Text Available In order to find reliable Stark width data, needed in plasma spectroscopy comparision between the existing measured, calculated and predicted Stark width values was performed for ten singly ionized emitters: C, N, O, F, Ne Si, P, S, Cl and Ar in the lower lying 3s - 3p, 3p - 3d and 4s - 4p transitions. These emitters are present in many cosmic light sources. On the basis of the agreement between mentioned values 17 spectral lines from six singly ionized spectra have been recommended, for the first time, for plasma spectroscopy as spectral lines with reliable Stark width data. Critical analysis of the existing Stark width data is also given.

  11. The determination of the C, N, O and trace element content of Triticum aestivum by activation analysis, X-ray excitation and mass spectrometry

    International Nuclear Information System (INIS)

    Leonhardt, J.W.; Dahn, E.; Dietze, H.J.; Freyer, K.; Geisler, M.; Hartmann, G.; Jung, K.; Schelhorn, H.

    1979-01-01

    The results of determinations of the C, N, O and trace element content of grains, sprouts and leaves of Triticum aestivum by means of various methods of activation analysis, X-ray excitation and mass spectrometry are presented. The C and O contents were determined by X-ray excitation; the O, N, P and Si contents were measured by NAA with 14-MeV neutrons, and the trace elements were determined by NAA with thermal neutrons. A mass-spectrometric survey analysis confirmed the results obtained by NAA. The use of neutron-induced nuclear reactions together with autoradiography enabled a representative picture to be formed of the spatial distribution in two dimensions of 14 N in biological specimens. (author)

  12. Determination of astrophysical 13N(p, γ)14O S-factors from the asymptotic normalization coefficient of 14C→13C + n

    International Nuclear Information System (INIS)

    Guo Bing; Li Zhihong

    2007-01-01

    The angular distribution of the 13 C(d,p) 14 C reaction is reanalysed using the Johnson-Soper approach. The squared asymptotic normalization coefficient (ANC) of virtual decay 14 C→ 13 C + n is then derived to be 21.4 ± 5.0 fm -1 . The squared ANC and spectroscopic factor (SF) of 14 O→ 13 N + p are extracted to be 30.4 ± 7.1 fm -1 and 1.94 ± 0.45, respectively. The astrophysical S-factors and reaction rates of 13 N(p, γ) 14 O are determined from the ANC of 14 O→ 13 N + p using the R-matrix approach. (authors)

  13. Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

    KAUST Repository

    Elshewy, Ahmed M.

    2013-12-01

    Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

  14. A quantitative relationship for the shock sensitivities of energetic compounds based on X-NO(2) (X=C, N, O) bond dissociation energy.

    Science.gov (United States)

    Li, Jinshan

    2010-08-15

    The ZPE-corrected X-NO(2) (X=C, N, O) bond dissociation energies (BDEs(ZPE)) of 11 energetic nitrocompounds of different types have been calculated employing density functional theory methods. Computed results show that using the 6-31G** basis set the UB3LYP calculated BDE(ZPE) is less than the UB3P86. For these typical energetic nitrocompounds the shock-initiated pressure (P(98)) is strongly related to the BDE(ZPE) indeed, and a polynomial correlation of ln(P(98)) with the BDE(ZPE) has been established successfully at different density functional theory levels, which provides a method to address the shock sensitivity problem. Copyright 2010 Elsevier B.V. All rights reserved.

  15. Geometrical Structures and Electronic Properties of Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl Clusters

    Directory of Open Access Journals (Sweden)

    Yanfei Hu

    2018-04-01

    Full Text Available Based on the unbiased CALYPSO (Crystal structure Analysis by Particle Swarm Optimization structure searching method in combination with density functional theory (DFT, the geometrical structures and electronic properties are investigated theoretically for Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl clusters. The PBE0 exchange-correlation functional and the 6-311G(d basis set is carried out to determine global minima on potential energy surfaces. The relative stabilities of the clusters are examined by the binding energies and substitution reaction. Following the predictions of the Jellium model, the Ga5B cluster with the 18 valence electrons is the most stable structure. At last, with the obtained lowest energy structures, some physical properties such as electrons transfer, molecular orbitals, and total and partial densities of states are discussed, respectively.

  16. Functional significance of tree species diversity and species identity on soil organic carbon, C/N ratio and pH in major European forest types

    DEFF Research Database (Denmark)

    Dawud, Seid Muhie

    Forests provide different ecosystem functions and services including soil carbon sequestration and nutrient supply to maintain growth and productivity. This PhD thesis explored tree species diversity and tree species identity (conifer proportion of basal area) effects on soil C stock and nutrient...... 8 and 12 years old common garden stands established in two contrasting bioclimatic regions. In all the studied contexts, tree species identity (confers versus broadleaves) was stronger than diversity in consistently driving variability of the examined soil properties and root characteristics......, particularly in topsoil layers. Diversity did not affect fine root characteristics of the young forests and effects on soil properties were different under the investigated contexts. Across the different European sites, diversity had no effect on C/N ratio and pH but under comparable environmental conditions...

  17. Precipitation Behaviour of Carbonitrides in Ti-Nb-C-N Microalloyed Steels and an Engineering Application with Homogenously Precipitated Nano-particles

    Directory of Open Access Journals (Sweden)

    Yanlin WANG

    2015-11-01

    Full Text Available A thermodynamic model enabling calculation of equilibrium carbonitride composition and relative amounts as a function of steel composition and temperature has been developed previously based on the chemical equilibrium method. In the present work, actual carbonitride precipitation behaviour has been verified in the Ti-Nb-C-N microalloyed steels. The Ti microalloyed steel after refining with 0.012 % Nb exhibited highly improved tensile strength without sacrificing ductility. According to further detailed SEM and TEM analysis, the improved mechanical properties of Ti/Nb microalloyed steel could be attributed to the larger solubility of Nb and Ti, inducing fine dispersion of the carbonitrides with particle size of 2 – 10 nm in the ferrite matrix.DOI: http://dx.doi.org/10.5755/j01.ms.21.4.9622

  18. Total electron scattering cross sections of molecules containing H, C, N, O and F in the energy range 0.2–6.0 keV

    Energy Technology Data Exchange (ETDEWEB)

    Gurung, Meera Devi; Ariyasinghe, W.M., E-mail: wickram_ariyasinghe@baylor.edu

    2017-03-15

    Based on the effective atomic total electron scattering cross sections (EATCS) of atoms in a molecular environment, a simple model is proposed to predict the total electron scattering cross sections (TCS) of H, C, N, O, and F containing molecules. The EATCS for these five atoms are reported for 0.2–6.0 keV energies. The predicted TCS by this model are compared with experimental TCS in the literature. The experimental TCS of CHF{sub 3}, C{sub 2}F{sub 4}, C{sub 2}F{sub 2}H{sub 2}, C{sub 4}F{sub 6}, and c-C{sub 4}F{sub 8} have been obtained for 0.2–4.5 keV electrons by measuring the attenuation of the electron beam through a gas cell.

  19. Cell surface acid-base properties of Escherichia coli and Bacillus brevis and variation as a function of growth phase, nitrogen source and C:N ratio.

    Science.gov (United States)

    Hong, Yongsuk; Brown, Derick G

    2006-07-01

    Potentiometric titration has been conducted to systematically examine the acid-base properties of the cell surfaces of Escherichia coli K-12 and Bacillus brevis as a function of growth phase, nitrogen source (ammonium or nitrate), and carbon to nitrogen (C:N) ratio of the growth substrate. The two bacterial species revealed four distinct proton binding sites, with pK(a) values in the range of 3.08-4.05 (pK(1)), 4.62-5.57 (pK(2)), 6.47-7.30 (pK(3)), and 9.68-10.89 (pK(4)) corresponding to phosphoric/carboxylic, carboxylic, phosphoric, and hydroxyl/amine groups, respectively. Two general observations in the data are that for B. brevis the first site concentration (N(1)), corresponding to phosphoric/carboxylic groups (pK(1)), varied as a function of nitrogen source, while for E. coli the fourth site concentration (N(4)), corresponding to hydroxyl/amine groups (pK(4)), varied as a function of C:N ratio. Correspondingly, it was found that N(1) was the highest of the four site concentrations for B. brevis and N(4) was the highest for E. coli. The concentrations of the remaining sites showed little variation. Finally, comparison between the titration data and a number of cell surface compositional studies in the literature indicates one distinct difference between the two bacteria is that pK(4) of the Gram-negative E. coli can be attributed to hydroxyl groups while that of the Gram-positive B. brevis can be attributed to amine groups.

  20. Effects of Combined Application of Biogas Slurry and Chemical Fertilizer on Soil Aggregation and C/N Distribution in an Ultisol

    Science.gov (United States)

    Zheng, Xuebo; Fan, Jianbo; Xu, Lei; Zhou, Jing

    2017-01-01

    Unreasonable use of chemical fertilizer (CF) on agricultural soil leads to massive losses of soil organic carbon (SOC) and total nitrogen (TN) in tropical and subtropical areas, where soil conditions are unfavorable for aggregate formation. This study evaluated the effects of combined application of biogas slurry (BS) plus CF on soil aggregation and aggregate—associated C/N concentration and storage in an Ultisol. Six treatments included: no fertilizer (T1), CF only (T2), partial (15% (T3), 30% (T4) and 45% (T5)) substitution of TN with BS and BS only (T6). Soil mechanical—stable aggregates (MSAs) formation and stability as well as MSAs—associated C/N concentration and storage were observed in different aggregate sizes (>5, 5–2, 2–1, 1.0–0.5, 0.50–0.25 and 5 mm significantly increased with BS substitution (T5), while the proportions of MSAs 1.0–0.5 mm, MSAs 0.50–0.25 mm and MSAs 0.5 mm that constituted 72–82% of MSAs. Stepwise regression analysis showed that MSAs >5 mm, SOC in MSAs >5 mm and TN in MSAs >5 mm were the dominant variables affecting aggregate stability. Meanwhile SOC in MSAs <0.25 mm and TN in MSAs 2–1 mm were independent variables affecting SOC and TN concentrations in bulk soils. Therefore, certain rate of combined application of BS plus CF is an effective, eco—friendly way to improve soil quality in an Ultisol. PMID:28125647

  1. Performance of single-pass and by-pass multi-step multi-soil-layering systems for low-(C/N)-ratio polluted river water treatment.

    Science.gov (United States)

    Wei, Cai-Jie; Wu, Wei-Zhong

    2018-09-01

    Two kinds of hybrid two-step multi-soil-layering (MSL) systems loaded with different filter medias (zeolite-ceramsite MSL-1 and ceramsite-red clay MSL-2) were set-up for the low-(C/N)-ratio polluted river water treatment. A long-term pollutant removal performance of these two kinds of MSL systems was evaluated for 214 days. By-pass was employed in MSL systems to evaluate its effect on nitrogen removal enhancement. Zeolite-ceramsite single-pass MSL-1 system owns outstanding ammonia removal capability (24 g NH 4 + -Nm -2 d -1 ), 3 times higher than MSL-2 without zeolite under low aeration rate condition (0.8 × 10 4  L m -2 .h -1 ). Aeration rate up to 1.6 × 10 4  L m -2 .h -1 well satisfied the requirement of complete nitrification in first unit of both two MSLs. However, weak denitrification in second unit was commonly observed. By-pass of 50% influent into second unit can improve about 20% TN removal rate for both MSL-1 and MSL-2. Complete nitrification and denitrification was achieved in by-pass MSL systems after addition of carbon source with the resulting C/N ratio up to 2.5. The characters of biofilms distributed in different sections inside MSL-1 system well illustrated the nitrogen removal mechanism inside MSL systems. Two kinds of MSLs are both promising as an appealing nitrifying biofilm reactor. Recirculation can be considered further for by-pass MSL-2 system to ensure a complete ammonia removal. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. Solid state CP/MAS 13C n.m.r. analysis of particle size and density fractions of soil incubated with uniformly labelled 13C-glucose

    International Nuclear Information System (INIS)

    Baldock, J.A.; Oades, J.M.

    1990-01-01

    A soil incubated for 34 days in the absence (control) and presence (treated) of uniformly labelled 13 C-glucose was dispersed using an ultrasonic probe and fractionated by sedimentation in water and a polytungstate solution of density 2.0 Mg m -3 . Solid state CP/MAS 13 C n.m.r. (cross polarization/magic angle spinning 13 C nuclear magnetic resonance) spectroscopy was used to characterize the chemical structure of the native soil organic carbon and the residual substrate carbon in the fractions of the control and treated soils. To obtain quantitative results it was essential to determine the spin lattice relaxation time in a rotating frame of the individual carbon types in the spectra as the relaxation behaviour of the native organic material in the clay fraction was different from that of the residual substrate carbon. The residual substrate carbon was found to accumulate in predominantly alkyl and O-alkyl structures in both fractions. However, significant amounts of acetal and carboxyl carbon were also observed in the clay fraction. Little if any aromatic or phenolic carbon was synthesized by the soil microorganisms utilizing substrate carbon. Dipolar dephasing CP/MAS 13 C n.m.r. experiments were also performed and allowed the proportion of each type of carbon which was protonated and nonprotonated to be estimated. Essentially all of the O-alkyl and acetal carbon, 25-40% of the aromatic carbon and 66-80% of the alkyl carbon was protonated in the fractions isolated from the treated soil. 24 refs., 4 figs., 2 tabs

  3. Changes in Soil C/N Ratio and Response of Growth of Hemp (Cannabis sativa L. to Different Levels of Animal Manure and Chemical Fertilizers

    Directory of Open Access Journals (Sweden)

    S Laleh

    2018-05-01

    Full Text Available Introduction Hemp is used in the food, drug, and natural fibers. Assessment of various systems of plant nutrition is one of the ways to improve field management and production of medicinal plants. Nitrogen is considered a necessary element in plant nutrition. Nitrogen uptake as ammonium compounds form, serves as starting material for amino acid biosynthesis and additional N-containing compound such as pyrimidine, purine bases, chlorophyll, proteins, nucleic acid, vitamins and other organic compounds, therefore, the higher plants require larger amount of nitrogen. Phosphorus is the second most important nutrient in plants. Studies show that application of animal manure provides different nutrients for plants. Application of animal manure in soil at the optimal level for plant growth provides a opportunities for soil fertility, conservation, sustainability, and protection against degradation but they need time to release their nutrient. Various studies showed that the combined usage the animal manure and chemical fertilizers (like N and P has positive effects on soil, growth and yield of plant with the aim of protecting the environment. Organic and inorganic fertilizers are effective on soil C/N ratio. Soil C/N ratio is important factor for plant and soil. It is important to study the different stages of plant growth responses to organic and chemical fertilizers for plants production. Therefore, the present study was undertaken to evaluate the effect of organic amendments enriched with chemical fertilizers of nitrogen and phosphorus and studying changes of soil C/N ratio in vegetative and reproductive stages of hemp. Materials and Methods To study the effect of different levels of animal manure and chemical fertilizers, a split factorial experiment, based on complete randomized blocks design with three replications was conducted at the Research Farm of Faculty of agriculture, University of Birjand, during the growing season 2013-2014. Experimental

  4. Tunable regioselectivity in 1,3-butadiene polymerization by using 2,6-bis(dimethyl-2-oxazolin-2-yl)pyridine incorporated transition metal (Cr, Fe and Co) catalysts

    KAUST Repository

    Gong, Dirong; Liu, Wen; Pan, Weijing; Chen, Tao; Jia, Xiaoyu; Huang, Kuo-Wei; Zhang, Xuequan

    2015-01-01

    Tridentate complexes Cr(III)Cl3L, [L = 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine], Fe(III)Cl3L, Fe(II)Cl2L and Co(II)Cl2L have been prepared and fully characterized. The solid structures of Cr(III)Cl3L, Fe(III)Cl3L and Co(II)Cl2L have been revealed by single crystal X-ray diffraction, and the Cr(III)Cl3L and Fe(III)Cl3L complexes both exhibit a distorted octahedral geometry, while the Co(II)Cl2L complex has a trigonal bipyramidal conformation. Four complexes have been examined in regioselective polymerization of butadiene in combination with MAO in toluene at room temperature. The trans-1,4, cis-1,4 enchainment of resultant polybutadiene are controlled by the metal center. Activated by MAO, complex Cr(III)Cl3L produces high level of trans-1,4 selectivity (trans-1,4 up to 93.3%) with moderate polymer yield, complexes Fe(III)Cl3L and Fe(II)Cl2L both show equal cis-1,4 and trans-1,4 with minor 1,2 selectivity (<10%), and Co(II)Cl2L catalyst displays predominated cis-1,4 selectivity, which can be shifted to 1,2 selectivity by adding PPh3 as an additive. Thus, tuning of the cis-1,4, trans-1,4 and 1,2 selectivity in full range via central metal and additive chosen by these 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine supported catalysts has been achieved. © 2015 Elsevier B.V. All rights reserved.

  5. Tunable regioselectivity in 1,3-butadiene polymerization by using 2,6-bis(dimethyl-2-oxazolin-2-yl)pyridine incorporated transition metal (Cr, Fe and Co) catalysts

    KAUST Repository

    Gong, Dirong

    2015-05-21

    Tridentate complexes Cr(III)Cl3L, [L = 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine], Fe(III)Cl3L, Fe(II)Cl2L and Co(II)Cl2L have been prepared and fully characterized. The solid structures of Cr(III)Cl3L, Fe(III)Cl3L and Co(II)Cl2L have been revealed by single crystal X-ray diffraction, and the Cr(III)Cl3L and Fe(III)Cl3L complexes both exhibit a distorted octahedral geometry, while the Co(II)Cl2L complex has a trigonal bipyramidal conformation. Four complexes have been examined in regioselective polymerization of butadiene in combination with MAO in toluene at room temperature. The trans-1,4, cis-1,4 enchainment of resultant polybutadiene are controlled by the metal center. Activated by MAO, complex Cr(III)Cl3L produces high level of trans-1,4 selectivity (trans-1,4 up to 93.3%) with moderate polymer yield, complexes Fe(III)Cl3L and Fe(II)Cl2L both show equal cis-1,4 and trans-1,4 with minor 1,2 selectivity (<10%), and Co(II)Cl2L catalyst displays predominated cis-1,4 selectivity, which can be shifted to 1,2 selectivity by adding PPh3 as an additive. Thus, tuning of the cis-1,4, trans-1,4 and 1,2 selectivity in full range via central metal and additive chosen by these 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine supported catalysts has been achieved. © 2015 Elsevier B.V. All rights reserved.

  6. Micellar induced regioselectivity in the two-step consecutive reaction of SO3(2-) with Br-(CH2CH2)n-Br (n=2-5).

    Science.gov (United States)

    Currie, Fredrik; Jarvoll, Patrik; Holmberg, Krister; Romsted, Laurence S; Gunaseelan, Krishnan

    2007-08-15

    High field (800 MHz) (1)H NMR was used to monitor the two-step consecutive reaction of excess SO(3)(2-) with symmetrical bifunctional alpha,omega-dibromoalkanes with butane (DBB), hexane (DBH), octane (DBO), and decane (DBD) chains in CTAB micelles at 25 degrees C. The first-order rate constant for the first substitution step for DBB and DBH is about 5 times faster than for the second, but the kinetics for DBO and DBD were not cleanly first-order. After 40 min, the solution contained about 80% of the intermediate bromoalkanesulfonate from DBB and DBH and the remainder is alkanedisulfonate and unreacted starting material. The same reactions were carried out in homogeneous MeOH/D(2)O solutions at 50 degrees C. The rate constants for all four alpha,omega-dibromoalkanes were first-order throughout the time course of the reaction and the same within +/-10%. However, because micellar solutions are organized on the nanoscale and bring together lipophilic and hydrophilic reactants into a small reaction volume at the micellar interface, they speed this substitution reaction considerably compared to reaction in MeOH/D(2)O. The CTAB micelles also induce a significant regioselectivity in product formation by speeding the first step of the consecutive reaction more than the second. The results are consistent with the bromoalkanesulfonate intermediates having a radial orientation within the micelles with the -CH(2)SO(3)(-) group in the interfacial region and the -CH(2)Br group directed into the micellar core such that the concentration of -CH(2)Br groups in the reactive zone, i.e., the micellar interface, is significantly reduced. These results provide the first example of self-assembled surfactant system altering the relative rates of the reaction steps of a consecutive reaction and, in doing so, enhancing monosubstitution of a symmetrically disubstituted species.

  7. Fitomassa e relação C/N em consórcios de sorgo e milho com espécies de cobertura Biomass and C/N ratio in intercrops of sorghum and maize with cover crops

    Directory of Open Access Journals (Sweden)

    Paulo Claudeir Gomes da Silva

    2009-11-01

    Full Text Available O objetivo deste trabalho foi quantificar a produtividade de fitomassa, o teor e acúmulo de nitrogênio (N, e a relação carbono/nitrogênio (C/N de monocultivos de sorgo (Sorghum bicolor e milho (Zea mays e de seus consórcios com guandu-anão (Cajanus cajan, crotalária (Crotalaria juncea, tremoço branco (Lupinus albus, girassol (Helianthus annuus e nabo-forrageiro (Raphanus sativus, manejados em diferentes estádios. O experimento foi conduzido de março a julho de 2008, em Argissolo Vermelho distroférrico de textura média, no sistema plantio direto. O delineamento experimental foi o de blocos completos ao acaso, com quatro repetições, e parcelas subdivididas, constituído pelos tratamentos: monocultivos de sorgo e milho e seus respectivos consórcios com guandu-anão, crotalária, girassol, nabo-forrageiro e tremoço branco, nas parcelas; e épocas de corte, aos 60, 90 e 120 dias após a semeadura nas subparcelas. Consórcios de sorgo e milho com outras espécies superaram expressivamente a produtividade de fitomassa de seus monocultivos que ainda acumularam menos N e apresentaram maiores relações C/N na fitomassa. Para aumentar a produtividade de fitomassa, a melhor época de corte é aos 120 dias após a semeadura das culturas de cobertura. O corte aos 90 dias após a semeadura propicia o maior acúmulo de N e as menores relações C/N.The objective of this work was to quantify the biomass production, the content and accumulation of nitrogen (N and the carbon/nitrogen (C/N relation in monocultures of sorghum (Sorghum bicolor and corn (Zea mays, and intercrops with pigeon pea (Cajanus cajan, sun hemp (Crotalaria juncea, white lupine (Lupinus albus, sunflower (Helianthus annuus and turnip forage (Raphanus sativus, managed in different stages. The experiment was carried out from March to July 2008, in a Haplic Acrisol, medium texture, under no-tillage. A randomized complete block design, with four replicates and split plots with the

  8. Alterações da relação C/N de um Latossolo Vermelho-Amarelo sob diferentes coberturas vegetais em Brasnorte – MT. Changes in C/N relation of a Red-Yellow Latosol under different plant cultivations in Brasnorte – MT.

    Directory of Open Access Journals (Sweden)

    Cristiane Ramos VIEIRA

    2014-12-01

    Full Text Available Este estudo objetivou analisar as alterações nos teores de carbono e de nitrogênio e na relação C/N em solos sob diferentes coberturas. Os sistemas avaliados foram: Floresta Secundária, pastagem, e plantios de teca (Tectona grandis com 8, 13, 16 e 19 anos, utilizando o delineamento inteiramente casualizado para a coleta do solo nas profundidades 0 a 5, 5 a 10 e 10 a 20 cm. Nas áreas dos plantios de T. grandis as amostras de solo foram coletadas na projeção da copa e nas entrelinhas, e nas áreas de pastagem e de Floresta Secundária a coleta foi aleatória. Verificou-se que os teores de carbono orgânico total – COT foram mais elevados nas primeiras camadas de solo, diminuindo conforme a profundidade. A manutenção dos teores de C e de N, semelhantes aos da Floresta Secundária, permitem caracterizar o solo dos sistemas pastagem e de cultivo de T. grandis como quimicamente não degradados, sendo que os valores de relação C/N indicam que o processo dominante em todos os sistemas foi a mineralização. This study aimed to analyze the changes in the levels of carbon and nitrogen and C/N relation in different soil covers. The systems evaluated were: Secondary Forest, pasture, and plantations of teak at 8, 13, 16 and 19 years old, using a completely randomized design in split plot to collect soil in three depths (0-5, 5-10 and 10-20 cm. In the area of teak plantations samples of soil were collected on the projection of the tree crown and between lines, in the pasture and Secondary Forest they were collected randomly. It was found that the concentration of total organic carbon – TOC was higher in the first depth, decreasing as the depth. The maintenance of the levels of C and N similar to Secondary Forest can characterize the soil of grass pastures systems and cultivation of teak as chemical not degraded and C/N relation indicates that the dominant process on all systems was the mineralization.

  9. Iodide, azide, and cyanide complexes of (N,C), (N,N), and (N,O) metallacycles of tetra- and pentavalent uranium

    International Nuclear Information System (INIS)

    Benaud, Olivier; Berthet, Jean-Claude; Thuery, Pierre; Ephritikhine, Michel

    2011-01-01

    In contrast to the neutral macrocycle [UN* 2 (N,C)] (1) [N* = N(SiMe 3 ) 3 ; N,C = CH 2 SiMe 2 N-(SiMe 3 )] which was quite inert toward I 2 , the anionic bismetallacycle [NaUN*(N,C) 2 ] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me 3 Si)NSiMe 2 CH 2 CH 2 SiMe 2 N(SiMe 3 )] resulting from C-C coupling of the two CH 2 groups, and [NaUN*(N,O) 2 ] (3) [N,O = OC(=CH 2 )SiMe 2 N(SiMe 3 )], which is devoid of any U-C bond, was oxidized into the UV bismetallacycle [Na{UN*(N,O) 2 }2(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN 3 or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN* 2 (N,C)(N 3 )] [M = Na, 7a or Na(15-crown-5), 7b], M[UN* 2 (N,C)(CN)] [M = NEt 4 , 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N 3 ) 2 ] [M = Na, 9a or Na(THF)4, 9b], [NEt 4 ][UN*(N,N)(CN) 2 ] (10), M[UN*(N,O) 2 (N 3 )] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O) 2 (CN)] [M = NEt 4 , 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral UV complex [U(N{SiMe 3 }-SiMe 2 C{CHI}O) 2 I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined. (authors)

  10. Comparison of different models for ground-level atmospheric turbulence strength (C(n)(2)) prediction with a new model according to local weather data for FSO applications.

    Science.gov (United States)

    Arockia Bazil Raj, A; Arputha Vijaya Selvi, J; Durairaj, S

    2015-02-01

    Atmospheric parameters strongly affect the performance of free-space optical communication (FSOC) systems when the optical wave is propagating through the inhomogeneous turbulence transmission medium. Developing a model to get an accurate prediction of the atmospheric turbulence strength (C(n)(2)) according to meteorological parameters (weather data) becomes significant to understand the behavior of the FSOC channel during different seasons. The construction of a dedicated free-space optical link for the range of 0.5 km at an altitude of 15.25 m built at Thanjavur (Tamil Nadu) is described in this paper. The power level and beam centroid information of the received signal are measured continuously with weather data at the same time using an optoelectronic assembly and the developed weather station, respectively, and are recorded in a data-logging computer. Existing models that exhibit relatively fewer prediction errors are briefed and are selected for comparative analysis. Measured weather data (as input factors) and C(n)(2) (as a response factor) of size [177,147×4] are used for linear regression analysis and to design mathematical models more suitable in the test field. Along with the model formulation methodologies, we have presented the contributions of the input factors' individual and combined effects on the response surface and the coefficient of determination (R(2)) estimated using analysis of variance tools. An R(2) value of 98.93% is obtained using the new model, model equation V, from a confirmatory test conducted with a testing data set of size [2000×4]. In addition, the prediction accuracies of the selected and the new models are investigated during different seasons in a one-year period using the statistics of day, week-averaged, month-averaged, and seasonal-averaged diurnal Cn2 profiles, and are verified in terms of the sum of absolute error (SAE). A Cn2 prediction maximum average SAE of 2.3×10(-13)  m(-2/3) is achieved using the new model in

  11. Revisiting the concept of Redfield ratios applied to plankton stoichiometry - Addressing model uncertainties with respect to the choice of C:N:P ratios for phytoplankton

    Science.gov (United States)

    Kreus, Markus; Paetsch, Johannes; Grosse, Fabian; Lenhart, Hermann; Peck, Myron; Pohlmann, Thomas

    2017-04-01

    Ongoing Ocean Acidification (OA) and climate change related trends impact on physical (temperature), chemical (CO2 buffer capacity) and biological (stoichiometric) properties of the marine environment. These threats affect the global ocean but they appear particularly pronounced in marginal and shelf seas. Marine biogeochemical models are often used to investigate the impacts of climate change and changes in OA on the marine system as well as its exchange with the atmosphere. Different studies showed that both the structural composition of the models and the elemental ratios of particulate organic matter in the surface ocean affect the key processes controlling the ocean's efficiency storing atmospheric excess carbon. Recent studies focus on the variability of the elemental ratios of phytoplankton and found that the high plasticity of C:N:P ratios enables the storage of large amounts of carbon by incorporation into carbohydrates and lipids. Our analysis focuses on the North Sea, a temperate European shelf sea, for the period 2000-2014. We performed an ensemble of model runs differing only in phytoplankton stoichiometry, representing combinations of C:P = [132.5, 106, 79.5] and N:P=[20, 16, 12] (i.e., Redfield ratio +/- 25%). We examine systematically the variations in annual averages of net primary production (NPP), net ecosystem production in the upper 30 m (NEP30), export production below 30 m depth (EXP30), and the air-sea flux of CO2 (ASF). Ensemble average fluxes (and standard deviations) resulted in NPP = 15.4 (2.8) mol C m-2 a-1, NEP30 = 5.4 (1.1) mol C m-2 a-1, EXP30 = 8.1 (1.1) mol C m-2 a-1 and ASF = 1.1 (0.5) mol C m-2 a-1. All key parameters exhibit only minor variations along the axis of constant C:N, but correlate positively with increasing C:P and decreasing N:P ratios. Concerning regional differences, lowest variations in local fluxes due to different stoichiometric ratios can be found in the shallow southern and coastal North Sea. Highest

  12. Predominant Non-additive Effects of Multiple Stressors on Autotroph C:N:P Ratios Propagate in Freshwater and Marine Food Webs

    Science.gov (United States)

    Villar-Argaiz, Manuel; Medina-Sánchez, Juan M.; Biddanda, Bopaiah A.; Carrillo, Presentación

    2018-01-01

    A continuing challenge for scientists is to understand how multiple interactive stressor factors affect biological interactions, and subsequently, ecosystems–in ways not easily predicted by single factor studies. In this review, we have compiled and analyzed available research on how multiple stressor pairs composed of temperature (T), light (L), ultraviolet radiation (UVR), nutrients (Nut), carbon dioxide (CO2), dissolved organic carbon (DOC), and salinity (S) impact the stoichiometry of autotrophs which in turn shapes the nature of their ecological interactions within lower trophic levels in streams, lakes and oceans. Our analysis from 66 studies with 320 observations of 11 stressor pairs, demonstrated that non-additive responses predominate across aquatic ecosystems and their net interactive effect depends on the stressor pair at play. Across systems, there was a prevalence of antagonism in freshwater (60–67% vs. 47% in marine systems) compared to marine systems where synergism was more common (49% vs. 33–40% in freshwaters). While the lack of data impeded comparisons among all of the paired stressors, we found pronounced system differences for the L × Nut interactions. For this interaction, our data for C:P and N:P is consistent with the initial hypothesis that the interaction was primarily synergistic in the oceans, but not for C:N. Our study found a wide range of variability in the net effects of the interactions in freshwater systems, with some observations supporting antagonism, and others synergism. Our results suggest that the nature of the stressor pairs interactions on C:N:P ratios regulates the “continuum” commensalistic-competitive-predatory relationship between algae and bacteria and the food chain efficiency at the algae-herbivore interface. Overall, the scarce number of studies with even more fewer replications in each study that are available for freshwater systems have prevented a more detailed, insightful analysis. Our findings

  13. Predominant Non-additive Effects of Multiple Stressors on Autotroph C:N:P Ratios Propagate in Freshwater and Marine Food Webs

    Directory of Open Access Journals (Sweden)

    Manuel Villar-Argaiz

    2018-01-01

    Full Text Available A continuing challenge for scientists is to understand how multiple interactive stressor factors affect biological interactions, and subsequently, ecosystems–in ways not easily predicted by single factor studies. In this review, we have compiled and analyzed available research on how multiple stressor pairs composed of temperature (T, light (L, ultraviolet radiation (UVR, nutrients (Nut, carbon dioxide (CO2, dissolved organic carbon (DOC, and salinity (S impact the stoichiometry of autotrophs which in turn shapes the nature of their ecological interactions within lower trophic levels in streams, lakes and oceans. Our analysis from 66 studies with 320 observations of 11 stressor pairs, demonstrated that non-additive responses predominate across aquatic ecosystems and their net interactive effect depends on the stressor pair at play. Across systems, there was a prevalence of antagonism in freshwater (60–67% vs. 47% in marine systems compared to marine systems where synergism was more common (49% vs. 33–40% in freshwaters. While the lack of data impeded comparisons among all of the paired stressors, we found pronounced system differences for the L × Nut interactions. For this interaction, our data for C:P and N:P is consistent with the initial hypothesis that the interaction was primarily synergistic in the oceans, but not for C:N. Our study found a wide range of variability in the net effects of the interactions in freshwater systems, with some observations supporting antagonism, and others synergism. Our results suggest that the nature of the stressor pairs interactions on C:N:P ratios regulates the “continuum” commensalistic-competitive-predatory relationship between algae and bacteria and the food chain efficiency at the algae-herbivore interface. Overall, the scarce number of studies with even more fewer replications in each study that are available for freshwater systems have prevented a more detailed, insightful analysis. Our

  14. Effect of SiC whisker addition on the microstructures and mechanical properties of Ti(C, N)-based cermets

    International Nuclear Information System (INIS)

    Wu, Peng; Zheng, Yong; Zhao, Yongle; Yu, Haizhou

    2011-01-01

    Ti(C, N)-based cermets with addition of SiC whisker (SiC w ) were prepared by vacuum sintering. The microstructures of the prepared cermets were investigated by using X-ray diffractometry (XRD) and scanning electron microscopy (SEM). Mechanical properties such as transverse rupture strength (TRS), fracture toughness (K IC ) and hardness (HRA) were also measured. It was found that the grain size of the cermets was affected by the SiC whisker addition. The cermets with 1.0 wt.% SiC whisker addition exhibited the smallest grain size. The porosities of the cermets increased with increasing SiC whisker additions. The addition of the SiC whisker had no influence on the phase constituents of the cermets. Compared with the cermets with no whisker addition, the highest TRS and fracture toughness for cermets with 1.0 wt.% SiC whisker addition increased by about 24% and 29%, respectively. The strengthening mechanisms were attributed to finer grain size, homogeneous microstructure and moderate thickness of rim phase. The toughening mechanisms were characterized by crack deflection, whisker bridging and whisker pulling-out.

  15. Redfield Ratios in Inland Waters: Higher Biological Control of C:N:P Ratios in Tropical Semi-arid High Water Residence Time Lakes

    Directory of Open Access Journals (Sweden)

    Ng H. They

    2017-08-01

    Full Text Available The canonical Redfield C:N:P ratio for algal biomass is often not achieved in inland waters due to higher C and N content and more variability when compared to the oceans. This has been attributed to much lower residence times and higher contributions of the watershed to the total organic matter pool of continental ecosystems. In this study we examined the effect of water residence times in low latitude lakes (in a gradient from humid to a semi-arid region on seston elemental ratios in different size fractions. We used lake water specific conductivity as a proxy for residence time in a region of Eastern Brazil where there is a strong precipitation gradient. The C:P ratios decreased in the seston and bacterial size-fractions and increased in the dissolved fraction with increasing water retention time, suggesting uptake of N and P from the dissolved pool. Bacterial abundance, production and respiration increased in response to increased residence time and intracellular nutrient availability in agreement with the growth rate hypothesis. Our results reinforce the role of microorganisms in shaping the chemical environment in aquatic systems particularly at long water residence times and highlights the importance of this factor in influencing ecological stoichiometry in all aquatic ecosystems.

  16. Oxide Structure Dependence of SiO2/SiOx/3C-SiC/n-Type Si Nonvolatile Resistive Memory on Memory Operation Characteristics

    Science.gov (United States)

    Yamaguchi, Yuichiro; Shouji, Masatsugu; Suda, Yoshiyuki

    2012-11-01

    We have investigated the dependence of the oxide layer structure of our previously proposed metal/SiO2/SiOx/3C-SiC/n-Si/metal metal-insulator-semiconductor (MIS) resistive memory device on the memory operation characteristics. The current-voltage (I-V) measurement and X-ray photoemission spectroscopy results suggest that SiOx defect states mainly caused by the oxidation of 3C-SiC at temperatures below 1000 °C are related to the hysteresis memory behavior in the I-V curve. By restricting the SiOx interface region, the number of switching cycles and the on/off current ratio are more enhanced. Compared with a memory device formed by one-step or two-step oxidation of 3C-SiC, a memory device formed by one-step oxidation of Si/3C-SiC exhibits a more restrictive SiOx interface with a more definitive SiO2 layer and higher memory performances for both the endurance switching cycle and on/off current ratio.

  17. Low C/N ratio raw textile wastewater reduced labile C and enhanced organic-inorganic N and enzymatic activities in a semiarid alkaline soil.

    Science.gov (United States)

    Roohi, Mahnaz; Riaz, Muhammad; Arif, Muhammad Saleem; Shahzad, Sher Muhammad; Yasmeen, Tahira; Ashraf, Muhammad Arslan; Riaz, Muhammad Atif; Mian, Ishaq A

    2017-02-01

    Application of raw and treated wastewater for irrigation is an extensive practice for agricultural production in arid and semiarid regions. Raw textile wastewater has been used for cultivation in urban and peri-urban areas in Pakistan without any systematic consideration to soil quality. We conducted a laboratory incubation study to investigate the effects of low C/N ratio raw textile wastewater on soil nitrogen (N) contents, labile carbon (C) as water-soluble C (WSC) contents, and activities of urease and dehydrogenase enzymes. The 60-day incubation study used an alkaline clay loam aridisol that received 0 (distilled water), 25, 50, and 100% wastewater concentrations, and microcosms were incubated aerobically under room temperature at 70% water holding capacity. Results revealed that raw wastewater significantly (p 50% of the soil total Kjeldahl N (TKN) contents and served as the major N pool. However, nitrification index (NO 3 - -N/NH 4 + -N ratio) decreased at high wastewater concentrations. A significant negative correlation was observed between EON and WSC (p production and accumulation of soil NO 3 - -N and EON contents in concentrated wastewater-treated soil could pose an ecological concern for soil fertility, biological health, and water quality. However, the EON could lead to mineral N pool but only if sufficient labile C source was present. The effects of wastewater irrigation on soil N cycling need to be assessed before it is recommended for crop production.

  18. Energy loss and straggling of 1–50 keV H, He, C, N, and O ions passing through few layer graphene

    International Nuclear Information System (INIS)

    Allegrini, Frédéric; Bedworth, Peter; Ebert, Robert W.; Fuselier, Stephen A.; Nicolaou, Georgios; Sinton, Steve

    2015-01-01

    Highlights: • Evaluation of graphene foils for space plasma instruments. • Energy loss and straggling of keV ions passing through graphene foils. • Lower energy loss than for ultra-thin carbon foils. • Thickness non-uniformity leads to higher straggling. - Abstract: Graphene could be an alternative to amorphous carbon foils, in particular in space plasma instrumentation. The interaction of ions or neutral atoms with these foils results in different effects: electron emission, charge exchange, angular scattering, and energy straggling. We showed in previous studies that (1) the charge exchange properties are similar for graphene and regular carbon foils, and (2) the scattering at low energies (few keVs) is less for graphene than for one of our thinnest practical carbon foils. In this study, we report measurements of the energy loss and straggling of ∼1–50 keV H, He, C, N, and O ions in graphene. We compare graphene and a carbon foil for hydrogen. We provide simple power law fits to the average energy loss, energy straggling, and skewness of the energy distributions. We find the energy loss for ions transiting through graphene to be reduced compared to thin carbon foils but the energy straggling to be larger, which we attribute to the non-uniformity of the graphene foils used in this study

  19. Synthesis and characterization of a polyborosilazane/Cp2ZrCl2 hybrid precursor for the Si-B-C-N-Zr multinary ceramic.

    Science.gov (United States)

    Long, Xin; Shao, Changwei; Wang, Hao; Wang, Jun

    2015-09-21

    A novel zirconium-contained polyborosilazane (PBSZ-Zr) was synthesized by chemical modification of a liquid polyborosilazane (LPBSZ) with Cp2ZrCl2. A Si-B-C-N-Zr multinary ceramic was prepared via pyrolysis of PBSZ-Zr. The properties and the ceramization process of PBSZ-Zr, as well as the microstructural development and properties of the derived SiBCN-Zr ceramic, were well studied. The active Si-H and N-H groups in LPBSZ react with Zr-Cl in Cp2ZrCl2 to form PBSZ-Zr polymers. The Zr content of the SiBCN-Zr ceramic was 3.39 wt% when the weight ratio of Cp2ZrCl2 to LPBSZ was 20 : 100. The SiBCN-Zr ceramic remains amorphous when pyrolyzed below 1600 °C, but the crystal phases of Zr2CN, ZrC, BN, SiC, and Si3N4 were detected from a 1600 °C treated sample. Due to the low activity of free carbon at the interface of the SiBCN-Zr ceramic, the oxidation resistance of the SiBCN-Zr ceramic under air was improved compared with the SiBCN ceramic.

  20. Application of new /sup 13/C N. M. R. techniques to the study of products from catalytic hydrodeoxygenation of SRC-II liquids

    Energy Technology Data Exchange (ETDEWEB)

    Dalling, D.K.; Haider, G.; Hull, W.E.; Pugmire, R.J.; Shabtai, J.

    1984-04-01

    A middle-heavy SRC-II distillate (b.p. 230-455/sup 0/C), containing 3.0 wt% of oxygen, has been studied by means of /sup 13/C n.m.r. at 75, 100 and 125 MHz. The magnetization refocusing techniques INEPT and J-resolved two-dimensional Fourier transform have been utilized to demonstrate methods by which resonance line multiplicities may be determined in complex liquid mixtures. Products derived from the above coal liquid by hydrodeoxygenation at temperatures from 200 to 370/sup 0/C, using sulphided Co-Mo and Ni-W catalysts, were also examined. The fraction of aromatic carbon in the hydrotreated liquids was found to correlate directly with their C/H atomic ratio and inversely with the hydrogen content. Comparison of O/C atomic ratios with f /SUB a/ values for these liquids indicates that hydrogen uptake <260/sup 0/C is associated primarily with hydrogenolytic oxygen removal without attendant ring hydrogenation, while at temperatures between 260 and 350/sup 0/C hydrodeoxygenation is accompanied by ring hydrogenation and dealkylation reactions.