Sample records for ammonolysis

  1. Study on the Hydrolysis and Ammonolysis Kinetics of a Monochlorotriazinyl Reactive Dye

    Institute of Scientific and Technical Information of China (English)

    XIA Jian-ming


    To understand the reaction behaviour of the reactive dye with amino groups on protein fibres, the reaction kinetics of competitive hydrolysis and ammonolysis of a monochlorotriazina reactive dye were studied at 50 -80℃ and pH = 8 - 10 by high performance liquid chromatography (HPLC). The results showed the pseudofirst-order phenomenon for the general reaction of concurrent hydrolysis and ammonolysis of the dyes. The ammonolysis reaction was always faster than the hydrolysis reaction in the range of temperature and pH employed, but the preference for ammonolysis to hydrolysis reaction decreased with the increase of temperature and pH value. The ratios of ammonolysis/hydrolysis rate constant reduced from 17.6 to 5.4 when the temperature increased from 50 to 80℃ in pH =10, and from 7.2 to 5.4 when the pH value increased from 8 to 10 at 80℃.

  2. A Computational Study on Water-assisted Ammonolysis of N-Methyl β-Sultam

    Institute of Scientific and Technical Information of China (English)


    The ring opening of β-sultam via an H2O-assisted ammonolysis process was studied by using Density Functional Theory(DFT) method at the B3LYP/6-31G* level as a further step in the theoretical investigation of the ammonolysis reaction of β-sultams. The calculated pathways are analogous to those previously described for the non-assisted ammonolysis reaction. Solvent effects were assessed by using the polarized continuum model(PCM) method. The results show that mode 1 and pathway a in channel Ⅱ are the most favorable ones in both the cases. The energy barrier of the cleavage of C-S bonds producing P1 is the highest among all the energy barriers. The presence of a solvent in the continuum model disfavors the reaction, whereas the participation of water in the ammonolysis reaction plays a positive role and reduces the active energy greatly. The relative energies of all the transition states in the assisted ammonolysis are 20-80 kJ/mol lower than those for the non-assisted reaction.

  3. Stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Osipova, Z.G.; Sokolovskii, V.D.


    The stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts GaSb/sub 19/O/sub x/, GaSb/sub 3/Ni/sub 1.5/0/sub x/, and GaSb/sub 2.5/Ni/sub 1.5/PW/sub 0//sub 0.25/O/sub x/ was studied at 450/sup 0/ and 550/sup 0/C by introducing alternating pulses of 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/helium (to reduce the steady-state catalytic surface) and 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/1.86Vertical Bar3< oxygen/helium mixtures into a fluidized-bed catalytic reactor. Over all the catalysts studied, the rates of acrylonitrile formation during the two types of pulses were very similar, but carbon dioxide was formed much faster during the reducing pulses, particularly at 450/sup 0/C. These findings suggested that acrylonitrile is formed by a stepwise redox mechanism involving consecutive interaction of propane and ammonia with the surface oxygen of the catalysts and oxidation of the reduced catalyst surface by gas-phase oxygen. The formation of carbon dioxide proceeds by both stepwise and associative mechanisms, the latter being more important at higher temperatures. The results are similar to published results for ammoxidation of propylene and olefins.

  4. Electronic diffuse reflectance spectra of Bi-V-Sb-Al catalysts for oxidative ammonolysis

    Energy Technology Data Exchange (ETDEWEB)

    Rizaev, R.G.; Akhverdiev, R.B.; Alieva, T.C.; Efendiev, M.R.; Krylov, O.V.; Magerranova, Z.Y.


    Diffuse reflectance spectra of monocomponent, binary, and tricomponent Bi-VSb-Al catalysts for the oxidative ammonolysis of aromatic compounds were taken in the 200- to 850-nm region and interpreted. It was established that vanadium ions in two valence states, V/sup 4 +/ and V/sup 5 +/, exist on the surface of ..gamma..-Al/sub 2/O/sub 3/. On treatment of V-Sb-Al with a reaction mixture of C/sub 7/H/sub 6/Cl/sub 2/ + O/sub 2/ + NH/sub 3/, V/sup 5 +/ ions are reduced to V/sup 4 +/ and Sb/sup 3 +/ ions are oxidized to Sb/sup 5 +/. This is also characteristic of the V-Al and Sb-Al oxide systems. In the case of V-Bi-Al, treatment with the reaction mixture does not lead to the reduction of V/sup 5 +/ ions. After treatment of Sb-Bi-Al with the reaction mixture, the presence of three phases, Sb/sub 2/O/sub 3/, Sb/sub 2/O/sub 5/, and Bi/sub 2/O/sub 3/ was detected spectroscopically. After treatment of the Bi-V-Sb-Al with the reaction mixture, the formation of a chemical compound of the bismuth vanadate type in which the V/sup 5 +/ ions are tightly held and resistant to oxidation was observed. The phases Sb/sub 2/O/sub 3/ and Sb/sub 2/O/sub 5/ were also found.

  5. Magnetic properties of the ammonolysis product of α-Fe powder containing a small amount of aluminum

    Energy Technology Data Exchange (ETDEWEB)

    Tsugawa, Yuta; Maubuchi, Yuji; Motohashi, Teruki; Kikkawa, Shinichi, E-mail:


    Magnetite was prepared containing a small amount of aluminum and its nitride was generated through low temperature ammonolysis following reduction under hydrogen. The nitrided product was determined by XRD to be a mixture of “α″-Fe{sub 16}N{sub 2}” having a slightly deformed crystal structure from α″-Fe{sub 16}N{sub 2} and the residual α-Fe. Magnetic coercivity of the mixture was decreased from the value of 150 mT obtained for the nitride product made without aluminum, due to the precipitation of nonmagnetic amorphous alumina in the low temperature nitrided bcc (Fe{sub 1−x}Al{sub x}) with x≤0.03. The aluminum-doped nitride product in which the “α″-Fe{sub 16}N{sub 2}” fraction was 30 at% exhibited magnetization at 1.5 T of approximately 200 Am{sup 2}kg{sup −1} at room temperature and its magnetic coercivity was 20 mT. - Graphical abstract: Magnetic iron nitride particles were separated by nonmagnetic amorphous γ-alumina. Magnetic coercivity was decreased by reducing the magnetic interaction between the particles. - Highlights: • Magnetic coercivity decreased in α”-Fe{sub 16}N{sub 2} like compound as a soft magnet. • Small amount of Al addition was effective in its preparation. • Magnetic interaction decreased between the “α”-Fe{sub 16}N{sub 2}” particles.

  6. Synthesis of uranium fluorides from uranium dioxide with ammonium bifluoride and ammonolysis of uranium fluorides to uranium nitrides (United States)

    Yeamans, Charles Burnett

    This work presents the chemical conversion of uranium oxides to uranium fluorides, and their subsequent conversion to uranium nitrides. Uranium dioxide reacts with ammonium bifluoride at 20°C to form compound in the ammonium-uranium fluoride chemical system. This reaction occurs between solid uranium dioxide at the surface of the particles and ammonium fluoride vapor. A shrinking-sphere model demonstrated surface reaction kinetics, not mass transport by diffusion through the product layer, limit the reaction rate when the starting material consists of 100 mum uranium dioxide particles. Powder x-ray diffraction showed the reaction to be complete within 8 hours, with (NH4) 4UF8 the reaction product. High-resolution electron microcopy revealed the product is largely amorphous on a micrometer-scale, but contains well-formed crystal domains on the order of 10x10 nm. X-ray diffraction showed the reaction progresses though beta-NH4UF5, delta-(NH 4)2UF6, and gamma-(NH4)2UF6 intermediate phases before finally forming (NH4)4UF 8. Modeling the system as a series of first-order reaction suggested a fourth intermediate, possibly UF4, is likely to occur. The reaction of (NH4)4UF8 with ammonia gas at 800°C forms alpha-U2N3/UN2 solid solution products with a composition of UN1.83. The x-ray powder diffraction pattern of this product is the fcc pattern commonly referenced as that of UN2 and the lattice parameter was 0.53050 nm. Surface area increased by a factor of ten during ammonolysis, consistent with the action of a hydriding agent. The alpha-U2N 3/UN2 solid solution system formed contained 1 wt% UO 2 as an impurity. Upon subsequent heating to 1150°C for 4.5 hours under argon, the nitride sample formed UN with a UO2 impurity of 9 wt%. Based on the HRTEM images, oxidation in the UN product appears to be limited to within 20 nm of particle surfaces and grain boundaries.

  7. 3,5-Diarylpyrazole Derivatives Obtained by Ammonolysis of the Total Flavonoids from Chrysanthemum indicum Extract Show Potential for the Treatment of Alzheimer's Disease. (United States)

    Wu, Taizong; Jiang, Cheng; Wang, Ling; Morris-Natschke, Susan L; Miao, Hui; Gu, Lianquan; Xu, Jun; Lee, Kuo-Hsiung; Gu, Qiong


    Four new 3,5-diarylpyrazole analogues (1-4) were isolated from an extract of the flowers of Chrysanthemun indicum using a combination of ammonolysis of the total flavonoid extract and an Aβ aggregation inhibitory activity guided purification procedure. All four compounds (1-4) showed moderate to potent activity against Aβ aggregation with EC50 values of 4.3, 15.8, 1.3, and 2.9 μM, respectively. Moreover, compound 3 showed low cytotoxicity and significant neuroprotective activity against Aβ-induced cytotoxicity in the SH-SY5Y cell line. This report is the first to show that 3,5-diarylpyrazole analogues can inhibit Aβ aggregation and exhibit neuroprotective activity with potential for the treatment of Alzheimer's disease. Taken together, the method presented here offers an alternative approach to yield bioactive compounds.

  8. Redox supercapacitor performance of nanocrystalline molybdenum nitrides obtained by ammonolysis of chloride- and amide-derived precursors (United States)

    Shah, S. Imran U.; Hector, Andrew L.; Owen, John R.


    Reactions of MoCl5 or Mo(NMe2)4 with ammonia result in cubic γ-Mo2N or hexagonal δ1-MoN depending on reaction time and temperature. At moderate temperatures the cubic product from Mo(NMe2)4 exhibits lattice distortions. Fairly high surface areas are observed in the porous particles of the chloride-derived materials and high capacitances of up to 275 F g-1 are observed when electrodes made from them are cycled in aqueous H2SO4 or K2SO4 electrolytes. The cyclic voltammograms suggest charge is largely stored in the electrochemical double layer at the surface of these materials. Amide-derived molybdenum nitrides have relatively low surface areas and smaller capacitances, but do exhibit strong redox features in their cyclic voltammograms, suggesting that redox capacitance is responsible for a significant proportion of the charge stored.


    Institute of Scientific and Technical Information of China (English)

    李慧青; 宗敏华; 何欢; 梁文峰


    从4种不同来源的脂肪酶,2种不同来源的蛋白酶中筛选出了具有较高活性和对映体选择性的能催化乙酸甲基苯甲酯氨解反应的脂肪酶Novozym 435.进一步探讨了氨源、酶浓度、底物浓度等因素对该酶反应的影响.结果表明,在优化条件下,氨解反应6h,转化率为51.6%,残留底物中(-)-乙酸甲基苯甲酯对映体过剩值可达99%以上.


    Institute of Scientific and Technical Information of China (English)

    李慧青; 宗敏华; 梁文峰; 何欢


    系统研究了反应介质、水活度、温度、pH等因素对脂肪酶Novozym 435催化乙酸甲基苯甲酯立体选择性氨解反应的影响.以正己烷为反应介质,酶表现出较高的催化活性和对映体选择性;适宜的反应温度为25℃~35℃;最适反应体系初始水活度为0.33;较适宜的pH范围为6~7.

  11. Short Synthesis of C-terminal Modified Peptides by a Series-connection Procedure

    Institute of Scientific and Technical Information of China (English)

    Gui Jie TIAN; Chuan Liang QIU; Zhe LIU; De Xin WANG


    Three peptide alcohols and four peptidyl N-akyl-amides were prepared by a series-connection procedure consisting of n-1 sequencial assembly on solid support followed by ammonolysis with glycinol, benzylamine or n-butylamine, and successive extractionelution through C-18 layer. All products were obtained from this procedure without further purification,in an overall yield of 75-86%.

  12. tert-Butyl 3-[N-(tert-butoxycarbonylmethylamino]-4-methoxyimino-3-methylpiperidine-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Huiyuan Guo


    Full Text Available The title compound, C18H33N3O5, was prepared from N-tert-butoxycarbonyl-4-piperidone using a nine-step reaction, including condensation, methylation, oximation, hydrolysis, esterification, ammonolysis, Hoffmann degradation, tert-butoxycarbonyl protection and methylation. The E configuration of the methyloxime geometry of the compound is confirmed.

  13. Studies on the use of supercritical ammonia for ceramic nitride synthesis and fabrication (United States)

    Cornell, Linda; Lin, Y. C.; Philipp, Warren H.


    The extractability of ammonia halides (including ammonium thiocyanate) formed as byproducts from the synthesis of Si(NH)2 via ammonolysis of the corresponding silicon tetrahalides using supercritical NH3 as the extraction medium was investigated. It was found that the NH4SCN byproduct of ammonolysis of Si(SCN)4 can be almost completely extracted from the insoluble Si(NH)2 forming a promising system for the synthesis of pure Si(NH)2, one of the best precursors for Si3N4. In addition it was found that Si3N4, AlN, BN, and Si(NH)2 are insoluble in SC ammonia. Also discussed are design considerations for a supercritical ammonia extraction unit.

  14. Synthesis of Cell Adhesive Motif RGD Tripeptide by a Novel Chemical Method and Its Purification

    Institute of Scientific and Technical Information of China (English)


    The cell adhesive motif RGD tripeptide was synthesized by using a novel chemical method. First, Gly-Asp(GD)was synthesized in two steps including the chloroacetylation of free L-aspartic acid and the ammonolysis of the chloroacetylated L-aspartic acid. The yield of chloroacetylated L-aspartic acid was 83.0%. For the ammonolysis of chloroacetylated L-aspartic acid, the yield of the ammonolyzed product was 92.3%. Second, the coupling between Arg and Gly-Asp was carried out by using the NCA method. The maximum yield of RGD was about 50% at 0℃ and pH =9. 5. The prepared RGD tripeptide was confirmed by using amino acid component analysis and mass spectrographic analysis.

  15. Gallium nitride optoelectronic devices (United States)

    Chu, T. L.; Chu, S. S.


    The growth of bulk gallium nitride crystals was achieved by the ammonolysis of gallium monochloride. Gallium nitride single crystals up to 2.5 x 0.5 cm in size were produced. The crystals are suitable as substrates for the epitaxial growth of gallium nitride. The epitaxial growth of gallium nitride on sapphire substrates with main faces of (0001) and (1T02) orientations was achieved by the ammonolysis of gallium monochloride in a gas flow system. The grown layers had electron concentrations in the range of 1 to 3 x 10 to the 19th power/cu cm and Hall mobilities in the range of 50 to 100 sq cm/v/sec at room temperature.

  16. Synthesis and Ceramic Conversion of Polysiloxazane to Silicon Oxynitride

    Institute of Scientific and Technical Information of China (English)


    Amorphous silicon oxynitride powders have been obtained by pyrolysis of polysiloxazane in a stream of anhydrous NH3 at the temperature up to 1000°C. The polysiloxazane is fabricated from ammonolysis of chloropolysiloxane that is produced by the hydrolysis of silicon tetrachloride. The conversion of polysiloxazane to silicon oxynitride and the structural features of the final powders have also been studied by infrared spectra, elemental composition and X-ray diffraction analysis and SEM observation.

  17. Certain Aliphatic Nitramines and Related Compounds (United States)


    Tho extracts wore combined and dried tritt) magnesium sulfato . After distilling off almost all of the ether, the residue was cooled in em acetcne...combined ortract was dried with magnesium sulfato . After re- moving the ether the residue Wul vacuum distilled. Thore was obtained a liquid (22.9 g...magnesium sulfato . The ether solution of N-fa- nitroxyethyl)nitrcurothaiio wa3 used directly for the ammonoly- sis. Ammonolysis of N-(e-nitro::yothyl

  18. Convenient synthesis of (4R,5R)-4,5-bis(aminomethyl)-2-isopropyl- 1,3-dioxolane

    Institute of Scientific and Technical Information of China (English)


    A convenient approach for the preparation of (4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-l,3-dioxolane is described. The target compound via two steps is synthesized from diethyl-2,3-O-isobutylidene-D-tartrate, through ammonolysis and reduction.(C) 2007 De Cai Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  19. Photocatalytic properties of CoOx-loaded nano-crystalline perovskite oxynitrides ABO2N (A = Ca, Sr, Ba, La; B = Nb, Ta) (United States)

    Oehler, Florian; Ebbinghaus, Stefan G.


    Highly crystalline niobium- and tantalum-based oxynitride perovskite nanoparticles were obtained from hydrothermally synthesized oxide precursors by thermal ammonolysis at different temperatures. The samples were studied with respect to their morphological, optical and thermal properties as well as their photocatalytic activity in the decomposition of methyl orange. Phase pure oxynitrides were obtained at rather low ammonolysis temperatures between 740 °C (CaNbO2N) and 1000 °C (BaTaO2N). Particle sizes were found to be in the range 27 nm-146 nm and large specific surface areas up to 37 m2 g-1 were observed. High photocatalytic activities were found for CaNbO2N and SrNbO2N prepared at low ammonolysis temperatures. CoOx as co-catalyst was loaded on the oxynitride particles resulting in a strong increase of the photocatalytic activities up to 30% methyl orange degradation within 3 h for SrNbO2N:CoOx.


    Directory of Open Access Journals (Sweden)

    K. P. Kolnogorov


    Full Text Available Summary. This article discusses how to obtain amide-containing salts of 3d-metals based on tall rosin. A scheme of obtaining amide containing salts 3dmetals. The scheme of obtaining amide-containing salts of 3d-metals presented here. Ammonolysis maleopimaric acid was carried out, the technological parameters of the process were identified. Found that the process of ammonolysis affected by the following controlled technological factors: the ratio of the components, the temperature of the reaction medium and the duration of holding ammonolysis. The results of studies of the effect of additives on the received technical and technological properties of the elastomer compositions, adhesion and corrosion resistance rubber-systems are presented. The most efficient promoters are metalcord-rubber adhesion systems for use in the manufacture of tires fitted. Providing the necessary technological properties of manufacturing rubber compounds achieved when using elastomeric compositions consisting of a cobalt salt of amide MTC. Found that necessary to adjust the composition of the vulcanizing system using the synthesized compounds. It was revealed that the elastomeric composition comprising cobalt salt of amide maleated rosin and cobalt naphthenate are less susceptible to oxygen and air at elevated temperature compared to rubber containing salts Mn (II and Cr (III amide MTC. The results of studies of bond strength rubber with steel showed that the adhesive properties of rubber-systems with the test components depend on the dosage and rubber compound. It was determined that the introduction of salts of Co (II, based on amide maleated tall oil rosin at a dosage of 1.5 wt. parts per 100 wt. phr produces indicators adhesion and corrosion properties at the level of those with industrial modifier cobalt naphthenate. The results of research of obtained compounds influence on the technical and technological properties of the elastomer compositions, adhesion and

  1. (-)-Arctigenin as a lead compound for anticancer agent. (United States)

    Chen, Gui-Rong; Li, Hong-Fu; Dou, De-Qiang; Xu, Yu-Bin; Jiang, Hong-Shuai; Li, Fu-Rui; Kang, Ting-Guo


    (-)-Arctigenin, an important active constituent of the traditional Chinese herb Fructus Arctii, was found to exhibit various bioactivities, so it can be used as a good lead compound for further structure modification in order to find a safer and more potent medicine. (-)-Arctigenin derivatives 1-5 of (-)-arctingen were obtained by modifying with ammonolysis at the lactone ring and sulphonylation at C (6') and C (6″) and O-demethylation at CH3O-C (3'), CH3O-C (3″) and CH3O-C (4″), and their anticancer bioactivities were examined.

  2. Amino acid analogs IV:4-fluoroisoleucine. (United States)

    Gershon, H; Shanks, L; Clarke, D D


    4-Fluoroisoleucine was produced by ammonolysis of 2-bromo-4-fluoro-3-methylpentanoic acid, which resulted from the bromofluorination of 4-methyl-2-pentenoic acid. It did not inhibit Plasmodium berghei in mice at 640 mg/kg and was not toxic to the animals. The fluoroamino acid inhibited Aspergillus niger, Trichoderma viride, Myrothecium verrucaria, Trichophyton mentagrophytes, and Mucor mucedo in Czapek solution agar at a concentration between 10(4) and 10(3) microgram/ml. Growth of Escherichia coli was inhibited 25% at 900 microgram/ml in a defined medium.

  3. Synthesis of ternary nitrides by mechanochemical alloying

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Zhu, J.J.; Lindelov, H.;


    Ternary metal nitrides ( of general formula MxM'N-y(z)) attract considerable interest because of their special mechanical, electrical, magnetic, and catalytic properties. Usually they are prepared by ammonolysis of ternary oxides (MxM'O-y(m)) at elevated temperatures. We show that ternary...... nitrides by mechanochemical alloying of a binary transition metal nitride (MxN) with an elemental transition metal. In this way, we have been able to prepare Fe3Mo3N and Co3Mo3N by ball-milling of Mo2N with Fe and Co, respectively. The transformation sequence from the starting materials ( the binary...

  4. Wet ammonia Synthesis of Semiconducting N:Ta2O5, Ta3N5 and β-TaON Films for Photoanode Applications


    Dabirian, A.; Van't Spijker, H; Van de Krol, R.


    Tantalum oxynitride (β-TaON) is a promising photoanode material for photoelectrochemical water splitting. However, the synthesis of phase-pure β-TaON films is a challenging task. This paper describes a novel approach to achieve this by the controlled nitridation of Ta2O5 films under a flow of ammonia gas (ammonolysis), which was obtained by bubbling argon through an aqueous ammonium hydroxide solution followed by a 5 Å molecular sieve to remove the water. Depending on the nitridation conditio...

  5. Percent {alpha} and {beta} phases present in the silicon nitride powder produced through intermediary silicon di imide; Estudo da porcentagem de fases {alpha} e {beta} presentes no po de nitreto de silicio produzido via intermediario diimida de silicio

    Energy Technology Data Exchange (ETDEWEB)

    Cavalcanti, Celso Berilo Cidade; Piorino Neto, Francisco; Shibuya, Hissao; Silva, Vitor Alexandre da; Silva, Cosme Roberto Moreira da [Centro Tecnico Aeroespacial, Sao Jose dos Campos, SP (Brazil). Inst. de Aeronautica e Espaco


    Ceramic powder must have appropriated characteristics which allow good mechanical final properties of the sintered material. The {alpha}/{beta} relationship on the starting powders is very important when we want to improve the fracture toughness. The present work evaluates the phase relationships on silicon nitride powder, produced by ammonolysis of silicon tetrachloride, by imide step, with variation of temperature and time of dimide pyrolysis. The synthesis condition was monitored and the existing {beta}-phases for the used conditions remained between 15 and 25%. (author) 1 tab.

  6. Syntheses and metal ions recognition of dendritic calix[n]arenes(n=6,8)amide derivative

    Institute of Scientific and Technical Information of China (English)

    WANG Yunyan; CAI Yahua; YAN Chaoguo


    Dendritic p-t'butylcalix[n]arene amide derivatives with terminal amino groups of the first and second generations were synthesized by using divergent methods from ammonolysis of ethyl calixarylacetate with 1,6-diaminohexane and Michael addition of methyl acrylate.Their structures were confirmed by IR,1H NMR.The recognition properties of these amide derivatives for several kinds of metal ions were studied with UV-Vis spectroscopy.The results showed a great affinity for soft Ag+ and UO22+ ions and formed 1:2 or 1:3 stoichiometric complexes.

  7. Optimized Synthesis Process of Piperine%胡椒碱的合成工艺优化

    Institute of Scientific and Technical Information of China (English)

    刘同星; 刘倩雯; 王丽梅; 李建发


    An optimized synthesis process of piperine was described. The process used triethylamine as catalyst for ammonolysis, the reaction yield was increased from 2.37% to 18%, and the reaction time was shortened from 40 h to 18 h. The optimal reaction conditions for ammonolysis were determined as follows: sodium methoxide 0.5 g, methanol 25 mL , methyl piperate 1.0 g, piperidine 3.44 g , triethylamine 0.73 g, the reflux temperature 80 ℃ and the reflux time 18 h.%介绍了胡椒碱合成路线的一条优化工艺,其中氨解反应采用三乙胺作为催化剂,反应收率由原来的2.37%提高到18%,反应时间由原来的40 h 缩短为18 h。合成胡椒碱中氨解反应的最佳反应条件为:依次加入0.5 g 甲醇钠、25 mL 甲醇、1.0 g 胡椒酸甲酯、3.44 g 哌啶、0.73 g 三乙胺于反应器中,80℃回流18 h。

  8. Bandgap tuning in SrTi(N,O,F){sub 3} by anionic-lattice variation

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Songhak; Maegli, Alexandra E.; Karvonen, Lassi; Matam, Santhosh K.; Shkabko, Andrey [Laboratory for Solid State Chemistry and Catalysis, Empa-Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf (Switzerland); Riegg, Stefan [Lehrstuhl für Experimentalphysik 5, EKM, Universität Augsburg, Universitätsstraße 1, 86135 Augsburg (Germany); Großmann, Thomas; Ebbinghaus, Stefan G. [Institut für Chemie, Martin-Luther Universität Halle-Wittenberg, Kurt-Mothes-Straße 2, 06120 Halle/Saale (Germany); Pokrant, Simone [Laboratory for Solid State Chemistry and Catalysis, Empa-Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf (Switzerland); Weidenkaff, Anke, E-mail: [Laboratory for Solid State Chemistry and Catalysis, Empa-Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf (Switzerland)


    Polycrystalline SrTiO{sub 3} and SrTi(O,F){sub 3} powders were synthesized by a solid-state reaction. A partial substitution of oxygen by nitrogen was subsequently carried out using thermal ammonolysis resulting in SrTi(N,O){sub 3} and SrTi(N,O,F){sub 3}. Powder X-ray diffraction (XRD) revealed a cubic perovskite structure with space group Pm-3m for all samples. The thermal ammonolysis slightly increased the lattice parameters, crystallite sizes and strain. As a result from the co-substitution of oxygen with nitrogen and fluorine for SrTi(N,O,F){sub 3}, highly distorted TiO{sub 6} octahedra were detected using X-ray absorption near edge structure (XANES) spectroscopy. The weakening of all active modes of the Raman spectra after thermal ammonolysis also indicated enhanced distortions in the local crystal structure. SrTi(N,O,F){sub 3} has the largest amount of nitrogen as well as fluorine among all four samples as determined by thermogravimetric analysis (TGA), elemental analysis and X-ray photoelectron spectroscopy (XPS). In the UV–vis spectra a distinctive shift of the absorption-edge energy was observed exclusively for the SrTi(N,O,F){sub 3} sample from 390 to 510 nm corresponding to a bandgap narrowing from 3.18 to 2.43 eV. - Graphical abstract: Figure shows the shift of the absorption-edge energy for the SrTi(N,O,F){sub 3} sample from 390 to 510 nm corresponding to a bandgap narrowing from 3.18 to 2.43 eV. Display Omitted - Highlights: • Synthesis of phase-pure SrTi(N,O,F){sub 3} via solid-state reaction. • The incorporated nitrogen contents increase by the presence of fluorine in SrTi(N,O,F){sub 3}. • Co-substitution with nitrogen and fluorine is beneficial for the bandgap narrowing compared to by only nitrogen or fluorine substitution.

  9. Silicon oxynitrides of KCC-1, SBA-15 and MCM-41 for CO 2 capture with excellent stability and regenerability

    KAUST Repository

    Patil, Umesh


    We report the use of silicon oxynitrides as novel adsorbents for CO 2 capture. Three series of functionalized materials based on KCC-1, SBA-15 and MCM-41 with Si-NH 2 groups were prepared using a simple one-step process via thermal ammonolysis using ammonia gas, and they demonstrated excellent CO 2 capture capabilities. These materials overcome several limitations of conventional amine-grafted mesoporous silica. They offer good CO 2 capture capacity, faster adsorption-desorption kinetics, efficient regeneration and reuse, more crucially excellent thermal and mechanical stability even in oxidative environments, and a clean and green synthesis route, which allows the overall CO 2 capture process to be practical and sustainable. This journal is © The Royal Society of Chemistry 2012.

  10. Synthesis of allylamine in ethanol%乙醇中烯丙基胺的合成

    Institute of Scientific and Technical Information of China (English)

    唐炳涛; 张淑芬; 杨锦宗


    Allylamine was prepared from the ammonolysis of allyl chloride or the reaction of allyl chloride with hexamethylenetetramine in ethanol. The selectivity of allylamine was improved from 21.4% to 67.6% when the reaction was carried out in ethanol instead of liquid ammonia. At the same time, the selectivity of allylamine was increased from 13.3% to 67.6% when the molar ratio of NH3 to allyl chloride was increased from 4.5∶1 to 25∶1.However, the reaction of allyl chloride and hexamethylenetetramine in ethanol produced allylamine with high selectivity (100%) and high yield (87%).The synthesis of allylamine from the reaction of allyl chloride and hexamethylenetetramine in ethanol was more straightforward and convenient.

  11. Preparation and application of a novel magnetic anion exchange resin for selective nitrate removal

    Institute of Scientific and Technical Information of China (English)

    Yang Zhou; Chen Dong Shuang; Qing Zhou; Man Cheng Zhang; Peng Hui Li; Ai Min Li


    A novel magnetic anion exchange resin NDM-1 was prepared through suspension polymerization and then functionalized with ammonolysis and alkylating agents.Its application for selective removal of nitrate was performed in comparison with MIEX(R).The results demonstrated that NDM-1 achieved higher efficiency in nitrate removal than MIEX(R) did,with or without the existence of competing anion SO42-ascribed to its longer alkyl chains on exchange sites.Combined with the advantage of easy separation due to γ-Fe2O3 implanted,the magnetic anion exchange resin NDM-1 was considered to be superior to MIEX(R) for nitrate removal in practical application.

  12. Synthesis and electrochemical characterization of TixTayAlzN1-δOγ for fuel cell catalyst supports (United States)

    Wakabayashi, Ryo H.; Abruña, Héctor D.; DiSalvo, Francis J.


    Quinary TixTayAlzN1-δOγ of various compositions have been prepared by a co-precipitation method followed by ammonolysis. The nitride samples were examined as potential catalyst supports in polymer electrolyte membrane fuel cells. The nitride products crystallized in the rock salt (NaCl) structure over a wide range of compositions. The addition of Ta and Al was highly beneficial towards improving the chemical and electrochemical stability of TiN, without a significant loss of electrical conductivity. Platinum particles were successfully deposited on the (oxy)nitride samples, and the composite samples at some compositions were found to be comparable to Pt/carbon in their stability and catalytic activity even without optimizing the Pt deposition and dispersion processes.

  13. Synthesis of Ni-poor NiO nanoparticles for p-DSSC applications (United States)

    Polteau, Baptiste; Tessier, Franck; Cheviré, François; Cario, Laurent; Odobel, Fabrice; Jobic, Stéphane


    To improve the performances of p-Dye Sensitized Solar Cell (p-DSSC) for the future, the synthesis of modified p-type nickel oxide semiconductor, commonly used as photocathode in such devices, was initiated with Ni3O2(OH)4 as precursor. This specific nickel oxyhydroxide was first characterized by X-ray photo-electron spectroscopy and magnetic susceptibility measurements. Then its thermal decomposition was thoroughly studied in order to control the particles size of the as-prepared NiO nanopowders. Low temperature decomposition in air of this precursor allows the formation of Ni1-xO nanoparticles with a large amount of Ni vacancies and specific surface areas up to 250 m2 g-1. Its ammonolysis at 250 °C leads to nanostructured N-doped NiO (NiO:N) materials.

  14. Synthesis of 2,3,8,9-Tetrahydropyrido[2,3-d:6,5-d']dipyrimidine-4,6-diones%2,3,8,9-四氢吡啶并[2,3-d:6,5-d]二嘧啶-4,6-二酮衍生物的合成

    Institute of Scientific and Technical Information of China (English)

    杨留攀; 李加荣; 柴洪新; 袁洪; 张奇; 史大昕


    以丙二腈、原羧酸三乙酯、吡啶为起始原料经环化、氨解,然后与酮在甲醇钠催化下反应得到了2,3,8,9-四氢吡啶并[2,3-d:6,5-d']二嘧啶-4,6-二酮衍生物.目标产物的结构经IR,NMR,ESI和元素分析确证.%2,3,8,9-Tetrahydropyrido[2,3-d:6,5-d']dipyrimidine-4,6-diones were synthesized by using malononitrile, or- tho-triethyl and pyridine as starting materials in three steps reaction including cyclization, ammonolysis and reaction with ke- tones under the catalysis of sodium methoxide. The structures of the products were confirmed by NMR, IR, ESI and elemental analysis.

  15. 无水溶胶-凝胶法制备非氧化物陶瓷的研究进展%Research Progress in Fabrication of Non-Oxide Ceramics via Non-Aqueous Sol-Gel Method

    Institute of Scientific and Technical Information of China (English)

    李书宏; 张宗波; 罗永明; 徐彩虹


    综述了基于氨解、胺解以及碳化二亚胺化三类反应的无水相溶胶-凝胶方法在制备SiCN、B(C)N、SiN、BN等非氧化物陶瓷材料方面的研究进展,并对其前景进行了展望.%This review mainly summarized recent progress on the fabrication of non-oxide ceramics, such as SiCN, BN, B ( C ) N, and SiN, by the non-aqueous sol-gel method, on the basis of ammonolysis reaction, aminolysis reaction, and the carbodiimide reaction. Future prospects of the method were also discussed.

  16. Synthesis, characterization, and catalytic activity of Zirconium oxide nitrides supported on high-surface SiO{sub 2}; Praeparation und Charakterisierung von SiO{sub 2}-getraegerten Zirconiumoxidnitriden mit hoher Oberflaeche und Untersuchung ihrer katalytischen Aktivitaet bei der Ammoniakzersetzung

    Energy Technology Data Exchange (ETDEWEB)

    Frenzel, Nancy; Otremba, Thorsten; Schomaecker, Reinhard; Ressler, Thorsten; Lerch, Martin [Technische Univ. Berlin (Germany). Inst. fuer Chemie


    Zirconium oxide nitrides are active ammonia decomposition catalysts for the production of hydrogen. We present a route to zirconium oxide nitrides with high surface area. The precursor used consisted of a high-surface-area silica material coated with zirconium alkoxide. Subsequent hydrolysis and calcination resulted in ZrO{sub 2} supported on SiO{sub 2}. The high surface area of the material could be maintained in the following ammonolysis procedure leading to the corresponding zirconium oxide nitride. In contrast to the as-prepared ZrO{sub 2}, the zirconium oxide nitrides exhibited a significant catalytic activity in ammonia decomposition, but compared to an iron oxide-based reference material, the new oxide nitrides showed a rather low activity. Nevertheless, zirconium oxide nitrides constitute suitable model systems for elucidating the effect of nitrogen in the anion substructure on the activity and selectivity of oxide-based ammonia decomposition catalysts. (orig.)

  17. Synthesis of Pinoxaden%除草剂唑啉草酯的合成研究

    Institute of Scientific and Technical Information of China (English)



    以2,6-二乙基-4-甲基苯胺为原料,经重氮化、偶联、醇解、酯胺解,最后与特戊酰氯酯化,制备得到唑啉草酯。产品质量分数大于97%,收率为26.6%(以2,6-二乙基-4-甲基苯胺计)。%Using 2,6-diethyl-4-methylaniline as starting material, pinoxaden was synthesized by diazotization, coupling, alcoholysis, ammonolysis and esterification. The purity of pinoxaden was more than 97%, and the total yield was 26.6%.

  18. β-重氮-α-羰基酰胺类化合物的合成及其与烯烃的环丙烷化反应%Synthesis ofβ-Diazo-α-ketoamides and Their Cyclopropanation Reaction with Alkenes

    Institute of Scientific and Technical Information of China (English)

    陈晓娜; 胡文浩; 李小六; 徐华栋


    A series of chiral 2-oxo-3-diazo amide alcohol' were synthesized from α-diazo-ethyl pyru vates and amino alcohols by the reaction of ammonolysis, their cyclo-propanation reactions with sim ple alkene to gave β-cyclopropyl-α-ketoamides bearing multiple handles for further chemical transfor mations. The structures were confirmed by 1H NMR, 13C NMR, IR and HR-MS.%以重氮丙酮酸乙酯和氨基醇为原料,经过氨解合成了一系列β-重氮-α-羰基酰胺类化合物,并与环己烯反应制备了环丙烷化产物,其结构经1H NMR,13C NMR,IR和HR-MS确证.

  19. Antimicrobial evaluation of new synthesized pyridine nucleosides under solvent-free conditions. (United States)

    Rateb, Nora M; El-Deab, Hany A; Abdou, Ibrahim M


    Two series of novel 3-cyano-2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxo) pyridines and 3-cyano-2-(2,3,5-tri-O-acetyl-β-D-ribofuranosyloxy)-4-trifluromethyl-6-phenyl pyridine were synthesized using efficient microwave methods. The targeted compounds were obtained in high yields by reacting 2-(1H)-pyridone or its salt with activated sugars using SiO₂ under solvent-free conditions. Ammonolysis of the resulted acetylated nucleosides produced 3-cyano-2-(β-D-glucopyranosyloxo)-pyridines and 3-cyano-2-(β-D-ribofuranosyloxy)-4-trifluoromethyl-6-phenyl pyridine. These new products were fully characterized using 1D and 2D NMR. These compounds were screened for their antibacterial activities against G(+) and G(-) bacteria and some found to exhibit better antibacterial activities than the control drug.

  20. Study on the synthesis of N(2)-L-alanyl-L-glutamine%N(2)-L-丙氨酰-L-谷氨酰胺的合成工艺研究

    Institute of Scientific and Technical Information of China (English)

    陈再新; 夏正君; 蒋龙


    N (2) -L-Alanyl-L-glutamine was synthesized by ammonolysis of N- (D-2-chloropropionyl) -L- glutamine, which was obtained by condensation of D-2-chloropropionic chloride and L-glutamine. The best re- sult of the condensation reaction was obtained in toluene-water two-phase system, at 0~5~C, and by using 2 e- quivalent of NaOH solution, which was added dropwise with D-2-chloropropionic chloride at the same time, the yield was 92 %. The best yield 67.5 % of the ammonolysis reaction was obtained at 60℃ and by using concentrat ed ammonia solution.%以D-2-氯代丙酰氯和L-谷氨酰胺为原料,缩合得到N-(D-2-氯丙酰)-L-谷氨酰胺,再经氨化后得到N(2)-L-丙氨酰-L-谷氨酰胺。缩合反应使用2倍氢氧化钠水溶液并采用与D-2-氯代丙酰氯同时滴加的方式、在两相的甲苯/水体系中、温度在0~5℃结果最佳,收率92%。氨解反应使用浓氨水、在60℃下结果最佳,收率67.5%。

  1. A novel LaFeO{sub 3-X}N{sub X} oxynitride. Synthesis and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Sierra Gallego, G., E-mail: [Escuela de Ingenieria de Materiales, Facultad de Minas, Universidad Nacional de Colombia, Calle 75 no. 79A-51, Bloque M17, Medellin (Colombia); Marin Alzate, N.; Arnache, O. [Institute of Physics, University of Antioquia, Calle 67, No. 53-108, A.A. 1226 Medellin (Colombia)


    Highlights: Black-Right-Pointing-Pointer LaFeO{sub 3} perovskite synthesized by auto combustion method. Black-Right-Pointing-Pointer LaFeO{sub 3-X}N{sub X} oxynitride produced by ammonolysis reaction. Black-Right-Pointing-Pointer Oxynitride characterized by XRD, Rietveld, SEM, EDX, BET, Raman, TGA and FTIR. Black-Right-Pointing-Pointer Partial replacement of oxygen by nitrogen increases slightly the cell parameters. Black-Right-Pointing-Pointer TGA shows that oxynitride start to decompose in air above 550 Degree-Sign C. Evolution of N{sub 2} and NO was detected. - Abstract: A perovskite LaFeO{sub 3} was synthesized by auto combustion method and then LaFeO{sub 3-X}N{sub X} oxynitride was produced by ammonolysis reaction. The synthesized LaFeO{sub 3-X}N{sub X} oxynitride was characterized by X-ray diffraction (XRD), Rietveld refinement, scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Brunauer-Emmett-Teller (BET) nitrogen adsorption, particle size distribution, Raman spectroscopy, thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). Nitrogen effect into the perovskite structure was confirmed by DRX. The structure refinement using the Rietveld method indicates that partial replacement of oxygen by nitrogen increases slightly the cell parameters of the LaFeO{sub 3} perovskite. FTIR analysis show that bands at 995 and 1070 cm{sup -1} in the oxynitrides spectra could be assigned to the stretching vibration modes of Fe-N bonds in the FeO{sub 6-X}N{sub X} octahedral. Thermogravimetric analysis (TGA) showed that LaFeO{sub 3-X}N{sub X} oxynitride series start to decompose in air above 550 Degree-Sign C. During the decomposition it was found that some amount of nitrogen stays retained in the structure forming intermediate compounds. MS analysis of the gaseous products reveals the evolution of N{sub 2} and NO, suggesting a complex reaction mechanism. To our knowledge, there are no reports on the synthesis and characterization

  2. Green House Gas Control and Agricultural Biomass for Sustainable Animal Agriculture in Developing Countries

    Directory of Open Access Journals (Sweden)

    J Takahashi


    Full Text Available Important green house gases (GHG attributed to animal agriculture are methane (CH4 and nitrous oxide (N2O, though carbon dioxide (CO2 contributes almost half of total greenhouse effect. Rumen CH4 production in an enteric fermentation can be accounted as the biggest anthropogenic source. Some of prebiotics and probiotics have been innovated to mitigate rumen CH4 emission. The possible use of agricultural biomass consisted of non-edible parts of crop plants such as cellulose and hemi cellulose and animal wastes was proposed as a renewable energy and nitrogen sources. The ammonia stripping from digested slurry of animal manure in biogas plant applied three options of nitrogen recycling to mitigate nitrous oxide emission. In the first option of the ammonia stripping, the effect of ammonolysis on feed value of cellulose biomass was evaluated on digestibility, energy metabolism and protein utilization. Saccharification of the NH3 treated cellulose biomass was confirmed in strictly anaerobic incubation with rumen cellulolytic bacteria, Ruminoccous flavefaciens, to produce bio-ethanol as the second option of ammonia stripping. In an attempt of NH3 fuel cell, the reformed hydrogen from the NH3 stripped from 20 liter of digested slurry in thermophilic biogas plant could generate 0.12 W electricity with proton exchange membrane fuel cell (PEM as the third option.

  3. One-step route to a hybrid TiO2/TixW1−xN nanocomposite by in situ selective carbothermal nitridation

    Directory of Open Access Journals (Sweden)

    Zoë Schnepp, Martin J Hollamby, Masahiko Tanaka, Yoshitaka Matsushita, Yoshio Katsuya and Yoshio Sakka


    Full Text Available Metal oxide/nitride nanocomposites have many existing and potential applications, e.g. in energy conversion or ammonia synthesis. Here, a hybrid oxide/nitride nanocomposite (anatase/TixW1−xN was synthesized by an ammonia-free sol–gel route. Synchrotron x-ray diffraction, complemented with electron microscopy and thermogravimetric analysis, was used to study the structure, composition and mechanism of formation of the nanocomposite. The nanocomposite contained nanoparticles (<5 nm diameter of two highly intermixed phases. This was found to arise from controlled nucleation and growth of a single oxide intermediate from the gel precursor, followed by phase separation and in situ selective carbothermal nitridation. Depending on the preparation conditions, the composition varied from anatase/TixW1−xN at low W content to an isostructural mixture of Ti-rich and W-rich TixW1−xN at high W content. In situ selective carbothermal nitridation offers a facile route to the synthesis of nitride-oxide nanocomposites. This conceptually new approach is a significant advance from previous methods, which generally require ammonolysis of a pre-synthesized oxide.

  4. Synthesis of tetrapeptide Bz-RGDS-NH2 by a combination of chemical and enzymatic methods. (United States)

    Huang, Yi-Bing; Cai, Yu; Yang, Sen; Wang, Hua; Hou, Rui-Zhen; Xu, Li; Xiao-Xia, Wu; Zhang, Xue-Zhong


    The tetrapeptide Bz-Arg-Gly-Asp-Ser-NH(2) (Bz-RGDS-NH(2)) was successfully synthesized by a combination of chemical and enzymatic methods in this study. Firstly, the precursor tripeptide Gly-Asp-Ser-NH(2) (GDS-NH(2)) was synthesized by a novel chemical method in four steps including chloroacetylation of l-aspartic acid, synthesis of chloroacetyl l-aspartic acid anhydride, the synthesis of ClCH(2)COAsp-SerOMe and ammonolysis of ClCH(2)COAsp-SerOMe. Secondly, lipase (PPL) was used to catalyze the formation of Bz-RGDS-NH(2) in aqueous water-miscible organic cosolvent systems using Bz-Arg-OEt as the acyl donor and GDS-NH(2) as the nucleophile. The optimum conditions were Bz-Arg-OEt 50 mM; GDS-NH(2) 400 mM; 10 degrees C, 0.1M phosphate buffer, pH 7.5; 60% DMF or 58% DMSO, PPL: 10 mg ml(-1) with the maximum yields of the tetrapeptide of 73.6% for DMF and 70.4% for DMSO, respectively. The secondary hydrolysis of the tetrapeptide product did not take place due to the absence of amidase activity of lipase.

  5. Preparation and Instability of Nanocrystalline Cuprous Nitride. (United States)

    Reichert, Malinda D; White, Miles A; Thompson, Michelle J; Miller, Gordon J; Vela, Javier


    Low-dimensional cuprous nitride (Cu3N) was synthesized by nitridation (ammonolysis) of cuprous oxide (Cu2O) nanocrystals using either ammonia (NH3) or urea (H2NCONH2) as the nitrogen source. The resulting nanocrystalline Cu3N spontaneously decomposes to nanocrystalline CuO in the presence of both water and oxygen from air at room temperature. Ammonia was produced in 60% chemical yield during Cu3N decomposition, as measured using the colorimetric indophenol method. Because Cu3N decomposition requires H2O and produces substoichiometric amounts of NH3, we conclude that this reaction proceeds through a complex stoichiometry that involves the concomitant release of both N2 and NH3. This is a thermodynamically unfavorable outcome, strongly indicating that H2O (and thus NH3 production) facilitate the kinetics of the reaction by lowering the energy barrier for Cu3N decomposition. The three different Cu2O, Cu3N, and CuO nanocrystalline phases were characterized by a combination of optical absorption, powder X-ray diffraction, transmission electron microscopy, and electronic density of states obtained from electronic structure calculations on the bulk solids. The relative ease of interconversion between these interesting and inexpensive materials bears possible implications for catalytic and optoelectronic applications.

  6. Incorporating different vegetable oils into an aqueous dispersion of hybrid organic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Samyn, Pieter, E-mail: [Albert-Luedwigs-University Freiburg, Institute for Forest Utilization (Germany); Schoukens, Gustaaf [Ghent University, Department of Textiles (Belgium); Stanssens, Dirk; Vonck, Leo; Van den Abbeele, Henk [Topchim N.V. (Belgium)


    Different vegetable oils including soy oil, high-oleic sunflower oil, corn oil, castor oil (CO), rapeseed oil, and hydrogenated CO were added to the imidization reaction of poly(styrene-maleic anhydride) or SMA, with ammonium hydroxide in aqueous medium. The oils favorably reduce viscosity during ammonolysis of the anhydride moieties and increase the maximum solid content of the dispersed imidized SMA to at least 50 wt%, compared to a maximum of 35 wt% for pure imidized SMA. The viscosity of imidized SMA with polyunsaturated oils was generally larger than for monosaturated oils, but it was highest for COs due to high contents of hydroxyl groups. Depending on the oil reactivity, homogeneous or core-shell nanoparticles with 20-60 nm diameters formed. The interactions of oil and organic phase were studied by Fourier-transform infrared spectroscopy, indicating qualitative variances between different oils, the fraction imidized SMA and remaining fraction of ammonolyzed SMA without leakage of oil upon diluting the dispersion and precipitation at low pH. A quantitative analysis with calculation of imide contents, amounts of reacted oil and chemical interactions was made by Fourier-transform-Raman spectroscopy suggesting that most interactions take place around the unsaturated oil moieties and ammonolyzed anhydride.

  7. Identification of neighbouring protein pairs in the rat liver 40-S ribosomal subunits cross-linked with dimethyl suberimidate. (United States)

    Terao, K; Uchiumi, T; Kobayashi, Y; Ogata, K


    (1) The 40-S ribosomal subunits of rat liver were treated with a bifunctional cross-linking reagent, dimethyl suberimidate. Cross-linked protein-protein dimers were separated by two-dimensional acrylamide gel electrophoresis. The stained cross-linked complexes within the gel were radioiodinated without the elution of proteins from the gel and were cloven into the original monomeric protein constituents by ammonolysis. The proteins in each dimer were finally identified by two-dimensional acrylamide gel electrophoresis of the cloven monomeric proteins, followed by radioautography of the stained gel. (2) The molecular weights of cross-linked complexes were determined by SDS-polyacrylamide gel electrophoresis and were compared with those of their constituent proteins. (3) The following dimers were proposed from these results: S3-S12 (S3 or S3a-S11), S4-S12 (S3b-S11, S5-S7 (S4-S6), S5-S22 (S4-S23 or S24), S6-S8 (S5-S7), S8-S16 (S7-S18), S17-S21 (S16--S19) and S22A-S22B (S23-S24), designated according to our numbering system [1]. The designations according to the proposed uniform nomenclature [2] are described in parentheses.

  8. 硅氧氮陶瓷先驱体的合成及表征%Synthesis and Characterization of Silicon Oxynitride Ceramic Precursor

    Institute of Scientific and Technical Information of China (English)

    罗晶; 张宗波; 罗永明; 彭志坚; 徐彩虹


    以MeViSiCl2、MeHSiCl2和MeSiCl3为原料,采用先部分水解再氨解的方法制备了硅氧氮陶瓷先驱体.利用FT-IR、1H-NMR、29Si-NMR、GPC以及TGA对聚合物先驱体的结构和热性能进行了表征.结果表明:合成的硅氧氮烷在DCP固化2 h后具有77.7%的陶瓷产率.%The polymer precursor for silicon oxynitride ceramic was prepared by partial hydrolysis of MeViSiCl2、MeHSiCl2 and MeSiCl3 followed by ammonolysis reaction of the hydrolyzed intermediates with NH3. The structure and thermal properties of the polymer precursor were studied by means of FT-IR,1H-NMR,29Si-NMR, GPC and TGA,which indicated that the ceramic yield of the polymer precursor doped with DCP cured for 2 h was 77. 7% .

  9. Improvement on Synthesis Process of C. I. Direct Blue 199%C.I.直接蓝199工艺改进

    Institute of Scientific and Technical Information of China (English)

    王雪梅; 郑玉安


    The Synthesis Process of C. I. Direct Blue 199 was improved. The reaction temperature of CuPc and chtorosulfonic acid was raised from 130℃ to 140 ℃, then the reaction temperature of the product with thionyl chloride was raised from 60 - 65 ℃ to 80 ℃ ; the dropping time of thionyl chloride was prolonged from 2 - 2. 5 hours to 4 hours; and ammonia was replaced by organic base in ammonolysis. By this new technology, the difficult problem in membrane filtration before salting out was resolved when the dye was applied in ink.%对C.I.直接蓝199的老工艺进行了改进。使铜酞菁与氯磺酸的反应温度由原来的130℃升至140℃左右,之后与氯化亚砜的反应温度由60~65℃提高到80℃,而且滴加氯化亚砜的时间从2~2.5延长至4小时,同时氨解用的氨水用有机碱替代。新工艺解决了此染料用于墨水时在盐析前膜过滤困难的问题。

  10. Structure and properties of molybdenum oxide nitrides as model systems for selective oxidation catalysts

    Directory of Open Access Journals (Sweden)

    Lerch Martin


    Full Text Available Abstract Molybdenum oxide nitride (denoted as Mo(O,N3 was obtained by ammonolysis of α-MoO3 with gaseous ammonia. Electronic and geometric structure, reducibility, and conductivity of Mo(O,N3 were investigated by XRD, XAS, UV-Vis spectroscopy, and impedance measurements. Catalytic performance in selective propene oxidation was determined by online mass spectrometry und gas chromatography. Upon incorporation of nitrogen, Mo(O,N3 maintained the characteristic layer structure of α-MoO3. XRD analysis showed an increased structural disorder in the layers while nitrogen is removed from the lattice of Mo(O,N3 at temperatures above ~600 K. Compared to regular α-MoO3, Mo(O,N3 exhibited a higher electronic and ionic conductivity and an onset of reduction in propene at lower temperatures. Surprisingly, α-MoO3 and Mo(O,N3 exhibited no detectable differences in onset temperatures of propene oxidation and catalytic selectivity or activity. Apparently, the increased reducibility, oxygen mobility, and conductivity of Mo(O,N3 compared to α-MoO3 had no effect on the catalytic behavior of the two catalysts. The results presented confirm the suitability of molybdenum oxide nitrides as model systems for studying bulk contributions to selective oxidation.

  11. Synthesis and crystal structure of Nb{sub 0.84}N

    Energy Technology Data Exchange (ETDEWEB)

    Frenzel, Nancy; Irran, Elisabeth; Lerch, Martin [Technische Univ. Berlin (Germany). Inst. fuer Chemie; Buchsteiner, Alexandra [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Berlin (Germany)


    A new compound of the composition Nb{sub 0.84}N was prepared by ammonolysis of NbO{sub 2} at 1100 C. The crystal structure refinement was performed by the Rietveld method using X-ray and neutron powder diffraction data. Nb{sub 0.84}N crystallizes in the trigonal space group R anti 3m (no. 166) with the lattice parameters a = 298.5(2) and c = 2384.3(4) pm. The niobium atoms form a close packing with a layer sequence which can be described by the Jagodzinski symbol hhc. The nitrogen atoms fill all octahedral voids. Along [001] a sequence of two layers of trigonal NbN{sub 6} prisms and one layer of NbN{sub 6} octahedra is formed. The nitrogen positions are fully occupied, the niobium positions only partially. Nb{sub 0.84}N is part of a family of crystal structures between the anti-NiAs and the NaCl type consisting of close-packed metal layers with varying stacking sequences. (orig.)

  12. Preparation of niobium based oxynitride nanosheets by exfoliation of Ruddlesden-Popper phase precursor (United States)

    da Silva Maia, Ary; Cheviré, François; Demange, Valérie; Bouquet, Valérie; Pasturel, Mathieu; Députier, Stéphanie; Lebullenger, Ronan; Guilloux-Viry, Marylline; Tessier, Franck


    A new oxynitride Ruddlesden-Popper phase K1.6Ca2Nb3O9.4N0.6.1.1H2O was synthesized by the topochemical ammonolysis reaction at 700 °C from the oxide Dion-Jacobson phase KCa2Nb3O10 in the presence of K2CO3. The oxynitride showed good stability with a little loss of nitrogen, even after a few months of exposure to air. Its crystal structure was solved by Rietveld refinement of X-ray powder diffraction data in space group P4/mmm and considering a two-phase mixture, due to the difference in the degree of hydration, with a = 3.894(2) Å and c = 17.90(8) Å for the most hydrated phase and a = 3.927(6) Å and c = 17.09(2) Å for the less one. Optical band gaps were measured by diffuse reflectance in the UV-Visible range indicating a red shift of Eg to the visible region. The oxynitride layered perovskite was then protonated and exfoliated into nanosheets. TEM images and SAED patterns of the nanosheets proved that exfoliation was successful, showing lattice parameters quite compatible with the Rietveld refinement.

  13. Comment on "High-temperature soft magnetic properties of antiperovskite nitrides ZnNFe3 and AlNFe3" by Yankun Fu, Shuai Lin, and Bosen Wang, J. Magn. Magn. Mater. 378 (2015) 54-58 (United States)

    Scholz, T.; Leineweber, A.; Dronskowski, R.


    The authors of the aforementioned manuscript have recently claimed the synthesis of the ternary nitrides ZnNFe3 (=ZnFe3N) and AlNFe3 (=AlFe3N), ordered substituted variants of the binary phase γ'-Fe4N [1]. While soft ferromagnets of such kind are presently attracting lots of attention, their history dates back for more than half a century. In particular, Al-substituted γ'-Fe4N has already been mentioned in 1961 [2], and the existence of AlFe3N has also been claimed in 2009 [3] from a two-step ammonolysis reaction combining a high-temperature sintering step and a low-temperature nitriding reaction [4]. Nonetheless, one of us had to withdraw the latter claim after finding out, by means of scanning-electron microscopy and elemental mapping, that all samples of "AlFe3N" consisted of an intimate solid mixture of γ'-Fe4N and amorphous Al2O3[5]. From what follows, we have strong reasons to believe that the authors of Ref. [1] overlooked our findings [5] and also did not synthesize ZnFe3N and AlFe3N.

  14. Prophylactic Modulation of Methane and Nitrous Oxide Emitted from Ruminants Livestock for Sustainable Animal Agriculture

    Directory of Open Access Journals (Sweden)

    J. Takahashi


    Full Text Available Major greenhouse gases (GHG attributed to animal agriculture sector are methane (CH4 and nitrous oxide (N2O, either generated from enteric fermentation or manure. The abatement mechanism of rumen CH4 emission may be divided to direct and indirect suppression to methanogens in the rumen.The most significant strategy to mitigate ruminal CH4 emission in indirect manner is to promote alternative metabolic pathway to dispose of the reducing power, competing with methanogenesis for H2 uptake. This includes prebiotics and probiotics (mostly propionate enhancers which consume metabolic hydrogen (H2 compete with methanogens and abate rumen methanogenesis in indirect manner. With regard to mitigate GHG emissions from manure, such waste has been proposed as a renewable energy and nitrogen sources through biogas plant. Furthermore, in advanced new biogas system, the ammonia stripping from digested slurry of livestock manure in biogas plant has been examined to apply to nitrogen recycling-options mitigating N2O emission. These options are: (1 ammonolysis on fiber-rich feedstuffs, (2 saccharification of the NH3 treated cellulose biomass to produce bio-ethanol, and (3 reformed hydrogen into NH3 fuel cell to generate electricity with proton exchange membrane fuel cell (PEM.

  15. Correlation between the band positions of (SrTiO3)1-x.(LaTiO2N)x solid solutions and photocatalytic properties under visible light irradiation. (United States)

    Luo, Wenjun; Li, Zhaosheng; Jiang, Xiaojun; Yu, Tao; Liu, Lifei; Chen, Xinyi; Ye, Jinhua; Zou, Zhigang


    N-doped SrTiO3 and (SrTiO3)1-x.(LaTiO2N)x samples were prepared by the thermal ammonolysis method. The photocatalytic activities of the samples were investigated in a water suspension system. Aqueous methanol solution (50 mL CH3OH + 220 mL H2O) for H2 evolution and aqueous silver nitrate solution (270 mL, 0.01 mol L(-1)) for O2 evolution were used as sacrificial reagents. The oxynitrides showed photocatalytic activities under visible light irradiation. The maximum rates of photocatalytic hydrogen and oxygen evolution under visible light irradiation (lambda > 420 nm) were 10 and 8 micromol h(-1), respectively. The samples were characterized by X-ray diffractometry, UV-Vis spectrophotometry, Fourier transform infrared spectrometry, and laser Raman spectroscopy. The unit cell edge length of (SrTiO3)1-x.(LaTiO2N)x increased linearly and their band gaps reduced from 3.18 to 2.04 eV with increasing x from 0 to 0.30. Moreover, the calculation results of (SrTiO3)0.75.(LaTiO2N)0.25 by density functional theory suggested that the band gap narrowing of the solid solutions came from the hybridization of N2p and O2p orbital. The band positions of the solid solutions were further investigated by Mott-Schottky and the onset potential method. The results suggested that the conduction band of the solid solution was lowered, which led to decrement of the hydrogen evolution rate.

  16. Comment on “High-temperature soft magnetic properties of antiperovskite nitrides ZnNFe{sub 3} and AlNFe{sub 3}” by Yankun Fu, Shuai Lin, and Bosen Wang, J. Magn. Magn. Mater. 378 (2015) 54–58

    Energy Technology Data Exchange (ETDEWEB)

    Scholz, T. [Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, Landoltweg 1, RWTH Aachen University, D-52056 Aachen (Germany); Leineweber, A. [Institute of Materials Science, TU Bergakademie Freiberg, Gustav-Zeuner-Str. 5, D-09599 Freiberg (Germany); Dronskowski, R., E-mail: [Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, Landoltweg 1, RWTH Aachen University, D-52056 Aachen (Germany)


    The authors of the aforementioned manuscript have recently claimed the synthesis of the ternary nitrides ZnNFe{sub 3} (=ZnFe{sub 3}N) and AlNFe{sub 3} (=AlFe{sub 3}N), ordered substituted variants of the binary phase γ‘-Fe{sub 4}N [1]. While soft ferromagnets of such kind are presently attracting lots of attention, their history dates back for more than half a century. In particular, Al-substituted γ‘-Fe{sub 4}N has already been mentioned in 1961 [2], and the existence of AlFe{sub 3}N has also been claimed in 2009 [3] from a two-step ammonolysis reaction combining a high-temperature sintering step and a low-temperature nitriding reaction [4]. Nonetheless, one of us had to withdraw the latter claim after finding out, by means of scanning-electron microscopy and elemental mapping, that all samples of “AlFe{sub 3}N” consisted of an intimate solid mixture of γ‘-Fe{sub 4}N and amorphous Al{sub 2}O{sub 3}[5]. From what follows, we have strong reasons to believe that the authors of Ref. [1] overlooked our findings [5] and also did not synthesize ZnFe{sub 3}N and AlFe{sub 3}N. - Highlights: • The synthesis of ZnFe{sub 3}N and AlFe{sub 3}N is questioned. • The diffraction data of ZnFe{sub 3}N and AlFe{sub 3}N resemble those of Fe{sub 4}N. • The magnetic data of ZnFe{sub 3}N and AlFe{sub 3}N are compatible with those of Fe{sub 4}N. • There is no physical evidence for the existence of ZnFe{sub 3}N and AlFe{sub 3}N.

  17. A study on the thermal conversion of scheelite-type ABO4 into perovskite-type AB(O,N)3. (United States)

    Li, Wenjie; Li, Duan; Gao, Xin; Gurlo, Aleksander; Zander, Stefan; Jones, Philip; Navrotsky, Alexandra; Shen, Zhijian; Riedel, Ralf; Ionescu, Emanuel


    Phase-pure scheelite AMoO4 and AWO4 (A = Ba, Sr, Ca) were thermally treated under an ammonia atmosphere at 400 to 900 °C. SrMoO4 and SrWO4 were shown to convert into cubic perovskite SrMoO2N and SrWO1.5N1.5, at 700 °C and 900 °C respectively, and to form metastable intermediate phases (scheelite SrMoO4-xNx and SrWO4-xNx), as revealed by X-ray diffraction (XRD), elemental analysis and FTIR spectroscopy. High-temperature oxide melt solution calorimetry reveals that the enthalpy of formation for SrM(O,N)3 (M = Mo, W) perovskites is less negative than that of the corresponding scheelite oxides, though the conversion of the scheelite oxides into perovskite oxynitrides is thermodynamically favorable at moderate temperatures. The reaction of BaMO4 with ammonia leads to the formation of rhombohedral Ba3M2(O,N)8 and the corresponding binary metal nitrides Mo3N2 and W4.6N4; similar behavior was observed for CaMO4, which converted upon ammonolysis into individual oxides and nitrides. Thus, BaMO4 and CaMO4 were shown to not provide access to perovskite oxynitrides. The influence of the starting scheelite oxide precursor, the structure distortion and the degree of covalency of the B-site-N bond are discussed within the context of the formability of perovskite oxynitrides.

  18. The Reaction and Applied Study of the Amide and P2S5

    Institute of Scientific and Technical Information of China (English)

    Guan zuowu; Ma Zhuang; Liu Xing; Cheng Tie-ming


    It is usually reported that reaction between carbonyl and P2S5 produce thiono group compound. The Products from carbonyl after ammonolysis and hydrazinolysis have the very import applied value in the synthesize of heterocyclic compound. Sulfuration reation if a nucleophilic attack,SPS2 anionsid obtained from P2S5 in the organic sovent, rather easier than thereationsof scheeren's reagent. The reation mechanism is as follows:The reation speed has something todo with the electronegative of R1R2 can be aliphatic group or aromatic group. The reaction can take place in the polar solvent or non-polar solent.But it is seldom reported that cyclic amide can be sulfured. In 1964, G.A, Archer et made the 7-chloro-1,3-dihyhro-5-phenyl 2H-1,4-ebnzodiazepin-2-thioue and in the reation of pyridine solent with 7-chloro-1,3-dilydro-5-phenyl-2H-1,4-benzodiazepin-2-one and P2S5. And the yield rate reached 40%. This reaction is very important in the pharmaceutical compound, but has quite low yield rate and high cost with present method. And the application is restricted duo to the pyridine,but it is a feasible way indeed. So we undertook further the deep studyof this, made P2S5 catalytic sulfurization in the proper solvent. And the yield rate of the reation has raised a lot. The quality of this product has been affirmed by UV. IR. 1HMNR.MS chart. This method successfully has been applied for the pharmaceutical compound, such as, Estazolam, Trithlozine Alprazolam, Triazolam Clozapine. This has been applied for manufacturing with obvious economic and social benefit.

  19. Synthesis and properties of m-aminophenylacetylene terminated poly( m-dietheynylbenzene-methylsilane) resin%间氨基苯乙炔封端聚(间二乙炔基苯-甲基氢硅烷)树脂的合成及性能

    Institute of Scientific and Technical Information of China (English)

    徐志飞; 周权; 梁旭天; 倪礼忠


    A novel heat-resistant resin, m-aminophenylacetylene terminated poly ( m-dietheynylbenzene-methylsilane ) ( AP-SA) , was synthesized from m-dietheynylbenzene,dichloromethylsilane and m-aminophenylacetylene by using Grignard reagent and ammonolysis method.The structure of APSA was characterized by FT-IR、1H-NMR、13C-NMR and multiple detectors GPC/SEC.The curing behavior of APSA was analyzed by DSC and thermal stability of the cured resin was studied by TGA. Then the dependences between silicon content in the structure and properties of the resin were also discussed. The results show that APSAwith moderate viscosity can be easily processed.The cured resin exhibits excellent thermal stability,the Td5(5% mass loss temperature) and resi-due at 1000 ℃ are up to 634 ℃ and 90.1% under nitrogen,respectively.%以间二乙炔基苯、甲基氢二氯硅烷和间氨基苯乙炔为主要原料,通过格氏试剂法和氨解法,合成了一种耐高温间氨基苯乙炔封端聚(间二乙炔基苯-甲基氢硅烷)树脂(简称APSA树脂). 采用FT-IR、1 H-NMR、13 C-NMR和多检测GPC/SEC对树脂结构进行表征,利用DSC和TGA研究了树脂的固化行为和耐热性能,探讨了结构中硅元素含量对树脂性能的影响. 结果表明,APSA树脂常温下粘度适中,交联固化物具有优异的耐热性能,在N2 气氛下Td5(质量损失5%的温度)达634 ℃,1 000 ℃下的质量保留率为90.1%.

  20. 香豆素杯[4]芳烃的合成及其锌(Ⅱ)配合物的光谱%Synthesis of Coumarin- Calix[ 4 ] arene Derivative and Spectral Properties of Its Zn(Ⅱ) Complex

    Institute of Scientific and Technical Information of China (English)

    王飞; 张晓梅; 徐国财


    为探寻对过渡金属离子具有配合作用的新型超分子配体,将杯[4]芳烃经醚化、氨解得到的中间体3与香豆素-3-甲酰氯反应,合成了新的合香豆素片段的杯[4]芳烃配体H2L,用1 HNMR、13CNMR、IR、MS( Maldi - Tof)表征其结构.H2L与醋酸锌反应,获得了相应锌(Ⅱ)配合物(LZn),元素分析及MS( ESI)分析结果表明,LZn的化学组成为L(ZnAc)2·2H2O.研究了锌(Ⅱ)配合物的UV和IR吸收光谱性质,还测定了它的荧光强度.结果表明,与H2L相比,锌(Ⅱ)配合物分子中共轭体系增大且平面刚性增加.%In order to seek a new supramolecular ligand with the capacity for coordination to transition metal I-ons, a new calix[4]arene derivative H2L with coumarin sections was synthesized by the reaction of coumarin -3 -formyl chloride with intermediater 3 prepared by etherification firstly and then ammonolysis of calix[4]arene, and its structure was characterized by 1HNMR, 13C NMR, IR and MS (Maldi -Tof). Reacting H2L with zinc acetate could produce a Zn(II) complex (LZn) , and the chemical composition of LZn was L(ZnAc)2 · 2H2O determined by elementary analysis and MS (ESI). Using IR and UV, the absorption spectra of LZn were studied, and the fluorescence intensity was examined also. Results showed that conjugation system in LZn was enlarged and plane rigidity increased by comparison with those in H2L.

  1. Design, synthesis and antifungal activity of 2-aryl-2, 3-dihydro-4H-1,3-benzothiazin-4-one derivatives%2-芳基-2,3-二氢-4H-1,3-苯并噻嗪-4-酮类化合物的设计、合成及抗真菌活性

    Institute of Scientific and Technical Information of China (English)

    耿红健; 高宁; 李裕鑫; 张卫军; 苏昕; 郭春


    目的 设计并合成2-芳基-2,3-二氢4H-1,3-苯并噻嗪-4-酮类化合物,测定体外抗真菌活性、建立初步构效关系.方法 以邻氨基苯甲酸为起始原料,经过重氮化及硫代反应制得二硫代水杨酸,再经过氯代、氨解、缩合等步骤制得目标化合物.采用2倍浓度稀释法,选用8种临床上常见的致病真菌为测试菌株,以氟康唑和伊曲康唑为阳性对照药,测试了目标化合物的体外抗真菌活性.结果与结论 设计并合成了24个2-芳基-2,3-二氢-4H-1,3-苯并噻嗪-4-酮类化合物,目标化合物的结构经1H-NMR、MS确证;活性测试结果表明,目标化合物对测试真菌表现出不同程度的体外抑菌活性,所有化合物对红色毛藓菌和根霉菌的活性均好于阳性对照药.%Objective To study the design, synthesis and antifungal activity of 2-aryl-2,3-dihydro-4-H-l ,3-benzothiazin-4-one derivatives and establish their preliminary SAR. Methods The target compounds were synthesized from anthranilic acid through diazotization, thionation reaction followed by chloronation, am-monolysis and condensation. The antifungal assay against eight isolates of fungi was carried out in vitro by two-fold dilution method,took fluoconazole and itroconazole as the control drugs. Results and Conclusions Twenty-four compounds were synthesized and characterized by 'H-NMR,ES-MS. Preliminary pharmacological results showed that all compounds displayed antifungal activities against the tested fungi in different levels , and exhibited better activity than that of control drugs against T. rubrum and Rhizopu

  2. Composition-induced structural, electrical, and magnetic phase transitions in AX-type mixed-valence cobalt oxynitride epitaxial thin films

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Jumpei; Oka, Daichi [Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); Hirose, Yasushi, E-mail:; Yang, Chang; Fukumura, Tomoteru; Hasegawa, Tetsuya [Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); CREST, Japan Science and Technology Agency, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Nakao, Shoichiro [Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); CREST, Japan Science and Technology Agency, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Harayama, Isao; Sekiba, Daiichiro [University of Tsukuba Tandem Accelerator Complex (UTTAC), 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8577 (Japan)


    Synthesis of mid- to late-transition metal oxynitrides is generally difficult by conventional thermal ammonolysis because of thermal instability. In this letter, we synthesized epitaxial thin films of AX-type phase-pure cobalt oxynitrides (CoO{sub x}N{sub y}) by using nitrogen-plasma-assisted pulsed laser deposition and investigated their structural, electrical, and magnetic properties. The CoO{sub x}N{sub y} thin films with 0 ≤ y/(x + y) ≤ 0.63 grown on MgO (100) substrates showed a structural phase transition from rock salt (RS) to zinc blend at the nitrogen content y/(x + y) ∼ 0.5. As the nitrogen content increased, the room-temperature electrical resistivity of the CoO{sub x}N{sub y} thin films monotonically decreased from the order of 10{sup 5} Ω cm to 10{sup −4} Ω cm. Furthermore, we observed an insulator-to-metal transition at y/(x + y) ∼ 0.34 in the RS-CoO{sub x}N{sub y} phase, which has not yet been reported in Co{sup 2+}/Co{sup 3+} mixed-valence cobalt oxides with octahedral coordination. The low resistivity in the RS-CoO{sub x}N{sub y} phase, on the 10{sup −3} Ω cm order, may have originated from the intermediate spin state of Co{sup 3+} stabilized by the lowered crystal field symmetry of the CoO{sub 6−n}N{sub n} octahedra (n = 1, 2,…5). Magnetization measurements suggested that a magnetic phase transition occurred in the RS-CoO{sub x}N{sub y} films during the insulator-to-metal transition. These results demonstrate that low-temperature epitaxial growth is a promising approach for exploring novel electronic functionalities in oxynitrides.

  3. Synthesis of antineoplastic agent linifanib%抗肿瘤药物linifanib的合成

    Institute of Scientific and Technical Information of China (English)

    刘海龙; 朱五福; 果秋婷; 王建强; 王晓; 宫平


    目的 合成抗肿瘤药物linifanib并优化其工艺.方法 以2,6-二氟苯甲腈为原料经取代、重氮化、环合等4步反应制得关键中间体3-氨基-4-碘吲唑(5);以对氟硝基苯为原料经Suzuki偶联、还原、缩合反应得到关键中间体1-(2-氟-5-甲基苯基)-3-[4-(4,4,5,5-四甲基-1,3,2-二氧杂环硼乙烷-2-基)苯基]脲(10);中间体5与10经Suzuki偶联反应制得抗肿瘤药linifanib(1).结果 目标化合物的结构经1 H-NMR谱和质谱确证,总收率为39.4%.结论 与文献报道的工艺比较,新工艺成本低廉,操作简单,反应时间缩短,有利于工业化生产.%Linifanib(ABT-869),a novel potent and selective inhibitor of the VEGF and PDGF platelet-derived growth factor families of RTKs,was designed to inhibit angiogenesis,tumor growth,and metastasis. In order to improve the synthesis of linifanib and to optimize its procedure, a confluent synthetic route was designed. The key intermediate 4-iodo-lff-indazol-3-amine(5) was synthesized from 2,6-difluorobenzonitrile via ammonolysis,diazo-reaction,cyclization with hydrazine hydrate. Another key intermediate l-(2-fluoro-5-methylphenyl)-3-[4-(4,4,5,5-tetramethyl-l ,3,2-dioxaborolan-2-yl)phenyl]urea(10) was prepared from l-fluoro-4-nitrobenzene via Suzuki cross coupling reaction, reduction and condensation with l-fluoro-2-iso-cyanato-4-methylbenzene. Finally ,5 reacted with 10 via Suzuki cross coupling reaction to afford target compound linifanib. The overall yield of the target compound was 39. 4% , and its structure was confirmed by 'H-NMR and MS. In comparison with the reported procedure, the improved process has the advantage of low cost, simple operation, short reaction time and it is also suitable for industrial production.

  4. Synthesis of oxiracetam derivatives and their nootropic activities%奥拉西坦衍生物的合成及其促智作用的研究

    Institute of Scientific and Technical Information of China (English)

    宋艳玲; 孙乔; 李柏娜; 刘晓娟


    目的:设计并合成一系列奥拉西坦衍生物,并对其促智作用进行研究。方法以氯乙酰乙酸乙酯为起始原料,通过还原、取代、环合、氨解反应得到目标产物。通过Morris水迷宫测试法测定小鼠的逃避潜伏期以评估小鼠的学习记忆能力。结果合成了3个目标化合物1~3,其结构经MS、1H-NMR确证。Morris水迷宫测试表明化合物1~3可明显缩短阿尔茨海默病(AD)小鼠的逃避潜伏期(P<0.01)。结论化合物1~3具有一定的促智活性,对进一步开展奥拉西坦衍生物的结构改造和促智作用研究提供参考。%Objective To design and synthesize a series of oxiracetam derivatives, and to assay their nootropic activities. Methods Chlorine ethylacetoacetate was used as starting material to synthesize the target compounds by reduction, alkylation, condensation, and ammonolysis reactions. To study the nootropic effects of target compounds, the escape latency was used to evaluate the memory ability of mice. Results The target compounds 1—3 were synthesized and characterized by MS and 1H-NMR. Water maze results showed that compounds 1—3 could shorten the escape latency of AD mice (P < 0.01). Conclusion Compounds 1—3 have the property of improving memory ability of mice, and provide some practical reference value for the further development on the structure modification of oxiracetam derivatives and nootropic activity.

  5. Ammonia Pretreatment of Corn Stover Enables Facile Lignin Extraction

    Energy Technology Data Exchange (ETDEWEB)

    Mittal, Ashutosh; Katahira, Rui; Donohoe, Bryon S.; Pattathil, Sivakumar; Kandemkavil, Sindhu; Reed, Michelle L.; Biddy, Mary J.; Beckham, Gregg T.


    Thermochemical pretreatment of lignocellulose is often employed to render polysaccharides more digestible by carbohydrate-active enzymes to maximize sugar yields. The fate of lignin during pretreatment, however, is highly dependent on the chemistry employed and must be considered in cases where lignin valorization is targeted alongside sugar conversion - an important feature of future biorefinery development. Here, a two-step process is demonstrated in which anhydrous ammonia (AA) pretreatment is followed by mild NaOH extraction on corn stover to solubilize and fractionate lignin. As known, AA pretreatment simultaneously alters the structure of cellulose with enhanced digestibility while redistributing lignin. The AA-pretreated residue is then extracted with dilute NaOH at mild conditions to maximize lignin separation, resulting in a digestible carbohydrate-rich solid fraction and a solubilized lignin stream. Lignin removal of more than 65% with over 84% carbohydrate retention is achieved after mild NaOH extraction of AA-pretreated corn stover with 0.1 M NaOH at 25 degrees C. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AA-pretreated residue shows that ammonolysis of ester bonds occurs to partially liberate hydroxycinnamic acids, and the AA-pretreated/NaOH-extracted residue exhibits a global reduction of all lignin moieties caused by reduced lignin content. A significant reduction (~70%) in the weight-average molecular weight (Mw) of extracted lignin is also achieved. Imaging of AA-pretreated/NaOH extracted residues show extensive delamination and disappearance of coalesced lignin globules from within the secondary cell walls. Glycome profiling analyses demonstrates ultrastructural level cell wall modifications induced by AA pretreatment and NaOH extraction, resulting in enhanced extractability of hemicellulosic glycans, indicating enhanced polysaccharide accessibility. The glucose and xylose yields from enzymatic hydrolysis of AA

  6. 一种枝杈型含氟季铵盐型阳离子表面活性剂的合成及其性能%Synthesis of Branched Fluorinated Cationic Surfactant and its Surface Tension Properties

    Institute of Scientific and Technical Information of China (English)

    武宏科; 沈海民; 史鸿鑫


    A novel branched fluorinated cationic surfactant diethyl-methyl-(2-{4-[3,4,4,4- tetrafluoro-2-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-1,3-bis-trifluoromethyl-but-1-enyloxy]-benzenesulfonylamino}-ethyl)-ammonium iodide(IV) was synthesized from ((1,1,1,4,5,5,5-heptafluoro-3-(per-fluoropropan-2-yl)-4-(trifluoromethyl)-pent-2-en-2-yl)oxy) benzene via sulphonating with chlorosulfonic acid, ammonolysis with N,N-diethylethylenediamine, methylation with iodomethane. The yield reaches 45 % and the structures were characterized by FT-IR, 1H-NMR and MS. The target compound was evaluated for its surface tension properties, which the surface tension at critical micelle concentration (CMC) 2.5×10-5 mol×L-1 is 21.0 mN×m-1. The effects of temperature, electrolyte and, the combination with hydrocarbon surfactant were investigated. The results indicate that the prepared branched fluorinated cationic surfactant displays good surfactant performance.%以枝杈型含氟醚(4-全氟-[(1,3-二甲基-2-异丙基)-1-丁烯]氧基苯基醚)为原料,通过磺酰化、胺解和季铵化,得到枝杈型含氟季铵盐型阳离子表面活性剂[N-[4-[全氟-(1,3-二甲基-2-异丙基)-1-丁烯]氧基苯磺酰胺基]乙基二乙基甲基碘化铵,其结构经IR、1H-NMR、MS得到确认;其水溶液的临界胶束浓度(CMC)为2.5×10-5 mol×L-1,此时的表面张力为21.0 mN×m-1通过对温度、电解质以及与碳氢表面活性剂的复配研究发现:随着温度的升高其水溶液的CMC和表面张力呈下降趋势;盐度对其影响不大且具有较好的复配性能。

  7. N-正丁基-1-脱氧野尻霉素合成方法的改进%An improved strategy to synthesize N-butyl-1-deoxynojirimycin

    Institute of Scientific and Technical Information of China (English)

    王佳佳; 张振兴; 李铁海; 郭利娜; 刘艳坤; 赵炜


    As an amino sugar derivative,N-butyl-1-deoxynojirimycin has promising therapeutics in treatment of diabetes, viral infections, metastatic cancers and Gancher's diseases. Low yield is the main obstacle for chemical synthetic of N-butyl-1-deoxynojirimycin. To improve the synthetic procedure,butyryl group was introduced to the nitrogen atom of 2,3,4,6-tetra-O-benzyl-D-gluconolactam (5) using butyryl chloride or buty-ric anhydride, respectively. The resulting compound N-butyryl-2,3,4,6-tetra-O-benzyl-D-gluconolac-tam(6) was treated with aluminium hydride to afford N-butyl-2,3,4,6-tetra-O-benzyl-deoxynojirimycin(7) in a satisfying yield. Compared with the previously reported synthetic strategy (yield of 23.4% ) ,the developed method can significantly increase the yield(54% ) from compound 5 to 7. In summary,we have successfully optimised the synthetic procedures of N-butyl-1-deoxynojirimycin. Besides, instead of methanolic ammonia,n-butylamine was used for ammonolysis,expected product and possible mechanism of forming the byproduct were discussed in the ring-close step.%目的 改进N-正丁基-1-脱氧野尻霉素的合成.方法:该文通过酰化反应分别用丁酰氯和丁酸酐将丁酰基引入到2,3,4,6-四苄基葡萄糖内酰胺的氮原子上,然后用氢化铝锂将两个羰基还原,得到N-正丁基-2,3,4,6-四苄基-1-脱氧野尻霉素.结果与结论该.方法:在改进部分将收率提高为相关文献的2~3倍,在氨解开环这一步,尝试用正丁基胺代替饱和氨气的甲醇溶液,并对其关环产物以及副产物的生成机制进行了探讨.

  8. Synthesis and chemistry of organoimidovanadium(V) compounds and their role in the formation of vanadium nitrides (United States)

    Gipson, Rocky Dean

    A series of vanadium(V) compounds of the formula (eta5-C 5Me5)V(NR)Cl2 (R = 1-adamantyl, tert-butyl, para-tolyl) have been prepared by the reaction of (eta5 -C5Me5)V(O)Cl2 with RNCO or by oxidation of [(eta5-C5Me5)VCl2] 3 with azide. The para-tolylimido compound undergoes chloride metathesis with monoanionic reagents NaOtBu, LiNEt 2, and Mg(CH2SiMe3)2 to produce mono- and disubstituted products. A discussion of ligand strength in this system using 51V NMR is presented. Ammonolysis of the dichloro compounds produces the symmetrically-bridged [(eta5-C5Me5)V(mu-N)Cl]2, in yields consistent with the basicity of the organoimido ligand. A comparison of this reactivity with that of (eta5-C5Me 5)V(NSiMe3)Cl2 is presented. An X-ray structural study of (eta5-C5Me5)V(NtBu)Cl 2 exhibits a 173° V-N-C imido linkage and V-N triple bond. Synthesis of (eta5-tBuC5H 4)V(NR)Cl2 compounds was performed utilizing (t-Bu)C 5H4SiMe3 as the cyclopentadiene reagent with V(NR)Cl 3. In contrast to the metathesis of V(NR)Cl3 compounds with Li(tBu)C5H4, reduction of the vanadium(V) is not observed. An X-ray crystal structure of (eta5- tBuC5H4)V(N-ptol)Cl2 reveals linear V-N-C bonding, and a short N-C bond of 139 pm. This is explained by delocalized bonding, which incorporates the imido carbon atoms as well as nitrogen and vanadium. Details of the structure and valence-bond descriptions are of this compound are presented. Organoimidotrichlorovanadium(V) compounds bind ligands L2 (L2 = 1,2-dimethoxyethane; N,N,N,N-tetramethylethylenediamine) to produce adducts V(NR)Cl3L2. The V(NR)Cl3L 2 compounds thermally react to form terminal nitrides V(N)Cl2L 2 via an unprecedented cleavage of the N-C bond of the organoimido ligand, with reactivity following the order t-butyl > 1-adamantyl > p-tolyl. The downfield 51V NMR shifts of the adducts relative to starting materials is discussed using crystal-field models. X-ray crystal structures of V(NAd)Cl3(DME) and V(N ptol)Cl3(TMEDA) are presented, and details

  9. Multifaceted metabolomics approaches for characterization of lignocellulosic biomass degradation products formed during ammonia fiber expansion pretreatment (United States)

    Vismeh, Ramin

    Lignocellulosic biomass represents a rather unused resource for production of biofuels, and it offers an alternative to food sources including corn starch. However, structural and compositional impediments limit the digestibility of sugar polymers in biomass cell walls. Thermochemical pretreatments improve accessibility of cellulose and hemicellulose to hydrolytic enzymes. However, most pretreatment methods generate compounds that either inhibit enzymatic hydrolysis or exhibit toxicity to fermentive microorganisms. Characterization and quantification of these products are essential for understanding chemistry of the pretreatment and optimizing the process efficiency to achieve higher ethanol yields. Identification of oligosaccharides released during pretreatment is also critical for choosing hydrolases necessary for cost-effective hydrolysis of cellulose and hemicellulose to fermentable monomeric sugars. Two chapters in this dissertation describe new mass spectrometry-based strategies for characterization and quantification of products that are formed during ammonia fiber expansion (AFEX) pretreatment of corn stover. Comparison of Liquid Chromatography Mass Spectrometry (LC/MS) profiles of AFEX-treated corn stover (AFEXTCS) and untreated corn stover (UTCS) extract shows that ammonolysis of lignin carbohydrate ester linkages generates a suite of nitrogenous compounds that are present only in the AFEXTCS extract and represent a loss of ammonia during processing. Several of these products including acetamide, feruloyl, coumaroyl and diferuloyl amides were characterized and quantified in the AFEXTCS extracts. The total amount of characterized and uncharacterized phenolic amides measured 17.4 mg/g AFEXTCS. Maillard reaction products including pyrazines and imidazoles were also identified and measured in the AFEXTCS extract totaling almost 1 mg/g AFEXTCS. The total of quantified nitrogenous products that are formed during AFEX was 43.4 mg/g AFEXTCS which was equivalent

  10. Theme-Based Bidisciplinary Chemistry Laboratory Modules (United States)

    Leber, Phyllis A.; Szczerbicki, Sandra K.


    methanol to effect transesterification (3) and examining the effect of variations in leaf type and season on lipid composition. A second "Plant Assay" study involves preparing and characterizing analogs of naphthalene-1-acetamide, which is the active growth-promoting ingredient in commercial preparations such as Transplantone® and Rootone®. There are two direct methods for synthesizing the amide from the native plant growth regulator ("auxin") or carboxylic acid: acid-catalyzed hydrolysis of the nitrile or ammonolysis of the acid chloride derivative, prepared in situ from the acid by treatment with thionyl chloride (4). In the spring of 1996, organic chemistry students synthesized the amide derivatives of a number of auxins via the acid chloride intermediate, which is more efficiently prepared using oxalyl chloride (40-60% overall yield) instead of thionyl chloride (20-40% overall yield), or via nitrile hydrolysis (72-99% yield). Plant bioassays, based on measurement of pea stem segment elongation (5) have only been performed on the acetamide derivatives of three auxins, indole-3-acetic acid (IAA), naphthalene-1-acetic acid (1-NAA), and naphthalene-2-acetic acid (2-NAA). In comparison with the control, indole-3-acetamide and naphthalene-1-acetamide promoted growth by 50% and 90%, respectively. The acetamide of 2-NAA impeded growth by 30% relative to the control, an observation consistent with the known antiauxin activity of 2-NAA (6). Acquisition of the necessary imaging system for the teaching laboratory will enable students to extend these quantitative studies to other auxin conjugates. Acknowledgment We are grateful to the NSF for financial support through the Division of Undergraduate Education (DUE-9455693 and DUE-9550890). Literature Cited 1. Mayo, D. W.; Pike, R. M.; Trumper, P. K. Microscale Organic Laboratory, 3rd ed; John Wiley & Sons: New York, 1994; pp 202-203. 2. Browse, J.; McCourt, P. J.; Somerville, C. R. Anal. Biochem. 1986, 152, 141. 3. Rodig, O. R