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Sample records for continuous methanol carbonylation

  1. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

    DEFF Research Database (Denmark)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter

    2006-01-01

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.......A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation....

  2. Efficient Nd Promoted Rh Catalysts for Vapor Phase Methanol Carbonylation

    Institute of Scientific and Technical Information of China (English)

    Shu Feng ZHANG; Qing Li QIAN; Ping Lai PAN; Yi CHEN; Guo Qing YUAN

    2005-01-01

    A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst under similar reaction condition. The difference between the activity of above two catalyst systems is clearly caused by the intrinsic properties generated by the introduction of Nd.

  3. IRC analysis of methanol carbonylation reaction catalyzed by rhodium complex

    Institute of Scientific and Technical Information of China (English)

    HAO Maorong; FENG Wenlin; JI Yongqiang; LEI Ming

    2004-01-01

    In the reaction cycle for methanol carbonylation catalyzed by Rh complex, the structure geometries of the reactant, intermediates, transition states and product of each elemental reaction have been studied by using the energy gradient method at HF/LANL2DZ level, and the changes of their potential profiles have also been calculated. Through IRC analyses of the transition states for each elemental reaction, it is confirmed that the various structure geometries obtained are stationary points on the cycle reaction pathway of methanol carbonylation catalyzed by Rh complex, and the changes are given in energies and structure geometries of the reactant molecules along the reaction pathway of lowest energy. It has been proposed that the geometrical conversions of intermediates play an important role during the cycle reaction. Through analyses of structure geometries, it has been suggested that, in addition to cis- and trans- structure exchange linkage of catalysis reactive species, the two pathways, cis- and trans-cata- lyzed cycle reactions, can also be linked through geometrical conversion of intermediates, of which the activation energy is 49.79 kJ/mol. Moreover, the reductive elimination elemental reaction may be neither cis-cycle nor trans- one, showing that the cycle reaction can be achieved through various pathways. However different the pathway, the oxidative addition elemental reaction of CH3I is the rate-controlling step.

  4. Direct Vapor Phase Carbonylation of Methanol over NiCl2/C Catalyst

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    @@ Introduction The carbonylation of alcohols via homogenous catalysis is important in manufacturing acetic acid and higher carboxylic acids and their esters[1,2]. The main route to produce acetic acid is to make methanol carbonylated by means of the Monsanto and BP process in which a homogeneous rhodium catalyst is used. Although the homogeneous carbonylation of methanol is a highly selective process, it is affected by the disadvantages associated with a highly corrosive reaction medium due to the use of methyl iodide as the promoter, and the difficulty of the product separation[3]. The use of a heterogeneous catalyst seems very interesting and attractive to us[4], especially the direct vapor phase carbonylation of methanol without a halide promoter is of considerable importance and is strong incentive economically. There has, however, been very little success in finding either heterogeneous or homogeneous catalysts that can catalyze the reaction effectively without the addition of a promoter[5,6]. According to the known carbonylation mechanism[7,8], the methyl iodide directly carbonylates with CO to from MeCOI which interacts with methanol(MeOH) to produce methyl acetate(MeCOOMe) and HI, and then MeOH reacts with HI to from CH3I. In fact, this carbonylation reaction is the indirect catalytic carbonylation of methanol[9]. In this work, a novel catalyst for the direct vapor phase carbonylation of methanol without the addition of any halide in the feed as a promoter was investigated. Compared to the known liquid phase methanol carbonylation process, some advantages of this vapor phase reaction are as follows:

  5. Reactivity of Ir(III) carbonyl complexes with water: alternative by-product formation pathways in catalytic methanol carbonylation.

    Science.gov (United States)

    Elliott, Paul I P; Haak, Susanne; Meijer, Anthony J H M; Sunley, Glenn J; Haynes, Anthony

    2013-12-21

    The reactions of water with a number of iridium(III) complexes relevant to the mechanism for catalytic methanol carbonylation are reported. The iridium acetyl, [Ir(CO)2I3(COMe)](-), reacts with water under mild conditions to release CO2 and CH4, rather than the expected acetic acid. Isotopic labeling and kinetic experiments are consistent with a mechanism involving nucleophilic attack by water on a terminal CO ligand of [Ir(CO)2I3(COMe)](-) to give an (undetected) hydroxycarbonyl species. Subsequent decarboxylation and elimination of methane gives [Ir(CO)2I2](-). Similar reactions with water are observed for [Ir(CO)2I3Me](-), [Ir(CO)2(NCMe)I2(COMe)] and [Ir(CO)3I2Me] with the neutral complexes exhibiting markedly higher rates. The results demonstrate that CO2 formation during methanol carbonylation is not restricted to the conventional water gas shift mechanism mediated by [Ir(CO)2I4](-) or [Ir(CO)3I3], but can arise directly from key organo-iridium(III) intermediates in the carbonylation cycle. An alternative pathway for methane formation not involving the intermediacy of H2 is also suggested. A mechanism is proposed for the conversion MeOH + CO → CO2 + CH4, which may account for the similar rates of formation of the two gaseous by-products during iridium-catalysed methanol carbonylation.

  6. Improvement on stability of square planar rhodium (Ⅰ) complexes for carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    蒋华; 潘平来; 袁国卿; 陈新滋

    1999-01-01

    A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment.

  7. Reactivity of Ir(III) carbonyl complexes with water: alternative by-product formation pathways in catalytic methanol carbonylation

    OpenAIRE

    Haynes, A.; Elliott, P. I. P.; Haak, S; Meijer, A.J.H.M.; Sunley, G.J

    2013-01-01

    The reactions of water with a number of iridium(III) complexes relevant to the mechanism for catalytic\\ud methanol carbonylation are reported. The iridium acetyl, [Ir(CO)2I3(COMe)]−, reacts with water under\\ud mild conditions to release CO2 and CH4, rather than the expected acetic acid. Isotopic labeling and\\ud kinetic experiments are consistent with a mechanism involving nucleophilic attack by water on a terminal\\ud CO ligand of [Ir(CO)2I3(COMe)]− to give an (undetected) hydroxycarbonyl spec...

  8. A catalyst for the carbonylation of methanol to acetic acid in gaseous phase

    Institute of Scientific and Technical Information of China (English)

    潘平来; 柳忠阳; 朱长城; 袁国卿

    1996-01-01

    A novel Rh/Ys catalyst for the carbonylation of methanol to acetic acid in gaseous phase is reported. The porous carbon beads (Ys) prepared from the carbonation of poly(vinylidene chloride) were used as the support. This catalyst has a specific surface area of 1 000 m2/g, high mechanical strength and thermal stability. The average diameter of the pore is in the range of 0.8 - 1.2nm. Experimental evidence showed that this catalyst was of high activity and selectivity, which could compare to those of the homogeneous catalyst from Monsanto. The catalytic rate could get to 900 g AcOH/g Rh·h during the carbonylation of methanol to acetic acid. The fine spreading of Ph over the Ys surface is the key factor for the activity.

  9. Kinetic studies on vapor phase carbonylation of methanol to acetic acid over Rh/Ys catalyst

    Institute of Scientific and Technical Information of China (English)

    柳忠阳; 潘平来; 朱长城; 袁国卿

    1997-01-01

    A novel catalyst Rh/Ys for the carbonylation of methanol to acetic acid with CH3I as the promoter shows excellent activity and selectivity.The reaction is kinetically controlled.The reaction rate is in proportion to the concentration of Rh and CH3I but has nothing to do with those of CH3OHH and CO.The surface active energy is Ea ~51.02 kJ/mol.A mechanism is also proposed.

  10. Carbonyl compound emissions from passenger cars fueled with methanol/gasoline blends.

    Science.gov (United States)

    Zhao, Hong; Ge, Yunshan; Hao, Chunxiao; Han, Xiukun; Fu, Mingliang; Yu, Linxiao; Shah, Asad Naeem

    2010-08-01

    Carbonyl compound emissions from two passenger cars fueled with different methanol/gasoline blends (M15 and M100) and operated with three-way catalytic converters (TWC) were investigated. The tests were performed on a chassis dynamometer with constant volume sampling over the New European Driving Cycle (NEDC). Carbonyls were trapped on dinitrophenylhydrazine (DNPH) cartridges. The hydrazones formed on the cartridge were analyzed by means of high-performance liquid chromatography (HPLC) and detected with a variable wavelength detector. The results show that when cars were fueled with methanol/gasoline blends, carbon monoxide (CO) and total hydrocarbon (THC) emissions decreased by 9-21% and 1-55% respectively, while nitrogen oxide (NO(x)) emissions increased by 175-233%. Compared with gasoline vehicles, formaldehyde emissions with M15 and M100 were two and four times higher respectively, and total carbonyls with M15 and M100 increased by 3% and 104% respectively. With the use of the new TWC, both regulated gas pollutants and formaldehyde decreased. The new TWC caused a decrease of 5% and 31% in formaldehyde concentration for M15 and M100, respectively. Specific reactivity (SR) with the new TWC was reduced from 5.92 to 5.72 for M15 and from 7.00 to 6.93 for M100, indicating that M15 and M100 with the new TWC were friendlier to the environment. 2010 Elsevier B.V. All rights reserved.

  11. Ab initio study on the mechanism of rhodium-complexcatalyzed carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    LEI; Ming

    2001-01-01

    [1]Thomas, R., Cundari, T. R., Computational studies of transition metal-main group multiple bonding, Chem. Rev., 2000,100: 807.[2]Maricel Torrent, Miquel Sola, Gernot Frenking, Theoretical studies of some transition-metal-mediated reactions of industrial and synthetic importance, Chem. Rev., 2000, 100: 439.[3]Paulik, F. E., Roth, J. F., Catalysts for the low-pressure carbonylation of menthanol to acetic acid, Chem. Commun., 1968,24: 1578.[4]Jiang Hua, Diao Kaisheng, Pan Pinglai et al., A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction, Chin. J. Chem., 2000, 18: 752.[5]Jiang Dazhi, Li Xiaobao, Wang Enlai, Synthesis Chemistry ofCarbonylation, Beijing: Chemical Technology Press, 1996.[6]Adamson, G. W., Daly, J. J., Forster, D., Reduction of iolocarbonyl rhodium ions with methyl iodide, structure of the rho-dium acetyl complex: [Me3PhN+], [Rh2I6-(Me(O)2(CO)2)]2-, J. Organomet. Chem., 1974, 71: C 17.[7]Forster, D., On the mechanism of a rhodium-complex-catalyzed carbonylation of methanol to acetic acid, J. Am. Chem.Soc., 1976, 98: 846.[8]Hjortkjaer, J., Jensen, O. R., Rhodium complexes catalyzed methanol carbonylation, Ind. Eng. Chem. Prod. Dev., 1976, 15:46.[9]Jeffrey, P., Wadt, W. R., Ab initio effective core potentials for molecular calculations, Potentials for the transition metalatoms Sc to Hg, J. Chem. Phys., 1995, 82: 270.[10]Frisch, M. J., Trunks, G. W., Schlegel, H. B. et al., Gaussian 94, Pittsburgh PA: Gaussian, Inc., 1995.[11]Lei Ming, Feng Wenlin, Xu Zhenfeng et al., A theoretical study on the key reactions of hydroformylation cycle by modi-fied carbonyl cobalt, Chemical Journal of Chinese University, 2001, 22: 455.[12]Lei Ming, Feng Wenlin, Xu Zhenfeng, Ab initio MO study on the reaction mechanism for carbonyl insertion catalyzed by the carbonyl cobalt complex, Chemical Research in Chinese University, 2000, 19:31.

  12. A NOVEL COPOLYMER-BOUND CIS- DICARBONYLRHODIUM COMPLEX FOR THE CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    YUAN Guoqing; CHEN Yuying; CHEN Rongyao

    1989-01-01

    A series of porous microspheres of linear and ethylene diacrylate (M ') cross-linked copolymers of 2 - vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol - acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions.

  13. A Novel Sulfided Mo/C Catalyst for Direct Vapor Phase Carbonylation of Methanol at Atmospheric Pressure

    Institute of Scientific and Technical Information of China (English)

    Feng Peng

    2003-01-01

    The direct carbonylation of methanol, without any halide in the feed as a promoter, ispresented. A series of Mo catalysts supported on activated carbon, γ-Al2O3 and SiO2 were prepared.The results show that the support greatly affects the Mo catalyst in the direct vapor-phase carbonylationof methanol, and activated carbon is the best supports of the investigated supports. In addition, therelationships between adsorptions of NH3 and CO and carbonylation of methanol were investigated. A novelsulfided Mo/C catalyst had high activity and selectivity for the vapor phase carbonylation of methanol tomethyl acetate without the addition ofa CH3I promoter to the feed. The reaction conditions were optimizedat a reaction temperature of 573 K, a methanol concentration of 23 mol% and a carbon monoxide spacevelocity of 3,000 L/(kg.h). Under these optimal conditions a methanol conversion of 50%, carbonylationselectivity of 80 mol%, and space-time yield of 8.0 mol/(kg.h) were obtained. The active phase of thisnovel sulfided Mo/C catalyst is the non-crystalline phase, and the active component is present as MoS2.5on the surface of the activated carbon.

  14. KINETIC STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A NOVEL COPOLYMER- BOUND CIS- DICARBONYLRHODIUM COMPLEX

    Institute of Scientific and Technical Information of China (English)

    CHEN Yuying; YUAN Guoqing; CHEN Rongyao

    1989-01-01

    The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh)coordinated with the ethylene diacrylate (M')crosslinked copolymer of methyl acrylate (M) and 2 - vinylpyridine (V) shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex . Polar solvents can accelerate the reaction .Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system . A mechanism similar to that of soluble rhodium catalyst was proposed .

  15. STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A BIDENTATE POLYMER BOUND CIS-DICARBONYLRHODIUM COMPLEX AS CATALYST

    Institute of Scientific and Technical Information of China (English)

    WANG Xiaojun; LIU Zhongyang; PAN Pinglai; YUAN Guoqing

    1996-01-01

    Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodium used as a catalyst for carbonylation of methanol to acetic acid and anhydride has been studied. The structural characteristics of the copolymer ligand and complex, and the influences of the reaction conditions on the carbonylation catalyzed by this polymer complex have been investigated. In comparison with small molecule catalyst of Rh complex, the bidentate copolymer coordinated complex has better thermal stability. The reaction mechanism of the carbonylation reaction is also illustrated.

  16. Catalysis of the Carbonylation of Alcohols to Carboxylic Acids Including Acetic Acid Synthesis from Methanol.

    Science.gov (United States)

    Forster, Denis; DeKleva, Thomas W.

    1986-01-01

    Monsanto's highly successful synthesis of acetic acid from methanol and carbon monoxide illustrates use of new starting materials to replace pretroleum-derived ethylene. Outlines the fundamental aspects of the acetic acid process and suggests ways of extending the synthesis to higher carboxylic acids. (JN)

  17. Kinetics of Methanol Carbonylation to Methyl Formate Catalyzed by Sodium Methoxide

    Institute of Scientific and Technical Information of China (English)

    Liang Chen; Jianghong Zhang; Ping Ning; Yunhua Chen; Wenbing Wu

    2004-01-01

    Kinetics of synthesis of methyl formate from carbon monoxide and methanol, using sodium methoxide as the catalyst and pyridine as the promoter in a batch reactor, was studied. Kinetic parameters such as the apparent reaction orders, the rate constant and the apparent activation energies were obtained.The experimental results showed that both the reaction orders with respect to CO and methanol equal to 1, the general reaction kinetic equation is (-r)=-dp(CO)/dt=k. p(CO).[MeOH], and the rate constant is decreased 6.44 k J/mol and the rate constant had increased more than 1.5 times when pyridine was used as the promoter in the catalyst system.

  18. Conversion du methanol en ethanol par carbonylation suivie d'hydrogenolyse

    Science.gov (United States)

    Gaucher, Melissa

    Ce projet de maîtrise s'inscrit dans le cadre des nouvelles filières énergétiques renouvelables et s'effectue au sein de la Chaire de recherche industrielle sur l'éthanol cellulosique créée par trois partenaires industriels (Enerkem, CRB et Ethanol Greenfield) et le gouvernement du Québec en collaboration avec l'Université de Sherbrooke. La stratégie d'un des partenaires, Enerkem, est de convertir par gazéification des résidus de biomasse non homogène en Syngas, ce gaz est ensuite converti en méthanol puis en éthanol. L'objectif principal de ce projet est la conversion catalytique de l'acétate en alcool. Un catalyseur commercial, composé de cuivre et de chrome, a permis l'obtention des conversions de plus de 95 % et une sélectivité pour l'éthanol de plus de 50 % avec l'acétate de méthyle, de 99 % avec l'acétate d'éthyle et de 50 % avec l'acétate de butyle. Les conditions optimales trouvées impliquent une température de 215 °C, une pression de 350 psig, une vitesse spatiale de 1800 h -1 H2 STP et un ratio H2 : Acétate de 7. Un catalyseur alternatif, à base de cuivre et de zinc, a aussi été testé. L'objectif secondaire est la carbonylation du méthanol en acétate. Cette étape a été réalisée en phase gazeuse où des rendements très élevés, soit plus de 2000 kg d'acétate de méthyle par kg de métal précieux à l'heure (kg AM/ kg métal précieux/h), ont été obtenus. Les conditions d'opérations testées impliquent une température variant entre 200-240 °C, une pression entre 250-600 psig, des ratios McOH : CO de 1 à 2,5. Mots clés: Carbonylation, Éthanol, Hydrogénolyse, Catalyse hétérogène.

  19. Enzyme-like specificity in zeolites: a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO.

    Science.gov (United States)

    Boronat, Mercedes; Martínez-Sánchez, Cristina; Law, David; Corma, Avelino

    2008-12-03

    The mechanism of methanol carbonylation at different positions of zeolite MOR is investigated by quantum-chemical methods in order to discover which are the active sites that can selectively catalyze the desired reaction. It is shown that when methanol carbonylation competes with hydrocarbon formation, the first reaction occurs preferentially within 8MR channels. However, the unique selectivity for the carbonylation of methanol and dimethyl ether in mordenite is not only due to the size of the 8MR channel: neither process occurs equally at the two T3-O31 and T3-O33 positions. We show that only the T3-O33 positions are selective and that this selectivity is due to the unusual orientation of the methoxy group in relation to the 8MR channel (parallel to the cylinder axis). Only in this situation does the transition state for the attack of CO fit perfectly in the 8MR channel, while the reaction with methanol or DME is sterically impeded. This result explains why T3-O31, while also located in the 8MR channel of mordenite, is not as selective as the T3-O33 position and why ferrierite, although it contains 8MR channels, is less selective than mordenite. The competing effect of water is explained at the molecular level, and the molecular microkinetic reaction model has been established.

  20. Oxidative Carbonylation of Methanol to Dimethyl Carbonate Over Cu(II)-1,10-Phenanthroline Bromide Complexes☆

    Institute of Scientific and Technical Information of China (English)

    Zhiping Du⁎; Lihua Xiong; Zhikun Lin; Xuli Li; Yigang Ding; Yuanxin Wu

    2014-01-01

    In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate (DMC), CuBr2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2, [Cu(phen)2Br]Br and [Cu(phen)3]Br2 (phen=1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2 exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)−1 with selectivity of 92.8%under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1 (below the explosion limit of CO) and catalyst concentration of 0.011 mol·L−1. Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.

  1. Osmium-ruthenium carbonyl clusters as methanol tolerant electrocatalysts for oxygen reduction

    Science.gov (United States)

    Borja-Arco, E.; Castellanos, R. H.; Uribe-Godínez, J.; Altamirano-Gutiérrez, A.; Jiménez-Sandoval, O.

    This work presents the synthesis and the structural and electrochemical characterization of novel mixed Os xRu y(CO) n electrocatalysts for oxygen reduction in 0.5 mol L -1 H 2SO 4; their monometallic Os x(CO) n and Ru y(CO) n counterparts were synthesized as well, for comparison purposes. The catalysts were obtained by thermolysis of Ru 3(CO) 12 and Os 3(CO) 12 (either alone or mixed) in three organic solvents: 1,2-dichlorobenzene (b.p. 178-180 °C), n-nonane (b.p. 150-151 °C) and o-xylene (b.p. 143-145 °C), under reflux conditions. The products were characterized by FT-IR spectroscopy and scanning electronic microscopy, and their chemical composition obtained by energy-dispersive X-ray spectroscopy. The electrocatalytic activity of the new materials was evaluated by room temperature RDE measurements, using the cyclic and linear sweep voltammetry techniques; all of them are methanol tolerant ORR catalysts, however, the bimetallic clusters, in general, show more favorable characteristics to perform this reaction than their monometallic analogues. On this basis, the novel catalysts can be considered as potential candidates to be used as cathodes in PEMFCs and DMFCs.

  2. Osmium-ruthenium carbonyl clusters as methanol tolerant electrocatalysts for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Borja-Arco, E.; Uribe-Godinez, J.; Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro, Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Castellanos, R.H. [Universidad del Papaloapan, Campus Tuxtepec, Circuito Central No. 2000, Col. Parque Industrial, Tuxtepec, Oax. 68301 (Mexico)

    2009-03-15

    This work presents the synthesis and the structural and electrochemical characterization of novel mixed Os{sub x}Ru{sub y}(CO){sub n} electrocatalysts for oxygen reduction in 0.5 mol L{sup -1} H{sub 2}SO{sub 4}; their monometallic Os{sub x}(CO){sub n} and Ru{sub y}(CO){sub n} counterparts were synthesized as well, for comparison purposes. The catalysts were obtained by thermolysis of Ru{sub 3}(CO){sub 12} and Os{sub 3}(CO){sub 12} (either alone or mixed) in three organic solvents: 1,2-dichlorobenzene (b.p. 178-180 C), n-nonane (b.p. 150-151 C) and o-xylene (b.p. 143-145 C), under reflux conditions. The products were characterized by FT-IR spectroscopy and scanning electronic microscopy, and their chemical composition obtained by energy-dispersive X-ray spectroscopy. The electrocatalytic activity of the new materials was evaluated by room temperature RDE measurements, using the cyclic and linear sweep voltammetry techniques; all of them are methanol tolerant ORR catalysts, however, the bimetallic clusters, in general, show more favorable characteristics to perform this reaction than their monometallic analogues. On this basis, the novel catalysts can be considered as potential candidates to be used as cathodes in PEMFCs and DMFCs. (author)

  3. Supported Ionic Liquid Phase (SILP) Catalysis for the Production of Acetic acid by Methanol Carbonylation

    DEFF Research Database (Denmark)

    Hanning, Christopher William

    to stop and re-start the reaction. This sort of continuous flow reaction is a subject of great research effort in recent years as it is more sustainable (and in some cases financially viable) that the current method of carrying out chemical reactions in large size batch reactions The project started right...

  4. Evaluation of osmium-ruthenium carbonyl cluster compounds as a cathode in a passive direct methanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Castellanos, R.H.; Borja-Arco, E.; Uribe-Godinez, J.; Ramirez-Rivera, J.C. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico)

    2006-07-01

    Methanol crossover is a major technical barrier to the application of direct methanol fuel cell (DMFC) technology. Methanol crossover causes a mixed potential on the cathode and reduces overall cell voltage. This paper studied the effect of methanol concentration on the performance of a passive DMFC using a different catalyst on the cathode. The membrane electrode assembly (MEA) was sandwiched between a current collector made of 316 stainless steel and a current collector made of aluminum (Al). Single cells were operated at room temperature and ambient pressure under passive conditions with varying concentrations of methanol. The cells were then analyzed to determine the effects of concentrations of methanol on their performance. Results showed that when 1.0 M methanol was used, the DMFC showed the highest voltage value. However, when higher concentrations of methanol were used, the voltage value decreased. Results also showed that performance of the passive DMFC improved through the use of an osmium (Os{sub x}Ru{sub y}(CO){sub n}) cathode when intermediated concentrations of methanol were used. It was concluded that optimal methanol concentrations ranged from 4 to 5 methanol molar. 3 refs., 2 figs.

  5. Lanthanum-Promoted Nickel Catalyst for Vapor-Phase Methanol Carbonylation%新型Ni-La催化剂催化甲醇气相羰基化反应

    Institute of Scientific and Technical Information of China (English)

    李峰波; 邹瑾; 袁国卿

    2003-01-01

    @@ Methanol carbonylation is the main process for producing acetic acid. The current technology is based on precious rhodium and iridium catalysts dissolved in liquid phase[1,2]. A heterogeneous catalyst based on a cheaper metal will have much theoretical and economic significance in improving the methanol carbonylation process, by solving many problems in homogeneous process. To achieve this purpose, a lanthanum-promoted nickel catalyst supported on polymer-derived carbon beads[3] with high activity and selectivity was developed by a new strategy.

  6. Fabrication of Yolk-Shell Cu@C Nanocomposites as High-Performance Catalysts in Oxidative Carbonylation of Methanol to Dimethyl Carbonate

    Science.gov (United States)

    Wang, Juan; Hao, Panpan; Shi, Ruina; Yang, Leilei; Liu, Shusen; Zhao, Jinxian; Ren, Jun; Li, Zhong

    2017-08-01

    A facile way was developed to fabricate yolk-shell composites with tunable Cu cores encapsulated within hollow carbon spheres (Cu@C) with an average diameter about 210 nm and cavity size about 80 nm. During pyrolysis, the confined nanospace of hollow cavity ensures that the nucleation-and-growth process of Cu nanocrystals take place exclusively inside the cavities. The size of Cu cores can be easily tuned from 30 to 55 nm by varying the copper salt concentration. By deliberately creating shell porosity through KOH chemical activation, at an optimized KOH/HCS mass ratio of 1/4, the catalytic performance for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) of the activated sample is enhanced remarkably with TOF up to 8.6 h-1 at methanol conversion of 17.1%. The activated yolk-shell catalyst shows promising catalytic properties involving the reusability with slight loss of catalytic activity and negligible leaching of activated components even after seven recycles, which is beneficial to the implementation of clean production for the eco-friendly chemical DMC thoroughly.

  7. NEAR-CONTINUOUS MEASUREMENT OF HYDROGEN SULFIDE AND CARBONYL SULFIDE BY AN AUTOMATIC GAS CHROMATOGRAPH

    Science.gov (United States)

    An automatic gas chromatograph with a flame photometric detector that samples and analyzes hydrogen sulfide and carbonyl sulfide at 30-s intervals is described. Temperature programming was used to elute trace amounts of carbon disulfide present in each injection from a Supelpak-S...

  8. Study of electrocatalytic properties of iridium carbonyl cluster and rhodium carbonyl cluster compounds for the oxygen reduction and hydrogen oxidation reactions in 0.5 MH{sub 2}SO{sub 4} in presence and absence of methanol and carbon monoxide, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Borja-Arco, E.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

    2006-07-01

    The suitability of carbonyl cluster compounds as a substitute to platinum (Pt) in fuel cell catalysts was investigated. Iridium (Ir{sub 4}(CO){sub 12} and rhodium (Rh{sub 6}(CO){sub 116}) cluster compounds were investigated as potential new electrocatalysts for oxygen reduction reaction (ORR) in the presence and absence of methanol at different concentrations, as well as for the hydrogen oxidation reaction (HOR) with pure hydrogen and a hydrogen/carbon monoxide mixture. The materials were studied using room temperature rotating disk electrode (RDE) measurements and cyclic and linear sweep voltammetry techniques (LSV). Tafel slope and exchange current density were calculated using the LSV polarization curves. Cyclic voltamperometry results suggested that the electrocatalysts were tolerant to methanol. However, electrochemical behaviour of the materials altered in the presence of CO, and peaks corresponding to CO oxidation were observed in both cases. The rhodium carbonyl showed a higher current density for the ORR than the iridium carbonyl. The current potential curves in the presence of methanol were similar to those obtained without methanol. Results confirmed the tolerance properties of the materials to perform the ORR. Decreased current density values were observed during HOR, and were attributed to changes in the hydrogen solubility and diffusion coefficient due to the presence of CO. The Tafel slopes indicated that the mechanics of the HOR were Heyrovsky-Volmer. Results showed that the materials are capable of performing both ORR and HOR in an acid medium. It was noted that the iridium carbonyl cluster followed a 4-electron transfer mechanism towards the formation of water. It was concluded that the compounds are suitable for use as both cathodes and anodes in proton exchange membrane fuel cells (PEMFCs) and as cathodes in direct methanol fuel cells (DMFCs). 3 refs., 2 tabs., 3 figs.

  9. Continuous low-temperature methanol synthesis from syngas using alcohol promoters

    Energy Technology Data Exchange (ETDEWEB)

    Prasert Reubroycharoen; Tetsuji Yamagami; Tharapong Vitidsant; Yoshiharu Yoneyama; Motoaki Ito; Noritatsu Tsubaki [Toyama University, Toyama (Japan). Department of Material System & Life Science, School of Engineering

    2003-08-01

    Continuous low-temperature methanol synthesis from syngas containing CO{sub 2} on various Cu/ZnO catalysts was investigated by using a semibatch autoclave reactor. Methanol was easily produced at a temperature as low as 443 K and with a pressure of 50 bar with the aid of 2-butanol, which showed a very high efficiency with a one-pass yield of 47.0% and a selectivity of 98.9%. Methanol itself used as alcohol promoter exhibited a higher activity than other 1-alcohols because it has the lowest spatial effect. 2-Alcohols, however, exhibited the highest conversion among the same carbon number because of its well-balanced effects produced by their of electronic and spatial factors. The one-pass conversion was improved by increasing the catalyst weight because no thermodynamic limitations existed at low temperatures. The continuous low-temperature methanol synthesis is a very promising process because completely purified syngas is not necessary. 23 refs., 3 figs., 4 tabs.

  10. Intermittent hemodialysis is superior to continuous veno-venous hemodialysis/hemodiafiltration to eliminate methanol and formate during treatment for methanol poisoning.

    Science.gov (United States)

    Zakharov, Sergey; Pelclova, Daniela; Navratil, Tomas; Belacek, Jaromir; Kurcova, Ivana; Komzak, Ondrej; Salek, Tomas; Latta, Jiri; Turek, Radovan; Bocek, Robert; Kucera, Cyril; Hubacek, Jaroslav A; Fenclova, Zdenka; Petrik, Vit; Cermak, Martin; Hovda, Knut Erik

    2014-07-01

    During an outbreak of methanol poisonings in the Czech Republic in 2012, we were able to study methanol and formate elimination half-lives during intermittent hemodialysis (IHD) and continuous veno-venous hemodialysis/hemodiafiltration (CVVHD/HDF) and the relative impact of dialysate and blood flow rates on elimination. Data were obtained from 11 IHD and 13 CVVHD/HDF patients. Serum methanol and formate concentrations were measured by gas chromatography and an enzymatic method. The groups were relatively comparable, but the CVVHD/HDF group was significantly more acidotic (mean pH 6.9 vs. 7.1 IHD). The mean elimination half-life of methanol was 3.7 and formate 1.6 h with IHD, versus 8.1 and 3.6 h, respectively, with CVVHD/HDF (both significant). The 54% greater reduction in methanol and 56% reduction in formate elimination half-life during IHD resulted from the higher blood and dialysate flow rates. Increased blood and dialysate flow on the CVVHD/HDF also increased elimination significantly. Thus, IHD is superior to CVVHD/HDF for more rapid methanol and formate elimination, and if CVVHD/HDF is the only treatment available then elimination is greater with greater blood and dialysate flow rates.

  11. Continuous In-situ Measurements of Carbonyl Sulfide to Constrain Ecosystem Carbon and Water Exchange

    Science.gov (United States)

    Rastogi, B.; Kim, Y.; Berkelhammer, M. B.; Noone, D. C.; Lai, C. T.; Hollinger, D. Y.; Bible, K.; Leen, J. B.; Gupta, M.; Still, C. J.

    2014-12-01

    Understanding the processes that control the terrestrial exchange of carbon and water are critical for examining the role of forested ecosystems in changing climates. A small but increasing number of studies have identified Carbonyl Sulfide (OCS) as a potential tracer for photosynthesis. OCS is hydrolyzed by an irreversible reaction in leaf mesophyll cells that is catalyzed by the enzyme, carbonic anhydrase. Leaf-level field and greenhouse studies indicate that OCS uptake is controlled by stomatal activity and that the ratio of OCS and CO2 uptake is reasonably constant. Existing studies on ecosystem OCS exchange have been based on laboratory measurements or short field campaigns and therefore little information on OCS exchange in a natural ecosystem over longer timescales is available. The objective of this study is to further assess the stability of OCS as a tracer for canopy photosynthesis in an active forested ecosystem and also to assess its utility for constraining transpiration, since both fluxes are mediated by canopy stomatal conductance. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W). Canopy air was sampled from three heights to measure vertical gradients of OCS within the canopy, and OCS exchange between the forest and the atmosphere. Here we take advantage of simultaneous measurements of the stable isotopologues of H2O and CO2 at corresponding heights as well as NEE (Net Ecosystem Exchange) from eddy covariance measurements to compare GPP (Gross Primary Production) and transpiration estimates from a variety of independent techniques. Our findings seek to allow assessment of the environmental and ecophysicological controls on evapotranspiration rates, which are projected to change in coming decades, and are otherwise poorly constrained.

  12. Reaction Mechanism and Intrinsic Kinetics of Acetic Acid Synthesized by Methanol Carbonylation in Gas Phase%甲醇气相羰化合成醋酸的反应机理及本征动力学

    Institute of Scientific and Technical Information of China (English)

    刘金红; 刘志军; 黄艳芳; 姚虎卿

    2011-01-01

    Complex catalyst Ni-Mo-La/AC was prepared by impregnation method. And kinetic data of acetic acid catalytic synthesized by methanol carbonylation in gas phase were measured in a plug flow reactor. The results indicated that methyl acetate was the first order product of the vapour phase carbonylation of methanol, and acetic acid was the second order product of the sequential reaction by hydrolysis from methyl acetate. The dimethyl ether was obtained through dehydration of methanol. Methyl iodide and activated carbon had the catalysis effect together on this reaction. The dimethyl ether could also produce methyl acetate by carbonlylation; methane was obtained by reaction of methyl iodide and the production of methanol decomposition. On the base of above analysis, a reaction kinetics model was set up and model parameters were obtained by linear regression of data.%用浸渍法制备了负载型Ni-Mo-La/AC复合催化剂,并在平推流反应器中对甲醇气相羰基化催化反应进行了动力学数据的测定.实验证明,醋酸甲酯是甲醇气相羰基化反应的中间产物,醋酸显示连串反应最终产物的特征由醋酸甲酯水解生成;二甲醚通过甲醇脱水生成,碘甲烷和活性炭共同对该反应起催化作用,二甲醚可进一步羰化生成醋酸甲酯;甲烷由甲醇分解后的产物氢气与碘甲烷反应生成.根据反应机理建立了幂函数动力学模型,由实验数据线性回归计算得到了动力学参数.

  13. 腐蚀金属对甲醇羰化合成醋酸反应的影响%Effects of corrosion metals on methanol carbonylation to acetica acid

    Institute of Scientific and Technical Information of China (English)

    赖春波; 王苏; 曾义红; 宁春利; 曹智龙; 张春雷

    2011-01-01

    The corrosion metals existed in commercial catalyst systems for the production of acetic acid, so the effects of corrosion metals on methanol carbonylation to acetic acid were investigated. The influence of Fe or Ni on the catalytic activity and selectivity of iridium-based or rhodium-based catalysts was studied by adding Fe(OAc)2 or Ni( OAc)2 in batch autoclave. The effects of corrosion metal on the stability of main catalyst were compared under the simulation industrial flash evaporation condition in the parallel reactor. The results showed that corrosion metals such as Fe or Ni could improve the carbonylation reactivity of rhodium-based catalyst system with low concentration of Fe or Ni, and reduce obviously the reaction rate in iridium-based catalyst system. The existence of Fe or Ni in rhodium-based or iridium-based catalyst systems had adverse effects on CO utilization rate and catalyst stability for methanol carbonylation.%结合工业生产催化体系中存在的腐蚀金属,研究了其对羰基合成醋酸反应的影响.在高压反应釜中,通过添加不同浓度的醋酸亚铁或醋酸镍考察腐蚀金属铁和镍对铑基催化剂和铱基催化剂反应活性和选择性的影响,并利用平行反应器在模拟闪蒸条件下考察腐蚀金属对主催化剂稳定性的影响.结果表明,少量腐蚀金属铁或镍的存在对铑催化羰基合成醋酸的反应活性有一定的促进作用,但在铱催化体系中铁和镍的存在对活性有明显的抑制作用.而铁和镍的存在,对铑或铱催化羰化反应的CO利用率和催化剂的稳定性均有不利影响.

  14. Continuous operation of the Berty reactor for the solvent methanol process

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, C.; Elliott, J.R. Jr. (Akron Univ., OH (United States). Dept. of Chemical Engineering); Berty, J.M. (Berty Reaction Engineers Ltd., Fogelsville, PA (US))

    1991-07-01

    In the solvent methanol process (SMP), an inert and selective solvent removes methanol as soon as it is formed from syngas. Conversions in the conventional vapor- phase methanol synthesis is limited because of equilibrium limitations due to the reverse reaction, but data presented in this paper demonstrate that high conversions can be obtained in the SMP. Rate data have been collected for the SMP at operating conditions typical of the vapor-phase process (7.8-10 MPa, 493-513 K). Single-pass H{sub 2} and CO conversions range from 30 to 80%. In some cases, conversions are higher than those predicted by vapor phase equilibrium calculations based on the feed composition, providing that SMP is able to overcome the equilibrium barrier. Rates are 2- 3 times lower than those encountered in the vapor-phase process owing to pore diffusion limitations from the presence of the liquid.

  15. Strong similarities between night-time deposition velocities of carbonyl sulphide and molecular hydrogen inferred from semi-continuous atmospheric observations in Gif-sur-Yvette, Paris region

    OpenAIRE

    Belviso, Sauveur; Schmidt, Martina; Yver, Camille; Ramonet, Michel; Gros, Valerie; Launois, Thomas

    2013-01-01

    We investigated the diurnal variations of atmospheric carbonyl sulphide (COS) during 2011 at Gif-sur-Yvette, a suburban atmospheric measurement site in France. These data were collected semi-continuously in parallel with hydrogen (H2), carbon monoxide (CO) and 222Radon (222Rn) measurements. Fluxes and deposition velocities were calculated for nocturnal situations of low boundary layer height using the Radon-Tracer Method. Contrary to CO and H2, the diurnal cycles of COS are not impacted by em...

  16. Electrocatalytic studies of osmium-ruthenium carbonyl cluster compounds for their application as methanol-tolerant cathodes for oxygen reduction reaction and carbon monoxide-tolerant anodes for hydrogen oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Borja-Arco, E.; Uribe-Godinez, J.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

    2006-07-01

    This paper provided details of an electrokinetic study of novel electrocatalytic materials capable of performing both the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). Osmium-ruthenium carbonyl cluster compounds (Os{sub x}Ru{sub 3}(CO){sub n}) were synthesized by chemical condensation in non-polar organic solvents at different boiling points and refluxing temperatures. Three different non-polar organic solvents were used: (1) n-nonane; o-xylene; and 1,2-dichlorobenzene. The electrocatalysts were characterized by Fourier Transform Infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A rotating disk electrode technique was used to analyze the materials. Results of the analysis showed that the materials performed ORR in both the presence and absence of carbon monoxide (CO), and that electrocatalysts were not poisoned by the presence of CO. Cyclic voltamperometry for the disk electrodes showed that the electrochemical behaviour of the compounds in the acid electrolyte was similar in the presence or absence of methanol. The Tafel slope, exchange current density and the transfer coefficient were also investigated. The electrokinetic parameters for the ORR indicated that the materials with the highest electrocatalytic activity were synthesized in 1,2-dichlorobenzene. Electrocatalytic activity during HOR were prepared in n-nonane. It was concluded that the new materials are good candidates for use as both a cathode and an anode in proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). 7 refs., 2 tabs., 7 figs.

  17. Continuous production of biodiesel from cottonseed oil and methanol using a column reactor packed with calcined sodium silicate base catalyst☆

    Institute of Scientific and Technical Information of China (English)

    Xia Gui; Sichen Chen; Zhi Yun

    2016-01-01

    Sodium silicate and that calcined at 400 °C for 2 h were used to catalyze the transesterification of cottonseed oil with methanol. Calcined sodium silicate (CSS) catalyst exhibited much higher catalytic activity and stability. A maximum biodiesel yield of 98.9%was achieved at methanol/oil mole ratio of 12:1, reaction temperature 65 °C, reaction time 3.0 h, and CSS/oil mass ratio of 2 wt%. After 7 consecutive reactions without any treatment, biodiesel yield reduced to 82.5%. Considering technological and economic feasibility, CSS base catalyst supported onθrings was prepared for continuous transesterification. The maximum yield was 99.1%under optimum conditions (reaction temperature 55 °C, methanol velocity 1 ml·min−1, oil velocity 3 ml·min−1, and 5 tower sec-tions). These results indicate that this new continuous biodiesel production process and apparatus present a great potential for industrial application in biodiesel.

  18. Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account.

    Science.gov (United States)

    Wu, Xiao-Feng; Fang, Xianjie; Wu, Lipeng; Jackstell, Ralf; Neumann, Helfried; Beller, Matthias

    2014-04-15

    Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO's use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of carbonylation catalysis, many important research questions and challenges remain. Notably, apart from academic developments, industry applies carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via carbonylation of methanol (Monsanto or Cativa process). The carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions. In this Account, we discuss our work on various carbonylations of unsaturated compounds and related reactions. Rhodium-catalyzed isomerization and hydroformylation reactions of internal olefins provide straightforward access to higher value aldehydes. Catalytic hydroaminomethylations offer an ideal way to synthesize substituted amines and even heterocycles directly. More recently, our group has also developed so-called alternative metal catalysts based on iridium, ruthenium, and iron. What about the future of carbonylation reactions? CO is already one of the most versatile C1 building blocks for organic synthesis and is widely used in industry. However, because of CO's high toxicity and gaseous nature, organic chemists are often reluctant to apply carbonylations more frequently. In addition, new regulations have recently made the transportation of carbon monoxide more difficult. Hence, researchers will need to develop and more frequently use practical and benign CO-generating reagents. Apart from formates, alcohols, and metal

  19. 羰基化制备乙酸工艺副产物-重组分残液回收的研究%Recovery of residue liquid from the process for carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    荆延; 华超; 校逸; 白芳

    2011-01-01

    通过刮膜蒸发器脱重和高精密精馏的方法对羰基化制备乙酸工艺副产物-重组分残液回收进行了实验.实验中首先采用刮膜蒸发器对甲醇羰基化制备乙酸后的废液进行初步刮膜蒸发,再进行精密精馏处理最终制得3种高纯度产品—乙酸,乙酰氧基乙酸和乙二醇二乙酸酯.采用气相色谱对分离的各组分进行定量分析.优化了操作参数,并验证了工艺可行性,为工业化放大提供可靠的基础数据.%Recovery of the residue liquid from the process for carbonylation of methanol to acetic acid was studied experimentally. The residue liquid firstly was evaporated by the Pope wiped-film molecular still and evaporator, then separated by precise rectification to obtain three high pure products-acetic acid, acetoxyacetic acid and ethylene glycol diacetate. Gas chromatography method was used to determine the separated components quantitatively. The optimized operation parameters of the whole recovery process were obtained and the process feasibility was verified, which provided reliable foundation data for its commercialization.

  20. Study on a process for recovering residual liquid from production of acetic acid by carbonylation of methanol%羰基化合成醋酸过程废液的回收工艺研究

    Institute of Scientific and Technical Information of China (English)

    白芳; 华超; 迪建东

    2012-01-01

    To solve the existing difficulties in recovering and utilizing the heavy residual liquid from the production of acetic acid by carbonylation of methanol, a new process was proposed, in which first using a wiped-film evaporator to obtain the concentrated acetic acid, ethylene glycol diacetate (EGDA) and acetoxyacetic acid (AAA) distillates from the residual liquid, then the distillates were further purified by a vacuum batch distillation process to obtain the pured products. The experimental results showed that the proposed process was feasible, and the purification of the recovered products was over 99% for acetic acid and over 95% for EDGA and AAA. The effects of operation conditions were investigated, and the optimum experimental operation conditions were determined.%针对羰基化生产醋酸过程中产生的重组分残液难以回收的现状,首次提出了采用刮膜蒸发器富集醋酸废液中的醋酸、乙二醇二乙酸酯(EGDA)和乙酰氧基乙酸(AAA)馏分,其后减压间歇精馏分离富集馏分,实现羰基化醋酸废液的回收利用.试验表明该方法是切实可行的,并获得了纯度为99%以上的醋酸产品和95%以上的EGDA和AAA副产品.研究了精馏操作对EGDA和AAA纯度的影响,获得了最佳实验条件.

  1. Continuous esterification of free fatty acids in crude biodiesel by an integrated process of supercritical methanol and sodium methoxide catalyst.

    Science.gov (United States)

    Zeng, Dan; Li, Ruosong; Feng, Mingjun; Fang, Tao

    2014-10-01

    An integrated process of supercritical methanol (SCM) and sodium methoxide catalyst was developed to produce fatty acid methyl esters (FAMEs) via continuous esterification from crude biodiesel. The crude biodiesel with high free fatty acid (FFA) content must be refined to reduce the acid value (AV) for meeting the quality standards. The process parameters were studied by Box-Behnken design (BBD) of response surface methodology (RSM). The experimental results revealed that the AV of crude biodiesel decreased from 18.66 to 0.55 mg KOH g(-1) at the reaction conditions of 350 °C, 0.5 % amount of sodium methoxide catalyst, and 10 MPa. Temperature shows the most significant effect on the esterification, followed by pressure and amount of sodium methoxide catalyst. This integrated process proved to be a potential route to refine the crude biodiesel because of its continuity, high efficiency, and less energy consumption with relatively moderate reaction conditions compared with conventional methods.

  2. Bilirubin degradation in methanol induced by continuous UV-B irradiation: a UHPLC--ESI-MS study.

    Science.gov (United States)

    Stanojević, J S; Zvezdanović, J B; Marković, D Z

    2015-04-01

    Degradation of bilirubin in aerobic methanol solution by continuous UV-B irradiation has been investigated in this work. The purpose of this study was to shed more light on bilirubin interaction with the UV-B component of natural sunlight, since bilirubin is a very efficient UV-B absorber located in the skin epidermis. The degradation products have been detected and studied by a combined method of Ultra High Performance Liquid Chromatography-Electrospray Ionization Mass Spectrometry (UHPLC-ESI-MS). Bilirubin, a toxic pigment which itself is a product of (hemoglobin) degradation in organisms, undergoes its own degradation under aerobic conditions of UV-B continuous irradiation (e.g. photooxidation) that can be partly self-sensitized. Two dipyrrolic structures have been identified as a result of the bilirubin degradation, not including the bilirubin derivative biliverdin whose increase in the irradiated system is synchronous with a time dynamics of bilirubin degradation. It appears that one of dipyrrolic products originates directly from bilirubin and biliverdin molecules, while the other one is probably connected to bilirubin self-sensitized degradation. The precursor role of biliverdin in the degradation process--related to the detected dipyrroles--has not been confirmed.

  3. Regulation of methanol oxidation and carbon dioxide fixation in Xanthobacter strain 25a grown in continuous culture

    NARCIS (Netherlands)

    Croes, L.M.; Meijer, Wilhelmus; Dijkhuizen, L.

    1991-01-01

    The regulation of C1-metabolism in Xanthobacter strain 25a was studied during growth of the organism on acetate, formate and methanol in chemostat cultures. No activity of methanol dehydrogenase (MDH), formate dehydrogenase (FDS) or ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisC/O) could be

  4. Regulation of methanol oxidation and carbon dioxide fixation in Xanthobacter strain 25a grown in continuous culture

    NARCIS (Netherlands)

    Croes, L.M.; Meijer, Wilhelmus; Dijkhuizen, L.

    1991-01-01

    The regulation of C1-metabolism in Xanthobacter strain 25a was studied during growth of the organism on acetate, formate and methanol in chemostat cultures. No activity of methanol dehydrogenase (MDH), formate dehydrogenase (FDS) or ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisC/O) could be

  5. Methanol unbalance of supply and demand situation will still continue%甲醇供需失衡局面仍将持续

    Institute of Scientific and Technical Information of China (English)

    王向前; 钱惠斌; 胡雪瑛; 袁本成; 王飞虎

    2012-01-01

    甲醇作为重要的化学工业基础原料和清洁液体燃料,被广泛应用于有机合成、医药、农药、涂料、染料等领域,主要用来生产甲醛、醋酸、MTBE、对苯二甲酸二甲酯、丙烯酸甲酯等产品以及醇醚燃料.随着甲醇制烯烃和甲醇燃料等新兴领域的不断开发,虽然为甲醇行业开拓了更为广阔的应用前景,但由于我国甲醇产能无序过快增长、大量进口产品的冲击、下游需求疲软以及投资新建装置热度不减等因素的影响,造成我国甲醇严重供过于求,我国甲醇供需失衡的局面仍将持续.%Methanol as an important chemical industry basis of raw materials and clean liquid fuel, is widely used in organic synthesis,pharmaceutical, pesticide,paint, dye and other fields,mainly used in the production of formaldehyde, acetic acid, MTBE, terephthalic acid methyl methacrylate, products and the alcohol or ether fuel. This paper mainly discusses the methanol to olefins and methanol fuel and other new product development,although for methanol industry to develop a more broad application prospects,but because our country methanol production capacity of disordered growth,many entrance product impact,weak demand and new plant investment heat and other factors,China methanol unbalance of supply and demand situation will still continue.

  6. Application of a Burkholderia cepacia lipase-immobilized silica monolith to batch and continuous biodiesel production with a stoichiometric mixture of methanol and crude Jatropha oil

    Directory of Open Access Journals (Sweden)

    Takahashi Ryo

    2011-10-01

    Full Text Available Abstract Background The enzymatic production of biodiesel through alcoholysis of triglycerides has become more attractive because it shows potential in overcoming the drawbacks of chemical processes. In this study, we investigate the production of biodiesel from crude, non-edible Jatropha oil and methanol to characterize Burkholderia cepacia lipase immobilized in an n-butyl-substituted hydrophobic silica monolith. We also evaluate the performance of a lipase-immobilized silica monolith bioreactor in the continuous production of biodiesel. Results The Jatropha oil used contained 18% free fatty acids, which is problematic in a base-catalyzed process. In the lipase-catalyzed reaction, the presence of free fatty acids made the reaction mixture homogeneous and allowed bioconversion to proceed to 90% biodiesel yield after a 12 hour reaction time. The optimal molar ratio of methanol to oil was 3.3 to 3.5 parts methanol to one part oil, with water content of 0.6% (w/w. Further experiments revealed that B. cepacia lipase immobilized in hydrophobic silicates was sufficiently tolerant to methanol, and glycerol adsorbed on the support disturbed the reaction to some extent in the present reaction system. The continuous production of biodiesel was performed at steady state using a lipase-immobilized silica monolith bioreactor loaded with 1.67 g of lipase. The yield of 95% was reached at a flow rate of 0.6 mL/h, although the performance of the continuous bioreactor was somewhat below that predicted from the batch reactor. The bioreactor was operated successfully for almost 50 days with 80% retention of the initial yield. Conclusions The presence of free fatty acids originally contained in Jatropha oil improved the reaction efficiency of the biodiesel production. A combination of B. cepacia lipase and its immobilization support, n-butyl-substituted silica monolith, was effective in the production of biodiesel. This procedure is easily applicable to the design

  7. Determination of nicotine, tar, volatile organic compounds and carbonyls in mainstream cigarette smoke using a glass filter and a sorbent cartridge followed by the two-phase/one-pot elution method with carbon disulfide and methanol.

    Science.gov (United States)

    Uchiyama, Shigehisa; Hayashida, Hideki; Izu, Rina; Inaba, Yohei; Nakagome, Hideki; Kunugita, Naoki

    2015-12-24

    We have developed a new analytical method for the determination of nicotine, tar, volatile organic compounds and carbonyls in main-stream cigarette smoke using a sorbent cartridge packed with Carboxen 572 (CX-572) and a Cambridge filter pad (CFP) followed by the two-phase/one-pot elution method. A CX-572 cartridge is installed between the intake of the CFP and the pump of the smoking machine. Gaseous compounds collected with the CX-572 cartridge and total particulate matter (TPM) collected with the CFP are coeluted simultaneously in the same vial and then analyzed by high-performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC/MS) and gas chromatograph-thermal conductivity detector (GC/TCD). Carbonyl compounds are determined by adding derivatizing reagent (2,4-dinitrophenylhydrazine, DNPH) to the eluate followed by HPLC analysis. VOCs and nicotine are determined by GC/MS, and water is determined by GC/TCD. The same sample eluate solution is used for HPLC, GC/MS and GC/TCD analyses. As a result of measuring main-stream cigarette smoke generated from reference cigarettes, almost all carbonyl compounds and VOCs except formaldehyde were passed through a CFP and trapped in a CX-572 cartridge. 100% of nicotine, tar and TPM were trapped in a CFP. 50% of water and 53% of formaldehyde were trapped in a CFP. The one-pot data is almost equal to the sums of CFP (particulate matter) and CX-572 (gaseous compounds) data. The two-phase/one-pot elution method can simultaneously measure nicotine, tar, volatile organic compounds and carbonyl compounds in cigarette smoke with simple operation and small amounts of reagents. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Methanol production method and system

    Science.gov (United States)

    Chen, Michael J.; Rathke, Jerome W.

    1984-01-01

    Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

  9. Methanol partial oxidation reformer

    Science.gov (United States)

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  10. 甲醇羰基合成碳酸二甲酯反应机理及多相催化剂研究进展%Advances in the reaction mechanism and heterogeneous catalysts of dimethyl carbonate synthesis by the carbonylation of methanol

    Institute of Scientific and Technical Information of China (English)

    杨雄; 刘定华; 刘晓勤

    2012-01-01

    针对甲醇羰基合成碳酸二甲酯(DMC)反应体系,在综合分析以氯化亚铜、氯化铜以及铜分子筛为催化剂的氧化羰基化反应机理的基础上,着重介绍了多相催化剂的种类、结构、活性中心以及制备工艺的研究进展,并对各类催化剂的催化性能进行了分析和评价。通过溶胶-凝胶技术和分子筛包覆的方法制备的钴系催化剂,其活性和稳定性得到了提高;钯铜系催化剂经过载体改性和加入适当的助剂,甲醇转化率增大并在一定程度上抑制了氯离子的流失;无氯铜系催化剂避免了对设备的腐蚀,但催化活性和DMC的选择性普遍较低。最后指出利用各种现代表征手段以及分析技术研究表面过程深刻了解甲醇羰基合成机理,才能在催化剂的设计和开发上取得创新和突破。%Based on the oxidative carbonylation mechanism of cuprous chloride,copper chloride,and copper zeolite catalysts,new research progress in heterogeneous catalysts,including category,structure,activity center and preparation are summarized.Their catalytic performances are analyzed respectively.The activity and stability of cobalt catalysts are improved by sol-gel technique and encapsulated in zeolite.For palladium and copper catalysts,the methanol conversion is increased and the loss of chlorine is suppressed after the modification of supports and the addition of appropriate promoters.Chlorine-free copper catalysts can avoid equipment corrosion,but there is some decrease in catalytic activity and selectivity of DMC.Finally,by utilizing variety of modern characterization and analysis techniques,the surface process can be studied to understand the mechanism of methanol carbonylation deeply,so that real innovations and breakthroughs can be made in the design and the development of catalysts.

  11. Carbonyl Emissions From Oil and Gas Production Facilities

    Science.gov (United States)

    Lyman, S. N.; O'Neil, T.; Tran, T.

    2015-12-01

    A number of recent studies have targeted emissions of methane and other hydrocarbons from oil and gas exploration and production activity. These measurements are greatly increasing understanding of the atmospheric impacts of oil and gas development. Very few measurements exist, however, of emissions of formaldehyde and other carbonyls from oil and gas equipment. Carbonyls are toxic and serve as important ozone precursors, especially during winter ozone episodes in places like Utah's Uintah Basin. Current air quality models are only able to reproduce observed high wintertime ozone if they incorporate emissions inventories with very high carbonyl emissions. We measured carbonyl emissions from oil and gas equipment and facilities—including glycol dehydrators, liquid storage tanks, raw gas leaks, raw gas-burning engines, and produced water surface impoundments—in Rocky Mountain oil and gas fields. Carbonyl emissions from raw gas were below detection, but emissions of formaldehyde, acetaldehyde, and other carbonyls were detected from liquid storage tanks, glycol dehydrators, and other oil and gas equipment. In some cases, carbonyls may be formed from the degradation of methanol and other chemicals used in oil and gas production, but the collected data provide evidence for other non-combustion formation pathways. Raw gas-burning engines also emitted carbonyls. Emissions from all measured sources were a small fraction of total volatile organic compound emissions. We incorporated our measurements into an emissions inventory, used that inventory in an air quality model (WRF-SMOKE-CAMx), and were unable to reproduce observed high wintertime ozone. This could be because (1) emission sources we have not yet measured, including compressors, gas processing plants, and others, are large; (2) non-carbonyl emissions, especially those that quickly degrade into carbonyls during photochemical processing, are underestimated in the inventory; or (3) the air quality model is unable

  12. Catalyst Initiation in the Oscillatory Carbonylation Reaction

    Directory of Open Access Journals (Sweden)

    Katarina Novakovic

    2011-01-01

    Full Text Available Palladium(II iodide is used as a catalyst in the phenylacetylene oxidative carbonylation reaction that has demonstrated oscillatory behaviour in both pH and heat of reaction. In an attempt to extract the reaction network responsible for the oscillatory nature of this reaction, the system was divided into smaller parts and they were studied. This paper focuses on understanding the reaction network responsible for the initial reactions of palladium(II iodide within this oscillatory reaction. The species researched include methanol, palladium(II iodide, potassium iodide, and carbon monoxide. Several chemical reactions were considered and applied in a modelling study. The study revealed the significant role played by traces of water contained in the standard HPLC grade methanol used.

  13. Selective methanol or formate production during continuous CO₂ fermentation by the acetogen biocatalysts engineered via integration of synthetic pathways using Tn7-tool.

    Science.gov (United States)

    Tyurin, Michael; Kiriukhin, Michael

    2013-09-01

    Methanol-resistant mutant acetogen Clostridium sp. MT1424 originally producing only 365 mM acetate from CO₂/CO was engineered to eliminate acetate production and spore formation using Cre-lox66/lox71-system to power subsequent methanol production via expressing synthetic methanol dehydrogenase, formaldehyde dehydrogenase and formate dehydrogenase, three copies of each, assembled in cluster and integrated to chromosome using Tn7-based approach. Production of 2.2 M methanol was steady (p IGCC power plant. Hydrogen may be produced in situ via powered by solar panels electrolysis.

  14. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna;

    2015-01-01

    Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial...

  15. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna

    2015-01-01

    Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial...... kits. We have further explored the potential causes of variance in carbonyl analysis in a ring study. A soluble protein fraction was prepared from rat liver and exposed to 0, 5 and 15min of UV irradiation. Lyophilised preparations were distributed to six different laboratories that routinely undertook...... protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5min of UV irradiation irrespective of method used. After irradiation for 15min, less oxidation was detected by half of the laboratories than after 5min...

  16. Effect of dilution rate and methanol-glycerol mixed feeding on heterologous Rhizopus oryzae lipase production with Pichia pastoris Mut(+) phenotype in continuous culture.

    Science.gov (United States)

    Canales, Christian; Altamirano, Claudia; Berrios, Julio

    2015-01-01

    The induction using substrate mixtures is an operational strategy for improving the productivity of heterologous protein production with Pichia pastoris. Glycerol as a cosubstrate allows for growth at a higher specific growth rate, but also has been reported to be repressor of the expression from the AOX1 promoter. Thus, further insights about the effects of glycerol are required for designing the induction stage with mixed substrates. The production of Rhizopus oryzae lipase (ROL) was used as a model system to investigate the application of methanol-glycerol feeding mixtures in fast metabolizing methanol phenotype. Cultures were performed in a simple chemostat system and the response surface methodology was used for the evaluation of both dilution rate and methanol-glycerol feeding composition as experimental factors. Our results indicate that productivity and yield of ROL are strongly affected by dilution rate, with no interaction effect between the involved factors. Productivity showed the highest value around 0.04-0.06 h(-1) , while ROL yield decreased along the whole dilution rate range evaluated (0.03-0.1 h(-1) ). Compared to production level achieved with methanol-only feeding, the highest specific productivity was similar in mixed feeding (0.9 UA g-biomass(-1) h(-1) ), but volumetric productivity was 70% higher. Kinetic analysis showed that these results are explained by the effects of dilution rate on specific methanol uptake rate, instead of a repressor effect caused by glycerol feeding. It is concluded that despite the effect of dilution rate on ROL yield, mixed feeding strategy is a proper process option to be applied to P. pastoris Mut(+) phenotype for heterologous protein production.

  17. Method for making methanol

    Science.gov (United States)

    Mednick, R. Lawrence; Blum, David B.

    1986-01-01

    Methanol is made in a liquid-phase methanol reactor by entraining a methanol-forming catalyst in an inert liquid and contacting said entrained catalyst with a synthesis gas comprising hydrogen and carbon monoxide.

  18. The toxicity of inhaled methanol vapors

    Energy Technology Data Exchange (ETDEWEB)

    Kavet, R.; Nauss, K.M. (Environmental Research Information, Inc., Palo Alto, CA (USA))

    1990-01-01

    Methanol could become a major automotive fuel in the U.S., and its use may result in increased exposure of the public to methanol vapor. Nearly all of the available information on methanol toxicity in humans relates to the consequences of acute, rather than chronic, exposures. Acute methanol toxicity evolves in a well-understood pattern and consists of an uncompensated metabolic acidosis with superimposed toxicity to the visual system. The toxic properties of methanol are rooted in the factors that govern both the conversion of methanol to formic acid and the subsequent metabolism of formate to carbon dioxide in the folate pathway. In short, the toxic syndrome sets in if formate generation continues at a rate that exceeds its rate of metabolism. Current evidence indicates that formate accumulation will not challenge the metabolic capacity of the folate pathway at the anticipated levels of exposure to automotive methanol vapor.117 references.

  19. 49 CFR 173.198 - Nickel carbonyl.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Nickel carbonyl. 173.198 Section 173.198... Nickel carbonyl. (a) Nickel carbonyl must be packed in specification steel or nickel cylinders as prescribed for any compressed gas except acetylene. A cylinder used exclusively for nickel carbonyl may...

  20. Carbonyl Compounds Generated from Electronic Cigarettes

    Directory of Open Access Journals (Sweden)

    Kanae Bekki

    2014-10-01

    Full Text Available Electronic cigarettes (e-cigarettes are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  1. Carbonyl compounds generated from electronic cigarettes.

    Science.gov (United States)

    Bekki, Kanae; Uchiyama, Shigehisa; Ohta, Kazushi; Inaba, Yohei; Nakagome, Hideki; Kunugita, Naoki

    2014-10-28

    Electronic cigarettes (e-cigarettes) are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols) when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  2. Accidental methanol ingestion: Case report

    Directory of Open Access Journals (Sweden)

    Bakker Jan

    2010-02-01

    Full Text Available Abstract Background The incidence of methanol (CH3OH intoxication differs enormously from country to country. Methanol intoxication is extremely rare in the Dutch population. Even a low dose can already be potentially lethal. Patients are conventionally treated with hemodialysis. Therefore we'd like to present a report of a foreign sailor in Rotterdam who accidentally caused himself severe methanol intoxication, with a maximum measured concentration of 4.4 g/L. Case presentation The patient presented with hemodynamic instability and severe metabolic acidosis with pH 6.69. The anion gap was 39 mmol/L and the osmol gap 73 mosmol/kg. Treatment with ethanol and continuous venovenous hemodiafiltration (CVVH-DF was initiated. Despite the hemodynamic instability it is was possible to achieve rapid correction of pH and methanol concentration with CVVH-DF while maintaining a stable and therapeutic ethanol serum concentration. Despite hemodynamic and acid-base improvement, our patient developed massive cerebral edema leading to brain death. Permission for organ donation was unfortunately not ascertained. Conclusions We conclude that in a hemodynamic instable situation high methanol concentrations and methanol-induced derangements of homeostasis are safely and effectively treated with CVVH-DF and that severe cerebral edema is another possible cause of death rather than the classical bleeding in the putamen area.

  3. Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

    Science.gov (United States)

    Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

    2016-12-30

    Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

  4. POLYMER—SUPPORTED RHODIUM CATALYSTS FOR CARBONYLATION OF METHYL ACETATE TO ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    CHENDean; HUANGShizhuan; 等

    1993-01-01

    Two kinds of rhodium catalysts supported on cross-linked styrene-divinylbenzene copolymers containing bipyridine or o-phenylene diamine have been prepared and found to display high activity for methyl acetate carbonylation to form acetic anhydride,the activities are even higher than their homogeneous counterparts. XPS analysis was used to characterize the synthetic catalysts.The apparent activation parameters were determined to be Eα=73.3KJ/mol,ΔH≠=66.3KJ/mol,ΔS≠=-28.6eu.These parameters are very close to those in methanol carbonylation and imply to have analogous mechanism in both cases.

  5. Preparation and microwave shielding property of silver-coated carbonyl iron powder

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xiao Guo, E-mail: xgcao@gdut.edu.cn [School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, Guangdong (China); Ren, Hao [Guangzhou Research Institute of O-M-E Technology, Guangzhou 510006, Guangdong (China); Zhang, Hai Yan [School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, Guangdong (China)

    2015-05-15

    Highlights: • The silver-coated carbonyl iron powder is prepared by the electroless plating process. • The silver-coated carbonyl iron powder is a new kind of conductive filler. • The reflection and absorption dominate the shielding mechanism of the prepared powder. • Increasing the thickness of electroconductive adhesive will increase the SE. - Abstract: Electroless silver coating of carbonyl iron powder is demonstrated in the present investigation. The carbonyl iron powders are characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the coating process. The relatively uniform and continuous silver coating is obtained under the given coating conditions. In this paper, the electromagnetic interference (EMI) shielding mechanism of the silver-coated carbonyl iron powder is suggested. The reflection of silver coating and absorption of carbonyl iron powder dominate the shielding mechanism of the silver-coated carbonyl iron powder. The silver-coated carbonyl iron powders are used as conductive filler in electroconductive adhesive for electromagnetic interference shielding applications. The effect of the thickness of electroconductive adhesive on the shielding effectiveness (SE) is investigated. The results indicate that the SE increases obviously with the increase of the thickness of electroconductive adhesive. The SE of the electroconductive adhesive with 0.35 mm thickness is above 38 dB across the tested frequency range.

  6. The Methanol Miracle

    Institute of Scientific and Technical Information of China (English)

    1995-01-01

    Methanol already makes a good fuel for camp stoves and even for a few cars. But in the future,say botanist Arthur Nonomura and biochemist Andrew Benson,methanol may fuel an agricultural revolution in hot and dry regions of the world. When the researchers recently sprayed diluted solutions of methanol on crops at Nonomura’s Arizona farm,they found they could double yields in some cases and halve water consumption in others.

  7. Kinetics of the Double Carbonylation of Benzylchloride

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    It is a multi-phase-catalyzed reaction to produce calcium phenylpyruvate by double carbonylation of benzylchloride. Based on the analysis of the reaction mechanism, a kinetic model of the carbonylation reaction was obtained. The model was verified through experiments in which the diffusion effect was neglected with the appropriate operation manner. But it is inevitable that the carbonylation process is controlled by diffusion as the autoclave scaling up.

  8. Methanol Asinger's vision today

    CERN Document Server

    Bertau, Martin; Plass, Ludolf; Schmidt, Friedrich; Wernicke, Hans-Jürgen

    2014-01-01

    Methanol - The Chemical and Energy Feedstock of the Future offers a visionary yet unbiased view of methanol technology. Based on the groundbreaking 1986 publication ""Methanol"" by Friedrich Asinger, this book includes contributions by more than 40 experts from industry and academia. The authors and editors provide a comprehensive exposition of methanol chemistry and technology which is useful for a wide variety of scientists working in chemistry and energy related industries as well as academic researchers and even decision-makers and organisations concerned with the future of chemical and e

  9. The Methanol Economy Project

    Energy Technology Data Exchange (ETDEWEB)

    Olah, George [Univ. of Southern California, Los Angeles, CA (United States); Prakash, G. K. [Univ. of Southern California, Los Angeles, CA (United States)

    2014-02-01

    The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO2 capture using supported amines, co-electrolysis of CO2 and water to formate and syngas, decomposition of formate to CO2 and H2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

  10. Transition metal catalyzed carbonylation reactions carbonylative activation of C-X bonds

    CERN Document Server

    Beller, Matthias

    2014-01-01

    This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. It discusses the past, present and future of carbonylation reactions.

  11. Hepatocyte cytotoxicity induced by hydroperoxide (oxidative stress model) or glyoxal (carbonylation model): prevention by bioactive nut extracts or catechins.

    Science.gov (United States)

    Banach, Monica S; Dong, Qiang; O'Brien, Peter J

    2009-03-16

    Carbonyl and oxidative stress play important roles in the development of diabetic complications and have been shown to be augmented by various natural compounds and pharmacological agents. Nuts are a rich source of bioactive compounds and antioxidants and various beneficial health effects of nuts have been reported. This study was conducted to evaluate the cytoprotectiveness of various nut extracts and bioactive compounds found in nuts for decreasing cytotoxicity, lipid peroxidation and protein carbonylation in cell toxicity models of diabetes-related carbonyl (glyoxal) and oxidative stress (hydroperoxide). Methanol, ethyl acetate or water were used to prepare crude hazelnut and walnut extracts, which were then used to screen for in vitro cytoprotection of freshly isolated rat hepatocytes against these toxins. The order of protection by nut extracts against hydroperoxide induced cell death was: walnut methanolic extract>walnut aqueous extract>lipophilic walnut extract>hazelnut aqueous extract>hazelnut methanolic extract whereas the lipophilic hazelnut extract did not protect against cell death. The order of protection against lipid peroxidation was the same except for the hazelnut methanolic extract, which prevented lipid peroxidation better than the hazelnut aqueous extract. Catechin, epicatechin and epigallocatechin gallate (EGCG) were investigated for possible protective effects against carbonyl stress cell death and protein carbonylation in hepatocytes. Catechin protected against glyoxal induced cell death and protein carbonylation, and even elicited protection when added to hepatocytes 30 min after the addition of glyoxal. When catechin and epicatechin were compared for protectiveness against glyoxal induced carbonyl stress in hepatocytes, epicatechin protected more effectively than catechin against cell death and protein carbonylation at 120 min. Both compounds also elicited better protection when premixed with glyoxal before addition to hepatocytes, compared

  12. Vacuum-Ultraviolet (VUV) Photoionization of Small Methanol and Methanol-Water Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Belau, Leonid; Wilson, Kevin R.; Ahmed, Musahid

    2008-04-24

    In this work, we report on the vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuum-ultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH+(n = 1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH n(H2O)H+ (n = 2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH+, (CH3OH)2+, (CH3OH)nH+ (n = 1-9), and (CH3OH)n(H2O)H+ (n = 2-9) as a function of photon energy. With an increasein the water content in the molecular beam, there is an enhancement of photoionization intensity for the methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  13. Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Musahid; Ahmed, Musahid; Wilson, Kevin R.; Belau, Leonid; Kostko, Oleg

    2008-05-12

    In this work we report on thevacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuumultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  14. Study of decomposing carbonyl slag

    Institute of Scientific and Technical Information of China (English)

    CHEN Ai-liang; SUN Pei-mei; ZHAO Zhong-wei; LI Hong-gui; CHEN Xing-yu

    2006-01-01

    A new technology was put forward to deal with the carbonyl slag at low acidity and low oxygen pressure in the kettle.With the orthogonal experiments for analyzing the sequence of four factors and some single factor experiments for the best conditions. The best conditions are used for extracting nickel, cobalt and copper and enriching precious metals: the cupric ion concentration is 5 g/L; and pH=6; the sulfur coefficient is 1.4; the oxygen pressure is 0.08 MPa; the time bubbling oxygen is 20 min;the ratio of liquid to solid is 8:1; the leaching time is 2 h; the heating time is 2.5 h. The leaching rates of nickel and cobalt are more than 98% and that of copper is above 97%. Nickel and cobalt can be separated efficiently from copper and precious metals from the carbonyl slag. Moreover, its leaching liquor has less copper. Nickel and cobalt can be reclaimed only once. During the whole process,the leaching rates of Au and Ag are more than 99.9%, while other precious metals are still in the residue without any loss.

  15. Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 11, January 1--March 31, 1997

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-06-11

    During this quarter, the third draft of the Topical Report on Process Economics Studies was issued for review. A recommendation to continue with design verification testing on the coproduction of methanol and dimethyl ether (DME) was made. A liquid phase dimethyl ether (LPDME) catalyst system with reasonable long-term activity and stability is being developed, and a decision to proceed with a proof-of-concept test run at the LaPorte Alternative Fuels Development Unit (AFDU) is pending the release of a memo from Air Products on the catalyst targets and corresponding economics for a commercially successful LPDME catalyst. The off-site product-use test plan is to be updated in June of 1997. During this quarter, Air Products and Acurex Environmental Corporation continued developing the listing of product-use test participants who are involved in fuel cell, transportation, and stationary power plant applications. Start-up activities (Task 3.1) began during the reporting period, and coal-derived synthesis gas (syngas) was introduced to the demonstration unit. The recycle compressor was tested successfully on syngas at line pressure of 700 psig, and the reactor loop reached 220 C for carbonyl burnout. Iron carbonyl in the balanced gas feed remained below the 10 ppbv detection limit for all samples but one. Within the reactor loop, iron carbonyl levels peaked out near 200 ppbv after about 40 hours on-stream, before decreasing to between 10--20 ppbv at 160 hours on -stream. Nickel carbonyl measurements reached a peak of about 60 ppbv, and decreased at all sampling locations to below the 10 ppbv detection limit by 70 hours on-stream. Catalyst activation of the nine 2,250 lb batches required for the initial catalyst charge began and concluded. All batches met or slightly exceeded the theoretical maximum uptake of 2.82 SCF of reducing gas/lb catalyst.

  16. Surface decorated platinum carbonyl clusters

    Science.gov (United States)

    Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Zarra, Salvatore

    2012-06-01

    Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters. CCDC 867747 and 867748. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30400g

  17. Measurement of airborne carbonyls using an automated sampling and analysis system.

    Science.gov (United States)

    Aiello, Mauro; McLaren, Robert

    2009-12-01

    Based upon the well established method of derivitization with 2,4-dinitrophenylhydrazine, an instrument was developed for ambient measurement of carbonyls with significantly improved temporal resolution and detection limits through automation, direct injection, and continuous use of a single microsilica DNPH cartridge. Kinetic experiments indicate that the derivitization reaction on the cartridge is fast enough for continuous measurements with 50 min air sampling. Reaction efficiencies measured on the cartridge were 100% for the carbonyls tested, including formaldehyde, acetaldehyde, propanal, acetone, and benzaldehyde. Transmission of the carbonyls through an ozone scrubber (KI) were in the range of 97-101%. Blank levels and detection limits were lower than those obtainable with conventional DNPH methods by an order of magnitude or greater. Mixing ratio detection limits of carbonyls in ambient air were 38-73 ppt for a 50 min air sample (2.5 L). The instrument made continuous measurements of carbonyls on a 2 h cycle over a period of 10 days during a field study in southwestern Ontario. Median mixing ratios were 0.58 ppb formaldehyde; 0.29 ppb acetaldehyde; 1.14 ppb acetone; and 0.45 ppb glyoxal. Glyoxal shows a significant correlation with ozone and zero intercept, consistent with a secondary source and minor direct source to the atmosphere. The method should easily be extendable to the detection of other low molecular weight carbonyls that have been previously reported using the DNPH technique.

  18. Dietary methanol and autism.

    Science.gov (United States)

    Walton, Ralph G; Monte, Woodrow C

    2015-10-01

    The authors sought to establish whether maternal dietary methanol during pregnancy was a factor in the etiology of autism spectrum disorders. A seven item questionnaire was given to women who had given birth to at least one child after 1984. The subjects were solicited from a large primary care practice and several internet sites and separated into two groups - mothers who had given birth to a child with autism and those who had not. Average weekly methanol consumption was calculated based on questionnaire responses. 550 questionnaires were completed by women who gave birth to a non-autistic child. On average these women consumed 66.71mg. of methanol weekly. 161 questionnaires were completed by women who had given birth to an autistic child. The average estimated weekly methanol consumption for this group was 142.31mg. Based on the results of the Wilcoxon rank sum-test, we see a significant difference between the reported methanol consumption rates of the two groups. This study suggests that women who have given birth to an autistic child are likely to have had higher intake of dietary sources of methanol than women who have not. Further investigation of a possible link of dietary methanol to autism is clearly warranted.

  19. Methanol Cannon Demonstrations Revisited.

    Science.gov (United States)

    Dolson, David A.; And Others

    1995-01-01

    Describes two variations on the traditional methanol cannon demonstration. The first variation is a chain reaction using real metal chains. The second example involves using easily available components to produce sequential explosions that can be musical in nature. (AIM)

  20. Trifluoromethylation of Carbonyl Compounds with Sodium Trifluoroacetate

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    In the presence of copper (Ⅰ) halide as catalyst, a variety of carbonyl compounds could be trifluoromethylated with sodium trifluoroacetate to give the corresponding alcohols in moderate to high yields.

  1. Ab Initio MO Studies on the Reaction Mechanism for Carbonyl Insertion Catalyzed by Carbonyl Cobalt Complex

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Ab initio method, under the effective core potential(ECP) approximation at HF/LANL2DZ level, has been employed to study the reaction mechanism of the carbonyl insertion of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)3. The two reaction paths have been discussed. The calculated potential energy barriers for the carbonyl migration and the ethyl group migration are 105.0 kJ/mol and 39.17 kJ/mol, respectively. The results indicate that the reaction path via ethyl migration is more energetically favorable than that via carbonyl insertion.

  2. Protein carbonylation and adipocyte mitochondrial function.

    Science.gov (United States)

    Curtis, Jessica M; Hahn, Wendy S; Stone, Matthew D; Inda, Jacob J; Droullard, David J; Kuzmicic, Jovan P; Donoghue, Margaret A; Long, Eric K; Armien, Anibal G; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J; Bernlohr, David A

    2012-09-21

    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte.

  3. Process assessment of small scale low temperature methanol synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hendriyana [Chemical Engineering Department, Faculty of Engineering, Jenderal Achmad Yani Univerity (Indonesia); Chemical Engineering Department, Faculty of Industrial Technology, InstitutTeknologi Bandung (Indonesia); Susanto, Herri, E-mail: herri@che.itb.ac.id; Subagjo [Chemical Engineering Department, Faculty of Industrial Technology, InstitutTeknologi Bandung (Indonesia)

    2015-12-29

    Biomass is a renewable energy resource and has the potential to make a significant impact on domestic fuel supplies. Biomass can be converted to fuel like methanol via several step process. The process can be split into following main steps: biomass preparation, gasification, gas cooling and cleaning, gas shift and methanol synthesis. Untill now these configuration still has a problem like high production cost, catalyst deactivation, economy of scale and a huge energy requirements. These problems become the leading inhibition for biomass conversion to methanol, which should be resolved to move towards the economical. To address these issues, we developed various process and new configurations for methanol synthesis via methyl formate. This configuration combining two reactors: the one reactor for the carbonylation of methanol and CO to form methyl formate, and the second for the hydrogenolysis of methyl formate and H{sub 2} to form two molecule of methanol. Four plant process configurations were compared with the biomass basis is 300 ton/day. The first configuration (A) is equipped with a steam reforming process for converting methane to CO and H{sub 2} for increasing H{sub 2}/CO ratio. CO{sub 2} removal is necessary to avoid poisoning the catalyst. COSORB process used for the purpose of increasing the partial pressure of CO in the feed gas. The steam reforming process in B configuration is not used with the aim of reducing the number of process equipment, so expect lower investment costs. For C configuration, the steam reforming process and COSORB are not used with the aim of reducing the number of process equipment, so expect lower investment costs. D configuration is almost similar to the configuration A. This configuration difference is in the synthesis of methanol which was held in a single reactor. Carbonylation and hydrogenolysis reactions carried out in the same reactor one. These processes were analyzed in term of technical process, material and energy

  4. Direct Methanol Fuel Cell, DMFC

    Directory of Open Access Journals (Sweden)

    Amornpitoksuk, P.

    2003-09-01

    Full Text Available Direct Methanol Fuel Cell, DMFC is a kind of fuel cell using methanol as a fuel for electric producing. Methanol is low cost chemical substance and it is less harmful than that of hydrogen fuel. From these reasons it can be commercial product. The electrocatalytic reaction of methanol fuel uses Pt-Ru metals as the most efficient catalyst. In addition, the property of membrane and system designation are also effect to the fuel cell efficient. Because of low power of methanol fuel cell therefore, direct methanol fuel cell is proper to use for the energy source of small electrical devices and vehicles etc.

  5. 乙醇在新型Mo/C催化剂上的气相羰基化反应%Vapor Phase Carbonylation of Ethanol over Novel Mo/C Catalyst

    Institute of Scientific and Technical Information of China (English)

    何红运; 彭峰

    2000-01-01

    @@ The carbonylation of alcohol to acid or ester is an important process in the chemical industry. The Monsanto process for acetic acid via the homoge neous carbonylation of methanol is an example of the largest scale commercial application of this route[1].Recently, ethanol carbonylation for manufacturing propionic acid and ethyl propionate became an at tractive approach, and many research efforts were made for an appropriate catalyst to carry out the va por phase carbonylation under atmospheric pres sure[2~4]. Although an iodide-promoted Ni/C cata lyst is found to exhibit satisfactory activity and se lectivity for the vapor phase carbonylation of ethanol, it is affected by the disadvantages associat ed with a highly corrosive reaction medium and dif ficult product separation owing to the use of ethyl iodide as promoter. There has been little success in finding heterogeneous or homogeneous catalyst that can operate effectively without a halide promoter[5].

  6. Carbonyl compounds indoors in a changing climate

    Directory of Open Access Journals (Sweden)

    Brimblecombe Peter

    2012-03-01

    Full Text Available Abstract Background Formic acid, acetic acid and formaldehyde are important compounds in the indoor environment because of the potential for these acids to degrade calcareous materials (shells, eggs, tiles and geological specimens, paper and corrode or tarnish metals, especially copper and lead. Carbonyl sulfide tarnishes both silver and copper encouraging the formation of surface sulfides. Results Carbonyls are evolved more quickly at higher temperatures likely in the Cartoon Gallery at Knole, an important historic house near Sevenoaks in Kent, England where the study is focused. There is a potential for higher concentrations to accumulate. However, it may well be that in warmer climates they will be depleted more rapidly if ventilation increases. Conclusions Carbonyls are likely to have a greater impact in the future.

  7. The toxicity of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Tephly, T.R. (Univ. of Iowa, Iowa City (USA))

    1991-01-01

    Methanol toxicity in humans and monkeys is characterized by a latent period of many hours followed by a metabolic acidosis and ocular toxicity. This is not observed in most lower animals. The metabolic acidosis and blindness is apparently due to formic acid accumulation in humans and monkeys, a feature not seen in lower animals. The accumulation of formate is due to a deficiency in formate metabolism which is, in turn, related, in part, to low hepatic tetrahydrofolate (H{sub 4}folate). An excellent correlation between hepatic H{sub 4} folate and formate oxidation rates has been shown within and across species. Thus, humans and monkeys possess low hepatic H{sub 4}folate levels, low rates of formate oxidation and accumulation of formate after methanol. Formate, itself, produces blindness in monkeys in the absence of metabolic acidosis. In addition to low hepatic H{sub 4}folate concentrations, monkeys and humans also have low hepatic 10-formyl H{sub 4}folate dehydrogenase levels, the enzyme which is the ultimate catalyst for conversion of formate to carbon dioxide. This review presents the basis for the role of folic acid-dependent reactions in the regulation of methanol toxicity.

  8. Millimeter wave spectra of carbonyl cyanide ⋆

    Science.gov (United States)

    Bteich, S.B.; Tercero, B.; Cernicharo, J.; Motiyenko, R.A.; Margulès, L.; Guillemin, J.-C.

    2016-01-01

    Context More than 30 cyanide derivatives of simple organic molecules have been detected in the interstellar medium, but only one dicarbonitrile has been found and that very recently. There is still a lack of high-resolution spectroscopic data particularly for dinitriles derivatives. The carbonyl cyanide molecule is a new and interesting candidate for astrophysical detection. It could be formed by the reaction of CO and CN radicals, or by substitution of the hydrogen atom by a cyano group in cyanoformaldehyde, HC(=O)CN, that has already been detected in the interstellar medium. Aims The available data on the rotational spectrum of carbonyl cyanide is limited in terms of quantum number values and frequency range, and does not allow accurate extrapolation of the spectrum into the millimeter-wave range. To provide a firm basis for astrophysical detection of carbonyl cyanide we studied its millimeter-wave spectrum. Methods The rotational spectrum of carbonyl cyanide was measured in the frequency range 152 - 308 GHz and analyzed using Watson’s A- and S-reduction Hamiltonians. Results The ground and first excited state of v5 vibrational mode were assigned and analyzed. More than 1100 distinct frequency lines of the ground state were fitted to produce an accurate set of rotational and centrifugal distortion constants up to the eighth order. The frequency predictions based on these constants should be accurate enough for astrophysical searches in the frequency range up to 500 GHz and for transition involving energy levels with J ≤ 100 and Ka ≤ 42. Based on the results we searched for interstellar carbonyl cyanide in available observational data without success. Thus, we derived upper limits to its column density in different sources. PMID:27738349

  9. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-01-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 seconds. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  10. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-05-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 s. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  11. Methane to acetic acid over Cu-exchanged zeolites: mechanistic insights from a site-specific carbonylation reaction.

    Science.gov (United States)

    Narsimhan, Karthik; Michaelis, Vladimir K; Mathies, Guinevere; Gunther, William R; Griffin, Robert G; Román-Leshkov, Yuriy

    2015-02-11

    The selective low temperature oxidation of methane is an attractive yet challenging pathway to convert abundant natural gas into value added chemicals. Copper-exchanged ZSM-5 and mordenite (MOR) zeolites have received attention due to their ability to oxidize methane into methanol using molecular oxygen. In this work, the conversion of methane into acetic acid is demonstrated using Cu-MOR by coupling oxidation with carbonylation reactions. The carbonylation reaction, known to occur predominantly in the 8-membered ring (8MR) pockets of MOR, is used as a site-specific probe to gain insight into important mechanistic differences existing between Cu-MOR and Cu-ZSM-5 during methane oxidation. For the tandem reaction sequence, Cu-MOR generated drastically higher amounts of acetic acid when compared to Cu-ZSM-5 (22 vs 4 μmol/g). Preferential titration with sodium showed a direct correlation between the number of acid sites in the 8MR pockets in MOR and acetic acid yield, indicating that methoxy species present in the MOR side pockets undergo carbonylation. Coupled spectroscopic and reactivity measurements were used to identify the genesis of the oxidation sites and to validate the migration of methoxy species from the oxidation site to the carbonylation site. Our results indicate that the Cu(II)-O-Cu(II) sites previously associated with methane oxidation in both Cu-MOR and Cu-ZSM-5 are oxidation active but carbonylation inactive. In turn, combined UV-vis and EPR spectroscopic studies showed that a novel Cu(2+) site is formed at Cu/Al <0.2 in MOR. These sites oxidize methane and promote the migration of the product to a Brønsted acid site in the 8MR to undergo carbonylation.

  12. Methanol - alternative fuel road traffic

    Energy Technology Data Exchange (ETDEWEB)

    Muendler, H.

    1980-09-01

    This brochure names the fuel properties that are required for road traffic, discusses the replacement of petrol by methanol, discusses the possibilities of manufacturing methanol, draws up a timetable and an organigram for a (M-15) large scale test and compares costs of petrol, methanol, synthesis process petrol and hydrogenation process petrol. Furthermore, the technical requirements of vehicles as well as test results of exhaust gas emissions are also discussed.

  13. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfact......A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts...... by the competition between chain‐branching and ‐propagating steps; modeling predictions are particularly sensitive to the branching fraction for the OCS + O reaction to form CO + SO or CO2 + S....

  14. Palladium-catalyzed Reppe carbonylation.

    Science.gov (United States)

    Kiss, G

    2001-11-01

    is typically more available and less expensive (for industrial applications CO is most often separated from syngas). (4) The acid component of the hydroesterification catalyst makes the process corrosive. It would be desirable to develop new hydroesterification catalysts that do not require acid stabilizer/activity booster. Clearly, any new hydroesterification technology will directly compete with the hydroformylation route. This is especially true for olefin feeds, since both processes add one CO to the olefin, yielding oxygenates that can be converted into identical products. For some niche applications, like the production of MMA from propyne, hydroesterification seems to have an advantage as compared to hydroformylation due to the high activity and selectivity of the Pd(OAc)2/(2-pyridyl)diphenylphosphine catalyst. Since hydroesterification is an emerging technology, it is reasonable to assume that the potential for improvement is greater than in the mature hydroformylation. It is therefore possible that hydroesterification will become competitive in the future; thus, continued effort in the field is warranted.

  15. Methylnaltrexone bromide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Xinbo Zhou

    2012-03-01

    Full Text Available In the title compound [systematic name: (4R,4aS,7aR,12bS-3-cyclopropylmethyl-4a,9-hydroxy-7-oxo-2,3,4,4a,5,6,7,7a-octahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-3-ium bromide methanol monosolvate], C21H26NO4+·Br−·CH3OH, two of the three six-membered rings adopt chair conformations while the third, which contains a C=C double bond, adopts an approximate half-boat conformation. The 2,3-dihydrofuran ring adopts an envelope conformation. In the crystal, the components are linked by O—H...O and O—H...Br hydrogen bonds. The absolute stereochemistry was inferred from one of the starting materials.

  16. Methanol synthesis beyond chemical equilibrium

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Winkelman, J. G. M.; Wilbers, E.; Assink, D.; Lemmens, K. P. J.; Heeres, H. J.

    2013-01-01

    In commercial methanol production from syngas, the conversion is thermodynamically limited to 0.3-0.7 leading to large recycles of non-converted syngas. This problem can be overcome to a significant extent by in situ condensation of methanol during its synthesis which is possible nowadays due to the

  17. Methanol as an energy carrier

    Energy Technology Data Exchange (ETDEWEB)

    Biedermann, P.; Grube, T.; Hoehlein, B. (eds.)

    2006-07-01

    For the future, a strongly growing energy demand is expected in the transport sector worldwide. Economically efficient oil production will run through a maximum in the next decade. Higher fuel prices and an environmentally desirable reduction of emissions will increase the pressure for reducing fuel consumption and emissions in road traffic. These criteria show the urgent necessity of structural changes in the fuel market. Due to its advantages concerning industrial-scale production, storage and global availability, methanol has the short- to medium-term potential for gaining increased significance as a substitution product in the energy market. Methanol can be produced both from fossil energy sources and from biomass or waste materials through the process steps of synthesis gas generation with subsequent methanol synthesis. Methanol has the potential to be used in an environmentally friendly manner in gasoline/methanol mixtures for flexible fuel vehicles with internal combustion engines and in diesel engines with pure methanol. Furthermore, it can be used in fuel cell vehicles with on-board hydrogen production in direct methanol fuel cell drives, and in stationary systems for electricity and heat generation as well as for hydrogen production. Finally, in portable applications it serves as an energy carrier for electric power generation. In this book, the processes for the production and use of methanol are presented and evaluated, markets and future options are discussed and issues of safety and environmental impacts are addressed by a team of well-known authors. (orig.)

  18. Carbonyl Emissions from Gasoline and Diesel Motor Vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Destaillats, Hugo; Jakober, Chris A.; Robert, Michael A.; Riddle, Sarah G.; Destaillats, Hugo; Charles, M. Judith; Green, Peter G.; Kleeman, Michael J.

    2007-12-01

    Carbonyls from gasoline powered light-duty vehicles (LDVs) and heavy-duty diesel powered vehicles (HDDVs) operated on chassis dynamometers were measured using an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery, 4-fluorobenzaldehyde forcarbonyls and 6-fluoro-4-chromanone for>_C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 ? 2000 ?g/L fuel for LDVs and 1.8 - 27000 mu g/L fuel for HDDVs. Gas-phase species accounted for 81-95percent of the total carbonyls from LDVs and 86-88percent from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19percent of particulate organic carbon (POC) emissions from low-emission LDVs and 37percent of POC emissions from three-way catalyst equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9percent depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas- and particle-phase under the dilution factors of 126-584 used in the current study.

  19. Depolymerization of polyethylene terephthalate in supercritical methanol

    Science.gov (United States)

    Goto, Motonobu; Koyamoto, Hiroshi; Kodama, Akio; Hirose, Tsutomu; Nagaoka, Shoji

    2002-11-01

    The degradation of polyethylene terephthalate (PET) in supercritical methanol was investigated with the aim of developing a process for chemical recycling of waste plastics. A batch reactor was used at temperatures of 573-623 K under an estimated pressure of 20 MPa for a reaction time of 2-120 min. PET was decomposed to its monomers, dimethyl terephthalate and ethylene glycol, by methanolysis in supercritical methanol. The reaction products were analysed using size-exclusion chromatography, gas chromatography-mass spectrometry, and reversed-phase liquid chromatography. The molecular weight distribution of the products was obtained as a function of reaction time. The yields of monomer components of the decomposition products including by-products were measured. Continuous kinetics analysis was performed on the experimental data.

  20. Biodegradation of methanol vapor in a biofilter

    Institute of Scientific and Technical Information of China (English)

    Durai Arulneyam; T. Swaminathan

    2003-01-01

    Volatile organic compounds (VOCs) are a new class of air pollutants posing threat to the environment. Newer technologies are being developed for their control among which biofiltration seem to be most attractive. Biofiltration of methanol vapor from air stream was evaluated in this study. Experimental investigations were conducted on a laboratory scale biofilter, containing mixture of compost and polystyrene inert particles as the filter materials. Mixed consortium of activated sludge was used as an inoculum. The continuous performance of biofilter for methanol removal was monitored for different concentrations and flow rates. The removal efficiencies decreased at higher concentrations and higher gas flow rates. A maximum elimination capacity of 85 g/(m3.h) was achieved. The response of biofilter to upset loading operation showed that the biofilm in the biofilters was quite stable and quickly adapted to adverse operational conditions.

  1. Pattern of occurrence and occupancy of carbonylation sites in proteins

    DEFF Research Database (Denmark)

    Rao, R Shyama Prasad; Møller, Ian Max

    2011-01-01

    Proteins are targets for modification by reactive oxygen species, and carbonylation is an important irreversible modification that increases during oxidative stress. While information on protein carbonylation is accumulating, its pattern is not yet understood. We have made a meta-analysis of the ......Proteins are targets for modification by reactive oxygen species, and carbonylation is an important irreversible modification that increases during oxidative stress. While information on protein carbonylation is accumulating, its pattern is not yet understood. We have made a meta...... sites. Comparison of metal-catalyzed oxidation of two closely related proteins indicates that this type of carbonylation might not be very specific in proteins. Interestingly, carbonylated sites show a very strong tendency to cluster together in the protein primary sequence hinting at some sort...

  2. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  3. Pollution survey of carbonyl compounds in train air

    Institute of Scientific and Technical Information of China (English)

    LU Hao; ZHU Lizhong

    2007-01-01

    The train iS an important vehicle in China,but its air quality has important impacts on passengers' health.In this work,pollution from carbonyl compounds was measured in the air of six trains.The obiectives of this work were to investigate carbonyl compound levels in selected air from trains,identify their emission sources,and assess the intake of carbonyl compounds for passengers.The methods for sampling and analyzing 10 carbonyl compounds such as formaldehyde,acetaldehyde,acrolein,acetone,propionalde hyde,crotonaldehyde,butyraldehyde,benzaldehyde,cyclo hexanone,and valeraldehyde in indoor air were proposed with the sampling efficiency,recovery,and detection limit being 92%-100%,91%-104%,and 0.26-0.82 ng/m3,respec tively.It was indicated that the total concentrations of carbonyl compounds were 0.159-0.2828 mg/m3 with the average concentration of 0.2330 mg/m3.The average concen trations of formaldehyde.acetaldehyde and acetone were 0.0922,0.0499,and 0.0580 mg/m3,accounting for 42.6%,21.4%.and 24.9% of the total concentrations of carbonyl compounds,respectively.The carbonyl compounds probably came from woodwork and cigarette smoking.The intake of carbonyl compounds for the passengers was approximately 0.043-0.076 mg/h.The carbonyl compounds in train air could be harmful to human health.

  4. Effect of hydrogen atoms on the structures of trinuclear metal carbonyl clusters: trinuclear manganese carbonyl hydrides.

    Science.gov (United States)

    Liu, Xian-mei; Wang, Chao-yang; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2009-05-18

    The structures of the trinuclear manganese carbonyl hydrides H(3)Mn(3)(CO)(n) (n = 12, 11, 10, 9) have been investigated by density functional theory (DFT). Optimization of H(3)Mn(3)(CO)(12) gives the experimentally known structure in which all carbonyl groups are terminal and each edge of a central Mn(3) equilateral triangle is bridged by a single hydrogen atom. This structure establishes the canonical distance 3.11 A for the Mn-Mn single bond satisfying the 18-electron rule. The central triangular (mu-H)(3)Mn(3) unit is retained in the lowest energy structure of H(3)Mn(3)(CO)(11), which may thus be derived from the H(3)Mn(3)(CO)(12) structure by removal of a carbonyl group with concurrent conversion of one of the remaining carbonyl groups into a semibridging carbonyl group to fill the resulting hole. The potential energy surface of H(3)Mn(3)(CO)(10) is relatively complicated with six singlet and five triplet structures. One of the lower energy H(3)Mn(3)(CO)(10) structures has one of the hydrogen atoms bridging the entire Mn(3) triangle and the other two hydrogen atoms bridging Mn-Mn edges. This H(3)Mn(3)(CO)(10) structure achieves the favored 18-electron configuration with a very short MnMn triple bond of 2.36 A. The other low energy H(3)Mn(3)(CO)(10) structure retains the (mu-H)(3)Mn(3) core of H(3)Mn(3)(CO)(12) but has a unique six-electron donor eta(2)-mu(3) carbonyl group bridging the entire Mn(3) triangle similar to the unique carbonyl group in the known compound Cp(3)Nb(3)(CO)(6)(eta(2)-mu(3)-CO). For H(3)Mn(3)(CO)(9) a structure with a central (mu(3)-H)(2)Mn(3) trigonal bipyramid lies >20 kcal/mol below any of the other structures. Triplet structures were found for the unsaturated H(3)Mn(3)(CO)(n) (n = 11, 10, 9) systems but at significantly higher energies than the lowest lying singlet structures.

  5. Characterization of a condensed-phase membrane introduction mass spectrometry (CP-MIMS) interface using a methanol acceptor phase coupled with electrospray ionization for the continuous on-line quantitation of polar, low-volatility analytes at trace levels in complex aqueous samples.

    Science.gov (United States)

    Duncan, K D; McCauley, E P B; Krogh, E T; Gill, C G

    2011-05-15

    We report the development and application of a capillary hollow fibre membrane interface using methanol as an acceptor phase to deliver target analytes to an electrospray ionization source and a triple quadrupole mass spectrometer. Superior fluid handling systems lead to greater signal stability and membrane integrity for the continuous on-line monitoring of polar and charged analytes in complex aqueous samples with detection limits in the parts-per-trillion to parts-per-billion range. The system can be operated in either a continuous flow or a stopped acceptor flow mode - the latter giving rise to greater sensitivity. We report detection limits, enrichment factors and signal response times for selected analytes with polydimethylsiloxane and Nafion® polymer membrane interfaces. In addition, we demonstrate the use of this interface to detect pharmaceuticals and other contaminants in natural water and artificial urine. The improved sensitivity and analytical response times of our CP-MIMS system make it possible to continuously monitor dynamic chemical systems with temporal resolutions on the order of minutes. Presented is a comparison of the performance of CP-MIMS versus direct infusion electrospray ionization, demonstrating the potential advantages over direct infusion for trace analyte measurements in complex, high ionic strength samples. Furthermore, by continuously flowing a reaction mixture in a closed loop over the interface, we demonstrate the use of the system as an in situ reaction-monitoring platform for the chlorination of a model organic compound in aqueous solution. Copyright © 2011 John Wiley & Sons, Ltd.

  6. Carbonyl sulfide: No remedy for global warming

    Science.gov (United States)

    Taubman, Steven J.; Kasting, James F.

    1995-04-01

    The enhancement of the stratospheric aerosol layer caused by the eruption of Mt. Pinatubo (June 15, 1991), and the subsequent cooling of the earth's lower atmosphere [Dutton and Christy, 1992; Minnis et al., 1993] shows that stratospheric aerosols can have a strong effect on the earth's climate. This supports the notion that the intentional enhancement of the stratospheric aerosol layer through increased carbonyl sulfide (OCS) emissions might be an effective means for counteracting global warming. Through the use of a one-dimensional photochemical model, we investigate what effect such a program might have on global average stratospheric ozone. In addition, we consider the impact of enhanced OCS emissions on rainwater acidity and on the overall health of both plants and animals. We find that while the warming produced by a single CO2 doubling (1 to 4°C) might be offset with ozone losses of less than 5%, any attempt to use carbonyl sulfide as a permanent solution to global warming could result in depletion of global average ozone by 30% or more. We estimate that in order to achieve cooling of 4°C rainwater pH would fall to between 3.5 and 3.8. Finally, a 4°C cooling at the surface will require that ambient near ground OCS levels rise to above 10 ppmv which is probably greater than the safe exposure limit for humans. Thus, enhanced OCS emissions do not provide an environmentally acceptable solution to the problem of global warming.

  7. Studies of methanol maser rings

    CERN Document Server

    Bartkiewicz, A; van Langevelde, H J; De Buizer, J M; Pihlström, Y

    2011-01-01

    We present the results of studies of a new class of 6.7 GHz methanol maser sources with a ring-like emission structure discovered recently with the EVN. We have used the VLA to search for water masers at 22 GHz and radio continuum at 8.4 GHz towards a sample of high-mass star forming regions showing a ring-like distribution of methanol maser spots. Using the Gemini telescopes we found mid-infrared (MIR) counterparts of five methanol rings with a resolution of 0."15. The centres of methanol maser rings are located within, typically, only 0."2 of the MIR emission peak, implying their physical relation with a central star. These results strongly support a scenario wherein the ring-like structures appear at the very early stage of massive star formation before either water-maser outflows or H II regions are seen.

  8. Gold/Iron Carbonyl Clusters for Tailored Au/FeOx Supported Catalysts

    Directory of Open Access Journals (Sweden)

    Stefania Albonetti

    2011-12-01

    Full Text Available A novel preparation method was developed for the preparation of gold/iron oxide supported catalysts using the bimetallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO16] and [NEt4][AuFe4(CO16] as precursors of highly dispersed nanoparticles over different supports. A series of catalysts with different metal loadings were prepared and tested in the complete oxidation of dichlorobenzene, toluene, methanol and in the preferential oxidation of CO in the presence of H2 (PROX as model reactions. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS point out the way the nature of the precursors and the thermal treatment conditions affected the dispersion of the active phase and their catalytic activity in the studied reactions.

  9. Carbonyl sulfide as an inverse tracer for biogenic organic carbon in gas and aerosol phases

    Science.gov (United States)

    de Gouw, J. A.; Warneke, C.; Montzka, S. A.; Holloway, J. S.; Parrish, D. D.; Fehsenfeld, F. C.; Atlas, E. L.; Weber, R. J.; Flocke, F. M.

    2009-03-01

    Carbonyl sulfide (COS) is a long-lived trace gas in the atmosphere with an oceanic source and a surface sink through the uptake by vegetation and soils. We demonstrate the use of COS as an inverse tracer for the impact of biogenic emissions on an air mass including the formation of secondary organic aerosol (SOA). Using airborne data from the summer of 2004 over the northeastern U.S., we find that air masses with reduced COS in the continental boundary layer had on average higher mixing ratios of biogenic VOCs (isoprene, monoterpenes, methanol) and their photo-oxidation products (methacrolein, methyl vinyl ketone, methyl furan and MPAN, a peroxyacyl nitrate derived from isoprene). Measurements of water-soluble organic carbon were only weakly correlated with COS, indicating that SOA formation from biogenic precursors was a small contribution to the total.

  10. Acute methanol toxicity in minipigs

    Energy Technology Data Exchange (ETDEWEB)

    Dorman, D.C.; Dye, J.A.; Nassise, M.P.; Ekuta, J.; Bolon, B.

    1993-01-01

    The pig has been proposed as a potential animal model for methanol-induced neuro-ocular toxicosis in humans because of its low liver tetrahydrofolate levels and slower rate of formate metabolism compared to those of humans. To examine the validity of this animal model, 12 4-month-old female minipigs (minipig YU) were given a single oral dose of water or methanol at 1.0, 2.5, or 5.0 g/kg body wt by gavage (n = 3 pigs/dose). Dose-dependent signs of acute methanol intoxication, which included mild CNS depression, tremors, ataxia, and recumbency, developed within 0.5 to 2.0 hr, and resolved by 52 hr. Methanol- and formate-dosed pigs did not develop optic nerve lesions, toxicologically significant formate accumulation, or metabolic acidosis. Based on results following a single dose, female minipigs do not appear to be overtly sensitive to methanol and thus may not be a suitable animal model for acute methanol-induced neuroocular toxicosis.

  11. Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs).

    Science.gov (United States)

    Cao, Kai; Murshid, Nimer; Wang, Xiaosong

    2015-04-01

    Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs) is difficult, mainly due to the instability of metal carbonyl complexes. Despite its challenge a number of MCMCOMs has been prepared by strategically using organometallic, organic, and polymer synthetic chemistry. Main contributions to this research field were reported by the groups of Tyler, Pannell, and Wang and are briefly summarized in this article.

  12. Bifunctional dendrons for multiple carbohydrate presentation via carbonyl chemistry

    Directory of Open Access Journals (Sweden)

    Davide Bini

    2014-07-01

    Full Text Available The synthesis of new dendrons of the generations 0, 1 and 2 with a double bond at the focal point and a carbonyl group at the termini has been carried out. The carbonyl group has been exploited for the multivalent conjugation to a sample saccharide by reductive amination and alkoxyamine conjugation.

  13. Characterization of oxidative carbonylation on recombinant monoclonal antibodies.

    Science.gov (United States)

    Yang, Yi; Stella, Cinzia; Wang, Weiru; Schöneich, Christian; Gennaro, Lynn

    2014-05-20

    In the biotechnology industry, oxidative carbonylation as a post-translational modification of protein pharmaceuticals has not been studied in detail. Using Quality by Design (QbD) principles, understanding the impact of oxidative carbonylation on product quality of protein pharmaceuticals, particularly from a site-specific perspective, is critical. However, comprehensive identification of carbonylation sites has so far remained a very difficult analytical challenge for the industry. In this paper, we report for the first time the identification of specific carbonylation sites on recombinant monoclonal antibodies with a new analytical approach via derivatization with Girard's Reagent T (GRT) and subsequent peptide mapping with high-resolution mass spectrometry. Enhanced ionization efficiency and high quality MS(2) data resulted from GRT derivatization were observed as key benefits of this approach, which enabled direct identification of carbonylation sites without any fractionation or affinity enrichment steps. A simple data filtering process was also incorporated to significantly reduce false positive assignments. Sensitivity and efficiency of this approach were demonstrated by identification of carbonylation sites on both unstressed and oxidized antibody bulk drug substances. The applicability of this approach was further demonstrated by identification of 14 common carbonylation sites on three highly similar IgG1s. Our approach represents a significant improvement to the existing analytical methodologies and facilitates extended characterization of oxidative carbonylation on recombinant monoclonal antibodies and potentially other protein pharmaceuticals in the biotechnology industry.

  14. Effect of methanol on the biofiltration of n-hexane.

    Science.gov (United States)

    Zehraoui, Abderrahman; Hassan, Ashraf Aly; Sorial, George A

    2012-06-15

    This study investigated the removal of recalcitrant compounds in the presence of a hydrophilic compound. n-Hexane is used as a model compound to represent hydrophobic compounds. Methanol has been introduced in mixture with n-hexane in order to increase the bioavailability of n-hexane in trickle-bed-air-biofilters (TBABs). The mixing ratios investigated were: 70% methanol:30% n-hexane, and 80% methanol:20% n-hexane by volume. n-Hexane loading rates (LRs) ranged from 0.9 to 13.2 g m(-3) h(-1). Methanol LRs varied from 4.6 to 64.5 g m(-3) h(-1) and from 2.3 to 45.2 g m(-3) h(-1) depending upon the mixing ratio used. Biofilter performance, effect of mixing ratios of methanol to n-hexane, removal profile along biofilter depth, COD/nitrogen consumption and CO(2) production were studied under continuous loading operation conditions. Results have shown that the degradation of n-hexane is significantly enhanced by the presence of methanol for n-hexane LRs less than 13.2 g m(-3) h(-1). For n-hexane LR greater than 13.2 g m(-3) h(-1), even though methanol had impacted n-hexane biodegradation, its removal efficiency was higher than our previous study for biodegradation of n-hexane alone, in presence of surfactant, or in presence of benzene. On the other hand, the degradation of methanol was not impacted by the presence of n-hexane.

  15. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  16. Unusual case of methanol poisoning

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, L.; Henderson, M. (St. James' s Univ. Hospital, Leeds (United Kingdom). Dept. of Chemical Pathology); Madi, S.; Mellor, L. (St. James' s Univ. Hospital, Leeds (United Kingdom). Dept. of Medicine, and Pharmacy)

    1993-01-09

    A 31-year-old man with a history of alcohol abuse presented to the accident and emergency department complaining of blurred vision. 4 h previously he had drunk 300 mL de-icer fluid. Electrolytes, urea, creatinine, glucose, and blood-gas analysis were normal. Measured osmolality, however, was 368 mosmol/kg with a calculated osmolality of 300 mosmol/kg, which indicated a greatly increased osmolar gap. He was therefore given 150 mL whisky and admitted. Methanol was later reported as 200 mg/dL. Ethylene glycol was not detected, but another glycol, propylene glycol, was present at 47 mg/dL. 10 h after ingestion an intravenous infusion of ethanol was started and he was hemodialysed for 7 h. After dialysis he was given a further 100 mL whisky and the rate of ethanol infusion was reduced to 11 g per h. Methanol and ethanol were measured twice daily until methanol was under 10/mg/dL: The recommendation is that blood ethanol be maintained between 100 and 200 mg/dL during treatment of methanol poisoning. This concentration was not achieved, presumably because of the high rate of ethanol metabolism often found in alcoholics. Antifreeze solutions commonly contain methanol and ethylene glycol. Sometimes propylene glycol is substituted because it has properties similar to those of ethylene glycol but is less toxic. The authors postulate that propylene glycol inhibited the metabolism of methanol in the patient, thus sparing him from the toxic effects of methanol.

  17. Metal-free carbonylations by photoredox catalysis.

    Science.gov (United States)

    Majek, Michal; Jacobi von Wangelin, Axel

    2015-02-01

    The synthesis of benzoates from aryl electrophiles and carbon monoxide is a prime example of a transition-metal-catalyzed carbonylation reaction which is widely applied in research and industrial processes. Such reactions proceed in the presence of Pd or Ni catalysts, suitable ligands, and stoichiometric bases. We have developed an alternative procedure that is free of any metal, ligand, and base. The method involves a redox reaction driven by visible light and catalyzed by eosin Y which affords alkyl benzoates from arene diazonium salts, carbon monoxide, and alcohols under mild conditions. Tertiary esters can also be prepared in high yields. DFT calculations and radical trapping experiments support a catalytic photoredox pathway without the requirement for sacrificial redox partners.

  18. Bench scale demonstration of the Supermethanol concept : The synthesis of methanol from glycerol derived syngas

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Assink, D.; Lemmens, K. P. J.; Heeres, H. J.

    2012-01-01

    An integrated process for the synthesis of methanol from aqueous glycerol involving reforming of the feed to syngas followed by methanol synthesis is successfully demonstrated in a continuous bench scale unit. Glycerol reforming was carried out at pressures of 24-27 MPa and temperatures of 948-998 K

  19. Reforming of methanol and glycerol in supercritical water

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Assink, D.; Heeres, H. J.

    2011-01-01

    Reforming of pure glycerol, crude glycerin, and methanol (pure and in the presence of Na(2)CO(3)) in supercritical water was investigated. Continuous experiments were carried out at temperatures between 450 and 650 degrees C, residence times between 6 and 173 s, and feed concentrations of 3-20 wt%.

  20. Scaledown of a methanol reactor

    Energy Technology Data Exchange (ETDEWEB)

    Berty, J.M.

    1983-07-01

    This article shows how it is possible to define operating conditions for pilot plants and development labs by scaling down a commercial reactor. Points out that scaledown consideration and experiment planning can be done in a similar manner for the boiling water-cooled, Lurgi-type reactor. Explains that although the design of large, single-train plants to produce methanol for fuel use has different economic objectives, product specifications, and technical constraints from the traditional commercial methanol plants, the same fundamental laws of thermodynamics and reaction kinetics apply to both types of operation.

  1. High throughput assay for evaluation of reactive carbonyl scavenging capacity

    Directory of Open Access Journals (Sweden)

    N. Vidal

    2014-01-01

    Full Text Available Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

  2. 16th Carbonyl Metabolism Meeting: from enzymology to genomics

    Directory of Open Access Journals (Sweden)

    Maser Edmund

    2012-12-01

    Full Text Available Abstract The 16th International Meeting on the Enzymology and Molecular Biology of Carbonyl Metabolism, Castle of Ploen (Schleswig-Holstein, Germany, July 10–15, 2012, covered all aspects of NAD(P-dependent oxido-reductases that are involved in the general metabolism of xenobiotic and physiological carbonyl compounds. Starting 30 years ago with enzyme purification, structure elucidation and enzyme kinetics, the Carbonyl Society members have meanwhile established internationally recognized enzyme nomenclature systems and now consider aspects of enzyme genomics and enzyme evolution along with their roles in diseases. The 16th international meeting included lectures from international speakers from all over the world.

  3. A New HPLC Method to Determine Carbonyl Compounds in Air

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, a new HPLC method was established to determine the carbonyl compounds in air. As the absorbent, 2, 4-dinitrophenylhydrazine (2, 4-DNPH) reacted with carbonyls specifically, which form the corresponding 2,4-dinitrophenylhydrazones, then analyzed by HPLC. The chromatographic conditions, the recovery rate, stability of samples, reagent blank, sampling efficiency were all studied systematically. The results showed that this established method had high sensitivity and good selectivity compared with other analytical methods, and it can determine ten carbonyl compounds in air in 26 min simultaneously.

  4. Catalytic gasification of bagasse for the production of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Baker, E.G.; Brown, M.D.; Robertus, R.J.

    1985-10-01

    The purpose of the study was to evaluate the technical and economic feasibility of catalytic gasification of bagasse to produce methanol. In previous studies, a catalytic steam gasification process was developed which converted wood to methanol synthesis gas in one step using nickel based catalysts in a fluid-bed gasifier. Tests in a nominal 1 ton/day process development unit (PDU) gasifier with these same catalysts showed bagasse to be a good feedstock for fluid-bed gasifiers, but the catalysts deactivated quite rapidly in the presence of bagasse. Laboratory catalyst screening tests showed K/sub 2/CO/sub 3/ doped on the bagasse to be a promising catalyst for converting bagasse to methanol synthesis gas. PDU tests with 10 wt % K/sub 2/CO/sub 3/ doped on bagasse showed the technical feasibility of this type of catalyst on a larger scale. A high quality synthesis gas was produced and carbon conversion to gas was high. The gasifier was successfully operated without forming agglomerates of catalyst, ash, and char in the gasifier. There was no loss of activity throughout the runs because catalysts is continually added with the bagasse. Laboratory tests showed about 80% of the potassium carbonate could be recovered and recycled with a simple water wash. An economic evaluation of the process for converting bagasse to methanol showed the required selling price of methanol to be significantly higher than the current market price of methanol. Several factors make this current evaluaton using bagasse as a feedstock less favorable: (1) capital costs are higher due to inflation and some extra costs required to use bagasse, (2) smaller plant sizes were considered so economies of scale are lost, and (3) the market price of methanol in the US has fallen 44% in the last six months. 24 refs., 14 figs., 16 tabs.

  5. Different Response of Carbonyl Carotenoids to Solvent Proticity Helps To Estimate Structure of the Unknown Carotenoid from Chromera velia.

    Science.gov (United States)

    Keşan, Gürkan; Durchan, Milan; Tichý, Josef; Minofar, Babak; Kuznetsova, Valentyna; Fuciman, Marcel; Šlouf, Václav; Parlak, Cemal; Polívka, Tomáš

    2015-10-01

    In order to estimate the possible structure of the unknown carbonyl carotenoid related to isofucoxanthin from Chromera velia denoted as isofucoxanthin-like carotenoid (Ifx-l), we employed steady-state and ultrafast time-resolved spectroscopic techniques to investigate spectroscopic properties of Ifx-l in various solvents. The results were compared with those measured for related carotenoids with known structure: fucoxanthin (Fx) and isofucoxanthin (Ifx). The experimental data were complemented by quantum chemistry calculations and molecular modeling. The data show that Ifx-l must have longer effective conjugation length than Ifx. Yet, the magnitude of polarity-dependent changes in Ifx-l is larger than for Ifx, suggesting significant differences in structure of these two carotenoids. The most interesting spectroscopic feature of Ifx-l is its response to solvent proticity. The transient absorption data show that (1) the magnitude of the ICT-like band of Ifx-l in acetonitrile is larger than in methanol and (2) the S1/ICT lifetime of Ifx-l in acetonitrile, 4 ps, is markedly shorter than in methanol (10 ps). This is opposite behavior than for Fx and Ifx whose S1/ICT lifetimes are always shorter in protic solvent methanol (20 and 13 ps) than in aprotic acetonitrile (30 and 17 ps). Comparison with other carbonyl carotenoids reported earlier showed that proticity response of Ifx-l is consistent with presence of a conjugated lactone ring. Combining the experimental data and quantum chemistry calculations, we estimated a possible structure of Ifx-l.

  6. Deposition of carbonyl sulphide to soils

    Science.gov (United States)

    Kluczewski, S. M.; Brown, K. A.; Bel, J. N. B.

    Carbonyl sulphide (COS) is a trace constituent of the atmosphere and is also the main form in which 35S is released from CO 2-cooled nuclear reactors. Measurements of its deposition velocity ( Vg) are therefore important for validating radiological dose models and for interpreting the role of COS in the global S cycle. The Vg of [ 35S]COS to thin layers of several contrasting soils was measured in a through-flow fumigation system. Deposition velocity was not significantly affected by soil type, although deposition to moist soil was significantly greater ( P dried soils, mean values being 5.71 × 10 -6 ms -1 and 3.06 × 10 -6 ms -1, respectively. The results obtained are about three orders of magnitude smaller than published Vg values for SO 2 to similar soils, which suggests that uptake by soils is not a major sink for atmospheric COS. The results are consistent with the hypothesis that deposition to soil of [ 35S]COS from nuclear reactors is unlikely to contribute significantly to radiation dose from the food chain pathway. The reduction in Vg observed in heat-treated soils indicates a microbial involvement in uptake. However, it seems unlikely that microbial metabolism is the rate-controlling step, since stimulation of the microflora by the addition of nutrients did not increase COS deposition.

  7. Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol

    DEFF Research Database (Denmark)

    Alberico, E.; Nielsen, Martin

    2015-01-01

    The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous...

  8. Study on Carbonyl Emissions of Diesel Engine Fueled with Biodiesel

    National Research Council Canada - National Science Library

    Ruina Li; Zhong Wang; Guangju Xu

    2017-01-01

      Biodiesel is a kind of high-quality alternative fuel of diesel engine. In this study, biodiesel and biodiesel/diesel blend were used in a single cylinder diesel engine to study the carbonyl emissions...

  9. Theoretical Estimate of Hydride Affinities of Aromatic Carbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

    AI Teng; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Aromatic carbonyl compounds are one type of the most important organic compounds, and the reductions ofthem by hydride agents such as LiAlH4 or NaBH4 are widely used in organic synthesis. The reactivity of carbonyl compounds generally increases in the following order: ketone < aldehyde, and amide < acid < ester < acid halide, which could be related to their hydride affinities (HA). In the previous paper, Robert[1] calculated the absolute HAof a series of small non-aromatic carbonyl compounds. In this paper, we use DFT method at B3LYP/6-311 + + G (2d, 2p)∥B3LYP/6-31 + G* level to estimate hydride affinities of five groups of aromatic carbonyl compounds. The detailed results are listed in Table 1.

  10. DNA damage by carbonyl stress in human skin cells

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, Michael J.; Wondrak, Georg T.; Laurean, Daniel Cervantes; Jacobson, Myron K.; Jacobson, Elaine L

    2003-01-28

    Reactive carbonyl species (RCS) are potent mediators of cellular carbonyl stress originating from endogenous chemical processes such as lipid peroxidation and glycation. Skin deterioration as observed in photoaging and diabetes has been linked to accumulative protein damage from glycation, but the effects of carbonyl stress on skin cell genomic integrity are ill defined. In this study, the genotoxic effects of acute carbonyl stress on HaCaT keratinocytes and CF3 fibroblasts were assessed. Administration of the {alpha}-dicarbonyl compounds glyoxal and methylglyoxal as physiologically relevant RCS inhibited skin cell proliferation, led to intra-cellular protein glycation as evidenced by the accumulation of N{sup {epsilon}}-(carboxymethyl)-L-lysine (CML) in histones, and caused extensive DNA strand cleavage as assessed by the comet assay. These effects were prevented by treatment with the carbonyl scavenger D-penicillamine. Both glyoxal and methylglyoxal damaged DNA in intact cells. Glyoxal caused DNA strand breaks while methylglyoxal produced extensive DNA-protein cross-linking as evidenced by pronounced nuclear condensation and total suppression of comet formation. Glycation by glyoxal and methylglyoxal resulted in histone cross-linking in vitro and induced oxygen-dependent cleavage of plasmid DNA, which was partly suppressed by the hydroxyl scavenger mannitol. We suggest that a chemical mechanism of cellular DNA damage by carbonyl stress occurs in which histone glycoxidation is followed by reactive oxygen induced DNA stand breaks. The genotoxic potential of RCS in cultured skin cells and its suppression by a carbonyl scavenger as described in this study have implications for skin damage and carcinogenesis and its prevention by agents selective for carbonyl stress.

  11. Carbonyl-Olefin Exchange Reaction and Related Chemistry

    Science.gov (United States)

    Jossifov, Christo; Kalinova, Radostina

    A new carbon—carbon double bond forming reaction (carbonyl olefin exchange reaction) mediated by transition metal catalytic systems has been discovered. The catalytic systems used (transition metal halides or oxohalides alone or in combination with Lewis acids) are active only in the case when the two reacting groups are in one molecules and are conjugated. In addition these systems accelerate other reactions which run simultaneously with the carbonyl olefin metathesis rendering a detailed investigation of the process very complicated.

  12. Effects of different mixing ratios on emissions from passenger cars fueled with methanol/gasoline blends.

    Science.gov (United States)

    Zhao, Hong; Ge, Yunshan; Tan, Jianwei; Yin, Hang; Guo, Jiadong; Zhao, Wei; Dai, Peipei

    2011-01-01

    Regulated and unregulated emissions from four passenger cars fueled with methanol/gasoline blends at different mixing ratios (M15, M20, M30, M50, M85 and M100) were tested over the New European Driving Cycle (NEDC). Volatile organic compounds (VOCs) were sampled by Tenax TA and analyzed by thermal desorption-gas chromatograph/mass spectrometer (TD-GC/MS). Carbonyls were trapped on dinitrophenylhydrazine (DNPH) cartridges and analyzed by high performance liquid chromatography (HPLC). The results showed that total emissions of VOCs and BTEX (benzene, toluene, ethylbenzene, p, m, o-xylene) from all vehicles fueled with methanol/gasoline blends were lower than those from vehicles fueled with only gasoline. Compared to the baseline, the use of M85 decreased BTEX emissions by 97.4%, while the use of M15 decreased it by 19.7%. At low-to-middle mixing ratios (M15, M20, M30 and M50), formaldehyde emissions showed a slight increase while those of high mixing ratios (M85 and M100) were three times compared with the baseline gasoline only. When the vehicles were retrofitted with new three-way catalytic converters (TWC), emissions of carbon monoxide (CO), total hydrocarbon (THC), and nitrogen oxides (NO(x)) were decreased by 24%-50%, 10%-35%, and 24%-58% respectively, compared with the cars using the original equipment manufacture (OEM) TWC. Using the new TWC, emissions of formaldehyde and BTEX were decreased, while those of other carbonyl increased. It is necessary that vehicles fueled with methanol/gasoline blends be retrofitted with a new TWC. In addition, the specific reactivity of emissions of vehicles fueled with M15 and retrofitted with the new TWC was reduced from 4.51 to 4.08 compared to the baseline vehicle. This indicates that the use of methanol/gasoline blend at a low mixing ratio may have lower effect on environment than gasoline.

  13. Carbonyl species characteristics during the evaporation of essential oils

    Science.gov (United States)

    Chiang, Hsiu-Mei; Chiu, Hua-Hsien; Lai, Yen-Ming; Chen, Ching-Yen; Chiang, Hung-Lung

    2010-06-01

    Carbonyls emitted from essential oils can affect the air quality when they are used in indoors, especially under poor ventilation conditions. Lavender, lemon, rose, rosemary, and tea tree oils were selected as typical and popular essential oils to investigate in terms of composition, thermal characteristics and fifteen carbonyl constituents. Based on thermogravimetric (TG) analysis, the activation energy was 7.6-8.3 kcal mol -1, the reaction order was in the range of 0.6-0.7 and the frequency factor was 360-2838 min -1. Formaldehyde, acetaldehyde, acetone, and propionaldehyde were the dominant carbonyl compounds, and their concentrations were 0.034-0.170 ppm. The emission factors of carbonyl compounds were 2.10-3.70 mg g -1, and acetone, propionaldehyde, acetaldehyde, and formaldehyde accounted for a high portion of the emission factor of carbonyl compounds in essential oil exhaust. Some unhealthy carbonyl species such as formaldehyde and valeraldehyde, were measured at low-temperature during the vaporization of essential oils, indicating a potential effect on indoor air quality and human health.

  14. Enhanced methanol utilization in direct methanol fuel cell

    Science.gov (United States)

    Ren, Xiaoming; Gottesfeld, Shimshon

    2001-10-02

    The fuel utilization of a direct methanol fuel cell is enhanced for improved cell efficiency. Distribution plates at the anode and cathode of the fuel cell are configured to distribute reactants vertically and laterally uniformly over a catalyzed membrane surface of the fuel cell. A conductive sheet between the anode distribution plate and the anodic membrane surface forms a mass transport barrier to the methanol fuel that is large relative to a mass transport barrier for a gaseous hydrogen fuel cell. In a preferred embodiment, the distribution plate is a perforated corrugated sheet. The mass transport barrier may be conveniently increased by increasing the thickness of an anode conductive sheet adjacent the membrane surface of the fuel cell.

  15. Fermentation of methanol in the sheep rumen.

    OpenAIRE

    Pol, A.; Demeyer, D. I.

    1988-01-01

    Sheep fed a hay-concentrate diet were adapted to pectin administration and ruminal infusion of methanol. Both treatments resulted in a strong increase in the rate of methanogenesis from methanol. Quantitative data show that methanol was exclusively converted into methane. Treatments did not influence ruminal volatile fatty acid percentages.

  16. The fate of methanol in anaerobic bioreactors

    NARCIS (Netherlands)

    Florencio, L.

    1994-01-01

    Methanol is an important component of certain industrial wastewaters. In anaerobic environments, methanol can be utilized by methanogens and acetogens. In wastewater treatment plants, the conversion of methanol into methane is preferred because this conversion is responsible for chemical

  17. The fate of methanol in anaerobic bioreactors.

    NARCIS (Netherlands)

    Florencio, L.

    1994-01-01

    Methanol is an important component of certain industrial wastewaters. In anaerobic environments, methanol can be utilized by methanogens and acetogens. In wastewater treatment plants, the conversion of methanol into methane is preferred because this conversion is responsible for chemical oxygen dema

  18. Withanolide artifacts formed in methanol.

    Science.gov (United States)

    Cao, Cong-Mei; Zhang, Huaping; Gallagher, Robert J; Timmermann, Barbara N

    2013-11-22

    Methanol solutions of the main withanolides (6-8) naturally present in Physalis longifolia yielded five artificial withanolides (1-5), including three new compounds (1-3). Withanolides 1 and 2 were identified as intramolecular Michael addition derivatives, while withanolides 3-5 were the result of intermolecular Michael addition. A comprehensive literature investigation was conducted to identify potential withanolide Michael addition artifacts isolated from Solanaceous species to date.

  19. Dispersion Performance of Methanol-Diesel Emulsiifed Fuel Prepared by High Gravity Technology

    Institute of Scientific and Technical Information of China (English)

    Jiao Weizhou; Li Jing; Liu Youzhi; Zhang Qiaoling; Liu Wenli; Xu Chengcheng; Guo Liang

    2014-01-01

    A new continuous process for preparing methanol-diesel emulsified fuel with an Impinging Stream-Rotating Packed Bed is proposed. The droplet size of dispersed phase (methanol) of the emulsiifed fuel has a signiifcant effect on the combustion of methanol-diesel emulsiifed fuel. In this paper, the methanol-diesel emulsiifed fuel uses diesel as the continu-ous phase and methanol as the dispersed phase. The Sauter mean diameter of the dispersed phase of methanol-diesel emulsi-ifed fuel was characterized with microphotography and arithmetic method. The experimental result showed that the Sauter mean diameter of the dispersed phase, which was decreased with the augmentation of the high gravity factor, liquid lfow rate and emulsiifer dosage, was inversely proportional to the methanol content. The Sauter mean diameter of the dispersed phase can be controlled and adjusted in the range of 12-40μm through the change of operating conditions. The correlative expressions of the Sauter mean diameter of emulsiifed fuel were obtained and the calculated values agreed well with the ex-perimental values.

  20. A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

    Science.gov (United States)

    Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

    The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid

  1. Determination of Carbonyl Compounds in Exhaled Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Moldoveanu S

    2014-12-01

    Full Text Available This paper presents the findings on a quantitative evaluation of carbonyl levels in exhaled cigarette smoke from human subjects. The cigarettes evaluated include products with 5.0 mg ‘tar’, 10.6 mg ‘tar’ and 16.2 mg ‘tar’, where ‘tar’ is defined as the weight of total wet particulate matter (TPM minus the weight of nicotine and water, and the cigarettes are smoked following U.S. Federal Trade Commission (FTC recommendations. The measured levels of carbonyls in the exhaled smoke were compared with calculated yields of carbonyls in the inhaled smoke and a retention efficiency was obtained. The number of human subjects included a total of ten smokers for the 10.6 mg ‘tar’, five for the 16.2 mg ‘tar’, and five for the 5.0 mg ‘tar’ product, each subject smoking three cigarettes. The analyzed carbonyl compounds included several aldehydes (formaldehyde, acetaldehyde, acrolein, propionaldehyde, crotonaldehyde and n-butyraldehyde, and two ketones (acetone and 2-butanone. The smoke collection from the human subjects was vacuum assisted. Exhaled smoke was collected on Cambridge pads pretreated with a solution of dinitrophenylhydrazine (DNPH followed by high performance liquid chromatography (HPLC analysis of the dinitrophenylhydrazones of the carbonyl compounds. The cigarette butts from the smokers were collected and analyzed for nicotine. The nicotine levels for the cigarette butts from the smokers were used to calculate the level of carbonyls in the inhaled smoke, based on calibration curves. These were generated separately by analyzing the carbonyls in smoke and the nicotine in the cigarette butts obtained by machine smoking under different puffing regimes. The comparison of the level of carbonyl compounds in exhaled smoke with that from the inhaled smoke showed high retention of all the carbonyls. The retention of aldehydes was above 95% for all three different ‘tar’ levels cigarettes. The ketones were retained with a

  2. New methodology for removing carbonyl compounds from sweet wines.

    Science.gov (United States)

    Blasi, Mélanie; Barbe, Jean-Christophe; Maillard, Bernard; Dubourdieu, Denis; Deleuze, Hervé

    2007-12-12

    Sweet white wines from botrytized grapes present high SO2 levels because of their high sulfur dioxide binding power. The objective of this work was to develop a new method for reducing this binding power by partially eliminating the carbonyl compounds naturally present in these wines that are responsible for this phenomenon. A selective liquid-solid removal technique was developed. Phenylsulfonylhydrazine was selected as the best candidate for removing carbonyl compounds. Its reactivity in the presence or absence of sulfur dioxide was verified in model media containing acetaldehyde, pyruvic acid, and 2-oxoglutaric acid, some of the main carbonyl compounds responsible for the SO2 binding power of sweet wines. The scavenging function was grafted on porous polymer supports, and its efficiency was evaluated in model wines. Dependent upon the supports used, different quantities of carbonyl compounds (over 90% in some cases) were removed in a few days. The presence of sulfur dioxide delayed removal without changing its quality. The results obtained showed that the method removed carbonyl compounds efficiently and was applicable to wines at any stage in winemaking.

  3. Atmospheric photooxidation of alkylbenzenes—I. Carbonyl product analyses

    Science.gov (United States)

    Yu, Jianzhen; Jeffries, Harvey E.; Sexton, Kenneth G.

    Six alkylbenzenes—toluene, p-xylene, m-xylene, o-xylene, 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene—were selected to investigate the carbonyl products resulting from OH-initiated oxidation of aromatic compounds. Experiments were conducted in both indoor and outdoor smog chambers under simulated atmospheric conditions. Both batch samples and 30 min interval samples were taken in the outdoor smog chamber experiments using 1 ppmV alkylbenzene, 0.67 ppm NO x and sunlight as the light source. A wide variety of carbonyl products were detected and identified using gas chromatography/mass spectrometric (GC/MS) detection by their O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) derivatives. Among the observed carbonyl products are aromatic aldehydes, quinones, di-unsaturated 1,6-dicarbonyls, unsaturated 1,4-dicarbonyls, saturated dicarbonyls, hydroxy dicarbonyls, glycolaldehyde, hydroxy acetone, and possibly triones and epoxy carbonyls. Quantification was achieved using 13C 3-acetone as a gas-phase internal standard. The numerous carbonyl products detected in itself partially explain previous difficulties in balancing the reacted carbon. They also provide additional insight into the oxidation mechanism for aromatic compounds, which will be discussed in this paper.

  4. Soil fluxes of carbonyl sulfide (COS) across four distinct ecosystems

    Science.gov (United States)

    Sun, W.; Maseyk, K. S.; Lett, C.; Juarez, S.; Kooijmans, L.; Mammarella, I.; Vesala, T.; Chen, H.; Seibt, U.

    2015-12-01

    Soils are additional but poorly resolved sinks of carbonyl sulfide (COS) in terrestrial ecosystems. COS has been proposed as a tracer for quantifying gross photosynthesis based on the coupled stomatal uptake of COS and CO2. But applying this tracer requires the soil COS flux to be subtracted from the ecosystem flux to obtain the actual plant flux. To simulate soil COS fluxes, we have built a 1-D diffusion-reaction model accounting for vertical transport in the soil, microbial sinks and sources, and a litter layer. Uptake and production of COS in the soil column are linked with soil temperature and moisture through empirical functions adapted from enzyme kinetics and lab incubations. We have measured soil COS fluxes and the related soil variables in four distinct ecosystems: a wheat field (Southern Great Plains, OK, USA), an oak woodland (Santa Monica Mountains, CA, USA), a tropical rainforest (La Selva Biological Station, Costa Rica) and a boreal pine forest (Hyytiälä, Finland). Across all sites, a lower soil temperature and a humid climate are generally favorable to soil COS uptake. Strong COS emissions were observed in the wheat field at high soil temperatures after harvesting but were absent in other ecosystems, indicating that COS exchange may behave differently in agricultural soils. We simulated the soil fluxes in all ecosystems using the diffusion-reaction model, and optimized the source/sink strength parameters with field data. The optimized model provides insights that are not attainable from data analysis alone: For example, the wheat field soil must have continued uptake activity even when it showed net emissions, and leaf litter contributed dominantly to the COS sink after rain in the oak woodland. We expect the new model to be useful for simulating global soil COS fluxes as field data on soil fluxes from a broader range of ecosystems become available.

  5. Metabolic methanol: molecular pathways and physiological roles.

    Science.gov (United States)

    Dorokhov, Yuri L; Shindyapina, Anastasia V; Sheshukova, Ekaterina V; Komarova, Tatiana V

    2015-04-01

    Methanol has been historically considered an exogenous product that leads only to pathological changes in the human body when consumed. However, in normal, healthy individuals, methanol and its short-lived oxidized product, formaldehyde, are naturally occurring compounds whose functions and origins have received limited attention. There are several sources of human physiological methanol. Fruits, vegetables, and alcoholic beverages are likely the main sources of exogenous methanol in the healthy human body. Metabolic methanol may occur as a result of fermentation by gut bacteria and metabolic processes involving S-adenosyl methionine. Regardless of its source, low levels of methanol in the body are maintained by physiological and metabolic clearance mechanisms. Although human blood contains small amounts of methanol and formaldehyde, the content of these molecules increases sharply after receiving even methanol-free ethanol, indicating an endogenous source of the metabolic methanol present at low levels in the blood regulated by a cluster of genes. Recent studies of the pathogenesis of neurological disorders indicate metabolic formaldehyde as a putative causative agent. The detection of increased formaldehyde content in the blood of both neurological patients and the elderly indicates the important role of genetic and biochemical mechanisms of maintaining low levels of methanol and formaldehyde.

  6. Endogenous methanol regulates mammalian gene activity.

    Directory of Open Access Journals (Sweden)

    Tatiana V Komarova

    Full Text Available We recently showed that methanol emitted by wounded plants might function as a signaling molecule for plant-to-plant and plant-to-animal communications. In mammals, methanol is considered a poison because the enzyme alcohol dehydrogenase (ADH converts methanol into toxic formaldehyde. However, the detection of methanol in the blood and exhaled air of healthy volunteers suggests that methanol may be a chemical with specific functions rather than a metabolic waste product. Using a genome-wide analysis of the mouse brain, we demonstrated that an increase in blood methanol concentration led to a change in the accumulation of mRNAs from genes primarily involved in detoxification processes and regulation of the alcohol/aldehyde dehydrogenases gene cluster. To test the role of ADH in the maintenance of low methanol concentration in the plasma, we used the specific ADH inhibitor 4-methylpyrazole (4-MP and showed that intraperitoneal administration of 4-MP resulted in a significant increase in the plasma methanol, ethanol and formaldehyde concentrations. Removal of the intestine significantly decreased the rate of methanol addition to the plasma and suggested that the gut flora may be involved in the endogenous production of methanol. ADH in the liver was identified as the main enzyme for metabolizing methanol because an increase in the methanol and ethanol contents in the liver homogenate was observed after 4-MP administration into the portal vein. Liver mRNA quantification showed changes in the accumulation of mRNAs from genes involved in cell signalling and detoxification processes. We hypothesized that endogenous methanol acts as a regulator of homeostasis by controlling the mRNA synthesis.

  7. A novel process for methanol synthesis. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Tierney, J.W.; Wender, I.

    1994-01-25

    The use of methanol (MeOH) as a fuel additive and in MTBE production has renewed interest in the search for improved MeOH processes. Commercial processes are characterized by high pressures and temperatures with low per pass conversion (10--12%). Efforts are underway to find improved MeOH synthesis processes. A slurry phase ``concurrent`` synthesis of MeOH/methyl formate (MeF) which operates under relatively mild conditions (100{degrees}C lower than present commercial processes) was the subject of investigation in this work. Evidence for a reaction scheme involving the carbonylation of MeOH to MeF followed by the hydrogenolysis of MeF to two molecules of MeOH -- the net result being the reaction of H{sub 2} with CO to give MeOH via MeF, is presented. Up to 90% per pass conversion and 98% selectivity to methanol at rates comparable to commercial processes have been obtained in spite of the presence of as much as 10,000 ppM CO{sub 2} and 3000 ppM H{sub 2}O in the gas and liquid respectively. The effect of process parameters such as temperature, pressure, H{sub 2}/CO ratio in the reactor, flow rate and catalyst loading were also investigated. The use of temperatures above 170{degrees}C at a pressure of 50 atm results in MeF being the limiting reactant. Small amounts of CH{sub 4} are also formed. Significant MeOH synthesis rates at a pressure in the range of 40--50 atm makes possible the elimination of an upstream shift reactor and the use of an air-blown syngas generator. The nature of the catalysts was studied and correlated with the behavior of the various species in the concurrent synthesis.

  8. Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol.

    Science.gov (United States)

    Alberico, E; Nielsen, M

    2015-04-21

    The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous catalytic systems have been reported which are able to promote either one or the other of the two reactions under mild conditions. Here, we review and discuss these developments.

  9. Development and Fielding of a Direct Methanol Fuel Cell

    Science.gov (United States)

    2010-03-01

    fuel cell to power operational test instrumentation in support of the future combat systems test and evaluation. This unit also has application by the German Bundeswehr as a battery-charging station and auxiliary power unit. The direct methanol fuel cell is characterized by its low noise emission, minimal thermal signature, and high fuel efficiency that will enable continuously sustained operation for long duration missions in the

  10. Hemodiafiltration efficacy in treatment of methanol and ethylene glycol poisoning in a 2-year-old girl.

    Science.gov (United States)

    Szmigielska, Agnieszka; Szymanik-Grzelak, Hanna; Kuźma-Mroczkowska, Elżbieta; Roszkowska-Blaim, Maria

    2015-01-01

    Every year about 2.4 million people in USA are exposed to toxic substances. Many of them are children below 6 years of age. Majority of poisonings in children are incidental and related to household products including for example drugs, cleaning products or antifreeze products. Antifreeze solutions contain ethylene glycol and methanol. Treatment of these toxic substances involves ethanol administration, fomepizole, hemodialysis and correction of metabolic acidosis. The aim of the study was to check the efficacy of continuous venovenous hemodiagiltration in intoxication with ethylene glycol and methanol. One year and 7 months old girl after intoxication with ethylene glycol and methanol was treated with continuous venovenous hemodiafiltration instead of hemodialysis because of technical problems (circulatory instability). Intravenous ethanol infusion with hemodialtration resulted in rapid elimination of methanol from the body and significantly reduced blood ethylene glycol level. Continuous venovenous hemodiafiltration can be helpful in treatment of ethylene glycol and methanol intoxication.

  11. The shock sensitivity of nitromethane/methanol mixtures

    Science.gov (United States)

    Bartram, Brian; Dattelbaum, Dana; Sheffield, Steve; Gibson, Lee

    2013-06-01

    The dilution of liquid explosives has multiple effects on detonation properties including an increase in critical diameter, spatiotemporal lengthening of the chemical reaction zone, and the development of propagating wave instabilities. Earlier detonation studies of NM/methanol mixtures have shown several effects of increasing dilution, including: 1) a continual increase in the critical diameter, 2) lowering of the Chapman-Jouguet detonation pressure, and 3) slowing of the steady detonation velocity (Koldunov et al., Comb. Expl. Shock Waves). Here, we present the results of a series of gas gun-driven plate-impact experiments to study the shock-to-detonation transition in NM/methanol mixtures. Embedded electromagnetic gauges were used to obtain in situ particle velocity wave profiles at multiple Lagrangian positions in the initiating explosive mixture. From the wave profiles obtained in each experiment, an unreacted Hugoniot locus, the initiation mechanism, and the overtake-time-to-detonation were obtained as a function of shock input condition for mixture concentrations from 100% NM to 50 wt%/50 wt% NM/methanol. Desensitization with dilution is less than expected. For example, little change in overtake time occurs in 80 wt%/20 wt% NM/methanol when compared with neat NM. Furthermore, the shock wave profiles from the gauges indicate that wave instabilities grow in as the overdriven detonation wave settles down following the shock-to-detonation transition.

  12. Continuous steam hydrolysis of tulip poplar

    Energy Technology Data Exchange (ETDEWEB)

    Fieber, C.A.; Roberts, R.S.; Faass, G.S.; Muzzy, J.D.; Colcord, A.R.; Bery, M.K.

    1982-01-01

    The continuous hydrolysis of poplar chips by steam at 300-350 psi resulted in the separation of hemicellulose (I) cellulose and lignin components. The I fraction was readily depolymerised by steam to acetic acid, furfural, methanol, and xylose.

  13. Carbonyl Sulfides as Possible Intermediates in the Photolysis of Oxathiiranes

    DEFF Research Database (Denmark)

    Carlsen, Lars; Snyder, J. P.; Holm, A.

    1981-01-01

    of sulfine to ketone via the oxathiirane and the subsequent blue intermediate implies the absence of triplet and biradical singlet transients. The unknown carbonyl sulfide functionality, R2C&z.dbnd;O&z.dbnd;S, thereby emerges as a strong candidate for producing the visible absorption. Comparison of the wave...... functions for CH2&z.dbnd;S&z.dbnd;O and CH2&z.dbnd;O&z.dbnd;S arising from MNDO limited CI geometry optimizations leads to the conclusion that the carbonyl sulfide structure is best described as a zwitterion rather than as a singlet biradical. The failure to observe cycloaddition products between the blue...

  14. Carbonyl Sulfides as Possible Intermediates in the Photolysis of Oxathiiranes

    DEFF Research Database (Denmark)

    Carlsen, Lars; Snyder, J. P.; Holm, A.

    1981-01-01

    of sulfine to ketone via the oxathiirane and the subsequent blue intermediate implies the absence of triplet and biradical singlet transients. The unknown carbonyl sulfide functionality, R2C&z.dbnd;O&z.dbnd;S, thereby emerges as a strong candidate for producing the visible absorption. Comparison of the wave...... functions for CH2&z.dbnd;S&z.dbnd;O and CH2&z.dbnd;O&z.dbnd;S arising from MNDO limited CI geometry optimizations leads to the conclusion that the carbonyl sulfide structure is best described as a zwitterion rather than as a singlet biradical. The failure to observe cycloaddition products between the blue...

  15. An alternative method for monitoring carbonyls, and the development of a 24-port fully automated carbonyl sampler for PAMS program

    Energy Technology Data Exchange (ETDEWEB)

    Parmar, S.S.; Ugarova, L. [Atmospheric Analysis and Consulting, Ventura, CA (United States); Fernandes, C.; Guyton, J.; Lee, C.P. [Arizona Dept. of Environmental Quality, Phoenix, AZ (United States)

    1994-12-31

    The authors have investigated the possibility of collecting different aldehydes and ketones on different sorbents such as silica gel, molecular sieve and charcoal followed by solvent extraction, DNPH derivatization and HPLC/UV analysis. Carbonyl collection efficiencies for these sorbents were calculated relative to a DNPH coated C{sub 18} sep-pak cartridge. From a limited number of laboratory experiments, at various concentrations, it appears that silica gel tubes can be used for sampling aldehydes (collection efficiencies {approximately} 1), whereas charcoal tubes are suitable for collecting ketones. Molecular sieve was found to be unsuitable for collecting most of the carbonyl studied. The authors also report the development of a fully automated 24-port carbonyl sampler specially designed for EPA`s PAMS program.

  16. Improvement of biodiesel methanol blends

    Directory of Open Access Journals (Sweden)

    Y. Datta Bharadwaz

    2016-06-01

    Full Text Available The main objective of this work was to improve the performance of biodiesel–methanol blends in a VCR engine by using optimized engine parameters. For optimization of the engine, operational parameters such as compression ratio, fuel blend, and load are taken as factors, whereas performance parameters such as brake thermal efficiency (Bth and brake specific fuel consumption (Bsfc and emission parameters such as carbon monoxide (CO, unburnt hydrocarbons (HC, Nitric oxides (NOx and smoke are taken as responses. Experimentation is carried out as per the design of experiments of the response surface methodology. Optimization of engine operational parameters is carried out using Derringers Desirability approach. From the results obtained it is inferred that the VCR engine has maximum performance and minimum emissions at 18 compression ratio, 5% fuel blend and at 9.03 kg of load. At this optimized operating conditions of the engine the responses such as brake thermal efficiency, brake specific fuel consumption, carbon monoxide, unburnt hydrocarbons, nitric oxide, and smoke are found to be 31.95%, 0.37 kg/kW h, 0.036%, 5 ppm, 531.23 ppm and 15.35% respectively. It is finally observed from the mathematical models and experimental data that biodiesel methanol blends have maximum efficiency and minimum emissions at optimized engine parameters.

  17. Studies of Producing Acetic Acid by Carbonylation of Methanol%甲醇羰基化制乙酸

    Institute of Scientific and Technical Information of China (English)

    王玉和; 贺德华; 徐柏庆

    2003-01-01

    Monsanto公司的甲醇羰基化制乙酸工艺具有甲醇转化率高、产物产率高等优点,但也存在着主催化剂铑价格昂贵、助催化剂碘化物腐蚀设备等缺点.本文重点从催化机理研究方面介绍了国内外对Monsanto技术的最新改进研究工作、英国石油(BP)公司的甲醇羰基化制乙酸铱基催化体系(名为CativaTM工艺),并介绍了无碘化物促进的甲醇羰基化催化体系,分析了不同催化体系的优缺点及研究发展趋势.

  18. - Wave Spectrum of Carbonyl Diazide in Pursuit of Diazirinone

    Science.gov (United States)

    Amberger, Brent K.; Esselman, Brian J.; Woods, R. Claude; McMahon, Robert J.

    2013-06-01

    Pyrolysis of carbonyl diazide (CO(N_3)_2) has been shown to give diazirinone (CON_2). While diazirione decomposes over the course of a few hours under terrestrial conditions, there is the possibility for it to exist in space. In the pursuit of obtaining a rotational spectrum for diazirinone, we have started with the rotational spectroscopy of its immediate precursor, carbonyl diazide. Carbonyl diazide is highly explosive, and requires careful synthesis. Spectra in the range of 260-360 GHz were collected at room temperature and at -60°C. Ab initio calculations at the CCSD/cc-pVDZ level predict that the conformation where both azide groups are syn to the carbonyl is preferred. A second conformation, where one azide is syn and one is anti, is calculated to lie about 2 kcal/ mol higher in energy. Pure rotational transitions for the ground state and multiple low-lying excited vibrational states of the syn- syn conformation are readily observed and assigned. X. Zeng, H. Beckers, H. Willner and J. F. Stanton, Angew. Chem. Int. Ed. 50 (2011), 1720-1723 A. M. Nolan, B. K. Amberger, B. J. Esselman, V. S. Thimmakondu, J. F. Stanton, R. C. Woods, and R. J. McMahon, Inorg. Chem. 51 (2012), 9846-9851

  19. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    DEFF Research Database (Denmark)

    Marek, Ales; Pedersen, Martin Holst Friborg

    2015-01-01

    An alternative and robust method for the reduction of carbonyl groups by frustrated Lewis pairs (FLPs) is reported in this paper. With its very mild reaction conditions, good to excellent yields, absolute regioselectivity and the non-metallic character of the reagent, it provides an excellent too...

  20. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  1. α-Carbonyl Radical Cyclizatio n in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    SHA Chin-Kang; CHIU Rei-Torng; LIH Shinn-Horng; SANTHOSH K. C.; CHANG Ching-Jung; TSENG Wei-Hong; HO Wen-Yueh

    2001-01-01

    @@ Intramolecular radical cyclization reactions are now used routinely to synthesize carbocyclic and heterocyclic structures. We have reported that α-carbonyl radicals 1, generated from the corresponding iodo ketones or enones, underwent intramolecular radical cyclization smoothly to afford products 2.1, 2,3

  2. N-heterocyclic carbene catalyzed direct carbonylation of dimethylamine.

    Science.gov (United States)

    Li, Xiaonian; Liu, Kun; Xu, Xiaoliang; Ma, Lei; Wang, Hong; Jiang, Dahao; Zhang, Qunfeng; Lu, Chunshan

    2011-07-21

    N-Heterocyclic carbene (NHC) catalyzed direct carbonylation of dimethylamine leading to the formation of DMF was successfully accomplished under metal-free conditions. The catalytic efficiency was investigated and the turnover numbers can reach as high as >300. The possible mechanism was also proposed.

  3. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    Science.gov (United States)

    Rathke, Jerome W.; Klingler, Robert J.

    1993-01-01

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  4. Reactions of allenic phosphonites with carbonyl compounds and with azomethines

    Energy Technology Data Exchange (ETDEWEB)

    Belakhov, V.V.; Yudelevich, V.I.; Yakovlev, A.A.; Ionin, B.I.

    1986-07-20

    The reactions of 2-propynyl hydrogen and propadienylphosphonite with some carbonyl compounds and azomethines lead to the formation of the corresponding propadienylphosphinic esters. The reactions of (3-methyl-1,2-butadienyl) phosphonous acid with aromatic aldehydes is accompanied by heterocyclization with the formation of 1,2-oxaphosphol-3-enes.

  5. Comparing Carbonyl Chemistry in Comprehensive Introductory Organic Chemistry Textbooks

    Science.gov (United States)

    Nelson, Donna J.; Kumar, Ravi; Ramasamy, Saravanan

    2015-01-01

    Learning the chemistry of compounds containing carbonyl groups is difficult for undergraduate students partly because of a convolution of multiple possible reaction sites, competitive reactions taking place at those sites, different criteria needed to discern between the mechanisms of these reactions, and no straightforward selection method…

  6. Contamination of coal benzol by carbonyl compound impurities

    Energy Technology Data Exchange (ETDEWEB)

    Yakovleva, T.P.

    1985-03-01

    The origin of most carbonyl compounds in nitration-grade benzene produced from coke-oven crude benzole (causing problems in isopropylbenzene production) was concluded to be the piperylene fraction (a by-product of isoprene manufacture) used as an additive in the washing of the benzene with sulphuric acid.

  7. Age-related variations of protein carbonyls in human saliva and plasma: is saliva protein carbonyls an alternative biomarker of aging?

    Science.gov (United States)

    Wang, Zhihui; Wang, Yanyi; Liu, Hongchen; Che, Yuwei; Xu, Yingying; E, Lingling

    2015-06-01

    Free radical hypothesis which is one of the most acknowledged aging theories was developed into oxidative stress hypothesis. Protein carbonylation is by far one of the most widely used markers of protein oxidation. We studied the role of age and gender in protein carbonyl content of saliva and plasma among 273 Chinese healthy subjects (137 females and 136 males aged between 20 and 79) and discussed the correlation between protein carbonyl content of saliva and plasma. Protein carbonyl content of saliva and plasma were, respectively, 2.391 ± 0.639 and 0.838 ± 0.274 nmol/mg. Variations of saliva and plasma different age groups all reached significant differences in both male and female (all p saliva and plasma protein carbonyls were found to be significantly correlated with age (r = 0.6582 and r = 0.5176, all p saliva and plasma protein carbonyl levels (all p > 0.05). Saliva and plasma protein carbonyls were positively related (r = 0.4405, p saliva and plasma protein carbonyls/ferric reducing ability of plasma (FRAP) ratios were proved to be significantly correlated with age (r = 0.7796 and r = 0.6938, all p saliva protein carbonyls/FRAP ratio and plasma protein carbonyls/FRAP ratio were also correlated (r = 0.5573, p saliva protein carbonyls seem to be an alternative biomarker of aging while the mechanisms of protein carbonylation and oxidative stress and the relationship between saliva protein carbonyls and diseases need to be further investigated.

  8. Plasma protein carbonyl levels and breast cancer risk.

    Science.gov (United States)

    Rossner, Pavel; Terry, Mary Beth; Gammon, Marilie D; Agrawal, Meenakshi; Zhang, Fang Fang; Ferris, Jennifer S; Teitelbaum, Susan L; Eng, Sybil M; Gaudet, Mia M; Neugut, Alfred I; Santella, Regina M

    2007-01-01

    To study the role of oxidative stress in breast cancer risk, we analysed plasma levels of protein carbonyls in 1050 cases and 1107 controls. We found a statistically significant trend in breast cancer risk in relation to increasing quartiles of plasma protein carbonyl levels (OR = 1.2, 95% CI = 0.9-1.5; OR = 1.5, 95% CI = 1.2-2.0; OR = 1.6, 95% CI = 1.2-2.1, for the 2(nd), 3(rd) and 4(th) quartile relative to the lowest quartile, respectively, P for trend = 0.0001). The increase in risk was similar for younger ( or = 15 grams/day for 4(th) quartile versus lowest quartile OR = 2.3, 95% CI = 1.1-4.7), and hormone replacement therapy use (HRT, OR = 2.6, 95% CI = 1.6-4.4 for 4(th) quartile versus lowest quartile). The multiplicative interaction terms were statistically significant only for physical activity and HRT. The positive association between plasma protein carbonyl levels and breast cancer risk was also observed when the analysis was restricted to women who had not received chemotherapy or radiation therapy prior to blood collection. Among controls, oxidized protein levels significantly increased with cigarette smoking and higher fruit and vegetable consumption, and decreased with alcohol consumption >30 grams per day. Women with higher levels of plasma protein carbonyl and urinary 15F(2t)-isoprostane had an 80% increase in breast cancer risk (OR = 1.8, 95% CI = 1.2-2.6) compared to women with levels below the median for both markers of oxidative stress. In summary, our results suggest that increased plasma protein carbonyl levels may be associated with breast cancer risk.

  9. 铑催化乙酸乙酯羰基化合成丙酸的研究%Rh Catalyzed Carbonylation of Ethyl Acetate to Propionic Acid

    Institute of Scientific and Technical Information of China (English)

    凌晨; 黄志军

    2013-01-01

    以乙酸乙酯为原料,在金属铑催化下与一氧化碳进行羰基化反应,生成丙酸.研究了碘化物添加剂和反应条件对丙酸产率的影响.由于避免了乙醇在酸性条件下的酯化和分子间脱水等副反应,丙酸产率显著提高.乙酸乙酯羰基化具有与甲醇羰基化相似的动力学行为.碘化物添加剂的加入能有效提高反应速率和丙酸选择性.通过优化反应条件,丙酸产率大于95%.%Rhodium was used to catalyze the carbonylation of ethyl acetate with carbon monoxide to propionic acid.The effect of iodide additives and reaction conditions on yield of propionic acid was studied.Because of avoiding the esterification and intermolecular dehydration of ethanol the yield of propionic acid was improved significantly.The kinetic behavior of ethyl acetate carbonylation was similar with methanol carbonylation.The reaction rate and propionic acid selectivity were increased obviously with the introduction of iodide additives.The propionic acid yield is greater than 95% under the optimum conditions.

  10. Developmental and Reproductive Toxicology of Methanol

    Science.gov (United States)

    Methanol is a high production volume chemical used as a feedstock for chemical syntheses and as a solvent and fuel additive. Methanol is acutely toxic to humans, causing acidosis, blindness in death at high dosages, but its developmental and reproductive toxicity in humans is poo...

  11. Hydrogenation of carbon dioxide for methanol production

    NARCIS (Netherlands)

    Ham, van der A.G.J.; Berg, van den H.; Benneker, A.; Simmelink, G.; Timmer, J.; Weerden, van S.

    2012-01-01

    A process for the hydrogenation of CO2 to methanol with a capacity of 10 kt/y methanol is designed in a systematic way. The challenge will be to obtain a process with a high net CO2 conversion. From initially four conceptual designs the most feasible is selected and designed in more detail. The feed

  12. Optimized biotin-hydrazide enrichment and mass spectrometry analysis of peptide carbonyls

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, K; Jensen, O. N.;

    Irreversible cell damage through protein carbonylation is the result of reaction with reactive oxygen species (ROS) and has been coupled to many diseases. The precise molecular consequences of protein carbonylation, however, are still not clear. The localization of the carbonylated amino acid is ...

  13. A specific gas chromatographic detector for carbonyl compounds, based on polarography.

    Science.gov (United States)

    Fleet, B; Risby, T H

    1969-07-01

    The evaluation of a specific gas Chromatographie detector for carbonyl compounds is described. This is based on the polarographic reduction of the Girard T hydrazone derivative which is formed when the carbonyl compound is absorbed in a buffered supporting electrolyte containing the carbonyl reagent. The detector was used to monitor the separation of a homologous series of alkanals.

  14. Low pressure carbonylation of benzyl chloride = Die carbonylierung von benzylchlorid bei niedrigen drücken

    NARCIS (Netherlands)

    Luggenhorst, H.J.; Westerterp, K.R.

    1986-01-01

    For carbonylations, metal carbonyls, particularly cobalt and iron carbonyls, are often used as catalysts. These reactions take place under rather drastic reaction conditions, e.g. 200–300 °C and 60–100 MPa. In some patents it is stated that similar reactions using the same catalysts can also be carr

  15. Recycling of greenhouse gases via methanol

    Energy Technology Data Exchange (ETDEWEB)

    Bill, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Eliasson, B.; Kogelschatz, U. [ABB Corporate Research Center, Baden-Daettwil (Switzerland)

    1997-06-01

    Greenhouse gas emissions to the atmosphere can be mitigated by using direct control technologies (capture, disposal or chemical recycling). We report on carbon dioxide and methane recycling with other chemicals, especially with hydrogen and oxygen, to methanol. Methanol synthesis from CO{sub 2} is investigated on various catalysts at moderate pressures ({<=}30 bar) and temperatures ({<=}300{sup o}C). The catalysts show good methanol activities and selectivities. The conversion of CO{sub 2} and CH{sub 4} to methanol is also studied in a silent electrical discharge at pressures of 1 to 4 bar and temperatures close to room temperature. Methanol yields are given for mixtures of CO{sub 2}/H{sub 2}, CH{sub 4}/O{sub 2} and also for CH{sub 4} and air mixtures. (author) 2 figs., 5 refs.

  16. A search for extragalactic methanol masers

    CERN Document Server

    Ellingsen, S P; Whiteoak, J B; Vaile, R A; McCulloch, P M; Price, M

    1994-01-01

    A sensitive search for 6.7--GHz methanol maser emission has been made towards 10 galaxies that have yielded detectable microwave molecular--line transitions. These include several which show OH megamaser or superluminous \\water\\/ maser emission. Within the Galaxy, \\methanol\\/ and OH masers often occur in the same star formation regions and, in most cases, the \\methanol\\/ masers have a greater peak flux density than their OH counterparts. Thus we might expect \\methanol\\/ masers to be associated with extragalactic OH maser sources. We failed to detect any emission or absorption above our 60--mJy detection limit. We conclude that if the physical conditions exist to produce \\methanol\\/ megamaser emission, they are incompatible with the conditions which produce OH megamaser emission.

  17. Production of methanol/DME from biomass

    DEFF Research Database (Denmark)

    Ahrenfeldt, Jesper; Henriksen, Ulrik Birk; Münster-Swendsen, Janus

    In this project the production of DME/methanol from biomass has been investigated. Production of DME/methanol from biomass requires the use of a gasifier to transform the solid fuel to a synthesis gas (syngas) - this syngas can then be catalytically converted to DME/methanol. Two different gasifier...... cleaning. This was proved by experiments. Thermodynamic computer models of DME and methanol plants based on using the Two-Stage Gasification concept were created to show the potential of such plants. The models showed that the potential biomass to DME/methanol + net electricity energy efficiency was 51...... gasification, but little information exists on using these types of gasifiers for biomass gasification. The experiments performed provided quantitative data on product and gas composition as a function of operation conditions. Biomass can be gasified with less oxygen consumption compared to coal. The organic...

  18. New catalysts for miniaturized methanol fuel cells

    DEFF Research Database (Denmark)

    Pedersen, Christoffer Mølleskov

    The methanol fuel cell is an interesting energy technology, capable of converting the chemical energy of methanol directly into electricity. The technology is specifically attractive for small mobile applications such as laptops, smartphones, tablets etc. since it offers almost instantaneously...... recharging by simply replacing the methanol liquid. The technology is currently being developed for hearing instruments in order to ease the handling of the device for users complaining about difficulties replacing the very small batteries in the hearing instrument. The technology has already been...... and methanol poisoning of the oxygen reduction are studied. Consequently, promising new candidates for replacing the standard catalyst are identified. One of these, Pt5Gd, exhibits improved oxygen reduction reaction activity even in the presence of methanol, thus making Pt5Gd an interesting candidate...

  19. Strong soil source of carbonyl sulfide in an agricultural field

    Science.gov (United States)

    Maseyk, K. S.; Seibt, U.; Berry, J. A.; Billesbach, D. P.; Campbell, J.; Torn, M. S.

    2012-12-01

    A promising new approach to constrain biosphere-atmosphere carbon and water exchange is the use of carbonyl sulfide (COS). COS is taken up by leaves via the same pathway as CO2, leading to a close coupling of vegetation COS and CO2 fluxes during photosynthesis. Therefore it has been proposed that the gross fluxes of photosynthesis and respiration can be quantified through the concurrent measurements of COS and CO2. A necessary requirement for this approach at ecosystem and continental scales are estimates of soil COS fluxes. Soil is largely considered a sink for COS, but our knowledge of in situ soil COS fluxes remains very limited. We measured soil COS fluxes in a wheat field in Oklahoma from April to June 2012, using a novel combination of an automated soil chamber coupled to a COS laser analyzer. We provide the first continuous record of soil COS fluxes under natural conditions, and report on a phenomenon that has not been observed before. In contrast to the majority of published results, we found that the agricultural soil was a strong source of COS under most conditions during the campaign. The COS flux over the study period was highly correlated with soil temperature. Up to a soil temperature of around 15°C, the soil acted as a COS sink. Above 15°C, it acted a source of COS, with fluxes of up to 25 pmol m-2 s-1. To locate the source of the COS production, we investigated different soil components. Wheat roots were found to be emitting COS under all conditions. Root-free soil was a COS sink up to a soil temperature of around 25°C, but turned into a COS source at higher soil temperatures. We also observed COS production from the roots of several other species, indicating that this may be a widespread phenomenon. Using eddy covariance data of COS and CO2 that was collected concurrently with the soil measurements, we also demonstrate how the soil COS source can be taken into account when partitioning net ecosystem exchange into photosynthesis and respiration.

  20. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke.

    Science.gov (United States)

    Pang, Xiaobing; Lewis, Alastair C

    2011-11-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 μg cigarette(-1) (μg cig(-1)) and the particulate carbonyl emissions varied in the range of 23-127 μg cig(-1). Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 μg cig(-1) gaseous and 141 μg cig(-1) particulate carbonyls, which is 2-4 times greater than the cigarettes.

  1. Carbonyl Alkyl Nitrates as Trace Constituents in Urban Air

    Science.gov (United States)

    Woidich, S.; Gruenert, A.; Ballschmiter, K.

    2003-04-01

    Organic nitrates, esters of nitric acid, significantly contribute to the entire pool of odd nitrogen (NOY) in the atmosphere. Organic nitrates are formed in NO rich air by degradation of alkanes and alkenes initiated by OH and NO3 radicals during daytime and nighttime, respectively. Bifunctional organonitrates like the alkyl dinitrates and hydroxy alkyl nitrates are formed primarily from alkenes. The two main sources for Alkenes are traffic emissions and naturally occurring terpenes. So far a broad spectrum of alkyl dinitrates and hydroxy alkyl nitrates including six different isoprene nitrates has been identified in urban and marine air (1-3). We report here for the first time about the group of C4 C7 carbonyl alkyl nitrates as trace constituents in urban air collected on the campus of the University of Ulm Germany, and in the downtown area of Salt Lake City, Utah. Air sampling was done by high volume sampling (flow rate 25 m3/h) using a layer of 100 g silica gel (particle diameter 0.2 - 0.5 mm) as adsorbent. The organic nitrates were eluted from the silica gel by pentane/acetone (4:1, w/w) and the extract was concentrated to a volume of 500 µL for a group separation using normal phase HPLC. Final analysis was performed by high resolution capillary gas chromatography with electron capture detection as well as by mass selective detection in the (CH4)NCI mode using NO2- = m/e 46 as the indicator mass. The carbonyl alkyl nitrates were identified by self synthesized reference standards . So far we have identified eight non-branched a-carbonyl alkyl nitrates (vicinal carbonyl alkyl nitrates), two b-carbonyl alkyl nitrates and one g-carbonyl alkyl nitrate with carbon chains ranging from C4 to C7. The mixing ratios are between 0.05 and 0.30 ppt(v) for daytime samples and are two to three times higher for samples taken at night. (1) M. Schneider, O. Luxenhofer, Angela Deißler, K. Ballschmiter: 2C1-C15 Alkyl Nitrates, Benzyl Nitrate, and Bifunctional Nitrates

  2. Temperature dependence of water interactions with the amide carbonyls of α-helices.

    Science.gov (United States)

    Brewer, Scott H; Tang, Yuefeng; Vu, Dung M; Gnanakaran, S; Raleigh, Daniel P; Dyer, R Brian

    2012-07-03

    Hydration is a key determinant of the folding, dynamics, and function of proteins. In this study, temperature-dependent Fourier transform infrared (FTIR) spectroscopy combined with singular value decomposition (SVD) and global fitting were used to investigate both the interaction of water with α-helical proteins and the cooperative thermal unfolding of these proteins. This methodology has been applied to an isolated α-helix (Fs peptide) and to globular α-helical proteins including the helical subdomain and full-length villin headpiece (HP36 and HP67). The results suggest a unique IR signature for the interaction of water with the helical amide carbonyl groups of the peptide backbone. The IR spectra indicate a weakening of the net hydrogen bond strength of water to the backbone carbonyls with increasing temperature. This weakening of the backbone solvation occurs as a discrete transition near the maximum of the temperature-dependent hydrophobic effect, not a continuous change with increasing temperature. Possible molecular origins of this effect are discussed with respect to previous molecular dynamics simulations of the temperature-dependent solvation of the helix backbone.

  3. Sources and seasonality of atmospheric methanol based on tall tower measurements in the US Upper Midwest

    Directory of Open Access Journals (Sweden)

    L. Hu

    2011-06-01

    Full Text Available We present over one year of continuous atmospheric methanol measurements from the University of Minnesota tall tower Trace Gas Observatory (KCMP tall tower; 244 m a.g.l., and interpret the dataset in terms of constraints on regional methanol sources and seasonality. The seasonal cycle of methanol concentrations observed at the KCMP tall tower is generally similar to that simulated by a global 3-D chemical transport model (GEOS-Chem, driven with MEGANv2.0 biogenic emissions except the seasonal peak occurs ~1 month earlier in the observations, apparently reflecting a model underestimate of emission rates for younger versus older leaves. Based on a source tracer approach, which we evaluate using GEOS-Chem and with multiple tracers, we estimate that anthropogenic emissions account for approximately 40 % of ambient methanol abundance during winter and 10 % during summer. During daytime in summer, methanol concentrations increase exponentially with temperature, reflecting the temperature sensitivity of the biogenic source, and the observed temperature dependence is statistically consistent with that in the model. Nevertheless, summertime concentrations are underestimated by on average 35 % in the model for this region. The seasonal importance of methanol as a source of formaldehyde (HCHO and carbon monoxide (CO is highest in spring through early summer, when biogenic methanol emissions are high but isoprene emissions are still relatively low. During that time observed methanol concentrations account for on average 20 % of the total CO and HCHO production rates as simulated by GEOS-Chem, compared to 12 % later in the summer and 12 % on an annual average basis. The biased seasonality in the model means that the photochemical role for methanol early in the growing season is presently underestimated.

  4. Engineering Escherichia coli for methanol conversion.

    Science.gov (United States)

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-03-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy genes" into Escherichia coli based on in silico considerations and flux balance analysis to enable methanol dissimilation and assimilation. We determined that the most promising approach allowing the utilization of methanol was the implementation of NAD-dependent methanol dehydrogenase and the establishment of the ribulose monophosphate cycle by expressing the genes for hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloisomerase (Phi). To test for the best-performing enzymes in the heterologous host, a number of enzyme candidates from different donor organisms were selected and systematically analyzed for their in vitro and in vivo activities in E. coli. Among these, Mdh2, Hps and Phi originating from Bacillus methanolicus were found to be the most effective. Labeling experiments using (13)C methanol with E. coli producing these enzymes showed up to 40% incorporation of methanol into central metabolites. The presence of the endogenous glutathione-dependent formaldehyde oxidation pathway of E. coli did not adversely affect the methanol conversion rate. Taken together, the results of this study represent a major advancement towards establishing synthetic methylotrophs by gene transfer.

  5. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products

    Science.gov (United States)

    Smith, Jeremy D.; Kinney, Haley; Anastasio, Cort

    2016-02-01

    We investigated the aqueous photochemistry of six phenolic carbonyls - vanillin, acetovanillone, guaiacyl acetone, syringaldehyde, acetosyringone, and coniferyl aldehyde - that are emitted from wood combustion. The phenolic carbonyls absorb significant amounts of solar radiation and decay rapidly via direct photodegradation, with lifetimes (τ) of 13-140 min under Davis, CA winter solstice sunlight at midday (solar zenith angle = 62°). The one exception is guaiacyl acetone, where the carbonyl group is not directly connected to the aromatic ring: This species absorbs very little sunlight and undergoes direct photodegradation very slowly (τ > 103 min). We also found that the triplet excited states (3C*) of the phenolic carbonyls rapidly oxidize syringol (a methoxyphenol without a carbonyl group), on timescales of 1-5 h for solutions containing 5 μM phenolic carbonyl. The direct photodegradation of the phenolic carbonyls, and the oxidation of syringol by 3C*, both efficiently produce low volatility products, with SOA mass yields ranging from 80 to 140%. Contrary to most aliphatic carbonyls, under typical fog conditions we find that the primary sink for the aromatic phenolic carbonyls is direct photodegradation in the aqueous phase. In areas of significant wood combustion, phenolic carbonyls appear to be small but significant sources of aqueous SOA: over the course of a few hours, nearly all of the phenolic carbonyls will be converted to SOA via direct photodegradation, enhancing the POA mass from wood combustion by approximately 3-5%.

  6. Sorption phenomena of methanol on heat treated coal; Netsushori wo hodokoshita sekitan no methanol kyuchaku tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Yasuda, H.; Kaiho, M.; Yamada, O.; Soneda, Y.; Kobayashi, M.; Makino, M. [National Institute for Resources and Environment, Tsukuba (Japan)

    1996-10-28

    Experiments were carried out to learn methanol sorption characteristics of heat-treated coal. When Taiheiyo coal is heat-treated at 125{degree}C, performed with a first methanol adsorption at 25{degree}C, and then desorption at 25{degree}C, a site with strong interaction with methanol and a site with relatively weak interaction are generated in test samples. A small amount of methanol remains in both sites. Then, when the methanol is desorbed at as low temperature as 70{degree}C, the methanol in the site with strong interaction remains as it has existed therein, but the methanol in the site with relatively weak interaction desorbs partially, hence the adsorption amount in a second adsorption at 25{degree}C increases. However, when desorption is performed at as high temperature as 125{degree}C, the methanol in the site with strong interaction also desorbs, resulting in increased adsorption heat in the second adsorption. The adsorption velocity drops, however. Existence of methanol in a site with strong interaction affects the adsorption velocity, but no effect is given by methanol in a site with weak interaction. 3 refs., 4 figs.

  7. Metal Carbonyl-Hydrosilane Reactions and Hydrosilation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A. R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a siloxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Three relevant catalytic reactions are shown. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(C0){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(I) precatalysts.

  8. Sorptive Removal of Odorous Carbonyl Gases by Water

    Directory of Open Access Journals (Sweden)

    Ehsanul Kabir

    2010-01-01

    Full Text Available In this study, the removal capacity of deionized water was investigated against five gaseous carbonyl compounds (i.e., acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and isovaleraldehyde by means of the gas stripping method. To determine the trapping behavior of these odorants by water, gaseous working standards prepared at three different concentration levels (i.e., for acetaldehyde around 300, 500, and 1,000 ppb were forced through pure water contained in an impinger at room temperature. The removal efficiency of the target compounds was inspected in terms of two major variables: (1 concentration levels of gaseous standard and (2 impinger water volume (20, 50, 100, and 150 mL. Although the extent of removal was affected fairly sensitively by changes in water volume, this was not the case for standard concentration level changes. Considering the efficiency of sorption media, gas stripping with aqueous solution can be employed as an effective tool for the removal of carbonyl odorants.

  9. Reactions of. cap alpha. -phosphorylated carbonyl compounds with amino alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Moskva, V.V.; Sitdikova, T.Sh.; Zykova, T.V.; Alparova, M.V.; Shagvaleev, F.Sh.

    1986-10-20

    2-Aminoethanol reacts with carbonyl compounds with the formation, depending on the structure of the latter, either of a mixture of azomethines and oxazolidines, or of only azomethines. In the development of investigations on the reactivity of ..cap alpha..-phosphorylated carbonyl compounds the authors studied the reactions of a number of amino alcohols with phosphorylated acetaldehyde and acetone. In both cases they observed the formation of compounds of enamine structure, oxazolidines and azomethines were not observed. By means of NMR spectroscopy they established clearly the formation of the E-isomeric products. The /sup 1/H, /sup 31/P, and /sup 13/C NMR spectra were recorded on a WP-80 spectrometer. Chemical shifts of protons and /sup 13/C nuclei are given relative to TMS, and phosphorus nuclei relative to orthophosphoric acid.

  10. Nuclear chemistry. Synthesis and detection of a seaborgium carbonyl complex.

    Science.gov (United States)

    Even, J; Yakushev, A; Düllmann, Ch E; Haba, H; Asai, M; Sato, T K; Brand, H; Di Nitto, A; Eichler, R; Fan, F L; Hartmann, W; Huang, M; Jäger, E; Kaji, D; Kanaya, J; Kaneya, Y; Khuyagbaatar, J; Kindler, B; Kratz, J V; Krier, J; Kudou, Y; Kurz, N; Lommel, B; Miyashita, S; Morimoto, K; Morita, K; Murakami, M; Nagame, Y; Nitsche, H; Ooe, K; Qin, Z; Schädel, M; Steiner, J; Sumita, T; Takeyama, M; Tanaka, K; Toyoshima, A; Tsukada, K; Türler, A; Usoltsev, I; Wakabayashi, Y; Wang, Y; Wiehl, N; Yamaki, S

    2014-09-19

    Experimental investigations of transactinoide elements provide benchmark results for chemical theory and probe the predictive power of trends in the periodic table. So far, in gas-phase chemical reactions, simple inorganic compounds with the transactinoide in its highest oxidation state have been synthesized. Single-atom production rates, short half-lives, and harsh experimental conditions limited the number of experimentally accessible compounds. We applied a gas-phase carbonylation technique previously tested on short-lived molybdenum (Mo) and tungsten (W) isotopes to the preparation of a carbonyl complex of seaborgium, the 106th element. The volatile seaborgium complex showed the same volatility and reactivity with a silicon dioxide surface as those of the hexacarbonyl complexes of the lighter homologs Mo and W. Comparison of the product's adsorption enthalpy with theoretical predictions and data for the lighter congeners supported a Sg(CO)6 formulation.

  11. Hydrogen Production from Methanol Using Corona Discharges

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Hydrogen production at room temperature from liquid methanol has been conductedusing corona discharge. The content of water in methanol solution has a significant effect on thisproduction. When water concentration increases from 1.0 % to 16.7 %, the methanol conversionrate changes from 0.196 to 0.284 mol/h. An important finding in this investigation is theformation of ethylene glycol as a major by-product. The yield of ethylene glycol is ranged from0.0045 to 0.0075 mol/h based on the water content.

  12. Emissions of Toxic Carbonyls in an Electronic Cigarette

    Directory of Open Access Journals (Sweden)

    Guthery William

    2016-01-01

    Full Text Available Electronic cigarettes (e-cigs provide a smoke-free alternative for inhalation of nicotine without the vast array of toxic and carcinogenic combustion products produced by tobacco smoke. Elevated levels of toxic carbonyls may be generated during vaporisation; however, it is unclear whether that is indicative of a fault with the device or is due to the applied conditions of the test. A device, designed and built at this facility, was tested to determine the levels of selected toxic carbonyls. The reservoir was filled with approximately 960 mg of an e-liquid formulation containing 1.8% (w/v nicotine. Devices were puffed 200 times in blocks of 40 using a standardised regime consisting of a 55 mL puff volume; 3 s puff duration; 30 s puff interval; square wave puff profile. Confirmatory testing for nicotine and total aerosol delivery resulted in mean (n = 8 values of 10 mg (RSD 12.3% and 716 mg (RSD 11.2%, respectively. Emissions of toxic carbonyls were highly variable yet were between < 0.1% and 22.9% of expected levels from a Kentucky Reference Cigarette (K3R4F puffed 200 times under Health Canada Intense smoking conditions. It has been shown that a device built to a high specification with relatively consistent nicotine and aerosol delivery emits inconsistent levels of carbonyls. The exposure is greatly reduced when compared with lit tobacco products. However, it was observed that as the reservoirs neared depletion then emission levels were significantly higher

  13. Methanol Along the Path from Envelope to Protoplanetary Disc

    CERN Document Server

    Drozdovskaya, Maria N; Visser, Ruud; Harsono, Daniel; van Dishoeck, Ewine F

    2014-01-01

    Interstellar methanol is considered to be a parent species of larger, more complex organic molecules. A physicochemical simulation of infalling parcels of matter is performed for a low-mass star-forming system to trace the chemical evolution from cloud to disc. An axisymmetric 2D semi-analytic model generates the time-dependent density and velocity distributions, and full continuum radiative transfer is performed to calculate the dust temperature and the UV radiation field at each position as a function of time. A comprehensive gas-grain chemical network is employed to compute the chemical abundances along infall trajectories. Two physical scenarios are studied, one in which the dominant disc growth mechanism is viscous spreading, and another in which continuous infall of matter prevails. The results show that the infall path influences the abundance of methanol entering each type of disc, ranging from complete loss of methanol to an enhancement by a factor of > 1 relative to the prestellar phase. Critical ch...

  14. Iron(III)-catalysed carbonyl-olefin metathesis

    Science.gov (United States)

    Ludwig, Jacob R.; Zimmerman, Paul M.; Gianino, Joseph B.; Schindler, Corinna S.

    2016-05-01

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  15. Carbonylation of Ethene Catalysed by Pd(II-Phosphine Complexes

    Directory of Open Access Journals (Sweden)

    Gianni Cavinato

    2014-09-01

    Full Text Available This review deals with olefin carbonylation catalysed by Pd(II-phosphine complexes in protic solvents. In particular, the results obtained in the carbonylation with ethene are reviewed. After a short description of the basic concepts relevant to this catalysis, the review treats in greater details the influence of the bite angle, skeletal rigidity, electronic and steric bulk properties of the ligand on the formation of the products, which range from high molecular weight perfectly alternating polyketones to methyl propanoate. It is shown that the steric bulk plays a major role in directing the selectivity. Particular emphasis is given to the factors governing the very active and selective catalysis to methyl propanoate, including the mechanism of the catalytic cycles with diphosphine- and monophosphine-catalysts. A brief note on the synthesis of methyl propanoate using a “Lucite” type catalyst in ionic liquids is also illustrated. A chapter is dedicated to the carbonylation of olefins in aqueous reaction media. The nonalternating CO-ethene copolymerization is also treated.

  16. Study on Carbonyl Emissions of Diesel Engine Fueled with Biodiesel

    Directory of Open Access Journals (Sweden)

    Ruina Li

    2017-01-01

    Full Text Available Biodiesel is a kind of high-quality alternative fuel of diesel engine. In this study, biodiesel and biodiesel/diesel blend were used in a single cylinder diesel engine to study the carbonyl emissions. The result shows that carbonyl pollutants of biodiesel and biodiesel/diesel blend are mainly aldehyde and ketone compounds with 1–3 carbon atoms, and formaldehyde concentration is higher than 80% of the total carbonyl pollutants for biodiesel. The formaldehyde concentration peak is reduced with the increase of intake temperature (T, intake pressure (P, and exhaust gas recirculation (EGR ratio and increased with the increase of compression ratio (ε. When excess air coefficient (λ is lower than 1.7, the formaldehyde concentration is increased with the increase of excess air ratio. When λ is higher than 1.7, the formaldehyde concentration is reduced with the increase of excess air ratio. The dilution of air can reduce formaldehyde concentration in the premixed flame of diesel effectively; however, it has less effect on biodiesel. Among the fuel pretreatment measures of adding hydrogen, CO, and methane, the addition of hydrogen shows the best effect on reducing formaldehyde of biodiesel.

  17. Iron(III)-catalysed carbonyl-olefin metathesis.

    Science.gov (United States)

    Ludwig, Jacob R; Zimmerman, Paul M; Gianino, Joseph B; Schindler, Corinna S

    2016-04-27

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  18. Photolysis of Carbonyl Diisocyanate: Generation of Isocyanatocarbonyl Nitrene and Diazomethanone.

    Science.gov (United States)

    Liu, Qifan; Li, Hongmin; Wu, Zhuang; Li, Dingqing; Beckers, Helmut; Rauhut, Guntram; Zeng, Xiaoqing

    2016-10-20

    The stepwise decomposition of carbonyl diisocyanate, OC(NCO)2 , has been studied by using IR spectroscopy in solid argon matrices at 16 K. Upon irradiation with an ArF laser (λ=193 nm), carbonyl diisocyanate split off CO and furnished a new carbonyl nitrene, OCNC(O)N, in its triplet ground state. Two conformers of the nitrene, syn and anti, that were derived from the two conformers of OC(NCO)2 (62 % syn-syn and 38 % syn-anti) were identified and characterized by combining IR spectroscopy and quantum chemical calculations. Subsequent irradiation with visible light (λ>395 nm) caused the Curtius rearrangement of the nitrene into OCNNCO. In addition to the expected decomposition products, N2 and CO, further photolysis of OCNNCO with the ArF laser yielded NOCN, through a diazomethanone (NNCO) intermediate. To further validate our proposed reaction mechanism, ArF-laser photolysis of the closely related NNNNCO and cyclo-N2 CO in solid argon matrices were also studied. The observations of NOCN and in situ CO-trapped product OCNNCO provided indirect evidence to support the initial generation of NNCO as a common intermediate during the laser photolysis of OCNNCO, NNNNCO, and cyclo-N2 CO. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. The Catalysis of NAD+ on Methanol Anode Oxidation Electrode for Direct Methanol Fuel Cell

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ping; PAN Mu; YUAN Run-zhang

    2004-01-01

    A tentative idea of developing a liquid-catalytic system on methanol anode oxidation was proposed by analyzing the characteristics of methanol anode oxidation in direct methanol fuel cell. The kinetics of methanol oxidation at a glassy carbon electrode in the presence of nicotinamide adenine dinucleotide (NAD+) was investigated. It is found that the current density of methanol oxidation increases greatly and the electrochemical reaction impedance reduces obviously in the presence of NAD+ compared with those in the absence of NAD+. The catalytic activity of NAD+ is sensitive to temperature. When the temperature preponderates over 45℃, NAD+ is out of function of catalysis for methanol oxidation, which is probably due to the denaturation of NAD+ at a relatively high temperature.

  20. Methanol production from fermentor off-gases

    Science.gov (United States)

    Dale, B. E.; Moreira, A. R.

    The off gases from an acetone butanol fermentation facility are composed mainly of CO2 and H2. Such a gas stream is an ideal candidate as a feed to a methanol synthesis plant utilizing modern technology recently developed and known as the CDH-methanol process. A detailed economic analysis for the incremental cost of a methanol synthesis plant utilizing the off gases from an acetone butanol fermentation indicates a profitable rate of return of 25 to 30% under the most likely production conditions. Bench scale studies at different fermentor mixing rates indicate that the volume of gases released during the fermentation is a strong function of the agitation rate and point to a potential interaction between the volume of H2 evolved and the levels of butanol present in the final fermented broth. Such interaction may require establishing optimum operating conditions for an integrated butanol fermentation methanol synthesis plant.

  1. Methanol: A Versatile Fuel for Immediate Use

    Science.gov (United States)

    Reed, T. B.; Lerner, R. M.

    1973-01-01

    Advocates the large-scale production and use of methanol as a substitute for the diminishing reserves of low-cost petroleum resources. Describes the manufacturing process and advantages of the versatile fuel. (JR)

  2. Quiet Changes in the Methanol Supply Mode

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ The coal chemicals sector, the new coal chemicals sector in particular, has been emerging fast in China in recent years. The production scale of methanol as an important coal chemical product has expanded constantly.

  3. Cancer chemopreventive property of Bidens pilosa methanolic ...

    African Journals Online (AJOL)

    admin

    Cancer chemopreventive property of Bidens pilosa methanolic extract on two stage in vivo skin carcinogenesis ... In the forestomach, kidney and lung, glutathione S-transferase and ..... weight gain profile or terminal in mice treated with the two ...

  4. Mixotrophic growth of two thermophilic Methanosarcina strains, Methanosarcina thermophila TM-1 and Methanosarcina sp. SO-2P, on methanol and hydrogen/carbon dioxide

    DEFF Research Database (Denmark)

    Mladenovska, Zuzana; Ahring, Birgitte Kiær

    1997-01-01

    Two thermophilic strains, Methanosarcina thermophila TM-1 and Methanosarcina sp. SO-2P, were capable of mixotrophic growth on methanol and H-2/CO2. Activated carbon was, however, found to be necessary to support good growth. Both strains used hydrogen and methanol simultaneously. When methanol wa...... was depleted, hydrogen utilization continued and methane was further produced with concurrent cell growth. UV epifluorescence microscopy revealed that aggregates of both strains exhibited a bright red fluorescence besides the usual blue-green fluorescence....

  5. Mixotrophic growth of two thermophilic Methanosarcina strains, Methanosarcina thermophila TM-1 and Methanosarcina sp. SO-2P, on methanol and hydrogen/carbon dioxide

    DEFF Research Database (Denmark)

    Mladenovska, Zuzana; Ahring, Birgitte Kiær

    1997-01-01

    Two thermophilic strains, Methanosarcina thermophila TM-1 and Methanosarcina sp. SO-2P, were capable of mixotrophic growth on methanol and H-2/CO2. Activated carbon was, however, found to be necessary to support good growth. Both strains used hydrogen and methanol simultaneously. When methanol wa...... was depleted, hydrogen utilization continued and methane was further produced with concurrent cell growth. UV epifluorescence microscopy revealed that aggregates of both strains exhibited a bright red fluorescence besides the usual blue-green fluorescence....

  6. Beads,Necklaces, Chains and Strings in Capping Carbonyl Clusters

    Directory of Open Access Journals (Sweden)

    Enos Masheija Kiremire

    2015-09-01

    Full Text Available The paper attempts to explain at length the close relationship between transition metal carbonyl clusters with main group clusters especially the boranes using the 14n and 4n rules. When the ‘shielding’ electrons are removed from a transition metal carbonyl cluster and becomes ‘naked’, it resembles a corresponding one in the main group elements. A an expanded table of osmium carbonyl clusters was constructed using the capping fragment Os(CO2(14n-2 and the fragment Os(CO3 (14n+0. The table reveals the fact that the known series such closo, nido and arachno are part and parcel of a wide range of series especially the capping series 14n+q, where q takes up negative multiple integers of two including 0 such as such = 0, -2,-4, -6, and so on. The linkage between capping series in transition metal carbonyl clusters has also been identified. Apart from the capping series generated in the table, there is another type of series where the skeletal cluster elements remained the same but the number of carbonyl ligands successively decreased. These types of series are referred to as stripping series. Mapping generating functions were also derived which produces any cluster formula or series required. Also the table shows that many clusters form utilizing some of its atoms as closo nucleus around which the larger ones are built and thus forming clusters within larger clusters. The table may be used to categorize a given cluster formula that falls within its range. Otherwise, using the 14n rule or 4n rule can be used for cluster classification. Furthermore, the table indicated that atoms, fragments and molecules can be classified into series. Through this approach of using series, Hoffmann’s important isolobal relationship of chemical species can splendidly be explained.Using the 14n rule and 4n rules creates a framework under which chemical species such as atoms, fragments, molecules and ions some of which may appear unrelated from main group

  7. Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol–methanol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Martinez-Guerra, Edith; Gude, Veera Gnaneswar, E-mail: gude@cee.msstate.edu

    2014-12-15

    Highlights: • Pulse sonication effect on transesterification of waste vegetable oil was studied. • Effects of ethanol, methanol, and alcohol mixtures on FAMEs yield were evaluated. • Effect of ultrasonic intensity, power density, and its output rates were evaluated. • Alcohol mixtures resulted in higher biodiesel yields due to better solubility. - Abstract: This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.

  8. Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

    Science.gov (United States)

    Zhu, Yimin; Zelenay, Piotr

    2006-03-21

    A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

  9. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Xiaobing, E-mail: pangxbyuanj@gmail.com [Department of Chemistry, University of York, Heslington, York, YO10 5DD (United Kingdom); Lewis, Alastair C., E-mail: ally.lewis@york.ac.uk [National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD (United Kingdom)

    2011-11-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 {mu}g cigarette{sup -1} ({mu}g cig{sup -1}) and the particulate carbonyl emissions varied in the range of 23-127 {mu}g cig{sup -1}. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 {mu}g cig{sup -1} gaseous and 141 {mu}g cig{sup -1} particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: {yields} Carbonyl

  10. Microfluidic distillation chip for methanol concentration detection.

    Science.gov (United States)

    Wang, Yao-Nan; Liu, Chan-Chiung; Yang, Ruey-Jen; Ju, Wei-Jhong; Fu, Lung-Ming

    2016-03-17

    An integrated microfluidic distillation system is proposed for separating a mixed ethanol-methanol-water solution into its constituent components. The microfluidic chip is fabricated using a CO2 laser system and comprises a serpentine channel, a boiling zone, a heating zone, and a cooled collection chamber filled with de-ionized (DI) water. In the proposed device, the ethanol-methanol-water solution is injected into the microfluidic chip and driven through the serpentine channel and into the collection chamber by means of a nitrogen carrier gas. Following the distillation process, the ethanol-methanol vapor flows into the collection chamber and condenses into the DI water. The resulting solution is removed from the collection tank and reacted with a mixed indicator. Finally, the methanol concentration is inversely derived from the absorbance measurements obtained using a spectrophotometer. The experimental results show the proposed microfluidic system achieves an average methanol distillation efficiency of 97%. The practicality of the proposed device is demonstrated by detecting the methanol concentrations of two commercial fruit wines. It is shown that the measured concentration values deviate by no more than 3% from those obtained using a conventional bench top system.

  11. Class I methanol masers: Masers with EGOs

    CERN Document Server

    Chen, Xi; Shen, Zhi-Qiang

    2009-01-01

    We have compared the results of a number of published class I methanol maser surveys with the catalogue of high-mass outflow candidates identified from the GLIMPSE survey (known as extended green objects or EGOs). We find class I methanol masers associated with approximately two-thirds of EGOs. Although the association between outflows and class I methanol masers has long been postulated on the basis of detailed studies of a small number of sources, this result demonstrates the relationship for the first time on a statistical basis. Despite the publication of a number of searches for class I methanol masers, a close physical association with another astrophysical object which could be targeted for the search is still lacking. The close association between class I methanol masers and EGOs therefore provides a large catalogue of candidate sources, most of which have not previously been searched for class I methanol masers. Interstellar masers and outflows have both been proposed to trace an evolutionary sequenc...

  12. Detection of Protein Carbonyls by Means of Biotin Hydrazide-Streptavidin Affinity Methods.

    Science.gov (United States)

    Hensley, Kenneth

    2015-01-01

    Oxidative posttranslational protein modifications occur as a normal process of cell biology and to a greater extent during pathogenic conditions. The detection and quantitation of protein oxidation has posed a continuing challenge to bioanalytical chemists because of the following reasons: The products of oxidative protein damage are chemically diverse; protein oxidation generally occurs at low background levels; and the complexity of biological samples introduces high background noise when standard techniques such as immunolabeling are applied to "dirty" tissue extracts containing endogenous immunoglobulins or small molecular weight, chemically reactive compounds has been developed which circumvents these difficulties by incorporating a biotin label at sites of protein carbonylation. Biotin hydrazide-labeled proteins are detectable using standard streptavidin-coupled detection techniques such as peroxidase-catalyzed chemiluminescence of immunoblots. Advantages of the biotin hydrazide-labeling technique are its sensitivity and its lack of reliance upon antibodies that inevitably suffer from nonspecific background noise and contaminating endogenous immunoglobulins.

  13. Indoor carbonyl compounds in an academic building in Beijing, China: concentrations and influencing factors

    Institute of Scientific and Technical Information of China (English)

    Chuanjia JIANG; Pengyi ZHANG

    2012-01-01

    Carbonyl compounds in indoor air are of great concern for their adverse health effects. Between February and May, 2009, concentrations of 13 carbonyl compounds were measured in an academic building in Beijing, China. Total concentration of the detected carbonyls ranged from 20.7 to 189.1 I.tg.m3, and among them acetone and formaldehyde were the most abundant, with mean concentrations of 26.4 and 22.6gg.m-3, respectively. Average indoor concentrations of other carbonyls were below I 0 gg. m~3. Principal component analysis identified a combined effect of common indoor carbonyl sources and ventilation on indoor carbonyl levels. Diurnal variations of the carbonyl compounds were investigated in one office room, and carbonyl concentrations tended to be lower in the daytime than at night, due to enhanced ventilation. Average concentrations of carbonyl compounds in the office room were generally higher in early May than in late February, indicating the influence of temperature. Carbo- nyl source emission rates from both the room and human occupants were estimated during two lectures, based on one-compartment mass balance model. The influence of human occupants on indoor carbonyl concentrations varies with environmental conditions, and may become signifi- cant in the case of a large human occupancy.

  14. [Chemical Characteristics and Sources of Atmospheric Carbonyls During the 2014 Beijing APEC].

    Science.gov (United States)

    He, Xiao-lang; Tan, Ji-hua; Guo, Song-jun; Ma, Yong-liang; He, Ke-bin

    2016-03-15

    Pollution characteristic and variation trend of atmospheric carbonyls were investigated in November during the 2014 Beijing APEC. Formaldehyde, acetaldehyde and acetone were the dominant carbonyls, accounting for 82.66% of total carbonyls, and especially, formaldehyde accounted for 40.12% of total carbonyls. Atmospheric concentrations of total carbonyls decreased by around 64.10% after the clean air policy was carried out during the Beijing APEC, and the variation trend of carbonyls showed a similar pattern to those of other pollutants like PM₂.₅ during the APEC. Strong correlations (R² of 0.67-0.98) were observed among formaldehyde, acetaldehyde, acetone and total carbonyls during and after the APEC, indicating that they had similar sources; however, poor correlations (R² of -0.11-0.42 and 0.16-0.94, respectively) were observed before the APEC, implying different emission sources for ambient carbonyls. The calculated ratios of C1/C2, C2/C3 and OC/EC indicated that both vehicles and coal emissions were responsible for atmospheric carbonyls before the APEC, and emissions from coal burning were the major contributor to atmospheric carbonyls during and after the APEC, especially after the APEC.

  15. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method

    Energy Technology Data Exchange (ETDEWEB)

    Black, Stuart; Ferrell, Jack R.

    2017-01-01

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 degrees C.

  16. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method.

    Science.gov (United States)

    Black, Stuart; Ferrell, Jack R

    2017-02-07

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 °C.

  17. Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, V.B.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Eng. Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Rangel, C.M. [Instituto Nacional de Energia e Geologia, Fuel Cells and Hydrogen, Estrada do Paco do Lumiar, 1649-038 Lisboa (Portugal)

    2009-08-15

    A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs. The main gain of this work is to systematically vary commercial MEA materials and check their influence on the cell performance of a direct methanol fuel cell operating at close to room temperature. A detailed experimental study on the performance of an <> developed DMFC with 25 cm{sup 2} of active membrane area, working near the ambient conditions is described. Tailored MEAs (membrane-electrode assemblies), with different structures and combinations of gas diffusion layers (GDLs), were designed and tested in order to select optimal working conditions at high methanol concentration levels without sacrificing performance. The experimental polarization and power density curves were successfully compared with the predictions of a steady state, one-dimensional model accounting for coupled heat and mass transfer, along with the electrochemical reactions occurring in the DMFC recently developed by the same authors. The influence of the anode gas diffusion layer media, the membrane thickness and the MEA properties on the cell performance are explained under the light of the predicted methanol crossover rate across the membrane. A tailored MEA build-up with the common available commercial materials was proposed to achieve relatively low methanol crossover, operating at high methanol concentrations. The use of adequate materials for the gas diffusion layers (carbon paper at the anode GDL and carbon cloth at the cathode GDL) enables the use of thinner membranes enhancing the water back diffusion which is essential to work at high methanol concentrations. (author)

  18. Behavioral pattern of a monopolar passive direct methanol fuel cell stack

    Science.gov (United States)

    Kim, Young-Jin; Bae, Byungchan; Scibioh, M. Aulice; Cho, EunAe; Ha, Heung Yong

    A passive, air-breathing, monopolar, liquid feed direct methanol fuel cell (DMFC) stack consisting of six unit cells with no external pump, fan or auxiliary devices to feed the reactants has been designed and fabricated for its possible employment as a portable power source. The configurations of the stack of monopolar passive feed DMFCs are different from those of bipolar active feed DMFCs and therefore its operational characteristics completely vary from the active ones. Our present investigation primarily focuses on understanding the unique behavioral patterns of monopolar stack under the influence of certain operating conditions, such as temperature, methanol concentration and reactants feeding methods. With passive reactants supply, the temperature of the stack and open circuit voltage (OCV) undergo changes over time due to a decrease in concentration of methanol in the reservoir as the reaction proceeds. Variations in performance and temperature of the stack are mainly influenced by the concentration of methanol. Continuous operation of the passive stack is influenced by the supply of methanol rather than air supply or water accumulation at the cathode. The monopolar stack made up of six unit cells exhibits a total power of 1000 mW (37 mW cm -2) with 4 M methanol under ambient conditions.

  19. Sterion membranes in Direct Methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Linares, J. J.; Lobato, J.; Canizares, P.; Rodrigo, M. A.; Fernandez, A.

    2005-07-01

    Direct Methanol Fuel Cells (DMFCs) has been postulated as an alternative to traditional hydrogen fed Polymer Electrolyte Membrane Fuel Cells (H2-PEMFCs). Among their advantages, it can be pointed out the low cost of the fuel, simplicity of design, large availability, easy handling and distribution. However, there are still some challenges in this field, such as the development of electrocatalysts which can enhance the electrokinetics of methanol oxidation, the discovery of an electrolyte membrane with high conductivity and low methanol crossover at the same time and the production of methanol-tolerant electrocatalysts with high activity for oxygen reduction. So far, Nafion 117 has been the polymer membrane most widely used in DMFCs. Yet, it is well known that Nafion (Du Pont Inc.) membranes are not good barrier for methanol, so that the coulombic efficiency of Nafion-based DMFCs is significantly reduced by the chemical oxidation of methanol in the cathode. Recently, a new perfluorinated polymer with sulphonic acid groups (PFSA) has been developed, under the commercial name of Sterion (David Fuel Cell Components). As a difference as opposed to Nafion, this membrane is cast by the solution casting method, which provides a different sulphonic cluster configuration as compared to the extrusion cast Nafion membranes, which may give rise to different methanol crossover behaviour. In this work, it has been studied and analysed the suitability of Sterion in the DMFCs field. For that, it has been measured the methanol permeability of this membrane at different solute concentration and temperature, and its performance in an actual fuel cell at different operational conditions, such as methanol concentration, temperature and back pressure. Tests have been made using both oxygen and air in the cathode and half-cell potentials have been evaluated in some measurements in order to discriminate the contribution of both semi-reactions to the overall cell overvoltage. A lifetime

  20. Production of methanol/DME from biomass

    Energy Technology Data Exchange (ETDEWEB)

    Ahrenfeldt, J.; Birk Henriksen, U.; Muenster-Swendsen, J.; Fink, A.; Roengaard Clausen, L.; Munkholt Christensen, J.; Qin, K.; Lin, W.; Arendt Jensen, P.; Degn Jensen, A.

    2011-07-01

    In this project the production of DME/methanol from biomass has been investigated. Production of DME/methanol from biomass requires the use of a gasifier to transform the solid fuel to a synthesis gas (syngas) - this syngas can then be catalytically converted to DME/methanol. Two different gasifier types have been investigated in this project: 1) The Two-Stage Gasifier (Viking Gasifier), designed to produce a very clean gas to be used in a gas engine, has been connected to a lab-scale methanol plant, to prove that the gas from the gasifier could be used for methanol production with a minimum of gas cleaning. This was proved by experiments. Thermodynamic computer models of DME and methanol plants based on using the Two-Stage Gasification concept were created to show the potential of such plants. The models showed that the potential biomass to DME/methanol + net electricity energy efficiency was 51-58% (LHV). By using waste heat from the plants for district heating, the total energy efficiencies could reach 87-88% (LHV). 2) A lab-scale electrically heated entrained flow gasifier has been used to gasify wood and straw. Entrained flow gasifiers are today the preferred gasifier type for commercial coal gasification, but little information exists on using these types of gasifiers for biomass gasification. The experiments performed provided quantitative data on product and gas composition as a function of operation conditions. Biomass can be gasified with less oxygen consumption compared to coal. The organic fraction of the biomass that is not converted to gas appears as soot. Thermodynamic computer models of DME and methanol plants based on using entrained flow gasification were created to show the potential of such plants. These models showed that the potential torrefied biomass to DME/methanol + net electricity energy efficiency was 65-71% (LHV). Different routes to produce liquid transport fuels from biomass are possible. They include production of RME (rapeseed oil

  1. Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor

    NARCIS (Netherlands)

    Balk, M.; Weijma, J.; Goorissen, H.P.; Ronteltap, M.; Hansen, T.A.; Stams, A.J.M.

    2007-01-01

    A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H-2/CO2, no ap

  2. Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol-methanol mixtures.

    Science.gov (United States)

    Martinez-Guerra, Edith; Gude, Veera Gnaneswar

    2014-12-01

    This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol-methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol-methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1-2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol-methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.

  3. Determination of Carbonyl Compounds in Cigarette Mainstream Smoke. The CORESTA 2010 Collaborative Study and Recommended Method

    Directory of Open Access Journals (Sweden)

    Intorp M

    2014-12-01

    Full Text Available A recommended method has been developed and published by CORESTA, applicable to the quantification of selected carbonyl compounds (acetaldehyde, formaldehyde, acetone, acrolein, methyl ethyl ketone, crotonaldehyde, propionaldehyde and butyraldehyde in cigarette mainstream smoke. The method involved smoke collection in impinger traps, derivatisation of carbonyls with 2,4-dinitrophenylhydrazine (DNPH, separation of carbonyl hydrazones by reversed phase high performance liquid chromatography and detection by ultra violet or diode array.

  4. Bioreduction of some common carbonylic compounds mediated by yeasts.

    Science.gov (United States)

    Silva, Javier; Alarcón, Julio; Aguila, Sergio A; Alderete, Joel B

    2010-01-01

    Bioreduction of several prochiral carbonylic compounds such as acetophenone (1), ethyl acetoacetate (2) and ethyl phenylpropionate (3) to the corresponding optically active sec-alcohols 1a-3a was performed using wild-type strains of Pichia pastoris UBB 1500, Rhodotorula sp., and Saccharomyces cerevisiae. The reductions showed moderate to excellent conversion and high enantiomeric excess, in an extremely mild and environmentally benign manner in aqueous medium, using glucose as cofactor regeneration system. The obtained alcohols follow Prelog's rule, but in the reduction of 1 with P. pastoris UBB 1500 the anti-Prelog enantiopreference was observed.

  5. Investigating the effects of methanol-water vapor mixture on a PBI-based high temperature PEM fuel cell

    DEFF Research Database (Denmark)

    Araya, Samuel Simon; Andreasen, Søren Juhl; Nielsen, Heidi Venstrup

    2012-01-01

    This paper investigates the effects of methanol and water vapor on the performance of a high temperature proton exchange membrane fuel cell (HT-PEMFC). A H3PO4-doped polybenzimidazole (PBI) membrane electrode assembly (MEA), Celtec P2100 of 45 cm2 of active surface area from BASF was employed....... A long-term durability test of around 1250 h was performed, in which the concentrations of methanol-water vapor mixture in the anode feed gas were varied. The fuel cell showed a continuous performance decay in the presence of vapor mixtures of methanol and water of 5% and 8% by volume in anode feed...

  6. Mechanistic and kinetic investigations on the role of methanol and dimethyl ether in the Methanol-To-Hydrocarbons reaction

    OpenAIRE

    Espín, Juan Salvador Martínez

    2017-01-01

    The main scope of this PhD thesis was to gain knowledge on the mechanistic and kinetic behavior of methanol and DME in the industrially relevant Methanol-To-Hydrocarbons (MTH) reaction with the use of zeolitic materials as catalysts. Industrial MTH processes use methanol, DME or combined methanol/DME feeds over zeolitic catalysts. Methanol and its dehydration product, DME, are conventionally attributed an analogous behavior in MTH; however, a thorough investigation on the theme is still missi...

  7. Methanol exchange between grassland and the atmosphere

    Directory of Open Access Journals (Sweden)

    A. Brunner

    2007-01-01

    Full Text Available Concentrations and fluxes of methanol were measured above two differently managed grassland fields (intensive and extensive in central Switzerland during summer 2004. The measurements were performed with a proton-transfer-reaction mass-spectrometer and fluxes were determined by the eddy covariance method. The observed methanol emission showed a distinct diurnal cycle and was strongly correlated with global radiation and water vapour flux. Mean and maximum daily emissions were found to depend on grassland species composition and, for the intensive field, also on the growing state. The extensive field with a more complex species composition had higher emissions than the graminoid-dominated intensive field, both on an area and on a biomass basis. A simple parameterisation depending on the water vapour flux and the leaf area index allowed a satisfying simulation of the temporal variation of methanol emissions over the growing phase. Accumulated carbon losses due to methanol emissions accounted for 0.024 and 0.048% of net primary productivity for the intensive and extensive field, respectively. The integral methanol emissions over the growing periods were more than one order of magnitude higher than the emissions related to cut and drying events.

  8. Photocatalytic degradation of mixed gaseous carbonyl compounds at low level on adsorptive TiO2/SiO2 photocatalyst using a fluidized bed reactor.

    Science.gov (United States)

    Zhang, Maolin; An, Taicheng; Fu, Jiamo; Sheng, Guoying; Wang, Xinming; Hu, Xiaohong; Ding, Xuejun

    2006-06-01

    An adsorptive silica-supported titania photocatalyst TiO(2)/SiO(2) was prepared by using nanosized titania (anatase) immobilized on silica gel by the sol-gel technique with the titanium tetra isopropoxide as the main raw material and acetic acid as the acid catalyst. Meanwhile the structure and properties of the TiO(2)/SiO(2) photocatalyst were studied by means of many modern analysis techniques such as TEM, XRD, and BET. Gas-solid heterogeneous photocatalytic decomposition of four carbonyl compounds mixture at low concentration levels over ultraviolet irradiated TiO(2)/SiO(2) photocatalyst were carried out with high degradation efficiencies in a coaxial triple-cylinder-type fluidized bed photocatalytic reactor, which provided efficient continuous contact of ultraviolet photons, silica-supported titania photocatalyst, and gaseous reactants. Experimental results showed that the photocatalyst had a high adsorption performance and a good photocatalytic activity for four carbonyl compounds mixture. Some factors influencing the photocatalytic decomposition of the mixed carbonyl compounds, i.e. the gas flowrate, relative humidity, concentration of oxygen, and illumination time, were discussed in detail. It is found that the photocatalytic reaction rate of four carbonyl compounds decreased in this order: propionaldehyde, acetone, acetaldehyde and formaldehyde.

  9. Research on compatibility of carbonylated piperylene petroleum resin and SBS%羰基化间戊二烯石油树脂与SBS相容性研究

    Institute of Scientific and Technical Information of China (English)

    毛兵; 张春梅; 李亮; 柳彩霞; 潘广勤

    2012-01-01

    The compatibility of carbonylated piperylene petroleum resin and SBS was investigated by analysis of glass-transition temperature of blend systems.The results showed that piperylene petroleum resin and hard block PS phase of SBS are incompatible.but the polarity of resin was improved after carbonylation,and the compatibility of resin and hard block PS phase was improved as well.The carbonylation time of resin is about 90 min,and the content of carbonylated resin in petroleum resin/SBS blends is more than 20%.The blends formed a homogeneous continuous phase,and they are completely compatible.%通过对共混体系玻璃化转变温度(Tg)的分析,研究了羰基化间戊二烯石油树脂与SBS的相容性.结果表明,间戊二烯石油树脂与SBS中的硬段PS不相容,经过羰基化处理后的树脂极性提高,相容性得到改善.羰基化处理时间为90min左右,羰基化石油树脂在共混体系中质量分数为20%以上,共混体系形成了均匀的连续相,2者完全相容.

  10. Two-dimensional gel electrophoretic detection of protein carbonyls derivatized with biotin-hydrazide.

    Science.gov (United States)

    Wu, Jinzi; Luo, Xiaoting; Jing, Siqun; Yan, Liang-Jun

    2016-04-15

    Protein carbonyls are protein oxidation products that are often used to measure the magnitude of protein oxidative damage induced by reactive oxygen or reactive nitrogen species. Protein carbonyls have been found to be elevated during aging and in age-related diseases such as stroke, diabetes, and neurodegenerative diseases. In the present article, we provide detailed protocols for detection of mitochondrial protein carbonyls labeled with biotin-hydrazide followed by 2-dimensional isoelectric focusing (IEF)/SDS-PAGE and Western blotting probed with horse-radish peroxidase-conjugated streptavidin. The presented procedures can also be modified for detection of carbonylation of non-mitochondrial proteins.

  11. A biotin enrichment strategy identifies novel carbonylated amino acids in proteins from human plasma

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, Katarzyna; Davies, Michael J.

    2017-01-01

    Protein carbonylation is an irreversible protein oxidation correlated with oxidative stress, various diseases and ageing. Here we describe a peptide-centric approach for identification and characterisation of up to 14 different types of carbonylated amino acids in proteins. The modified residues...... in vitro metal ion-catalysed oxidation. Furthermore, we assigned 133 carbonylated sites in 36 proteins in native human plasma protein samples. The optimised workflow enabled detection of 10 hitherto undetected types of carbonylated amino acids in proteins: aldehyde and ketone modifications of leucine...

  12. Nano-Aluminum Powder Mediated Allylation of Carbonyl Compounds in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    YUAN Shi-Zhen; LIU Jin

    2008-01-01

    A new and effective Barbier-Grignard allylation of aldehydes or ketones has been carried out with nano-aluminum powder in aqueous 0.1 mol·L-1 NH4Cl (aq.) under an atmosphere of nitrogen. Aromatic carbonyl compounds gave homoallylic alcohols in good yields. The effectiveness of reaction was strongly influenced by the steric environment surrounding the carbonyl group. Aliphatic carbonyl compounds proceeded in low yields. The dominant stereoisomer was an erythro-isomer when an ortho-hydroxyl carbonyl compound was reacted under such a reaction condition.

  13. Radiolysis study of genistein in methanolic solution

    Science.gov (United States)

    Jung, Hee Jin; Park, Hae Ran; Jung, Uhee; Jo, Sung Kee

    2009-06-01

    The aim of the present work was to identify products obtained from genistein by ionizing radiation and to enhance the antioxidant properties of genistein through radiation-induced transformation. Genistein dissolved in methanol was irradiated γ-rays at a dose of 100 kGy. NMR and (HR) EI-MS spectroscopy were used to identify radiolysis products (GM1 and GM2). We proposed that rad CH 2OH may be implicated in the formation GM1 and GM2 during radiolysis of genistein in methanol. The genistein in methanol solution showed higher DPPH radical scavenging activity after γ-irradiation. Then, the antioxidant activities of radiolysis products were evaluated and compared to those of genistein.

  14. Methanol sensor operated in a passive mode

    Science.gov (United States)

    Ren, Xiaoming; Gottesfeld, Shimshon

    2002-01-01

    A sensor outputs a signal related to a concentration of methanol in an aqueous solution adjacent the sensor. A membrane electrode assembly (MEA) is included with an anode side and a cathode side. An anode current collector supports the anode side of the MEA and has a flow channel therethrough for flowing a stream of the aqueous solution and forms a physical barrier to control access of the methanol to the anode side of the MEA. A cathode current collector supports the cathode side of the MEA and is configured for air access to the cathode side of the MEA. A current sensor is connected to measure the current in a short circuit across the sensor electrodes to provide an output signal functionally related to the concentration of methanol in the aqueous solution.

  15. Polarisation of Class II Methanol Masers

    CERN Document Server

    Stack, P D

    2011-01-01

    We have used the University of Tasmania Mt Pleasant 26m radio telescope to investigate the polarisation characteristics of a sample of strong 6.7 GHz methanol masers, the first spectral line polarisation observations to be undertaken with this instrument. As part of this process we have developed a new technique for calibrating linear polarisation spectral line observations. This calibration method gives results consistent with more traditional techniques, but requires much less observing time on the telescope. We have made the first polarisation measurements of a number of 6.7 GHz methanol masers and find linear polarisation at levels of a few - 10% in most of the sources we observed, consistent with previous results. We also investigated the circular polarisation produced by Zeeman splitting in the 6.7 GHz methanol maser G9.62+0.20 to get an estimate of the line of sight magnetic field strength of 35+/-7 mG.

  16. Efficient green methanol synthesis from glycerol

    Science.gov (United States)

    Haider, Muhammad H.; Dummer, Nicholas F.; Knight, David W.; Jenkins, Robert L.; Howard, Mark; Moulijn, Jacob; Taylor, Stuart H.; Hutchings, Graham J.

    2015-12-01

    The production of biodiesel from the transesterification of plant-derived triglycerides with methanol has been commercialized extensively. Impure glycerol is obtained as a by-product at roughly one-tenth the mass of the biodiesel. Utilization of this crude glycerol is important in improving the viability of the overall process. Here we show that crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low-pressure process. Our discovery opens up the possibility of recycling the crude glycerol produced during biodiesel manufacture. Furthermore, we show that molecules containing at least two hydroxyl groups can be converted into methanol, which demonstrates some aspects of the generality of this new chemistry.

  17. Effects of methanol on the growth of gastrointestinal anaerobes

    Energy Technology Data Exchange (ETDEWEB)

    Caldwell, D.R. (Univ. of Wyoming, Laramie, WY (USA))

    1989-01-01

    The effects of methanol on the growth of representative, predominant, anaerobic gut bacteria were studied. Growth yields and rates were determined in a base medium to which methanol was added to produce media with methanol concentrations varying, in twofold steps, over a concentration range of 0.01 to 25%, by volume. The growth of many of the organisms were completely inhibited by a methanol concentration equal to, or less than, 6.2%. Isolates representing cellulolytic species were completely inhibited at a methanol concentration of 3.1%, and inhibitory effects on the yield of some cellulolytic isolates were found at a methanol concentration as small as 0.01%. Although most of the organisms studied were inhibited at relatively small methanol concentrations, isolates of Selenomonas ruminantium, Bacteroides ovatus, and Fusobacterium necrophorum were relatively methanol resistant. A methanol concentration of 12.5% was required to completely inhibit S. ruminantium. Substantial growth of B. ovatus was obtained in media containing 12.5% methanol, and for F. necrophorum, substantial growth occurred in media containing 25% methanol. The yields of F. necrophorum strain B85 and S. ruminantum strain PC18 were enhanced by relatively small methanol concentrations and reduced with further methanol concentration increase. Anaerobic, nonsporing gut bacteria exhibit a diversity of responses to methanol. 12 refs., 2 figs., 4 tabs.

  18. Photocatalytic conversion of methane to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, C.E.; Noceti, R.P.; D`Este, J.R. [Pittsburgh Energy Technology Center, PA (United States)

    1995-12-31

    A long-term goal of our research group is the exploration of novel pathways for the direct oxidation of methane to liquid fuels, chemicals, and intermediates. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol is attractive. The products of reaction, methanol and hydrogen, are both commercially desirable, methanol being used as is or converted to a variety of other chemicals, and the hydrogen could be utilized in petroleum and/or chemical manufacturing. Methane is produced as a by-product of coal gasification. Depending upon reactor design and operating conditions, up to 18% of total gasifier product may be methane. In addition, there are vast proven reserves of geologic methane in the world. Unfortunately, a large fraction of these reserves are in regions where there is little local demand for methane and it is not economically feasible to transport it to a market. There is a global research effort under way in academia, industry, and government to find methods to convert methane to useful, more readily transportable and storable materials. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of the methane while satisfying transportation and storage requirements. Investigation of direct conversion of methane to transportation fuels has been an ongoing effort at PETC for over 10 years. One of the current areas of research is the conversion of methane to methanol, under mild conditions, using light, water, and a semiconductor photocatalyst. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol, is attractive. Research in the laboratory is directed toward applying the techniques developed for the photocatalytic splitting of the water and the photochemical conversion of methane.

  19. Glutathione Adduct Patterns of Michael-Acceptor Carbonyls.

    Science.gov (United States)

    Slawik, Christian; Rickmeyer, Christiane; Brehm, Martin; Böhme, Alexander; Schüürmann, Gerrit

    2017-02-22

    Glutathione (GSH) has so far been considered to facilitate detoxification of soft organic electrophiles through covalent binding at its cysteine (Cys) thiol group, followed by stepwise catalyzed degradation and eventual elimination along the mercapturic acid pathway. Here we show that in contrast to expectation from HSAB theory, Michael-acceptor ketones, aldehydes and esters may form also single, double and triple adducts with GSH involving β-carbon attack at the much harder N-terminus of the γ-glutamyl (Glu) unit of GSH. In particular, formation of the GSH-N single adduct contradicts the traditional view that S alkylation always forms the initial reaction of GSH with Michael-acceptor carbonyls. To this end, chemoassay analyses of the adduct formation of GSH with nine α,β-unsaturated carbonyls employing high performance liquid chromatography and tandem mass spectrometry have been performed. Besides enriching the GSH adductome and potential biomarker applications, electrophilic N-terminus functio-nalization is likely to impair GSH homeostasis substantially through blocking the γ-glutamyl transferase catalysis of the first breakdown step of modified GSH, and thus its timely reconstitution. The discussion includes a comparison with cyclic adducts of GSH and furan metabolites as reported in literature, and quantum chemically calculated thermodynamics of hard-hard, hard-soft and soft-soft adducts.

  20. Reactive Carbonyl Species In Vivo: Generation and Dual Biological Effects

    Directory of Open Access Journals (Sweden)

    Halyna M. Semchyshyn

    2014-01-01

    Full Text Available Reactive carbonyls are widespread species in living organisms and mainly known for their damaging effects. The most abundant reactive carbonyl species (RCS are derived from oxidation of carbohydrates, lipids, and amino acids. Chemical modification of proteins, nucleic acids, and aminophospholipids by RCS results in cytotoxicity and mutagenicity. In addition to their direct toxicity, modification of biomolecules by RCS gives rise to a multitude of adducts and cross links that are increasingly implicated in aging and pathology of a wide range of human diseases. Understanding of the relationship between metabolism of RCS and the development of pathological disorders and diseases may help to develop effective approaches to prevent a number of disorders and diseases. On the other hand, constant persistence of RCS in cells suggests that they perform some useful role in living organisms. The most beneficial effects of RCS are their establishment as regulators of cell signal transduction and gene expression. Since RCS can modulate different biological processes, new tools are required to decipher the precise mechanisms underlying dual effects of RCS.

  1. Reactions of benzaldehyde with trialkylsilyl metal carbonyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, D.L.; Gladysz, J.A.

    1979-10-10

    The use of trialkylsilyl metal carbonyl complexes as reagents for organometallic synthesis was investigated. In this communication it was reported that the metal silanes (CO)/sub 5/MnSi(CH/sub 3/)/sub 3/(1), (CO)/sub 4/Fe(SiCH/sub 3/)/sub 3/)/sub 2/(2), and (CO/sub 4/)FeSi(CH/sub 3/)/sub 2/(CH/sub 2/CH/sub 2/Si(CH/sub 3/)/sub 2/(3) undergo reactions with benzaldehyde which result, under appropriate conditions, in the formation of ..cap alpha..-silyloxybenzyl- and benzylidene-derived ligands. It was reported that a strongly oxygenophilic group must be present on manganese in order for a benzaldehyde adduct to be detectably formed. The catalytic hydrosilyation of aldehydes and ketones has been postulated to involve a similar carbonyl group addition by a catalytically active L/sb n/M(H)SiR/sub 3/ species. The presence of chelating disilane ligand enables the chemistry of 3 to dramaticaly diverge from that of 2. With aliphatic aldehydes and ketones, 1 and 2 react differently. (DP)

  2. Abacavir methanol 2.5-solvate

    Directory of Open Access Journals (Sweden)

    Phuong-Truc T. Pham

    2009-08-01

    Full Text Available The structure of abacavir (systematic name: {(1S,4R-4-[2-amino-6-(cyclopropylamino-9H-purin-9-yl]cyclopent-2-en-1-yl}methanol, C14H18N6O·2.5CH3OH, consists of hydrogen-bonded ribbons which are further held together by additional hydrogen bonds involving the hydroxyl group and two N atoms on an adjacent purine. The asymmetric unit also contains 2.5 molecules of methanol solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009. Acta Cryst. D65, 148–155].

  3. Silicon Based Direct Methanol Fuel Cells

    DEFF Research Database (Denmark)

    Larsen, Jackie Vincent

    The purpose of this project has been to investigate and fabricate small scale Micro Direct Methanol Fuel Cells (μDMFC). They are investigated as a possible alternative for Zinc-air batteries in small size consumer devices such as hearing aids. In such devices the conventional rechargeable batteries...... such as lithium-ion batteries have insufficiently low energy density. Methanol is a promising fuel for such devices due to the high energy density and ease of refueling compared to charging batteries, making μDMFC a suitable replacement energy source. In this Ph.D. dissertation, silicon micro fabrication...

  4. Synthesis and Optimization of a Methanol Process

    DEFF Research Database (Denmark)

    Grue, J.; Bendtsen, Jan Dimon

    2003-01-01

    In the present paper, a simulation model for a methanol process is proposed. The objective is to develop a model for flowsheet optimization, which requires simple thermodynamic and unit operation models. Simplified thermodynamic models are combined with a more advanced model for the rate of react......In the present paper, a simulation model for a methanol process is proposed. The objective is to develop a model for flowsheet optimization, which requires simple thermodynamic and unit operation models. Simplified thermodynamic models are combined with a more advanced model for the rate...

  5. 37 GHz methanol masers : Horsemen of the Apocalypse for the class II methanol maser phase?

    CERN Document Server

    Ellingsen, S P; Sobolev, A M; Voronkov, M A; Caswell, J L; Lo, N

    2011-01-01

    We report the results of a search for class II methanol masers at 37.7, 38.3 and 38.5 GHz towards a sample of 70 high-mass star formation regions. We primarily searched towards regions known to show emission either from the 107 GHz class II methanol maser transition, or from the 6.035 GHz excited OH transition. We detected maser emission from 13 sources in the 37.7 GHz transition, eight of these being new detections. We detected maser emission from three sources in the 38 GHz transitions, one of which is a new detection. We find that 37.7 GHz methanol masers are only associated with the most luminous 6.7 and 12.2 GHz methanol maser sources, which in turn are hypothesised to be the oldest class II methanol sources. We suggest that the 37.7 GHz methanol masers are associated with a brief evolutionary phase (of 1000-4000 years) prior to the cessation of class II methanol maser activity in the associated high-mass star formation region.

  6. A step-by-step protocol for assaying protein carbonylation in biological samples.

    Science.gov (United States)

    Colombo, Graziano; Clerici, Marco; Garavaglia, Maria Elisa; Giustarini, Daniela; Rossi, Ranieri; Milzani, Aldo; Dalle-Donne, Isabella

    2016-04-15

    Protein carbonylation represents the most frequent and usually irreversible oxidative modification affecting proteins. This modification is chemically stable and this feature is particularly important for storage and detection of carbonylated proteins. Many biochemical and analytical methods have been developed during the last thirty years to assay protein carbonylation. The most successful method consists on protein carbonyl (PCO) derivatization with 2,4-dinitrophenylhydrazine (DNPH) and consequent spectrophotometric assay. This assay allows a global quantification of PCO content due to the ability of DNPH to react with carbonyl giving rise to an adduct able to absorb at 366 nm. Similar approaches were also developed employing chromatographic separation, in particular HPLC, and parallel detection of absorbing adducts. Subsequently, immunological techniques, such as Western immunoblot or ELISA, have been developed leading to an increase of sensitivity in protein carbonylation detection. Currently, they are widely employed to evaluate change in total protein carbonylation and eventually to highlight the specific proteins undergoing selective oxidation. In the last decade, many mass spectrometry (MS) approaches have been developed for the identification of the carbonylated proteins and the relative amino acid residues modified to carbonyl derivatives. Although these MS methods are much more focused and detailed due to their ability to identify the amino acid residues undergoing carbonylation, they still require too expensive equipments and, therefore, are limited in distribution. In this protocol paper, we summarise and comment on the most diffuse protocols that a standard laboratory can employ to assess protein carbonylation; in particular, we describe step-by-step the different protocols, adding suggestions coming from our on-bench experience.

  7. Influences of characteristic meteorological conditions on atmospheric carbonyls in Beijing, China

    Science.gov (United States)

    Pang, Xiaobing; Mu, Yujing; Lee, Xinqing; Zhang, Yujie; Xu, Zhu

    2009-08-01

    Atmospheric pollutants are controlled not only by their production rates but also by meteorological conditions. The influences of dust storm, sauna weather (haze with high temperature and high humidity), wet precipitation and wind speed on atmospheric carbonyls in Beijing were investigated. During a severe dust episode (April 17, 2006), the mixing ratios of carbonyls were significantly elevated to 13-27 ppbV from 7 to 13 ppbV in the previous non-dust days (April 15 and 16) with the increasing extents of 38-154%. The accumulating effect and the lower photolysis rate in the dust day may be responsible for the increases of carbonyls' levels. Additionally, the contribution from heterogeneous reactions occurring on dust particles to formaldehyde and acetaldehyde cannot be ruled out. During the period of typical sauna weather, the concentrations of atmospheric carbonyls increased to 18-60 ppbV from 10 to 17 ppbV before the sauna days. The air mass over Beijing during the sauna days was controlled by a subtropical anticyclone and the boundary layer became quite stable, which was beneficial to the rapid accumulation of air pollutants including carbonyls. Wet precipitation was found to be an effective removal process to the atmospheric carbonyls. After one-hour of rain in summer, the total concentrations of atmospheric carbonyls decreased to less than half of that before the rainfall. The similar temporal varying patterns of carbonyls and inorganic ions in rainwater indicated that carbonyls were mainly washed out from the atmosphere into rainwater as inorganic ions were. Strong wind could evidently dilute atmospheric carbonyls and a negative correlation was found between wind speeds and the concentrations of carbonyls in spring in Beijing.

  8. METHANOL REMOVAL FROM METHANOL-WATER MIXTURE USING ACTIVATED SLUDGE, AIR STRIPPING AND ADSORPTION PROCESS: COMPARATIVE STUDY

    Directory of Open Access Journals (Sweden)

    SALAM K. AL-DAWERY

    2015-12-01

    Full Text Available An experimental research has been carried out in order to examine the removal of methanol from methanol-water mixtures using three different methods; activated sludge; activated carbon and air stripping. The results showed that the methanol was totally consumed by the bacteria as quickly as the feed entered the activated sludge vessel. Air stripping process has a limited ability for removing of methanol due to strong intermolecular forces between methanol and water; however, the results showed that the percentage of methanol removed using air pressure at 0.5 bar was higher than that of using air pressure of 0.25 bar. Removal of methanol from the mixture with a methanol content of 5% using activated carbon was not successful due to the limited capacity of the of the activated carbon. Thus, the activated sludge process can be considered as the most suitable process for the treatment of methanol-water mixtures.

  9. Effect of Methanol Crossover in a Liquid-FeedPolymer-Electrolyte Direct Methanol Fuel Cell

    OpenAIRE

    Ravikumar, MK; Shukla, AK

    1996-01-01

    The performance of a liquid-feed direct methanol fuel cell employing a proton-exchange membrane electrolyte with Pt-Ru/C as anode and Pt/C as cathode is reported. The fuel cell can deliver a power density of ca. 0.2 $W/cm^2$ at 95°C, sufficient to suggest that the stack construction is well worthwhile.Methanol crossover across the polymer electrolyte at concentrations beyond 2 M methanol affects the performance of the cell which appreciates with increasing operating temperature.

  10. A multipurpose reduced chemical-kinetic mechanism for methanol combustion

    Science.gov (United States)

    Fernández-Tarrazo, Eduardo; Sánchez-Sanz, Mario; Sánchez, Antonio L.; Williams, Forman A.

    2016-07-01

    A multipurpose reduced chemical-kinetic mechanism for methanol combustion comprising 8 overall reactions and 11 reacting chemical species is presented. The development starts by investigating the minimum set of elementary reactions needed to describe methanol combustion with reasonable accuracy over a range of conditions of temperature, pressure, and composition of interest in combustion. Starting from a 27-step mechanism that has been previously tested and found to give accurate predictions of ignition processes for these conditions, it is determined that the addition of 11 elementary reactions taken from its basis (San Diego) mechanism extends the validity of the description to premixed-flame propagation, strain-induced extinction of non-premixed flames, and equilibrium composition and temperatures, giving results that compare favourably with experimental measurements and also with computations using the 247-step detailed San Diego mechanism involving 50 reactive species. Specifically, premixed-flame propagation velocities and extinction strain rates for non-premixed counterflow flames calculated with the 38-step mechanism show departures from experimental measurements and detailed-chemistry computations that are roughly on the order of 10%, comparable with expected experimental uncertainties. Similar accuracy is found in comparisons of autoignition times over the range considered, except at very high temperatures, under which conditions the computations tend to overpredict induction times for all of the chemistry descriptions tested. From this 38-step mechanism, the simplification is continued by introducing steady-state approximations for the intermediate species CH3, CH4, HCO, CH3O, CH2OH, and O, leading to an 8-step reduced mechanism that provides satisfactory accuracy for all conditions tested. The flame computations indicate that thermal diffusion has a negligible influence on methanol combustion in all cases considered and that a mixture-average species

  11. Methanol in diesel engines with increased efficiency by means of methanol dissociation. Methanol in dieselmotoren met verhoogd rendement door middel van methanoldissociatie

    Energy Technology Data Exchange (ETDEWEB)

    Ter Rele, R.R.J.; Van Asch, R.; Van der Does, C.

    1988-06-01

    The methanol dissociation project had the purpose to demonstrate a system in a diesel engine in which a part of the diesel fuel is replaced by dissociated methanol. The demonstration has been executed in a DAF 615 diesel engine under pressure. A previous developed diesel mixing operating system provided for correct gas quantity for all the load conditions. The Dutch State Mines (DSM) did research on the most appropriate catalyst and designed a methanol dissociation reactor. Descriptions of the fuel system, methanol evaporator and methanol dissociation reactor are given. Results of several measurements are presented: measurements on the diesel motor as a standard design, measurements for evaporated methanol as a substitute fuel for diesel and measurements for dissociated methanol or synthetic dissociation gas as substitute fuels. Differences between diesel and the substitutes are discussed. 12 figs., 4 ills., 3 tabs., 10 apps.

  12. Methanol Adsorption and Reaction on Samaria Thin Films on Pt(111

    Directory of Open Access Journals (Sweden)

    Jin-Hao Jhang

    2015-09-01

    Full Text Available We investigated the adsorption and reaction of methanol on continuous and discontinuous films of samarium oxide (SmOx grown on Pt(111 in ultrahigh vacuum. The methanol decomposition was studied by temperature programmed desorption (TPD and infrared reflection absorption spectroscopy (IRRAS, while structural changes of the oxide surface were monitored by low-energy electron diffraction (LEED. Methanol dehydrogenates to adsorbed methoxy species on both the continuous and discontinuous SmOx films, eventually leading to the desorption of CO and H2 which desorbs at temperatures in the range 400–600 K. Small quantities of CO2 are also detected mainly on as-prepared Sm2O3 thin films, but the production of CO2 is limited during repeated TPD runs. The discontinuous film exhibits the highest reactivity compared to the continuous film and the Pt(111 substrate. The reactivity of methanol on reduced and reoxidized films was also investigated, revealing how SmOx structures influence the chemical behavior. Over repeated TPD experiments, a SmOx structural/chemical equilibrium condition is found which can be approached either from oxidized or reduced films. We also observed hydrogen absence in TPD which indicates that hydrogen is stored either in SmOx films or as OH groups on the SmOx surfaces.

  13. Hydrogen production with a solar steam–methanol reformer and colloid nanocatalyst

    KAUST Repository

    Lee, Ming-Tsang

    2010-01-01

    In the present study a small steam-methanol reformer with a colloid nanocatalyst is utilized to produce hydrogen. Radiation from a focused continuous green light laser (514 nm wavelength) is used to provide the energy for steam-methanol reforming. Nanocatalyst particles, fabricated by using pulsed laser ablation technology, result in a highly active catalyst with high surface to volume ratio. A small novel reformer fabricated with a borosilicate capillary is employed to increase the local temperature of the reformer and thereby increase hydrogen production. The hydrogen production output efficiency is determined and a value of 5% is achieved. Experiments using concentrated solar simulator light as the radiation source are also carried out. The results show that hydrogen production by solar steam-methanol colloid nanocatalyst reforming is both feasible and promising. © 2009 Professor T. Nejat Veziroglu.

  14. Engineering Escherichia coli for methanol conversion

    NARCIS (Netherlands)

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-01-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy

  15. Methanol emission from low mass protostars

    CERN Document Server

    Maret, S; Tielens, A G G M; Caux, E; Le Floc'h, B; Faure, A; Castets, A; Flower, D R

    2005-01-01

    We present observations of methanol lines in a sample of Class 0 low mass protostars. Using a 1-D radiative transfer model, we derive the abundances in the envelopes. In two sources of the sample, the observations can only be reproduced by the model if the methanol abundance is enhanced by about two order of magnitude in the inner hot region of the envelope. Two other sources show similar jumps, although at a lower confidence level. The observations for the other three sources are well reproduced with a constant abundance, but the presence of a jump cannot be ruled out. The observed methanol abundances in the warm gas around low mass protostars are orders of magnitude higher than gas phase chemistry models predict. Hence, in agreement with other evidences, this suggest that the high methanol abundance reflects recent evaporation of ices due to the heating by the newly formed star. The observed abundance ratios of CH3 OH, H2 CO, and CO are in good agreement with grain surface chemistry models. However, the abs...

  16. Metacridamide B methanol-d4 monosolvate

    Science.gov (United States)

    The title compound was extracted from conidia of the fungus Metarhizium acridum. Crystals were obtained as a methanol-d4 solvate. The tail part of the 4-methylhexan-2-yl group exhibits disorder over two positions, with an occupancy ratio of 0.682 (9):0.318 (9). The crystal structure confirms the abs...

  17. Methanol and acetaldehyde fluxes over ryegrass

    Science.gov (United States)

    Custer, Thomas; Schade, Gunnar

    2007-09-01

    Oxygenated volatile organic compounds (OVOCs) play an active role in tropospheric chemistry but our knowledge concerning their release and ultimate fate is limited. However, the recent introduction of Proton Transfer Reaction Mass Spectrometry (PTRMS) has improved our capability to make direct field observations of OVOC mixing ratios and fluxes. We used PTRMS in an eddy covariance setup to measure selected OVOC exchange rates above a well-characterized agricultural plot in Northern Germany. In fall 2003, mixing ratios of methanol and acetaldehyde 2 m above the field ranged from 1 to 10 and 0.4 to 2.1 ppb, respectively, well correlated with one another. Fluxes of both gases were followed for growing Italian ryegrass (Lolium multiflorum) over a significant portion of its life cycle. Diurnally fluctuating emissions of methanol and very small acetaldehyde fluxes were observed up to the cutting and removal of the grass. Methanol emissions were exponentially related to ambient temperatures and appeared to be higher during the grass' rapid leaf area expansion and after a rain event. Acetaldehyde exchanges averaged over the whole period indicated very slow deposition. Our measurements confirm previous, similar results, as well as presumptions that grasses are comparatively low methanol emitters compared to non-grass species.

  18. Antihyperlipidemic effect of Casearia sylvestris methanolic extract.

    Science.gov (United States)

    Schoenfelder, Tatiana; Pich, Claus T; Geremias, Reginaldo; Avila, Silvio; Daminelli, Elaine N; Pedrosa, Rozangela C; Bettiol, Jane

    2008-09-01

    Casearia sylvestris methanolic extract (MCE) was screened at doses of 125-500 mg/kg for its antihyperlipidemic activity. The antihyperlipidemic effect was evaluated in olive oil-loaded mice. Acute treatment caused inhibition in the triglyceride (TG) and serum lipase elevation-induced by 5 ml/kg of olive oil.

  19. Engineering Escherichia coli for methanol conversion

    NARCIS (Netherlands)

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-01-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy

  20. Parameters affecting methanol utilization by yeasts

    Energy Technology Data Exchange (ETDEWEB)

    Foda, M.S.; El-Masry, H.G.

    1981-01-01

    Screening of 28 yeast cultures, representing 22 species of various yeasts, with respect to their capabilities to assimilate methanol, has shown that this property was mostly found in certain species of the two genera Hansenula and Candida. When methanol was used as a sole carbon source for a methanol-adapted strain of Hansenula polymorpha, a linear yield response could be obtained with increasing alcohol up to 2% concentration. The amount of inoculum proved to be the decisive factor in determining a priori the ability of the organism to grow at 6% methanol as final concentration. The optimum pH values for growth ranged between 4.5-5.5 with no growth at pH 6.5 or higher. A marked growth stimulation was obtained when the medium was supplied with phosphate up to 0.08 M as final concentration. Within the nitrogen sources tested, corn steep liquor concentrate gave the highest yield of cells. The significance of the obtained results are discussed with reference to feasibilities of application.

  1. Synthesis and Optimization of a Methanol Proces

    DEFF Research Database (Denmark)

    Grue, J.; Bendtsen, Jan Dimon

    2003-01-01

    In the present paper, a simulation model for a methanol process is proposed. The objective is to develop a model for flowsheet optimization, which requires simple thermodynamic and unit operation models. Simplified thermodynamic models are combined with a more advanced model for the rate of react...

  2. Analysis of protein carbonylation - pitfalls and promise in commonly used methods

    DEFF Research Database (Denmark)

    Rogowska-Wrzesinska, A.; Wojdyla, K.; Nedic, O.

    2014-01-01

    . Several methods for measuring protein carbonylation have been implemented in different laboratories around the world. However, to date no methods prevail as the most accurate, reliable, and robust. The present paper aims at giving an overview of the common methods used to determine protein carbonylation...

  3. Structural characteristics of green tea catechins for formation of protein carbonyl in human serum albumin.

    Science.gov (United States)

    Ishii, Takeshi; Mori, Taiki; Ichikawa, Tatsuya; Kaku, Maiko; Kusaka, Koji; Uekusa, Yoshinori; Akagawa, Mitsugu; Aihara, Yoshiyuki; Furuta, Takumi; Wakimoto, Toshiyuki; Kan, Toshiyuki; Nakayama, Tsutomu

    2010-07-15

    Catechins are polyphenolic antioxidants found in green tea leaves. Recent studies have reported that various polyphenolic compounds, including catechins, cause protein carbonyl formation in proteins via their pro-oxidant actions. In this study, we evaluate the formation of protein carbonyl in human serum albumin (HSA) by tea catechins and investigate the relationship between catechin chemical structure and its pro-oxidant property. To assess the formation of protein carbonyl in HSA, HSA was incubated with four individual catechins under physiological conditions to generate biotin-LC-hydrazide labeled protein carbonyls. Comparison of catechins using Western blotting revealed that the formation of protein carbonyl in HSA was higher for pyrogallol-type catechins than the corresponding catechol-type catechins. In addition, the formation of protein carbonyl was also found to be higher for the catechins having a galloyl group than the corresponding catechins lacking a galloyl group. The importance of the pyrogallol structural motif in the B-ring and the galloyl group was confirmed using methylated catechins and phenolic acids. These results indicate that the most important structural element contributing to the formation of protein carbonyl in HSA by tea catechins is the pyrogallol structural motif in the B-ring, followed by the galloyl group. The oxidation stability and binding affinity of tea catechins with proteins are responsible for the formation of protein carbonyl, and consequently the difference in these properties of each catechin may contribute to the magnitude of their biological activities.

  4. Iron(III)-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Saá, Carlos

    2016-09-01

    Recent developments in catalytic carbonyl-olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl-olefin metathesis (RCCOM) in high yield under very mild conditions.

  5. In Situ Derivatization and Quantification of Seven Carbonyls in Cigarette Mainstream Smoke.

    Science.gov (United States)

    Ding, Yan S; Yan, Xizheng; Wong, Joshua; Chan, Michele; Watson, Clifford H

    2016-01-19

    Carbonyls, especially aldehydes, are a group of harmful volatile organic compounds that are found in tobacco smoke. Seven carbonyls are listed on the FDA's harmful and potential harmful constituents list for tobacco or tobacco smoke. Carbonyls have reactive functional groups and thus are challenging to quantitatively measure in cigarette smoke. The traditional method of measuring carbonyls in smoke involves solvent-filled impinger trapping and derivatization. This procedure is labor-intensive and generates significant volumes of hazardous waste. We have developed a new method to efficiently derivatize and trap carbonyls from mainstream smoke in situ on Cambridge filter pads. The derivatized carbonyls are extracted from the pads and subsequently quantified by ultra-high-pressure liquid chromatography coupled with tandem mass spectrometry. The new method has been validated and applied to research and commercial cigarettes. Carbonyl yields from research cigarettes are comparable to those from other published literature data. With a convenient smoke collection apparatus, a 4 min sample analysis time, and a low- or submicrogram detection limit, this new method not only simplifies and speeds the detection of an important class of chemical constituents in mainstream smoke but also reduces reactive losses and provides a more accurate assessment of carbonyl levels in smoke. Excellent accuracy (average 98%) and precision (14% average relative standard deviation in research cigarettes) ensure this new method's sufficient fidelity to characterize conventional combusted tobacco products, with potential application toward new or emerging products.

  6. Optimized fuel cell grade hydrogen from methanol

    Science.gov (United States)

    Choi, Yongtaek

    2003-10-01

    To evaluate reaction rates liar making hydrogen from methanol, kinetic studies of methanol decomposition, methanol steam reforming, water gas shift reaction, and CO selective oxidation have been performed. These reactions were studied in a micro reactor testing unit using a commercial Cu-ZnO/Al2O3 catalyst for the first three reactions and Pt-Fe/gamma-alumina catalyst for the last reaction. The activity tests were performed between 120˜325°C and atmospheric pressure with a range of feed rates and compositions. For methanol decomposition, water addition to the feed increased the yield of hydrogen and reduced the formation of by-products. XPS analysis of used catalyst samples and time on-stream data showed that the Cu2+ oxidation state of copper favors methanol decomposition. A simplified reaction network of 5 elementary reactions was proposed and all five rate expressions were obtained using non-linear least squares optimization, numerical integration of a one-dimensional PFR model, and extensive experimental data. Similar numerical analysis was carried out to obtain the rate expressions for methanol steam reaction, the water gas shift reaction, and CO selective oxidation. For the kinetics of the water gas shift reaction, an empirical rate expression was obtained from the experimental data. Based on a review of published work on the WGS reaction mechanism, our study found that a rate expression derived from a regenerative mechanism and another rate expression derived from adsorptive mechanism fit the experimental data equally well. For the kinetics of CO preferential oxidation, a reaction model in which three reactions (CO oxidation, H2 oxidation and the WGS reaction) occur simultaneously was chosen to predict the reactor performance. In particular the reverse water gas shift reaction had an important role when fitting the experimental data precisely and explained the selectivity decrease at higher reaction temperatures. Combining the three reactors and several

  7. 6.7GHz Methanol Maser Associated Outflows: An evolutionary sequence

    CERN Document Server

    de Villiers, H M; Thompson, M A; Urquhart, J S; Breen, S L; Burton, M G; Ellingsen, S P; Fuller, G A; Pestalozzi, M; Voronkov, M A; Ward-Thompson, D

    2015-01-01

    We present a continuing study of a sample 44 molecular outflows, observed in 13CO lines, closely associated with 6.7GHz methanol masers, hence called Methanol Maser Associated Outflows (MMAOs). We compare MMAO properties with those of outflows from other surveys in the literature. In general, MMAOs follow similar trends, but show a deficit in number at low masses and momenta, with a corresponding higher fraction at the high end of the distributions. A similar trend is seen for the dynamical timescales of MMAOs. We argue that the lack of relatively low mass and young flows in MMAOs is due to the inherent selection-bias in the sample, i.e. its direct association with 6.7GHz methanol masers. This implies that methanol masers must switch on after the onset of outflows (hence accretion), and not before a sufficient abundance of methanol is liberated from icy dust mantles. Consequently the average dynamical age of MMAOs is older than for the general population of molecular outflows. We propose an adjusted evolution...

  8. Selectivity of Direct Methanol Fuel Cell Membranes

    Directory of Open Access Journals (Sweden)

    Antonino S. Aricò

    2015-11-01

    Full Text Available Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK, new generation perfluorosulfonic acid (PFSA systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC. The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2. This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115.

  9. Selectivity of Direct Methanol Fuel Cell Membranes

    Science.gov (United States)

    Aricò, Antonino S.; Sebastian, David; Schuster, Michael; Bauer, Bernd; D’Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

    2015-01-01

    Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2). This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115). PMID:26610582

  10. Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, R S P

    2011-01-01

    Proteins can become oxidatively modified in many different ways, either by direct oxidation of amino acid side chains and protein backbone or indirectly by conjugation with oxidation products of polyunsaturated fatty acids and carbohydrates. While reversible oxidative modifications are thought...... to be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO) in vivo...... and in vitro with an emphasis on cellular metal ion homeostasis and metal binding. We then review proteomic methods currently used for identifying carbonylated proteins and their sites of modification. Finally, we discuss the identified carbonylated proteins and the pattern of carbonylation sites in relation...

  11. High-resolution X-ray absorption spectroscopy of iron carbonyl complexes.

    Science.gov (United States)

    Atkins, Andrew J; Bauer, Matthias; Jacob, Christoph R

    2015-06-07

    We apply high-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) to study iron carbonyl complexes. Mono-, bi-, and tri-nuclear carbonyl complexes and pure carbonyl complexes as well as carbonyl complexes containing hydrocarbon ligands are considered. The HERFD-XANES spectra reveal multiple pre-edge peaks with individual signatures for each complex, which could not be detected previously with conventional XANES spectroscopy. These peaks are assigned and analysed with the help of TD-DFT calculations. We demonstrate that the pre-edge peaks can be used to distinguish the different types of iron-iron interactions in carbonyl complexes. This opens up new possibilities for applying HERFD-XANES spectroscopy to probe the electronic structure of iron catalysts.

  12. Impact of HVAC filter on indoor air quality in terms of ozone removal and carbonyls generation

    Science.gov (United States)

    Lin, Chi-Chi; Chen, Hsuan-Yu

    2014-06-01

    This study aims at detecting ozone removal rates and corresponding carbonyls generated by ozone reaction with HVAC filters from various building, i.e., shopping mall, school, and office building. Studies were conducted in a small-scale environmental chamber. By examining dust properties including organic carbon proportion and specific surface area of dusts adsorbed on filters along with ozone removal rates and carbonyls generation rate, the relationship among dust properties, ozone removal rates, and carbonyls generation was identified. The results indicate a well-defined positive correlation between ozone removal efficiency and carbonyls generation on filters, as well as a positive correlation among the mass of organic carbon on filters, ozone removal efficiency and carbonyls generations.

  13. Carbonyl Sulfide Isotopologues: Ultraviolet Absorption Cross Sections and Stratospheric Photolysis

    DEFF Research Database (Denmark)

    Danielache, Sebastian Oscar; Nanbu, Shinkoh; Eskebjerg, Carsten

    2009-01-01

    Ultraviolet absorption cross sections of the main and substituted carbonyl sulfide isotopologues were calculated using wavepacket dynamics. The calculated absorption cross section of 16O12C32S is in very good agreement with the accepted experimental spectrum between 190 and 250 nm. Relative to 16O......12C32S, isotopic substitution shows a significant enhancement of the cross section for 16O13C32S, a significant reduction for 18O12C32S and 17O12C32S and almost no change for the sulfur isotopologues 16O12C33S, 16O12C34S, and 16O12C36S. The analysis of the initial wavepackets shows that these changes...

  14. Study of indoor air pollution by carbonyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Grimaldi, F.; Botti, P.; Bouthiba, M.; Gouezo, F.; Viala, A. [Faculte de Medecine, 13 - Marseille (France)

    1996-01-01

    Carbonyl compounds reach indoor occasionally high air concentrations. They must be taken into attentive considerations, particularly because of their irritative and possibly carcinogenic effects. They were sampled in air through dinitro-2,4- phenylhydrazinc (DNPH)-Silica cartridges. The 2,4-dinitrophenylhydrazones formed were then eluted with acetonitrile and determined by high-performance liquid chromatography. The used method is selective and gives a linear reproducible and sensitive response. The obtained results (for formaldehyde, acetaldehyde, acetone, acrolein, crotonaldehyde, butyraldehyde, benzaldehyde, isovaleraldehyde, o-tolualdehyde) inside teaching and other premises showed that it is necessary to avoid the stopping up, to ensure an efficient ventilation and to eliminate, at less to restrict a possible release, by using appropriate building and coating material and furniture. (authors). 14 refs., 2 figs., 5 tabs.

  15. Carbonyl mediated conductance through metal bound peptides: a computational study

    Science.gov (United States)

    Perrine, Trilisa M.; Dunietz, Barry D.

    2007-10-01

    Large increases in the conductance of peptides upon binding to metal ions have recently been reported experimentally. The mechanism of the conductance switching is examined computationally. It is suggested that oxidation of the metal ion occurs after binding to the peptide. This is caused by the bias potential placed across the metal-peptide complex. A combination of configurational changes, metal ion involvement and interactions between carbonyl group oxygen atoms and the gold leads are all shown to be necessary for the large improvement in the conductance seen experimentally. Differences in the molecular orbitals of the nickel and copper complexes are noted and serve to explain the variation of the improvement in conductance upon binding to either a nickel or copper ion.

  16. Uptake and conversion of carbonyl sulfide in a lawn soil

    Science.gov (United States)

    Liu, Junfeng; Mu, Yujing; Geng, Chunmei; Yu, Yunbo; He, Hong; Zhang, Yuanhang

    Carbonyl sulfide (COS) exchange fluxes between a lawn soil and the atmosphere as well as influencing factors (temperature and water content of soil) were investigated using a static cuvette. The optimal soil temperature and water content for COS consumption were about 298 K and 12.5%, respectively. The converting products of the consumed COS in the lawn soil were researched using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The peaks of gas-phase products of CO2 and surface HCO3-, HS-, SO32-, HSO3-, and SO42- species were observed. The possible mechanism of COS conversion in the lawn soil was discussed. The conversion rates of consumed COS into water-soluble sulfate in the lawn soil were studied by ion chromatography (IC). The experimental results show that about 50% sulfur from the soil consumed COS was eventually converted into water-soluble sulfate.

  17. Methanol poisoning. VI. Role of folic acid in the production of methanol poisoning in the rat

    Energy Technology Data Exchange (ETDEWEB)

    Makar, A.B. (Alexandria Univ., Egypt); Tephly, T.R.

    1977-05-01

    Methanol poisoning is well known to occur in humans but does not develop in common laboratory animals such as the rat. Rodents display neither metabolic acidosis nor ocular toxicity after methanol treatment, findings that commonly result in humans and that have recently been described in the monkey. Since methanol administration in the monkey leads to marked accumulation of formic acid and metabolic acidosis, experiments were devised to reduce formate metabolism in the rat and thereby study whether methanol administration would lead to the accumulation of formic acid and acidosis in that species. Several methods were employed to induce a state of folate deficiency in the rat, a prerequisite to producing a decrease in formate oxidation to CO/sub 2/ in that species. Rats placed on a folate-deficient diet for 10-12 wk showed a marked decrease in formate oxidation and a marked sensitivity to methanol poisoning, as evidenced by high blood formate levels and marked decreases in blood pH. Treatment of rats with methotrexate was relatively ineffective in inducing decreases in formate oxidation, but in rats fed a folate-deficient diet for 9 days and injected once daily for 9 days with 1 mg/kg methotrexate, a significant elevation of blood formate and decrease in blood pH was observed. In rats that were acidotic following methanol administration no accumulation of formaldehyde was observed. These results indicate that it is possible to sensitize the rat to methanol poisoning by reducing its capacity to oxidize formate. They also show that once the rat is susceptible to methanol poisoning, metabolic acidosis and formate accumulation occur without the accumulation of formaldehyde.

  18. Anti-Amoebic Properties of Carbonyl Thiourea Derivatives

    Directory of Open Access Journals (Sweden)

    Maizatul Akma Ibrahim

    2014-04-01

    Full Text Available Thiourea derivatives display a broad spectrum of applications in chemistry, various industries, medicines and various other fields. Recently, different thiourea derivatives have been synthesized and explored for their anti-microbial properties. In this study, four carbonyl thiourea derivatives were synthesized and characterized, and then further tested for their anti-amoebic properties on two potential pathogenic species of Acanthamoeba, namely A. castellanii (CCAP 1501/2A and A. polyphaga (CCAP 1501/3A. The results indicate that these newly-synthesized thiourea derivatives are active against both Acanthamoeba species. The IC50 values obtained were in the range of 2.39–8.77 µg·mL‑1 (9.47–30.46 µM for A. castellanii and 3.74–9.30 µg·mL‑1 (14.84–31.91 µM for A. polyphaga. Observations on the amoeba morphology indicated that the compounds caused the reduction of the amoeba size, shortening of their acanthopodia structures, and gave no distinct vacuolar and nuclear structures in the amoeba cells. Meanwhile, fluorescence microscopic observation using acridine orange and propidium iodide (AOPI staining revealed that the synthesized compounds induced compromised-membrane in the amoeba cells. The results of this study proved that these new carbonyl thiourea derivatives, especially compounds M1 and M2 provide potent cytotoxic properties toward pathogenic Acanthamoeba to suggest that they can be developed as new anti-amoebic agents for the treatment of Acanthamoeba keratitis.

  19. Methanol production from Eucalyptus wood chips. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Fishkind, H.H.

    1982-06-01

    This feasibility study includes all phases of methanol production from seedling to delivery of finished methanol. The study examines: production of 55 million, high quality, Eucalyptus seedlings through tissue culture; establishment of a Eucalyptus energy plantation on approximately 70,000 acres; engineering for a 100 million gallon-per-day methanol production facility; potential environmental impacts of the whole project; safety and health aspects of producing and using methanol; and development of site specific cost estimates.

  20. Simultaneous observation of water and class I methanol masers toward class II methanol maser sources

    CERN Document Server

    Kang, Hyunwoo; Byun, Do-Young; Lee, Seokho; Park, Yong-Sun

    2015-01-01

    We present a simultaneous single-dish survey of 22 GHz water maser and 44 GHz and 95 GHz class I methanol masers toward 77 6.7 GHz class II methanol maser sources, which were selected from the Arecibo methanol maser Galactic plane survey (AMGPS) catalog.Water maser emission is detected in 39 (51%) sources, of which 15 are new detections. Methanol maser emission at 44 GHz and 95 GHz is found in 25 (32%) and 19 (25%) sources, of which 21 and 13 sources are newly detected, respectively. We find 4 high-velocity (> 30 km/s) water maser sources, including 3 dominant blue- or redshifted outflows.The 95 GHz masers always appear with the 44 GHz maser emission. They are strongly correlated with 44 GHz masers in velocity, flux density, and luminosity, while they are not correlated with either water or 6.7 GHz class II methanol masers. The average peak flux density ratio of 95 GHz to 44 GHz masers is close to unity, which is two times higher than previous estimates. The flux densities of class I methanol masers are more ...

  1. Forest fluxes of carbonyl sulfide: the balance between photosynthetic and soil uptake

    Science.gov (United States)

    Commane, R.; Herndon, S. C.; McLaren, J.; McManus, J. B.; Meredith, L. K.; Munger, J. W.; Nelson, D. D.; Zahniser, M. S.; Wofsy, S. C.

    2011-12-01

    Recent studies have suggested that carbonyl sulfide (COS) can be used as a proxy for partitioning between photosynthetic uptake and respiratory emission of CO2, a balance which cannot be directly determined through the measurement of CO2 fluxes. COS is the most abundant sulfur containing gas in the atmosphere, with a dominant sink in the terrestrial biosphere. COS is taken up by plants through photosynthesis, but is not respired. It is also lost via uptake to soils. However, in terrestrial ecosystems the magnitudes of soil vs. leaf uptake are not well resolved. We report data from direct, continuous measurements of COS using infrared laser absorption (3 std deviation of less than 10 ppt in 30 s), operated continuously since October, 2010 at Harvard Forest in Western Massachusetts. These data were collected in parallel with long term CO2 and H2 flux measurements. We present seasonal variations of the gradients and fluxes of COS through the forest canopy. Additionally, we investigate the relationship of COS with photosynthesis and soil processes through comparison with CO2 and H2 trace gases, respectively.

  2. A comparative study of biodiesel production using methanol, ethanol, and tert-butyl methyl ether (MTBE) under supercritical conditions.

    Science.gov (United States)

    Farobie, Obie; Matsumura, Yukihiko

    2015-09-01

    In this study, biodiesel production under supercritical conditions among methanol, ethanol, and tert-butyl methyl ether (MTBE) was compared in order to elucidate the differences in their reaction behavior. A continuous reactor was employed, and experiments were conducted at various reaction temperatures (270-400 °C) and reaction times (3-30 min) and at a fixed pressure of 20 MPa and an oil-to-reactant molar ratio of 1:40. The results showed that under the same reaction conditions, the supercritical methanol method provided the highest yield of biodiesel. At 350 °C and 20 MPa, canola oil was completely converted to biodiesel after 10, 30, and 30 min in the case of - supercritical methanol, ethanol, and MTBE, respectively. The reaction kinetics of biodiesel production was also compared for supercritical methanol, ethanol, and MTBE.

  3. The significance of peroxisomes in methanol metabolism in methylotrophic yeast

    NARCIS (Netherlands)

    Klei, Ida J. van der; Yurimoto, Hiroya; Sakai, Yasuyoshi; Veenhuis, Marten

    2006-01-01

    The capacity to use methanol as sole source of carbon and energy is restricted to relatively few yeast species. This may be related to the low efficiency of methanol metabolism in yeast, relative to that of prokaryotes. This contribution describes the details of methanol metabolism in yeast and focu

  4. A Methanol Intoxication Outbreak From Recreational Ingestion of Fracking Fluid.

    Science.gov (United States)

    Collister, David; Duff, Graham; Palatnick, Wesley; Komenda, Paul; Tangri, Navdeep; Hingwala, Jay

    2017-01-19

    Single-patient methanol intoxications are a common clinical presentation, but outbreaks are rare and usually occur in settings in which there is limited access to ethanol and methanol is consumed as a substitute. In this case report, we describe an outbreak of methanol intoxications that was challenging from a public health perspective and discuss strategies for managing such an outbreak.

  5. Acidities of Water and Methanol in Aqueous Solution and DMSO

    Science.gov (United States)

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  6. Acidities of Water and Methanol in Aqueous Solution and DMSO

    Science.gov (United States)

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  7. Experimental Validation of Methanol Crossover in a Three-dimensional, Two-Fluid Model of a Direct Methanol Fuel Cell

    DEFF Research Database (Denmark)

    Olesen, Anders Christian; Berning, Torsten; Kær, Søren Knudsen

    2012-01-01

    in the ionomer phase of the catalytic layer, and detailed membrane transport of methanol and water. In order to verify the models ability to predict methanol crossover, simulation results are compared with experimental measurements under different current densities along with air and methanol stoichiometries...

  8. Visible-light driven oxidation of gaseous aliphatic alcohols to the corresponding carbonyls via TiO2 sensitized by a perylene derivative.

    Science.gov (United States)

    Guarisco, Chiara; Palmisano, Giovanni; Calogero, Giuseppe; Ciriminna, Rosaria; Di Marco, Gaetano; Loddo, Vittorio; Pagliaro, Mario; Parrino, Francesco

    2014-10-01

    Sensitized P25 TiO2 was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N'-bis(2-(1-piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO2 allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2-propanol. The reaction was carried out under cut-off (λ > 400 nm) simulated solar radiation in O2 atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was evaluated by cyclic voltammetry. The optimal organic sensitizing amount was found to be 5.6 % w/w in terms of yield in carbonyl derivatives. Moreover, no change in reactivity/selectivity was observed after 10-h irradiation thus confirming the catalyst stability. Yields into formaldehyde, acetaldehyde, and acetone were 67, 70, and 96 %, respectively. No significant amounts of organic byproducts were detected but for methanol oxidation, whereas a minor amount of the substrate degraded to CO2.

  9. Investigations into low pressure methanol synthesis

    DEFF Research Database (Denmark)

    Sharafutdinov, Irek

    The central topic of this work has been synthesis, characterization and optimization of novel Ni-Ga based catalysts for hydrogenation of CO2 to methanol. The overall goal was to search for materials that could be used as a low temperature (and low pressure) methanol synthesis catalyst....... Among them, Ni-Ga has been chosen, primarily due to low price of constituent metals. After the preliminary optimization work, an optimal catalyst composition and preparation method has been suggested. Indeed, for an optimal catalyst, which is a SiO2 supported Ni-Ga prepared from a solution of nitrates...... due to carbon formation) and under accelerated ageing conditions (due to dealloying). However, the initial activity could always be restored after treatment in hydrogen flow at elevated temperatures. The work in the direction of suppression of deactivation and by-product formation is still in progress....

  10. Stevioside methanol tetra­solvate

    Science.gov (United States)

    Wu, Yunshan; Rodenburg, Douglas L.; Ibrahim, Mohamed A.; McChesney, James D.; Avery, Mitchell A.

    2013-01-01

    Stevioside is a naturally occurring diterpenoid glycoside in Stevia rebaudiana Bertoni. The title compound, C38H60O18·4CH3OH, crystallized as its methanol tetrasolvate. Stevioside consists of an aglycone steviol (a tetra­cyclic diterpene in which the four-fused-ring system consists of three six-membered rings and one five-membered ring) and a sugar part (three glucose units). A weak intra­molecular O—H⋯O hydrogen bond occurs. In the crystal, the methanol mol­ecules participate in a two-dimensional hydrogen-bonded network parallel to b axis with the sugars and together they form a hydrophilic tunnel which encloses the lipophilic part of the molecule. PMID:23476589

  11. Electroless plating preparation and electromagnetic properties of Co-coated carbonyl iron particles/polyimide composite

    Science.gov (United States)

    Zhou, Yingying; Zhou, Wancheng; Li, Rong; Qing, Yuchang; Luo, Fa; Zhu, Dongmei

    2016-03-01

    To solve the serious electromagnetic interference problems at elevated temperature, one thin microwave-absorbing sheet employing Co-coated carbonyl iron particles and polyimide was prepared. The Co-coated carbonyl iron particles were successfully prepared using an electroless plating method. The microstructure, composition, phase and static magnetic properties of Co-coated carbonyl iron particles were characterized by combination of scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). The electromagnetic parameters of Co-coated carbonyl iron particles/polyimide composite were measured in the frequency range of 2-18 GHz, and the electromagnetic loss mechanism of the material-obtained was discussed. The microwave absorption properties of composites before and after heat treatment at 300 °C for 100 h were characterized in 2-18 GHz frequency range. It was established that composites based on Co-coated carbonyl iron demonstrate thermomagnetic stability, indicating that Co coating reduces the oxidation of carbonyl iron. Thus, Co-coated carbonyl iron particles/polyimide composites are useful in the design of microwave absorbers operating at temperatures up to 300 °C.

  12. Variation of ambient carbonyl levels in urban Beijing between 2005 and 2012

    Science.gov (United States)

    Chen, Wentai; Shao, Min; Wang, Ming; Lu, Sihua; Liu, Ying; Yuan, Bin; Yang, Yudong; Zeng, Limin; Chen, Zhongming; Chang, Chih-Chung; Zhang, Qian; Hu, Min

    2016-03-01

    Carbonyl compounds are important precursors of secondary air pollutants. With the rapid economic development and the implementation of stricter control measures in Beijing, the sources of carbonyls possibly changed. Based on measurement data obtained at an urban site in Beijing between 2005 and 2012, we investigated annual variations in carbonyl levels and sources during these years. In summer, formaldehyde and acetaldehyde levels decreased significantly at a rate of 9.1%/year and 7.2%/year, respectively, while acetone levels increased at a rate of 4.3%/year. In winter, formaldehyde levels increased and acetaldehyde levels decreased. We also investigated the factors driving the variation in carbonyls levels during summer by determination of emission ratios for carbonyls and their precursors, and calculation of photochemical formation of carbonyls. The relative declines for primary formaldehyde and acetaldehyde levels were larger than those for secondary formation. This is possibly due to the increasing usage of natural gas and liquefied petroleum gas which could result in the rise of carbonyl precursor emission ratios. The increase in acetone levels might be related to the rising solvent usage in Beijing during these years. The influences of these sources should be paid more attention in future research.

  13. Paraquat exposure and Sod2 knockdown have dissimilar impacts on the Drosophila melanogaster carbonylated protein proteome.

    Science.gov (United States)

    Narayanasamy, Suresh K; Simpson, David C; Martin, Ian; Grotewiel, Mike; Gronert, Scott

    2014-11-01

    Exposure to Paraquat and RNA interference knockdown of mitochondrial superoxide dismutase (Sod2) are known to result in significant lifespan reduction, locomotor dysfunction, and mitochondrial degeneration in Drosophila melanogaster. Both perturbations increase the flux of the progenitor ROS, superoxide, but the molecular underpinnings of the resulting phenotypes are poorly understood. Improved understanding of such processes could lead to advances in the treatment of numerous age-related disorders. Superoxide toxicity can act through protein carbonylation. Analysis of carbonylated proteins is attractive since carbonyl groups are not present in the 20 canonical amino acids and are amenable to labeling and enrichment strategies. Here, carbonylated proteins were labeled with biotin hydrazide and enriched on streptavidin beads. On-bead digestion was used to release carbonylated protein peptides, with relative abundance ratios versus controls obtained using the iTRAQ MS-based proteomics approach. Western blotting and biotin quantitation assay approaches were also investigated. By both Western blotting and proteomics, Paraquat exposure, but not Sod2 knockdown, resulted in increased carbonylated protein relative abundance. For Paraquat exposure versus control, the median carbonylated protein relative abundance ratio (1.53) determined using MS-based proteomics was in good agreement with that obtained using a commercial biotin quantitation kit (1.36).

  14. Salinity promotes opposite patterns of carbonylation and nitrosylation of C4 phosphoenolpyruvate carboxylase in sorghum leaves.

    Science.gov (United States)

    Baena, Guillermo; Feria, Ana B; Echevarría, Cristina; Monreal, José A; García-Mauriño, Sofía

    2017-08-21

    Carbonylation inactivates sorghum C 4 PEPCase while nitrosylation has little impact on its activity but holds back carbonylation. This interplay could be important to preserve photosynthetic C4 PEPCase activity in salinity. Previous work had shown that nitric acid (NO) increased phosphoenolpyruvate carboxylase kinase (PEPCase-k) activity, promoting the phosphorylation of phosphoenolpyruvate carboxylase (PEPCase) in sorghum leaves (Monreal et al. in Planta 238:859-869, 2013b). The present work investigates the effect of NO on C4 PEPCase in sorghum leaves and its interplay with carbonylation, an oxidative modification frequently observed under salt stress. The PEPCase of sorghum leaves could be carbonylated in vitro and in vivo, and this post-translational modification (PTM) was accompanied by a loss of its activity. Similarly, PEPCase could be S-nitrosylated in vitro and in vivo, and this PTM had little impact on its activity. The S-nitrosylated PEPCase showed increased resistance towards subsequent carbonylation, both in vitro and in vivo. Under salt shock, carbonylation of PEPCase increased in parallel with decreased S-nitrosylation of the enzyme. Subsequent increase of S-nitrosylation was accompanied by decreased carbonylation. Taken together, the results suggest that S-nitrosylation could contribute to maintain C4 PEPCase activity in stressed sorghum plants. Thus, salt-induced NO synthesis would be protecting photosynthetic PEPCase activity from oxidative inactivation while promoting its phosphorylation, which will guarantee its optimal functioning in suboptimal conditions.

  15. Method for the Determination of Carbonyl Compounds in E-Cigarette Aerosols

    Science.gov (United States)

    Flora, Jason W.; Wilkinson, Celeste T.; Wilkinson, James W.; Lipowicz, Peter J.; Skapars, James A.; Anderson, Adam; Miller, John H.

    2017-01-01

    Low levels of thermal degradation products such as carbonyls (formaldehyde, acetaldehyde, acrolein, crotonaldehyde) have been reported in e-cigarette aerosols. The collection and analysis of e-cigarette aerosol carbonyls are often adapted from methods developed for tobacco cigarette smoke. These methodologies are often not sensitive enough to detect low carbonyl levels in e-cigarette aerosols. One objective of this work was to develop and validate a rapid, selective and sensitive ultra-performance liquid chromatography with mass spectrometry method optimized for analysis of carbonyls in e-cigarette aerosols. Aerosols were trapped in 20-puff collections, 4-s durations, 55-mL volumes, 30-s intervals, square wave puff profiles. Collection apparatus involved a linear smoking machine with Cambridge filter pad followed by a glass impinger containing acidified 2,4-dinitrophenylhydrazine. This method showed limits of quantitation and detection of 0.016 and 0.003 µg puff−1, respectively, and run time of 4 min. Six e-cigarettes were evaluated (five devices each). All contained measurable levels of carbonyls. Levels were mostly well below those in conventional cigarettes. However, for some e-cigarettes, formaldehyde levels were above those for tobacco cigarettes (highest at 14.1 µg puff−1). Temperatures related to carbonyl yields in e-cigarette aerosols were explored to better understand carbonyl formation: formation of formaldehyde is low at temperatures below 350°C. PMID:28087758

  16. Formation of Carbonyl and Carboxyl Groups on Cellulosic Pulps: Effect on Alkali Resistance

    Directory of Open Access Journals (Sweden)

    Jordan Perrin

    2014-10-01

    Full Text Available Ozone bleaching generates carbonyl groups on the cellulose polymer when applied to unbleached kraft pulps. This suggests that pulp fully bleached with a totally chlorine-free (TCF sequence may contain more oxidized groups than standard elemental chlorine-free (ECF bleached pulp. A fully bleached pulp was treated with sodium hypochlorite to form oxidized groups (mostly carbonyls on the pure carbohydrates, which were investigated during subsequent alkaline treatment. Carbonyl groups had a strong impact on color development during alkaline treatment. Among the carbonyls, the keto groups were the most active. This was confirmed by the behavior of carbohydrate model compounds that contained aldehyde, keto, and/or carboxyl groups when subjected to alkaline conditions. A subsequent hydrogen peroxide (P stage effectively decreased the carbonyl content, which reduced yellowing during alkaline treatment. However, the oxidized cellulose was severely depolymerized. The addition of magnesium sulfate (Mg into the P stage minimized depolymerization while maintaining some of the carbonyls in the carbohydrates. It is proposed that Mg cations can hinder alkaline β-elimination, possibly by forming a complex with the carbonyl groups.

  17. Synthesis and Characterization of Tc(I) Carbonyl Nitrosyl Species Relevant to the Hanford Tank Waste: FY 2016 Status Report

    Energy Technology Data Exchange (ETDEWEB)

    Hall, Gabriel B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Chatterjee, Sayandev [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Levitskaia, Tatiana G. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Martin, Thibaut J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wall, Nathalie [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walter, Eric D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-11-24

    Among long-lived radioactive constituents in the Hanford tank waste, Tc presents a unique challenge in that it exists predominantly in the liquid phase, generally in the anionic form of pertechnetate, TcO4-, which is highly volatile at low-activity waste (LAW) vitrification melter temperatures and mobile in the Hanford site’s subsurface environment. The complex behavior of Tc under storage, treatment, and immobilization conditions significantly affects its management options, which to-date remain uncertain. In strongly alkaline environments, Tc exists as pertechnetate, TcO4- (oxidation state +7), and in the reduced forms (oxidation state < +7) collectively known as non-pertechnetate species. Pertechnetate is a well-characterized, anionic Tc species that can be removed from LAW by anion exchange or solvent extraction methods. There is no definitive information on the origin of the non-pertechnetate Tc species, nor is there a comprehensive description of their composition and behavior. It has been recently proposed that the non-pertechnetate species can comprise Tc(I) metal center and carbonyl or mixed carbonyl nitrosyl ligands stabilizing low-valent Tc. Recent work by our group has significantly expanded this previous work, generating a series of Tc(I) carbonyl compounds and demonstrating that they can be generated from reduction of TcO4- in the simulated Hanford tank waste in presence of CO at elevated temperature (Levitskaia et al. 2014). These results are consistent with the previous proposal that [Tc(CO)3]+ species can be present in the Hanford tank waste and suggest that the low Tc(I) oxidation state is stabilized by the π-accepting ability of the CO ligands. The continuation work has been initiated to develop model Tc carbonyl nitrosyl compounds and investigate their potential presence in the Hanford tank wastes. This report summarizes our to-date results.

  18. Liquid methanol under a static electric field

    Energy Technology Data Exchange (ETDEWEB)

    Cassone, Giuseppe, E-mail: giuseppe.cassone@impmc.upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, UMR 7590, IMPMC, F-75005 Paris (France); CNRS, UMR 7590, IMPMC, F-75005 Paris (France); Università degli Studi di Messina, Dipartimento di Fisica e di Scienze della Terra, Contrada Papardo, 98166 Messina (Italy); CNR-IPCF, Viale Ferdinando Stagno d’Alcontres 37, 98158 Messina (Italy); Giaquinta, Paolo V., E-mail: paolo.giaquinta@unime.it [Università degli Studi di Messina, Dipartimento di Fisica e di Scienze della Terra, Contrada Papardo, 98166 Messina (Italy); Saija, Franz, E-mail: saija@ipcf.cnr.it [CNR-IPCF, Viale Ferdinando Stagno d’Alcontres 37, 98158 Messina (Italy); Saitta, A. Marco, E-mail: marco.saitta@impmc.upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, UMR 7590, IMPMC, F-75005 Paris (France); CNRS, UMR 7590, IMPMC, F-75005 Paris (France)

    2015-02-07

    We report on an ab initio molecular dynamics study of liquid methanol under the effect of a static electric field. We found that the hydrogen-bond structure of methanol is more robust and persistent for field intensities below the molecular dissociation threshold whose value (≈0.31 V/Å) turns out to be moderately larger than the corresponding estimate obtained for liquid water. A sustained ionic current, with ohmic current-voltage behavior, flows in this material for field intensities above 0.36 V/Å, as is also the case of water, but the resulting ionic conductivity (≈0.40 S cm{sup −1}) is at least one order of magnitude lower than that of water, a circumstance that evidences a lower efficiency of proton transfer processes. We surmise that this study may be relevant for the understanding of the properties and functioning of technological materials which exploit ionic conduction, such as direct-methanol fuel cells and Nafion membranes.

  19. Neurological Complications Resulting from Non-Oral Occupational Methanol Poisoning

    Science.gov (United States)

    Lee, Seung Keun; Gil, Young-Eun; Kim, Hyunjoo; Choi, Jun Young

    2017-01-01

    Methanol poisoning results in neurological complications including visual disturbances, bilateral putaminal hemorrhagic necrosis, parkinsonism, cerebral edema, coma, or seizures. Almost all reported cases of methanol poisoning are caused by oral ingestion of methanol. However, recently there was an outbreak of methanol poisoning via non-oral exposure that resulted in severe neurological complications to a few workers at industrial sites in Korea. We present 3 patients who had severe neurological complications resulting from non-oral occupational methanol poisoning. Even though initial metabolic acidosis and mental changes were improved with hemodialysis, all of the 3 patients presented optic atrophy and ataxia or parkinsonism as neurological complications resulting from methanol poisoning. In order to manage it adequately, as well as to prevent it, physicians should recognize that methanol poisoning by non-oral exposure can cause neurologic complications. PMID:28049252

  20. Kinetics of methanol steam reforming over COPZr-2 catalyst

    Institute of Scientific and Technical Information of China (English)

    Yongfeng Li; Weiming Lin; Lin Yu; Zhifeng Hao; Rongjian Mai

    2008-01-01

    The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction kinetics of methanol steam reforming over this type of catalyst. First, the effects of methanol conversion to outlet CO2 and methanol conversion to outlet CO on methanol pseudo contact time W/FMeOH were investigated. Then by applying the reaction route that methanol direct reforming (DR) and methanol decomposition (DE) were carried out in parallel, the reaction kinetic model with power function type was established. And the parameters for the model were estimated using a non-linear regression program which computed weighted least squares of the defined objects function. Finally, the kinetic model passed the correlation test and the F-test.

  1. Visible Light-Induced Carbonylation Reactions with Organic Dyes as the Photosensitizers.

    Science.gov (United States)

    Peng, Jin-Bao; Qi, Xinxin; Wu, Xiao-Feng

    2016-09-08

    Dyes can CO do it: Organic dyes and pigments are usually applied in textile dyeing, which can be dated back to the Neolithic period. Interestingly, the possibility to use organic dyes as photoredox catalysts has also been noticed by organic chemists and applied in organic synthesis. Carbonylation reactions as a powerful procedure in carbonyl-containing compound preparation have also been studied. In this manuscript, the recent achievements in using organic dyes as visible-light sensitizers in carbonylation chemistry are summarized and discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products.

  3. Alternative energies for road traffic - methanol. Alternative Energien fuer den Strassenverkehr - Methanol

    Energy Technology Data Exchange (ETDEWEB)

    1983-01-01

    Methanol motor fuels are alternative fuels which can supplement to the supply with petrol and diesel fuel from mineral oil to a greater extent. Since 1979, a fleet comprising more than 1,000 vehicles is being tested by customers in a practical large-scale test involving the motor fuels M15 and M100. The study on hand was produced by means of forecasts and facts based on today's technology and state of experience. The part concerning demand development and availability demonstrates in what quantities methanol could be available till the year 2000 (demand tendencies, future methanol production capacity in the world). The part concerning technology examines how the methanol quantities mentioned before could be used in road traffic (Otto engine, diesel engine, state of testing and trial, fuel technology) introduction phase, cost). The part concerning framework conditions notes that, in principle, there are no unsurmountable obstacles with setting up or amending methanol-specific technical and legal regulations.

  4. Rovibrational Spectroscopy of Aluminum Carbonyl Clusters in Helium Nanodroplets

    Science.gov (United States)

    Liang, T.; Morrison, A. M.; Flynn, S. D.; Douberly, G. E.

    2011-06-01

    Helium nanodroplet isolation and a tunable quantum cascade laser are used to probe the fundamental CO stretch bands of Aluminum Carbonyl complexes, Al-(CO)N (n ≤ 5). The droplets are doped with single aluminum atoms via the resistive heating of an aluminum wetted tantalum wire. The downstream sequential pick-up of CO molecules leads to the rapid formation and cooling of Al-(CO)N clusters within the droplets. Near 1900 Cm-1, rotational fine structure is resolved in bands that are assigned to the CO stretch of a 2Π1/2 linear Al-CO species, and the asymmetric and symmetric CO stretch vibrations of a planar C2v Al-(CO)2 complex in a 2B1 electronic state. Bands corresponding to clusters with n ≥ 3 lack resolved rotational fine structure; nevertheless, the small frequency shifts from the n=2 bands indicate that these clusters consist of an Al-(CO)2 core with additional CO molecules attached via van-der-Waals interactions. A second n=2 band is observed near the CO stretch of Al-CO, indicating a local minimum on the n=2 potential consisting of an ``unreacted" Al-CO-(CO) cluster. The linewidth of this band is ˜0.5 cm-1, which is over 50 times broader than transitions within the Al-CO band. The additional broadening is consistent with a homogeneous mechanism corresponding to a rapid vibrational excitation induced reaction within the Al-CO-(CO) cluster to form the covalently bonded Al-(CO)2 complex. For the n=1,2 complexes, CCSD(T) calculations and Natural Bond Orbital (NBO) analyses are carried out to investigate the nature of the bonding in these complexes. The NBO calculations show that both π ``back" donation (from the occupied aluminum p-orbital into the π antibonding CO orbital) and σ donation (from CO into the empty aluminum p-orbitals) play a significant role in the bonding, analogous to transition metal carbonyl complexes. The large redshift of the CO stretch vibrations is consistent with this bonding analysis.

  5. Kinetics of exchange between zero-, one-, and two-hydrogen-bonded states of methyl and ethyl acetate in methanol.

    Science.gov (United States)

    Chuntonov, Lev; Pazos, Ileana M; Ma, Jianqiang; Gai, Feng

    2015-03-26

    It has recently been shown that the ester carbonyl stretching vibration can be used as a sensitive probe of local electrostatic field in molecular systems. To further characterize this vibrational probe and extend its potential applications, we studied the kinetics of chemical exchange between differently hydrogen-bonded (H-bonded) ester carbonyl groups of methyl acetate (MA) and ethyl acetate (EA) in methanol. We found that, while both MA and EA can form zero, one, or two H-bonds with the solvent, the population of the 2hb state in MA is significantly smaller than that in EA. Using a combination of linear and nonlinear infrared measurements and numerical simulations, we further determined the rate constants for the exchange between these differently H-bonded states. We found that for MA the chemical exchange reaction between the two dominant states (i.e., 0hb and 1hb states) has a relaxation rate constant of 0.14 ps(-1), whereas for EA the three-state chemical exchange reaction occurs in a predominantly sequential manner with the following relaxation rate constants: 0.11 ps(-1) for exchange between 0hb and 1hb states and 0.12 ps(-1) for exchange between 1hb and 2hb states.

  6. Continuous auditing & continuous monitoring : Continuous value?

    NARCIS (Netherlands)

    van Hillo, Rutger; Weigand, Hans; Espana, S; Ralyte, J; Souveyet, C

    2016-01-01

    Advancements in information technology, new laws and regulations and rapidly changing business conditions have led to a need for more timely and ongoing assurance with effectively working controls. Continuous Auditing (CA) and Continuous Monitoring (CM) technologies have made this possible by obtain

  7. Continuous auditing & continuous monitoring : Continuous value?

    NARCIS (Netherlands)

    van Hillo, Rutger; Weigand, Hans; Espana, S; Ralyte, J; Souveyet, C

    2016-01-01

    Advancements in information technology, new laws and regulations and rapidly changing business conditions have led to a need for more timely and ongoing assurance with effectively working controls. Continuous Auditing (CA) and Continuous Monitoring (CM) technologies have made this possible by obtain

  8. Continuous auditing & continuous monitoring : Continuous value?

    NARCIS (Netherlands)

    van Hillo, Rutger; Weigand, Hans; Espana, S; Ralyte, J; Souveyet, C

    2016-01-01

    Advancements in information technology, new laws and regulations and rapidly changing business conditions have led to a need for more timely and ongoing assurance with effectively working controls. Continuous Auditing (CA) and Continuous Monitoring (CM) technologies have made this possible by

  9. Carbonyl iron powder surface modification of magnetorheological elastomers for vibration absorbing application

    Science.gov (United States)

    Chen, Dong; Yu, Miao; Zhu, Mi; Qi, Song; Fu, Jie

    2016-11-01

    With excellent characteristic of magnetic-control stiffness, magnetorheological elastomer (MRE) is well suited as a spring element of vibration absorber. To improve the vibration attenuation performance of MRE vibration absorbers, this paper expects to improve the mechanical strength and reduce the loss factor of MRE by interface modification. The surface of carbonyl iron powder (CIP) was modified with silica coating by a simple and convenient approach. Several MRE samples, with different proportions of modified CIPs were fabricated under a constant magnetic field. The morphology and composition of modified CIP were characterized by scanning electron microscope and Fourier transform infrared spectra. The results indicated that the modified CIPs were coated with uniform and continuous silica, which can make a better combination between particle and matrix. The tensile strength, magnetorheological properties and the damping properties of the MRE samples were tested by material testing machine and rheometer. The experimental results demonstrated that the loss factor of the MRE which incorporated with modified CIPs decreased markedly, and the tensile strength of such material has been much improved, at the same time this kind of MRE kept high MR effect. It is expected that this MRE material will meet the requirements of vibration absorber.

  10. Carbonyl sulfide and dimethyl sulfide exchange between lawn and the atmosphere

    Science.gov (United States)

    Geng, Chunmei; Mu, Yujing

    2004-06-01

    The exchange of carbonyl sulfide (COS) between lawn and the atmosphere was investigated by using a static enclosure under natural field conditions. The results indicated that the lawn acted as a sink for atmospheric COS and a source of dimethyl sulfide (DMS). The exchange fluxes of COS and DMS ranged between -3.24 pmol m-2 s-1 and -94.52 pmol m-2 s-1, and between 0 and 3.14 pmol m-2 s-1, respectively. The lawn was capable of continuously absorbing COS in nighttime as well as in daytime. The COS fluxes depended strongly on the ambient COS mixing ratios. The dependency of DMS emission fluxes on temperature was observed in November 2002. Soil also acted as a sink for COS during our study. However, the COS exchange fluxes of the lawn were much higher than that of the soil. The average COS and DMS fluxes were much higher in spring than in autumn and in summer. The daytime vertical profiles of COS also indicated that the lawn acted as a net sink for COS.

  11. Salt marsh vegetation as a carbonyl sulfide (COS) source to the atmosphere

    Science.gov (United States)

    Whelan, Mary E.; Min, Dong-Ha; Rhew, Robert C.

    2013-07-01

    Carbonyl sulfide (COS) is the most abundant and longest-lived reduced sulfur compound in the atmosphere; changes in its atmospheric concentration could significantly affect global climate and the biogeochemical sulfur cycle. The largest sink of COS in the troposphere is its destruction in plant leaves by the enzymes involved in photosynthesis. In this study, net fluxes of COS were measured from a coastal salt marsh on a subtropical barrier island on the Texas shore of the Gulf of Mexico. We find net emissions from sites with the common salt marsh plant Batis maritima compared to the net uptake from vegetated plots of most previously investigated biomes. The magnitude of the COS production from vegetated plots in this study was twice the emissions of soil-only salt marsh plots. This is the first time that emissions of COS have been found to be significantly enhanced by the presence of vegetation compared to soil alone. COS fluxes exceeded +110 pmol m-2 s-1 for non-inundated plots during daytime hours and were correlated with soil temperature at the depth of 5 cm. Tidal flooding inhibited soil COS exchange; however, we found continued net emissions from emergent B. maritima. This study suggests that emissions of COS resulted from interactions with the plants themselves, which would mean that B. maritima can mediate the production of atmospheric COS.

  12. Tropical sources and sinks of carbonyl sulfide observed from space

    Science.gov (United States)

    Glatthor, Norbert; Höpfner, Michael; Baker, Ian T.; Berry, Joe; Campbell, Elliott; Kawa, Stephan R.; Krysztofiak, Gisele; Sinnhuber, Björn-Martin; Stiller, Gabriele; Stinecipher, Jim; von Clarmann, Thomas

    2016-04-01

    According to current budget estimations the seasonal variation of carbonyl sulfide (COS) is governed by oceanic release and vegetation uptake. Its assimilation by plants is assumed to be similar to the photosynthetic uptake of CO2 but, contrary to the latter process, to be irreversible. Therefore COS has been suggested as co-tracer of the carbon cycle. Observations of COS, however, are sparse, especially in tropical regions. We use the comprehensive data set of spaceborne measurements of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) to analyze its global distribution. Two major features are observed in the tropical upper troposphere around 250 hPa: enhanced amounts over the western Pacific and the Maritime Continent, peaking around 550 pptv in boreal summer, and a seasonally varying depletion of COS extending from tropical South America to Africa. The large-scale COS depletion, which in austral summer amounts up to -40 pptv as compared to the rest of the respective latitude band, has not been observed before and reveals the seasonality of COS uptake through tropical vegetation. The observations can only be reproduced by global models, when a large vegetation uptake and a corresponding increase in oceanic emissions as proposed in several recent publications is assumed.

  13. Carbonyl Sulfide for Tracing Carbon Fluxes Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J. Elliott [Univ. of California, Merced, CA (United States); Berry, Joseph A. [Carnegie Inst. of Science, Stanford, CA (United States); Billesbach, Dave [Univ. of Nebraska, Lincoln, NE (United States); Torn, Margaret S [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zahniser, Mark [Aerodyne Research, Inc., Billerica, MA (United States); Seibt, Ulrike [Univ. of California, Los Angeles, CA (United States); Maseyk, Kadmiel [Pierre and Marie Curie Univ., Paris (France)

    2016-04-01

    The April-June 2012 campaign was located at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) site Central Facility and had three purposes. One goal was to demonstrate the ability of current instrumentation to correctly measure fluxes of atmospheric carbonyl sulfide (COS). The approach has been describe previously as a critical approach to advancing carbon cycle science1,2, but requires further investigation at the canopy scale to resolve ecosystem processes. Previous canopy-scale efforts were limited to data rates of 1Hz. While 1 Hz measurements may work in a few ecosystems, it is widely accepted that data rates of 10 to 20 Hz are needed to fully capture the exchange of traces gases between the atmosphere and vegetative canopy. A second goal of this campaign was to determine if canopy observations could provide information to help interpret the seasonal double peak in airborne observations at SGP of CO2 and COS mixing ratios. A third goal was to detect potential sources and sinks of COS that must be resolved before using COS as a tracer of gross primary productivity (GPP).

  14. The oceanic cycle and global atmospheric budget of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, P.S.

    1994-12-31

    A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux.

  15. Mechanism of heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    Science.gov (United States)

    Liu, Yongchun; He, Hong; Xu, Wenqing; Yu, Yunbo

    2007-05-24

    Heterogeneous reaction of carbonyl sulfide (OCS) on magnesium oxide (MgO) under ambient conditions was investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), quadrupole mass spectrometer (QMS), and density functional theory (DFT) calculations. It reveals that OCS can be catalytically hydrolyzed by surface hydroxyl on MgO to produce carbon dioxide (CO2) and hydrogen sulfide (H2S), and then H2S can be further catalytically oxidized by surface oxygen or gaseous oxygen on MgO to form sulfite (SO3(2-)) and sulfate (SO4(2-)). Hydrogen thiocarbonate (HSCO2-) was found to be the crucial intermediate. Surface hydrogen sulfide (HS), sulfur dioxide (SO2), and surface sulfite (SO3(2-)) were also found to be intermediates for the formation of sulfate. Furthermore, the surface hydroxyl contributes not only to the formation of HSCO2- but also to HSCO2- decomposition. On the basis of experimental results, the heterogeneous reaction mechanism of OCS on MgO was discussed.

  16. Hydroxyl radical substitution in halogenated carbonyls: oxalic acid formation.

    Science.gov (United States)

    Christiansen, Carrie J; Dalal, Shakeel S; Francisco, Joseph S; Mebel, Alexander M; Gaffney, Jeffrey S

    2010-03-04

    An ab initio study of OH radical substitution reactions in halogenated carbonyls is conducted. Hydroxyl radical substitution into oxalyl dichloride [ClC(O)C(O)Cl] and oxalyl dibromide [BrC(O)C(O)Br], resulting in the formation of oxalic acid, is presented. Analogous substitution reactions in formyl chloride [ClCH(O)], acetyl chloride [ClC(O)CH(3)], formyl bromide [BrCH(O)], and acetyl bromide [BrC(O)CH(3)] are considered. Energetics of competing hydrogen abstraction reactions for all applicable species are computed for comparison. Geometry optimizations and frequency computations are performed using the second-order Møller-Plesset perturbation theory (MP2) and the 6-31G(d) basis set for all minimum species and transition states. Single point energy computations are performed using fourth-order Møller-Plesset perturbation theory (MP4) and coupled cluster theory [CCSD(T)]. Potential energy surfaces, including activation energies and enthalpies, are determined from the computations. These potential energy surfaces show that OH substitution into ClC(O)C(O)Cl and BrC(O)C(O)Br, resulting in the formation of oxalic acid and other minor products, is energetically favorable. Energetics of analogous reactions with ClCH(O), BrCH(O), ClC(O)CH(3), and BrC(O)CH(3) are also computed.

  17. Regional-Scale Carbon Flux Partitioning Using Atmospheric Carbonyl Sulfide

    Science.gov (United States)

    Abu-Naser, M.; Campbell, J. E.; Berry, J. A.

    2011-12-01

    Simultaneous analysis of atmospheric concentrations of carbonyl sulfide (COS) and carbon dioxide (CO2) has been proposed as an approach to partitioning gross primary production and respiration fluxes at regional and global scales. The basis for this approach was that the observation and regional gradients in atmospheric CO2 are dominated by net ecosystem fluxes while regional gradients in atmospheric COS are dominated by GPP-related plant uptake. Here we investigate the spatial and temporal gradients in airborne COS and CO2 measurements in comparison to flux estimates from ecosystem models and eddy covariance methods over North America. The spatial gradients in the ecosystem relative uptake (ERU), the normalized ratio of COS and CO2 vertical gradients, were consistent with the theoretical relationship to flux estimates from ecosystem models and eddy covariance methods. The seasonality of the gross primary productivity flux estimates was consistent with airborne observations in the midwestern region but had mixed results in the southeastern region. Inter-annual changes in the ERU and regional drought index data suggested a potential relationship between drought stress and low ratios of gross primary production to net ecosystem exchange.

  18. Thermal characterization of magnetically aligned carbonyl iron/agar composites.

    Science.gov (United States)

    Diaz-Bleis, D; Vales-Pinzón, C; Freile-Pelegrín, Y; Alvarado-Gil, J J

    2014-01-01

    Composites of magnetic particles into polymeric matrices have received increasing research interest due to their capacity to respond to external magnetic or electromagnetic fields. In this study, agar from Gelidium robustum has been chosen as natural biocompatible polymer to build the matrix of the magnetic carbonyl iron particles (CIP) for their uses in biomedical fields. Heat transfer behavior of the CIP-agar composites containing different concentrations (5, 10, 15, 20, 25 and 30% w/w) of magnetically aligned and non-aligned CIP in the agar matrix was studied using photothermal radiometry (PTR) in the back-propagation emission configuration. The morphology of the CIP-agar composites with aligned and non-aligned CIP under magnetic field was also evaluated by scanning electron microscopy (SEM). The results revealed a dominant effect of CIP concentration over the alignment patterns induced by the magnetic field, which agrees with the behavior of the thermal diffusivity and thermal conductivity. Agar served as a perfect matrix to be used with CIP, and CIP-agar composites magnetically aligned at 20% CIP concentration can be considered as promising 'smart' material for hyperthermia treatments in the biomedical field.

  19. Photodecomposition of Molybdenum andTungsten Carbonyl Complexes

    Directory of Open Access Journals (Sweden)

    Thamer A. Alwani

    2009-01-01

    Full Text Available The photodecomposition of four different colored organometallic molybdenum and tungsten carbonyl complexes, i.e. [Mo(CO52LA] (complex I, [(Mo(CO3(bipy2LB] (complex II, [(W(CO3(tmen2LB] (complex III and [Mo(CO2LC]2 (complex I V where LA 2-phenyl-1,3-indandionebis(2-methyl anilines, LB 2-phenyl-1,3-indandione bis (4-hydroxy anilines and LCbis (2-hydroxo-benzalydine benzidine ion have been performed at 365 nm in chloroform at 25 °C under oxygen atmosphere. The absorbance spectrum of these complexes has been recorded with the time of irradiation in order to examine the kinetics of photodecomposition. The rate of the photodecomposition process was investigated and the relative values of the rate constants of dissociation (Kd for the first-order reaction are tabulated. The apparent rate constant of photodecomposition was found to be (8.33-11.50 × 10-5 s-1.

  20. Carbonyl sulfide uptake and chloroform emissions from an Arctic site

    Science.gov (United States)

    Elkins, J. W.; Dutton, G. S.; Montzka, S. A.; Nance, J. D.; Hall, B. D.; Thoning, K. W.; Miller, J. B.; White, J.; Vaugh, B.; Manning, A.

    2008-12-01

    The Arctic Region is most sensitive to future climate change. Quantifying emissions and sinks of many important biogenic trace gases there may become important indicators of potential climate feedback. Once snowmelt at Pt. Barrow, Alaska (77o N) occurs, ground cover is exposed by sunlight and higher temperatures, then photosynthesis starts up. Peaks of chloroform (CHCl3) appear throughout the summer from southerly-based air masses based over northern Alaska and northwest Canada. Carbonyl sulfide (COS) undergoes uptake throughout the summer season through the same enzymes that uptake carbon dioxide (CO2). We will calculate the footprint of emissions of CHCl3 and uptake of COS using high frequency in situ observations, and the NAME and FLEXPART models. Previous studies show a large source of CHCl3 (8% of the total budget) may be coming from soils in high latitude pine forests. We will examine emissions of CHCl3 to see whether or not they are coming from the tundra just south of Pt. Barrow. We will identify the regions for uptake of COS and CO2 from the footprint generated from the models.

  1. Degradation of ambient carbonyl sulfide by Mycobacterium spp. in soil.

    Science.gov (United States)

    Kato, Hiromi; Saito, Masahiko; Nagahata, Yoshiko; Katayama, Yoko

    2008-01-01

    The ability to degrade carbonyl sulfide (COS) was confirmed in seven bacterial strains that were isolated from soil, without the addition of COS. Comparative 16S rRNA gene sequence analysis indicated that these isolates belonged to the genera Mycobacterium, Williamsia and Cupriavidus. For example, Mycobacterium sp. strain THI401, grown on PYG agar medium, was able to degrade an initial level of 30 parts per million by volume COS within 1 h, while 60 % of the initial COS was decreased by abiotic conversion in 30 h. Considering natural COS flux between soil and the atmosphere, COS degradation by these bacteria was confirmed at an ambient level of 500 parts per trillion by volume (p.p.t.v.), using sterilized soil to cultivate the bacterium. Autoclave sterilization of soil resulted in a small amount of COS emission, while Mycobacterium spp. degraded COS at a faster rate than it was emitted from the soil, and reduced the COS mixing ratio to a level that was lower than the ambient level: THI401 degraded COS from an initial level of 530 p.p.t.v. to a level of 330 p.p.t.v. in 30 h. These results provide experimental evidence of microbial activity in soil as a sink for atmospheric COS.

  2. Teratogenicity and embryotoxicity of nickel carbonyl in Syrian hamsters

    Energy Technology Data Exchange (ETDEWEB)

    Sunderman, F.W. Jr.; Shen, S.K.; Reid, M.C.; Allpass, P.R.

    1980-01-01

    Nickel carbonyl was administered to groups of pregnant hamsters by inhalation on days 4, 5, 6, 7, or 8 of gestation. The dams were killed on day 15 of gestation, and the fetuses were examined for malformations. Exposure to Ni(CO)/sub 4/ on days 4 or 5 of gestation resulted in malformation in 5.5% and 5.8% of the progeny, respectively. Progeny included 9 fetuses with cystic lungs, 7 fetuses with exencephaly, 1 fetus with exencephaly plus fused rib and 1 fetus with anophthalmia plus cleft palate. Hemorrhages into serious cavities were found. In progeny of dams exposed to Ni(CO)/sub 4/ on days 6 or 7 of gestation, there was 1 fetus with fused ribs and there were 2 fetuses with hydronephrosis. In another experiment, pregnant hamsters were exposed to inhalation of Ni(CO)/sub 4/ on day 5 of gestation; these dams were permitted to deliver their litters and to nurse their pups. There was no significant difference in the average number of live pups in the Ni(CO)/sub 4/-exposed litters compared to control litters. Neonatal mortality was increased in Ni(CO)/sub 4/-exposed litters. This study demonstrates that Ni(CO)/sub 4/ is teratogenic and embryotoxic in Syrian hamsters.

  3. Heterogeneous oxidation of carbonyl sulfide on mineral oxides

    Institute of Scientific and Technical Information of China (English)

    LIU YongChun; LIU JunFeng; HE Hong; YU YunBo; XUE Li

    2007-01-01

    Heterogeneous oxidation of carbonyl sulfide (OCS) on mineral oxides including SiO2, Fe2O3, CaO, MgO, ZnO and TiO2, which are the main components of atmospheric particles, were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS), ion chromatography (IC), temperature-programmed desorption (TPD), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods. The main products and intermediates of the heterogeneous oxidation of OCS on these oxides were identified with in situ DRIFTS and IC. The reaction mechanism and kinetics were also discussed. It is found that the reaction mechanism on these mineral oxides is the same as that on Al2O3 for the same final products and the intermediates at room temperature. Namely, OCS can be catalytically oxidized to produce surface SO42- species and gaseous CO2 through the surface hydrogen thiocarbonate (HSCO2-) and HSO3- species. The activity series for heterogeneous oxidation of OCS follows: Al2O3 ≈ CaO>MgO>TiO2 ≈ ZnO>Fe2O3>SiO2. The specific area, basic hydroxyl and surface basicity of these oxides have effect on the reactivity. This study suggests that heterogeneous reactions of OCS on mineral dust may be an unneglectable sink of OCS.

  4. Dynamics of supercritical methanol of varying density from first principles simulations: hydrogen bond fluctuations, vibrational spectral diffusion, and orientational relaxation.

    Science.gov (United States)

    Yadav, Vivek Kumar; Chandra, Amalendu

    2013-06-14

    A first principles study of the dynamics of supercritical methanol is carried out by means of ab initio molecular dynamics simulations. In particular, the fluctuation dynamics of hydroxyl stretch frequencies, hydrogen bonds, dangling hydroxyl groups, and orientation of methanol molecules are investigated for three different densities at 523 K. Apart from the dynamical properties, various equilibrium properties of supercritical methanol such as the local density distributions and structural correlations, hydrogen bonding aspects, frequency-structure correlations, and dipole distributions of methanol molecules are also investigated. In addition to the density dependence of various equilibrium and dynamical properties, their dependencies on dispersion interactions are also studied by carrying out additional simulations using a dispersion corrected density functional for all the systems. It is found that the hydrogen bonding between methanol molecules decreases significantly as we move to the supercritical state from the ambient one. The inclusion of dispersion interactions is found to increase the number of hydrogen bonds to some extent. Calculations of the frequency-structure correlation coefficient reveal that a statistical correlation between the hydroxyl stretch frequency and the nearest hydrogen-oxygen distance continues to exist even at supercritical states of methanol, although it is weakened with increase of temperature and decrease of density. In the supercritical state, the frequency time correlation function is found to decay with two time scales: One around or less than 100 fs and the other in the region of 250-700 fs. It is found that, for supercritical methanol, the times scales of vibrational spectral diffusion are determined by an interplay between the dynamics of hydrogen bonds, dangling OD groups, and inertial rotation of methanol molecules and the roles of these various components are found to vary with density of the supercritical solvent. Effects

  5. Efficient Synthesis of Dimethyl Ether from Methanol in a Bifunctional Zeolite Membrane Reactor.

    Science.gov (United States)

    Zhou, Chen; Wang, Nanyi; Qian, Yanan; Liu, Xiaoxing; Caro, Jürgen; Huang, Aisheng

    2016-10-04

    A sandwich FAU-LTA zeolite dual-layer membrane has been developed and used as a catalytic membrane reactor for the synthesis of dimethyl ether (DME). In the top H-FAU layer with mild acidity, methanol is dehydrated to DME. The other reaction product, water, is removed in situ through a hydrophilic Na-LTA layer, which is located between the porous alumina support and the H-FAU top layer. The combination of mild acidity with the continuous removal of water results in high methanol conversion (90.9 % at 310 °C) and essentially 100 % DME selectivity. Furthermore, owing to the selective and continuous removal of water through the Na-LTA membrane, catalyst deactivation can be effectively suppressed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schindler, Matthias, E-mail: matthias.schindler@physik.uni-erlangen.de; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-15

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO{sub 2} and reduced to graphite to determine {sup 14}C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  7. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Science.gov (United States)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-01

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  8. Incorporating Cobalt Carbonyl Moieties onto Ethynylthiophene-Based Dithienylcyclopentene Switches. 1. Photochemistry

    NARCIS (Netherlands)

    Harvey, Emma C.; Areephong, Jetsuda; Cafolla, Attilio A.; Long, Conor; Browne, Wesley R.; Pryce, Mary T.; Feringa, Bernard

    2014-01-01

    The synthesis and characterization of a series of dithienyl perhydro- and perfluorocyclopentene photochromic molecular switches appended with cobalt carbonyl binding 3-ethynylthiophene and phenyl-3-ethynylthiophene substituents are reported. Their photochromic properties, fatigue resistance, and the

  9. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu

    2014-02-07

    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  10. Protective mechanisms of Cucumis sativus in diabetes-related models of oxidative stress and carbonyl stress

    Directory of Open Access Journals (Sweden)

    Himan Heidari

    2016-03-01

    Conclusion: It can be concluded that C. sativus has protective effects in diabetes complications and can be considered a safe and suitable candidate for decreasing the oxidative stress and carbonyl stress that is typically observed in diabetes mellitus.

  11. Carbonyl-bridged energetic materials: biomimetic synthesis, organic catalytic synthesis, and energetic performances.

    Science.gov (United States)

    Feng, Yong-An; Qiu, Hao; Yang, Sa-Sha; Du, Jiang; Zhang, Tong-Lai

    2016-11-01

    In order to obtain high-performance energetic materials, in this work, carbonyl groups (C[double bond, length as m-dash]O) have been newly introduced as sole bridging groups in the field of energetic materials. To this end, two tailored green methods for the synthesis of carbonyl-bridged energetic compounds have been developed for the first time. One is a biomimetic synthesis, in which the conversion route of heme to biliverdin has been used to obtain metal-containing energetic compounds. The other one is an organocatalysis, in which guanidinium serves as an energetic catalyst to afford other energetic compounds. Experimental studies and theoretical calculations have shown that carbonyl-bridged energetic compounds exhibit excellent energetic properties, which is promising for the carbonyl group as a new important and effective linker in energetic materials.

  12. Corrosion inhibition of α,β-unsaturated carbonyl compounds on steel in acid medium

    Institute of Scientific and Technical Information of China (English)

    Gao Jiancun; Weng Yongji; Salitanate; Feng Li; Yue Hong

    2009-01-01

    Corrosion inhibition of three α,β-unsaturated carbonyl compounds on N80 steel at high temperature and in concentrated acid medium was evaluated, and the inhibition mechanism was investigated.The results proved that both cinnamaidehyde and benzalacetone had an evident anticorrosion effect and could reduce the corrosion of steel effectively in acid medium, α,β-unsaturated carbonyl compounds with a benzene ring structure had good adsorption on steel surface.The experiments proved that polymerization of α,β-unsaturated carbonyl compounds on the steel surface at a high temperature and in concentrated acid medium resulted in a good corrosion inhibiting effect, which was attributed to the structures of α,β-unsaturated carbonyl compounds.

  13. A quantitative analysis of the benefits of mixed feeds of sorbitol and methanol for the production of recombinant avidin with Pichia pastoris.

    Science.gov (United States)

    Jungo, Carmen; Schenk, Jonas; Pasquier, Muriel; Marison, Ian William; von Stockar, Urs

    2007-08-01

    The advantages of mixed feeds of sorbitol and methanol for the production of recombinant proteins with Pichia pastoris were analyzed quantitatively. The influence of the methanol-sorbitol ratio in the feed medium was investigated on growth stoichiometry and recombinant protein productivity with a P. pastoris Mut(+) strain secreting avidin by performing a transient nutrient gradient in continuous cultivation at a dilution rate of 0.03h(-1). Results showed that mixed feeds of sorbitol and methanol instead of methanol as sole carbon source can improve the productivity in recombinant avidin due to increased biomass yields during mixed substrate growth. The highest volumetric avidin productivity was achieved at a methanol fraction of 43%C-molC-mol(-1) in the feed medium: the volumetric avidin productivity was 1.3-fold higher than during chemostat culture on methanol. The heat production and the oxygen consumption rates were reduced by about 38% for a given dry cell weight concentration at this methanol fraction, features which are very useful for high cell density cultures. Results were in good agreement with a high cell density fed-batch culture performed with a mixed feed of 43% methanol and 57% sorbitol C-molC-mol(-1) at a specific growth rate of 0.03h(-1) during the induction phase. Moreover, it was confirmed that sorbitol accumulation in the culture medium does not affect recombinant avidin productivity, which can especially be advantageous during large-scale cultures where transient substrate accumulation can result from imperfect mixing.

  14. Mechanisms of ultrafast fluorescence depletion spectroscopy and applications to measure slovation dynamics of coummarin 153 in methanol

    Energy Technology Data Exchange (ETDEWEB)

    Yang Songqiu, E-mail: sqyang@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Liu Jianyong, E-mail: beam@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Zhou Panwang, E-mail: pwzhou@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Chen Junsheng, E-mail: junshengchen@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Han Keli, E-mail: klhan@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); He Guozhong, E-mail: gzhe@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

    2012-09-15

    Subpicosecond fluorescence depletion spectroscopy (FDS) was used to measure the solvation dynamics of coumarin 153 (C153) in methanol. The FDS mechanisms were discussed. A quasi-continuous model was used to describe the solvational relaxation of excited states. The perturbations of the probe pulse on the excited sample system, including up-conversion and stimulated emission, were sufficiently discussed. For a probe molecule used in the FDS experiment, ensuring that the up-conversion perturbation can be negligible is important. FDS was found to be a good technique for measuring the solvation dynamics of C153 in methanol. - Highlights: Black-Right-Pointing-Pointer Mechanisms of subpicosecond fluorescence depletion spectroscopy. Black-Right-Pointing-Pointer Quasi-continuous model was used to describe the solvational relaxation. Black-Right-Pointing-Pointer The solvation dynamics of coumarin 153 in methanol has been measured.

  15. Biogenic methanol and its impacts on tropospheric oxidants

    Science.gov (United States)

    Tie, Xuexi; Guenther, Alex; Holland, Elisabeth

    2003-09-01

    We use a global chemical transport model (MOZART-2) to estimate the effects of surface emissions of methanol on tropospheric oxidants. The importance of methanol in tropospheric chemistry is two fold. First, methanol has a relatively large surface emission with an estimated global emission of 70 to 350 Tg methanol/year. The estimated methanol flux is comparable to other major hydrocarbon surface emissions such as isoprene and total monoterpenes, but the chemical lifetime of methanol is several days (in the boundary layer) to a few weeks (in the upper troposphere), which is much longer than the chemical lifetime of isoprene or monoterpenes (For example, the chemical lifetime of isoprene is about 2 hours). With a surface emission of 104 to 312 Tg methanol/year (encompasses estimated uncertainty in methanol emissions), the calculation shows that on average, the inclusion of methanol emission produces approximately 1-2% increase in O3, 1-3% decrease in OH, 3-5% increase in HO2, and 3-9% increase in CH2O globally. The maximum perturbation to the oxidants occurs in the tropical upper troposphere. However, the uncertainty associated with current methanol emission estimates produces significantly different model predictions of tropospheric oxidant distributions.

  16. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    Energy Technology Data Exchange (ETDEWEB)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young [Dept. of Energy Systems Research, Ajou University, Suwon (Korea, Republic of)

    2017-03-15

    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields.

  17. Efficient alpha-Methylenation of Carbonyl Compounds in Ionic Liquids at Room Temperature

    OpenAIRE

    Vale, JA; Zanchetta, DF; Moran, PJS; RODRIGUES, JAR

    2009-01-01

    The application of several 1-butyl-3-methylimidazolium (BMIM) salt ionic liquids as solvent in the alpha-methylenation of carbonyl compounds at room temperature is reported. The ionic liquid [BMIM][NTf(2)] gave a clean reaction in a short time and good yields of several alpha-methylene carbonyl compounds. This ionic liquid was reused without affecting the reaction rates or yields over seven runs.

  18. Biosynthesis of poly-3-hydroxybutyrate with a high molecular weight by methanotroph from methane and methanol

    Institute of Scientific and Technical Information of China (English)

    Yingxin Zhang; Jiaying Xin; Linlin Chen; Hao Song; Chungu Xia

    2008-01-01

    Poly-3-hydroxybutyrate (PHB) can be produced by various species of bacteria. Among the possible carbon sources, both methane and methanol could be a suitable substrate for the production of PHB. Methane is cheap and plentiful not only as natural gas, but also as biogas. Methanol can also maintain methanotrophic activity in some conditions. The methanotrophic strain Methylosinus trichosporium IMV3011 can accumulate PHB with methane and methanol in a brief nonsterile process. Liquid methanol (0.1%) was added to improve the oxidization of methane. The studies were carried out using shake flasks. Cultivation was performed in two stages: a continuous growth phase and a PHB accumulation phase under the conditions short of essential nutrients (ammonium, nitrate, phosphorus, copper, iron (III), magnesium or ethylenediamine tetraacetate (EDTA)) in batch culture. It was found that the most suitable growth time for the cell is 144 h. Then an optimized culture condition for second stage was determined, in which the PHB concentration could be much increased to 0.6 g/L. In order to increase PHB content, citric acid was added as an inhibitor of tricarboxylic acid cycle (TCA). It was found that citric acid is favorable for the PHB accumulation, and the PHB yield was increased to 40% (w/w) from the initial yield of 12% (w/w) after nutrient deficiency cultivation. The PHB produced is of very high quality with molecular weight up to 1.5 ×106Da.

  19. Direct photolysis of carbonyl compounds dissolved in cloud and fog droplets

    Science.gov (United States)

    Epstein, S. A.; Tapavicza, E.; Furche, F.; Nizkorodov, S. A.

    2013-04-01

    Gas phase photolysis is an important tropospheric sink for many carbonyl compounds, however the significance of direct photolysis of carbonyl compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived Henry's law parameters, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will not have competitive aqueous photolysis rates. We also present molecular dynamics simulations of atmospherically relevant carbonyl compounds designed to estimate gas and aqueous phase extinction coefficients. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only three out of the 92 carbonyl compounds investigated, pyruvic acid, 3-oxobutanoic acid, and 3-oxopropanoic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α, β conjugation, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected.

  20. Oxidative Stress and Carbonyl Lesions in Ulcerative Colitis and Associated Colorectal Cancer

    Science.gov (United States)

    Wang, Zhiqi; Li, Sai; Cao, Yu; Tian, Xuefei; Zeng, Rong; Liao, Duan-Fang; Cao, Deliang

    2016-01-01

    Oxidative stress has long been known as a pathogenic factor of ulcerative colitis (UC) and colitis-associated colorectal cancer (CAC), but the effects of secondary carbonyl lesions receive less emphasis. In inflammatory conditions, reactive oxygen species (ROS), such as superoxide anion free radical (O2 ∙−), hydrogen peroxide (H2O2), and hydroxyl radical (HO∙), are produced at high levels and accumulated to cause oxidative stress (OS). In oxidative status, accumulated ROS can cause protein dysfunction and DNA damage, leading to gene mutations and cell death. Accumulated ROS could also act as chemical messengers to activate signaling pathways, such as NF-κB and p38 MAPK, to affect cell proliferation, differentiation, and apoptosis. More importantly, electrophilic carbonyl compounds produced by lipid peroxidation may function as secondary pathogenic factors, causing further protein and membrane lesions. This may in turn exaggerate oxidative stress, forming a vicious cycle. Electrophilic carbonyls could also cause DNA mutations and breaks, driving malignant progression of UC. The secondary lesions caused by carbonyl compounds may be exceptionally important in the case of host carbonyl defensive system deficit, such as aldo-keto reductase 1B10 deficiency. This review article updates the current understanding of oxidative stress and carbonyl lesions in the development and progression of UC and CAC. PMID:26823956

  1. A biotin enrichment strategy identifies novel carbonylated amino acids in proteins from human plasma.

    Science.gov (United States)

    Havelund, Jesper F; Wojdyla, Katarzyna; Davies, Michael J; Jensen, Ole N; Møller, Ian Max; Rogowska-Wrzesinska, Adelina

    2017-03-06

    Protein carbonylation is an irreversible protein oxidation correlated with oxidative stress, various diseases and ageing. Here we describe a peptide-centric approach for identification and characterisation of up to 14 different types of carbonylated amino acids in proteins. The modified residues are derivatised with biotin-hydrazide, enriched and characterised by tandem mass spectrometry. The strength of the method lies in an improved elution of biotinylated peptides from monomeric avidin resin using hot water (95°C) and increased sensitivity achieved by reduction of analyte losses during sample preparation and chromatography. For the first time MS/MS data analysis utilising diagnostic biotin fragment ions is used to pinpoint sites of biotin labelling and improve the confidence of carbonyl peptide assignments. We identified a total of 125 carbonylated residues in bovine serum albumin after extensive in vitro metal ion-catalysed oxidation. Furthermore, we assigned 133 carbonylated sites in 36 proteins in native human plasma protein samples. The optimised workflow enabled detection of 10 hitherto undetected types of carbonylated amino acids in proteins: aldehyde and ketone modifications of leucine, valine, alanine, isoleucine, glutamine, lysine and glutamic acid (+14Da), an oxidised form of methionine - aspartate semialdehyde (-32Da) - and decarboxylated glutamic acid and aspartic acid (-30Da).

  2. Oxidative Stress and Carbonyl Lesions in Ulcerative Colitis and Associated Colorectal Cancer

    Directory of Open Access Journals (Sweden)

    Zhiqi Wang

    2016-01-01

    Full Text Available Oxidative stress has long been known as a pathogenic factor of ulcerative colitis (UC and colitis-associated colorectal cancer (CAC, but the effects of secondary carbonyl lesions receive less emphasis. In inflammatory conditions, reactive oxygen species (ROS, such as superoxide anion free radical (O2∙-, hydrogen peroxide (H2O2, and hydroxyl radical (HO∙, are produced at high levels and accumulated to cause oxidative stress (OS. In oxidative status, accumulated ROS can cause protein dysfunction and DNA damage, leading to gene mutations and cell death. Accumulated ROS could also act as chemical messengers to activate signaling pathways, such as NF-κB and p38 MAPK, to affect cell proliferation, differentiation, and apoptosis. More importantly, electrophilic carbonyl compounds produced by lipid peroxidation may function as secondary pathogenic factors, causing further protein and membrane lesions. This may in turn exaggerate oxidative stress, forming a vicious cycle. Electrophilic carbonyls could also cause DNA mutations and breaks, driving malignant progression of UC. The secondary lesions caused by carbonyl compounds may be exceptionally important in the case of host carbonyl defensive system deficit, such as aldo-keto reductase 1B10 deficiency. This review article updates the current understanding of oxidative stress and carbonyl lesions in the development and progression of UC and CAC.

  3. Methanol may function as a cross-kingdom signal.

    Directory of Open Access Journals (Sweden)

    Yuri L Dorokhov

    Full Text Available Recently, we demonstrated that leaf wounding results in the synthesis of pectin methylesterase (PME, which causes the plant to release methanol into the air. Methanol emitted by a wounded plant increases the accumulation of methanol-inducible gene mRNA and enhances antibacterial resistance as well as cell-to-cell communication, which facilitates virus spreading in neighboring plants. We concluded that methanol is a signaling molecule involved in within-plant and plant-to-plant communication. Methanol is considered to be a poison in humans because of the alcohol dehydrogenase (ADH-mediated conversion of methanol into toxic formaldehyde. However, recent data showed that methanol is a natural compound in normal, healthy humans. These data call into question whether human methanol is a metabolic waste product or whether methanol has specific function in humans. Here, to reveal human methanol-responsive genes (MRGs, we used suppression subtractive hybridization cDNA libraries of HeLa cells lacking ADH and exposed to methanol. This design allowed us to exclude genes involved in formaldehyde and formic acid detoxification from our analysis. We identified MRGs and revealed a correlation between increases in methanol content in the plasma and changes in human leukocyte MRG mRNA levels after fresh salad consumption by volunteers. Subsequently, we showed that the methanol generated by the pectin/PME complex in the gastrointestinal tract of mice induces the up- and downregulation of brain MRG mRNA. We used an adapted Y-maze to measure the locomotor behavior of the mice while breathing wounded plant vapors in two-choice assays. We showed that mice prefer the odor of methanol to other plant volatiles and that methanol changed MRG mRNA accumulation in the mouse brain.We hypothesize that the methanol emitted by wounded plants may have a role in plant-animal signaling. The known positive effect of plant food intake on human health suggests a role for

  4. Direct methanol feed fuel cell and system

    Science.gov (United States)

    Surampudi, Subbarao (Inventor); Frank, Harvey A. (Inventor); Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Kindler, Andrew (Inventor); Halpert, Gerald (Inventor)

    2009-01-01

    Improvements to non acid methanol fuel cells include new formulations for materials. The platinum and ruthenium are more exactly mixed together. Different materials are substituted for these materials. The backing material for the fuel cell electrode is specially treated to improve its characteristics. A special sputtered electrode is formed which is extremely porous. The fuel cell system also comprises a fuel supplying part including a meter which meters an amount of fuel which is used by the fuel cell, and controls the supply of fuel based on said metering.

  5. Methanol adsorption studies of electrified ACF by MD simulations

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    [1]Wang, R. Z., Jia, J. P., Teng, Y. et al., A potential solid adsorption refrigeration pair-active carbon fiber- methanol, Acta Energ. Solar. Sinica (in Chinese), 1997, 18(2): 222-227.[2]Wang, R. Z., Wu, J. Y., Xu, Y. X. et al., Experiment on a continuous heat regenerative adsorption refrigerator using spiral plate heat exchanger as adsorbers, Applied Thermal Eng., 1998, 18(1-2): 13-23.[3]Vagner, C., Finqueneisel, G., Zimny, T. et al., Isotherms and kinetics of methanol vapor adsorption on carbon fibers and activated carbons, New Carbon Materials, 2003, 18(2): 133-136.[4]Wang, D. R., Development and application of activated carbon nanofiber, Carbon (in Chinese), 2003, 1: 35-41.[5]Su, J. C., Qiu, J. Sh., Preparation of activated carbon fiber-based composite adsorbent and its gas separation performance, Carbon Techniques (in Chinese), 2001, 3: 1-4.[6]Gasteiger, J., Marsili, M., Iterative partial equalization of orbital electronegativity-a rapid access to atomic charges, Tetrahedron, 1980, 36: 3219-3288.[7]Cornell, W. D., Cieplak, P., Bayly, C. I. et al., A second generation force field for the simulation of peoteins, nucleic acids, and organic molecules, J. Am. Chem. Soc., 1995, 117: 5179-5197.[8]Ewald, P. P., Die Berechnung optischer und elektrostatischer gitterpotentiale, Ann. Phys., 1921, 64: 253-287.[9]Allen, M. P., Tildesley, D. J., Computer Simulation of Liquids, Oxford: Oxford University Press, 1987, 157-162.[10]Leach, A. R., Molecular Modelling: Principles and Applications, London: Addison Wesley Longman Limited, 1996, 294-298.

  6. Thermodynamic properties of direct methanol polymer electrolyte fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Seong, Ji Yun; Bae, Young Chan [Division of Chemical Engineering and Molecular Thermodynamics Laboratory, Hanyang University, Sungdonggu Haengdangdong 17, Seoul 133-791 (Korea, Republic of); Sun, Yang Kook [Division of Chemical Engineering and Center for Information and Communication, Materials, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2005-08-18

    A new semi-empirical model is established to describe the cell voltage of a direct methanol fuel cell (DMFC) as a function of current density. The model equation is validated experimental data over a wide range of a methanol concentration and temperatures. A number of existing models are semi-empirical. They, however, have a serious mathematical defect. When the current density, j, becomes zero, the equation should reduce to the open circuit voltage, E{sub 0}. These models, however, do not meet the mathematical boundary condition. The proposed model focuses on very unfavorable conditions for the cell operation, i.e. low methanol solution concentrations and relatively low cell temperatures. A newly developed semi-empirical equation with reasonable boundary conditions includes the methanol crossover effect that plays a major role in determining the cell voltage of DMFC. Also, it contains methanol activity based on thermodynamic functions to represent methanol crossover effect. (author)

  7. Protein carbonylation, protein aggregation and neuronal cell death in a murine model of multiple sclerosis

    Science.gov (United States)

    Dasgupta, Anushka

    Many studies have suggested that oxidative stress plays an important role in the pathophysiology of both multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Yet, the mechanism by which oxidative stress leads to tissue damage in these disorders is unclear. Recent work from our laboratory has revealed that protein carbonylation, a major oxidative modification caused by severe and/or chronic oxidative stress conditions, is elevated in MS and EAE. Furthermore, protein carbonylation has been shown to alter protein structure leading to misfolding/aggregation. These findings prompted me to hypothesize that carbonylated proteins, formed as a consequence of oxidative stress and/or decreased proteasomal activity, promote protein aggregation to mediate neuronal apoptosis in vitro and in EAE. To test this novel hypothesis, I first characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of myelin-oligodendrocyte glycoprotein (MOG)35-55 peptide-induced EAE in C57BL/6 mice [Chapter 2]. The results show that carbonylated proteins accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. I discovered not only that there is a temporal correlation between protein carbonylation and apoptosis but also that carbonyl levels are significantly higher in apoptotic cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are also present during the course of EAE, which seems to be due to reduced autophagy. In chapter 3, I show that when gluthathione levels are reduced to those in EAE spinal cord, both neuron-like PC12 (nPC12) cells and primary neuronal cultures accumulate carbonylated proteins and undergo cell death (both by necrosis and apoptosis). Immunocytochemical and biochemical studies also revealed a temporal

  8. Methanol Observation of IRAS 19312+1950: A Possible New Type of Class I Methanol Masers

    CERN Document Server

    Nakashima, Jun-ichi; Salii, Svetlana V; Zhang, Yong; Yung, Bosco H K; Deguchi, Shuji

    2015-01-01

    We report the result of a systematic methanol observation toward IRAS 19312+1950. The properties of the SiO, H2O and OH masers of this object are consistent with those of mass-losing evolved stars, but some other properties are difficult to explain in the standard scheme of stellar evolution in its late stage. Interestingly, a tentative detection of radio methanol lines was suggested toward this object by a previous observation. To date, there are no confirmed detections of methanol emission towards evolved stars, so investigation of this possible detection is important to better understand the circumstellar physical/chemical environment of IRAS 19312+1950. In this study, we systematically observed multiple methanol lines of IRAS 19312+1950 in the lambda=3mm, 7mm, and 13mm bands, and detected 6 lines including 4 thermal lines and 2 class I maser lines. We derived basic physical parameters including kinetic temperature and relative abundances by fitting a radiative transfer model. According to the derived exci...

  9. Metabolism of bupropion by carbonyl reductases in liver and intestine.

    Science.gov (United States)

    Connarn, Jamie N; Zhang, Xinyuan; Babiskin, Andrew; Sun, Duxin

    2015-07-01

    Bupropion's metabolism and the formation of hydroxybupropion in the liver by cytochrome P450 2B6 (CYP2B6) has been extensively studied; however, the metabolism and formation of erythro/threohydrobupropion in the liver and intestine by carbonyl reductases (CR) has not been well characterized. The purpose of this investigation was to compare the relative contribution of the two metabolism pathways of bupropion (by CYP2B6 and CR) in the subcellular fractions of liver and intestine and to identify the CRs responsible for erythro/threohydrobupropion formation in the liver and the intestine. The results showed that the liver microsome generated the highest amount of hydroxybupropion (Vmax = 131 pmol/min per milligram, Km = 87 μM). In addition, liver microsome and S9 fractions formed similar levels of threohydrobupropion by CR (Vmax = 98-99 pmol/min per milligram and Km = 186-265 μM). Interestingly, the liver has similar capability to form hydroxybupropion (by CYP2B6) and threohydrobupropion (by CR). In contrast, none of the intestinal fractions generate hydroxybupropion, suggesting that the intestine does not have CYP2B6 available for metabolism of bupropion. However, intestinal S9 fraction formed threohydrobupropion to the extent of 25% of the amount of threohydrobupropion formed by liver S9 fraction. Enzyme inhibition and Western blots identified that 11β-dehydrogenase isozyme 1 in the liver microsome fraction is mainly responsible for the formation of threohydrobupropion, and in the intestine AKR7 may be responsible for the same metabolite formation. These quantitative comparisons of bupropion metabolism by CR in the liver and intestine may provide new insight into its efficacy and side effects with respect to these metabolites.

  10. Fast retrievals of tropospheric carbonyl sulfide with IASI

    Science.gov (United States)

    Vincent, R. Anthony; Dudhia, Anu

    2017-02-01

    Iterative retrievals of trace gases, such as carbonyl sulfide (OCS), from satellites can be exceedingly slow. The algorithm may even fail to keep pace with data acquisition such that analysis is limited to local events of special interest and short time spans. With this in mind, a linear retrieval scheme was developed to estimate total column amounts of OCS at a rate roughly 104 times faster than a typical iterative retrieval. This scheme incorporates two concepts not utilized in previously published linear estimates. First, all physical parameters affecting the signal are included in the state vector and accounted for jointly, rather than treated as effective noise. Second, the initialization point is determined from an ensemble of atmospheres based on comparing the model spectra to the observations, thus improving the linearity of the problem. All of the 2014 data from the Infrared Atmospheric Sounding Interferometer (IASI), instruments A and B, were analysed and showed spatial features of OCS total columns, including depletions over tropical rainforests, seasonal enhancements over the oceans, and distinct OCS features over land. Error due to assuming linearity was found to be on the order of 11 % globally for OCS. However, systematic errors from effects such as varying surface emissivity and extinction due to aerosols have yet to be robustly characterized. Comparisons to surface volume mixing ratio in situ samples taken by NOAA show seasonal correlations greater than 0.7 for five out of seven sites across the globe. Furthermore, this linear scheme was applied to OCS, but may also be used as a rapid estimator of any detectable trace gas using IASI or similar nadir-viewing instruments.

  11. Intramolecular Hydrogen Bond in Biologically Active o-Carbonyl Hydroquinones

    Directory of Open Access Journals (Sweden)

    Maximiliano Martínez-Cifuentes

    2014-07-01

    Full Text Available Intramolecular hydrogen bonds (IHBs play a central role in the molecular structure, chemical reactivity and interactions of biologically active molecules. Here, we study the IHBs of seven related o-carbonyl hydroquinones and one structurally-related aromatic lactone, some of which have shown anticancer and antioxidant activity. Experimental NMR data were correlated with theoretical calculations at the DFT and ab initio levels. Natural bond orbital (NBO and molecular electrostatic potential (MEP calculations were used to study the electronic characteristics of these IHB. As expected, our results show that NBO calculations are better than MEP to describe the strength of the IHBs. NBO energies (∆Eij(2 show that the main contributions to energy stabilization correspond to LPàσ* interactions for IHBs, O1…O2-H2 and the delocalization LPàπ* for O2-C2 = Cα(β. For the O1…O2-H2 interaction, the values of ∆Eij(2 can be attributed to the difference in the overlap ability between orbitals i and j (Fij, instead of the energy difference between them. The large energy for the LP O2àπ* C2 = Cα(β interaction in the compounds 9-Hydroxy-5-oxo-4,8, 8-trimethyl-l,9(8H-anthracenecarbolactone (VIII and 9,10-dihydroxy-4,4-dimethylanthracen-1(4H-one (VII (55.49 and 60.70 kcal/mol, respectively when compared with the remaining molecules (all less than 50 kcal/mol, suggests that the IHBs in VIII and VII are strongly resonance assisted.

  12. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  13. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.

    2011-02-01

    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

  14. Effect of methanolic extract of Allium sativum (AS) in delaying cataract in STZ-induced diabetic rats.

    Science.gov (United States)

    Raju, T Naga; Kanth, V Rajani; Lavanya, K

    2008-03-01

    Glycemic-induced stress is a major culprit contributing to oxidative insult that has far-reaching effects in diabetic cataract worldwide. In an attempt to prevent/delay cataract, many therapeutic agents have been identified, and among these, natural dietary sources have gained pharmacological significance. Hence, we investigated the efficacy of the methanolic garlic extract against diabetic cataract in Wistar rats. Methanolic garlic extract scavenged the transition metal ion-generated H(2)O(2) with an IC(50) of 768.8 +/- 1.76 mug/ml, showing its potential ability as an antioxidant. We have noticed lenticular opacity and oxidative damage in streptozotocin (STZ)-induced hyperglycemic rats. This is evident by the elevation of Ca(2+), Cu(2+), Na(+), Mg(2+), thiobarbituric acid reacting substances (TBARS), and carbonyl content and increased activities of polyol enzymes, glutathione peroxidase (GPx), superoxide dismutase (SOD), and up regulation of iNOS transcript and protein aggregation/cross-linking followed by a decrease in reduced glutathione (GSH), K(+) content, and tryptophan fluorescence in the cataractous lenses of STZ-induced diabetic rats. Garlic administration in a dose-dependent manner attenuated the glycemia-mediated oxidative stress as all the parameters have been found normalized more or less to that of control rats and thus delaying the progression of the lens opacity. We conclude that garlic extract has hypoglycemic and anti oxidant properties that can delay the progression of cataract as revealed in this study.

  15. Synthesis and refining of sunflower biodiesel in a cascade of continuous centrifugal contactor separators

    NARCIS (Netherlands)

    Bin Abu Ghazali, Yusuf; van Ulden, Wouter; van de Bovenkamp, Hendrik; Teddy, T; Picchioni, Francesco; Manurung, Robert; Heeres, Hero J.

    2015-01-01

    The synthesis of fatty acid methyl esters (FAME) from sunflower oil and methanol was studied in a continuous centrifugal contactor separator (CCCS) using sodium methoxide as the catalyst. The effect of relevant process variables like oil and methanol flow rate, rotational speed and catalyst concentr

  16. Synthesis and refining of sunflower biodiesel in a cascade of continuous centrifugal contactor separators

    NARCIS (Netherlands)

    Bin Abu Ghazali, Yusuf; van Ulden, Wouter; van de Bovenkamp, Hendrik; Teddy, T; Picchioni, Francesco; Manurung, Robert; Heeres, Hero J.

    2015-01-01

    The synthesis of fatty acid methyl esters (FAME) from sunflower oil and methanol was studied in a continuous centrifugal contactor separator (CCCS) using sodium methoxide as the catalyst. The effect of relevant process variables like oil and methanol flow rate, rotational speed and catalyst concentr

  17. Deuterated methanol in Orion BN/KL

    CERN Document Server

    Peng, T -C; Brouillet, N; Parise, B; Baudry, A

    2012-01-01

    Deuterated molecules have been detected and studied toward Orion BN/KL in the past decades, mostly with single-dish telescopes. However, high angular resolution data are critical not only for interpreting the spatial distribution of the deuteration ratio but also for understanding this complex region in terms of cloud evolution involving star-forming activities and stellar feedbacks. We present here the first high angular resolution (1.8 arcsec \\times 0.8 arcsec) images of deuterated methanol CH2DOH in Orion BN/KL observed with the IRAM Plateau de Bure Interferometer from 1999 to 2007 in the 1 to 3 mm range. Six CH2DOH lines were detected around 105.8, 223.5, and 225.9 GHz. In addition, three E-type methanol lines around 101-102 GHz were detected and were used to derive the corresponding CH3OH rotational temperatures and column densities toward different regions across Orion BN/KL. The strongest CH2DOH and CH3OH emissions come from the Hot Core southwest region with an LSR velocity of about 8 km/s. We derive ...

  18. Performance of supercritical methanol in polyurethane degradation

    Directory of Open Access Journals (Sweden)

    Liu Lu

    2016-01-01

    Full Text Available Polyurethane is a group of block copolymer which is composed of diisocyanate, chain extender, and polyol, including polyurethane foam, polyurethane elastomer, waterborne polyurethane, etc. This research focused on thermoplastic polyurethane elastomer (TPU which is formed with 4,4’-diphenylmethane diisocyanate (MDI, poly(1,4-butanediol-hexanedioic acid diolpolyester(PBA and extended with 1,4-butanediol(BDO.The degradation of TPU was carried out with the help of methanol as the supercritical solvent. The SEM of the reaction residues revealed the process of the depolymerisation. The products were measured by GC-MS and found out to be PBA, BDO and 4,4’-methylene diphenyl carbamate(MDC which is themethylate of MDI.GC-FID, HPLC-UV and GPC were used to further analysis. The experimental results showed that supercritical methanol performed outstandingly in TPU recycling, it needed lower temperature and shorter time than regular methods. At 230°C/70min, over 90% raw materials of TPU could be recovered.

  19. Catalysts for the Selective Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Catherine Brookes

    2016-06-01

    Full Text Available In industry, one of the main catalysts typically employed for the selective oxidation of methanol to formaldehyde is a multi-component oxide containing both bulk Fe2(MoO43 and excess MoO3. It is thought that the excess MoO3 primarily acts to replace any molybdenum lost through sublimation at elevated temperatures, therefore preventing the formation of an unselective Fe2O3 phase. With both oxide phases present however, debate has arisen regarding the active component of the catalyst. Work here highlights how catalyst surfaces are significantly different from bulk structures, a difference crucial for catalyst performance. Specifically, Mo has been isolated at the surface as the active surface species. This leaves the role of the Fe in the catalyst enigmatic, with many theories postulated for its requirement. It has been suggested that the supporting Fe molybdate phase enables lattice oxygen transfer to the surface, to help prevent the selectivity loss which would occur in the resulting oxygen deficit environment. To assess this phenomenon in further detail, anaerobic reaction with methanol has been adopted to evaluate the performance of the catalyst under reducing conditions.

  20. X-ray photodesorption from methanol ice

    Science.gov (United States)

    Andrade, D. P. P.; Rocco, M. L. M.; Boechat-Roberty, H. M.

    2010-12-01

    The abundances of molecules and ions depend on the mechanisms of their formation and destruction that can occur both in the gas phase and in the condensed phase on grain surfaces. Photodesorption of grain surface species may explain the relative high abundances of gaseous neutral or ionic species detected in cold environments. X-ray photons from young stars are able to penetrate cold and dense regions inside protoplanetary discs, leading to molecular dissociation and desorption of photo-products from icy molecules on grain mantles. This paper aims to experimentally investigate the contribution of ion desorption from methanol ice stimulated by soft X-rays for producing chemically active ions in protoplanetary discs. The measurements were carried out at the Brazilian synchrotron light source (LNLS), using X-ray photons at the methanol O1s resonance energy (537 eV). Some possible pathways for the H- and O- formation from singly charged desorbed ions are suggested. The photodesorption yields for positive and negative ions were determined and compared with previous results obtained using different ionization agents, such as electrons, heavy ions and photons at different energies. We also correlate our results to the ion production in protoplanetary discs.

  1. [Extraction of alpha-cypermethrin from aqueous methanol solutions].

    Science.gov (United States)

    Shormanov, V K; Chigareva, E N; Belousova, O V

    2010-01-01

    Alpha cypermethrin was extracted from aqueous methanol solutions using hydrophobic organic solvents. The efficiency of extraction was shown to depend on the chemical nature of the solvent, the water to methanol ratio, and saturation of the aqueous methanol layer with an electrolyte. Optimal extraction of alpha-cypermethrin was achieved using toluene as the solvent under desalinization conditions. The extraction factor for the removal of the sought amount of alpha-cypermethrin from the water-methanol solution (4:1) using various solvents was calculated.

  2. Computer simulation of methanol exchange dynamics around cations and anions

    Energy Technology Data Exchange (ETDEWEB)

    Roy, Santanu; Dang, Liem X.

    2016-03-03

    In this paper, we present the first computer simulation of methanol exchange dynamics between the first and second solvation shells around different cations and anions. After water, methanol is the most frequently used solvent for ions. Methanol has different structural and dynamical properties than water, so its ion solvation process is different. To this end, we performed molecular dynamics simulations using polarizable potential models to describe methanol-methanol and ion-methanol interactions. In particular, we computed methanol exchange rates by employing the transition state theory, the Impey-Madden-McDonald method, the reactive flux approach, and the Grote-Hynes theory. We observed that methanol exchange occurs at a nanosecond time scale for Na+ and at a picosecond time scale for other ions. We also observed a trend in which, for like charges, the exchange rate is slower for smaller ions because they are more strongly bound to methanol. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.

  3. Methanol production from eucalyptus wood chips. Attachment IV. Health and safety aspects of the eucalypt biomass to methanol energy system

    Energy Technology Data Exchange (ETDEWEB)

    Fishkind, H.H.

    1982-06-01

    The basic eucalyptus-to-methanol energy process is described and possible health and safety risks are identified at all steps of the process. The toxicology and treatment for exposure to these substances are described and mitigating measures are proposed. The health and safety impacts and risks of the wood gasification/methanol synthesis system are compared to those of the coal liquefaction and conversion system. The scope of this report includes the health and safety risks of workers (1) in the laboratory and greenhouse, where eucalyptus seedlings are developed, (2) at the biomass plantation, where these seedlings are planted and mature trees harvested, (3) transporting these logs and chips to the refinery, (4) in the hammermill, where the logs and chips will be reduced to small particles, (5) in the methanol synthesis plant, where the wood particles will be converted to methanol, and (6) transporting and dispensing the methanol. Finally, the health and safety risks of consumers using methanol is discussed.

  4. Mechanistic studies of the methanol-to-olefin process on acidic zeolite catalysts by in situ solid-state NMR-UV/Vis spectroscopy

    OpenAIRE

    Jiang, Yijiao

    2007-01-01

    Due to the increasing demand for light olefins, the catalytic conversion of methanol-to-olefins (MTO) on acidic zeolite catalysts continues to be an industrially interesting process in heterogeneous catalysis. During the last decades, increasing efforts were made to clarify the mechanism of the MTO process. Recent progress revealed that, in the MTO process, the conversion of an equilibrium mixture of methanol and dimethyl ether (DME) is dominated by a “hydrocarbon pool” route in which methano...

  5. Efficient light-harvesting using non-carbonyl carotenoids: Energy transfer dynamics in the VCP complex from Nannochloropsis oceanica.

    Science.gov (United States)

    Keşan, Gürkan; Litvín, Radek; Bína, David; Durchan, Milan; Šlouf, Václav; Polívka, Tomáš

    2016-04-01

    Violaxanthin-chlorophyll a protein (VCP) from Nannochloropsis oceanica is a Chl a-only member of the LHC family of light-harvesting proteins. VCP binds carotenoids violaxanthin (Vio), vaucheriaxanthin (Vau), and vaucheriaxanthin-ester (Vau-ester). Here we report on energy transfer pathways in the VCP complex. The overall carotenoid-to-Chla energy transfer has efficiency over 90%. Based on their energy transfer properties, the carotenoids in VCP can be divided into two groups; blue carotenoids with the lowest energy absorption band around 480nm and red carotenoids with absorption extended up to 530nm. Both carotenoid groups transfer energy efficiently from their S2 states, reaching efficiencies of ~70% (blue) and ~60% (red). The S1 pathway, however, is efficient only for the red carotenoid pool for which two S1 routes characterized by 0.33 and 2.4ps time constants were identified. For the blue carotenoids the S1-mediated pathway is represented only by a minor route likely involving a hot S1 state. The relaxed S1 state of blue carotenoids decays to the ground state within 21ps. Presence of a fraction of non-transferring red carotenoids with the S1 lifetime of 13ps indicates some specific carotenoid-protein interaction that must shorten the intrinsic S1 lifetime of Vio and/or Vau whose S1 lifetimes in methanol are 26 and 29ps, respectively. The VCP complex from N. oceanica is the first example of a light-harvesting complex binding only non-carbonyl carotenoids with carotenoid-to-chlorophyll energy transfer efficiency over 90%.

  6. Methanol Tolerant PWA-Pt/C Catalyst with Excellent Electrocatalytic Activity for Oxygen Reduction in Direct Methanol Fuel Cell

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    It was reported for the first time that phosphorictungstenic acid (PWA) could promote the oxygen reduction reaction (ORR) and inhibit the methanol oxidation reaction at the cathodic Pt/C catalyst in the direct methanol fuel cell (DMFC). When the weight ratio of PWA to Pt/C is 1,the composite catalyst increases the reduction current of oxygen by about 38% and decreases the oxidation current of methanol by about 76% compared with that of the Pt/C catalyst.

  7. Alzheimer's disease and methanol toxicity (part 1): chronic methanol feeding led to memory impairments and tau hyperphosphorylation in mice.

    Science.gov (United States)

    Yang, Meifeng; Lu, Jing; Miao, Junye; Rizak, Joshua; Yang, Jianzhen; Zhai, Rongwei; Zhou, Jun; Qu, Jiagui; Wang, Jianhong; Yang, Shangchuan; Ma, Yuanye; Hu, Xintian; He, Rongqiao

    2014-01-01

    Although methanol toxicity is well known for acute neurological sequelae leading to blindness or death, there is a new impetus to investigate the chronic effects of methanol exposure. These include a recently established link between formaldehyde, a methanol metabolite, and Alzheimer's disease (AD) pathology. In the present study, mice were fed with methanol to revisit the chronic effects of methanol toxicity, especially as it pertains to AD progression. Three groups of mice (n = 9) were given either water as a control or a methanol solution (concentrations of 2% or 3.8%) over a 6-week period. The methanol-fed mice were found to have impaired spatial recognition and olfactory memory in Y-maze and olfactory memory paradigms. Immunohistochemical analysis of the mouse brains found increased neuronal tau phosphorylation in the hippocampus and an increased cellular apoptotic marker in hippocampal CA1 neurons (~10% of neurons displayed chromatin condensation) in the methanol-fed groups. Two additional in vitro experiments in mouse embryonic cerebral cortex neurons and mouse neuroblastoma N2a cells found that formaldehyde, but not methanol or the methanol end product formic acid, induced microtubule disintegration and tau protein hyperphosphorylation. The findings of the behavioral tests and immunohistochemical analysis suggested that the methanol-fed mice presented with partial AD-like symptoms. The in vitro experiments suggested that formaldehyde was most likely the detrimental component of methanol toxicity related to hippocampal tau phosphorylation and the subsequent impaired memory in the mice. These findings add to a growing body of evidence that links formaldehyde to AD pathology.

  8. Chemical mutagenesis of Gluconobacter frateurii to construct methanol-resistant mutants showing glyceric acid production from methanol-containing glycerol.

    Science.gov (United States)

    Sato, Shun; Kitamoto, Dai; Habe, Hiroshi

    2014-02-01

    To produce glyceric acid (GA) from methanol-containing glycerol, resistance to methanol of Gluconobacter frateurii NBRC103465 was improved by chemical mutagenesis using N-methyl-N'-nitro-N-nitrosoguanidine. The obtained mutant Gf398 produced 6.3 g/L GA in 5% (v/v) methanol-containing 17% (w/v) glycerol medium, in which the wild-type strain neither grew nor produced GA.

  9. Carbonyl and nitrogen dioxide emissions from gasoline- and diesel-powered motor vehicles.

    Science.gov (United States)

    Ban-Weiss, George A; McLaughlin, John P; Harley, Robert A; Kean, Andrew J; Grosjean, Eric; Grosjean, Daniel

    2008-06-01

    Carbonyls can be toxic and highly reactive in the atmosphere. To quantify trends in carbonyl emissions from light-duty (LD) vehicles, measurements were made in a San Francisco Bay area highwaytunnel bore containing essentially all LD vehicles during the summers of 1999, 2001, and 2006. The LD vehicle emission factor for formaldehyde, the most abundant carbonyl, did not change between 1999 and 2001, then decreased by 61 +/- 7% between 2001 and 2006. This reduction was due to fleet turnover and the removal of MTBE from gasoline. Acetaldehyde emissions decreased by 19 +/- 2% between 1999 and 2001 and by the same amount between 2001 and 2006. Absent the increased use of ethanol in gasoline after 2003, acetaldehyde emissions would have further decreased by 2006. Carbonyl emission factors for medium- (MD) and heavy-duty (HD) diesel trucks were measured in 2006 in a separate mixed-traffic bore of the tunnel. Emission factors for diesel trucks were higher than those for LD vehicles for all reported carbonyls. Diesel engine exhaust dominates over gasoline engines as a direct source of carbonyl emissions in California. Carbonyl concentrations were also measured in liquid-gasoline samples and were found to be low (gasoline brands that contained ethanol showed higher concentrations of acetaldehyde in unburned fuel versus gasoline that was formulated without ethanol. Measurements of NO2 showed a yearly rate of decrease for LD vehicle emissions similar to that of total NOx in this study. The observed NO2/NOx ratio was 1.2 +/- 0.3% and 3.7 +/- 0.3% for LD vehicles and diesel trucks, respectively.

  10. Proteomic identification of carbonylated proteins in F344 rat hippocampus after 1-bromopropane exposure

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhenlie [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Department of Toxicology, Guangdong Prevention and Treatment Center for Occupational Diseases, Guangzhou 510‐300 (China); Ichihara, Sahoko [Graduate School of Regional Innovation Studies, Mie University, Tsu 514‐8507 (Japan); Oikawa, Shinji [Department of Environmental and Molecular Medicine, Mie University Graduate School of Medicine, Mie 514‐8507 (Japan); Chang, Jie; Zhang, Lingyi; Subramanian, Kaviarasan; Mohideen, Sahabudeen Sheik [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Ichihara, Gaku, E-mail: gak@med.nagoya-u.ac.jp [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan)

    2012-08-15

    1-Bromopropane (1-BP) is neurotoxic in both experimental animals and humans. Previous proteomic analysis of rat hippocampus implicated alteration of protein expression in oxidative stress, suggesting that oxidative stress plays a role in 1-BP-induced neurotoxicity. To understand this role at the protein level, we exposed male F344 rats to 1-BP at 0, 400, or 1000 ppm for 8 h/day for 1 week or 4 weeks by inhalation and quantitated changes in hippocampal protein carbonyl using a protein carbonyl assay, two-dimensional gel electrophoresis (2-DE), immunoblotting, and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-TOF/MS). Hippocampal reactive oxygen species and protein carbonyl were significantly increased, demonstrating 1-BP-associated induction of oxidative stress and protein damage. MALDI-TOF-TOF/MS identified 10 individual proteins with increased carbonyl modification (p < 0.05; fold-change ≥ 1.5). The identified proteins were involved in diverse biological processes including glycolysis, ATP production, tyrosine catabolism, GTP binding, guanine degradation, and neuronal metabolism of dopamine. Hippocampal triosephosphate isomerase (TPI) activity was significantly reduced and negatively correlated with TPI carbonylation (p < 0.001; r = 0.83). Advanced glycation end-product (AGE) levels were significantly elevated both in the hippocampus and plasma, and hippocampal AGEs correlated negatively with TPI activity (p < 0.001; r = 0.71). In conclusion, 1-BP-induced neurotoxicity in the rat hippocampus seems to involve oxidative damage of cellular proteins, decreased TPI activity, and elevated AGEs. -- Highlights: ► 1-BP increases hippocampal ROS levels and hippocampal and plasma protein carbonyls. ► 1-BP increases TPI carbonylation and decreases TPI activity in the hippocampus. ► 1-BP increases hippocampal and plasma AGE levels.

  11. Concentrations of formaldehyde and other carbonyls in environments affected by incense burning.

    Science.gov (United States)

    Ho, Steven Sai Hang; Yu, Jian Zhen

    2002-10-01

    Burning incense to pay homage to deities is common in Chinese homes and temples. Air samples were collected and analyzed for carbonyls from a home and a temple in Hong Kong where incense burning occurs on a daily basis. Carbonyls in the air were trapped on a solid sorbent coated with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine, followed by thermal desorption and subsequent GC/MS analysis. The carbonyls identified include formaldehyde, acetaldehyde, acrolein, 2-furfural, benzaldehyde, glyoxal, and methylglyoxal. The levels of the above carbonyls correlate with the intensity of the incense-burning activities. The total mixing ratios of the carbonyls in the temple exceed those in the ambient air outside the temple by 11-23 times. Formaldehyde is the most abundant species, contributing to approximately 55% of the total carbonyl mixing ratios in both the temple and the home environments during incense burning. The mixing ratio of formaldehyde ranges from 108 to 346 ppbv in the temple and averages 103 ppbv in the home during incense burning. These values exceed the World Health Organization (WHO) air quality guideline of 100 microg m(-3) (88 ppbv) for formaldehyde. The highest formaldehyde level in the temple exceeds the WHO guideline by 3 times at peak incense burning hours. The mixing ratio of acrolein in the temple ranges from 20 to 99 ppbv, approaching or exceeding the WHO air quality guideline of 50 microg m(-3) (22 ppbv) for acrolein. Our measurements indicate that incense burning significantly elevates the concentrations of a number of carbonyls, most notably formaldehyde and acrolein, in the surrounding environments. This study provides preliminary insights on indoor air quality problems created by incense burning.

  12. Molecular Engineering with Organic Carbonyl Electrode Materials for Advanced Stationary and Redox Flow Rechargeable Batteries.

    Science.gov (United States)

    Zhao, Qing; Zhu, Zhiqiang; Chen, Jun

    2017-04-03

    Organic carbonyl electrode materials that have the advantages of high capacity, low cost and being environmentally friendly, are regarded as powerful candidates for next-generation stationary and redox flow rechargeable batteries (RFBs). However, low carbonyl utilization, poor electronic conductivity and undesired dissolution in electrolyte are urgent issues to be solved. Here, we summarize a molecular engineering approach for tuning the capacity, working potential, concentration of active species, kinetics, and stability of stationary and redox flow batteries, which well resolves the problems of organic carbonyl electrode materials. As an example, in stationary batteries, 9,10-anthraquinone (AQ) with two carbonyls delivers a capacity of 257 mAh g(-1) (2.27 V vs Li(+) /Li), while increasing the number of carbonyls to four with the formation of 5,7,12,14-pentacenetetrone results in a higher capacity of 317 mAh g(-1) (2.60 V vs Li(+) /Li). In RFBs, AQ, which is less soluble in aqueous electrolyte, reaches 1 M by grafting -SO3 H with the formation of 9,10-anthraquinone-2,7-disulphonic acid, resulting in a power density exceeding 0.6 W cm(-2) with long cycling life. Therefore, through regulating substituent groups, conjugated structures, Coulomb interactions, and the molecular weight, the electrochemical performance of carbonyl electrode materials can be rationally optimized. This review offers fundamental principles and insight into designing advanced carbonyl materials for the electrodes of next-generation rechargeable batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Electrocatalytic performance of Pt/Ru/Sn/W fullerene electrode for methanol oxidation in direct methanol fuel cell

    Institute of Scientific and Technical Information of China (English)

    Mohammad Karimi; Forouzan Aboufazeli; Hamid Reza Lotfi Zadeh Zhad; Omid Sadeghi; Ezzatollah Najafi

    2013-01-01

    In this work,fullerene was modified by platinum,ruthenium,tin and tungsten nanoparticles.The material was characterized by XRD,ICP-OES and TEM micrograph.The average nanoparticle size on fullerene was 5 ~ 8 nm.The application of this material was investigated as a catalyst for methanol oxidation in direct methanol fuel cell.A glassy carbon electrode was modified by Pt/Ru/Sn/W fullerene and electrocatalytic activity of the electrode toward methanol oxidation in basic medium has been demonstrated and investigated using cyclic voltammetry.The catalyst showed good reactivity for methanol oxidation.

  14. Alzheimer's disease and methanol toxicity (part 2): lessons from four rhesus macaques (Macaca mulatta) chronically fed methanol.

    Science.gov (United States)

    Yang, Meifeng; Miao, Junye; Rizak, Joshua; Zhai, Rongwei; Wang, Zhengbo; Huma, Tanzeel; Li, Ting; Zheng, Na; Wu, Shihao; Zheng, Yingwei; Fan, Xiaona; Yang, Jianzhen; Wang, Jianhong; Yang, Shangchuan; Ma, Yuanye; Lü, Longbao; He, Rongqiao; Hu, Xintian

    2014-01-01

    A recently established link between formaldehyde, a methanol metabolite, and Alzheimer's disease (AD) pathology has provided a new impetus to investigate the chronic effects of methanol exposure. This paper expands this investigation to the non-human primate, rhesus macaque, through the chronic feeding of young male monkeys with 3% methanol ad libitum. Variable Spatial Delay Response Tasks of the monkeys found that the methanol feeding led to persistent memory decline in the monkeys that lasted 6 months beyond the feeding regimen. This change coincided with increases in tau protein phosphorylation at residues T181 and S396 in cerebrospinal fluid during feeding as well as with increases in tau phosphorylated aggregates and amyloid plaques in four brain regions postmortem: the frontal lobe, parietal lobe, temporal lobe, and the hippocampus. Tau phosphorylation in cerebrospinal fluid was found to be dependent on methanol feeding status, but phosphorylation changes in the brain were found to be persistent 6 months after the methanol feeding stopped. This suggested the methanol feeding caused long-lasting and persistent pathological changes that were related to AD development in the monkey. Most notably, the presence of amyloid plaque formations in the monkeys highlighted a marked difference in animal systems used in AD investigations, suggesting that the innate defenses in mice against methanol toxicity may have limited previous investigations into AD pathology. Nonetheless, these findings support a growing body of evidence that links methanol and its metabolite formaldehyde to AD pathology.

  15. Evidence of anomalous behavior of intermolecular interactions at low concentration of methanol in ethanol-methanol binary system.

    Science.gov (United States)

    Nilavarasi, K; Kartha, Thejus R; Madhurima, V

    2018-01-05

    At low concentrations of methanol in a binary system of ethanol and methanol, uniquely complex molecular interactions are reported here. Previous studies indicate that ethanol molecules form aggregates held together by hydrogen bonding (O-H-O) and also dispersive forces. Addition of small amount of methanol tends to break the hydrogen bond network of ethanol due to the larger polarity of methanol. This leads to the ethanol molecules becoming somewhat isolated from each other within a scaffolding network of methanol molecules, as seen from the present molecular dynamics simulations. This is an indication of a repulsive force that dominates among the two different alcohols. At higher molar concentration of methanol (Xm > 0.3817), the strength and extent (number) of formation of hydrogen bonds between ethanol and methanol increase. The geometry of molecular structure at high concentration favors the fitting of component molecules with each other. Intermolecular interactions in the ethanol-methanol binary system over the entire concentration range were investigated in detail using broadband dielectric spectroscopy, FTIR, surface tension and refractive index studies. Molecular dynamics simulations show that the hydrogen bond density is a direct function of the number of methanol molecules present, as the ethanol aggregates are not strictly hydrogen-bond constructed which is in agreement with the experimental results. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Carbonyl trapping and antiglycative activities of olive oil mill wastewater.

    Science.gov (United States)

    Navarro, Marta; Fiore, Alberto; Fogliano, Vincenzo; Morales, Francisco J

    2015-02-01

    The use of natural compounds as antiglycative agents to reduce the load of advanced glycation end products from diet is very promising. Olive mill wastewater is a by-product of the olive oil extraction processes with a high content of hydroxytyrosol, hydroxytyrosol derivatives and molecules containing o-dihydroxyl functions such as verbascoside. Two powders were obtained after the ultrafiltration and nanofiltration of olive mill wastewater, and successive spray drying with maltodextrin and acacia fiber. The samples were characterized by phenolic composition and antioxidant capacity. Antiglycative capacity was evaluated by in vitro BSA-glucose and BSA-methylglyoxal assays, formation of Amadori products and direct trapping of reactive dicarbonyls (methylglyoxal and glyoxal). Both ultrafiltered and nanofiltered olive mill wastewater powders had an activity comparable to quercetin and hydroxytyrosol against the inhibition of protein glycation (IC50 = 0.3 mg mL(-1)). The antiglycative activity of the powder was further investigated after separation by reverse phase solid extraction. Fractions extracted with the methanol content higher than 40% and rich in hydroxytyrosol and verbascoside exerted the highest reactivity against dicarbonyls. Data confirmed that the direct trapping of dicarbonyl compounds is the main route explaining the antiglycative action rather than of the already known antioxidant capacity. Results support further investigations to evaluate the technological feasibility to use olive mill wastewater powders as antiglycative ingredients in foods or in pharmacological preparations in future.

  17. Water-methanol separation with carbon nanotubes and electric fields

    Science.gov (United States)

    Winarto, Affa; Takaiwa, Daisuke; Yamamoto, Eiji; Yasuoka, Kenji

    2015-07-01

    Methanol is used in various applications, such as fuel for transportation vehicles, fuel cells, and in chemical industrial processes. Conventionally, separation of methanol from aqueous solution is by distillation. However, this method consumes a large amount of energy; hence development of a new method is needed. In this work, molecular dynamics simulations are performed to investigate the effect of an electric field on water-methanol separation by carbon nanotubes (CNTs) with diameters of 0.81 to 4.07 nm. Without an electric field, methanol molecules fill the CNTs in preference to water molecules. The preference of methanol to occupy the CNTs over water results in a separation effect. This separation effect is strong for small CNT diameters and significantly decreases with increasing diameter. In contrast, under an electric field, water molecules strongly prefer to occupy the CNTs over methanol molecules, resulting in a separation effect for water. More interestingly, the separation effect for water does not decrease with increasing CNT diameter. Formation of water structures in CNTs induced by an electric field has an important role in the separation of water from methanol.Methanol is used in various applications, such as fuel for transportation vehicles, fuel cells, and in chemical industrial processes. Conventionally, separation of methanol from aqueous solution is by distillation. However, this method consumes a large amount of energy; hence development of a new method is needed. In this work, molecular dynamics simulations are performed to investigate the effect of an electric field on water-methanol separation by carbon nanotubes (CNTs) with diameters of 0.81 to 4.07 nm. Without an electric field, methanol molecules fill the CNTs in preference to water molecules. The preference of methanol to occupy the CNTs over water results in a separation effect. This separation effect is strong for small CNT diameters and significantly decreases with increasing

  18. Metabolic engineering of Corynebacterium glutamicum for methanol metabolism.

    Science.gov (United States)

    Witthoff, Sabrina; Schmitz, Katja; Niedenführ, Sebastian; Nöh, Katharina; Noack, Stephan; Bott, Michael; Marienhagen, Jan

    2015-03-01

    Methanol is already an important carbon feedstock in the chemical industry, but it has found only limited application in biotechnological production processes. This can be mostly attributed to the inability of most microbial platform organisms to utilize methanol as a carbon and energy source. With the aim to turn methanol into a suitable feedstock for microbial production processes, we engineered the industrially important but nonmethylotrophic bacterium Corynebacterium glutamicum toward the utilization of methanol as an auxiliary carbon source in a sugar-based medium. Initial oxidation of methanol to formaldehyde was achieved by heterologous expression of a methanol dehydrogenase from Bacillus methanolicus, whereas assimilation of formaldehyde was realized by implementing the two key enzymes of the ribulose monophosphate pathway of Bacillus subtilis: 3-hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase. The recombinant C. glutamicum strain showed an average methanol consumption rate of 1.7 ± 0.3 mM/h (mean ± standard deviation) in a glucose-methanol medium, and the culture grew to a higher cell density than in medium without methanol. In addition, [(13)C]methanol-labeling experiments revealed labeling fractions of 3 to 10% in the m + 1 mass isotopomers of various intracellular metabolites. In the background of a C. glutamicum Δald ΔadhE mutant being strongly impaired in its ability to oxidize formaldehyde to CO2, the m + 1 labeling of these intermediates was increased (8 to 25%), pointing toward higher formaldehyde assimilation capabilities of this strain. The engineered C. glutamicum strains represent a promising starting point for the development of sugar-based biotechnological production processes using methanol as an auxiliary substrate.

  19. 从超临界二氧化碳和甲醇直接合成碳酸二甲酯%DIRECT SYNTHESIS OF DIMETHYL CARBONATE FROM SUPERCRITICAL CARBON DIOXIDE AND METHANOL

    Institute of Scientific and Technical Information of China (English)

    赵天生; 韩怡卓; 孙予罕; 杨彩虹; 李文彬

    1999-01-01

    @@ Dimethyl carbonate (DMC), an environmentally benign intermediate for organic synthesis, has been mainly synthesized through non-phosgene route of oxidative carbonylation[1]. Direct synthesis of DMC from carbon dioxide and methanol is of more significance due to atom economy. Organometallic compounds of formulae R2M(OR)2, M(OR)2 or M(OR)4[2,3] were employed as catalysts in direct synthesis of DMC, where an activation mechanism of CO2 insertion into metal-oxygen bond was supposed. Unfortunately, the yield of DMC was low even in the presence of chemical dehydrants because mainly of thermodynamic limit.

  20. Positive trends in Southern Hemisphere observations of carbonyl sulfide

    Science.gov (United States)

    Kremser, Stefanie; Jones, Nicholas; Smale, Dan; Palm, Mathias; Lejeune, Bernard; Wang, Yuting; Deutscher, Nicholas

    2016-04-01

    Carbonyl sulfide (OCS; lifetime of about 5.7 years) is the longest lived reduced sulfur-containing gas in the atmosphere. The primary source of OCS is the ocean, which is both a direct source (through OCS emission) and an indirect source (due to oxidation of carbon disulfide, CS2, and dimethyl sulfide). Other natural sources of OCS include volcanic outgassing and direct fluxes from wetland regions. The removal of OCS from the atmosphere is dominated by soil and vegetation uptake, with minor contributions from reactions with the hydroxyl radical. Small anthropogenic sources of OCS are coal combustion, biomass burning, and aluminum production. A dominant indirect source results from CS2 emissions from the rayon industry. Transport of tropospheric OCS to the stratosphere during volcanically quiescent periods has been suggested to contribute sulfur to the stratospheric aerosol layer which affects atmospheric radiative balance. If, however, production of stratospheric aerosols from OCS oxidation is smaller than typical estimates, this OCS contribution would be overestimated. The magnitude of the OCS flux to the stratosphere is currently not well quantified as is the relative contribution of OCS to background aerosol loading. While earlier model simulations indicate OCS fluxes into the atmosphere exceeding removal, past total column observations of OCS show no significant trend. Analysis of tropospheric OCS columns at Arrival Heights (Antarctica) and Lauder (New Zealand) show strong positive trends from 2001-2008 followed by weaker trends to 2015, with unexpected temporal coherence. Since trends in ocean and land sources/sinks at these two sites, respectively, are unlikely to be similar, the coherence in trend structure likely results from changes in transport of OCS from the tropics to middle and high latitudes. Potential causes for OCS increases are (i) increases in tropical lower stratospheric OCS and/or (ii) strengthening of the large-scale circulation which

  1. Flexibility in design of large-scale methanol plants

    Institute of Scientific and Technical Information of China (English)

    Esben Lauge Sφrensen; Helge Holm-Larsen; Haldor Topsφe A/S

    2006-01-01

    This paper presents a cost effective design for large-scale methanol production. It is demonstrated how recent technological progress can be utilised to design a methanol plant,which is inexpensive and easy to operate, while at the same time very robust towards variations in feed-stock composition and product specifications.

  2. Methanol conversion in high-rate anaerobic reactors

    NARCIS (Netherlands)

    Weijma, J.; Stams, A.J.M.

    2001-01-01

    An overview on methanol conversion in high-rate anaerobic reactors is presented, with the focus on technological as well as microbiological aspects. The simple C1-compound methanol can be degraded anaerobically in a complex way, in which methanogens, sulfate reducing bacteria and homoacetogens

  3. Effect of cobalt on the Anaerobic Thermophilic Conversion of Methanol

    NARCIS (Netherlands)

    Paulo, P.L.; Jiang, B.; Cysneiros, D.; Stams, A.J.M.

    2004-01-01

    The importance of cobalt on the anaerobic conversion of methanol under thermophilic conditions was studied in three parallel lab-scale UASB-reactors and in cobalt-limited enriched cultures. Reactors R1, R2, and R3 were fed with methanol in a bicarbonate-buffered medium, supplied with iron and

  4. Development of new membrane materials for direct methanol fuel cells

    NARCIS (Netherlands)

    Yildirim, Mustafa Hakan

    2009-01-01

    Development of new membrane materials for direct methanol fuel cells Direct methanol fuel cells (DMFCs) can convert the chemical energy of a fuel directly into electrical energy with high efficiency and low emission of pollutants. DMFCs can be used as the power sources to portable electronic devices

  5. Novel efficient process for methanol synthesis by CO2 hydrogenation

    NARCIS (Netherlands)

    Kiss, Anton Alexandru; Pragt, J.J.; Vos, H.J.; Bargeman, Gerrald; de Groot, M.T.

    2016-01-01

    Methanol is an alternative fuel that offers a convenient solution for efficient energy storage. Complementary to carbon capture activities, significant effort is devoted to the development of technologies for methanol synthesis by hydrogenation of carbon dioxide. While CO2 is available from plenty

  6. Four new depsides in Origanum dictamnus methanol extract

    NARCIS (Netherlands)

    Exarchou, V.; Takis, P.G.; Malouta, M.; Vervoort, J.; Karali, E.; Troganis, A.N.

    2013-01-01

    We herein describe the identification of four new depsides present in methanol extract of Origanum dictamnus. O. dictamnus’ (dittany) aerial parts methanol extract was subjected to semi-preparative RP-HPLC fractionation followed by identification of individual compounds in each fraction using 1D/2D

  7. The fate of methanol in thermophilic-anaerobic environments

    NARCIS (Netherlands)

    Paulo, P.L.

    2002-01-01

    Methanol is a simple C1-compound, which sustains a complex web of possible degradation routes under anaerobic conditions. Methanol can be the main pollutant in some specific wastewaters, but it is also a compound that may be formed under natural conditions, as intermediate in the decomposition of or

  8. Novel efficient process for methanol synthesis by CO2 hydrogenation

    NARCIS (Netherlands)

    Kiss, Anton A.; Pragt, J.J.; Vos, H.J.; Bargeman, G.; Groot, de M.T.

    2016-01-01

    Methanol is an alternative fuel that offers a convenient solution for efficient energy storage. Complementary to carbon capture activities, significant effort is devoted to the development of technologies for methanol synthesis by hydrogenation of carbon dioxide. While CO2 is available from plenty o

  9. Development of new membrane materials for direct methanol fuel cells

    NARCIS (Netherlands)

    Yildirim, M.H.

    2009-01-01

    Development of new membrane materials for direct methanol fuel cells Direct methanol fuel cells (DMFCs) can convert the chemical energy of a fuel directly into electrical energy with high efficiency and low emission of pollutants. DMFCs can be used as the power sources to portable electronic devices

  10. Fructose-Induced Carbonyl/Oxidative Stress in S. cerevisiae: Involvement of TOR.

    Science.gov (United States)

    Valishkevych, Bohdana V; Vasylkovska, Ruslana A; Lozinska, Liudmyla M; Semchyshyn, Halyna M

    2016-01-01

    The TOR (target of rapamycin) signaling pathway first described in the budding yeast Saccharomyces cerevisiae is highly conserved in eukaryotes effector of cell growth, longevity, and stress response. TOR activation by nitrogen sources, in particular amino acids, is well studied; however its interplay with carbohydrates and carbonyl stress is poorly investigated. Fructose is a more potent glycoxidation agent capable of producing greater amounts of reactive carbonyl (RCS) and oxygen species (ROS) than glucose. The increased RCS/ROS production, as a result of glycoxidation in vivo, is supposed to be involved in carbonyl/oxidative stress, metabolic disorders, and lifespan shortening of eukaryotes. In this work we aim to expand our understanding of how TOR is involved in carbonyl/oxidative stress caused by reducing monosaccharides. It was found that in fructose-grown compared with glucose-grown cells the level of carbonyl/oxidative stress markers was higher. The defects in the TOR pathway inhibited metabolic rate and suppressed generation of glycoxidation products in fructose-grown yeast.

  11. Waterpipe smoking: the role of humectants in the release of toxic carbonyls.

    Science.gov (United States)

    Schubert, Jens; Heinke, Volkmar; Bewersdorff, Jana; Luch, Andreas; Schulz, Thomas G

    2012-08-01

    In recent years, the number of waterpipe smokers has increased substantially worldwide. Here, we present a study on the identification and quantification of seven carbonylic compounds including formaldehyde, acetaldehyde and acrolein in the mainstream smoke of the waterpipe. Smoking was conducted with a smoking machine, and carbonyls were scavenged from the smoke with two impingers containing an acidic solution of 2,4-dinitrophenylhydrazine. The derivatives were then analyzed by high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). For instance, during one waterpipe smoking session, up to 111 ± 12 μg formaldehyde could be detected. This value is about 5 times higher when compared to one 2R4F reference cigarette. We also found a distinct filter effect of the bowl water for all carbonyls investigated. Our data further demonstrate that increasing amounts of humectants in the unburned tobacco lowers the temperature in the waterpipe head during smoking, thereby resulting in decreasing levels of carbonyls in the smoke produced. Altogether, considerable amounts of toxic carbonyls are present in the waterpipe smoke, thus conferring a health risk to waterpipe smokers.

  12. Novel DNPH-based method for determination of protein carbonylation in muscle and meat.

    Science.gov (United States)

    Soglia, Francesca; Petracci, Massimiliano; Ertbjerg, Per

    2016-04-15

    Protein oxidation is considered an ongoing deteriorative process during storage of fresh and processed meat. Carbonyl compounds have traditionally been detected spectrophotometrically after derivatization with 2,4-dinitrophenylhydrazine (DNPH) to form protein-bound hydrazones with absorbance at 370 nm. Here we describe a novel DNPH-based method to quantify protein carbonylation in muscle and meat. The additional steps of the novel method aimed at increasing the protein solubility and inducing protein unfolding before labeling with DNPH. Compared to the traditional method, the new procedure reflected an increased protein carbonylation level measuring overall two to fourfold more carbonyls in muscles from different species as well as in soluble, salt-soluble and insoluble protein fractions. The study suggested that protein unfolding is a more important phenomenon than solubilization for increased DNPH labeling. The novel method resulted in three to fourfold larger carbonyl content determined in chicken, pork and beef (2.8, 3.6 and 3.1 nmol/mg of protein, respectively). Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOTH) Process

    Energy Technology Data Exchange (ETDEWEB)

    None

    1998-12-21

    The Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOI-P Process Demonstration Unit was built at a site located at the Eastman coal-to-chemicals complex in Kingsport. During this quarter, initial planning and procurement work continued on the seven project sites which have been accepted for participation in the off-site, product-use test program. Approximately 12,000 gallons of fuel-grade methanol (98+ wt% methanol, 4 wt% water) produced during operation on carbon monoxide (CO)-rich syngas at the LPMEOW Demonstration Unit was loaded into trailers and shipped off-site for Mure product-use testing. At one of the projects, three buses have been tested on chemical-grade methanol and on fhel-grade methanol from the LPMEOW Demonstration Project. During the reporting period, planning for a proof-of-concept test run of the Liquid Phase Dimethyl Ether (LPDME~ Process at the Alternative Fuels Development Unit (AFDU) in LaPorte, TX continued. The commercial catalyst manufacturer (Calsicat) has prepared the first batch of dehydration catalyst in large-scale equipment. Air Products will test a sample of this material in the laboratory autoclave. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for freshly reduced catalyst (as determined in the laborato~ autoclave), was monitored for the initial extended operation at the lower initial reactor operating temperature of 235oC. At this condition, the decrease in catalyst activity with time from the period 20 December 1997 through 27 January 1998 occurred at a rate of 1.0% per

  14. Studies on Methanol Crossover in Liquid-Feed Direct Methanol Pem Fuel Cells

    Science.gov (United States)

    Narayanan, S. R.

    1995-01-01

    The performance of liquid feed direct methanol fuel cells using various types of Nafion membranes as the solid polymer electrolyte have been studied. The rate of fuel crossover and electrical performance has been measured for cells with Nafion membranes of various thicknesses and equivalent weights. The crossover rate is found to decrease with increasing thickness and applied current. The dependence of crossover rate on current density can be understood in terms of a simple linear diffusion model which suggests that the crossover rate can be influenced by the electrode structure in addition to the membrane. The studies suggest that Nafion EW 1500 is a very promising alternate to Nafion EW 1100 for direct methanol fuel cells.

  15. Characterization of a direct methanol fuel cell using Hilbert curve fractal current collectors

    Energy Technology Data Exchange (ETDEWEB)

    Kuan, Yean-Der [Department of Refrigeration, Air-Conditioning and Energy Engineering, National Chun-Yi University of Technology, NO 35, Lane 215, Section 1, Chung-Shan Road, Taiping City, 411 Taichung County (China); Chang, Jing-Yi [Department of Mechanical and Electro-Mechanical Engineering, Tamkang University, Tamsui, 251 Taipei County (China); Lee, Shi-Min [Department of Aerospace Engineering, Tamkang University, Tamsui, 251 Taipei County (China); Lee, Shah-Rong [Department of Mechanical Engineering, Technology and Science Institute of Northern Taiwan, Peitou, 112 Taipei (China)

    2009-02-01

    The current collector or bi-polar plate is a key component in direct methanol fuel cells (DMFCs). Current collector geometric designs have significant influence on cell performance. This paper presents a continuous type fractal geometry using the Hilbert curve applied to current collector design in a direct methanol fuel cell. The Hilbert curve fractal geometry current collector is named HFCC (Hilbert curve fractal current collector). This research designs the current collector using a first, second and third order open carved HFCC shape. The cell performances of the different current collector geometries were measured and compared. Two important factors, the free open ratio and total perimeter length of the open carved design are discussed. The results show that both the larger free open ratio and longer carved open perimeter length present higher performance. (author)

  16. Characterization of a direct methanol fuel cell using Hilbert curve fractal current collectors

    Science.gov (United States)

    Kuan, Yean-Der; Chang, Jing-Yi; Lee, Shi-Min; Lee, Shah-Rong

    The current collector or bi-polar plate is a key component in direct methanol fuel cells (DMFCs). Current collector geometric designs have significant influence on cell performance. This paper presents a continuous type fractal geometry using the Hilbert curve applied to current collector design in a direct methanol fuel cell. The Hilbert curve fractal geometry current collector is named HFCC (Hilbert curve fractal current collector). This research designs the current collector using a first, second and third order open carved HFCC shape. The cell performances of the different current collector geometries were measured and compared. Two important factors, the free open ratio and total perimeter length of the open carved design are discussed. The results show that both the larger free open ratio and longer carved open perimeter length present higher performance.

  17. Investigation of biological reactor designs for treatment of methanol and thiodiglycol waste streams

    Energy Technology Data Exchange (ETDEWEB)

    Sines, B.J.; Teather, E.W.; Weigand, W.A. (Univ. of Maryland, College Park, MD (United States)); Harvey, S.P. (Army Edgewood, Aberdeen Proving Ground, MD (United States))

    Biological reactor designs for the degradation of the toxic compounds methanol and thiodiglycol are compared to determine the smallest volume. Both compounds exhibit substrate-inhibited cell growth behavior. Design equations were used to simulate a continuous stirred tanks in series, and an optimized repeated fed-batch reactor. Thiodiglycol is the primary hydrolysis product of sulfur mustard (2,2[prime]-dichlorodiethyl sulfide), commonly referred to as [open quotes]mustard gas[close quotes]. Experimental data for the growth of Alcaligenes xylosoxidans xylosoxidans (SH42) on thiodiglycol was fit by an Andrews type inhibition equation, while the data and model for the growth of methanol was taken from the literature. The simulation results indicate that the repeated fed-batch reactor leads to significant volume reduction compared to the other two reactor configurations. 11 refs., 7 figs., 7 tabs.

  18. Radiation and atmospheric circulation controls on carbonyl sulfide concentrations in the marine boundary layer

    Science.gov (United States)

    Berkelhammer, M.; Steen-Larsen, H. C.; Cosgrove, A.; Peters, A. J.; Johnson, R.; Hayden, M.; Montzka, S. A.

    2016-11-01

    A potential closure of the global carbonyl sulfide (COS or OCS) budget has recently been attained through a combination of remote sensing, modeling, and extended surface measurements. However, significant uncertainties in the spatial and temporal dynamics of the marine flux still persist. In order to isolate the terrestrial photosynthetic component of the global atmospheric OCS budget, tighter constraints on the marine flux are needed. We present 6 months of nearly continuous in situ OCS concentrations from the North Atlantic during the fall and winter of 2014-2015 using a combination of research vessel and fixed tower measurements. The data are characterized by synoptic-scale ˜100 pmol mol-1 variations in marine boundary layer air during transitions from subtropical to midlatitude source regions. The synoptic OCS variability is shown here to be a linear function of the radiation history along an air parcel's trajectory with no apparent sensitivity to the chlorophyll concentration of the surface waters that the air mass interacted with. This latter observation contradicts expectations and suggests a simple radiation limitation for the combined direct and indirect marine OCS emissions. Because the concentration of OCS in the marine boundary layer is so strongly influenced by an air parcel's history, marine and atmospheric concentrations would rarely be near equilibrium and thus even if marine production rates are held constant at a given location, the ocean-atmosphere flux would be sensitive to changes in atmospheric circulation alone. We hypothesize that changes in atmospheric circulation including latitudinal shifts in the storm tracks could affect the marine flux through this effect.

  19. Quantifying Carbon-Climate Processes at the Regional Scale Using Atmospheric Carbonyl Sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, Elliott [Univ. of California, Merced, CA (United States); Berry, Joe [Carnegie Inst. of Washington, Washington, DC (United States); Torn, Margaret [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); David, Billesbach [Univ. of Nebraska, Lincoln, NE (United States); Seibt, Ulrike [Univ. of California, Los Angeles, CA (United States)

    2013-10-08

    Atmospheric carbonyl sulfide (COS) analysis has the potentially transformative capability for partitioning the regional carbon flux into respiration and photosynthesis components. This emerging approach is based on the observation that continental atmospheric CO2 gradients are dominated by net ecosystem fluxes while continental atmospheric COS gradients are dominated by photosynthesis-related plant uptake. Regional flux partitioning represents a critical knowledge gap due to a lack of robust methods for regional-scale flux partitioning and large uncertainties in forecasting carbon-climate feedbacks. Our completed project characterized the relationship between COS and CO2 surface fluxes using a novel measurement and modeling system in a winter wheat field at the U.S. Department of Energy?s Atmospheric and Radiation Measurement program Central Facility (DOE-ARM CF). The scope of this project included canopy flux measurements, soil flux measurements, regional atmospheric modeling, and analysis of COS and CO2 airborne observations at SGP. Three critical discoveries emerged from this investigation: (1) the new measurement system provided the first field evidence of a robust relationship between COS leaf fluxes and GPP; (2) a previously unknown seasonal soil source of COS was observed and characterized; (3) the regional atmospheric analysis of airborne measurements provided the first COS-based constraints on GPP parameterizations used in earth systems models. Dissemination of these results includes three publications [Billesbach et al., In Press; Campbell et al., In Preparation; Seibt et al., In Review], three presentations at the AGU Fall Meeting (2012), and four invited presentations to department seminars. We have leveraged this foundational project to continue our work on understanding carbon cycle processes at large scales through one funded project (DOE Lab Fee, 2012-2015) and one proposal that is under review (DOE/NASA/USDA/NOAA, 2014-2016).

  20. Soil-atmosphere carbonyl sulfide (COS) exchange in a tropical rainforest at La Selva, Costa Rica

    Science.gov (United States)

    Sun, W.; Maseyk, K. S.; Juarez, S.; Lett, C.; Seibt, U. H.

    2014-12-01

    Carbonyl sulfide (COS) has recently been proposed as a promising tracer for partitioning ecosystem carbon assimilation due to the close analogy between leaf uptake processes of COS and CO2. This emerging framework requires accurate characterization of the source and sink components of COS, including soil fluxes. Here we present the first direct, continuous observations of soil COS fluxes for 4 months at a tropical rainforest, La Selva Biological Station, Costa Rica. Three soil plots with contrasting water content were selected for chamber measurements. Our observations confirmed that soils are principally COS sinks, with daily mean COS fluxes averaged across all chambers ranging from -3 to 0 pmol m-2 s-1. When compared with net ecosystem COS uptake which peaks around -30 pmol m-2 s-1, their contributions should be considered in ecosystem COS balance. We did not find a temperature optimum, but soil COS uptake slightly increased with soil temperature, indicating biotic control on soil COS fluxes. Diurnal cycles of COS fluxes were observed during drying out periods after rain. The diel periodicity of COS fluxes was probably obscured by frequent raining at the site. Diffusional control of soil COS fluxes is shown from increasing soil COS uptake at lower soil water-filled pore space. These confirm that soil COS fluxes are mediated both by soil physical and biological factors. Using a depth-resolved diffusion-reaction model with data-driven enzyme activity parameterization, we simulated the COS fluxes from measured soil environmental variables, consistent with observations. This modeling scheme is useful for separating soil COS fluxes from net ecosystem COS fluxes, which lends support to the emergent COS-based approach of carbon flux partitioning.

  1. Sources and sinks of carbonyl sulfide in an agricultural field in the Southern Great Plains.

    Science.gov (United States)

    Maseyk, Kadmiel; Berry, Joseph A; Billesbach, Dave; Campbell, John Elliott; Torn, Margaret S; Zahniser, Mark; Seibt, Ulli

    2014-06-24

    Net photosynthesis is the largest single flux in the global carbon cycle, but controls over its variability are poorly understood because there is no direct way of measuring it at the ecosystem scale. We report observations of ecosystem carbonyl sulfide (COS) and CO2 fluxes that resolve key gaps in an emerging framework for using concurrent COS and CO2 measurements to quantify terrestrial gross primary productivity. At a wheat field in Oklahoma we found that in the peak growing season the flux-weighted leaf relative uptake of COS and CO2 during photosynthesis was 1.3, at the lower end of values from laboratory studies, and varied systematically with light. Due to nocturnal stomatal conductance, COS uptake by vegetation continued at night, contributing a large fraction (29%) of daily net ecosystem COS fluxes. In comparison, the contribution of soil fluxes was small (1-6%) during the peak growing season. Upland soils are usually considered sinks of COS. In contrast, the well-aerated soil at the site switched from COS uptake to emissions at a soil temperature of around 15 °C. We observed COS production from the roots of wheat and other species and COS uptake by root-free soil up to a soil temperature of around 25 °C. Our dataset demonstrates that vegetation uptake is the dominant ecosystem COS flux in the peak growing season, providing support of COS as an independent tracer of terrestrial photosynthesis. However, the observation that ecosystems may become a COS source at high temperature needs to be considered in global modeling studies.

  2. Constraining surface carbon fluxes using in situ measurements of carbonyl sulfide and carbon dioxide

    Science.gov (United States)

    Berkelhammer, M.; Asaf, D.; Still, C.; Montzka, S.; Noone, D.; Gupta, M.; Provencal, R.; Chen, H.; Yakir, D.

    2014-02-01

    Understanding the processes that control the terrestrial exchange of carbon is critical for assessing atmospheric CO2 budgets. Carbonyl sulfide (COS) is taken up by vegetation during photosynthesis following a pathway that mirrors CO2 but has a small or nonexistent emission component, providing a possible tracer for gross primary production. Field measurements of COS and CO2 mixing ratios were made in forest, senescent grassland, and riparian ecosystems using a laser absorption spectrometer installed in a mobile trailer. Measurements of leaf fluxes with a branch-bag gas-exchange system were made across species from 10 genera of trees, and soil fluxes were measured with a flow-through chamber. These data show (1) the existence of a narrow normalized daytime uptake ratio of COS to CO2 across vascular plant species of 1.7, providing critical information for the application of COS to estimate photosynthetic CO2 fluxes and (2) a temperature-dependent normalized uptake ratio of COS to CO2 from soils. Significant nighttime uptake of COS was observed in broad-leafed species and revealed active stomatal opening prior to sunrise. Continuous high-resolution joint measurements of COS and CO2 concentrations in the boundary layer are used here alongside the flux measurements to partition the influence that leaf and soil fluxes and entrainment of air from above have on the surface carbon budget. The results provide a number of critical constraints on the processes that control surface COS exchange, which can be used to diagnose the robustness of global models that are beginning to use COS to constrain terrestrial carbon exchange.

  3. Soil carbonyl sulfide fluxes in a Mediterranean ecosystem: insights from model-data fusion analysis

    Science.gov (United States)

    Sun, W.; Seibt, U. H.; Maseyk, K. S.; Lett, C.

    2013-12-01

    Carbonyl sulfide (COS) is linked to biosphere components of the carbon cycle, due in large part to its hydrolysis by the enzyme carbonic anhydrase (CA). Stomatal diffusion models and observations at leaf and ecosystem scales have demonstrated the potential of COS as a tracer for Gross Primary Production (GPP). Although considered small relative to canopy COS fluxes, accurate knowledge of soil COS fluxes is required for the use of net ecosystem COS fluxes in carbon flux partitioning. However, extensive field measurements of soil COS fluxes are rare and process-based modeling is limited. Here we report continuous chamber measurements of soil COS fluxes in a Mediterranean ecosystem in the Santa Monica Mountains, California during April and early May 2013. Both COS uptake and emissions were observed, but the soil acted as a net sink in most conditions and was a net source only when soil temperatures were above 22 C. COS sink fluxes were positively correlated with soil water content and CO2 fluxes. COS uptake had a maximum at a temperature around 15 C. However, no single environmental variable could be correlated to COS fluxes with an r-square > 0.6. COS fluxes from soil chambers ranged from -9 to 2.5 pmol m-2 s-1. Leaf litter appeared to increase soil COS metabolic activity. We observed huge bursts of soil COS uptake induced by a precipitation event, probably due to enhanced soil microbial activity resulting from alleviated water limitation and a decrease in soil temperature towards the optimum. We used a soil gas exchange model coupled with CA enzyme kinetics to simulate the soil COS fluxes. Micrometeorological and soil data were used to drive the soil flux model. Model simulations indicated that diurnal and synoptic variations of COS fluxes were driven by soil temperature and water content, controlling both CA activity and diffusion. We suggest that multiple parameters need to be optimized to reduce uncertainties in models of soil COS fluxes at larger scales.

  4. ACUTE METHANOL INTOXICATIONS – A CHALLENGE FOR CLINICAL TOXICOLOGY

    Directory of Open Access Journals (Sweden)

    Petko Marinov

    2016-10-01

    Full Text Available Purpose: Methanol (CH3OH is a monohydric alcohol, vastly used both in housekeeping and industry. Although the acute methanol intoxications are rare, they may include life-threatening symptoms, substantial lethality and negative consequences such as neurological disorders and vision damage. Aim of the work is to conduct a retrospective study on the acute methanol intoxications within Varna region for a 10-year period (2006-2015. Material/Methods: This study covers 39 patients of the Clinic for Intensive Treatment of Acute Intoxications and Toxicoallergies at Naval Hospital – Varna, all of which had their diagnosis confirmed, including gas chromatography methods. Results: Methanol intoxication prevalence showed male/female ratio close to 2.9:1. The major part of the cases concerned economically active population, the age group of 25-60 being the most affected. In all instances an oral methanol intake has been involved. Death occurred in 14 cases (35.9%

  5. Macroscopic Modeling of Transport Phenomena in Direct Methanol Fuel Cells

    DEFF Research Database (Denmark)

    Olesen, Anders Christian

    An increasing need for energy efficiency and high energy density has sparked a growing interest in direct methanol fuel cells for portable power applications. This type of fuel cell directly generates electricity from a fuel mixture consisting of methanol and water. Although this technology...... for studying their transport. In this PhD dissertation the macroscopic transport phenomena governing direct methanol fuel cell operation are analyzed, discussed and modeled using the two-fluid approach in the computational fluid dynamics framework of CFX 14. The overall objective of this work is to extend...... the present fundamental understanding of direct methanol fuel cell operation by developing a three-dimensional, two-phase, multi-component, non-isotherm mathematical model including detailed non-ideal thermodynamics, non-equilibrium phase change and non-equilibrium sorption-desorption of methanol and water...

  6. Bifunctional anode catalysts for direct methanol fuel cells

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Ferrin, Peter; Tritsaris, Georgios

    2012-01-01

    Using the binding energy of OH* and CO* on close-packed surfaces as reactivity descriptors, we screen bulk and surface alloy catalysts for methanol electro-oxidation activity. Using these two descriptors, we illustrate that a good methanol electro-oxidation catalyst must have three key properties......: (1) the ability to activate methanol, (2) the ability to activate water, and (3) the ability to react off surface intermediates (such as CO* and OH*). Based on this analysis, an alloy catalyst made up of Cu and Pt should have a synergistic effect facilitating the activity towards methanol electro....... Adding Cu to a Pt(111) surface increases the methanol oxidation current by more than a factor of three, supporting our theoretical predictions for improved electrocatalysts....

  7. A sensitive search for methanol line emission toward evolved stars

    CERN Document Server

    Gomez, J F; Suarez, O; Rizzo, J R; de Gregorio-Monsalvo, I

    2014-01-01

    We present a sensitive search for methanol line emission in evolved stars at 1 cm, aiming to detect, for the first time, methanol masers in this type of objects. Our sample comprised post-AGB stars and young planetary nebulae (PNe), whose mass-loss processes and circumstellar structures resemble those of young stellar objects (YSOs), where methanol masers are detected. Class I masers were searched for in 73 objects, whereas Class II ones were searched in 16. No detection was obtained. The non-detection of Class I methanol masers indicated that methanol production in dust grains and/or the enhancement of its gas-phase abundance in the shocked regions of evolved objects are not as efficient as in YSOs. We suggest that relatively more evolved PNe might have a better probability of harboring Class II masers.

  8. Biodiesel Production from Acidified Oils via Supercritical Methanol

    Directory of Open Access Journals (Sweden)

    Jianxin Li

    2011-12-01

    Full Text Available In biodiesel production, the vegetable oil used as raw material for transesterification should be free of water and free fatty acids (FFAs, which may consume catalyst and reduce catalyst efficiency. In this work biodiesel was prepared from acidified oils (AO through a supercritical methanol route, in which the esterification of FFAs and transesterification of glyceride with methanol occurred simultaneously. The effects of the mass ratio of methanol to AO, the operation temperature as well as the water content on the FFAs conversion and glycerol yield were investigated. The results indicated that the FFAs conversion for esterification under the condition of 1:1 methanol/oil ratio, 310 °C and 15 min reaction time reached 98.7%, and the glycerol yield for transesterification under 0.25:1 methanol/oil ratio, 290 °C and 20 min reaction time reached 63.5% respectively.

  9. Production of methanol from biomass waste via pyrolysis.

    Science.gov (United States)

    Kamarudin, S K; Shamsul, N S; Ghani, J A; Chia, S K; Liew, H S; Samsudin, A S

    2013-02-01

    The production of methanol from agricultural, forestry, livestock, poultry, and fishery waste via pyrolysis was investigated. Pyrolysis was conducted in a tube furnace at 450-500 °C. Sugarcane bagasse showed the methanol production (5.93 wt.%), followed by roots and sawdust with 4.36 and 4.22 wt.%, respectively. Animal waste offered the lowest content of methanol, as only 0.46, 0.80, and 0.61 wt.% were obtained from fishery, goat, and cow waste, respectively. It was also observed that the percentage of methanol increased with an increase in volatile compounds while the percentage of ethanol increased with the percentage of ash and fix carbon. The data indicate that, pyrolysis is a means for production of methanol and ethanol after further optimization of the process and sample treatment.

  10. The Revised Version of Class I Methanol Maser Catalog

    CERN Document Server

    Val'tts, I E; Bayandina, O S

    2010-01-01

    The revised version of the class I methanol maser catalog is presented. It contains 182 sources - new class I methanol masers detected in the direction of EGOs were added to the previous number (~160 sources have been published in the first version of this catalog - see reference in the text). Electronic version has been generated in the form of html file - http://www.asc.rssi.ru/MMI. A statistical analysis was carried out within 2' around a maser position to find an identification of class I methanol masers with any objects typical for star-forming regions - UCHII regions, IRAS sources, bipolar outflows, CS lines as of dense gas tracer, masers (class II methanol masers, OH and H2O) and EGO. None of the bipolar outflow, already registered in the direction of class I methanol maser, did not coincide with EGO. The result is submitted in a form of a diagram.

  11. Toxic cocktail: methanol poisoning in a tourist to Indonesia.

    Science.gov (United States)

    Gee, Paul; Martin, Elizabeth

    2012-08-01

    Methanol poisoning has become very uncommon in Australasia with regulations that have reduced its retail availability. This report describes a young tourist who developed sudden onset visual failure and rapid breathing 2 days after ingestion of a complimentary local drink called Arrack when travelling in Indonesia. She presented to a hospital in New Zealand with severe metabolic acidosis and a highly toxic methanol level at 17 mmol/L. The cocktail was consumed at a popular tourist bar but is likely to have been mixed from home-brewed or 'moonshine' alcohol tainted with methanol. The aetiology of methanol poisoning, its optic toxicology and therapeutic measures are discussed, as is the concerning number of methanol poisoning cases among tourists to Indonesia over recent years.

  12. Alternative energies for road traffic. Partial project: Alcohol fuels. Methanol pilot project. Final report. Alternative Energien fuer den Strassenverkehr. Teilprojekt Alkoholkraftstoffe. Methanol-Pilotprogramm. Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Decker, G.; Steinke, D.

    1989-06-01

    The trial phase of the methanol-fuelled vehicles showed the problems that have still to be solved. In order to increase the acceptance of methanol technologies a concept was developed for multifuel operation with methanol and petrol. A particular advantage of methanol-fuelled vehicles lies in the more favourable emission behaviour. Considerable reduction of ozone formation can be expected. (EF).

  13. A Nafion-Ceria Composite Membrane Electrolyte for Reduced Methanol Crossover in Direct Methanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    Parthiban Velayutham

    2017-02-01

    Full Text Available An alternative Nafion composite membrane was prepared by incorporating various loadings of CeO2 nanoparticles into the Nafion matrix and evaluated its potential application in direct methanol fuel cells (DMFCs. The effects of CeO2 in the Nafion matrix were systematically studied in terms of surface morphology, thermal and mechanical stability, proton conductivity and methanol permeability. The composite membrane with optimum filler content (1 wt. % CeO2 exhibits a proton conductivity of 176 mS·cm−1 at 70 °C, which is about 30% higher than that of the unmodified membrane. Moreover, all the composite membranes possess a much lower methanol crossover compared to pristine Nafion membrane. In a single cell DMFC test, MEA fabricated with the optimized composite membrane delivered a peak power density of 120 mW·cm−2 at 70 °C, which is about two times higher in comparison with the pristine Nafion membrane under identical operating conditions.

  14. Development and evaluation of antimicrobial herbal formulations containing the methanolic extract of Samadera indica for skin diseases.

    Science.gov (United States)

    Viswanad, Vidya; Aleykutty, N A; Jayakar, B; Zacharia, Subin Mary; Thomas, Litha

    2012-04-01

    Samadera indica Gaetrn (Simaroubaceae) is claimed to possess various pharmacological activities like antioxidant, antifungal, antitumor, antiviral, and so on, but its taste is bitter. The aim of the present study is to investigate the toxicity of the methanolic extract and to develop suitable herbal formulations of the methanolic extract of Samadera indica, having efficient antimicrobial activity. The methanolic extract prepared from the dried leaves of Samadera indica by continuous hot percolation, were used to examine the toxicity, according to the OECD 423 guidelines, in Swiss Albino mice. Topical formulations were prepared by incorporating Samadera indica (5% w / w) in an emulsifying ointment and a carbopol gel base and evaluated for physical parameters and in-vitro antimicrobial activity (S. aureus, P. aeruginosa and C. albicans). The study reveals that no animals under the study showed any clinical signs of toxicity or mortality when administered a dose of 5 - 2000 mg / kg body weight. Therefore, the maximum tolerated dose of the methanolic extract of Samadera indica was above 2000 mg / kg body weight. The formulated ointment and gel had acceptable physical parameters that showed that they were compatible with the skin, and in addition to this, these formulations passed the short-term stability studies. The in-vitro antimicrobial activity studies showed that the formulated ointment showed significantly strong (p gel. Thus, the present study concludes that the formulated ointment and gel are safe and efficient antimicrobial formulations for the topical delivery of the methanolic extract of Samadera indica.

  15. Interaction of Methanol Spray and Water-Deficit Stress on Photosynthesis and Biochemical Characteristics of Phaseolus vulgaris L. cv. Sadry.

    Science.gov (United States)

    Armand, Nezam; Amiri, Hamzeh; Ismaili, Ahmad

    2016-01-01

    This study was a factorial experiment with a completely randomized design and three replications. The four levels of methanol spraying were used. Spraying was carried out three times during the growing season at 10-day intervals beginning at 4 weeks after sowing. The spraying of solution continued until saturation of droplets on the leaves was achieved. The levels of water-deficit stress applied were nonstress, moderate water stress and severe water stress. The results showed that there was a significant difference (P ≤ 0.05) between the methanol and water-deficit stress treatments for chlorophyll (Chl) a and Chl b, carotenoid, total chlorophyll, net photosynthesis (PN ), intercellular CO2 (Ci ), maximal quantum yield of photosystem II photochemistry (Fv /Fm ), leaf moisture, water use efficiency and relative water content. The application of foliar methanol at all levels of water-deficit stress significantly decreased the catalase activity of the roots. Under all levels of water-deficit stress, the 30% (v/v) methanol treatment significantly decreased peroxidase activity in the roots over that for the control. The results suggest that foliar application of methanol can decrease the negative effects of water-deficit stress on Phaseolus vulgaris L. cv. Sadry.

  16. Effects of Methanolic Jatropha multifida L. Extract in Wound Healing Assessed by the Total Number of PMN Leukocytes and Fibroblasts

    Directory of Open Access Journals (Sweden)

    Juniarti

    2012-12-01

    Full Text Available Objective: The aim of this study was to evaluate the effects of methanol extract of Jatropha multifida leaves on the wound healing process and to investigate the wound healing activity based on reduced numbers of PMN (polymorpho nuclear leukocytes and increased numbers of fibroblasts. Method: methanol extract of dried leaves of Jatropha multifida was used in the wound healing activity studies. The study subjects were 36 white male Sprague Dawlay rats aged 2 months with 150-200 gram body weight. The subjects were divided into 4 groups and experimentally injured: Group I (negative control underwent injury without subsequent treatment; group II (positive control received topical treatment with Bethasone-N after injury; group III (solvent control was treated with 70% methanol; group IV (treatment group was treated with 10 mg methanol extract of Jatropha multifida Each group consisted of 3 rats, which were decapitated on days 3, 6, and 13 after the start of treatment. Histological preparation was stained with hematoxyline-eosin (HE and was continuously examined by counting the numbers of PMN leukocytes and fibroblasts as indicators of wound healing on days 3, 6, and 13 of treatment. The study showed lower numbers of PMN leukocytes in subjects treated with the extract of Jatropha multifida as compared to the other groups. The numbers of fibroblasts were significantly higher on days 6 and 13 of treatment. In conclusion, the treatment of injuries with methanol extract of leaves from Jatropha multifida provided better results compared to the other groups in our study.

  17. New process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis has been developed. Some alcohols, especially 2-alcohol, were found to have high cata-lytic promoting effect on the synthesis of methanol from CO hydrogenation. At 443 K and 5 MPa, the synthesis of methanol could process high effectively, resulting from the synergic catalysis of Cu/ZnO solid catalyst and 2-alcohol solvent catalyst. The primary results showed that when 2-butanol was used as reaction solvent, the one-pass average yield and the selectivity of methanol, in 40 h con-tinuous reaction at temperature as low as 443 K and 5 MPa, were high up to 46.51% and 98.94% respectively. The catalytic activity was stable and the reaction temperature was 80 K or so lower than that in current industry synthesis process. This new process hopefully will become a practical method for methanol synthesis at low temperature.

  18. New process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis

    Institute of Scientific and Technical Information of China (English)

    曾健青; TSUBAKINoritatsu; FUJIMOTOKaoru

    2002-01-01

    A new process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis has been developed. Some alcohols, especially 2-alcohol, were found to have high catalytic promoting effect on the synthesis of methanol from CO hydrogenation. At 443 K and 5 MPa, the synthesis of methanol could process high effectively, resulting from the synergic catalysis of Cu/ZnO solid catalyst and 2-alcohol solvent catalyst. The primary results showed that when 2-butanol was used as reaction solvent, the one-pass average yield and the selectivity of methanol, in 40 h continuous reaction at temperature as low as 443 K and 5 MPa, were high up to 46.51% and 98.94% respectively. The catalytic activity was stable and the reaction temperature was 80 K or so lower than that in current industry synthesis process. This new process hopefully will become a practical method for methanol synthesis at low temperature.

  19. Information draft on the development of air standards for methanol

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-01-01

    Methanol is a clear, colourless. very mobile liquid with a slightly alcoholic odour in pure form, but a repulsive pungent odour in crude form. Methanol is the raw material in the production of many gasoline additives, is used as a solvent or antifreeze in paint strippers, aerosol spray paints, wall paints, carburetor cleaners, and car windshield washer compounds. Methanol is one of the top pollutants by release quantities in Ontario, the highest release being generated by the pulp and paper industry. Other large emissions come from the plastics and synthetic resin industry. Total release to the air in Canada was 3,668 tonnes in 1996 and the top ten methanol emitting facilities were in Ontario. Methanol is readily absorbed through inhalation, ingestion and skin exposures. Once absorbed, it is oxidized to formaldehyde and then to formic acid. Common symptoms of exposure are visual disturbances, dizziness, nausea, vertigo, pain in the extremities, and headaches. No information was found as to the carcinogenicity of methanol to humans or animals. Current Ontario half-hour POI standard for methanol is 84,000 microgram/cubic meter and the 24-hour AAQC is 28,000 microgram/cubic meter. Both values were established more than 20 years ago. Review of relevant literature, summarized in this report, indicates that five US states have promulgated air quality guidelines or reference exposure levels for methanol, based on occupational exposure limits. The US Environmental Protection Agency is currently reviewing its reference concentration value for methanol. The World Health Organization and the Canadian federal government have not set air quality guidelines for methanol. 37 refs., 1 tab., appendix.

  20. Regulation of methanol metabolism in the yeast Hansenula polymorpha. Isolation and characterization of mutants blocked in methanol assimilatory enzymes

    NARCIS (Netherlands)

    Koning, W. de; Gleeson, M.A.G.; Harder, W.; Dijkhuizen, L.

    1987-01-01

    A study of enzyme profiles in Hansenula polymorpha grown on various carbon substrates revealed that the synthesis of the methanol dissimilatory and assimilatory enzymes is regulated in the same way, namely by catabolite repression and induction by methanol. Mutants of H. polymorpha blocked in dihydr

  1. Modifications for use of methanol or methanol-gasoline blends in automotive vehicles, September 1976-January 1980

    Energy Technology Data Exchange (ETDEWEB)

    Patterson, D.J.; Bolt, J.A.; Cole, D.E.

    1980-01-01

    Methanol or blends of methanol and gasoline as automotive fuels may be attractive means for extending the nation's petroleum reserves. The present study was aimed at identifying potential problems and solutions for this use of methanol. Retrofitting of existing vehicles as well as future vehicle design have been considered. The use of ethanol or higher alcohols was not addressed in this study but will be included at a later date. Several potentially serious problems have been identified with methanol use. The most attractive solutions depend upon an integrated combination of vehicle modifications and fuel design. No vehicle problems were found which could not be solved with relatively minor developments of existing technology providing the methanol or blend fuel was itself engineered to ameliorate the solution. Research needs have been identified in the areas of lubrication and materials. These, while apparently solvable, must precede use of methanol or methanol-gasoline blends as motor fuels. Because of the substantial costs and complexities of a retrofitting program, use of methanol must be evaluated in relation to other petroleum-saving alternatives. Future vehicles can be designed initially to operate satisfactorily on these alternate fuels. However a specific fuel composition must be specified around which the future engines and vehicles can be designed.

  2. Cytochemical Studies on the Localization of Methanol Oxidase and Other Oxidases in Peroxisomes of Methanol-Grown Hansenula polyrnorpha

    NARCIS (Netherlands)

    Veenhuis, M.; Dijken, J.P. van; Harder, W.

    1976-01-01

    The localization of methanol oxidase activity in cells of methanol-limited chemostat cultures of the yeast Hansenula polymorpha has been studied with different cytochemical staining techniques. The methods were based on enzymatic or chemical trapping of the hydrogen peroxide produced by the enzyme d

  3. Influence of carbonyl iron particle coating with silica on the properties of magnetorheological elastomers

    Science.gov (United States)

    Małecki, P.; Królewicz, M.; Hiptmair, F.; Krzak, J.; Kaleta, J.; Major, Z.; Pigłowski, J.

    2016-10-01

    In this paper, the influence of encapsulating carbonyl iron particles with various silica coatings on the properties of magnetorheological elastomers (MREs) was investigated. A soft styrene-ethylene-butylene-styrene thermoplastic elastomer was used as the composite’s polymer matrix. Spherical carbonyl iron powder (CIP) acted as the ferromagnetic filler. In order to improve the metal-polymer interaction, carbonyl iron particles were coated with two types of single and six types of double silica layers. The first layer was created through a TMOS or TEOS hydrolysis whereas the second one was composed of organosilanes. The mechanical properties of MREs containing 38.5 vol% of CIP were analysed under dynamic loading conditions. To investigate the magnetorheological effect in these composites, a 430 mT magnetic field, generated by an array of permanent magnets, was applied during testing. The results revealed that the magnetomechanical response of the MREs differs substantially, depending on the kind of particle coating.

  4. A cleavable biotin tagging reagent that enables the enrichment and identification of carbonylation sites in proteins.

    Science.gov (United States)

    Coffey, Chelsea M; Gronert, Scott

    2016-01-01

    The utility of a new, cleavable tag for identifying and enriching protein carbonyls is examined. Using a model system, human serum albumin modified with acrolein, the EZ-Link alkoxyamine-PEG4-SS-PEG4-biotin affinity tag, was tested for its ability to label protein carbonyls in proteomic analyses of protein carbonylation. The efficiency of the labeling was assayed and compared to standard biotin hydrazide reagents. The label was also tested in liquid chromatography-tandem mass spectrometry (LC/MS/MS) experiments. The quality of the fragmentation spectra was assessed and the relative detection efficiency of various modification sites was compared to standard biotin hydrazide reagents. Finally, the viability of using the label with streptavidin bead enrichment protocols in a standard proteomics workflow was probed.

  5. Influence of the Dielectric Medium on the Carbonyl Infrared Absorption Peak of Acetylferrocene

    Directory of Open Access Journals (Sweden)

    F. López-Linares

    2005-02-01

    Full Text Available The solvent effect on the position of the carbonyl vibrational stretching ofacetylferrocene in aprotic media was studied in this work. The solvent-induced shifts in thisorganometallic compound were interpreted in terms of the alternative reaction field model(SCRF-MO proposed by Kolling. In contrast to the established trends for carbonyl groupsin organic systems, the results suggest that the continuum models for the reaction field arenot adequate and that the influence of dipolarity-polarizability described by aninhomogeneous coupling function θ (ε L(n 2 that assumes optical dielectric saturation isresponsible for the carbonyl band shift and, there is empirical evidence that the effect offield-induced intermolecular interaction on band shift, interpreted in terms of the van derWaals forces from the solvent, have a important contribution to this phenomena.

  6. Synthesis of Carbazoles and Carbazole-Containing Heterocycles via Rhodium-Catalyzed Tandem Carbonylative Benzannulations.

    Science.gov (United States)

    Song, Wangze; Li, Xiaoxun; Yang, Ka; Zhao, Xian-liang; Glazier, Daniel A; Xi, Bao-min; Tang, Weiping

    2016-04-01

    Polycyclic aromatic compounds are important constituents of pharmaceuticals and other materials. We have developed a series of Rh-catalyzed tandem carbonylative benzannulations for the synthesis of tri-, tetra-, and pentacyclic heterocycles from different types of aryl propargylic alcohols. These tandem reactions provide efficient access to highly substituted carbazoles, furocarbazoles, pyrrolocarbazoles, thiophenocarbazoles, and indolocarbazoles. While tricyclic heterocycles could be derived from vinyl aryl propargylic alcohols, tetra- and pentacyclic heterocycles were synthesized from diaryl propargylic alcohols. The tandem carbonylative benzannulation is initiated by a π-acidic rhodium(I) catalyst-mediated nucleophilic addition to alkyne to generate a key metal-carbene intermediate, which is then trapped by carbon monoxide to form a ketene species for 6π electrocyclization. Overall, three bonds and two rings are formed in all of these tandem carbonylative benzannulation reactions.

  7. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    Science.gov (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  8. Adaptation of Hansenula polymorpha to methanol: a transcriptome analysis

    Directory of Open Access Journals (Sweden)

    Kuipers Oscar P

    2010-01-01

    Full Text Available Abstract Background Methylotrophic yeast species (e.g. Hansenula polymorpha, Pichia pastoris can grow on methanol as sole source of carbon and energy. These organisms are important cell factories for the production of recombinant proteins, but are also used in fundamental research as model organisms to study peroxisome biology. During exponential growth on glucose, cells of H. polymorpha typically contain a single, small peroxisome that is redundant for growth while on methanol multiple, enlarged peroxisomes are present. These organelles are crucial to support growth on methanol, as they contain key enzymes of methanol metabolism. In this study, changes in the transcriptional profiles during adaptation of H. polymorpha cells from glucose- to methanol-containing media were investigated using DNA-microarray analyses. Results Two hours after the shift of cells from glucose to methanol nearly 20% (1184 genes of the approximately 6000 annotated H. polymorpha genes were significantly upregulated with at least a two-fold differential expression. Highest upregulation (> 300-fold was observed for the genes encoding the transcription factor Mpp1 and formate dehydrogenase, an enzyme of the methanol dissimilation pathway. Upregulated genes also included genes encoding other enzymes of methanol metabolism as well as of peroxisomal β-oxidation. A moderate increase in transcriptional levels (up to 4-fold was observed for several PEX genes, which are involved in peroxisome biogenesis. Only PEX11 and PEX32 were higher upregulated. In addition, an increase was observed in expression of the several ATG genes, which encode proteins involved in autophagy and autophagy processes. The strongest upregulation was observed for ATG8 and ATG11. Approximately 20% (1246 genes of the genes were downregulated. These included glycolytic genes as well as genes involved in transcription and translation. Conclusion Transcriptional profiling of H. polymorpha cells shifted from

  9. Ab initio determination of dark structures in radiationless transitions for aromatic carbonyl compounds.

    Science.gov (United States)

    Fang, Wei-Hai

    2008-03-01

    Mechanistic photodissociation of a polyatomic molecule has long been regarded as an intellectually challenging area of chemical physics, the results of which are relevant to atmospheric chemistry, biological systems, and many application fields. Carbonyl compounds play a unique role in the development of our understanding of the spectroscopy, photochemistry, and photophysics of polyatomic molecules and their photodissociation has been the subject of numerous studies over many decades. Upon irradiation, a molecule can undergo internal conversion (IC) and intersystem crossing (ISC) processes, besides photochemical and other photophysical processes. Transient intermediates formed in the IC and ISC radiationless processes, which are termed "dark", are not amenable to detection by conventional light absorption or emission. However, these dark intermediates play critical roles in IC and ISC processes and thus are essential to understanding mechanistic photochemistry of a polyatomic molecule. We have applied the multiconfiguration complete active space self-consistent field (CASSCF) method to determine the dark transient structures involved in radiationless processes for acetophenone and the related aromatic carbonyl compounds. The electronic and geometric structures predicted for the dark states are in a good agreement with those determined by ultrafast electron diffraction experiments. Intersection structure of different electronic states provides a very efficient "funnel" for the IC or ISC process. However, experimental determination of the intersection structure involved in radiationless transitions of a polyatomic molecule is impossible at present. We have discovered a minimum energy crossing point among the three potential energy surfaces (S1, T1, and T2) that appears to be common to a wide variety of aromatic carbonyl compounds with a constant structure. This new type of crossing point holds the key to understanding much about radiationless processes after

  10. Is carbonyl sulfide a precursor for carbon disulfide in vegetation and soil? Interconversion of carbonyl sulfide and carbon disulfide in fresh grain tissues in vitro.

    Science.gov (United States)

    Ren, Y

    1999-05-01

    The interconversion of carbonyl sulfide (COS) and carbon disulfide (CS(2)) was studied in the roots and shoots of barley and chickpeas. Ratios of conversion gases, K, 40 h after the addition of COS or CS(2) are recorded. The proportion of COS converted to each of CS(2), CO, and H(2)S and the proportion of CS(2) converted to COS were greater in roots than in shoots. More COS was converted to CS(2) than CS(2) to COS in roots and shoots of barley and chickpeas. The amount of COS converted to H(2)S and CO was 8 times the amount converted to CS(2) in barley and 3-4 times the amount in chickpeas. Carbonyl sulfide may be a precursor for CS(2) in vegetation and soil, just as the reverse is true in the atmosphere. These two different results might form a cycle of COS and CS(2).

  11. First Satellite Observations of Lower Tropospheric Ammonia and Methanol

    Science.gov (United States)

    Beer, Reinhard; Shephard, Mark W.; Kulawik, Susan S.; Clough, Shepard A.; Eldering, Annmarie; Bowman, Kevin W.; Sander, Stanley P.; Fisher, Brendan M.; Payne, Vivienne H.; Luo, Mingzhao; Osterman, Gregory B.; Worden, John R.

    2008-01-01

    The Tropospheric Emission Spectrometer (TES) on the EOS Aura satellite makes global measurements of infrared radiances which are used to derive profiles of species such as O3, CO, H2O, HDO and CH4 as routine standard products. In addition, TES has a variety of special modes that provide denser spatial mapping over a limited geographical area. A continuous-coverage mode (called ''transect'', about 460 km long) has now been used to detect additional molecules indicative of regional air pollution. On 10 July 2007 at about 05:37 UTC (13:24 LMST) TES conducted such a transect observation over the Beijing area in northeast China. Examination of the residual spectral radiances following the retrieval of the TES standard products revealed surprisingly strong features attributable to enhanced concentrations of ammonia (NH3) and methanol (CH3OH), well above the normal background levels. This is the first time that these molecules have been detected in space-based nadir viewing measurements that penetrate into the lower atmosphere.

  12. Methanol to propylene. From development to commercialization

    Energy Technology Data Exchange (ETDEWEB)

    Haag, S.; Rothaemel, M. [Air Liquide Forschung und Entwicklung GmbH, Frankfurt am Main (Germany); Pohl, S.; Gorny, M. [Lurgie GmbH, Frankfurt am Main (Germany). Air Liquide Global E and C Solutions

    2012-07-01

    In the late 1990s the development of the so-called MTP {sup registered} (methanol-to-propylene) process, a Lurgi Technology (by Air Liquide Global E and C Solutions) started. This constitutes a novel route to a valuable product that would not rely on crude oil as feedstock (as conventional propylene production does), but instead utilizes coal or natural gas and potentially biomass. These alternative feedstocks are first converted to synthesis gas, cleaned, and then converted to methanol. The development of the methanol-to-propylene conversion was achieved in a close collaboration between R and D and engineering. Two pilot plants at the R and D center in Frankfurt and a demonstration plant in Norway have been used to demonstrate the yields, catalyst lifetime and product quality and to support the engineering team in plant design and scale-up. Especially the last item is important as it was clear from the very beginning that the first commercial MTP {sup registered} plant would already be world-scale, actually one of the largest propylene producing plants in the world. This required a safe and diligent scale-up as the MTP {sup registered} reactors in the commercial plant receive about 7,000 times the feed of the demo unit and as much as 100,000 times the feed of the pilot plant. The catalyst used is a zeolite ZSM-5 that was developed by our long-term cooperation partner Sued-Chemie (now Clariant). At the end of 2010, the first commercial MTP {sup registered} plant in Ningdong in the Chinese province of Ningxia was started up as part of a coal-to-chemicals complex owned by the Shenhua Ningxia Coal Industry Group. In this complex the complete chain starting from coal through to the final polypropylene product is realized. The customer successful started the polymer-grade propylene production in April 2011 and then announced in May 2011 that he sold the first 1000 tons of polypropylene made with propylene coming from the MTP {sup registered} unit. Following this

  13. Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

    DEFF Research Database (Denmark)

    Poppendieck, D.G.; Hubbard, H.F.; Weschler, Charles J.;

    2007-01-01

    from 1 to 20 mg m(-2), with most of the carbonyls being of lower molecular weight (C-1-C-4). In contrast, total BOBP mass released from wood-based products ranged from 20 to 100 mg m(-2), with a greater fraction of the BOBPs being heavier carbonyls (C-5-C-9). The total BOBP mass released during...... relatively high BOBP releases. The greatest overall BOBP mass releases were observed for three materials that building occupants might have significant contact with: paper, office partition, and medium density fiberboard, e.g., often used in office furniture. These materials also exhibited extended BOBP...

  14. Impaired cardiac SIRT1 activity by carbonyl stress contributes to aging-related ischemic intolerance.

    Directory of Open Access Journals (Sweden)

    Chunhu Gu

    Full Text Available Reactive aldehydes can initiate protein oxidative damage which may contribute to heart senescence. Sirtuin 1 (SIRT1 is considered to be a potential interventional target for I/R injury management in the elderly. We hypothesized that aldehyde mediated carbonyl stress increases susceptibility of aged hearts to ischemia/reperfusion (I/R injury, and elucidate the underlying mechanisms with a focus on SIRT1. Male C57BL/6 young (4-6 mo and aged (22-24 mo mice were subjected to myocardial I/R. Cardiac aldehyde dehydrogenase (ALDH2, SIRT1 activity and protein carbonyls were assessed. Our data revealed that aged heart exhibited increased endogenous aldehyde/carbonyl stress due to impaired ALDH2 activity concomitant with blunted SIRT1 activity (P<0.05. Exogenous toxic aldehydes (4-HNE exposure in isolated cardiomyocyte verified that aldehyde-induced carbonyl modification on SIRT1 impaired SIRT1 activity leading to worse hypoxia/reoxygenation (H/R injury, which could all be rescued by Alda-1 (ALDH2 activator (all P<0.05. However, SIRT1 inhibitor blocked the protective effect of Alda-1 on H/R cardiomyocyte. Interestingly, myocardial I/R leads to higher carbonylation but lower activity of SIRT1 in aged hearts than that seen in young hearts (P<0.05. The application of Alda-1 significantly reduced the carbonylation on SIRT1 and markedly improved the tolerance to in vivo I/R injury in aged hearts, but failed to protect Sirt1(+/- knockout mice against myocardial I/R injury. This was verified by Alda-1 treatment improved postischemic contractile function recovery in ex vivo perfused aged but not in Sirt1(+/- hearts. Thus, aldehyde/carbonyl stress is accelerated in aging heart. These results provide a new insight that impaired cardiac SIRT1 activity by carbonyl stress plays a critical role in the increased susceptibility of aged heart to I/R injury. ALDH2 activation can restore this aging-related myocardial ischemic intolerance.

  15. Photophysical properties of a synthetic, carbonyl-containing (N = 6+Cdbnd O) carotenoid analogue

    Science.gov (United States)

    Niedzwiedzki, Dariusz M.

    2014-05-01

    Retinyl-1 is a synthetic carotenoid analogue belonging to the retinal analogues family. It has six conjugated carbon-carbon double bonds with a carbonyl group conjugated to the π-electron system. Presence of the carbonyl group in vicinity of the conjugated carbon-carbon backbone leads to unique excited state properties that are extremely sensitive to solvent polarity and temperature. The simplicity of the synthesis of Retinyl-1 and ease of attachment to synthetic tetrapyrrole chromophores make Retinyl-1 attractive for use in artificial photosynthetic systems.

  16. Photophysical properties of a synthetic, carbonyl-containing (N=6+CO) carotenoid analogue

    Energy Technology Data Exchange (ETDEWEB)

    Niedzwiedzki, Dariusz M. [Washington Univ., St. Louis, MO (United States)

    2014-05-01

    Retinyl-1 is a synthetic carotenoid analogue belonging to the retinal analogues family. It has six conjugated carbon–carbon double bonds with a carbonyl group conjugated to the π-electron system. Presence of the carbonyl group in vicinity of the conjugated carbon–carbon backbone leads to unique excited state properties that are extremely sensitive to solvent polarity and temperature. The simplicity of the synthesis of Retinyl-1 and ease of attachment to synthetic tetrapyrrole chromophores make Retinyl-1 attractive for use in artificial photosynthetic systems.

  17. Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols.

    Science.gov (United States)

    Jang, Myoseon; Carroll, Brian; Chandramouli, Bharadwaj; Kamens, Richard M

    2003-09-01

    Aerosol growth by the heterogeneous reactions of different aliphatic and alpha,beta-unsaturated carbonyls in the presence/absence of acidified seed aerosols was studied in a 2 m long flow reactor (2.5 cm i.d.) and a 0.5-m3 Teflon film bag under darkness. For the flow reactor experiments, 2,4-hexadienal, 5-methyl-3-hexen-2-one, 2-cyclohexenone, 3-methyl-2-cyclopentenone, 3-methyl-2-cyclohexenone, and octanal were studied. The carbonyls were selected based on their reactivity for acid-catalyzed reactions, their proton affinity, and their similarity to the ring-opening products from the atmospheric oxidation of aromatics. To facilitate acid-catalyzed heterogeneous hemiacetal/acetal formation, glycerol was injected along with inorganic seed aerosols into the flow reactor system. Carbonyl heterogeneous reactions were accelerated in the presence of acid catalysts (H2SO4), leading to higher aerosol yields than in their absence. Aldehydes were more reactive than ketones for acid-catalyzed reactions. The conjugated functionality also resulted in higher organic aerosol yieldsthan saturated aliphatic carbonyls because conjugation with the olefinic bond increases the basicity of the carbonyl leading to increased stability of the protonated carbonyl. Aerosol population was measured from a series of sampling ports along the length of the flow reactor using a scanning mobility particle sizer. Fourier transform infrared spectrometry of either an impacted liquid aerosol layer or direct reaction of carbonyls as a thin liquid layer on a zinc selenide FTIR disk was employed to demonstrate the direct transformation of chemical functional groups via the acid-catalyzed reactions. These results strongly indicate that atmospheric multifunctional organic carbonyls, which are created by atmospheric photooxidation reactions, can contribute significantly to secondary organic aerosol formation through acid-catalyzed heterogeneous reactions. Exploratory studies in 25- and 190-m3 outdoor chambers

  18. Ab initio MO study of reaction mechanism for carbonyl migration of Co complex

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Ab initio method under the effective core potential (ECP) approximation is employed to study the reaction mechanism of carbonyl migration of the cycle of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)3 at Hartree-Fock (HF) level. The structures of the reactant, transition state and product for the reaction are determined. The energy of each stationary point is corrected at MP2/LAN2DZ//LANL2DZ+ZPE (zero-point energy) level. The calculated activation barrier is 28.89 kJ/mol.

  19. Selenium-catalyzed Oxidative Carbonylation of Benzylamines to 1,3-Dibenzylureas

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiaopeng; LI Zhengwei; WANG Ping; FAN Xuesen; ZHANG Guisheng

    2017-01-01

    A facile,efficient and cost-effective approach to 1,3-dibenzylurea was reported.With cheap and recyclable nonmetal selenium as catalyst,carbon monoxide instead of phosgene derivatives as carbonylation agent and oxygen as oxidant,the selenium-catalyzed oxidative carbonylation reaction of benzylamines can proceed efficiently in one-pot manner in the presence of triethylamine to afford the desired 1,3-dibenzylureas mostly in moderate to excellent yields.Selenium catalyst can be easily recovered due to its phase-transfer catalytic function and recycled.

  20. Hydrolysis of Carbonyl Sulfide in Binary Mixture of Diethylene Glycol Diethyl Ether and Water

    Institute of Scientific and Technical Information of China (English)

    李新学; 刘迎新; 魏雄辉

    2005-01-01

    The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.

  1. Relaxation-optimised Hartmann-Hahn transfer using a specifically Tailored MOCCA-XY16 mixing sequence for carbonyl-carbonyl correlation spectroscopy in {sup 13}C direct detection NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Felli, Isabella C.; Pierattelli, Roberta [University of Florence, Department of Chemistry and Magnetic Resonance Center (CERM) (Italy); Glaser, Steffen J.; Luy, Burkhard [Technische Universitaet Muenchen, Department of Chemistry (Germany)], E-mail: Burkhard.Luy@ch.tum.de

    2009-03-15

    Isotropic mixing sequences are one of the key methods to achieve efficient coherence transfer. Among them, the MOCCA-XY16, which keeps the magnetization longitudinal for a significant amount of time, is characterised by favourable relaxation properties. We show here that its adapted version is particularly suited for carbonyl-carbonyl correlations in {sup 13}C direct detection NMR experiments.

  2. Studies on an ultrasonic atomization feed direct methanol fuel cell.

    Science.gov (United States)

    Wu, Chaoqun; Liu, Linghao; Tang, Kai; Chen, Tao

    2017-01-01

    Direct methanol fuel cell (DMFC) is promising as an energy conversion device for the replacement of conventional chemical cell in future, owing to its convenient fuel storage, high energy density and low working temperature. The development of DMFC technology is currently limited by catalyst poison and methanol crossover. To alleviate the methanol crossover, a novel fuel supply system based on ultrasonic atomization is proposed. Experimental investigations on this fuel supply system to evaluate methanol permeation rates, open circuit voltages (OCVs) and polarization curves under a series of conditions have been carried out and reported in this paper. In comparison with the traditional liquid feed DMFC system, it can be found that the methanol crossover under the ultrasonic atomization feed system was significantly reduced because the DMFC reaches a large stable OCV value. Moreover, the polarization performance does not vary significantly with the liquid feed style. Therefore, the cell fed by ultrasonic atomization can be operated with a high concentration methanol to improve the energy density of DMFC. Under the supply condition of relatively high concentration methanol such as 4M and 8M, the maximum power density fed by ultrasonic atomization is higher than liquid by 6.05% and 12.94% respectively.

  3. Water–methanol separation with carbon nanotubes and electric fields.

    Science.gov (United States)

    Winarto; Takaiwa, Daisuke; Yamamoto, Eiji; Yasuoka, Kenji

    2015-08-07

    Methanol is used in various applications, such as fuel for transportation vehicles, fuel cells, and in chemical industrial processes. Conventionally, separation of methanol from aqueous solution is by distillation. However, this method consumes a large amount of energy; hence development of a new method is needed. In this work, molecular dynamics simulations are performed to investigate the effect of an electric field on water–methanol separation by carbon nanotubes (CNTs) with diameters of 0.81 to 4.07 nm. Without an electric field, methanol molecules fill the CNTs in preference to water molecules. The preference of methanol to occupy the CNTs over water results in a separation effect. This separation effect is strong for small CNT diameters and significantly decreases with increasing diameter. In contrast, under an electric field, water molecules strongly prefer to occupy the CNTs over methanol molecules, resulting in a separation effect for water. More interestingly, the separation effect for water does not decrease with increasing CNT diameter. Formation of water structures in CNTs induced by an electric field has an important role in the separation of water from methanol.

  4. Methanol Production by a Broad Phylogenetic Array of Marine Phytoplankton.

    Science.gov (United States)

    Mincer, Tracy J; Aicher, Athena C

    2016-01-01

    Methanol is a major volatile organic compound on Earth and serves as an important carbon and energy substrate for abundant methylotrophic microbes. Previous geochemical surveys coupled with predictive models suggest that the marine contributions are exceedingly large, rivaling terrestrial sources. Although well studied in terrestrial ecosystems, methanol sources are poorly understood in the marine environment and warrant further investigation. To this end, we adapted a Purge and Trap Gas Chromatography/Mass Spectrometry (P&T-GC/MS) method which allowed reliable measurements of methanol in seawater and marine phytoplankton cultures with a method detection limit of 120 nanomolar. All phytoplankton tested (cyanobacteria: Synechococcus spp. 8102 and 8103, Trichodesmium erythraeum, and Prochlorococcus marinus), and Eukarya (heterokont diatom: Phaeodactylum tricornutum, coccolithophore: Emiliania huxleyi, cryptophyte: Rhodomonas salina, and non-diatom heterokont: Nannochloropsis oculata) produced methanol, ranging from 0.8-13.7 micromolar in culture and methanol per total cellular carbon were measured in the ranges of 0.09-0.3%. Phytoplankton culture time-course measurements displayed a punctuated production pattern with maxima near early stationary phase. Stabile isotope labeled bicarbonate incorporation experiments confirmed that methanol was produced from phytoplankton biomass. Overall, our findings suggest that phytoplankton are a major source of methanol in the upper water column of the world's oceans.

  5. Waste-to-methanol: Process and economics assessment.

    Science.gov (United States)

    Iaquaniello, Gaetano; Centi, Gabriele; Salladini, Annarita; Palo, Emma; Perathoner, Siglinda; Spadaccini, Luca

    2017-07-01

    The waste-to-methanol (WtM) process and related economics are assessed to evidence that WtM is a valuable solution both from economic, strategic and environmental perspectives. Bio-methanol from Refuse-derived-fuels (RdF) has an estimated cost of production of about 110€/t for a new WtM 300t/d plant. With respect to waste-to-energy (WtE) approach, this solution allows various advantages. In considering the average market cost of methanol and the premium as biofuel, the WtM approach results in a ROI (Return of Investment) of about 29%, e.g. a payback time of about 4years. In a hybrid scheme of integration with an existing methanol plant from natural gas, the cost of production becomes a profit even without considering the cap for bio-methanol production. The WtM process allows to produce methanol with about 40% and 30-35% reduction in greenhouse gas emissions with respect to methanol production from fossil fuels and bio-resources, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Methanol Production by a Broad Phylogenetic Array of Marine Phytoplankton.

    Directory of Open Access Journals (Sweden)

    Tracy J Mincer

    Full Text Available Methanol is a major volatile organic compound on Earth and serves as an important carbon and energy substrate for abundant methylotrophic microbes. Previous geochemical surveys coupled with predictive models suggest that the marine contributions are exceedingly large, rivaling terrestrial sources. Although well studied in terrestrial ecosystems, methanol sources are poorly understood in the marine environment and warrant further investigation. To this end, we adapted a Purge and Trap Gas Chromatography/Mass Spectrometry (P&T-GC/MS method which allowed reliable measurements of methanol in seawater and marine phytoplankton cultures with a method detection limit of 120 nanomolar. All phytoplankton tested (cyanobacteria: Synechococcus spp. 8102 and 8103, Trichodesmium erythraeum, and Prochlorococcus marinus, and Eukarya (heterokont diatom: Phaeodactylum tricornutum, coccolithophore: Emiliania huxleyi, cryptophyte: Rhodomonas salina, and non-diatom heterokont: Nannochloropsis oculata produced methanol, ranging from 0.8-13.7 micromolar in culture and methanol per total cellular carbon were measured in the ranges of 0.09-0.3%. Phytoplankton culture time-course measurements displayed a punctuated production pattern with maxima near early stationary phase. Stabile isotope labeled bicarbonate incorporation experiments confirmed that methanol was produced from phytoplankton biomass. Overall, our findings suggest that phytoplankton are a major source of methanol in the upper water column of the world's oceans.

  7. Nano-Engineered Catalysts for Direct Methanol Fuel Cells

    Science.gov (United States)

    Myung, Nosang; Narayanan, Sekharipuram; Wiberg, Dean

    2008-01-01

    Nano-engineered catalysts, and a method of fabricating them, have been developed in a continuing effort to improve the performances of direct methanol fuel cells as candidate power sources to supplant primary and secondary batteries in a variety of portable electronic products. In order to realize the potential for high energy densities (as much as 1.5 W h/g) of direct methanol fuel cells, it will be necessary to optimize the chemical compositions and geometric configurations of catalyst layers and electrode structures. High performance can be achieved when catalyst particles and electrode structures have the necessary small feature sizes (typically of the order of nanometers), large surface areas, optimal metal compositions, high porosity, and hydrophobicity. The present method involves electrodeposition of one or more catalytic metal(s) or a catalytic-metal/polytetrafluoroethylene nanocomposite on an alumina nanotemplate. The alumina nanotemplate is then dissolved, leaving the desired metal or metal/polytetrafluoroethylene-composite catalyst layer. Unlike some prior methods of making fine metal catalysts, this method does not involve processing at elevated temperature; all processing can be done at room temperature. In addition, this method involves fewer steps and is more amenable to scaling up for mass production. Alumina nanotemplates are porous alumina membranes that have been fabricated, variously, by anodizing either pure aluminum or aluminum that has been deposited on silicon by electronbeam evaporation. The diameters of the pores (7 to 300 nm), areal densities of pores (as much as 7 x 10(exp 10)sq cm), and lengths of pores (up to about 100 nm) can be tailored by selection of fabrication conditions. In a given case, the catalytic metal, catalytic metal alloy, or catalytic metal/ polytetrafluoroethylene composite is electrodeposited in the pores of the alumina nanotemplate. The dimensions of the pores, together with the electrodeposition conditions

  8. Continuity theory

    CERN Document Server

    Nel, Louis

    2016-01-01

    This book presents a detailed, self-contained theory of continuous mappings. It is mainly addressed to students who have already studied these mappings in the setting of metric spaces, as well as multidimensional differential calculus. The needed background facts about sets, metric spaces and linear algebra are developed in detail, so as to provide a seamless transition between students' previous studies and new material. In view of its many novel features, this book will be of interest also to mature readers who have studied continuous mappings from the subject's classical texts and wish to become acquainted with a new approach. The theory of continuous mappings serves as infrastructure for more specialized mathematical theories like differential equations, integral equations, operator theory, dynamical systems, global analysis, topological groups, topological rings and many more. In light of the centrality of the topic, a book of this kind fits a variety of applications, especially those that contribute to ...

  9. Short Review: Mitigation of Current Environmental Concerns from Methanol Synthesis

    Directory of Open Access Journals (Sweden)

    Andrew Young

    2013-06-01

    Full Text Available Methanol has become a widely used and globally distributed product. Methanol is very important due to the current depletion of fossil fuels. Industrially, methanol produced from the catalytic reaction of synthetic gas composed of hydrogen, carbon monoxide, and carbon dioxide. Methanol production has brought great attention due to carbon dioxide as the main source of greenhouse gas emissions. Combined of reducing CO2 emissions and supplying an alternative fuel source has created the idea of a carbon neutral cycle called “the methanol economy”. The best catalyst for the methanol economy would show a high CO2 conversion and high selectivity for methanol production. This paper investigates research focused on catalyst development for efficient methanol synthesis from hydrogenation of carbon dioxide through added various supports and additives such as silica, zirconium, and palladium. Catalysts that displayed the highest activity included a zirconia and silicon-titanium oxide promoted Cu/Zn/Al2O3 catalyst. Alternative method of catalyst preparation, include the oxalate-gel, solid-state reaction, co-precipitation and combustion method also investigated.  © 2013 BCREC UNDIP. All rights reservedReceived: 10th October 2012; Revised: 7th February 2012; Accepted: 10th February 2013[How to Cite: Young, A., Lesmana, D., Dai, D.J., Wu, H.S. (2013. Short Review: Mitigation of Current En-vironmental Concerns from Methanol Synthesis. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 1-13. (doi:10.9767/bcrec.8.1.4055.1-13][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4055.1-13] | View in  |

  10. New constraints on terrestrial and oceanic sources of atmospheric methanol

    Directory of Open Access Journals (Sweden)

    D. B. Millet

    2008-12-01

    Full Text Available We use a global 3-D chemical transport model (GEOS-Chem to interpret new aircraft, surface, and oceanic observations of methanol in terms of the constraints that they place on the atmospheric methanol budget. Recent measurements of methanol concentrations in the ocean mixed layer (OML imply that in situ biological production must be the main methanol source in the OML, dominating over uptake from the atmosphere. It follows that oceanic emission and uptake must be viewed as independent terms in the atmospheric methanol budget. We deduce that the marine biosphere is a large primary source (85 Tg a−1 of methanol to the atmosphere and is also a large sink (101 Tg a−1, comparable in magnitude to atmospheric oxidation by OH (88 Tg a−1. The resulting atmospheric lifetime of methanol in the model is 4.7 days. Aircraft measurements in the North American boundary layer imply that terrestrial plants are a much weaker source than presently thought, likely reflecting an overestimate of broadleaf tree emissions, and this is also generally consistent with surface measurements. We deduce a terrestrial plant source of 80 Tg a−1, comparable in magnitude to the ocean source. The aircraft measurements show a strong correlation with CO (R2=0.51−0.61 over North America during summer. We reproduce this correlation and slope in the model with the reduced plant source, which also confirms that the anthropogenic source of methanol must be small. Our reduced plant source also provides a better simulation of methanol observations over tropical South America.

  11. Mutagenic and cytotoxic activities of Limonium globuliferum methanol extracts.

    Science.gov (United States)

    Eren, Yasin

    2016-10-01

    Unmonitored use of plant extractions alone or in combination with drugs may cause important health problems and toxic effects. Limonium (Plumbaginaceae) plants are known as antibacterial, anticancer and antivirus agent. But it is possible that this genus may have toxic effects. This study evaluated the mutagenic and cytotoxic effects of Limonium globuliferum (Boiss. et Heldr.) O. Kuntze (Plumbaginaceae) acetone/methanol (2:1), and methanol extracts of root, stem, and leaf. Different parts of this species were used in order to compare the mutagenic and cytotoxic effects of these parts. Ames test was carried out with S. typhimurium TA98, and TA100 strains. Strains were incubated at 37 °C for 72 h. MDBK cell line was used in MTT test. 10,000, 1000, 100, 10, 1 and 0.1 µg/plate concentrations of plant extracts were used in Ames test. 50, 25, 12.5, 6.25 and 3.125 µg/ml concentrations of root, stem and leaf acetone/methanol (2:1) and methanol extracts were used in MTT test. Ames test results indicated that only methanol leaf extract (10,000 µg/plate) had mutagenic activity. L. globuliferum root methanol extracts (3.125 and 6.25 µg/ml) increased the proliferation rates. Root acetone/methanol (2:1) extracts were found highly cytotoxic in all treatments. The results indicated that leaf extracts had lower cytotoxic effects than root and stem extracts. High concentrations of L. globuliferum stem and leaf methanol extracts showed cytotoxic activity in all treatment periods while low concentrations of the stem methanol extracts increased the proliferation rates.

  12. Synthesis of the [beta]-D-glucosyl ester of [carbonyl-[sup 13]C]-indole-3-acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Jakas, A.; Magnus, V. (Rudjer Boskovic Inst., Zagreb (Croatia)); Horvat, S.; Sandberg, G. (Swedish Univ. of Agricultural Sciences, Uppsala (Sweden))

    1993-10-01

    An efficient, operationally simple synthetic approach to 1-O-([carbonyl-[sup 13]C]-indole-3'-ylacetyl)-[beta]-D-glucopyranose is described. The synthesis was carried out by fusing a fully benzylated 1-O-glucosylpseudourea intermediate with [carbonyl-[sup 13]C]-indole-3-acetic acid, followed by hydrogenolytic removal of the protective groups. (Author).

  13. Green Synthesis and Regioselective Control of Sn/I2 Mediated Allylation of Carbonyl Compounds with Crotyl Halide in Water

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yan; ZHA,Zhang-Gen; ZHOU,Yu-Qing; WANG,Zhi-Yong

    2004-01-01

    @@ Barbier-type carbonyl allylation is particularly useful due to ease of operation and the availability and tractability of allylic substrates,[1] Metals such as indium, zinc and tin are often used as the mediator. Here we present a green approach toward the synthesis, that is, Sn/I2 mediated allylation of carbonyl compounds with crotyl halide in water.

  14. Enhanced antioxidation and electromagnetic properties of Co-coated flaky carbonyl iron particles prepared by electroless plating

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yingying, E-mail: zyzlchappy1989@163.com [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Zhou, Wancheng [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Li, Rong [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); No. 603 Faculty, Xi’an Institute of High Technology, Xi’an 710025 (China); Mu, Yang; Qing, Yuchang [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China)

    2015-07-15

    Highlights: • Co-coated carbonyl iron particles were prepared by electroless plating method. • The obvious weight gain of carbonyl iron was deferred to 400 °C after Co-coated. • The permeability of the Co-coated particle composite kept almost invariable. • Co-coated carbonyl iron composite reserves a better absorption after heat treatment. - Abstract: Co was successfully coated on the surface of flaky carbonyl iron particles using an electroless plating method. The morphologies, composition, as well as magnetic, antioxidation and electromagnetic properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), vibrating sample magnetometer (VSM), thermogravimetric (TG) and microwave network analyzer. TG curve shows that the obvious weight gain of carbonyl iron was deferred from 300 to 400 °C after Co-coated. In contrast to raw carbonyl iron, the Co-coated carbonyl iron shows better stability on electromagnetic properties after 300 °C heat treatment for 10 h, demonstrating that the Co coating can act as the protection of carbonyl iron.

  15. Photopromoted carbonylation of olefins with carbon dioxide and labelling studies with 13CO2 and 13CH3OH

    Institute of Scientific and Technical Information of China (English)

    YIN Jingmei; GAO Dabin; HU Jiehan; ZHOU Guangyun; JIA Yingping; WANG Xiangsheng

    2003-01-01

    Photopromoted carbonylation of olefins with carbon dioxide can be completed in ambient conditions (room temperatures and atmospheric pressure) by Co(OAc)2 catalysis. It was found that in carbonyl carbons of methyl ester of aliphatic acid 50% is from CO2 and the other 50% from CH3OH by labelling experimental with 13CO2 and 13CH3OH.

  16. Regiospecific oxidation of an alkyl group of aromatic amine to carbonyl group by DDQ in aq.medium

    Institute of Scientific and Technical Information of China (English)

    Madhav S. Mane; Ravi S. Balaskar; Sandip N. Gavade; Pramod N. Pabrekar; Murlidhar S. Shingare; Dhananjay V. Mane

    2011-01-01

    The regiospecific oxidation of alkyl group of both sterically hindered and unhindered aromatic amine to corresponding carbonyl compound was done in aq. medium by using DDQ. The optimized reaction protocol was found to be most simple, high yielding and novel method for oxidation of alkyl group of aromatic amine in to its carbonyl compound.

  17. Synthesis of 3,3'-carbonyl-bis(chromones) and their activity as mammalian alkaline phosphatase inhibitors.

    Science.gov (United States)

    Miliutina, Mariia; Ejaz, Syeda Abida; Iaroshenko, Viktor O; Villinger, Alexander; Iqbal, Jamshed; Langer, Peter

    2016-01-14

    Hitherto unknown 3,3'-carbonyl-bis(chromones) 8, dimeric chromones bridged by a carbonyl group, were prepared by reaction of chromone-3-carboxylic acid chloride with 3-(dimethylamino)-1- (2-hydroxyphenyl)-2-propen-1-ones 9. The method is generally applicable for the synthesis of novel symmetrical or non-symmetrical products which were found to inhibit mammalian alkaline phosphatases.

  18. Mitochondrial ATP synthase is a target for TNBS-induced protein carbonylation in XS-106 dendritic cells.

    Science.gov (United States)

    Je, Jeong Hwan; Lee, Tae Hyung; Kim, Dong Hyun; Cho, Young Hun; Lee, Ju Hee; Kim, Soo Chan; Lee, Sang-Kyou; Lee, Jaewon; Lee, Min-Geol

    2008-06-01

    ROS are produced in dendritic cells (DCs) during antigen presentation in contact hypersensitivity (CHS). As a result, ROS cause a number of nonenzymatic protein modifications, including carbonylation, which is the most widely used marker of oxidative stress. 2,4,6-Trinitrobenzene sulfonic acid (TNBS) is a well-characterized contact allergen that results in the formation of ROS. However, proteins that are carbonylated in DCs in response to TNBS have not been identified. To study ROS-dependent protein carbonylation in response to TNBS, we used the well-established mouse DC line, XS-106. We focused on the effects of TNBS on oxidation by examining selected oxidative markers. We identified TNBS-induced ROS and myeloperoxidase (MPO) proteins and demonstrated that the increase in ROS resulted in IL-12 production. The increase in oxidation was further confirmed by an oxidation-dependent increase in protein modifications, such as carbonylation. In fact, TNBS strongly induced carbonylation of mitochondrial adenosine triphosphate (ATP) synthase in XS-106 DCs, as determined by MALDI-TOF analysis and 2-D Western blotting. ROS production and protein carbonylation were confirmed in human monocyte-derived DCs (Mo-DCs). Furthermore, glutathione (GSH) decreased ROS and protein carbonylation in Mo-DCs. Carbonylation of ATP synthase in DCs may contribute to the pathophysiology of CHS.

  19. Real-time monitoring of methanol concentration using a shear horizontal surface acoustic wave sensor for direct methanol fuel cell without reference liquid measurement

    Science.gov (United States)

    Tada, Kyosuke; Nozawa, Takuya; Kondoh, Jun

    2017-07-01

    In recent years, there has been an increasing demand for sensors that continuously measure liquid concentrations and detect abnormalities in liquid environments. In this study, a shear horizontal surface acoustic wave (SH-SAW) sensor is applied for the continuous monitoring of liquid concentrations. As the SH-SAW sensor functions using the relative measurement method, it normally needs a reference at each measurement. However, if the sensor is installed in a liquid flow cell, it is difficult to measure a reference liquid. Therefore, it is important to establish an estimation method for liquid concentrations using the SH-SAW sensor without requiring a reference measurement. In this study, the SH-SAW sensor is installed in a direct methanol fuel cell to monitor the methanol concentration. The estimated concentration is compared with a conventional density meter. Moreover, the effect of formic acid is examined. When the fuel temperature is higher than 70 °C, it is necessary to consider the influence of liquid conductivity. Here, an estimation method for these cases is also proposed.

  20. Application of methanol synthesis reactor to large-scale plants

    Institute of Scientific and Technical Information of China (English)

    LOU Ren; XU Rong-liang; LOU Shou-lin

    2006-01-01

    The developing status of world large-scale methanol production technology is analyzed and Linda's JW low-pressure methanol synthesis reactor with uniform temperature is described. JW serial reactors have been successfully introduced in and applied in Harbin Gasification Plant and the productivity has been increased by 50% and now nine sets of equipments are successfully running in Harbin Gasification Plant,Jiangsu Xinya, Shandong Kenli,Henan Zhongyuan, Handan Xinyangguang,' Shanxi Weihua and Inner Mongolia Tianye. Now it has manufacturing the reactors of 300,000 t/a for Liaoning Dahua. Some solutions for the structure problems of 1000 ~5000 t/d methanol synthesis rectors are put forward.

  1. Recent Progress in Direct Partial Oxidation of Methane to Methanol

    Institute of Scientific and Technical Information of China (English)

    Qijian Zhang; Dehua He; Qiming Zhu

    2003-01-01

    The direct conversion of methane to methanol has attracted a great deal of attention for nearly a century since it was first found possible in 1902, and it is still a challenging task. This review article describes recent advancements in the direct partial oxidation of methane to methanol. The history of direct oxidation of methane and the difficulties encountered in the partial oxidation of methane to methanol are briefly summarized. Recently reported developments in gas-phase homogeneous oxidation, heterogeneous catalytic oxidation and liquid phase homogeneous catalytic oxidation of methane are reviewed.

  2. Study of Methanol Conversion over Fe-Zn-Zr Catalyst

    Institute of Scientific and Technical Information of China (English)

    Xiaoming Ni; Yisheng Tan; Yizhuo Han

    2007-01-01

    The methanol conversion over Fe-Zn-Zr catalyst was studied at 0.1 MPa and 280-360℃.The experimental results indicate that the main products of methanol conversion are methane and butane,and that other hydrocarbons are scarcely produced.All results show that propylene is most probably the olefin formed first in methanol conversion rather than ethene over Fe-Zn-Zr catalyst.Methane is formed from methoxy group,and C4 is possibly yielded on the surface from propylene through binding with a methoxy group.

  3. Novel Materials for High Efficiency Direct Methanol Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Carson, Stephen; Mountz, David; He, Wensheng; Zhang, Tao

    2013-12-31

    Direct methanol fuel cell membranes were developed using blends of different polyelectrolytes with PVDF. The membranes showed complex relationships between polyelectrolyte chemistry, morphology, and processing. Although the PVDF grade was found to have little effect on the membrane permselectivity, it does impact membrane conductivity and methanol permeation values. Other factors, such as varying the polyelectrolyte polarity, using varying crosslinking agents, and adjusting the equivalent weight of the membranes impacted methanol permeation, permselectivity, and areal resistance. We now understand, within the scope of the project work completed, how these inter-related performance properties can be tailored to achieve a balance of performance.

  4. Catalytic Conversion of Methanol by Oxidative Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    This study investigates the effects of addition of oxygen on the oxidative dehydrogenation (ODH) of methanol when a fluorotetrasilicic mica ion-exchanged with palladium (Pd2+-TSM) was used as the catalyst. The reaction proceeded at a very low temperature in the presence of oxygen, and HCOOCH3 was obtained at high selectivity. By calculating the equilibrium conversion, it has been shown that substantial ODH took place for HCOOCH3 production. Consequently, this reaction would make dehydrogenation the dominant reaction at equilibrium. Not all the H dissociated from CH3OH was converted to H2O by oxidation. It has been shown that the H2O was not produced from oxidative dehydrogenation by the direct reaction of CH3OH and O2 when an attempt was made to carry out oxidative dehydrogenation using an isotope oxygen trace method in the gas phase. Therefore, when CH3OH was converted to CO2 and dehydrogenated to HCOOCH3, the C-O bonds were not dissociated.

  5. Antidiabetic and antidiarrheal effects of the methanolic extract of Phyllanthus reticulatus leaves in mice

    Institute of Scientific and Technical Information of China (English)

    Mst Hajera Khatun; Mst Luthfun Nesa; Rafikul Islam; Farhana Alam Ripa; Al mamum; Shahin Kadir

    2014-01-01

    Objective: To assess the anti-diabetic and antidiarrheal activity of methanolic extract of Phyllanthus reticulates (P. reticulates) leaves in an animal model. Methods: Phytochemical screening of methanolic extract of P. reticulatus leaves has been performed. Antidiabetic activity have been done by OGTT, normoglycemic hyperglycemia and alloxan induced diabetic mice. Plant extracts (150 mg/kg and 300 mg/kg, b.w.) were administered orally in fasting glucose loaded mice with regard to normal control and in alloxan induced (110 mg/kg body weight i.p.) diabetic mice in comparison with reference drug Metformin hydrochloride (100 mg/kg) during 7 day test period. Antidiarrheal test was conducted by castor oil and magnesium sulfate. Results:Findings confirmed that the continuous post-treatment for 7 days with both extracts showed significant (P<0.05) hypoglycemic activity in OGTT, normoglycemic and alloxan induced mouse models. Castor oil and Magnesium sulfate induced diarrheal test of the extract (200 and 400 mg/kg) has given significant effect in compairing to control diarrheal group. Conclusion:Methanolic extract of P. reticulatus leaves have shown significant antidiabetic and antidiarrheal properties.

  6. Methanolic Extract of Dill Leaves Inhibits AGEs Formation and Shows Potential Hepatoprotective Effects in CCl4 Induced Liver Toxicity in Rat

    Directory of Open Access Journals (Sweden)

    Ebrahim Abbasi Oshaghi

    2017-01-01

    Full Text Available The research was aimed at evaluating the antiglycation, antioxidant, and hepatoprotective properties of methanolic extract of Anethum graveolens (dill. The antioxidant properties, photochemical characteristics, and antiglycation effects of dill extract were measured. Carbon tetrachloride-induced hepatotoxic rats were used to show the hepatoprotective activity of dill leaves. Different concentration of dill extract (0.032, 0.065, 0.125, 0.25, 0.5, and 1 mg/mL showed potential antioxidant ability. The extract of dill leaves significantly reduced AGEs formation and also fructosamine and protein carbonyl levels in rats’ liver. Thiol groups’ oxidation, amyloid cross-β, and protein fragmentation (P<0.001 significantly reduced in treated rats. Liver damage markers significantly reduced in dill-treated animals (P<0.05. Dill with potential antioxidant, antiglycation, and hepatoprotective effects can be suggested for treatment of diabetes complications.

  7. Visualizing ignition and combustion of methanol mixtures in a diesel engine; Methanol funmu no glow chakka to nensho no kashika

    Energy Technology Data Exchange (ETDEWEB)

    Inomoto, Y.; Harada, T.; Kusaka, J.; Daisho, Y.; Kihara, R.; Saito, T. [Waseda University, Tokyo (Japan)

    1997-10-01

    A glow-assisted ignition system tends to suffer from poor ignitability and slow flame propagation at low load in a direct-injection diesel engine fueled with methanol. To investigate the ignition process and improve such disadvantages, methanol sprays, their ignition and flames were visualized at high pressures and temperatures using a modified two-stroke engine. The results show that parameters influencing ignition, the location of a glow-plug, swirl level, pressure and temperature are important. In addition, a full kinetics calculation was conducted to predict the delay of methanol mixture ignition by taking into account 39 chemical species and 157 elementary reactions. 3 refs., 9 figs.

  8. Efficient preparation of carbamates by Rh-catalysed oxidative carbonylation: unveiling the role of the oxidant.

    Science.gov (United States)

    Iturmendi, Amaia; Iglesias, Manuel; Munárriz, Julen; Polo, Victor; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-12-22

    The synthesis of a wide variety of carbamates from amines, alcohols and carbon monoxide has been achieved by means of a Rh-catalysed oxidative carbonylation reaction that uses Oxone as a stoichiometric oxidant. In-depth studies on the reaction mechanism shed light on the intimate role of Oxone in the catalytic cycle.

  9. Weak carbonyl-methyl intermolecular interactions in acetone clusters explored by IR plus VUV spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Guan, Jiwen [MOE Key Laboratory of Laser Life Science and Institute of Laser Life Science, College of Biophotonics, South China Normal University, Guangzhou 510631 (China); Hu, Yongjun, E-mail: yjhu@scnu.edu.cn [MOE Key Laboratory of Laser Life Science and Institute of Laser Life Science, College of Biophotonics, South China Normal University, Guangzhou 510631 (China); Xie, Min [MOE Key Laboratory of Laser Life Science and Institute of Laser Life Science, College of Biophotonics, South China Normal University, Guangzhou 510631 (China); Bernstein, Elliot R. [Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872 (United States)

    2012-09-11

    Highlights: Black-Right-Pointing-Pointer The carbonyl overtone of acetone clusters is observed by IR-VUV spectroscopy. Black-Right-Pointing-Pointer Acetone molecules in the dimer are stacked with an antiparallel way. Black-Right-Pointing-Pointer The structure of the acetone trimer and the tetramer are the cyclic structures. Black-Right-Pointing-Pointer The carbonyl groups would interact with the methyl groups in acetone clusters. Black-Right-Pointing-Pointer These weak interactions are further confirmed by H/D substitution experiment. -- Abstract: Size-selected IR-VUV spectroscopy is employed to detect vibrational characteristics in the region 2850 {approx} 3550 cm{sup -1} of neutral acetone and its clusters (CH{sub 3}COCH{sub 3}){sub n} (n = 1-4). Features around 3440 cm{sup -1} in the spectra of acetone monomer and its clusters are assigned to the carbonyl stretch (CO) overtone. These features red-shift from 3455 to 3433 cm{sup -1} as the size of the clusters increases from the monomer to the tetramer. Based on calculations, the experimental IR spectra in the C=O overtone region suggest that the dominant structures for the acetone trimer and tetramer should be cyclic in the supersonic expansion sample. This study also suggests that the carbonyl groups interact with the methyl groups in the acetone clusters. These weak interactions are further confirmed by the use of deuterium substitution.

  10. Hydration and hydrogen bonding of carbonyls in dimyristoyl-phosphatidylcholine bilayer.

    Science.gov (United States)

    Volkov, Victor V; Nuti, Francesca; Takaoka, Yuji; Chelli, Riccardo; Papini, Anna Maria; Righini, Roberto

    2006-07-26

    We combine two-color ultrafast infrared spectroscopy and molecular dynamics simulation to investigate the hydration of carbonyl moieties in a dimyristoyl-phosphatidylcholine bilayer. Excitation with femtosecond infrared pulses of the OD stretching mode of heavy water produces a time dependent change of the absorption band of the phospholipid carbonyl groups. This intermolecular vibrational coupling affects the entire C=O band, thus suggesting that the optical inhomogeneity of the infrared response of carbonyl in phospholipid membranes cannot be attributed to the variance in hydration. Both the experimental and the theoretical results demonstrate that sn-1 carbonyl has a higher propensity to form hydrogen bonds with water in comparison to sn-2. The time-resolved experiment allows following the evolution of the system from a nonequilibrium localization of energy in the OD stretching mode to a thermally equilibrated condition and provides the characteristic time constants of the process. The approach opens a new opportunity for investigation of intermolecular structural relations in complex systems, like membranes, polymers, proteins, and glasses.

  11. Additive role of attapulgite nanoclay on carbonyl iron-based magnetorheological suspension

    CSIR Research Space (South Africa)

    Chae, HS

    2014-09-01

    Full Text Available -1 Colloid Polym Sci DOI 10.1007/s00396-014-3389-3 Additive role of attapulgite nanoclay on carbonyl iron- based magnetorheological suspension Hyun Sik Chae1, Shang Hao Piao1, Arjun Maity2 and Hyoung Jin Choi1 1Department of Polymer Science...

  12. Synthesis of an Epoxide Carbonylation Catalyst: Exploration of Contemporary Chemistry for Advanced Undergraduates

    Science.gov (United States)

    Getzler, Yutan D. Y. L.; Schmidt, Joseph A. R.; Coates, Geoffrey W.

    2005-01-01

    A class of highly active, well-defined compounds for the catalytic carbonylation of epoxides and aziridines to beta-lactones and beta-lactams are introduced. The synthesis of one of the catalysts involves a simple imine condensation to form the ligand followed by air-sensitive metalation and salt metathesis steps.

  13. Palladium-catalyzed carbonylative synthesis of quinazolinones from 2-aminobenzamide and aryl bromides.

    Science.gov (United States)

    Wu, Xiao-Feng; He, Lin; Neumann, Helfried; Beller, Matthias

    2013-09-16

    C from CO! A straightforward procedure for the carbonylative synthesis of quinazolinones from readily available 2-aminobenzamide and aryl bromides has been developed. In the presence of a palladium catalyst, various quinazolinones were produced in moderate to excellent yields. Remarkably, no chromatography was needed for purification (see scheme).

  14. Palladium-catalyzed carbonylation reaction of aryl bromides with 2-hydroxyacetophenones to form flavones.

    Science.gov (United States)

    Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias

    2012-10-01

    Flavone of the month: a general and efficient method for the palladium-catalyzed carbonylative synthesis of flavones has been developed. Starting from aryl bromides and 2-hydroxyacetophenones, the corresponding flavones have been isolated in good yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Palladium-catalyzed carbonylative sonogashira coupling of aryl bromides using near stoichiometric carbon monoxide

    DEFF Research Database (Denmark)

    Neumann, Karoline T.; Laursen, Simon R.; Lindhardt, Anders T.

    2014-01-01

    A general procedure for the palladium-catalyzed carbonylative Sonogashira coupling of aryl bromides is reported, using near stoichiometric amounts of carbon monoxide. The method allows a broad substrate scope in moderate to excellent yields. The formed alkynone motive serves as a platform...

  16. Chemo- and Stereoselective Reduction of Polyfunctional Carbonyl Compounds by Mucor rouxii

    Directory of Open Access Journals (Sweden)

    Constanza P. Mangone

    2000-03-01

    Full Text Available Several polyfunctional carbonyl compounds, such as α- and β-ketoesters, were chemo- and stereoselectively reduced by Mucor rouxii cultures in water and in organic solvents. Results show that reductions can be carried out in a variety of organic solvents.

  17. Protein carbonylation and heat shock proteins in human skeletal muscle: relationships to age and sarcopenia.

    Science.gov (United States)

    Beltran Valls, Maria R; Wilkinson, Daniel J; Narici, Marco V; Smith, Kenneth; Phillips, Bethan E; Caporossi, Daniela; Atherton, Philip J

    2015-02-01

    Aging is associated with a gradual loss of muscle mass termed sarcopenia, which has significant impact on quality-of-life. Because oxidative stress is proposed to negatively impact upon musculoskeletal aging, we investigated links between human aging and markers of oxidative stress, and relationships to muscle mass and strength in young and old nonsarcopenic and sarcopenic adults. Sixteen young and 16 old males (further subdivided into "old" and "old sarcopenic") were studied. The abundance of protein carbonyl adducts within skeletal muscle sarcoplasmic, myofibrillar, and mitochondrial protein subfractions from musculus vastus lateralis biopsies were determined using Oxyblot immunoblotting techniques. In addition, concentrations of recognized cytoprotective proteins (eg, heat shock proteins [HSP], αβ-crystallin) were also assayed. Aging was associated with increased mitochondrial (but not myofibrillar or sarcoplasmic) protein carbonyl adducts, independently of (stage-I) sarcopenia. Correlation analyses of all subjects revealed that mitochondrial protein carbonyl abundance negatively correlated with muscle strength ([1-repetition maximum], p = .02, r (2) = -.16), but not muscle mass (p = .13, r (2) = -.08). Abundance of cytoprotective proteins, including various HSPs (HSP 27 and 70), were unaffected by aging/sarcopenia. To conclude, these data reveal that mitochondrial protein carbonylation increases moderately with age, and that this increase may impact upon skeletal muscle function, but is not a hallmark of (stage-I) sarcopenia, per se. © The Author 2014. Published by Oxford University Press on behalf of The Gerontological Society of America.

  18. Proteomic and carbonylation profile analysis of rat skeletal muscles following acute swimming exercise.

    Directory of Open Access Journals (Sweden)

    Francesca Magherini

    Full Text Available Previous studies by us and other groups characterized protein expression variation following long-term moderate training, whereas the effects of single bursts of exercise are less known. Making use of a proteomic approach, we investigated the effects of acute swimming exercise (ASE on protein expression and carbonylation patterns in two hind limb muscles: the Extensor Digitorum Longus (EDL and the Soleus, mostly composed of fast-twitch and slow-twitch fibres, respectively. Carbonylation is one of the most common oxidative modifications of proteins and a marker of oxidative stress. In fact, several studies suggest that physical activity and the consequent increase in oxygen consumption can lead to increase in reactive oxygen and nitrogen species (RONS production, hence the interest in examining the impact of RONS on skeletal muscle proteins following ASE. Results indicate that protein expression is unaffected by ASE in both muscle types. Unexpectedly, the protein carbonylation level was reduced following ASE. In particular, the analysis found 31 and 5 spots, in Soleus and EDL muscles respectively, whose carbonylation is reduced after ASE. Lipid peroxidation levels in Soleus were markedly reduced as well. Most of the decarbonylated proteins are involved either in the regulation of muscle contractions or in the regulation of energy metabolism. A number of hypotheses may be advanced to account for such results, which will be addressed in future studies.

  19. NMR Studies of Structure-Reactivity Relationships in Carbonyl Reduction: A Collaborative Advanced Laboratory Experiment

    Science.gov (United States)

    Marincean, Simona; Smith, Sheila R.; Fritz, Michael; Lee, Byung Joo; Rizk, Zeinab

    2012-01-01

    An upper-division laboratory project has been developed as a collaborative investigation of a reaction routinely taught in organic chemistry courses: the reduction of carbonyl compounds by borohydride reagents. Determination of several trends regarding structure-activity relationship was possible because each student contributed his or her results…

  20. Synthesis, spectroscopic characterizations, crystal structures and DFT studies of nalidixic acid carbonyl hydrazones derivatives

    Science.gov (United States)

    Bergamini, F. R. G.; Ribeiro, M. A.; Lancellotti, M.; Machado, D.; Miranda, P. C. M. L.; Cuin, A.; Formiga, A. L. B.; Corbi, P. P.

    2016-09-01

    This article describes the synthesis and characterization of the 1-ethyl-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazide (hzd) and six carbonyl hydrazones derivatives of the nalidixic with 1H-pyrrol-2-ylmethylidene (hpyrr), 1H-imidazol-2-ylmethylidene (h2imi), pyridin-2-ylmethylidene (h2py), pyridin-3-ylmethylidene (h3py), pyridin-4-ylmethylidene(h4py) and (2-hydroxyphenyl)methylidene (hsali). The carbonyl hydrazones were characterized by elemental and ESI-QTOF-MS analyses, IR and detailed NMR spectroscopic measurements. The 2D NMR experiments allowed the unambiguous assignment of the hydrogen, carbon and nitrogen atoms, which have not been reported for nalidixic acid carbonyl hydrazone derivatives so far. Crystal structures of hzd and the new carbonyl hydrazones h2imi, hpyrr and h3py were determined by X-ray diffraction studies. Although the synthesis of hzd was reported decades ago, the hzd crystal structure have not been reported yet. Geometric optimizations of all the characterized structures were performed with the aid of DFT studies. Despite the fact that the hydrazones with 2-pyridine carboxylic acid (h2py) and salicyl aldehyde (hsali) were already reported by literature, a detailed spectroscopic study followed by DFT studies are also reported for such compounds in this manuscript. Antimicrobial studies of the compounds are also presented.

  1. A comprehensive evaluation of the toxicology of cigarette ingredients: aromatic carbonyl compounds.

    Science.gov (United States)

    Coggins, Christopher R E; Sena, Erica J; Langston, Timothy B; Oldham, Michael J

    2011-06-01

    Aromatic carbonyls are typically used in the processing or flavoring of tobacco used in the manufacture of cigarettes. A battery of tests was used to compare the toxicity of mainstream smoke from experimental cigarettes containing different added levels of aromatic carbonyl compounds. Ten aromatic carbonyl compounds, nine of which have been reported in tobacco or in tobacco smoke, were added individually to experimental cigarettes at three different levels. The tenth compound, not found naturally in tobacco, was 2-phenoxyethyl isobutyrate. The lowest target inclusion level was 100 ppm and the highest was 10,000 ppm. Smoke from each of the 10 experimental cigarette types was evaluated using analytical chemistry, in vitro cytotoxicity, and mutagenicity testing. For one of the compounds, ethyl vanillin, a 90-day smoke inhalation study using rats was also performed. Smoke chemistry was effectively unchanged by the addition of any of the compounds. Cytotoxicity, assessed by the neutral red uptake assay and using both gas-vapor and particulate phases of smoke, was unaffected by the addition of any of the test compounds. Mutagenicity, assessed by five strains of Salmonella typhimurium treated with smoke condensate, also was unaffected by any of the test compounds. In the rat inhalation study, there were effectively no differences between cigarettes without added ethyl vanillin and cigarettes containing ~8000 ppm of ethyl vanillin. Even at the exaggerated inclusion levels in cigarette tobacco used in these tests, no adverse toxicological responses occurred for any of aromatic carbonyl compounds tested.

  2. Reductive Deoxygenation of Carbonyl to Methylene by LiAlH4/InBr3

    Institute of Scientific and Technical Information of China (English)

    Nan Yan FU; Xue Mei ZHAO; Yao Feng YUAN; Ji Tao WANG

    2003-01-01

    The reductive deoxygenation of aldehydes and ketones into the corresponding alkanes isaccomplished by LiA1H4 in the presence of Lewis acid InBr3. It provides a convenient method tocomplete the transformation from carbonyl compounds to alkanes.

  3. Preparation and characterization of carbonyl iron/glass composite absorber as matched load for isolator

    Science.gov (United States)

    Feng, Yongbao; Li, Yujiao; Qiu, Tai

    2012-09-01

    Composite absorbers made from 66 wt% carbonyl iron and 34 wt% low melting point glass powder were prepared by a pressureless sintering technique in a nitrogen atmosphere. Apparent porosity and bending strength of the as-prepared composites were investigated. The microstructure, heat resisting properties and electromagnetic properties were characterized by scanning electron microscopy, thermal gravimetric analysis-differential scanning calorimetry and vector network analyzer. The results show that the carbonyl iron/glass composite absorbers were difficult to densify. As the sintering temperature and soaking time increased, the apparent porosity first decreased and then increased, whereas the bending strength showed the opposite change. The composite absorber sintered at 520 °C for 40 min achieved the minimum apparent porosity of 13.08% and the highest bending strength of 52 MPa. Compared to the carbonyl iron/silicone rubber absorber, the carbonyl iron/glass composite absorber exhibited better heat resisting properties, and the initial oxidation temperature was increased about 200 °C. The composite absorber with a thickness of 1.25 mm showed a good microwave absorbing property in 8-12 GHz.

  4. NMR Studies of Structure-Reactivity Relationships in Carbonyl Reduction: A Collaborative Advanced Laboratory Experiment

    Science.gov (United States)

    Marincean, Simona; Smith, Sheila R.; Fritz, Michael; Lee, Byung Joo; Rizk, Zeinab

    2012-01-01

    An upper-division laboratory project has been developed as a collaborative investigation of a reaction routinely taught in organic chemistry courses: the reduction of carbonyl compounds by borohydride reagents. Determination of several trends regarding structure-activity relationship was possible because each student contributed his or her results…

  5. α-Carbonyl Radical Cyclization for the Total Synthesis of Natural Products

    Institute of Scientific and Technical Information of China (English)

    SHA Chin-Kang; CHIU Rei-Torng; LIH Shinn-Horng; SANTHOSH K. C.; CHANG Ching-Jung; TSENG Wei-Hong; HO Wen-Yueh

    2003-01-01

    @@ Intramolecular radical cyclization reactions are now used routinely to synthesize carbocyclic and heterocyclicstructures. We have reported that α-carbonyl radicals 1, generated from the corresponding iodo ketones or enones,underwent intramolecular radical cyclization smoothly to afford products 2. [1,2

  6. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  7. Study on the Carbonyl Iron Powder Based Nano-Composite Radar Wave Absorbing Coatings

    Institute of Scientific and Technical Information of China (English)

    HUANG Dong-zhen; WANG Zhi-hui; LV Yan-hong; HU Chuan-xin; LI Wan-zhi; LIANG wen-ting; YAO Jun-min

    2004-01-01

    With the rapid development of stealth technique, carbonyl iron powder is regarded as an ideal radar absorbing material. In this paper, radar absorbing properties of carbonyl iron powder was investigated by using nano composite and macroscopic multi- layer composite approach. The machine- chemistry composite methods were employed during the experiment to produce nano composite absorbent. Two carbonyl iron powders named HP1, HP2 and nano powder named HP3 were employed. Absorbents were obtained by adding 10% HP3 powder with average size of 28 nm to the HP1 and HP2 carbonyl iron powders by weight respectively. By a series of composite techniques, sample plate with the radar absorbing coating was prepared. Compared with the single coating, the wave absorbing properties were significantly improved. The working band in which the wave reflectivity was less than 5 db was 4.8 ~ 18 GHz with the coating thickness of 1.0 mm. The lowest reflectivity was found to be 12.34 db at 8 GHz. The wave absorbing coating with thin thickness,broadband and strong absorbing properties was obtained.

  8. Direct photolysis of carbonyl compounds dissolved in cloud and fog~droplets

    Science.gov (United States)

    Epstein, S. A.; Tapavicza, E.; Furche, F.; Nizkorodov, S. A.

    2013-09-01

    Gas-phase photolysis is an important tropospheric sink for many carbonyl compounds; however the significance of direct photolysis of these compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived effective Henry's law constants, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will (or will not) have competitive aqueous photolysis rates. We also present molecular dynamics simulations designed to estimate gas- and aqueous-phase extinction coefficients of unstudied atmospherically relevant compounds found in d-limonene and isoprene secondary organic aerosol. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water-soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only two out of the 92 carbonyl compounds investigated, pyruvic acid and acetoacetic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α,β-conjugation that were investigated, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected under typical atmospheric conditions.

  9. Peculiar features of composition of carbonyl components of surface lipids in aquatic plants

    OpenAIRE

    І. О. Alexeevs’ka; V. M. Shepelenko; N. I. Shtemenko

    2006-01-01

    Carbonyl components content of aquatic plants’ surface lipids has been studied. High concentration of oxo-compounds in surface lipids of aquatic plants has been shown. It could reach 60 % of total value. Sufficient heterogeneity of surface lipids has been demonstrated. Unsaturated character of oxo-components in aquatic plants’ surface lipids has been assumed in the present work.

  10. Levels, sources and health risks of carbonyls and BTEX in the ambient air of Beijing, China.

    Science.gov (United States)

    Zhang, Yujie; Mu, Yujing; Liu, Junfeng; Mellouki, Abdelwahid

    2012-01-01

    The atmospheric concentrations of carbonyls and BTEX (benzene, toluene, ethylbenzene, m,p-xylene and o-xylene) were measured simultaneously at a same sampling site in Beijing from September 2008 to August 2010. The average concentrations of the total measured carbonyls during autumn, winter, spring, and summer were 37.7, 31.3, 39.7, 50.5 microg/m3, respectively, and maximal values for their diurnal variations usually happened at noontime. In contrast to carbonyls, the average concentrations of the total measured BTEX during the four seasons were 27.2, 31.9, 23.2, 19.1 microg/m3, respectively, and minimal values for their diurnal variations always occurred in the early afternoon. The average concentration for carbonyls increased about 24% from September 2008-August 2009 to September 2009-August 2010, for BTEX, increased about 15%. Integrated life time cancer risks for three carcinogens (benzene, formaldehyde and acetaldehyde) in Beijing exceeded the value of 1E-06, and the hazard quotient (HQ) of non-cancer risk of exposure to formaldehyde exceeded unity.

  11. The Solvent Mixture Sensitivity of Carbonyl Stretching Frequencies of 2-Pyrrolidinones and Related Compounds

    NARCIS (Netherlands)

    Perjessy, A.; Engberts, J.B.F.N.; Blandamer, M.J.

    1995-01-01

    The carbonyl stretching frequencies of 1-substituted 2-pyrrolidinones and related compounds were measured in binary mixtures of hexane-CDCl3 and acetonitrile-D2O and plotted against the mole fraction of the less polar co-solvent The v(C=O) vs. mole fraction correlations enabled to recognize and assi

  12. The carbonylation of phenyl bromide and its derivatives under visible light irradiation

    Institute of Scientific and Technical Information of China (English)

    Wen Hui Zhong; Ying Na Cui; Shen Min Li; Ying Ping Jia; Jing Mei Yin

    2012-01-01

    The carbonylation of phenyl bromide catalyzed by Co(OAc)2 has been investigated with PhCOPh as a sensitizer under visible light in the presence of basic additive.With strong base CH3ONa,PhCOOCH3 is produced in 70% yield with 100% selectivity,the similar results are also obtained with a stronger base (CH3)3CONa.However,with another strong base NaOH,the yield of the ester is only 40%.On the other hand,with weak base NaOAc or (n-C4Hg)3N,phenyl bromide cannot be carbonylated.The results of carbonylation of the six substituted phenyl bromides suggest that the activities of o,m,p-BrC6H4CH3 are similar to phenyl bromide,while the activities of o,m,p-BrC6H4Cl are higher with the high yields (≥93%) of the corresponding chloro-esters.In addition,the relative position of bromine and chlorine or methyl on phenyl ring has little effect on the activity of the carbonylation.

  13. Analysis of selected carbonyl oxidation products in wine by liquid chromatography with diode array detection.

    Science.gov (United States)

    Elias, Ryan J; Laurie, V Felipe; Ebeler, Susan E; Wong, Jon W; Waterhouse, Andrew L

    2008-09-19

    A high performance liquid chromatography (HPLC) method for the detection and quantitation of acetaldehyde, glyceraldehyde, pyruvic acid, 2-ketoglutaric acid, and formaldehyde in wine, based on the formation of the 2,4-dinitrophenylhydrazones, is presented. These carbonyl compounds often result from the chemical oxidation of major wine components, and are known to affect flavor and color stability. Their analysis in wine is complicated due to their instability and their tendency to react reversibly with bisulfite to form alpha-hydroxysulfonates. Published methods that break down the sulfonates for the quantitation of total carbonyls in wine involve alkaline hydrolysis of sulfite-bound carbonyls, but we show, for the first time, that this alkaline treatment step significantly increases the concentration of carbonyls during analysis. A solution based on oxygen exclusion is described. The technique offers good specificity, reproducibility (%RSD 0.45-10.6), and limits of detection (1.29-7.53microgL(-1)). The method was successfully used to monitor concentration changes of these compounds in both white and red wines.

  14. Catalyst for the carboxylation of carbonylated compounds in the gas phase

    DEFF Research Database (Denmark)

    2013-01-01

    The invention relates to a catalyst for the carboxylation of carbonylated compounds in the gas phase. Said catalyst consists of a metal complex which is active when the carboxylation is under reaction conditions and an organic salt, which is solid under normal conditions and liquid under reaction...

  15. Palladium-Catalyzed Carbonylation of Primary Amines in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 江焕峰; 陈鸣才

    2001-01-01

    The chemoselectity of the palladimm-catalyzed carbonylation of amines was affected by the addition of MeOH in supercritical carbon dioxide. The results show different selectivity in supercritical carbon dioxide CO2(sc) from that in alcohol.Methyl carbamate and its derivatives were obtained in high yields in CO2(sc).

  16. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...

  17. N-Heterocyclic Carbene-Palladium Complex Catalyzed Oxidative Carbonylation of Amines to Ureas

    Institute of Scientific and Technical Information of China (English)

    ZHENG,Shu-Zhan; PENG,Xin-Gao; LIU,Jian-Ming; SUN,Wei; XIA,Chun-Gu

    2007-01-01

    Palladium carbene shows high efficiency without any promoter on oxidative carbonylation of amines to ureas and a new type of palladium carbene complex containing both an aniline and an NHC ligands was found to be the active species for the reaction.

  18. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin;

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated...

  19. [pi] Backbonding in Carbonyl Complexes and Carbon-Oxygen Stretching Frequencies: A Molecular Modeling Exercise

    Science.gov (United States)

    Montgomery, Craig D.

    2007-01-01

    An exercise is described that has illustrated the effect of various factors on [pi] backbonding to carbonyl ligands, where the students can view the molecular orbitals corresponding to the M-CO [pi] interaction as well as the competing interaction between the metal and co-ligands. The visual and hands-on nature of the modeling exercise has helped…

  20. Towards a General Understanding of Carbonyl-Stabilised Ammonium Ylide-Mediated Epoxidation Reactions.

    Science.gov (United States)

    Novacek, Johanna; Roiser, Lukas; Zielke, Katharina; Robiette, Raphaël; Waser, Mario

    2016-08-01

    The key factors for carbonyl-stabilised ammonium ylide-mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine-based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.