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Sample records for cyanamides

  1. The dimers of cyanamide

    NASA Astrophysics Data System (ADS)

    Moffat, J. B.

    Ab initio calculations have been performed on various dimeric forms of cyanamide. The "nondissociative" dimerization of cyanamide leads to cyclic molecules all of which are unstable with respect to cyanamide. However, the molecules produced by "dissociative" dimerization are stable relative to cyanamide. Dicyandiamide is found to be the most stable of nine dimeric configurations.

  2. Safe transport of cyanamide.

    PubMed

    Wehrstedt, Klaus-Dieter; Wildner, Werner; Güthner, Thomas; Holzrichter, Klaus; Mertschenk, Bernd; Ulrich, Armin

    2009-10-30

    For many years cyanamide (CAS no. 420-04-2) was not commercially available due to its unstable nature. Since about 1965 the former "Süddeutsche Kalkstickstoffwerke AG" (current name: AlzChem Trostberg GmbH) developed a special stabilizing system. It was to be investigated to which Class (e.g. "Corrosive Substances", Class 8) or Division (e.g. "Self-reactive Substances", Division 4.1) of the International Regulations for the Transport of Dangerous Goods cyanamide (pure or as a 50% solution in water) should be assigned and based on this which maximum quantities are allowed to transport e.g. in tanks. Cyanamide is used for the synthesis of pharmaceutical and agrochemical actives, biocides, dyestuffs and fine chemicals. During the last years cyanamide was tested at BAM and AQura. The results and an appraisal are presented in this paper. Thus, cyanamide should be classified according to the UN Recommendations on the Transport of Dangerous Goods in Class 8, UN number 2922 (50% solution in water) and UN number 2923 (pure substance) respectively, packaging group III, danger labels 8+6.1. Cyanamide, 50% solution in water, can be transported in portable tanks under specific conditions.

  3. Determination of Calcium Cyanamide in Crude Calcium Cyanamide

    DTIC Science & Technology

    1981-01-01

    the cold finger surface. After sublimation, the pure cyanamide was quickly dissolved in 100 mL of water. Ten percent ammoniacal silver nitrate was...glacial acetic acid to the acetate solution and dilute to 1 L with distilled water. Silver nitrate solution - Add sufficient concentrated ammonium...addition of ammonium hydroxide. Dilute the solution to 1 L with water. Ferric alum indicator - Dissolve 140 g of ferric ammonium sulfate, reagent

  4. Evidence of cyanamide production in hairy vetch Vicia villosa.

    PubMed

    Kamo, Tsunashi; Kato, Kenji; Hiradate, Syuntaro; Nakajima, Eri; Fujii, Yoshiharu; Hirota, Mitsuru

    2006-05-10

    Cyanamide (NH(2)CN) has recently been isolated as a plant growth inhibitor from Vicia villosa, which is the first discovery of cyanamide from natural sources. To reveal the presence of the biosynthesized cyanamide in plants, 3.4 mM potassium ((15)N)nitrate was administered to 15- to 35-day-old plants of V. villosa, from which the cyanamide was purified and subjected to GC/MS analysis. The isotopic ratio (15)N/((14)N + (15)N) of the cyanamide was calculated to be 0.143, while that of the cyanamide extracted from V. villosa grown in the presence of a natural N source was 0.0065. The (15)N-enrichment proved de novo biosynthesis of cyanamide.

  5. Two Duplicated Genes DDI2 and DDI3 in Budding Yeast Encode a Cyanamide Hydratase and Are Induced by Cyanamide*

    PubMed Central

    Li, Jia; Biss, Michael; Fu, Yu; Xu, Xin; Moore, Stanley A.; Xiao, Wei

    2015-01-01

    Two DNA damage-inducible genes in Saccharomyces cerevisiae, DDI2 and DDI3, are identical and encode putative HD domain-containing proteins, whose functions are currently unknown. Because Ddi2/3 also shows limited homology to a fungal cyanamide hydratase that converts cyanamide to urea, we tested the enzymatic activity of recombinant Ddi2. To this end, we developed a novel enzymatic assay and determined that the Km value of the recombinant Ddi2/3 for cyanamide is 17.3 ± 0.05 mm, and its activity requires conserved residues in the HD domain. Unlike most other DNA damage-inducible genes, DDI2/3 is only induced by a specific set of alkylating agents and surprisingly is strongly induced by cyanamide. To characterize the biological function of DDI2/3, we sequentially deleted both DDI genes and found that the double mutant was unable to metabolize cyanamide and became much more sensitive to growth inhibition by cyanamide, suggesting that the DDI2/3 genes protect host cells from cyanamide toxicity. Despite the physiological relevance of the cyanamide induction, DDI2/3 is not involved in its own transcriptional regulation. The significance of cyanamide hydratase activity and its induced expression is discussed. PMID:25847245

  6. Low-energy electron scattering from cyanamide

    NASA Astrophysics Data System (ADS)

    Wang, Kedong; Guo, Shuangcheng; Meng, Ju; Huang, Xiaotian; Wang, Yongfeng

    2016-09-01

    The low-energy electron collisions with cyanamide molecule are investigated by using the UK molecular R -matrix codes for electron energies ranging from 0.01 eV to 10 eV. Three models including static-exchange, static-exchange plus polarization, and close-coupling (CC) approximations are employed to reveal the dynamic interaction. Elastic (integrated and differential), momentum-transfer, and excitation cross sections from the ground state to the three low-lying electron excited states have been presented. Two shape resonances, two core-excited resonances, and two Feshbach resonances are detected in the CC approximation. The role of active space in the target and scattering problem including the resonances is discussed. The precise resonance parameters are found to be sensitive to the treatment of polarization effects employed. These resonances may be responsible for the fragments observed in a recent experiment of the dissociative electron attachments to cyanamide. Since the cyanamide molecule has a large permanent dipole moment, a Born closure procedure is used to account for the contribution of partial waves higher than l =4 to obtain converged cross sections.

  7. PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE CYANAMIDE (LN) OVEN BUILDING, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE CYANAMIDE (L-N) OVEN BUILDING, AMMONIA SPHERES IN FOREGROUND. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  8. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING NORTHWEST AT A C. 1932 CHICAGO PNEUMATIC COMPRESSOR. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  9. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING WEST AT INGERSOLL-RAND COMPRESSORS #BE565 & 564. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  10. PERSPECTIVE VIEW LOOKING NORTHWEST AT CYANAMIDE (LN) COOLING SHED, MILL ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    PERSPECTIVE VIEW LOOKING NORTHWEST AT CYANAMIDE (L-N) COOLING SHED, MILL BUILDING AND CONVEYOR BRIDGE. NOTE CORNERSTONE ON THE MILL BUILDING. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  11. 65. INTERIOR VIEW OF THE LIMENITROGEN (CALCIUM CYANAMIDE) OVEN BUILDING, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    65. INTERIOR VIEW OF THE LIME-NITROGEN (CALCIUM CYANAMIDE) OVEN BUILDING, LOOKING AT 2 BANKS OF OVENS. MARCH 2, 1919. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  12. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING NORTHEAST AT A C. 1932 CHICAGO PNEUMATIC COMPRESSOR. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  13. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING SOUTHEAST AT INGERSOLL-RAND COMPRESSORS #BE565 & 564. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  14. The rotation-inversion spectrum of cyanamide

    NASA Astrophysics Data System (ADS)

    Read, W. G.; Cohen, E. A.; Pickett, H. M.

    1986-02-01

    The microwave, millimeter, and submillimeter spectra of cyanamide were studied to better determine the inversion-rotation parameters of the ground and first excited states. A total of 146 transitions including 64 rotation-inversion frequencies between 7 and 500 GHz have been measured at this laboratory. An additional 118 a-type R-branch transitions between 139 and 262 GHz measured by Möller and Winnewisser at Justus Liebig University, Giessen, have also been included in the analysis. The data were fitted to a Hamiltonian which contains a rotation-inversion interaction as an off-diagonal inertial term. The interpretation of the interaction term in terms of the molecular structure and inversion motion is in good agreement with experiment. Higher order rotational effects were handled with a Watson " S" centrifugal distortion Hamiltonian. The inversion splitting, rotational constants, centrifugal distortion constants, nitrogen nuclear quadrupole coupling tensors including χac for the amino nitrogen, and the a and c components of the electric dipole moment are reported.

  15. First isolation of natural cyanamide as a possible allelochemical from hairy vetch Vicia villosa.

    PubMed

    Kamo, Tsunashi; Hiradate, Syuntaro; Fujii, Yoshiharu

    2003-02-01

    Cyanamide was isolated from the leaves and stems of hairy vetch (Vicia villosa), guided by plant growth inhibitory activity against lettuce (Lectuca sativa) seedlings. A large proportion of the inhibitory activity in the crude extract was explained by the presence of cyanamide, suggesting it to be a possible allelochemical in this species. The amount in a 9-day-old seedling, which had been grown without nutrients, reached approx. 40 times that of a nongerminated seed, demonstrating cyanamide biosynthesis in the seedlings. This is the first report on the isolation of a possible allelochemical from hairy vetch and also of the finding of cyanamide as a natural product.

  16. Non-precious metal catalysts prepared from precursor comprising cyanamide

    SciTech Connect

    Chung, Hoon Taek; Zelenay, Piotr

    2015-10-27

    Catalyst comprising graphitic carbon and methods of making thereof; said graphitic carbon comprising a metal species, a nitrogen-containing species and a sulfur containing species. A catalyst for oxygen reduction reaction for an alkaline fuel cell was prepared by heating a mixture of cyanamide, carbon black, and a salt selected from an iron sulfate salt and an iron acetate salt at a temperature of from about 700.degree. C. to about 1100.degree. C. under an inert atmosphere. Afterward, the mixture was treated with sulfuric acid at elevated temperature to remove acid soluble components, and the resultant mixture was heated again under an inert atmosphere at the same temperature as the first heat treatment step.

  17. Process for decontaminating radioactive liquids using a calcium cyanamide-containing composition. [Patent application

    DOEpatents

    Silver, G.L.

    1980-09-24

    The present invention provides a process for decontaminating a radioactive liquid containing a radioactive element capable of forming a hydroxide. This process includes the steps of contacting the radioactive liquid with a decontaminating composition and separating the resulting radioactive sludge from the resulting liquid. The decontaminating composition contains calcium cyanamide.

  18. Inhibition of tomato (Solanum lycopersicum L.) root growth by cyanamide is not always accompanied with enhancement of ROS production

    PubMed Central

    Soltys, Dorota; Gniazdowska, Agnieszka; Bogatek, Renata

    2013-01-01

    Mode of action of allelochemicals in target plants is currently widely studied. Cyanamide is one of the newly discovered allelochemical, biosynthesized in hairy vetch. Recently, it has been recognized that cyanamide is plant growth inhibitor, which affects mitosis in root tip cells and causes,e.g., disorder in phytohormonal balance. We also demonstrated that CA may act as oxidative stress agent but it strictly depends on plant species, exposure time and doses. Roots of tomato seedling treated with water solution of 1.2 mM cyanamide did not exhibit elevated reactive oxygen species concentration during the whole culture period. PMID:23428892

  19. Experimental study of water-ice catalyzed thermal isomerization of cyanamide into carbodiimide: implication for prebiotic chemistry.

    PubMed

    Duvernay, Fabrice; Chiavassa, Thierry; Borget, Fabien; Aycard, Jean-Pierre

    2004-06-30

    Cyanamide (NH2CN) is a molecule of interstellar interest which can be implied in prebiotic chemistry. We showed, by FTIR spectroscopy, that cyanamide can be isomerized in carbodiimide (HNCNH), another interstellar relevant molecule, by a reaction involving the amorphous water-ice surface as catalyst. This isomerization occurs at low temperature (T < 100 K) which agrees quite well with that expected in the interstellar clouds composed of dust grains in which water is the most predominant constituent.

  20. Cyanamide mode of action during inhibition of onion (Allium cepa L.) root growth involves disturbances in cell division and cytoskeleton formation.

    PubMed

    Soltys, Dorota; Rudzińska-Langwald, Anna; Kurek, Wojciech; Gniazdowska, Agnieszka; Sliwinska, Elwira; Bogatek, Renata

    2011-09-01

    Cyanamide is an allelochemical produced by hairy vetch (Vicia villosa Roth.). Its phyotoxic effect on plant growth was examined on roots of onion (Allium cepa L.) bulbs. Water solution of cyanamide (2-10 mM) restricted growth of onion roots in a dose-dependent manner. Treatment of onion roots with cyanamide resulted in a decrease in root growth rate accompanied by a decrease in accumulation of fresh and dry weight. The inhibitory effect of cyanamide was reversed by its removal from the environment, but full recovery was observed only for tissue treated with this chemical at low concentration (2-6 mM). Cytological observations of root tip cells suggest that disturbances in cell division may explain the strong cyanamide allelopathic activity. Moreover, in cyanamide-treated onion the following changes were detected: reduction of mitotic cells, inhibition of proliferation of meristematic cells and cell cycle, and modifications of cytoskeleton arrangement.

  1. Prebiotic nucleotide oligomerization in a fluctuating environment - Effects of kaolinite and cyanamide

    NASA Technical Reports Server (NTRS)

    Odom, D. G.; Lahav, N.; Chang, S.

    1979-01-01

    The clay kaolinite was tested for its ability to promote nucleotide oligomerization in model prebiotic systems. Heterogeneous mixtures of clay, water and nucleotide were repeatedly evaporated to dryness at 60 C and redissolved in water in cyclic fashion in the presence or absence of cyanamide and/or ammonium chloride. With or without cycling, kaolinite alone did not promote the oligomerization of nucleotides at detectable levels. Cycling of clay in combination with cyanamide, however, promoted high levels of condensation to a mixture of oligonucleotides and dinucleotide pyrophosphate without requiring ammonium chloride. Although cycling with clay favored synthesis of dinucleotide pyrophosphate, cycling without clay enhanced formation of oligonucleotides. These results support the hypothesis that the presence of clays in fluctuating environments would have influenced the course of prebiotic condensation reactions.

  2. Rapid quantification of cyanamide by ultra-high-pressure liquid chromatography in fertilizer, soil or plant samples.

    PubMed

    Nagumo, Yoshifumi; Tanaka, Kazuya; Tewari, Kaushal; Thiraporn, Khwankaew; Tsuchida, Toru; Honma, Toshimitsu; Ohtake, Norikuni; Sueyoshi, Kuni; Takahashi, Yoshihiko; Ohyama, Takuji

    2009-07-17

    A rapid and simple method for determination of cyanamide in fertilizer, soil and plants has been developed. In this method, cyanamide is extracted with 2% acetic acid and the extract separated by centrifugation. It is then purified by passing through a membrane filter. The extract was derivatized with 6-aminoquinolyl-N-hydroxysuccinimidyl-carbamate and the derivatized compound separated by ultra-high-pressure liquid chromatography. It is then detected with a UV detector at 260 nm by the same method as is used for amino acid analysis. The proposed method is fast, simple and cheap and also has good selectivity and sensitivity for the determination of cyanamide in a wide range of biotic and abiotic materials.

  3. Iron-catalyzed cycloaddition reaction of diynes and cyanamides at room temperature.

    PubMed

    Wang, Chunxiang; Wang, Dongping; Xu, Fen; Pan, Bin; Wan, Boshun

    2013-04-05

    An iron-catalyzed [2 + 2 + 2] cycloaddition reaction of diynes and cyanamides at room temperature is reported. Highly substituted 2-aminopyridines were obtained in good to excellent yields with high regioselectivity. Insights toward the reaction process were investigated through in situ IR spectra and control experiments. In this iron-catalyzed cycloaddition reaction, the active iron species was generated only in the presence of both alkynes and nitriles. The lower reaction temperature, broad substrates scope, and inversed regioselectivity make it a complementary method to the previously developed iron catalytic system.

  4. Industrial cogeneration case study No. 2: American Cyanamid Chemical Company, Bound Brook, New Jersey

    SciTech Connect

    Not Available

    1980-01-01

    Within a project for evaluating the economics of cogeneration for industrial plants with an electrical capacity of 10,000 to 30,000 kW, the American Cyanamid plant at Bound Brook, NJ was selected for study. Built between 1915 and 1920 this power plant was converted in the 1960's from coal-fueling to oil and natural gas. Information is presented on the plant site, fuel usage, generation costs, comparative cost of purchasable electric power, equipment used, performance, and reliability and capital and maintenance costs. (LCL)

  5. Rational design of carbon nitride photocatalysts by identification of cyanamide defects as catalytically relevant sites

    NASA Astrophysics Data System (ADS)

    Lau, Vincent Wing-Hei; Moudrakovski, Igor; Botari, Tiago; Weinberger, Simon; Mesch, Maria B.; Duppel, Viola; Senker, Jürgen; Blum, Volker; Lotsch, Bettina V.

    2016-07-01

    The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4) is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches because of a lack of fundamental understanding of its mechanistic operation. Here we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant `defect'. We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12 and 16 times the hydrogen evolution rate and apparent quantum efficiency (400 nm), respectively, compared with the unmodified melon. Computational modelling and material characterization suggest that this moiety improves coordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photogenerated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high-performance heptazine-based photocatalysts.

  6. Rational design of carbon nitride photocatalysts by identification of cyanamide defects as catalytically relevant sites

    PubMed Central

    Lau, Vincent Wing-hei; Moudrakovski, Igor; Botari, Tiago; Weinberger, Simon; Mesch, Maria B.; Duppel, Viola; Senker, Jürgen; Blum, Volker; Lotsch, Bettina V.

    2016-01-01

    The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4) is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches because of a lack of fundamental understanding of its mechanistic operation. Here we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant ‘defect'. We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12 and 16 times the hydrogen evolution rate and apparent quantum efficiency (400 nm), respectively, compared with the unmodified melon. Computational modelling and material characterization suggest that this moiety improves coordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photogenerated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high-performance heptazine-based photocatalysts. PMID:27387536

  7. Ruthenium-Catalyzed [2 + 2 + 2] Cycloaddition Reaction Forming 2-Aminopyridine Derivatives from α,ω-Diynes and Cyanamides.

    PubMed

    Ye, Fei; Haddad, Mansour; Ratovelomanana-Vidal, Virginie; Michelet, Véronique

    2017-02-22

    A novel, efficient, and mild synthetic route for the preparation of 2-aminopyridines via ruthenium-mediated [2 + 2 + 2] cycloaddition of α,ω-diynes and cyanamides has been developed. This atom-economical catalytic process demonstrated remarkable regioselectivities to access pyridine derivatives of high synthetic utility.

  8. catena-Poly[[(N,N-di-methyl-cyanamide-κN)lithium]-μ3-bromido].

    PubMed

    Xie, Qianwen; Tong, Hongbo; Zhou, Meisu

    2014-02-01

    The title complex, [LiBr(C3H6N2)] n , is the unexpected product of a reaction beteween (Dipp)N(Li)SiMe3 (Dipp = 2,6-diiso-propyl-phen-yl), Me2NCN and CuBr. The compound is a one-dimensional polymer with a step structure derived from the association of inversion dimers, formed by bromido ligands bridging two Li(+) cations, each of which carries a di-methyl-cyanamide ligand. The planar (LiBr)2 unit of the polymer core has a regular rhombic shape [Li-Br-Li 77.55 (16)° and Br-Li-Br 102.45 (16)°]. These (LiBr·NCNMe2)2 dimers represent the repeat unit of a polymer system propagated by additional Br-Li and Li-Br bonds generating an infinite step structure along the a-axis direction.

  9. Industrywide studies report of indepth survey: American Cyanamid Company, Fortier Plant, Westwego, Louisiana

    SciTech Connect

    Hills, B.

    1985-10-08

    An indepth survey of the American Cyanamid Company, Westwego, Louisiana was conducted in May, 1984. The facility produced acrylamide monomers and polyacrylamide. Acrylamide was produced by catalytic hydration of acrylonitrile within a closed reactor system to yield a 50% solution, which was then polymerized. Potential acrylamide exposures could occur from leaks in defective valves, during quality control sampling, while loading trucks and rail cars, and from contact with polymers that contained a monomer residue. Much of the acrylamide production area was open to natural ventilation. The author concludes that the mean acrylamide exposure at the facility is approximately 17% of the OSHA standard. Recommendations include rinsing the production equipment and conducting short term monitoring, especially when loading trucks.

  10. Cyanamide mediated synthesis under plausible primitive earth conditions. VI - The synthesis of glycerol and glycerophosphates

    NASA Technical Reports Server (NTRS)

    Epps, D. E.; Nooner, D. W.; Eichberg, J.; Sherwood, E.; Oro, J.

    1979-01-01

    The formation of glycerol occurs when a solution of DL-glyceraldehyde is heated in the presence of hydrogen sulfide at room temperature. DL-glyceraldehyde and dihydroxyacetone treated with hydrazine, as well as DL-glyceraldehyde incubated with formaldehyde are also partially converted to glycerol. The yields of the above reactions are from approximately 1% to about 3%. The formation of glycerophosphates occurs when glycerol is heated with ammonium dihydrogen phosphate and either urea or cyanamide. The yield of glycerophosphates is about 30%, most of which is sn-glycero-1(3)-phosphate. These findings indicate that glycerol and sn-glycero-3-phosphate, which are moieties of glycerolipids, could have been formed under conditions which may have prevailed on the primitive earth.

  11. Preparation and reactivity towards hydrazines of bis(cyanamide) and bis(cyanoguanidine) complexes of the iron triad.

    PubMed

    Albertin, Gabriele; Antoniutti, Stefano; Caia, Alfonso; Castro, Jesús

    2014-05-21

    Bis(diethylcyanamide) [Fe(N≡CNEt2)2L4](BPh4)2 1a and bis(cyanoguanidine) [Fe{N≡CN(H)C(NH2)=NH}2L4](BPh4)2 1b [L = P(OEt)3] complexes were prepared by allowing iron(II) chloride to react first with an excess of P(OEt)3 and then of the appropriate cyanamide, followed by addition of an excess of NaBPh4. Instead, bis(complexes) of ruthenium and osmium [M(N≡CNEt2)2L4](BPh4)2 2a, 3a and [M{N≡CN(H)C(NH2)=NH}2L4](BPh4)2 2b, 3b (M = Ru 2, Os 3) were prepared by reacting hydrides MH2L4 first with either triflic acid HOTf or methyltriflate MeOTf and then with an excess of the appropriate cyanamide. Hydride-diethylcyanamide [MH(N≡CNEt2)L4]BPh4 4a, 5a and hydride-cyanoguanidine complexes [MH{N≡CN(H)C(NH2)=NH}L4](BPh4)2 4b, 5b (M = Ru 4, Os 5) were also obtained by reacting MH2L4 first with one equivalent of HOTf or MeOTf and then with the appropriate cyanamide. Treatment of bis(cyanamide) and bis(cyanoguanidine) complexes 1-3 with hydrazines RNHNH2 afforded hydrazinecarboximidamide derivatives [M{η(2)-N(H)=C(NEt2)N(R)NH2}L4](BPh4)2 6a-12a and [M{η(2)-N(H)=C[N=C(NH2)2]N(R)NH2}L4](BPh4)2 6b-12b (M = Fe 6-8, Ru 9, 10, Os 11, 12; R = H 6, 9, 11, Me 7, 10, 12, Ph 8). A reaction path involving nucleophilic attack by hydrazine on the cyanamide carbon atom is proposed. All the complexes were characterised by spectroscopy and X-ray crystal structure determination of [Os{η(2)-NH=C[N=C(NH2)2]N(CH3)NH2}{P(OEt)3}4](BPh4)2 12b.

  12. The impact of the Cyanamid Canada Co. discharges to benthic invertebrates in the Welland River in Niagara falls, Canada.

    PubMed

    Dickman, M; Rygiel, G

    1993-06-01

    : In 1986, the International Joint Commission (IJC) recommended that the Niagara River watershed should be declared an Area of Concern (AOC). This IJC recommendation was ratified by the 4 signatories of the Great Lakes Water Quality Agreement. In order to delist an AOC, it is necessary to locate any areas of impairment within the watershed and carry out remediation projects that permit uses that were previously impaired. To this end we attempted to determine whether or not the sediments at 7 study sites near the Cyanamid Canada (Chemical) Co. were contaminated at levels that would result in the impairment of the natural biota which inhabit the watershed.The Cyanamid Canada (Chemical) Co. discharges ammonia wastes, cyanide, arsenic and a variety of heavy metals into treatment systems which ultimately discharge to the Welland River, the major Canadian tributary to the Niagara River. This portion of the Welland River near the factory was designated a Provincially significant (Class one) wetlands by the Ontario Ministry of Natural Resources. In 1986, the mean discharge to a creek from Cyanamid Canada Co. was 27,342 m(3) per day (MOE, 1987). Similar discharge volumes occurred in 1989. In 1991, the total discharge was 25,000 m(3) per day (MOE, 1991).The majority of the benthic invertebrates collected from the study area were pollution tolerant taxa (e.g., sludge worms constituted 68% of all the organisms collected). The lowest chironomid densities were observed at stations 1, 2, and 4, which were the only stations situated close to Cyanamid's discharge pipes. The absence, of clams and mayflies which burrow to greater depths than do chironomids and sludge worms, probably reflects the inability of the deeper dwelling burrowers to tolerate the contaminants which we recorded at these 3 stations. The absence of all crustaceans from these same 3 stations (stations 1, 2 and 4) when coupled with their low biotic diversity and the elevated heavy metal concentrations in the

  13. Low energy electron attachment to cyanamide (NH{sub 2}CN)

    SciTech Connect

    Tanzer, Katrin; Denifl, Stephan E-mail: Stephan.Denifl@uibk.ac.at; Pelc, Andrzej E-mail: Stephan.Denifl@uibk.ac.at; Huber, Stefan E.; Czupyt, Z.

    2015-01-21

    Cyanamide (NH{sub 2}CN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. In the present investigation, dissociative electron attachment to NH{sub 2}CN has been studied in a crossed electron–molecular beams experiment in the electron energy range from about 0 eV to 14 eV. The following anionic species were detected: NHCN{sup −}, NCN{sup −}, CN{sup −}, NH{sub 2}{sup −}, NH{sup −}, and CH{sub 2}{sup −}. The anion formation proceeds within two broad electron energy regions, one between about 0.5 and 4.5 eV and a second between 4.5 and 12 eV. A discussion of possible reaction channels for all measured negative ions is provided. The experimental results are compared with calculations of the thermochemical thresholds of the anions observed. For the dehydrogenated parent anion, we explain the deviation between the experimental appearance energy of the anion with the calculated corresponding reaction threshold by electron attachment to the isomeric form of NH{sub 2}CN—carbodiimide.

  14. Health-hazard evaluation report HETA 87-075-1988, American Cyanamid, Wallingford, Connecticut

    SciTech Connect

    Bicknell, R.; McManus, K.P.; Kaiser, E.A.; Koenig, J.; Fidler, A.T.

    1989-09-01

    An evaluation was made of possible hazardous exposures to workers in the Metal Coated Fibers (MCF) department of American Cyanamid, Wallingford, Connecticut. A walk-through evaluation was made of the MCF where 24 employees worked to unwind graphite fibers as a continuous strand through plating tanks, plate nickel onto the fiber, dry it and rewind it. A second operation involved the use of epoxy resins on the nickel-coated fiber and then cutting the fiber into various sizes. Air-quality monitoring revealed the following concentrations: methyl chloroform, 7.7 to 48.15 mg/cu m; methylene chloride, 13.9 to 74.7 mg/cu m; nickel, 7.3 to 51.2 micrograms/cu m; and synthetic graphite, 0.00003 to 0.23 mg/cu m. Respirators were used in portions of the operation so that these amounts do not necessarily reflect employee exposure levels. Medical examinations revealed seven of 56 workers had a work-related rash. Only two employees had a positive patch test to nickel. The report concludes that excessive exposure to nickel and potential exposure to methylene chloride existed in the MCF department. Irritant dermatitis was apparently associated with exposures on the sizing line. Measures to be taken to reduce exposures to nickel and other chemicals are recommended.

  15. Regioselective Iron-Catalyzed [2 + 2 + 2] Cycloaddition Reaction Forming 4,6-Disubstituted 2-Aminopyridines from Terminal Alkynes and Cyanamides.

    PubMed

    Spahn, Nathan A; Nguyen, Minh H; Renner, Jonas; Lane, Timothy K; Louie, Janis

    2017-01-06

    Iron complexes bound by redox-active pyridine dialdimine (PDAI) ligands catalyze the cycloaddition of two terminal alkynes and one cyanamide. The reaction is both chemo- and regioselective, as only 4,6-disubstituted 2-aminopyridine products are formed in moderate to high yields. Isolation of an iron azametallacycle (4) suggests that catalyst deactivation occurs with a large excess of cyanamide over longer reaction times. Fe-catalyzed cycloaddition allowed for a straightforward synthesis of a variety of aminopyridines, including known estrogen receptor ligands.

  16. Industry-wide studies report of walk-through survey of American Cyanamid Plant, Fortier Plant, Westwego, Louisana

    SciTech Connect

    Hills, B.

    1985-06-12

    A walk-through survey was conducted at American Cyanamid Company, Fortier Plant, Westwego, Louisiana, a manufacturer of acrylamide and polyacrylamide. The purpose of the survey was to obtain information on the facility, workforce, processes, personal records, medical records, and industrial hygiene program for an acrylamide exposure study being conducted by NIOSH researchers. Based on the preliminary survey, approximately 60 employees were identified as being potentially exposed to acrylamide. Since this plant is one out of four acrylamide manufacturing sites in the United States, an in-depth industrial hygiene survey should be conducted to determine exposure levels.

  17. Hydrogen cyanamide on citrus: Phytotoxicity, influences on flush in potted and field trees and effects on bloom and cropload in the field

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bloom in individual citrus trees typically continues for more than a month in south Florida. Prolonged bloom increases susceptibility to postbloom fruit drop disease (caused by Colletotrichum acutatum) and contributes to variable fruit maturity at harvest. Hydrogen cyanamide (HCN) is used to acceler...

  18. The quest for the elusive carbodiimide ion HN dbnd C dbnd NH rad + and its generation from ionized cyanamide by proton-transport catalysis

    NASA Astrophysics Data System (ADS)

    Jobst, Karl J.; Gerbaux, Pascal; Dimopoulos-Italiano, Georgina; Ruttink, Paul J. A.; Terlouw, Johan K.

    2009-08-01

    Tandem mass spectrometry based collision experiments and computational chemistry (CBS-QB3/APNO methods) indicate that the elusive carbodiimide ion HN dbnd C dbnd NH rad + is a stable species in the gas-phase. The ion is the most stable of the family of CHN2rad + ions and a very high barrier (87 kcal mol -1) separates it from its tautomer ionized cyanamide, H 2N-C tbnd N rad + . The computations also predict that, in the presence of a single H 2O molecule as the catalyst, the cyanamide ion isomerizes into the carbodiimide ion. Experiments on the ion-molecule reaction of H 2N-C tbnd N rad + and H 2O, a reaction of potential interest in astrochemistry, confirm this prediction.

  19. Quantification of canavanine, 2-aminoethanol, and cyanamide in Aphis craccivora and its host plants, Robinia pseudoacacia and Vicia angustifolia: effects of these compounds on larval survivorship of Harmonia axyridis.

    PubMed

    Kamo, Tsunashi; Tokuoka, Yoshinori; Miyazaki, Masahisa

    2012-12-01

    The cowpea aphid Aphis craccivora that infests the black locust Robinia pseudoacacia shows toxicity to its predator, the multicolored Asian ladybird beetle, Harmonia axyridis. In contrast, the same aphid species that infests the common vetch, Vicia angustifolia, is suitable prey for H. axyridis larvae. Previously, it was reported that the toxicity of A. craccivora infesting R. pseudoacacia was due to canavanine and 2-aminoethanol, but there was some doubt about the toxicity of these compounds and their concentrations in the aphids. In the present study, we determined the concentrations of cyanamide, canavanine, and 2-aminoethanol in A. craccivora infesting the two host plants. In the extracts of A. craccivora that infested either of the host plants, canavanine was undetectable, and 2-aminoethanol was detected at the concentration of 3.0-4.0 μg/g fresh weight. Cyanamide was detected in the extract of A. craccivora that infested R. pseudoacacia (7.7 μg/g fresh weight) but not in that infesting V. angustifolia. The toxicity of canavanine, 2-aminoethanol, and cyanamide was evaluated against H. axyridis larvae in a bioassay by using an artificial diet containing these compounds at various concentrations. Cyanamide exhibited 10-100 times stronger toxicity than canavanine and 2-aminoethanol. These results indicate that the toxicity is at least partly due to cyanamide, which is present in the toxic A. craccivora that infests R. pseudoacacia but absent from the non-toxic A. craccivora that infests V. angustifolia.

  20. Effect of calcium cyanamide, ammonium bicarbonate and lime mixture, and ammonia water on survival of Ralstonia solanacearum and microbial community

    NASA Astrophysics Data System (ADS)

    Liu, Lijuan; Sun, Chengliang; Liu, Xingxing; He, Xiaolin; Liu, Miao; Wu, Hao; Tang, Caixian; Jin, Chongwei; Zhang, Yongsong

    2016-01-01

    The inorganic nitrogenous amendments calcium cyanamide (CC), ammonia water (AW), and a mixture of ammonium bicarbonate with lime (A+L) are popularly used as fumigants to control soil-borne disease in China. However, it is unclear which of these fumigants is more effective in controlling R. solanacearum. This present study compared the efficiencies of the three nitrogenous amendments listed above at four nitrogen levels in suppressing the survival of R. solanacearum in soil. The CC showed the best ability to suppress R. solanacearum due to its highest capacity to increase soil and NO2‑ contents and pH. However, AW was more suitable to controlling bacterial wilt caused by R. solanacearum because it had a lower cost and its application rate of 0.25 g N kg‑1 soil could effectively suppress the survival of R. solanacearum. Additionally, soil microbial activity and community populations were restored to their initial state four weeks after the application of each fumigant, indicating that the three fumigants had few detrimental impacts on soil microbial activity and community structure with an exception of the suppression of R. solanacearum. The present study provides guidance for the selection of a suitable alkaline nitrogenous amendment and its application rate in controlling bacterial wilt.

  1. A rapid transcriptional activation is induced by the dormancy-breaking chemical hydrogen cyanamide in kiwifruit (Actinidia deliciosa) buds

    PubMed Central

    Walton, Eric F.; Wu, Rong-Mei; Richardson, Annette C.; Davy, Marcus; Hellens, Roger P.; Thodey, Kate; Janssen, Bart J.; Gleave, Andrew P.; Rae, Georgina M.; Wood, Marion; Schaffer, Robert J.

    2009-01-01

    Budbreak in kiwifruit (Actinidia deliciosa) can be poor in locations that have warm winters with insufficient winter chilling. Kiwifruit vines are often treated with the dormancy-breaking chemical hydrogen cyanamide (HC) to increase and synchronize budbreak. This treatment also offers a tool to understand the processes involved in budbreak. A genomics approach is presented here to increase our understanding of budbreak in kiwifruit. Most genes identified following HC application appear to be associated with responses to stress, but a number of genes appear to be associated with the reactivation of growth. Three patterns of gene expression were identified: Profile 1, an HC-induced transient activation; Profile 2, an HC-induced transient activation followed by a growth-related activation; and Profile 3, HC- and growth-repressed. One group of genes that was rapidly up-regulated in response to HC was the glutathione S-transferase (GST) class of genes, which have been associated with stress and signalling. Previous budbreak studies, in three other species, also report up-regulated GST expression. Phylogenetic analysis of these GSTs showed that they clustered into two sub-clades, suggesting a strong correlation between their expression and budbreak across species. PMID:19651683

  2. Effect of calcium cyanamide, ammonium bicarbonate and lime mixture, and ammonia water on survival of Ralstonia solanacearum and microbial community

    PubMed Central

    Liu, Lijuan; Sun, Chengliang; Liu, Xingxing; He, Xiaolin; Liu, Miao; Wu, Hao; Tang, Caixian; Jin, Chongwei; Zhang, Yongsong

    2016-01-01

    The inorganic nitrogenous amendments calcium cyanamide (CC), ammonia water (AW), and a mixture of ammonium bicarbonate with lime (A+L) are popularly used as fumigants to control soil-borne disease in China. However, it is unclear which of these fumigants is more effective in controlling R. solanacearum. This present study compared the efficiencies of the three nitrogenous amendments listed above at four nitrogen levels in suppressing the survival of R. solanacearum in soil. The CC showed the best ability to suppress R. solanacearum due to its highest capacity to increase soil and NO2− contents and pH. However, AW was more suitable to controlling bacterial wilt caused by R. solanacearum because it had a lower cost and its application rate of 0.25 g N kg−1 soil could effectively suppress the survival of R. solanacearum. Additionally, soil microbial activity and community populations were restored to their initial state four weeks after the application of each fumigant, indicating that the three fumigants had few detrimental impacts on soil microbial activity and community structure with an exception of the suppression of R. solanacearum. The present study provides guidance for the selection of a suitable alkaline nitrogenous amendment and its application rate in controlling bacterial wilt. PMID:26738601

  3. Effect of calcium cyanamide, ammonium bicarbonate and lime mixture, and ammonia water on survival of Ralstonia solanacearum and microbial community.

    PubMed

    Liu, Lijuan; Sun, Chengliang; Liu, Xingxing; He, Xiaolin; Liu, Miao; Wu, Hao; Tang, Caixian; Jin, Chongwei; Zhang, Yongsong

    2016-01-07

    The inorganic nitrogenous amendments calcium cyanamide (CC), ammonia water (AW), and a mixture of ammonium bicarbonate with lime (A+L) are popularly used as fumigants to control soil-borne disease in China. However, it is unclear which of these fumigants is more effective in controlling R. solanacearum. This present study compared the efficiencies of the three nitrogenous amendments listed above at four nitrogen levels in suppressing the survival of R. solanacearum in soil. The CC showed the best ability to suppress R. solanacearum due to its highest capacity to increase soil and NO2(-) contents and pH. However, AW was more suitable to controlling bacterial wilt caused by R. solanacearum because it had a lower cost and its application rate of 0.25 g N kg(-1) soil could effectively suppress the survival of R. solanacearum. Additionally, soil microbial activity and community populations were restored to their initial state four weeks after the application of each fumigant, indicating that the three fumigants had few detrimental impacts on soil microbial activity and community structure with an exception of the suppression of R. solanacearum. The present study provides guidance for the selection of a suitable alkaline nitrogenous amendment and its application rate in controlling bacterial wilt.

  4. A rapid transcriptional activation is induced by the dormancy-breaking chemical hydrogen cyanamide in kiwifruit (Actinidia deliciosa) buds.

    PubMed

    Walton, Eric F; Wu, Rong-Mei; Richardson, Annette C; Davy, Marcus; Hellens, Roger P; Thodey, Kate; Janssen, Bart J; Gleave, Andrew P; Rae, Georgina M; Wood, Marion; Schaffer, Robert J

    2009-01-01

    Budbreak in kiwifruit (Actinidia deliciosa) can be poor in locations that have warm winters with insufficient winter chilling. Kiwifruit vines are often treated with the dormancy-breaking chemical hydrogen cyanamide (HC) to increase and synchronize budbreak. This treatment also offers a tool to understand the processes involved in budbreak. A genomics approach is presented here to increase our understanding of budbreak in kiwifruit. Most genes identified following HC application appear to be associated with responses to stress, but a number of genes appear to be associated with the reactivation of growth. Three patterns of gene expression were identified: Profile 1, an HC-induced transient activation; Profile 2, an HC-induced transient activation followed by a growth-related activation; and Profile 3, HC- and growth-repressed. One group of genes that was rapidly up-regulated in response to HC was the glutathione S-transferase (GST) class of genes, which have been associated with stress and signalling. Previous budbreak studies, in three other species, also report up-regulated GST expression. Phylogenetic analysis of these GSTs showed that they clustered into two sub-clades, suggesting a strong correlation between their expression and budbreak across species.

  5. Phytotoxic cyanamide affects maize (Zea mays) root growth and root tip function: from structure to gene expression.

    PubMed

    Soltys, Dorota; Rudzińska-Langwald, Anna; Kurek, Wojciech; Szajko, Katarzyna; Sliwinska, Elwira; Bogatek, Renata; Gniazdowska, Agnieszka

    2014-05-01

    Cyanamide (CA) is a phytotoxic compound produced by four Fabaceae species: hairy vetch, bird vetch, purple vetch and black locust. Its toxicity is due to complex activity that involves the modification of both cellular structures and physiological processes. To date, CA has been investigated mainly in dicot plants. The goal of this study was to investigate the effects of CA in the restriction of the root growth of maize (Zea mays), representing the monocot species. CA (3mM) reduced the number of border cells in the root tips of maize seedlings and degraded their protoplasts. However, CA did not induce any significant changes in the organelle structure of other root cells, apart from increased vacuolization. CA toxicity was also demonstrated by its effect on cell cycle activity, endoreduplication intensity, and modifications of cyclins CycA2, CycD2, and histone HisH3 gene expression. In contrast, the arrangement of microtubules was not altered by CA. Treatment of maize seedlings with CA did not completely arrest mitotic activity, although the frequency of dividing cells was reduced. Furthermore, prolonged CA treatment increased the proportion of endopolyploid cells in the root tip. Cytological malformations were accompanied by an induction of oxidative stress in root cells, which manifested as enhanced accumulation of H2O2. Exposure of maize seedlings to CA resulted in an increased concentration of auxin and stimulated ethylene emission. Taken together, these findings suggested that the inhibition of root growth by CA may be a consequence of stress-induced morphogenic responses.

  6. Developmental lead exposure induces opposite effects on ethanol intake and locomotion in response to central vs. systemic cyanamide administration.

    PubMed

    Mattalloni, Mara Soledad; Deza-Ponzio, Romina; Albrecht, Paula Alejandra; Cancela, Liliana Marina; Virgolini, Miriam Beatriz

    2017-02-01

    Lead (Pb) is a developmental neurotoxicant that elicits differential responses to drugs of abuse. Particularly, ethanol consumption has been demonstrated to be increased as a consequence of environmental Pb exposure, with catalase (CAT) and brain acetaldehyde (ACD, the first metabolite of ethanol) playing a role. The present study sought to interfere with ethanol metabolism by inhibiting ALDH2 (mitochondrial aldehyde dehydrogenase) activity in both liver and brain from control and Pb-exposed rats as a strategy to accumulate ACD, a substance that plays a major role in the drug's reinforcing and/or aversive effects. To evaluate the impact on a 2-h chronic voluntary ethanol intake test, developmentally Pb-exposed and control rats were administered with cyanamide (CY, an ALDH inhibitor) either systemically or intracerebroventricularly (i.c.v.) on the last 4 sessions of the experiment. Furthermore, on the last session and after locomotor activity was assessed, all animals were sacrificed to obtain brain and liver samples for ALDH2 and CAT activity determination. Systemic CY administration reduced the elevated ethanol intake already reported in the Pb-exposed animals (but not in the controls) accompanied by liver (but not brain) ALDH2 inactivation. On the other hand, a 0.3 mg i.c.v. CY administration enhanced both ethanol intake and locomotor activity accompanied by brain ALDH2 inactivation in control animals, while an increase in ethanol consumption was also observed in the Pb-exposed group, although in the absence of brain ALDH2 blockade. No changes were observed in CAT activity as a consequence of CY administration. These results support the participation of liver and brain ACD in ethanol intake and locomotor activity, responses that are modulated by developmental Pb exposure.

  7. Synthesis of new structurally related cyanamide compounds LiM(CN{sub 2}){sub 2} where M is Al{sup 3+}, In{sup 3+} or Yb{sup 3+}

    SciTech Connect

    Kubus, Mariusz; Heinicke, Robert; Ströbele, Markus; Enseling, David; Jüstel, Thomas; Meyer, H.-Jürgen

    2015-02-15

    Highlights: • New cyanamide compounds LiM(CN{sub 2}){sub 2} where M is Al{sup 3+}, In{sup 3+} or Yb{sup 3+}. • New luminescent material LiIn(CN{sub 2}){sub 2}:Tb{sup 3+}. • Reduction in efficiency of luminescence with temperature increase. - Abstract: New ternary cyanamide compounds isostructural to LiY(CN{sub 2}){sub 2} were obtained by solid state metathesis reaction. The crystal structure of LiAl(CN{sub 2}){sub 2} was determined by single crystal X-ray diffraction, the structures of LiIn(CN{sub 2}){sub 2} and LiYb(CN{sub 2}){sub 2} were solved from X-ray powder diffraction data. Photoluminescence properties of Tb{sup 3+}-doped LiIn(CN{sub 2}){sub 2} are reported too.

  8. Kinetics of the Reaction of beta-Methoxy-alpha-nitrostilbene with Cyanamide in 50 DMSO-50 Water. Failure to Detect the S(N)V Intermediate.

    PubMed

    Bernasconi, Claude F.; Leyes, Aquiles E.; Rappoport, Zvi

    1999-04-16

    A kinetic study of the reaction of beta-methoxy-alpha-nitrostilbene (1-OMe) with cyanamide (CNA) over a pH range from 8.5 to 12.4 shows that it is the anion (CNA(-), pK(a) = 11.38) rather than the neutral amine that is the reactive species. Attempts at monitoring the reaction with the neutral CNA at low pH were unsuccessful because of competing hydrolysis. It is shown that the nucleophilic reactivity of CNA is abnormally low, probably because of a resonance effect, and that the reactivity of CNA(-) is high, higher than that of strongly basic oxyanion because of relatively weak solvation. The high reactivity of both 1-OMe and CNA(-) appeared to constitute favorable conditions conducive to the detection of the S(N)V intermediate, as has been the case in the reactions of 1-OMe with thiolate ions, alkoxide ions, and some amines. However, no intermediate was observed. Reasons for this failure are discussed.

  9. High-rate Li4Ti5O12/N-doped reduced graphene oxide composite using cyanamide both as nanospacer and a nitrogen doping source

    NASA Astrophysics Data System (ADS)

    Jeong, Jun Hui; Kim, Myeong-Seong; Kim, Young-Hwan; Roh, Kwang Chul; Kim, Kwang-Bum

    2016-12-01

    A Li4Ti5O12(LTO)/N-doped reduced graphene oxide (RGO) composite is proposed using dual functional nitrogen doping source to prevent RGO restacking and achieve uniform nitrogen doping on RGO sheets to increase the rate performance of high-rate lithium ion batteries. The pore structure (both meso- and macro pores) is developed when RGO restacking is prevented, facilitating electrolyte ion diffusion to active sites with lower resistance. Uniform nitrogen doping on RGO sheets with high nitrogen contents provides additional free electrons to the sheets, resulting in increased electronic conductivity. Cyanamide is used as the nitrogen doping source for the N-doped RGO as well as a nanospacer between the RGO sheets. In the composite, the nitrogen content of the RGO sheets is 2.3 wt%, which increases the electronic conductivity of the composite to 1.60 S cm-1. The specific surface area of the composite is increased to 35.8 m2 g-1. Thus, the composite structure with the N-doped RGO sheets and porous secondary particles has high electrical conductivity and high ion accessibility. The LTO/N-doped RGO composite demonstrates excellent electrochemical performance with a low resistance of 48.4 Ω, a high specific capacity of 117.8 mAh g-1 at 30 C, and good cycle stability.

  10. The reactivity of [PhP(Se)(mu-Se)]2 and (PhP)3Se2 towards acetylenes and cyanamides: X-ray crystal structures of some P-Se-C and P-Se-C-N heterocycles.

    PubMed

    Bhattacharyya, Pravat; Slawin, Alexandra M Z; Woollins, J Derek

    2002-06-17

    Several unusual P-Se-C and P-Se-C-N heterocycles are formed by the reaction of [PhP(Se)(mu-Se)]2 or (PhP)3Se2 with alkynes or cyanamides, generated by the fragmentation of the organophosphorus-selenium compound and addition across the C identical to C or C identical to N triple bond of the organic substrate. X-ray crystallographic analysis reveals an unexpected diversity of structural motifs within these heterocyclic systems, including P2SeCN, P2C2Se and PC2Se2 rings.

  11. Reactivity towards nitriles, cyanamides, and carbodiimides of palladium complexes derived from benzyl alcohol. Synthesis of a mixed Pd2Ag complex.

    PubMed

    Fernández-Rodríguez, María-José; Martínez-Viviente, Eloísa; Vicente, José; Jones, Peter G

    2016-01-14

    The chelate complex [Pd(κ(2)-C,O-C6H4CH2O-2)(bpy)] () reacts with acetonitrile, cyanamides, or carbodiimides, in the presence of AgOTf (1 : 5 : 1 molar ratio) and residual water, to form complexes [Pd{κ(2)-C,N-C6H4{CH2OC([double bond, length as m-dash]NX)Y}-2}(bpy)](OTf), where X = H, Y = Me (), NMe2 (), NEt2 (), X = R, Y = NHR (R = (i)Pr (), Tol ()), as a result of the insertion of the unsaturated reagent into the O-Pd bond of and the protonation of one of the N atoms. In the absence of AgOTf the reaction of with TolN[double bond, length as m-dash]C[double bond, length as m-dash]NTol (Tol = p-Tolyl) results in the formation of the neutral complex [Pd{κ(2)-C,N-C6H4{CH2OC([double bond, length as m-dash]NTol)NTol}-2}(bpy)] (). Complexes and can be interconverted by deprotonation ( + KO(t)Bu) or protonation ( + KOTf + HOTf) reactions. When the reaction of with TolN[double bond, length as m-dash]C[double bond, length as m-dash]NTol in the presence of AgOTf is carried out in a 1 : 1 : 1 stoichiometric ratio, or for a short period of time, a mixture of and a mixed heterometallic Ag2Pd complex is obtained ( = [Ag(N-)2](OTf)). Complex is the major product when the AgOTf is added before the carbodiimide, and the reaction is stopped immediately. can also be obtained by reaction of with 0.5 equiv. of AgOTf. When complex [PdI(C6H4CH2OH-2)(bpy)] () reacts with (i)PrN[double bond, length as m-dash]C[double bond, length as m-dash]N(i)Pr in the presence of TlOTf, instead of AgOTf, a ca. 1 : 1 mixture of and [Pd{κ(2)-O,N-OCH2{C6H4{C([double bond, length as m-dash]NH(i)Pr)N(i)Pr}-2}}(bpy)](OTf) () forms. Complex is the result of the insertion of the carbodiimide into the C-Pd bond. Complexes have been extensively characterized by NMR spectroscopy, and the crystal structures of , , and ·2.5CHCl3·0.5Et2O have been determined by X-ray diffraction studies.

  12. Extraction and separation of Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) from hydrochloric acid solutions with selected cyanamides as novel extractants.

    PubMed

    Mowafy, E A; Aly, H F

    2007-10-22

    Three structurally related novel extractants namely: N,N-dihexylcyanamide (DHCY), N,N-di(2-ethylhexyl)cyanamide (DEHCY) and N,N-di-octylcyanamide (DOCY) were synthesized in our laboratory and characterized by different techniques. The general method for synthesizing these extractants was based on the reaction of relevant secondary amines with cyanogen bromide in presence of sodium acetate anhydride. Their extracting ability in toluene as a diluent for Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) from hydrochloric acid media has been studied. The extraction of hydrochloric acid was studied also. Pd(II) was strongly extracted by these extractants at low hydrochloric acid concentrations and the extraction decreased with increasing hydrochloric acid concentration while the reverse was obtained in the extraction of Pt(IV), Fe(III) and Zn(II). Under similar extraction conditions Cu(II) and Ag(I) were found poorly extracted. Hydrochloric acid was extracted only in its high concentration region. A systematic investigation has been carried out on the extraction of Pd(II) using two of the synthesized extractants. Pd(II) was extracted as a solvated complex with the composition, metal:chloride ion:extractant=1:2:2. The extracted species were studied also using IR spectra.

  13. PSD Reconstruction Requirements American Cyanamid Company

    EPA Pesticide Factsheets

    This document may be of assistance in applying the New Source Review (NSR) air permitting regulations including the Prevention of Significant Deterioration (PSD) requirements. This document is part of the NSR Policy and Guidance Database. Some documents in the database are a scanned or retyped version of a paper photocopy of the original. Although we have taken considerable effort to quality assure the documents, some may contain typographical errors. Contact the office that issued the document if you need a copy of the original.

  14. Hydrogen cyanamide on citrus: preliminary data on phytotoxicity and influence on flush in potted and field trees

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bloom in individual citrus trees typically continues for more than a month in south Florida, with even greater bloom duration within most orchard blocks because of variation in bloom timing between trees. Prolonged bloom contributes to variable fruit maturity as harvest approaches and increases seve...

  15. Ionic liquid 1-butyl-3-methylimidazolium cyanamide (bmim [dca]) as a solvent and catalyst for acylation of maltodextrin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have found a novel method to prepare maltodextrin stearate with DS upto 0.60 in 90% yields from maltodextrin in IL bmim[dca] reacted with vinyl stearate or stearic acid. In this work we have demonstrated that IL could simultaneously act as a solvent and as a catalyst for reaction of maltodextrin...

  16. Cyclization of nitriles. XXIV. Reactions of cyanamide derivatives of thiocarbamic acids with cyanothioacetamide. Crystal structure of 2-allylamino-4-amino-5-benzoyl-1,3-thiazole

    SciTech Connect

    Nesterov, V.N.; Sharanin, Yu.A.; Shestopalov, A.M.; Shklover, V.E.; Struchkov, Yu.T.

    1988-09-20

    2-Allylamino-4-amino-5-aroyl-1,3-thiazoles were obtained from S-alkylisoureas. An x-ray crystallographic investigation of 2-allylamino-4-amino-5-benzoyl-1,3-thiazole was undertaken. Dimethyl dithiocarbamate was used in the synthesis of 2-amino-4-methylthio-5-cyano-1H-pyrimidine-6-thione and, from the latter, 4-allylthio-2-amino-6-methylthio-5-cyanopyrimidine. The latter is easily quaternized by the action of iodine to 4-amino-3-iodomethyl-7-methylthio-8-cyano-2,3-dihydrothiazolo(3,2-c)pyrimidinium triiodide. In reaction with iodine 2-allyl-amino-1,3-thiazoles form N-allyl-N-iodo derivatives of 1,3-thiazole and not imidazo(2,3-b)thiazolium salts.

  17. Characterization of Thick Glass Reinforced Composites

    DTIC Science & Technology

    1992-07-01

    24 ounces per square yard. The matrices were different polyester resin systems from American Cyanamid and Owens Corning . Specimen thicknesses ranged...fab- ricated similar size plates using the American Cyanamid resin. The Owens Corning plates con- tained 53% volume fraction fiber while the American...thicknesses for the Owens Corning and four for the American Cyanamid. Specimens were loaded in three point bending at a displacement rate that was changed

  18. A Feasibility Study of Burning Waste Paper in Coal-Fired Boilers on Air Force Installations

    DTIC Science & Technology

    1993-09-01

    Calcium cyanamide 105602 ................ .Caprolactam 133062 ................ .Captan 63252 ................. . Carbaryl 75150...Propiolactone 123386 ................ .Propionaldehyde 114261 .... ............. Propoxur (Baygon) 78875 ................. .Propylene dichloride (1,2

  19. 48 CFR 25.104 - Nonavailable articles.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ...; not printed in the United States and for which domestic editions are not available. Brazil nuts, unroasted. Cadmium, ores and flue dust. Calcium cyanamide. Capers. Cashew nuts. Castor beans and castor...

  20. 48 CFR 25.104 - Nonavailable articles.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...; not printed in the United States and for which domestic editions are not available. Brazil nuts, unroasted. Cadmium, ores and flue dust. Calcium cyanamide. Capers. Cashew nuts. Castor beans and castor...

  1. Evaluation of Toxic Air Emissions

    DTIC Science & Technology

    1995-06-01

    108394 106445 98828 94757 3547044 334883 Calcium Cyanamide Caprolactam Captan Carbaryl Carbon disulfide Carbon Tetrachloride Carbonyl sulfide Catechol...Phosphorus Phthalic anhydride Polychlorinated biphenyls (Aroclors) 1,3-Propane sultone beta-Propiolactone Propionaldehyde Propoxur (Baygon) Propylene

  2. PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE EAST SIDE OF THE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE EAST SIDE OF THE CYANAMIDE (L-N) OVEN BUILDING. PIECES OF A DISASSEMBLED RAIL CAR IN FOREGROUND. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  3. Formation of urea and guanidine by irradiation of ammonium cyanide.

    NASA Technical Reports Server (NTRS)

    Lohrmann, R.

    1972-01-01

    Aqueous solutions of ammonium cyanide yield urea, cyanamide and guanidine when exposed to sunlight or an unfiltered 254 nm ultraviolet source. The prebiotic significance of these results is discussed.

  4. SYNTHETIC STUDIES ON PEPTIDES.

    DTIC Science & Technology

    In an effort to devise a new protecting group (amidino group) for the thiol group of cysteine the reaction of N-benzyloxycarbonyl-L- cysteine with...cyanamide was explored. A crystalline product obtained from the reaction between N-benzyloxycarbonyl-L- cysteine and cyanamide was shown to possess the...elemental composition C12H13O3N3S. A cyclic sturcture (Formula VI) appears to represent the correct formulation for this compound. L- Cysteine

  5. Fatigue Behavior of Adhesively Bonded Joints. Volume I.

    DTIC Science & Technology

    1980-04-01

    electron spectroscopy (AES) and/or XPS scans. The adhesive used is FM-73M, a 2500F-cure tape from American Cyanamid of Havre de Grace, MD. This...34PABST Technical Bulletin No. 1", March 28, 1975. 14. FM 73 Adhesive Film, Data Bulletin BPT 20B, Cyanamid Bloom- ingdale Aerospace Products, Havre de...Joints," J. Appl. Mech. 11, 1944 , A17-A27. 29. Hart-Smith, L. C., Adhesive-Bonded Single-Lap Joints, NASA, CR-11236, January 1973. 30. Quarterly Progress

  6. A Review of the Literature and of Work Done in A.R.D and C.R.D.D. on Picrite and its Intermediates with a View to Finding a Cheap and Economical Process

    DTIC Science & Technology

    1947-05-01

    illegible. DSTL ltr dtd 13 Feb 2007; DSTL ltr dtd 13 Feb 2007 3C7/K/47 l ’ rj COPY Na \\ ON: Mjjlfe£_ h. Date ~k^ CONFIDENTIAL OAljg Ministry of...method of manufacturing picrite other’ than through carbide then the methods most worthy of further study and detailed costing are methods ( l ) and (7...Cyanamide is formed by the action of bromine on potassium cyanide dissolved in liquid ammonia.(4°) ( l ) Cyanamide and carbon dioxide are fof^ed by the

  7. 48 CFR 25.104 - Nonavailable articles.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ..., unroasted. Cadmium, ores and flue dust. Calcium cyanamide. Capers. Cashew nuts. Castor beans and castor oil..., or other primary ore and metal forms. Cocoa beans. Coconut and coconut meat, unsweetened, in shredded, desiccated, or similarly prepared form. Coffee, raw or green bean. Colchicine alkaloid, raw. Copra....

  8. 48 CFR 25.104 - Nonavailable articles.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ..., unroasted. Cadmium, ores and flue dust. Calcium cyanamide. Capers. Cashew nuts. Castor beans and castor oil..., or other primary ore and metal forms. Cocoa beans. Coconut and coconut meat, unsweetened, in shredded, desiccated, or similarly prepared form. Coffee, raw or green bean. Colchicine alkaloid, raw. Copra....

  9. The National Shipbuilding Research Program. Historical Overview of Efforts to Reduce VOC Emissions Through Coating Reformulations and Analysis of VOC vs HAP Content in Marine Coatings

    DTIC Science & Technology

    1995-05-01

    79118 532274 108907 510156 67663 107302 126998 1319773 95287 108394 106445 1,3-Butadiene Calcium Cyanamide Caprolactam Captan Carbaryl Carbon disulfide...96093 1746016 79345 127184 7550450 108883 95807 584849 95534 8001352 120821 79005 79016 Propionaldehyde Propoxur (Baygon) Propylene dichloride (1,2

  10. The Environmental Assessment and Management (TEAM) Guide; Rhode Island Supplement, Revised March 1998

    DTIC Science & Technology

    1998-03-01

    BUTADIENE 106990 0-24 CALCRJM CYANAMIDE 156627 0-25 CAPROLACTAM 105602 0-26 CAPTAN 133062 0-27 CARBARYL 63252 0-28 CARBON DISULFIDE 75150 0-29 CARBON...0-138 BETA-PROPIOLACTONE 57578 0-139 PROPIONALDEHYDE 123386 0-140 PROPOXUR (BAYGON) 114261 0-141 PROPYLENE DICHLORIDE (1,2- DICHLOROPROPANE

  11. Environmental Compliance Assessment System (ECAS). South Carolina Supplement. U.S. Army

    DTIC Science & Technology

    1994-04-01

    Cyanamide. 156627 2.50 Captan 133062 25.00 Carbaryl 63252 25.00 Carbon Disulfide 75150 150.00 Carbon Tetrachloride 56235 150.00. Carbonyl Sulfide...1120714 + b-Propiolactone 57578 7.50 Propoxur 114261 2.50 Propylene Dichloride 78875 1750.00 1,2 Propylene Oxide 75569 250.00 Propylenimine (1,2

  12. Fire retardant cellulosic foam

    NASA Technical Reports Server (NTRS)

    Luttinger, M.

    1973-01-01

    Method mixture of cyanamide, phosphoric acid, and monobasic ammonium phosphates for preliminary treatment of paper. Papier-mache, in second step, is pulped in water and latex is added. Urea formaldehyde solution mixed to maximize foaming and resin dispersion is added. Mixture is then cast within 30 to 60 seconds and dried twice.

  13. Use of fourier transform infrared spectroscopy to follow the heterocumulene aided thermal dehydration of phthalic and naphthalic acids.

    PubMed

    Rigout, Muriel L A; Lewis, David M

    2006-12-01

    Fourier transform infrared (FT-IR) spectroscopy has been successfully employed to follow the formation of phthalic anhydride and 1,8-naphthalic anhydride on heating their corresponding acids. The effects of three heterocumulenes, cyanamide, dicyandiamide, and sodium cyanate, on the temperature of formation of the anhydrides were also investigated using this method. It was found that the carbodiimides cyanamide and dicyandiamide dramatically lowered the temperature at which thermal dehydration of the acid led to anhydride formation. It was noted that cyanamide had a stronger catalytic effect than dicyandiamide, presumably due to the electron-withdrawing effect of the amidine group. Sodium cyanate was also found to promote the thermal dehydration of the acids to form the corresponding anhydrides. Under more severe conditions, phthalic acid anhydride formed is seen to react further, leading to the formation of phthalimide. The discrepancy between the products obtained with cyanamide and sodium cyanate leads to the conclusion that, unlike earlier claims, imide formation is not due to the reaction of the anhydride with the urea formed but with sodium cyanate itself. However, only the phthalic anhydride five-membered ring system is sufficiently reactive towards the CNO- nucleophile to form the imide; the six-membered 1,8-naphthalic anhydride system does not react in this way.

  14. Winter shading of blueberry plants in the southeastern United States

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In Central Florida, southern highbush blueberries are treated with hydrogen cyanamide to replace lack of chilling and enhance flowering and fruiting. Experiments were conducted to determine the effects of repeated applications of processed kaolin particle and flat-top shade structure on blueberry p...

  15. Ionic Liquid as a Solvent and Catalyst for Acylation of Maltodextrin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Catalyst-free esterification of maltodextrin was carried out in ionic liquid. Stearate esters of maltodextrin were obtained in various degree of substitution (DS) when vinyl stearate or stearic acid was heated with maltodextrin in ionic liquid, 1-butyl-3-methylimidazolium cyanamide (bmim[dca]). Re...

  16. Tailoring the mesoporous texture of graphitic carbon nitride.

    PubMed

    Yang, Jae-Hun; Kim, Gain; Domen, Kazunari; Choy, Jin-Ho

    2013-11-01

    Recently, graphitic carbon nitride (g-C3N4) materials have received a great attention from many researchers due to their various roles as a visible light harvesting photocatalyst, metal-free catalyst, reactive template, nitrogen source of nitridation reaction, etc. g-C3N4 could be prepared by temperature-induced polymerization of cyanamide or melamine. In this study, we report a preparation of mesoporous graphitic carbon nitrides with tailored porous texture including pore size, and specific surface area from cyanamide and colloidal silica nanoparticles (Ludox). At first, cyanamide-silica nanocomposites were prepared by mixing colloidal silica with different size in the range of 7-22 nm and cyanamide, followed by evaporating the solvent in the resulting mixture. Mesoporous g-C3N4 samples were prepared by calcining cyanamide-silica nanocomposite at 550 degrees C for 4 hrs and removing the silica nanoparticles by using ammonium hydrogen fluoride. The formation of g-C3N4 was confirmed by the sharp (002) peak (d = 3.25 A) of graphitic interlayer stacking, and the broad (100) peak (d = 6.86 A) of in-plane repeating unit in the X-ray diffraction patterns. According to N2 adsorption-desorption analysis, the pore size of mesoporous carbon nitrides was similar to the size of colloidal silica used as hard template (7-22 nm). The specific surface area of mesoporous g-C3N4 could be tailored in the range of 189 m2/g-288 m2/g.

  17. Synthesis ofN-(2-chloro-5-methylthiophenyl)-N'-(3-methyl-thiophenyl)-N'-[3H3]methylguanidine, l brace [3H3]CNS-5161 r brace

    SciTech Connect

    Gibbs, Andrew R.; Morimoto, Hiromi; VanBrocklin, Henry F.; Williams, Philip G.; Biegon, Anat

    2001-09-28

    The preparation of the title compound, [{sup 3}H{sub 3}]CNS-5161, was accomplished in three steps starting with the production of [{sup 3}H{sub 3}]iodomethane (CT{sub 3}I). The intermediate N-[{sup 3}H{sub 3}]methyl-3-(thiomethylphenyl)cyanamide was prepared in 77% yield by the addition of CT{sub 3}I to 3-(thiomethylphenyl)cyanamide, previously treated with sodium hydride. Reaction of this tritiated intermediate with 2-chloro-5-thiomethylaniline hydrochloride formed the guanidine compound [{sup 3}H{sub 3}]CNS-5161. Purification by HPLC gave the desired labeled product in an overall yield of 9% with greater than 96% radiochemical purity and a final specific activity of 66 Ci mmol{sup -1}.

  18. Microcontact-printing-assisted access of graphitic carbon nitride films with favorable textures toward photoelectrochemical application.

    PubMed

    Liu, Jian; Wang, Hongqiang; Chen, Zu Peng; Moehwald, Helmuth; Fiechter, Sebastian; van de Krol, Roel; Wen, Liping; Jiang, Lei; Antonietti, Markus

    2015-01-27

    An "ink" (cyanamide) infiltrated anodic aluminum oxide (AAO) stamp is found capable of printing carbon nitride films featuring regular microstructures of the stamp onto the substrates via in situ "chemical vapor deposition". A photocurrent density of 30.2 μA cm(-2 --) at 1.23 VRHE is achieved for a film on a conductive substrate, which is so far the highest value for pure carbon nitride based photoelectrochemical devices.

  19. Criterion buys Akzo`s naphtha reforming catalysts business

    SciTech Connect

    Rotman, D.

    1993-12-08

    In a move that further consolidates the refinery catalysts market, Criterion Catalyst (Houston) has bought Akzo`s reforming business for an undisclosed price. The acquisition gives Criterion-a joint venture between Shell and American Cyanamid-roughly 35% of the $50-million/year worldwide reforming market. Akzo says it is quitting the business to focus on larger refinery catalysts applications in hydroprocessing and fluid cracking catalysts.

  20. Preparation of nitrogen-doped carbon tubes

    SciTech Connect

    Chung, Hoon Taek; Zelenay, Piotr

    2015-12-22

    A method for synthesizing nitrogen-doped carbon tubes involves preparing a solution of cyanamide and a suitable transition metal-containing salt in a solvent, evaporating the solvent to form a solid, and pyrolyzing the solid under an inert atmosphere under conditions suitable for the production of nitrogen-doped carbon tubes from the solid. Pyrolyzing for a shorter period of time followed by rapid cooling resulted in a tubes with a narrower average diameter.

  1. Syntheses of (3) H-labeled, (14) C-labeled, and (2) H4 -labeled SCH 444877, phosphodiesterase type 5 inhibitors.

    PubMed

    Ren, Sumei; Hesk, David; McNamara, Paul; Koharski, David; Hendershot, Sharon

    2013-01-01

    The syntheses of [(3) H]SCH 444877, [(2) H4 ]SCH 444877, and [(14) C]SCH 444877 are described. [(3) H]SCH 444877 was prepared in three steps from tritium gas. [(2) H4 ]SCH 444877 was synthesized from [(2) H4 ]ethanolamine in four steps with an overall yield of 40%. [(14) C]SCH 444877 was prepared from barium [(14) C]cyanamide in 10 steps with an overall yield of 8.1%.

  2. Molecular Modeling in Drug Design for the Development of Organophosphorus Antidotes/Prophylactics.

    DTIC Science & Technology

    1986-06-01

    R176 274 MOLECULAR MODELING IN DRUG DESIGN FOR THE DEVELOPMENT 1/1OF ORGANOPI4OSPHORUS (U) AMERICA CYANAMID CO PEARL RIVER NY LEDERLE LAOS DIV R...MOLECULAR MODELING IN DRUG DESIGN FOR THE DEVELO ’"ENT OF ORGANOPHOSPHORUS ANTIDOTES/PROPHYLACTICS Final Report R. Venkataraghavan, Ph.D. June 1, 1986 I...Security Classification) (U) .Molecular Modeling in Drug Design for the Development of Organophosphorus Antidotes/Prophylactics 12 PERSONAL AUTHOR(S) R

  3. The ethanol metabolite acetaldehyde induces water and salt intake via two distinct pathways in the central nervous system of rats.

    PubMed

    Ujihara, Izumi; Hitomi, Suzuro; Ono, Kentaro; Kakinoki, Yasuaki; Hashimoto, Hirofumi; Ueta, Yoichi; Inenaga, Kiyotoshi

    2015-12-01

    The sensation of thirst experienced after heavy alcohol drinking is widely regarded as a consequence of ethanol (EtOH)-induced diuresis, but EtOH in high doses actually induces anti-diuresis. The present study was designed to investigate the introduction mechanism of water and salt intake after heavy alcohol drinking, focusing on action of acetaldehyde, a metabolite of EtOH and a toxic substance, using rats. The aldehyde dehydrogenase (ALDH) inhibitor cyanamide was used to mimic the effect of prolonged acetaldehyde exposure because acetaldehyde is quickly degraded by ALDH. Systemic administration of a high-dose of EtOH at 2.5 g/kg induced water and salt intake with anti-diuresis. Cyanamide enhanced the fluid intake following EtOH and acetaldehyde administration. Systemic administration of acetaldehyde with cyanamide suppressed blood pressure and increased plasma renin activity. Blockade of central angiotensin receptor AT1R suppressed the acetaldehyde-induced fluid intake and c-Fos expression in the circumventricular organs (CVOs), which form part of dipsogenic mechanism in the brain. In addition, central administration of acetaldehyde together with cyanamide selectively induced water but not salt intake without changes in blood pressure. In electrophysiological recordings from slice preparations, acetaldehyde specifically excited angiotensin-sensitive neurons in the CVO. These results suggest that acetaldehyde evokes the thirst sensation following heavy alcohol drinking, by two distinct and previously unsuspected mechanisms, independent of diuresis. First acetaldehyde indirectly activates AT1R in the dipsogenic centers via the peripheral renin-angiotensin system following the depressor response and induces both water and salt intake. Secondly acetaldehyde directly activates neurons in the dipsogenic centers and induces only water intake.

  4. Oxalate Ester Chemiluminescence, Improved Low Temperature Formulations.

    DTIC Science & Technology

    1985-05-01

    phenylethynyl)anthracene ( BPEA ) and 1-chloro-9,10-bis- (phenylethynyl)anthracene (C1BPEA) were purchased from the American Cyanamid Company. 2-Ethyl...results of Figure 2 also suggest an electronic effect in the fluorescer reaction rate: the electron-donating methyl and ethyl sub- stituents on BPEA ...show increased rates, while the electron-withdrawing chloro group slows the reaction. BPEA , itself, was not included in the study due to poor solubility

  5. The prebiotic synthesis of deoxythymidine oligonucleotides

    NASA Technical Reports Server (NTRS)

    Stephen-Sherwood, E.; Odom, D. G.; Oro, J.

    1974-01-01

    Deoxythymidine 5 prime-triphosphate in the presence of deoxythymidine 5 prime-phosphate, cyanamide and 4-amino-5-imidazole carboxamide polymerizes under drying conditions at moderate temperatures (60 to 90 C) to yield oligonucleotides of up to four units in length. Enzymatic analysis indicated that the majority of these oligomers contained natural 3 prime-5 prime phosphodiester bonds. This reaction offers a possible method for the formation of deoxyoligonucleotides under primitive earth conditions.

  6. Short and general procedure for synthesizing cis-1,2-fused 1,3-oxathiolan-, 1,3-oxaselenolan-, and 1,3-oxazolidin-2-imine carbohydrate derivatives.

    PubMed

    Castilla, Javier; Marín, Irene; Matheu, M Isabel; Díaz, Yolanda; Castillón, Sergio

    2010-01-15

    Novel cis-1,2-fused 1,3-oxathiolan-, 1,3-oxaselenolan-, and 1,3-oxazolidin-2-imine carbohydrate derivatives have been prepared by treatment of the corresponding 1,2-anhydrosugars with potassium thiocyanate, potassium selenocyanate, and sodium cyanamide, respectively. The procedure is compatible with several protecting groups such as acyl, benzyl, and silyl and also with sugars of different configurations.

  7. Review of Laboratory Program on Degradation Mechanisms in Soil of Wastewater From Nitroguanidine Manufacture

    DTIC Science & Technology

    1987-03-01

    nitrogen (Personal communication, Fred Pepper , Whey Products Institute). Glucose contains in g/mole: hydrogen 12; carbon 72; and • oxygen 96. 3.5...as added to the the quantitative determination of cyan - of 1.002-rn,. light path was used for blood arfd the tube shaken VigOrOu~L\\ I amide in...micro- provided the reagent blank solution. cium and a solution of calcium cyan - gram quantities of cyanamide have This reagent solution had an absor

  8. Synthesis of the coenzymes adenosine diphosphate glucose, guanosine diphosphate glucose, and cytidine diphosphoethanolamine under primitive Earth conditions

    NASA Technical Reports Server (NTRS)

    Mar, A.; Oro, J.

    1991-01-01

    The nonenzymatic synthesis of the coenzymes adenosine diphosphate glucose (ADPG), guanosine diphosphate glucose (GDPG), and cytidine diphosphoethanolamine (CDP-ethanolamine) has been carried out under conditions considered to have been prevalent on the early Earth. The production of these compounds was performed by allowing simple precursor molecules to react under aqueous solutions, at moderate temperatures and short periods of time, with mediation by cyanamide or urea. These two condensing agents are considered to have been present in significant amounts on the primitive Earth and have been previously used in the nonenzymatic synthesis of several other important biochemical compounds. In our experiments, ADPG was obtained by heating glucose-1-phosphate (G1P) and ATP in the presence of cyanamide for 24 h at 70 degrees C. The reaction of G1P and GTP under the same conditions yielded GDPG. The cyanamide-mediated production of CDP-ethanolamine was carried out by reacting a mixture of ethanolamine phosphate and CTP for 24 h at 70 degrees C. The separation and identification of the reaction products was carried out by paper chromatography, thin-layer chromatography, high performance thin-layer chromatography, high performance liquid chromatography, both normal and reverse-phase, UV spectroscopy, enzymatic assays, and acid hydrolysis. Due to the mild conditions employed, and to the relative ease of these reactions, these studies offer a simple attractive system for the nonenzymatic synthesis of phosphorylated high-energy metabolic intermediates under conditions considered to have been prevalent on the ancient Earth.

  9. The Capital Budgeting Policies of the U. S. Shipbuilding Industry: An Analysis of Defense Industry Behavior

    DTIC Science & Technology

    1979-10-01

    Johns - Manville ) and one whose net worth was comparable in 1976 (Cluett Peabody). • One company whose asset base was comparable to Lockheed’s in 1967...AVERAGE2 30.2 ’ KODAK ARMCO SFERRY RAND JOHNS - MANVILLE CLCETt PEABODY AMER.CYANAMID SINGER-1’ N.A. N.A. N.A. N.A. N.A. M.A. N.A. 9 11 10 22 4 13 N.A. 10...JIM WALTER 8 23 CUMMINS 58 8 MARTIN MARIETTA 9 90 SQUIBB 851 KOPPERS 708 UNION CAMP 624 INT’L MINING 68 2 JOHNS MANVILLE 814 EMERSON ELEC

  10. Non-enzymatic synthesis of the coenzymes, uridine diphosphate glucose and cytidine diphosphate choline, and other phosphorylated metabolic intermediates

    NASA Technical Reports Server (NTRS)

    Mar, A.; Dworkin, J.; Oro, J.

    1987-01-01

    Using urea and cyanamide, the two condensing agents considered to have been present on the primitive earth, uridine diphosphate glucose (UDPG), cytidine diphosphate choline (CDP-choline), glucose-1-phosphate (G1P), and glucose-6-phosphate (G6P) were synthesized under simulated prebiotic conditions. The reaction products were separated and identified using paper chromatography, thin layer chromatography, enzymatic analyses, and ion-pair reverse-phase high performance liquid chromatography. The possibility of nonenzymatic synthesis of metabolic intermediates on the primitive earth from simple precursors was thus demonstrated.

  11. Air Emissions Inventory Guidance Document for Mobile Sources at Air Force Installations

    DTIC Science & Technology

    2002-01-01

    Compounds 156-62-7 Calcium cyanamide 133-06-2 Captan 63-25-2 Carbaryl 75-15-0 Carbon disulfide 56-23-5 Carbon tetrachloride 463-58-1 Carbonyl sulfide...1120-71-4 1,3-Propane sultone 57-57-8 beta-Propiolactone, 123-38-6 Propionaldehyde 114-26-1 Propoxur (Baygon) 78-87-5 Propylene dichloride, (1 ,2...Dichlorvos 62-75-9 N-Nitrosodimethylamine 63-25-2 Carbaryl 64-67-5 Diethyl sulfate 67-56-1 Methanol 67-66-3 Chloroform 67-72-1 Hexachloroethane 68-12-2

  12. Studies on precellular evolution - The encapsulation of polyribonucleotides by liposomes

    NASA Technical Reports Server (NTRS)

    Baeza, I.; Ibanez, M.; Santiago, J. C.; Wong, C.; Lazcano, A.

    1986-01-01

    Liposomes have been suggested as possible models of precellular systems formed in the early Archean earth from lipids of nonenzymatic origin. Since it is generally accepted that RNA molecules preceded double-stranded DNA molecules as genetic material, the encapsulation of polyribonucleotides within liposomes (made from dipalmitoyl phosphatidylcholine and from egg yolk phosphatidylcholine) was studied. Quantitative determinations show that approximately 50 percent of the available lipids form liposomes, and that up to 5 percent of the polyribonucleotides can be entrapped by them. Also studied was the encapsulation of polyribonucleotides in the presence of urea and cyanamide and of Zn(2+) and Pb(2+).

  13. Flammability Characteristics of Fiber-Reinforced Composite Materials for the Composite Infantry Fighting Vehicle

    DTIC Science & Technology

    1990-09-01

    30 E-701 Baseline MTL-2 S2/Polyester* 70/30 Owens - Corning MTL-3 S2/Polyester* 70/30 American-Cyanamide MTL-4 Kevlar/Phenolic-PVBt 84/16 Russell C...3rporation MTL-5 S2/Phenolic 80/20 Owens - Corning ;Resin formulation isproprietary. Resin is 50/50 Phenolic-PVB. Organic polymers are one of the major...Dihydroanthracene 35 Diisopropenylphthalate 36 2-Phenyl naphthalene 12 Table 7. PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY OF MTL-2, OWENS - CORNING ; 9000C

  14. Prebiotic synthesis of histidyl-histidine

    NASA Technical Reports Server (NTRS)

    Shen, C.; Mills, T.; Oro, J.

    1990-01-01

    Histidyl-histidine (His-His) has been synthesized in a yield of up to 14.4% under plausible prebiotic conditions using histidine (His), cyanamide, and 4-amino-5-imidazole carboxamide. A trace amount of His trimer was also detected. Because the imidazole group of His is involved in a number of important enzymatic reactions, and His-His has been shown to catalyze the prebiotic synthesis of glycyl-glycine, we expect this work will stimulate further studies on the catalytic activities of simple His-containing peptides in prebiotic reactions.

  15. One-pot synthesis of holey MoS2 nanostructures as efficient electrocatalysts for hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Wang, Lanlan; Li, Xuan; Zhang, Jian; Liu, Hongzhong; Jiang, Weitao; Zhao, Hong

    2017-02-01

    In this work, highly porous MoS2 nanostructures have been synthesized via a one-pot and versatile calcination of cyanamide and (NH4)2MoS4 precursors. At first, the thermal polymerization of cyanamide into carbon nitride suppresses the aggregation of MoS2. Then, the thermal decomposition of the formed carbon nitride brings about plentiful pores with a size of 4-70 nm in MoS2 nanostructures, generating an extremely large specific surface area up to 311 m2 g-1. Due to the high specific surface area and abundant exposed edge sites, the resultant porous MoS2 (p-MoS2) nanostructures exhibited outstanding electrochemical hydrogen evolution (HER) activity in a 0.5 M H2SO4 aqueous solution. The onset overpotential and the overpotential at a current density of 10 mA/cm2 were as low as ∼30 mV and ∼130 mV, respectively, which is superior to the previously-reported MoS2-based HER electrocatalysts.

  16. Liposomes with polyribonucleotides as model of precellular systems

    NASA Astrophysics Data System (ADS)

    Baeza, Isabel; Ibañez, Miguel; Lazcano, Antonio; Santiago, Carlos; Arguello, Carlos; Wong, Carlos; Oró, J.

    1987-09-01

    A study of the encapsulation of poly(U) and poly(C) within liposomes made from dipalmitoylphosphatidyl choline (DPPC), from egg yold phosphatidyl choline (PC), and from PC with cholesterol (CHOL) was made. The liposomes were prepared under anoxic conditions following the reverse-phase evaporation method. Determinations showed that 36 to 70% of the available lipids form liposomes and 2 to 5% of the polyribonucleotides can be entrapped by liposomes. The encapsulation of polyribonucleotides has also been measured in the presence of urea, cyanamide and Zn++, condensing agents in prebiotic polymerization reactions. DPPC and PC:CHOL liposomes were formed in the presence of 1.0 M urea, although no PC liposomes were formed. The three types of liposomes were readily formed at 0.01 M urea, but in no case an enhancement of encapsulation efficiency of poly(U) was observed due to the presence of urea. Similar results were obtained with cyanamide. An enhanced encapsulation of poly(U) by the three types of liposomes was observed when Zn++ was in the range of 0.001 to 0.01 M. Poly(U) encapsulation was 15 to 25 times higher when liposomes were prepared from DPPC at 0.01 M Zn++. Similar results were obtained with poly(C). The advantages of DPPC-polyribonucleotide liposomes as precellular systems are discussed.

  17. Synthesis, structure and spectroscopic study of Rh III polypyridine complexes with phenylcyanamide derivative ligands

    NASA Astrophysics Data System (ADS)

    Hadadzadeh, Hassan; Rezvani, Ali R.; Belanger-Gariepy, Francine

    2005-04-01

    Several new Rh III complexes, [Rh(tpy)(bpy)L](PF 6) 2 (tpy=2,2':6',2″-terpyridine, bpy=2,2'-bipyridine, and L=monoanions of phenylcyanamide(pcyd)), 4-methylphenylcyanamide (4-MePcyd), 2,4-dimethylphenylcyanamide (2,4-Me 2pcyd), 4-methoxyphenylcyanamide (4-MeOPcyd), 2-chlorophenylcyanamide (2-Clpcyd) and 2,5-dichlorophenylcyanamide (2,5-Cl 2pcyd) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic absorption spectroscopies. ORTEP drawing of [Rh(tpy)(bpy)(2,5-Cl 2pcyd)](PF 6) 2·1/2CH 3CN shows three pyridyl rings of the tpy ligand that are nearly coplanar, as are the two rings of bpy. The anionic cyanamide group is coordinated end-on by the nitrile nitrogen to the Rh III. The Rh III-NCN bond is bent, having an angle of 125.4°. This bent bond is largely determined by the σ-bonding interaction of a cyanamide non-bonding electron pair in a sp 2 hybrid orbital.

  18. Mixed dinitrogen-organocyanamide complexes of molybdenum(0) and their protic conversion into hydrazide and amidoazavinylidene derivatives.

    PubMed

    Cunha, Sónia M P R M; Guedes da Silva, M Fátima C; Pombeiro, Armando J L

    2003-03-24

    Organocyanamides, Ntbd1;CNR(2) (R = Me or Et), react with trans-[Mo(N(2))(2)(dppe)(2)] (1, dppe = Ph(2)PCH(2)CH(2)PPh(2)), in THF, to give the first mixed molybdenum dinitrogen-cyanamide complexes trans-[Mo(N(2))(NCNR(2))(dppe)(2)] (R = Me 2a or Et 2b) which are selectively protonated at N(2) by HBF(4) to yield the hydrazide(2-) complexes trans-[Mo(NNH(2))(NCNR(2))(dppe)(2)][BF(4)](2) (R = Me, 3a, or Et, 3b). On treatment with Ag[BF(4)], oxidation and metal fluorination occur, and the ligating cyanamide undergoes an unprecedented beta-protonation at the unsaturated C atom to form trans-[MoF(NCHNR(2))(dppe)(2)][BF(4)](2) (R = Me, 4a, or Et, 4b) compounds which present the novel amidoazavinylidene (or amidomethyleneamide) ligands. Complexes 4 are also formed from the corresponding compounds 3, with liberation of ammonia and hydrazine. The crystal structure of 2b was determined by single-crystal X-ray diffraction analysis which indicates that the N atom of the amide group has a trigonal planar geometry.

  19. Allelopathy in the natural and agricultural ecosystems and isolation of potent allelochemicals from Velvet bean (Mucuna pruriens) and Hairy vetch (Vicia villosa).

    PubMed

    Fujii, Yoshiharu

    2003-06-01

    We have studied on allelopathy of plants and developed methods to identify the effective substances in root exudates, leaf leacheate, and volatile chemicals emitted from plants. We found traditional cover plants that show allelopathic activity are useful for weed control. It could eliminate the use of synthetic chemicals for this purpose. Allelopathy is a natural power of plants to protect themselves by producing natural organic chemicals. Some endemic plants in Asia, already known by farmers in the region, as either cover crops used in intercropping, hedgerow, or agroforestry, were found to possess strong allelopathic abilities. Our group identified several allelochemicals from these plants. These allelopathic cover crops, mostly leguminous plants, provide protein rich food, and grow easily without artificial fertilizers, herbicides, insecticides and fungicides. In this regards, these allelopathic cover crops could save food shortage in rural area, and are useful for environmental conservation. Screenings of allelopathic plants by specific bioassays and field tests have been conducted. Hairy vetch (Vicia villosa) and Velvet bean (Mucuna pruriens) are two promising species for the practical application of allelopathy. An amino acid, L-DOPA, unusual in plants, plays an important role as allelochemical in Velvet bean (Mucuna pruriens). Hairy vetch is the most promising cover plant for the weed control in orchard, vegetable and rice production and even for landscape amendment in abandoned field in Japan. We have isolated "cyanamide", a well known nitrogen fertilizer, from Hairy vetch. This is the first finding of naturally produced cyanamide in the world.

  20. Synthesis of phosphatidylcholine under possible primitive earth conditions

    NASA Technical Reports Server (NTRS)

    Rao, M.; Eichberg, J.; Oro, J.

    1982-01-01

    Using a primitive earth evaporating pond model, the synthesis of phosphatidylcholine was accomplished when a reaction mixture of choline chloride and disodium phosphatidate, in the presence of cyanamide and traces of acid, was evaporated and heated at temperatures ranging from 25 to 100 C for 7 hours. Optimum yields of about 15% were obtained at 80 C. Phosphatidylcholine was identified by chromatographic, chemical and enzymatic degradation methods. On enzymatic hydrolysis with phospholipase A2 and phospholipase C, lysophosphatidylcholine and phosphorylcholine were formed, respectively. Alkaline hydrolysis gave glycerophosphorylcholine. The synthesis of phosphatidylcholine as the major compound was accompanied by the formation of lysophosphatidylcholine in smaller amounts. Cyanamide was found to be essential for the formation of phosphatidylcholine, and only traces of HCl, of the order of that required to convert the disodium phosphatidate to free phosphatidic acid were found necessary for the synthesis. This work suggests that phosphatidylcholine, which is an essential component of most biological membranes, could have been synthesized on the primitive earth.

  1. Enhanced catabolism to acetaldehyde in rostral ventrolateral medullary neurons accounts for the pressor effect of ethanol in spontaneously hypertensive rats.

    PubMed

    El-Mas, Mahmoud M; Abdel-Rahman, Abdel A

    2012-02-01

    We have previously shown that ethanol microinjection into the rostral ventrolateral medulla (RVLM) elicits sympathoexcitation and hypertension in conscious spontaneously hypertensive rats (SHRs) but not in Wistar-Kyoto (WKY) rats. In this study, evidence was sought to implicate the oxidative breakdown of ethanol in this strain-dependent hypertensive action of ethanol. Biochemical experiments revealed significantly higher catalase activity and similar aldehyde dehydrogenase (ALDH) activity in the RVLM of SHRs compared with WKY rats. We also investigated the influence of pharmacological inhibition of catalase (3-aminotriazole) or ALDH (cyanamide) on the cardiovascular effects of intra-RVLM ethanol or its metabolic product acetaldehyde in conscious rats. Compared with vehicle, ethanol (10 μg/rat) elicited a significant increase in blood pressure in SHRs that lasted for the 60-min observation period but had no effect on blood pressure in WKY rats. The first oxidation product, acetaldehyde, played a critical role in ethanol-evoked hypertension because 1) catalase inhibition (3-aminotriazole treatment) virtually abolished the ethanol-evoked pressor response in SHRs, 2) intra-RVLM acetaldehyde (2 μg/rat) reproduced the strain-dependent hypertensive effect of intra-RVLM ethanol, and 3) ALDH inhibition (cyanamide treatment) uncovered a pressor response to intra-RVLM acetaldehyde in WKY rats similar to the response observed in SHRs. These findings support the hypothesis that local production of acetaldehyde, due to enhanced catalase activity, in the RVLM mediates the ethanol-evoked pressor response in SHRs.

  2. Methoxyacetaldehyde, an intermediate metabolite of 2-methoxyethanol, is immunosuppressive in the rat.

    PubMed

    Smialowicz, R J; Riddle, M M; Williams, W C

    1993-07-01

    2-Methoxyethanol (ME) is metabolized to 2-methoxyacetic acid (MAA) via the intermediate metabolite methoxyacetaldehyde (MAAD). Both ME and MAA have been shown in this laboratory to be immunosuppressive in rats following oral dosing. In this study, the plaque-forming cell (PFC) response to trinitrophenyl-lipopolysaccharide (TNP-LPS) was used to determine if MAAD is immunosuppressive in rats. Rats pretreated with the aldehyde dehydrogenase inhibitors disulfiram (2 mmol/kg) or cyanamide (0.48 mmol/kg) followed by oral dosing with ME (2.64 mmol/kg) resulted in suppressed PFC responses equivalent to the suppressed responses of rats dosed with ME alone. Rats pretreated with disulfiram and then dosed with 2.64 mmol/kg 2-methoxyethyl acetate (MEA), also resulted in suppressed PFC responses similar to that of MEA alone. In contrast, coadministration of the alcohol dehydrogenase inhibitor 4-methylpyrazole (1.2 mmol/kg) with ME or MEA blocked suppression of the PFC response following exposure to ME or MEA alone. Oral dosing with equimolar (2.64 mmol/kg) concentrations of ME, MAA, or MAAD resulted in equivalent suppression of the TNP-LPS PFC response. Rats exposed to either disulfiram or cyanamide and MAAD also resulted in suppression of the PFC response. These results indicate that metabolism of ME to either MAAD or MAA is required for immunosuppression, and that these two metabolites are equipotent immunosuppressants in the rat.

  3. Endogenous ethanol--its metabolic, behavioral and biomedical significance.

    PubMed

    Ostrovsky YuM

    1986-01-01

    Ethanol is constantly formed endogenously from acetaldehyde, and level of the former can be measured in both human beings and animals. Acetaldehyde can be generated in situ from the metabolism of pyruvate, threonine, deoxyribose-5-phosphate, phosphoethanolamine, alanine and presumably from other substrates. The levels of blood and tissue endogenous ethanol change as a function of various physiologic and experimental conditions such as starvation, aging, stress, cooling, adrenalectomy, etc. and are regulated by many exogenous compounds such as antimetabolites, derivatives of amino acids, lithium salts, disulfiram, cyanamide, etc. Under free choice alcohol selection situations, the levels of endogenous ethanol in rat blood and alcohol preference by the animals are negatively correlated. Similar negative correlations have been found between the levels of blood endogenous ethanol and the frequency of delirium in alcoholic patients undergoing alcohol withdrawal. Endogenous ethanol and acetaldehyde can therefore be regarded as compounds which fulfil substrate, regulatory and modulator functions.

  4. Dark Photocatalysis: Storage of Solar Energy in Carbon Nitride for Time-Delayed Hydrogen Generation.

    PubMed

    Lau, Vincent Wing-Hei; Klose, Daniel; Kasap, Hatice; Podjaski, Filip; Pignié, Marie-Claire; Reisner, Erwin; Jeschke, Gunnar; Lotsch, Bettina V

    2017-01-09

    While natural photosynthesis serves as the model system for efficient charge separation and decoupling of redox reactions, bio-inspired artificial systems typically lack applicability owing to synthetic challenges and structural complexity. We present herein a simple and inexpensive system that, under solar irradiation, forms highly reductive radicals in the presence of an electron donor, with lifetimes exceeding the diurnal cycle. This radical species is formed within a cyanamide-functionalized polymeric network of heptazine units and can give off its trapped electrons in the dark to yield H2 , triggered by a co-catalyst, thus enabling the temporal decoupling of the light and dark reactions of photocatalytic hydrogen production through the radical's longevity. The system introduced here thus demonstrates a new approach for storing sunlight as long-lived radicals, and provides the structural basis for designing photocatalysts with long-lived photo-induced states.

  5. Air Emissions Inventory Guidance Document for Stationary Sources at Air Force Installations.

    DTIC Science & Technology

    1999-05-01

    Bifenox 2.4 x 10-6 Bromacil acid 3.1 x 10-7 Bromoxynil butyrate ester 1.0 x 10-4 Butylate 1.3 x 10-2 Captan 8.0 x 10-1 Carbaryl 1.2 x 10-6 Carbofuran 6.0...1.2 x 10-6 Propachlor 2.3 x 10-4 Propanil 4.0 x 10-’ Propargite 3.0 x 10-3 Propazine 1.3 x 10-7 Propoxur 9.7 x 10-6 Siduron 4.0 x 10-9 Simazine 2.2 x 10...99-0 1,3-Butadiene Cadmium Compounds 156-62-7 Calcium cyanamide 133-06-2 Captan 63-25-2 Carbaryl 75-15-0 Carbon disulfide 56-23-5 Carbon tetrachloride

  6. Colloidal Monolayer β-In2Se3 Nanosheets with High Photoresponsivity.

    PubMed

    Almeida, Guilherme; Dogan, Sedat; Bertoni, Giovanni; Giannini, Cinzia; Gaspari, Roberto; Perissinotto, Stefano; Krahne, Roman; Ghosh, Sandeep; Manna, Liberato

    2017-03-01

    We report a low-temperature colloidal synthesis of single-layer, five-atom-thick, β-In2Se3 nanosheets with lateral sizes tunable from ∼300 to ∼900 nm, using short aminonitriles (dicyandiamide or cyanamide) as shape controlling agents. The phase and the monolayer nature of the nanosheets were ascertained by analyzing the intensity ratio between two diffraction peaks from two-dimensional slabs of the various phases, determined by diffraction simulations. These findings were further backed-up by comparing and fitting the experimental X-ray diffraction pattern with Debye formula simulated patterns and with side-view high-resolution transmission electron microscopy imaging and simulation. The β-In2Se3 nanosheets were found to be indirect band gap semiconductors (Eg = 1.55 eV), and single nanosheet photodetectors demonstrated high photoresponsivity and fast response times.

  7. Metabolic engineering of microbial competitive advantage for industrial fermentation processes.

    PubMed

    Shaw, A Joe; Lam, Felix H; Hamilton, Maureen; Consiglio, Andrew; MacEwen, Kyle; Brevnova, Elena E; Greenhagen, Emily; LaTouf, W Greg; South, Colin R; van Dijken, Hans; Stephanopoulos, Gregory

    2016-08-05

    Microbial contamination is an obstacle to widespread production of advanced biofuels and chemicals. Current practices such as process sterilization or antibiotic dosage carry excess costs or encourage the development of antibiotic resistance. We engineered Escherichia coli to assimilate melamine, a xenobiotic compound containing nitrogen. After adaptive laboratory evolution to improve pathway efficiency, the engineered strain rapidly outcompeted a control strain when melamine was supplied as the nitrogen source. We additionally engineered the yeasts Saccharomyces cerevisiae and Yarrowia lipolytica to assimilate nitrogen from cyanamide and phosphorus from potassium phosphite, and they outcompeted contaminating strains in several low-cost feedstocks. Supplying essential growth nutrients through xenobiotic or ecologically rare chemicals provides microbial competitive advantage with minimal external risks, given that engineered biocatalysts only have improved fitness within the customized fermentation environment.

  8. Synthesis of cytidine ribonucleotides by stepwise assembly of the heterocycle on a sugar phosphate.

    PubMed

    Ingar, Abdul-Aziz; Luke, Richard W A; Hayter, Barry R; Sutherland, John D

    2003-06-06

    Although various syntheses of the nucleic acid bases exist and ribose is a product of the formose reaction, no prebiotically plausible methods for attaching pyrimidine bases to ribose to give nucleosides have been described. Kinetic and thermodynamic factors are thought to mitigate against such condensation reactions in aqueous solution. This inability to produce pyrimidine nucleosides and hence nucleotides is a major stumbling block of the "RNA World" hypothesis and has led to suggestions of alternative nucleic acids as evolutionary precursors to RNA. Here, we show that a process in which the base is assembled in stages on a sugar phosphate can produce cytidine nucleotides. The sequential action of cyanamide and cyanoacetylene on arabinose-3-phosphate produces cytidine-2',3'-cyclophosphate and arabinocytidine-3'-phosphate.

  9. INTERSTELLAR CARBODIIMIDE (HNCNH): A NEW ASTRONOMICAL DETECTION FROM THE GBT PRIMOS SURVEY VIA MASER EMISSION FEATURES

    SciTech Connect

    McGuire, Brett A.; Loomis, Ryan A.; Charness, Cameron M.; Corby, Joanna F.; Blake, Geoffrey A.; Hollis, Jan M.; Lovas, Frank J.; Jewell, Philip R.; Remijan, Anthony J.

    2012-10-20

    In this work, we identify carbodiimide (HNCNH), which is an isomer of the well-known interstellar species cyanamide (NH{sub 2}CN), in weak maser emission, using data from the Green Bank Telescope PRIMOS survey toward Sgr B2(N). All spectral lines observed are in emission and have energy levels in excess of 170 K, indicating that the molecule likely resides in relatively hot gas that characterizes the denser regions of this star-forming region. The anticipated abundance of this molecule from ice mantle experiments is {approx}10% of the abundance of NH{sub 2}CN, which in Sgr B2(N) corresponds to {approx}2 Multiplication-Sign 10{sup 13} cm{sup -2}. Such an abundance results in transition intensities well below the detection limit of any current astronomical facility and, as such, HNCNH could only be detected by those transitions which are amplified by masing.

  10. Process for the reduction of nitrogen oxides in an effluent

    SciTech Connect

    Epperly, W.R.; Sullivan, J.C.

    1988-09-13

    A process is described for reducing the concentration of nitrogen oxides in an effluent from the combustion of a carbonaceous fuel, which process comprises injecting into the effluent ammonia and an enhancer selected from the group consisting of hexamethylenetetramine, a lower carbon alcohol, a hydroxyl amino hydrocarbon, sugar, furfural, furfural derivatives, an amino acid, a protein-containing composition, mixtures of ortho-, meta-, and para-methyl phenols, guanidine, guanidine carbonate, biguanidine, guanylurea sulfate, melamine, dicyandiamide, calcium cyanamide, biuret, 1,1'-azobisformamide, methylol urea, methylol urea-urea condensation product, dimethylol urea, methyl urea, dimethyl urea, and mixtures thereof, at an effluent temperature above about 1300/sup 0/F and a molar ratio of nitrogen in the ammonia and enhancer to the baseline nitrogen oxides level of about 1:5 to about 6:1 wherein the excess of oxygen in the effluent is no greater than about 6%.

  11. Abiotic origin of biopolymers

    NASA Technical Reports Server (NTRS)

    Oro, J.; Stephen-Sherwood, E.

    1976-01-01

    A variety of methods have been investigated in different laboratories for the polymerization of amino acids and nucleotides under abiotic conditions. They include (1) thermal polymerization; (2) direct polymerization of certain amino acid nitriles, amides, or esters; (3) polymerization using polyphosphate esters; (4) polymerization under aqueous or drying conditions at moderate temperatures using a variety of simple catalysts or condensing agents like cyanamide, dicyandiamide, or imidazole; and (5) polymerization under similar mild conditions but employing activated monomers or abiotically synthesized high-energy compounds such as adenosine 5'-triphosphate (ATP). The role and significance of these methods for the synthesis of oligopeptides and oligonucleotides under possible primitive-earth conditions is evaluated. It is concluded that the more recent approach involving chemical processes similar to those used by contemporary living organisms appears to offer a reasonable solution to the prebiotic synthesis of these biopolymers.

  12. A plausible simultaneous synthesis of amino acids and simple peptides on the primordial Earth.

    PubMed

    Parker, Eric T; Zhou, Manshui; Burton, Aaron S; Glavin, Daniel P; Dworkin, Jason P; Krishnamurthy, Ramanarayanan; Fernández, Facundo M; Bada, Jeffrey L

    2014-07-28

    Following his seminal work in 1953, Stanley Miller conducted an experiment in 1958 to study the polymerization of amino acids under simulated early Earth conditions. In the experiment, Miller sparked a gas mixture of CH4, NH3, and H2O, while intermittently adding the plausible prebiotic condensing reagent cyanamide. For unknown reasons, an analysis of the samples was not reported. We analyzed the archived samples for amino acids, dipeptides, and diketopiperazines by liquid chromatography, ion mobility spectrometry, and mass spectrometry. A dozen amino acids, 10 glycine-containing dipeptides, and 3 glycine-containing diketopiperazines were detected. Miller's experiment was repeated and similar polymerization products were observed. Aqueous heating experiments indicate that Strecker synthesis intermediates play a key role in facilitating polymerization. These results highlight the potential importance of condensing reagents in generating diversity within the prebiotic chemical inventory.

  13. Combination of carbon nitride and carbon nanotubes: synergistic catalysts for energy conversion.

    PubMed

    Gong, Yutong; Wang, Jing; Wei, Zhongzhe; Zhang, Pengfei; Li, Haoran; Wang, Yong

    2014-08-01

    Due to their versatile features and environmental friendliness, functionalized carbon materials show great potential in practical applications, especially in energy conversion. Developing carbon composites with properties that can be modulated by simply changing the ratio of the original materials is an intriguing synthetic strategy. Here, we took cyanamide and multiwalled carbon nanotubes as precursors and introduced a facile method to fabricate a series of graphitic carbon nitride/carbon nanotubes (g-C3 N4 /CNTs) composites. These composites demonstrated different practical applications with different weight ratios of the components, that is, they showed synergistic effects in optoelectronic conversion when g-C3 N4 was the main ingredient and in oxygen reduction reaction (ORR) when CNTs dominated the composites. Our experiments indicated that the high electrical conductivity of carbon nanotubes promoted the transmission of the charges in both cases.

  14. Patents, antibiotics, and autarky in Spain.

    PubMed

    Romero De Pablos, Ana

    2014-01-01

    Patents on antibiotics were introduced in Spain in 1949. Preliminary research reveals diversification in the types of antibiotics: patents relating to penicillin were followed by those relating to streptomycin, erythromycin and tetracycline. There was also diversification in the firms that applied for patents: while Merck & Co. Incorporated and Schenley Industries Inc. were the main partners with Spanish antibiotics manufacturers in the late 1940s, this industrial space also included many others, such as Eli Lilly & Company, Abbott Laboratories, Chas. Pfizer & Co. Incorporated, and American Cyanamid Company in the mid-1970s. The introduction of these drugs in Spain adds new elements to a re-evaluation of the autarkic politics of the early years of the Franco dictatorship.

  15. Green synthesis of CuO nanoparticles by aqueous extract of Gundelia tournefortii and evaluation of their catalytic activity for the synthesis of N-monosubstituted ureas and reduction of 4-nitrophenol.

    PubMed

    Nasrollahzadeh, Mahmoud; Maham, Mehdi; Sajadi, S Mohammad

    2015-10-01

    A facile, efficient and environmentally-friendly protocol has been developed for the green synthesis of CuO nanoparticles (NPs) by aqueous extract of Gundelia tournefortii as a mild, renewable and non-toxic reducing agent. CuO NPs were characterized by SEM, TEM, XRD, EDS, FT-IR and UV-vis spectroscopy. More importantly, the green synthesized CuO NPs presented excellent catalytic activity for reduction of 4-nitrophenol and synthesis of N-monosubstituted ureas via hydration of cyanamides with the aid of acetaldoxime as an effective water surrogate in ethanol as a green solvent. The catalyst was easily separated and the recovered catalyst was reused many times without any significant loss of the catalytic activity.

  16. Structure-activity relationship studies on 1-heteroaryl-3-phenoxypropan-2-ones acting as inhibitors of cytosolic phospholipase A2α and fatty acid amide hydrolase: replacement of the activated ketone group by other serine traps.

    PubMed

    Sundermann, Tom; Hanekamp, Walburga; Lehr, Matthias

    2016-08-01

    Cytosolic phospholipase A2α (cPLA2α) and fatty acid amide hydrolase (FAAH) are serine hydrolases. cPLA2α is involved in the generation of pro-inflammatory lipid mediators, FAAH terminates the anti-inflammatory effects of endocannabinoids. Therefore, inhibitors of these enzymes may represent new drug candidates for the treatment of inflammation. We have reported that certain 1-heteroarylpropan-2-ones are potent inhibitors of cPLA2α and FAAH. The serine reactive ketone group of these compounds, which is crucial for enzyme inhibition, is readily metabolized resulting in inactive alcohol derivatives. In order to obtain metabolically more stable inhibitors, we replaced this moiety by α-ketoheterocyle, cyanamide and nitrile serine traps. Investigations on activity and metabolic stability of these substances revealed that in all cases an increased metabolic stability was accompanied by a loss of inhibitory potency against cPLA2α and FAAH, respectively.

  17. Metabolic basis of ethylene glycol monobutyl ether (2-butoxyethanol) toxicity: role of alcohol and aldehyde dehydrogenases

    SciTech Connect

    Ghanayem, B.I.; Burka, L.T.; Matthews, H.B.

    1987-07-01

    2-Butoxyethanol (BE) is a massively produced glycol ether of which more than 230 million pounds was produced in the United States in 1983. It is extensively used in aerosols and cleaning agents intended for household use. This creates a high potential for human exposure during its manufacturing and use. A single exposure of rats to BE causes severe hemolytic anemia accompanied by secondary hemoglobinuria as well as liver and kidney damage. Butoxyacetic acid (BAA) was earlier identified as a urinary metabolite of BE. In addition, we have recently identified two additional urinary metabolites of BE, namely, BE-glucuronide and BE-sulfate conjugates. The current studies were undertaken to investigate the metabolic basis of BE-induced hematotoxicity in male F344 rats. Treatment of rats with pyrazole (alcohol dehydrogenase inhibitor) protected rats against BE-induced hematotoxicity and inhibited BE metabolism to BAA. Pyrazole inhibition of BE metabolism to BAA was accompanied by increased BE metabolism to BE-glucuronide and BE-sulfate as determined by quantitative high-performance liquid chromatography analysis of BE metabolites in urine. There was approximately a 10-fold decrease in the ratio of BAA to BE-glucuronide + BE-sulfate in the urine of rats treated with pyrazole + BE compared to rats treated with BE alone. Pretreatment of rats with cyanamide (aldehyde dehydrogenase inhibitor) also significantly protected rats against BE-induced hematotoxicity and modified BE metabolism in a manner similar to that caused by pyrazole. Administration of equimolar doses of BE, the metabolic intermediate butoxyacetaldehyde, or the ultimate metabolite BAA caused similar hematotoxic effects. Cyanamide also protected rats against butoxyacetaldehyde-induced hematotoxicity.

  18. Evaluation of a diverse set of potential P1 carboxylic acid bioisosteres in hepatitis C virus NS3 protease inhibitors.

    PubMed

    Rönn, Robert; Gossas, Thomas; Sabnis, Yogesh A; Daoud, Hanna; Kerblom, Eva; Danielson, U Helena; Sandström, Anja

    2007-06-15

    There is an urgent need for more efficient therapies for people infected with hepatitis C virus (HCV). HCV NS3 protease inhibitors have shown proof-of-concept in clinical trials, which make the virally encoded NS3 protease an attractive drug target. Product-based NS3 protease inhibitors comprising a P1 C-terminal carboxylic acid have shown to be effective and we were interested in finding alternatives to this crucial carboxylic acid group. Thus, a series of diverse P1 functional groups with different acidity and with possibilities to form a similar, or an even more powerful, hydrogen bond network as compared to the carboxylic acid were synthesized and incorporated into potential inhibitors of the NS3 protease. Biochemical evaluation of the inhibitors was performed in both enzyme and cell-based assays. Several non-acidic C-terminal groups, such as amides and hydrazides, were evaluated but failed to produce inhibitors more potent than the corresponding carboxylic acid inhibitor. The tetrazole moiety, although of similar acidity to a carboxylic acid, provided an inhibitor with mediocre potencies in both assays. However, the acyl cyanamide and the acyl sulfinamide groups rendered compounds with low nanomolar inhibitory potencies and were more potent than the corresponding carboxylic acid inhibitor in the enzymatic assay. Additionally, results from a pH-study suggest that the P(1) C-terminal of the inhibitors comprising a carboxylic acid, an acyl sulfonamide or an acyl cyanamide group binds in a similar mode in the active site of the NS3 protease.

  19. Aldehyde dehydrogenase-2 inhibition blocks remote preconditioning in experimental and human models.

    PubMed

    Contractor, Hussain; Støttrup, Nicolaj B; Cunnington, Colin; Manlhiot, Cedric; Diesch, Jonathan; Ormerod, Julian O M; Jensen, Rebekka; Bøtker, Hans Erik; Redington, Andrew; Schmidt, Michael R; Ashrafian, Houman; Kharbanda, Rajesh K

    2013-05-01

    Mitochondrial aldehyde dehydrogenase-2 (ALDH-2) is involved in preconditioning pathways, but its role in remote ischaemic preconditioning (rIPC) is unknown. We investigated its role in animal and human models of rIPC. (i) In a rabbit model of myocardial infarction, rIPC alone reduced infarct size [69 ± 5.8 % (n = 11) to 40 ± 6.5 % (n = 12), P = 0.019]. However, rIPC protection was lost after pre-treatment with the ALDH-2 inhibitor cyanamide (62 ± 7.6 % controls, n = 10, versus 61 ± 6.9 % rIPC after cyanamide, n = 10, P > 0.05). (ii) In a forearm plethysmography model of endothelial ischaemia-reperfusion injury, 24 individuals of Asian ethnic origin underwent combined rIPC and ischaemia-reperfusion (IR). 11 had wild-type (WT) enzyme and 13 carried the Glu504Lys (ALDH2*2) polymorphism (rendering ALDH-2 functionally inactive). In WT individuals, rIPC protected against impairment of response to acetylcholine (P = 0.9), but rIPC failed to protect carriers of Glu504Lys polymorphism (P = 0.004). (iii) In a second model of endothelial IR injury, 12 individuals participated in a double-blind placebo-controlled crossover study, receiving the ALDH-2 inhibitor disulfiram 600 mg od or placebo for 48 h prior to assessment of flow-mediated dilation (FMD) before and after combined rIPC and IR. With placebo, rIPC was effective with no difference in FMD before and after IR (6.18 ± 1.03 % and 4.76 ± 0.93 % P = 0.1), but disulfiram inhibited rIPC with a reduction in FMD after IR (7.87 ± 1.27 % and 3.05 ± 0.53 %, P = 0.001). This study demonstrates that ALDH-2 is involved in the rIPC pathway in three distinct rabbit and human models. This has potential implications for future clinical studies of remote conditioning.

  20. The infrared spectra of nitriles and related compounds frozen in Ar and H2O

    NASA Technical Reports Server (NTRS)

    Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

    1997-01-01

    We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2

  1. The Infrared Spectra of Nitriles and Related Compounds Frozen in Ar and H2O

    NASA Technical Reports Server (NTRS)

    Bernstain, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Witteborn, Fred C. (Technical Monitor)

    1996-01-01

    We present the 2320-2050/cm (4.31-4.88 micron) infrared spectra of 16 solid state nitrites, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C(is congruent to)N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile phenylcyanide) 9-anthracenecarbonitrile, dimethylcyanamide, isopropy1nitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyr-uvonitrile, dicyandiamide, cyanamide, n-butyfisocyanide, methylisocyanoacetate, dilsopropylcarbodiimide, and hydrogen cyanide. The C(is congruent to)N stretching bands of the majority of nitrites fall in the 2300-2200/cm (4.35-4.55 micron) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contest, the isonitriles and a few exceptional nitrites and related species produce bands at lower frequencies spanning the 2200-2080/cm (4.55-4.81 micron) range. These features also have similar positions in both Am and H2O matrices and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C(is congruent to)N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165/cm (4.62 micron) "XCN" interstellar feature and the 4550/cm (2.2 micron) feature of

  2. The Infrared Spectra of Nitriles and Related Compounds Frozen in Ar and H2O

    NASA Astrophysics Data System (ADS)

    Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.

    1997-02-01

    We present the 2320-2050 cm-1 (4.31-4.88 μm) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C≡N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C≡N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 μm) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 μm) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C≡N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 μm) ``XCN'' interstellar feature and the 4550 cm-1 (2.2 μm) feature of various objects in the solar system are

  3. The Millimeter/submillimeter Spectrum of Cyanophosphine, PH_2CN ({X^1A^')

    NASA Astrophysics Data System (ADS)

    Halfen, D. T.; Clouthier, D. J.; Ziurys, L. M.

    2010-06-01

    Cyanophosphine, PH_2CN (~X1A^'), is the third row analog of cyanamide, a known interstellar molecule, and could be a potential interstellar species. However, only the microwave spectrum has been measured to date, and predictions at millimeter/submillimeter wavelengths have high uncertainities. Therefore, the millimeter/submillimeter spectrum of cyanophosphine has been measured using direct absorption techniques. This molecule was created by the reaction of gas-phase phosphorus, (CN)_2, and H_2 in the presence of argon carrier gas and an AC glow discharge. Eleven transitions have been recorded in the range 305-422 GHz each with multiple asymmetry components from K_a = 0 to 8. No evidence of inversion splitting was visible in the spectrum. The data have been fit with an asymmetric top Hamiltonian, and the spectroscopic constants have been determined. The A rotational constant and several higher-order centrifugal distortion parameters have been determined for the first time, allowing accurate predictions in the millimeter/submillimeter region. Here we report our laboratory measurements and an astronomical search.

  4. Decorating in situ ultrasmall tin particles on crumpled N-doped graphene for lithium-ion batteries with a long life cycle

    NASA Astrophysics Data System (ADS)

    Liu, Lianjun; Huang, Xingkang; Guo, Xiaoru; Mao, Shun; Chen, Junhong

    2016-10-01

    The practical application of Sn, a promising anode material for lithium-ion batteries, is hindered primarily by its huge volume change (up to 260%) upon lithiation. To tackle this obstacle, here we report a facile one-pot method, i.e., pyrolysis of a mixture of GO, SnCl4, and cyanamide at elevated temperatures to create in situ a novel mesoporous structure of Sn@N-doped graphene (Sn@NG). In the constructed architecture, the ultrasmall Sn nanoparticles (2-3 nm) are uniformly embedded in the NG network while the crumpled NG provides good electronic conductivity, abundant defects, high surface area, and large mesopore volume. Due to the combination of these merits, Sn@NG exhibits extremely long-term cycling stability, even at high rates, retaining a capacity of 568 mAh g-1 at 1 A g-1 (90% retention) and 535 mAh g-1 at 2 A g-1 (91.6% retention) after 1000 and 900 cycles, respectively. This performance is superior to that of Sn@G (without N-doping) and Sn//NG prepared using a two-step process with large particle sizes (>30 nm) and uneven dispersion of Sn. The findings from this work will shed light on the design of efficient and stable Sn and other metal-based materials for energy storage and conversion.

  5. The Chemistry of Nitroxyl-Releasing Compounds

    PubMed Central

    DuMond, Jenna F.

    2011-01-01

    Abstract Nitroxyl (HNO) demonstrates a diverse and unique biological profile compared to nitric oxide, a redox-related compound. Although numerous studies support the use of HNO as a therapeutic agent, the inherent chemical reactivity of HNO requires the use of donor molecules. Two general chemical strategies currently exist for HNO generation from nitrogen-containing molecules: (i) the disproportionation of hydroxylamine derivatives containing good leaving groups attached to the nitrogen atom and (ii) the decomposition of nitroso compounds (X-N=O, where X represents a good leaving group). This review summarizes the synthesis and structure, the HNO-releasing mechanisms, kinetics and by-product formation, and alternative reactions of six major groups of HNO donors: Angeli's salt, Piloty's acid and its derivatives, cyanamide, diazenium diolate-derived compounds, acyl nitroso compounds, and acyloxy nitroso compounds. A large body of work exists defining these six groups of HNO donors and the overall chemistry of each donor requires consideration in light of its ability to produce HNO. The increasing interest in HNO biology and the potential of HNO-based therapeutics presents exciting opportunities to further develop HNO donors as both research tools and potential treatments. Antioxid. Redox Signal. 14, 1637–1648. PMID:21235345

  6. Polymer-assisted iron oxide magnetic nanoparticle immobilized keratinase

    NASA Astrophysics Data System (ADS)

    Konwarh, Rocktotpal; Karak, Niranjan; Rai, Sudhir Kumar; Mukherjee, Ashis Kumar

    2009-06-01

    Nanotechnology holds the prospect for avant-garde changes to improve the performance of materials in various sectors. The domain of enzyme biotechnology is no exception. Immobilization of industrially important enzymes onto nanomaterials, with improved performance, would pave the way to myriad application-based commercialization. Keratinase produced by Bacillus subtilis was immobilized onto poly(ethylene glycol)-supported Fe3O4 superparamagnetic nanoparticles. The optimization process showed that the highest enzyme activity was noted when immobilized onto cyanamide-activated PEG-assisted MNP prepared under conditions of 25 °C and pH 7.2 of the reaction mixture before addition of H2O2 (3% w/w), 2% (w/v) PEG6000 and 0.062:1 molar ratio of PEG to FeCl2·4H2O. Further statistical optimization using response surface methodology yielded an R2 value that could explain more than 94% of the sample variations. Along with the magnetization studies, the immobilization of the enzyme onto the PEG-assisted MNP was characterized by UV, XRD, FTIR and TEM. The immobilization process had resulted in an almost fourfold increase in the enzyme activity over the free enzyme. Furthermore, the immobilized enzyme exhibited a significant thermostability, storage stability and recyclability. The leather-industry-oriented application of the immobilized enzyme was tested for the dehairing of goat-skin.

  7. Non-metal photocatalyst nitrogen-doped carbon nanotubes modified mpg-C3N4: facile synthesis and the enhanced visible-light photocatalytic activity.

    PubMed

    Liu, Jinyuan; Song, Yanhua; Xu, Hui; Zhu, Xingwang; Lian, Jiabiao; Xu, Yuanguo; Zhao, Yan; Huang, Liying; Ji, Haiyan; Li, Huaming

    2017-05-15

    Nitrogen-doped carbon nanotubes (N-CNT) is a promising metal-free candidate and electronic acceptor. It has been employed to modify mesoporous carbon nitride (mpg-C3N4) for photocatalytic degradation of organic dye and antibiotics under visible-light irradiation. Herein, we report a facile synthesis strategy involving polymerization of cyanamide as the precursor in the presence of N-CNT via thermal polycondensation. The morphology and structure of as-prepared N-CNT/mpg-C3N4 were analyzed by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The N-CNT/mpg-C3N4-15 exhibited increased photocatalytic activity for rhodamine B (RhB), methyl orange (MO) and tetracycline hydrochloride (TC) degradation compared with the pure one under visible-light irradiation, which is mainly due to the efficiently separation of photogenerated electron-hole pairs for the introduction of N-CNT as electronic acceptor. The photocatalytic reaction can fit the first order kinetics. Additionally, superoxide radical (O2(-)) was regarded as main reactive species participating in the photodegradation reaction process. Furthermore, the reason for enhancing photocatalytic activity of N-CNT/mpg-C3N4 is mainly attributed to synergistic effects between mpg-C3N4 as main ingredient and N-CNT as electron acceptor.

  8. Development of improved mobility control agents for surfactant/polymer flooding. First annual report, September 29, 1978-September 30, 1979

    SciTech Connect

    Martin, F.D.

    1980-05-01

    Phase 1: Based on a literature survey and input solicited from industry, academic, and government sources, inadequacies of the currently used mobility control materials were assessed. Phase 2: Baseline screening of commercially available polymers began in January 1979. Rheological measurements and mobility control test in Berea cores have been completed on Dow Pusher 700, Betz Hi Vis, Nalco Nal-flo, Cyanamid 960S, Kelco Xanflood, and Abbott Xanthan Broth. Similar tests were completed for Pusher 500, Pusher 1000, Amoco Sweepaid 103, and Pfizer Flocon Biopolymer 1035. Shear degradation tests in Berea core plugs have been completed for one acrylamide-type polymer and one xanthan polymer in 0.3% NaCl. Similar tests in 3% NaCl plus 0.3% CaCl/sub 2/ are in progress. Viscosity and screen factor data have been collected for most of the commercially available polymers. Long-term thermal stability tests with one polyacrylamide polymer and one xanthan polymer have been initiated. Phase 3: The polymer synthesis phase of the program is in progress. A series of N-alkyl (N-methyl, N-isopropyl, and N-butyl) acrylamide homopolymers and copolymers with acrylic acid has been synthesized. Variations of the substituents on the acrylamide nitrogen atom did not substantially change the properties of the parent compound. Increasing the molecular weight tends to impart increased shear sensitivity. Degree of hydrolysis also affects performance of the modified polymer. 25 figures, 40 tables.

  9. Mechanical properties testing of candidate polymer matrix materials for use in high performance composites

    NASA Technical Reports Server (NTRS)

    Zimmerman, R. S.; Adams, D. F.

    1985-01-01

    The mechanical properties of four candidate neat resin systems for use in graphite/epoxy composites are characterized. This includes tensile and shear stiffnesses and strengths, coefficients of thermal and moisture expansion, and fracture toughness. Tests are conducted on specimens in the dry state and moisture-saturated, at temperatures of 23C, 82C and 121C. The neat resins tested are Hexcel HX-1504, Narmco 5245-C, American Cyanamid CYCOM 907, and Union Carbide ERX-4901A (MDA). Results are compared with those obtained for four other epoxy resins tested in a prior program, i.e., Hercules 3502, 2220-1, and 2220-3, and Ciba-Geigy Fibredux 914, as well as with available Hercules 3501-6 data. Scanning electron microscopic examination of fracture surfaces is performed to permit the correlation of observed failure modes with the environmental test conditions. A finite element micromechanics analysis is used to predict unidirectional composite response under various test conditions, using the measured neat resin properties as input data.

  10. Mechanical properties of neat polymer matrix materials and their unidirectional carbon fiber-reinforced composites

    NASA Technical Reports Server (NTRS)

    Zimmerman, Richard S.; Adams, Donald F.

    1988-01-01

    The mechanical properties of two neat resin systems for use in carbon fiber epoxy composites were characterized. This included tensile and shear stiffness and strengths, coefficients of thermal and moisture expansion, and fracture toughness. Tests were conducted on specimens in the dry and moisture-saturated states, at temperatures of 23, 82 and 121 C. The neat resins tested were American Cyanamid 1806 and Union Carbide ERX-4901B(MPDA). Results were compared to previously tested neat resins. Four unidirectional carbon fiber reinforced composites were mechanically characterized. Axial and transverse tension and in-plane shear strengths and stiffness were measured, as well as transverse coefficients of thermal and moisture expansion. Tests were conducted on dry specimens only at 23 and 100 C. The materials tested were AS4/3502, AS6/5245-C, T300/BP907, and C6000/1806 unidirectional composites. Scanning electron microscopic examination of fracture surfaces was performed to permit the correlation of observed failure modes with the environmental test conditions.

  11. Retention of radiolead by human erythrocytes in vitro

    SciTech Connect

    Barton, J.C.

    1989-06-15

    An in vitro method was developed to assess human erythrocyte lead uptake and release directly, rapidly, and reproducibly; the technique requires small aliquots of blood and uses silicone fluid to separate erythrocytes from their suspending media. Uptake occurred rapidly and was directly related to temperature. Increasing quantities of available elemental lead were associated with increasing absolute quantities but decreasing percentages of uptake. Low values of pH diminished the uptake and enhanced the release of radiolead by erythrocytes, and could be correlated with diminished lead-hemoglobin binding para-Chloromecuribenzoate increased and dithiothreitol inhibited radiolead uptake but neither compound affected lead release, suggesting that sulfhydryl groups are important for lead binding to the erythrocyte. Cyanamide and N-ethylmaleimide did not significantly affect the net uptake or release of radiolead. Calcium disodium EDTA, penicillamine, and dimercaprol significantly reduced lead uptake, although only incubation with dimercaprol resulted in a net removal of lead from erythrocytes. Iron and ceruloplasmin significantly decreased radiolead uptake, but inorganic metal cations other than iron, hyperosmolarity, human serum albumin, cholesterol, and transferrin had no significant effect on uptake or release.

  12. Liver glycogen bodies: ground-glass hepatocytes in transplanted patients.

    PubMed

    Bejarano, Pablo A; Garcia, Monica T; Rodriguez, Maria M; Ruiz, Phillip; Tzakis, Andreas G

    2006-11-01

    Ground-glass hepatocytes have been described in Lafora's disease, fibrinogen deposition, hepatitis B, type IV glycogenosis, and alcohol aversion (cyanamide) therapy. We encountered ground-glass hepatocytes with intracytoplasmic inclusions in four liver biopsies from three transplanted patients who had none of the above-mentioned underlying diseases. One patient was a 4-year-old boy who had a kidney transplant for severe ureterovesical reflux. Patient 2 was a 52-year-old man who had two liver transplants because of hepatitis C. The third patient was a 7-month-old girl who underwent a multivisceral transplant because of necrotizing enterocolitis and liver failure induced by total parenteral nutrition. The patients developed liver abnormalities from 45 days to 4 years after their transplants. The livers showed conspicuous ground-glass hepatocytes in 90% of the children's samples and 30% of the adult liver cells. The cytoplasmic bodies stained strongly for Gomori methenamine-silver; they were positive for periodic acid-Schiff without diastase, but negative after diastase digestion. They were negative for colloidal iron and hepatitis B core and surface antigens. Electron microscopy revealed non-membrane bound aggregates of glycogen. Idiopathic ground-glass hepatocytes occur in transplanted patients and represent accumulation of altered glycogen. However, their clinical significance and cause are not entirely elucidated.

  13. Theoretical studies on the formation mechanism and explosive performance of nitro-substituted 1,3,5-triazines.

    PubMed

    Yang, Kiyull; Park, Young Hee; Cho, Soo Gyeong; Lee, Hai Whang; Kim, Chan Kyung; Koo, Hyun-Joo

    2010-10-01

    To develop new highly energetic materials, we have considered the design of molecules with high nitrogen content. Possible candidates include 1,3,5-triazine derivatives. In this work, we studied potential synthetic routes for melamine using the MP2/6-31+G(d,p)//B3LYP/6-31G(d) level of theory. The mechanisms studied here are stepwise mechanism beginning with the dimerization of cyanamide and one-step termolecular mechanism. The same type of mechanism is also applied to nitro-substituted 1,3,5-triazines. Values for the heat of formation in the solid phase were predicted from density functional theory calculations. Densities were estimated from a regression equation obtained by molecular surface electrostatic potentials. The Cheetah program was used to study the explosive performance of these compounds. In this study, we found that the explosive properties of 2-amino-4, 6-dinitro-1, 3,5-triazine (ADNTA), and 2,4,6-trinitro-1,3,5-triazine (TNTA) are similar to those of RDX and HMX, respectively.

  14. The effect of alterations in total coenzyme A on metabolic pathways in the liver and heart

    SciTech Connect

    Schlosser, C.A.S.

    1989-01-01

    The first set of experiments involved in vitro experiments using primary cultures of rat hepatocytes. A range of conditions were developed which resulted in cell cultures with variations in total CoA over a range of 1.3 to 2.9 nmol/mg protein with identical hormonal activation which simulated metabolic stress. Elevations of total CoA levels above that of controls due to preincubation with cyanamide plus pantothenate were correlated with diminished rates of total ketone body production, 3-hydroxybutyrate production and ratios of 3 hydroxybutyrate/acetoactetate with palmitate as substrate. In contrast, cells with elevated total CoA levels had higher rates of ({sup 14}C) CO{sub 2} production from radioactive palmitate which implied greater flux of acetyl CoA units into the TCA cycle and less to the pathway of ketogenesis. The second set of experiments were designed to alter total CoA levels in vivo by maintaining rats on a chronic ethanol diet with or without pantothenate-supplementation. The effect of alterations of CoA on mitochondrial metabolism was evaluated by measuring substrate oxidation rates in liver and heat mitochondria as well as ketone body production with palmitoyl-1-carnitine as substrate.

  15. Enhanced Catalytic Activity of Pt Supported on Nitrogen-Doped Reduced Graphene Oxide Electrodes for Fuel Cells.

    PubMed

    Sun, Qizhong; Park, Soo-Jin; Kim, Seok

    2015-11-01

    We report an efficient method for the synthesis of nitrogen-doped reduced graphene oxide supported Pt nanocatalysts (Pt/N-RGO). Nitrogen-doped reduced graphene oxide (N-RGO) was prepared by pyrolysis of graphene oxide with cyanamide as a nitrogen source. Then, the Pt nanoparticles were deposited over N-RGO by one-step chemical polyol reduction process. The morphology and structure of as-prepared catalysts were characterized by transmission electron microscopy (TEM), and X-ray diffraction (XRD). Subsequently, electrocatalytic activities of the catalysts were evaluated by cyclic voltammetry (CV). As a result, the Pt/N-RGO catalysts exhibit the superior electrochemical activity toward methanol oxidation in compared with that of Pt loaded on undoped reduced graphene oxide (Pt/RGO) and Pt/carbon blacks (Pt/C). This was mainly attributed to the better distribution of Pt nanoparticles as well as the synergistic electrochemical effects of the nitrogen doped supports. These results demonstrate that N-RGO could be a promising candidate as a high performance catalyst support for a fuel cell application.

  16. The effect of resin toughness and modulus on compressive failure modes of quasi-isotropic graphite/epoxy laminates

    NASA Technical Reports Server (NTRS)

    Sohi, M. M.; Hahn, H. T.; Williams, J. G.

    1986-01-01

    Compressive failure mechanisms in quasi-isotropic graphite/epoxy laminates were characterized for both unnotched and notched specimens and also following damage by impact. Two types of fibers (Thornel 300 and 700) and four resin systems (Narmco 5208, American Cyanamid BP907, and Union Carbide 4901/MDA and 4901/mPDA) were studied. For all material combinations, failure of unnotched specimens was initiated by kinking of fibers in the 0-degree plies. A major difference was observed, however, in the mode of failure propagation after the 0-degree ply failure. The strength of quasi-isotropic laminates in general increased with increasing resin tensile modulus. The laminates made with Thornel 700 fibers exhibited slightly lower compressive strengths than did the laminates made with Thornel 300 fibers. The notch sensitivity as measured by the hole strength was lowest for the BP907 resin and highest for the 5208 resin. For the materials studied, however, the type of fiber had no effect on the notch sensitivity.

  17. Hybrid process for nitrogen oxides reduction

    SciTech Connect

    Epperly, W.R.; Sprague, B.N.

    1991-09-10

    This patent describes a process for reducing the nitrogen oxide concentration in the effluent from the combustion of a carbonaceous fuel. It comprises introducing into the effluent a first treatment agent comprising a nitrogenous composition selected from the group consisting of urea, ammonia, hexamethylenetetramine, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, NH{sub 4}-lignosulfonate, fur-furylamine, tetrahydrofurylamine, hexamethylenediamine, barbituric acid, guanidine, guanidine carbonate, biguanidine, guanylurea sulfate, melamine, dicyandiamide, biuret, 1.1{prime}-azobisformamide, methylol urea, methylol urea-urea condensation product, dimethylol urea, methyl urea, dimethyl urea, calcium cyanamide, and mixtures thereof under conditions effective to reduce the nitrogen oxides concentration and ensure the presence of ammonia in the effluent; introducing into the effluent a second treatment agent comprising an oxygenated hydrocarbon at an effluent temperature of about 500{degrees} F. to about 1600{degrees} F. under conditions effective to oxidize nitric oxide in the effluent to nitrogen dioxide and ensure the presence of ammonia at a weight ratio of ammonia to nitrogen dioxide of about 1:5 to about 5:1; and contacting the effluent with an aqueous scrubbing solution having a pH of 12 or lower under conditions effective to cause nitrogen dioxide to be absorbed therein.

  18. Mulit-stage process for reducing the concentration of pollutants in an effluent

    SciTech Connect

    Epperly, W.R.; Peter-Hoblyn, J.D.; Shulof, Jr.,G.F.; Sullivan, J.C.

    1988-10-11

    This patent describes a process for reducing the concentration of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel, the process comprising: a. injecting a first treatment agent comprising urea or ammonia into the effluent at a first temperature zone where the effluent is at a temperature of greater than about 1700F; b. injecting a second treatment agent comprising urea or ammonia, each of which further comprises an enhancer selected from the group consisting of hexamethylenetetramine, an oxygenated hydrocarbon, a hydroxy amino hydrocarbon, an amino acid, a protein-containing composition, guanidine, guanidine carbonate, biguanidine, guanylurea sulfate, melamine, dicyandiamide, calcium cyanamide, diuret, 1,1' -azobisformamide, methylol urea, methylol urea-urea condensation product, dimethylol urea, methyl urea, dimethyl urea, and mixtures thereof into the effluent at a second temperature zone where the effluent temperature is about 1350F to about 1750F; and c. injecting a third treatment agent comprising a composition selected from the group consisting of paraffinic, olefinic, aromatic, oxygenated and hydroxy amino hydrocarbons, and hydrogen peroxide, and mixtures thereof into the effluent at a third temperature zone where the effluent temperature is below about 1400F; wherein the treatment agents are injected under conditions effective to reduce the effluent pollution index.

  19. Alcohol-induced hepatotoxicity: a role for oxygen free radicals.

    PubMed

    Younes, M; Strubelt, O

    1987-01-01

    Perfusion of isolated rat livers with ethanol at a concentration of 2 g/l (%o) resulted in a release of glutamate-pyruvate-transaminase (GPT) and sorbitol dehydrogenase (SDH) into the perfusate as markers of toxicity. Inhibition of alcohol dehydrogenase by 4-methylpyrazole or of aldehyde dehydrogenase by cyanamide totally abolished ethanol hepatotoxicity despite of a severalfold increase in acetaldehyde concentration in the perfusate. Addition of superoxide dismutase or catalase clearly suppressed the ethanol-induced release of GPT and SDH, suggesting that .O2- and H2O2 are involved in this process. Also, chelation of iron ions by means of desferrioxamine displayed a clear inhibitory action, suggesting the involvement of an iron-catalyzed Haber-Weiss-reaction leading to the formation of .OH radicals in the hepatotoxic response to ethanol. Our data suggest that during the metabolism of acetaldehyde primary reactive oxygen species (.O2-, H2O2) are produced which may interact to yield hydroxyl or .OH-like radicals, which possibly represent the hepatotoxic principle of ethanol.

  20. Methanex, Hoechst Celanese dissolve methanol partnership

    SciTech Connect

    Morris, G.D.L.

    1993-03-31

    One of the many joint venture alliances recently announced in the petrochemical sector is ending in divorce. Hoechst Celanese Chemical (Dallas) and Methanex Corp. (Vancouver) are in the process of dissolving the partnership they had formed to restart Hoechst Celanese's methanol plant at Clear Lake, TX. Hoechst Celanese says it is actively seeking replacement partners and has several likely prospects, while Methanex is concentrating on its other ventures. Those include its just-completed acquisition of Fletcher Challenge's (Auckland, NZ) methanol business and a joint venture with American Cyanamid to convert an ammonia plant at Fortier, LA to methanol. Methanex will still be the world's largest producer of methanol. Officially, the negotiations between Methanex and Hoechst Celanese just broke down over the last month or so,' says Steve Yurich, operations manager for the Clear Lake plant. Market sources, however, say that Methanex found itself with too many irons in the fire' and pulled out before it ran into financial or perhaps even antitrust difficulties.

  1. Historic American Engineering Record, Idaho National Laboratory, Idaho Chemical Processing Plant, Fuel Reprocessing Complex

    SciTech Connect

    Susan Stacy; Julie Braun

    2006-12-01

    Just as automobiles need fuel to operate, so do nuclear reactors. When fossil fuels such as gasoline are burned to power an automobile, they are consumed immediately and nearly completely in the process. When the fuel is gone, energy production stops. Nuclear reactors are incapable of achieving this near complete burn-up because as the fuel (uranium) that powers them is burned through the process of nuclear fission, a variety of other elements are also created and become intimately associated with the uranium. Because they absorb neutrons, which energize the fission process, these accumulating fission products eventually poison the fuel by stopping the production of energy from it. The fission products may also damage the structural integrity of the fuel elements. Even though the uranium fuel is still present, sometimes in significant quantities, it is unburnable and will not power a reactor unless it is separated from the neutron-absorbing fission products by a method called fuel reprocessing. Construction of the Fuel Reprocessing Complex at the Chem Plant started in 1950 with the Bechtel Corporation serving as construction contractor and American Cyanamid Company as operating contractor. Although the Foster Wheeler Corporation assumed responsibility for the detailed working design of the overall plant, scientists at Oak Ridge designed all of the equipment that would be employed in the uranium separations process. After three years of construction activity and extensive testing, the plant was ready to handle its first load of irradiated fuel.

  2. Identification of antigenic differences of recombinant and pituitary bovine growth hormone using monoclonal antibodies.

    PubMed

    Erhard, M H; Kellner, J; Schmidhuber, S; Schams, D; Lösch, U

    1994-02-01

    For characterization and determination of recombinant bovine GH (rbGH) eight monoclonal antibodies (MAb) were produced against rbGH from Monsanto. The various MAb showed different affinities to rbGH, pituitary bovine GH (pbGH), and pituitary ovine GH (poGH). With epitope analysis several MAb were shown to recognize different epitopes of rbGH. The MAb MUC-rbGH-3A11 and MUC-rbGH-1E5 were used to develop a Sandwich ELISA. By checking the specificity of the assay no cross reactivity was found with pituitary porcine GH, pituitary human GH, bovine or ovine prolactin and little cross reactivity with poGH could be found. The Sandwich ELISA detected various rbGH (Monsanto, Elanco, Cyanamid) with different N-terminal amino acids and discriminated between rbGH and pituitary bovine GH by an affinity factor of 2.0. The detection level was 2 ng rbGH per ml PBS buffer. The recovery was about 86% in bovine serum. It might therefore be possible to detect rbGH-treated cows using a Sandwich ELISA, but this would need a field study.

  3. Suppression on plant-parasitic nematodes using a soil fumigation strategy based on ammonium bicarbonate and its effects on the nematode community

    PubMed Central

    Su, Lanxi; Ruan, Yunze; Yang, Xiujuan; Wang, Kang; Li, Rong; Shen, Qirong

    2015-01-01

    Banana production is severely hindered by plant-parasitic nematodes in acidic, sandy soil. This study investigated the possibility of applying a novel fumigation agent based on ammonium bicarbonate as a strategy for controlling plant-parasitic nematodes under sealed conditions. Moreover, its effects on the nematode community in pot and field experiments were also measured using morphology and feeding-habit based classification and the PCR-DGGE method. Results showed that a mixture (LAB) of lime (L) and ammonium bicarbonate (AB) in suitable additive amounts (0.857 g kg−1 of L and 0.428 g kg−1 of AB) showed stronger nematicidal ability than did the use of AB alone or the use of ammonium hydroxide (AH) and calcium cyanamide (CC) with an equal nitrogen amount. The nematode community was altered by the different fumigants, and LAB showed an excellent plant-parasitic nematicidal ability, especially for Meloidogyne and Rotylenchulus, as revealed by morphology and feeding-habit based classification, and for Meloidogyne, as revealed by the PCR-DGGE method. Fungivores and omnivore-predators were more sensitive to the direct effects of the chemicals than bacterivores. This study explored a novel fumigation agent for controlling plant-parasitic nematodes based on LAB and provides a potential strategy to ensure the worldwide development of the banana industry. PMID:26621630

  4. Synthesis of ordered porous graphitic-C3N4 and regularly arranged Ta3N5 nanoparticles by using self-assembled silica nanospheres as a primary template.

    PubMed

    Fukasawa, Yuki; Takanabe, Kazuhiro; Shimojima, Atsushi; Antonietti, Markus; Domen, Kazunari; Okubo, Tatsuya

    2011-01-03

    Uniform-sized silica nanospheres (SNSs) assembled into close-packed structures were used as a primary template for ordered porous graphitic carbon nitride (g-C(3)N(4)), which was subsequently used as a hard template to generate regularly arranged Ta(3)N(5) nanoparticles of well-controlled size. Inverse opal g-C(3)N(4) structures with the uniform pore size of 20-80 nm were synthesized by polymerization of cyanamide and subsequent dissolution of the SNSs with an aqueous HF solution. Back-filling of the C(3)N(4) pores with tantalum precursors, followed by nitridation in an NH(3) flow gave regularly arranged, crystalline Ta(3)N(5) nanoparticles that are connected with each other. The surface areas of the Ta(3)N(5) samples were as high as 60 m(2) g(-1), and their particle size was tunable from 20 to 80 nm, which reflects the pore size of g-C(3)N(4). Polycrystalline hollow nanoparticles of Ta(3)N(5) were also obtained by infiltration of a reduced amount of the tantalum source into the g-C(3)N(4) template. An improved photocatalytic activity for H(2) evolution on the assembly of the Ta(3)N(5) nanoparticles under visible-light irradiation was attained as compared with that on a conventional Ta(3)N(5) bulk material with low surface area.

  5. Are Polyphosphates or Phosphate Esters Prebiotic Reagents?

    NASA Technical Reports Server (NTRS)

    Keefe, Anthony D.; Miller, Stanley L.

    1995-01-01

    It is widely held that there was a phosphate compound in prebiotic chemistry that played the role of adenosine triphosphate and that the first living organisms had ribose-phosphate in the backbone of their genetic material. However, there are no known efficient prebiotic synthesis of high-energy phosphates or phosphate esters. We review the occurrence of phosphates in nature, the efficiency of the volcanic synthesis of P4O10, the efficiency of polyphosphate synthesis by heating phosphate minerals under geological conditions, and the use of high-energy organic compounds such as cyanamide or hydrogen cyanide. These are shown to be inefficient processes especially when the hydrolysis of the polyphosphates is taken into account. For example, if a whole atmosphere of methane or carbon monoxide were converted to cyanide which somehow synthesized polyphosphates quantitatively, the polyphosphate concentration in the ocean would still have been insignificant. We also attempted to find more efficient high-energy polymerizing agents by spark discharge syntheses, but without success. There may still be undiscovered robust prebiotic syntheses of polyphosphates, or mechanisms for concentrating them, but we conclude that phosphate esters may not have been constituents of the first genetic material. Phosphoanhydrides are also unlikely as prebiotic energy sources.

  6. Effect of template-induced surface species on electronic structure and photocatalytic activity of g-C3N4

    NASA Astrophysics Data System (ADS)

    Shen, Yu; Guo, Xiaojuan; Bo, Xiangkun; Wang, Yongzheng; Guo, Xiangke; Xie, Mingjiang; Guo, Xuefeng

    2017-02-01

    In view of the fact that the photocatalytic activity of graphitic carbon nitride (g-C3N4) is greatly influenced by its electronic structure, herein, effect of templates induced surface species variation on the electronic structure and photocatalytic activity of the templated g-C3N4 was investigated. By mixing the precursor of cyanamide with different templates (SiO2, Al2O3 and template-free) in the preparation of graphitic carbon nitride (g-C3N4), carbon nitrides with different surface species were obtained. The obtained carbon nitride (g-C3N4-Si) templated by SiO2 nanoparticles exhibits enlarged band gap (3.26 eV) and enhanced photo-degradation ability towards Methyl Orange (MO) compared to that of bulk g-C3N4 (2.67 eV) synthesized from direct condensation/carbonization of melamine and Al2O3-templated g-C3N4-Al (2.76 eV). Detailed characterizations confirm that the introduction of templates in the synthesis process resulted in more non-graphitic species (sp3sbnd Csbnd Csbnd and sbnd NHx) on the surface of the derived carbon nitrides, exerting remarkable effect on the electronic structure and photocatalytic performance.

  7. NOVP: a novel chemotherapeutic regimen with minimal toxicity for treatment of Hodgkin's disease

    SciTech Connect

    Hagemeister, F.B.; Cabanillas, F.; Velasquez, W.S.; Meistrich, M.L.; Liang, J.C.; McLaughlin, P.; Redman, J.R.; Romaguera, J.E.; Rodriguez, M.A.; Swan, F. Jr. )

    1990-12-01

    Patients with early-staged Hodgkin's disease have had a higher relapse rate following radiotherapy alone if they have B symptoms, large mediastinal masses, hilar involvement, or stage III disease. From June 1988 to December 1989, 27 previously untreated patients with early-staged Hodgkin's disease with adverse features for disease-free survival received combined-modality therapy. Seventeen patients had stage I or II disease, 10 had stage III, 5 had B symptoms, 13 had large mediastinal masses, and 6 had peripheral masses measuring 10 cm or more in diameter. All patients initially received three cycles of a novel chemotherapeutic regimen combining Novantrone (mitoxantrone, American Cyanamid Company), vincristine, vinblastine, and prednisone (NOVP). Twenty-four patients with clinically staged I or II disease with adverse features or stage III disease did not undergo laparotomy; three patients had favorable stage I or II disease and at laparotomy had stage III disease. Radiotherapy-treatment fields depended on the extent of nodal involvement. Twenty-six patients completed all therapy as planned to complete remission (CR) and one of these has had progression; she is in second CR following additional radiotherapy. With a median follow-up of 12 months, all patients are alive. Tolerance to treatment was excellent with only grade 1 or 2 nausea, alopecia and myalgias, and brief myelosuppression. NOVP is an effective adjuvant chemotherapy regimen for inducing responses, with minimal toxicity, prior to definitive radiotherapy for patients with early-staged Hodgkin's disease.

  8. Exploration and Pharmacokinetic Profiling of Phenylalanine Based Carbamates as Novel Substance P 1–7 Analogues

    PubMed Central

    2014-01-01

    The bioactive metabolite of Substance P, the heptapeptide SP1–7 (H-Arg-Pro-Lys-Pro-Gln-Gln-Phe-OH), has been shown to attenuate signs of hyperalgesia in diabetic mice, which indicate a possible use of compounds targeting the SP1–7 binding site as analgesics for neuropathic pain. Aiming at the development of drug-like SP1–7 peptidomimetics we have previously reported on the discovery of H-Phe-Phe-NH2 as a high affinity lead compound. Unfortunately, the pharmacophore of this compound was accompanied by a poor pharmacokinetic (PK) profile. Herein, further lead optimization of H-Phe-Phe-NH2 by substituting the N-terminal phenylalanine for a benzylcarbamate group giving a new type of SP1–7 analogues with good binding affinities is reported. Extensive in vitro as well as in vivo PK characterization is presented for this compound. Evaluation of different C-terminal functional groups, i.e., hydroxamic acid, acyl sulfonamide, acyl cyanamide, acyl hydrazine, and oxadiazole, suggested hydroxamic acid as a bioisosteric replacement for the original primary amide. PMID:25516784

  9. Expression and genomic structure of the dormancy-associated MADS box genes MADS13 in Japanese pears (Pyrus pyrifolia Nakai) that differ in their chilling requirement for endodormancy release.

    PubMed

    Saito, Takanori; Bai, Songling; Ito, Akiko; Sakamoto, Daisuke; Saito, Toshihiro; Ubi, Banjamin Ewa; Imai, Tsuyoshi; Moriguchi, Takaya

    2013-06-01

    We isolated three dormancy-associated MADS-box (DAM) genes (MADS13-1, MADS13-2 and MADS13-3) and showed regulated expression concomitant with endodormancy establishment and release in the leaf buds of Japanese pear 'Kosui'. Comparative analysis between 'Kosui' and Taiwanese pear TP-85-119 ('Hengshanli'), a less dormant pear cultivar, showed reduction of MADS13-1 expression level in 'Hengshanli' earlier than in 'Kosui' towards endodormancy release, suggesting the possible relationship between chilling requirement and MADS13-1 expression. Application of hydrogen cyanamide accelerated endodormancy release with a reduction in MADS13 expression, whereas heat treatment in autumn inhibited endodormancy establishment without induction of MADS13 expression, indicating a close relationship between the MADS13 expression pattern and endodormancy phase transitions. Moreover, both the cis-acting regulatory elements and the methylation status in the 5' upstream region of the MADS13-1 gene were not largely different between 'Kosui' and 'Hengshanli'. Genomic structures of MADS13-1 from 'Kosui' and 'Hengshanli' revealed a 3218 bp insertion in the first intron of 'Hengshanli' that might be ascribed to the lower expression of MADS13-1tw; however, this insertion was also found in pear genotypes with a high chilling requirement. These results indicated that the low expression of MADS13-1 in 'Hengshanli' towards endodormancy release could not be explained by the identified cis-acting regulatory elements, the methylation status of the putative promoter or by intron insertion.

  10. Identification of nitrogenous organic species in Titan aerosols analogs: Nitrogen fixation routes in early atmospheres

    NASA Astrophysics Data System (ADS)

    He, Chao; Smith, Mark A.

    2013-09-01

    Titan, an icy world surrounded by auburn organic haze, is considered as one of the best targets for studying abiotic planetary organic chemistry. In spite of a great many efforts being made, the chemistry in Titan’s atmosphere and its resulting chemical structures are still not fully understood. In our previous work, we have investigated the structure of Titan aerosols analogs (tholin) by NMR and identified hexamethylenetetramine as a dominant small molecule in Titan tholin. Here we report a more complete and definitive structural investigation of the small molecule inventory in Titan tholin. We identified several nitrogenous organic molecules including cyanamide, guanidine, 2-cyanoguanidine, melamine, N‧-cyanoformamidine and 1,2,4-triazole in Titan tholin by using NMR and GC-MS and standard sample comparison. The structural characteristics of these molecules suggest a possible formation pathway from the reaction of HCN and NH3, both of which are known to exist in appreciable density in the atmosphere and were tentatively detected by the Huygens probe.

  11. Effect of organic amendments on quality indexes in an italian agricultural soil

    NASA Astrophysics Data System (ADS)

    Scotti, R.; Rao, M. A.; D'Ascoli, R.; Scelza, R.; Marzaioli, R.; Rutigliano, F. A.; Gianfreda, L.

    2009-04-01

    Intensive agricultural practices can determine a decline in soil fertility which represents the main constraint to agricultural productivity. In particular, the progressive reduction in soil organic matter, without an adequate restoration, may threaten soil fertility and agriculture sustainability. Some soil management practices can improve soil quality by adding organic amendments as alternative to the sole use of mineral fertilizers for increasing plant quality and growth. A large number of soil properties can be used to define changes in soil quality. In particular, although more emphasis has been given in literature to physical and chemical properties, biological properties, strictly linked to soil fertility, can be valid even more sensitive indicators. Among these, soil enzyme activities and microbial biomass may provide an "early warning" of soil quality and health changes. The aim of this work was to study the effect of preventive sterilization treatment and organic fertilization on enzymatic activities (dehydrogenase, arylsulphatase, beta-glucosidase, phosphatase, urease) and microbial biomass C in an agricultural soil under crop rotation. The study was carried out on an agricultural soil sited in Campania region (South Italy). At the beginning of experiment sterilizing treatments to control soilborne pathogens and weeds were performed by solarization and calcium cyanamide addition to soil. Organic fertilization was carried out by adding compost from vegetable residues, ricin seed exhaust (Rigen) and straw, singly or in association. Three samplings were performed at three different stages of crop rotation: I) September 2005, immediately after the treatments; II) December 2005, after a lettuce cycle; III) January 2007, after peppers and lettuce cycles. The soil sampling followed a W scheme, with five sub-samples for each plot. Soils were sieved at 2 mm mesh and air dried to determine physical and chemical properties; in addition a suitable amount of soils

  12. Activation of ALDH2 with Low Concentration of Ethanol Attenuates Myocardial Ischemia/Reperfusion Injury in Diabetes Rat Model.

    PubMed

    Kang, Pin-Fang; Wu, Wen-Juan; Tang, Yang; Xuan, Ling; Guan, Su-Dong; Tang, Bi; Zhang, Heng; Gao, Qin; Wang, Hong-Ju

    2016-01-01

    The aim of this paper is to observe the change of mitochondrial aldehyde dehydrogenase 2 (ALDH2) when diabetes mellitus (DM) rat heart was subjected to ischemia/reperfusion (I/R) intervention and analyze its underlying mechanisms. DM rat hearts were subjected to 30 min regional ischemia and 120 min reperfusion in vitro and pretreated with ALDH2 activator ethanol (EtOH); cardiomyocyte in high glucose (HG) condition was pretreated with ALDH2 activator Alda-1. In control I/R group, myocardial tissue structure collapse appeared. Compared with control I/R group, left ventricular parameters, SOD activity, the level of Bcl-2/Bax mRNA, ALDH2 mRNA, and protein expressions were decreased and LDH and MDA contents were increased, meanwhile the aggravation of myocardial structure injury in DM I/R group. When DM I/R rats were pretreated with EtOH, left ventricular parameters, SOD, Bcl-2/Bax, and ALDH2 expression were increased; LDH, MDA, and myocardial structure injury were attenuated. Compared with DM + EtOH I/R group, cyanamide (ALDH2 nonspecific blocker), atractyloside (mitoPTP opener), and wortmannin (PI3K inhibitor) groups all decreased left ventricular parameters, SOD, Bcl-2/Bax, and ALDH2 and increased LDH, MDA, and myocardial injury. When cardiomyocyte was under HG condition, CCK-8 activity and ALDH2 protein expression were decreased. Alda-1 increased CCK-8 and ALDH2. Our findings suggested enhanced ALDH2 expression in diabetic I/R rats played the cardioprotective role, maybe through activating PI3K and inhibiting mitoPTP opening.

  13. Activation of ALDH2 with Low Concentration of Ethanol Attenuates Myocardial Ischemia/Reperfusion Injury in Diabetes Rat Model

    PubMed Central

    Kang, Pin-Fang; Wu, Wen-Juan; Tang, Yang; Xuan, Ling; Guan, Su-Dong; Tang, Bi; Zhang, Heng

    2016-01-01

    The aim of this paper is to observe the change of mitochondrial aldehyde dehydrogenase 2 (ALDH2) when diabetes mellitus (DM) rat heart was subjected to ischemia/reperfusion (I/R) intervention and analyze its underlying mechanisms. DM rat hearts were subjected to 30 min regional ischemia and 120 min reperfusion in vitro and pretreated with ALDH2 activator ethanol (EtOH); cardiomyocyte in high glucose (HG) condition was pretreated with ALDH2 activator Alda-1. In control I/R group, myocardial tissue structure collapse appeared. Compared with control I/R group, left ventricular parameters, SOD activity, the level of Bcl-2/Bax mRNA, ALDH2 mRNA, and protein expressions were decreased and LDH and MDA contents were increased, meanwhile the aggravation of myocardial structure injury in DM I/R group. When DM I/R rats were pretreated with EtOH, left ventricular parameters, SOD, Bcl-2/Bax, and ALDH2 expression were increased; LDH, MDA, and myocardial structure injury were attenuated. Compared with DM + EtOH I/R group, cyanamide (ALDH2 nonspecific blocker), atractyloside (mitoPTP opener), and wortmannin (PI3K inhibitor) groups all decreased left ventricular parameters, SOD, Bcl-2/Bax, and ALDH2 and increased LDH, MDA, and myocardial injury. When cardiomyocyte was under HG condition, CCK-8 activity and ALDH2 protein expression were decreased. Alda-1 increased CCK-8 and ALDH2. Our findings suggested enhanced ALDH2 expression in diabetic I/R rats played the cardioprotective role, maybe through activating PI3K and inhibiting mitoPTP opening. PMID:27829984

  14. Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride-Molecular Ni Catalyst System.

    PubMed

    Kasap, Hatice; Caputo, Christine A; Martindale, Benjamin C M; Godin, Robert; Lau, Vincent Wing-Hei; Lotsch, Bettina V; Durrant, James R; Reisner, Erwin

    2016-07-27

    Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride ((NCN)CNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The (NCN)CNx-NiP system showed an activity of 763 μmol (g CNx)(-1) h(-1) toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h(-1), and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of (NCN)CNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited (NCN)CNx in the presence of an organic substrate can accumulate ultralong-lived "trapped electrons", which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel.

  15. Structural characterization of charcoal size-fractions from a burnt Pinus pinea forest by FT-IR, Raman and surface-enhanced Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Francioso, Ornella; Sanchez-Cortes, Santiago; Bonora, Sergio; Roldán, Maria Lorena; Certini, Giacomo

    2011-05-01

    Charcoal is mainly composed by aromatic C but is characterized by several degrees of aromaticity, which complicate its identification and quantification in natural environments by conventional analyses. Charcoal is an almost ubiquitous component of soil, although often occurring in minor amounts. Hence, there is a great interest in studying the charcoal structure and understanding the behavior of charcoal in soils. In soil, it has been demonstrated that the chemical structure of charcoal is also dependant on its particle-size. In this paper we have applied infrared, normal Raman, SERS and SEF spectroscopies to study four size-fractions of charcoal (>2 mm, 2-1 mm, 1-0.5 mm and <0.5 mm) and their alkaline extracts from a burnt Pinus pinea forest. Second derivative FT-IR in agreement with the normal Raman spectroscopy have given information about the size of aromatic rings and the nature of substituted groups in size-fractions of charcoal. Carbon cluster size progressively decreased in the smallest fractions suggesting that higher graphitization and crystallization occurred in the coarsest fraction (>2 mm). The presence of organic N was well evidenced by the vibration of iso-cyanate and cyanamide groups in the fractions. This result is of great environmental importance because N may be immobilized in form of stable molecules like N-heterocyclic poliaromatic structures, and so persists in soils. The soluble organic C (SOC) extracted from charcoal size-fractions did not differ from the bulk charcoal in terms of IR and Raman spectra. Instead SERS and SEF provided further information regarding the ratio between the aromatic component and the aliphatic cross-linking one in studied fractions.

  16. Gravimetric measurements of materials outgassing applied to graphite-epoxy laminates

    SciTech Connect

    Scialdone, J.J.

    1989-12-01

    The outgassing rates of two graphite-epoxy laminates, American Cyanamide 985B-626 and HST-7B-112, were obtained using a gravimetric method. The rates as a function of time and temperature were derived from the measurements of their mass losses at temperatures varying from 25 to 150 C and for a time span of up to 400 hours in a vacuum. The data from those measurements were reduced to obtain the outgassing activation energies, the mass losses per unit mass or area, and the corresponding outgassing rates. The rates are expressed in closed-form equations and are directly usable for medling computations. The procedures to obtain these parameters are shown and may be used for the evaluation of other materials. The results of the tests show that the activation energies of the two materials are: 4630 cal/mole for the 985B-626 materials and 4791 cal/mole for the HST-7B-112 sample no. 10 Graphite Exoxy. The outgassing rates of these materials are in the 10E-5 g/sq cm/hr range and they decay according to a power of time of 0.60 at 25 C, indicating that the outgassing process is mainly a diffusion at that temperature. The normalized mass losses versus time obtained from these tests were compared to the discrete results obtained from the ASTM-E595 tests. The comparison provides general indications on the effects of temperature and time in relation to the ASTM test values obtained at 125 C for a 24-hour test duration.

  17. Abscisic acid (ABA) regulates grape bud dormancy, and dormancy release stimuli may act through modification of ABA metabolism

    PubMed Central

    Zheng, Chuanlin; Halaly, Tamar; Acheampong, Atiako Kwame; Takebayashi, Yumiko; Jikumaru, Yusuke; Kamiya, Yuji; Or, Etti

    2015-01-01

    In warm-winter regions, induction of dormancy release by hydrogen cyanamide (HC) is mandatory for commercial table grape production. Induction of respiratory stress by HC leads to dormancy release via an uncharacterized biochemical cascade that could reveal the mechanism underlying this phenomenon. Previous studies proposed a central role for abscisic acid (ABA) in the repression of bud meristem activity, and suggested its removal as a critical step in the HC-induced cascade. In the current study, support for these assumptions was sought. The data show that ABA indeed inhibits dormancy release in grape (Vitis vinifera) buds and attenuates the advancing effect of HC. However, HC-dependent recovery was detected, and was affected by dormancy status. HC reduced VvXERICO and VvNCED transcript levels and induced levels of VvABA8’OH homologues. Regulation of these central players in ABA metabolism correlated with decreased ABA and increased ABA catabolite levels in HC-treated buds. Interestingly, an inhibitor of ethylene signalling attenuated these effects of HC on ABA metabolism. HC also modulated the expression of ABA signalling regulators, in a manner that supports a decreased ABA level and response. Taken together, the data support HC-induced removal of ABA-mediated repression via regulation of ABA metabolism and signalling. Expression profiling during the natural dormancy cycle revealed that at maximal dormancy, the HC-regulated VvNCED1 transcript level starts to drop. In parallel, levels of VvA8H-CYP707A4 transcript and ABA catabolites increase sharply. This may provide initial support for the involvement of ABA metabolism also in the execution of natural dormancy. PMID:25560179

  18. Expressional regulation of PpDAM5 and PpDAM6, peach (Prunus persica) dormancy-associated MADS-box genes, by low temperature and dormancy-breaking reagent treatment.

    PubMed

    Yamane, Hisayo; Ooka, Tomomi; Jotatsu, Hiroaki; Hosaka, Yukari; Sasaki, Ryuta; Tao, Ryutaro

    2011-06-01

    The present study investigated the expressional regulation of PpDAM5 and PpDAM6, two of the six peach (Prunus persica) dormancy-associated MADS-box genes, in relation to lateral bud endodormancy. PpDAM5 and PpDAM6 were originally identified as homologues of Arabidopsis SHORT VEGETATIVE PHASE/AGAMOUS-LIKE 24 identified in the EVERGROWING locus of peach. Furthermore, PpDAM5 and PpDAM6 have recently been suggested to be involved in terminal bud dormancy. In this study, seasonal expression analyses using leaves, stems, and lateral buds of high-chill and low-chill peaches in field conditions indicated that both genes were up-regulated during the endodormancy period and down-regulated with endodormancy release. Controlled environment experiments showed that the expression of both PpDAM5 and PpDAM6 were up-regulated by ambient cool temperatures in autumn, while they were down-regulated by the prolonged period of cold temperatures in winter. A negative correlation between expression levels of PpDAM5 and PpDAM6 and bud burst percentage was found in the prolonged cold temperature treatment. Application of the dormancy-breaking reagent cyanamide to endo/ecodormant lateral buds induced early bud break and down-regulation of PpDAM5 and PpDAM6 expression at the same time. These results collectively suggest that PpDAM5 and PpDAM6 may function in the chilling requirement of peach lateral buds through growth-inhibiting functions for bud break.

  19. Opposite motor responses elicited by ethanol in the posterior VTA: the role of acetaldehyde and the non-metabolized fraction of ethanol.

    PubMed

    Martí-Prats, Lucía; Sánchez-Catalán, María José; Orrico, Alejandro; Zornoza, Teodoro; Polache, Ana; Granero, Luis

    2013-09-01

    Recent electrophysiological evidence suggests that ethanol simultaneously exerts opposite effects on the activity of dopamine (DA) neurons in the ventral tegmental area (VTA) through two parallel mechanisms, one promoting and the other reducing the GABA release onto VTA DA neurons. Here we explore the possible behavioural implications of these findings by investigating the role displayed by acetaldehyde (the main metabolite of ethanol) and the non-metabolized fraction of ethanol in motor activity of rats. We analyse the appearance of motor activation or depression after intra-VTA administration of ethanol in rats subjected to different pharmacological pre-treatments designed to preferentially test either the effects of acetaldehyde or the non-metabolized ethanol. Motor activity was evaluated after intra-VTA administration of 35 nmol of ethanol, an apparently ineffective dose that does not modify the motor activity of animals. Pharmacological pre-treatments were used in order to either increase (cyanamide, 10 mg/kg, ip) or decrease (D-penicillamine, 50 mg/kg, ip and sodium azide, 7 mg/kg, ip) acetaldehyde levels in the VTA. Pre-treatments aimed to augment acetaldehyde, increased motor activity of rats. Otherwise, pre-treatments intended to decrease local acetaldehyde levels evoked significant reductions in motor activity that were prevented by the local blockade (bicuculline, 17.5 pmol) of the GABAA receptors. Our findings suggest that the brain-generated acetaldehyde is involved in the stimulant effects of ethanol, whereas the non-biotransformed fraction of ethanol, acting through the GABAA receptors, would account for the depressant effects. The present behavioural findings suggest that ethanol dually modulates the activity of DA neurons.

  20. Rapid detection of economic adulterants in fresh milk by liquid chromatography-tandem mass spectrometry.

    PubMed

    Abernethy, Grant; Higgs, Kerianne

    2013-05-03

    A method to aid in the detection of the economically driven adulteration of fresh milk with a range of small, nitrogen containing compounds, including melamine, ammeline, ammelide, cyanuric acid, allantoin, thiourea, urea, biuret, triuret, semicarbazide, aminotriazine, 3- and 4-aminotriazole, cyanamide, dicyandiamide, guanidine, choline, hydroxyproline, nitrate, and a range of amino acids, has been developed. (15)N2-Urea is used as an internal standard. The adulteration of milk with exogenous urea has previously been difficult to detect because of the variation in the naturally occurring levels of urea in milk. However, by monitoring the contaminants biuret and triuret, which comprise up to 1% of synthetic urea, the adulteration of milk with urea-based fertilizer can be detected. We estimate that to be economically viable, adulteration of the order of 90-4000ppm of the above adulterants would need to be added to fresh milk. For most of the compounds, an arbitrary detection threshold of 2ppm is therefore more than sufficient. For biuret, a lower detection threshold, better than 0.5ppm, is desirable and the sensitivity for biuret and triuret can be improved by the post-column addition of lithium to create lithium adducts under electrospray ionisation. Sample handling involves a two-step solvent precipitation method that is deployed in a 96-well plate format, and the hydrophilic interaction liquid chromatography uses a rapid gradient (1.2min). Three separate injections, to detect the positively charged compounds, the negatively charged compounds and amino acids and finally the lithium adducts, are used. This rapid and qualitative survey method may be deployed as a second tier screening method to quickly reduce sample numbers indicated as irregular by an FTIR based screening system, and to direct analysis to appropriate quantification methods.

  1. Fabrication and photoelectrochemical properties of silicon nanowires/g-C3N4 core/shell arrays

    NASA Astrophysics Data System (ADS)

    Chen, Zhen; Ma, Ge; Chen, Zhihong; Zhang, Yongguang; Zhang, Zhe; Gao, Jinwei; Meng, Qingguo; Yuan, Mingzhe; Wang, Xin; Liu, Jun-ming; Zhou, Guofu

    2017-02-01

    A photoelectrochemical (PEC) cell made of metal-free carbon nitride (g-C3N4) @siliconnanowire(Si NW) arrays (denoted as Si NWs/g-C3N4) is presented in this work. The as-prepared photoelectrodes with different mass contents of g-C3N4 have been synthesized via a metal-catalyzed electroless etching (MCEE), liquid atomic layer deposition (LALD) and annealing methods. The amount of g-C3N4 on the Si NW arrays can be controlled by tuning the concentration of the cyanamide solution used in the LALD procedure. The dense and vertically aligned Si NWs/g-C3N4 core/shell nanostructures were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). In comparison with FTO/g-C3N4 and Si NW samples, the Si NWs/g-C3N4 samples showed significantly enhanced photocurrents over the entire potential sweep range. Electrochemical impedance spectroscopy (EIS) was conducted to investigate the properties of the charge transfer process, and the results indicated that the enhanced PEC performance may be due to the increased photo-generated interfacial charge transfer between the Si NWs and g-C3N4. The photocurrent density reached 45 μA/cm2 under 100 mW/cm2 (AM 1.5 G) illumination at 0 V (vs. Pt) in neutral Na2SO4 solution (pH ∼ 7.62). Finally, a systematical PEC mechanism of the Si NWs/g-C3N4 was proposed.

  2. Prebiotic Lipidic Amphiphiles and Condensing Agents on the Early Earth

    PubMed Central

    Fiore, Michele; Strazewski, Peter

    2016-01-01

    It is still uncertain how the first minimal cellular systems evolved to the complexity required for life to begin, but it is obvious that the role of amphiphilic compounds in the origin of life is one of huge relevance. Over the last four decades a number of studies have demonstrated how amphiphilic molecules can be synthesized under plausibly prebiotic conditions. The majority of these experiments also gave evidence for the ability of so formed amphiphiles to assemble in closed membranes of vesicles that, in principle, could have compartmented first biological processes on early Earth, including the emergence of self-replicating systems. For a competitive selection of the best performing molecular replicators to become operative, some kind of bounded units capable of harboring them are indispensable. Without the competition between dynamic populations of different compartments, life itself could not be distinguished from an otherwise disparate array or network of molecular interactions. In this review, we describe experiments that demonstrate how different prebiotically-available building blocks can become precursors of phospholipids that form vesicles. We discuss the experimental conditions that resemble plausibly those of the early Earth (or elsewhere) and consider the analytical methods that were used to characterize synthetic products. Two brief sections focus on phosphorylating agents, catalysts and coupling agents with particular attention given to their geochemical context. In Section 5, we describe how condensing agents such as cyanamide and urea can promote the abiotic synthesis of phospholipids. We conclude the review by reflecting on future studies of phospholipid compartments, particularly, on evolvable chemical systems that include giant vesicles composed of different lipidic amphiphiles. PMID:27043635

  3. Increased brain nitric oxide levels following ethanol administration.

    PubMed

    Finnerty, Niall; O'Riordan, Saidhbhe L; Klamer, Daniel; Lowry, John; Pålsson, Erik

    2015-05-01

    Nitric oxide is a ubiquitous messenger molecule, which at elevated concentrations has been implicated in the pathogenesis of several neurological disorders. Its role in oxidative stress, attributed in particular to the formation of peroxynitrite, proceeds through its high affinity for the superoxide radical. Alcoholism has recently been associated with the induction of oxidative stress, which is generally defined as a shift in equilibrium between pro-oxidant and anti-oxidant species in the direction of the former. Furthermore, its primary metabolite acetaldehyde, has been extensively associated with oxidative damage related toxic effects following alcohol ingestion. The principal objective of this study was the application of long term in vivo electrochemistry (LIVE) to investigate the effect of ethanol (0.125, 0.5 and 2.0 g kg(-1)) and acetaldehyde (12.5, 50 and 200 mg kg(-1)) on NO levels in the nucleus accumbens of freely moving rats. Systemic administrations of ethanol and acetaldehyde resulted in a dose-dependent increases in NO levels, albeit with very differing time courses. Subsequent to this the effect on accumbal NO levels, of subjecting the animal to different drug combinations, was also elucidated. The nitric oxide synthase inhibitor L-NAME (20 mg kg(-1)) and acetaldehyde sequestering agent D-penicillamine (50 mg kg(-1)) both attenuated the increase in NO levels following ethanol (1 g kg(-1)) administration. Conversely, the alcohol dehydrogenase inhibitor 4-methylpyrazole (25 mg kg(-1)) and catalase inhibitor sodium azide (10 mg kg(-1)) potentiated the increase in NO levels following ethanol administration. Finally, dual inhibition of aldehyde dehydrogenase and catalase by cyanamide (25 mg kg(-1)) caused an attenuation of ethanol effects on NO levels. Taken together these data highlight a robust increase in brain NO levels following systemic alcohol administration which is dependent on NO synthase activity and may involve both alcohol- and acetaldehyde

  4. Structures of heterogeneous proton-bond dimers with a high dipole moment monomer: covalent vs electrostatic interactions.

    PubMed

    Fridgen, Travis D

    2006-05-11

    A number of calculated structures of heterogeneous proton-bound dimers containing monomers such as acetonitrile, cyanamide, vinylene carbonate, and propiolactone, which have high dipole moments, are presented. These proton-bound dimers are predicted to have a structural anomaly pertaining to the bond distances between the central proton and the basic sites on each of the monomers. The monomers with the high dipole moments also have the larger proton affinity and, on the basis of difference in proton affinities, it would be expected that the proton would be closer to this monomer than the one with the lower proton affinity. However, the proton is found to lie substantially closer to the monomer with the lower proton affinity in most cases, unless the difference in proton affinity is too large. Simply stated, the difference in proton affinities is smaller than the difference in the affinity to form an ion-dipole complex for the two monomers and it is the larger affinity for the high dipole moment monomer (which also has the higher proton affinity) to form an ion-dipole complex that is responsible for the proton lying closer to the low proton affinity monomer. The bond distances between the central proton and the monomers are found to be related to the difference in proton affinity. It is found, though, that the proton-bound dimers can be grouped into two separate groups, one where the proton-bound dimer contains a high dipole moment monomer and one group where the proton-bound dimer does not contain a high dipole moment monomer. From these plots it has been determined that a high dipole moment monomer is one that has a dipole moment greater than 2.9 D.

  5. A 3-year continuous record on the influence of daytime, season, and fertilizer treatment on methane emission rates from an Italian rice paddy

    SciTech Connect

    Schuetz, H.; Holzapfel-Pschorn, A.; Conrad, R.; Rennenberg, H.; Seiler, W. )

    1989-11-20

    CH{sub 4} emission rates have been measured in an Italian rice paddy between 1984 and 1986, covering three vegetation periods. For these measurements a fully automated, computerized sampling and analyzing system was developed which allowed the simultaneous determination of CH{sub 4} emission rates at 16 different field plots. CH{sub 4} emission rates showed strong diurnal and seasonal variations. Diurnal changes correlated with changes in soil temperature. During the season, CH{sub 4} emission rates showed a first maximum in May--June before tillering and a second maximum in July during the reproductive stage of the rice plants. In 1985 and 1986 two maxima were observed during summer in addition to the first maximum in the rate of CH{sub 4} emission during spring. Application of mineral and/or organic fertilizer application. Thus the rates decreased by at most 40% and 60% after fertilization by deep incorporation with 200 kg N/ha urea and 200 kg N/ha ammonium sulfate, respectively. Application of 200 kg N/ha calcium cyanamide led to a reduction of the first maximum of CH{sub 4} emission but caused the second maximum to increase, the overall result being that the seasonally averaged CH{sub 4} emission rate was comparable to that observed in unfertilized fields. Application of rice straw at a rate of 12t/ha enhanced the rate of CH{sub 4} emission by a factor of 2 compared with the control. Higher application rates of rice straw did not cause a further increase in CH{sub 4} emission.

  6. Involvement of EARLY BUD-BREAK, an AP2/ERF Transcription Factor Gene, in Bud Break in Japanese Pear (Pyrus pyrifolia Nakai) Lateral Flower Buds: Expression, Histone Modifications and Possible Target Genes.

    PubMed

    Anh Tuan, Pham; Bai, Songling; Saito, Takanori; Imai, Tsuyoshi; Ito, Akiko; Moriguchi, Takaya

    2016-05-01

    In the Japanese pear (Pyrus pyrifolia Nakai) 'Kosui', three developmental stages of lateral flower buds have been proposed to occur during ecodormancy to the flowering phase, i.e. rapid enlargement, sprouting and flowering. Here, we report an APETALA2/ethylene-responsive factor (AP2/ERF) transcription factor gene, named pear EARLY BUD-BREAK (PpEBB), which was highly expressed during the rapid enlargement stage occurring prior to the onset of bud break in flower buds. Gene expression analysis revealed that PpEBB expression was dramatically increased during the rapid enlargement stage in three successive growing seasons. PpEBB transcript levels peaked 1 week prior to onset of bud break in 'Kosui' potted plants treated with hydrogen cyanamide or water under forcing conditions. Chromatin immunoprecipitation-quantitative PCR showed that higher levels of active histone modifications (trimethylation of the histone H3 tail at Lys4) in the 5'-upstream and start codon regions of the PpEBB gene were associated with the induced expression level of PpEBB during the rapid enlargement stage. In addition, we provide evidence that PpEBB may interact with and regulate pear four D-type cyclin (PpCYCD3) genes during bud break in 'Kosui' lateral flower buds. PpEBB significantly increased the promoter activities of four PpCYCD3 genes in a dual-luciferase assay using tobacco leaves. Taken together, our findings uncovered aspects of the bud break regulatory mechanism in the Japanese pear and provided further evidence that the EBB family plays an important role in bud break in perennial plants.

  7. Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride–Molecular Ni Catalyst System

    PubMed Central

    2016-01-01

    Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride (NCNCNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The NCNCNx–NiP system showed an activity of 763 μmol (g CNx)−1 h–1 toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h–1, and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of NCNCNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited NCNCNx in the presence of an organic substrate can accumulate ultralong-lived “trapped electrons”, which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel. PMID:27337491

  8. Degradation of Adenine on the Martian Surface in the Presence of Perchlorates and Ionizing Radiation: A Reflectron Time-of-flight Mass Spectrometric Study

    NASA Astrophysics Data System (ADS)

    Góbi, Sándor; Bergantini, Alexandre; Kaiser, Ralf I.

    2017-04-01

    The aim of the present work is to unravel the radiolytic decomposition of adenine (C5H5N5) under conditions relevant to the Martian surface. Being the fundamental building block of (deoxy)ribonucleic acids, the possibility of survival of this biomolecule on the Martian surface is of primary importance to the astrobiology community. Here, neat adenine and adenine–magnesium perchlorate mixtures were prepared and irradiated with energetic electrons that simulate the secondary electrons originating from the interaction of the galactic cosmic rays with the Martian surface. Perchlorates were added to the samples since they are abundant—and therefore relevant oxidizers on the surface of Mars—and they have been previously shown to facilitate the radiolysis of organics such as glycine. The degradation of the samples were monitored in situ via Fourier transformation infrared spectroscopy and the electron ionization quadruple mass spectrometric method; temperature-programmed desorption profiles were then collected by means of the state-of-the-art single photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), allowing for the detection of the species subliming from the sample. The results showed that perchlorates do increase the destruction rate of adenine by opening alternative reaction channels, including the concurrent radiolysis/oxidation of the sample. This new pathway provides a plethora of different radiolysis products that were identified for the first time. These are carbon dioxide (CO2), isocyanic acid (HNCO), isocyanate (OCN‑), carbon monoxide (CO), and nitrogen monoxide (NO); an oxidation product containing carbonyl groups (R1R2–C=O) with a constrained five-membered cyclic structure could also be observed. Cyanamide (H2N–C≡N) was detected in both irradiated samples as well.

  9. Non-platinum group metal oxgyen reduction catalysts and their mechanism in both acid and alkaline media: The effect of the catalyst precursor and the ionomer on oxygen reduction

    NASA Astrophysics Data System (ADS)

    Robson, Michael H.

    Non-platinum catalysts are an attractive strategy for lowering the cost of fuel cells, but much more development is needed in order to replace platinum, especially at the cathode where oxygen is reduced. Research groups worldwide have donated material for a study in which precursor structure to catalyst activity correlations are made. The donated samples have been divided into three classes based on their precursor; macrocyclic chelates, small molecule, and polymeric precursors. The precursor is one activity-dictating factor among many, but it is one of the most influential. It was found that macrocyclic chelates on average produced the most active catalysts, having the highest limiting, diffusion-limited, kinetic, and exchange current densities, as well as the lowest overpotentials and H2O2 production. This suggests that the M-N4 atomic structure of the precursor remains largely static throughout heat treatment, as the M-Nx motif is the accepted active site conformation. The other classes were somewhat less active, but the breadth of precursor materials that range in structure and functionality, as well as low associated costs, make them attractive precursor materials. Careful precursor selection based on this analysis was applied to a new generation of catalyst derived from iron salt and 4-aminoantipyrine. An extensive investigation of the reduction of oxygen on the material performed in both acid and alkaline media, and it was found that reduction follows a two-step pathway. While the peroxide reducing step is also very fast, the first step is so rapid that, even at low active site density, the material is almost as active as platinum if all diffusion limitations are removed. In addition to bottom-up catalyst design, the catalyst:ionomer complex, by which catalyst is incorporated into the membrane electrode assembly, also affects reductive kinetics. A series of novel anionically conductive ionomers have been evaluated using a well-described cyanamide derived

  10. Materials processing and in-vivo animal studies of nitrided hydroxyapatite bioceramics

    NASA Astrophysics Data System (ADS)

    Rashid, Nancy Elizabeth

    2000-10-01

    Calcium phosphate bioceramics are currently being used in medicine and dentistry, for reconstruction or repair of diseased or injured bone, but with limited success. Incorporating nitrogen into phosphate glasses has resulted in improved properties, and it is proposed that similar benefits may be gained from nitriding calcium phosphate bioceramics for bone implants as well. This work focuses on processing of hydroxyapatite and tricalcium phosphate bioceramics nitrided by using solid, liquid, gas and ion sources. These materials were characterized by chemical, structural, mechanical, and biological methods to determine both the material structure and their suitability as implant materials. Calcium nitride and NaPON glass were unsatisfactory sources of nitrogen for hydroxyapatite (HA) and/or tricalcium phosphate (TCP) ceramics. Calcium nitride, Ca3N2, is reacts with water vapor in the air, releasing ammonia, and leaving behind crystals of calcium oxide, CaO. The calcium oxide byproduct decreases the chemical stability of hydroxyapatite and HA/TCP composites in simulated body fluid. Sodium phosphorus oxynitride (NaPON) glass, in the form of a liquid sintering aid for HA, produces an inhomogeneous, composite as well. Hydroxyapatite heated at 800C in an ammonia atmosphere produces a homogeneous material with up to 2 wt% N. Infrared spectroscopy indicates cyanamide ions, CN22-, are formed by the incorporated nitrogen and impurity carbon. The use of 15N-doped ammonia results in an 15N NMR peak at 83.2 ppm, indicating P--N bonding. Raman spectroscopy may also indicate P--N bonding, but it is inconclusive. In a limited study, nitrogen may decrease the hardness and fracture toughness of the phosphate ceramic, hydroxyapatite, contrary to results expected for nitrogen in phosphate glasses. Nitrogen ions are incorporated in hydroxyapatite by ion implantation, with lower energies producing higher nitrogen contents. The highest concentration achieved was 3.55 wt% N, as determined

  11. Solid state and dynamic solution structures of O-carbamidine amidoximes gives further insight into the mechanism of zinc(II)-mediated generation of 1,2,4-oxadiazoles

    NASA Astrophysics Data System (ADS)

    Kulish, Kirill I.; Novikov, Alexander S.; Tolstoy, Peter M.; Bolotin, Dmitrii S.; Bokach, Nadezhda A.; Zolotarev, Andrey A.; Kukushkin, Vadim Yu.

    2016-05-01

    Three new iminium salts [H2Ndbnd C(R)ONdbnd C(R‧)NH2](p-TolSO3)·½H2O ([1-3](p-TolSO3)·½H2O; R/R‧ = NMe2/PhCH21, NMe2/p-BrC6H42, N(CH2)5/p-BrC6H43) were synthesized via ZnII-mediated amidoxime-cyanamide coupling and their solid structures were studied by X-ray diffraction. Solution structure and conformational changes of [1-3](p-TolSO3)·½H2O were studied by dynamic NMR. The obtained quantitative data were supported by DFT calculations. All the obtained results help to understand the relative stability of the salts [H2Ndbnd C(R)ONdbnd C(R‧)NH2](X) (R = NAlk2, Alk, Ar) and give a further insight into the mechanism of ZnII-mediated generation of 1,2,4-oxadiazoles. The electron delocalization and sesquialteral bonds in the [H2Ndbnd C(NR2)ONdbnd C(R‧)NH2]+ system was recognized by estimation of values of activation energy barriers (14-18 kcal/mol by DNMR and 16-17 kcal/mol by DFT calculations) for the rotation around the CN bonds for the NR2 groups and inspection of the solid-state X-ray data along with the Wiberg bond indices (intermediate single/double bond order for the CN distances). This electron delocalization is responsible for the stabilization of the positively charged iminium cation. The moderate strength hydrogen bonding between the oxime N atom and the =NH2 group, which is verified from the X-ray, DNMR experiments, and by using quantum chemical calculations, stabilizes the iminium salt, but it is still weak to prevent the heterocyclization. Theoretical calculations of the heterocyclization of [H2Ndbnd C(R)ONdbnd C(R‧)NH2]+ to 1,2,4-oxadiazoles demonstrated that it is kinetically hindered to a greater extent for R = NAlk2 and this explains their lower reactivity as compared to the iminium salts with R = Alk, Ar.

  12. Nitrite-mediated renal vasodilatation is increased during ischemic conditions via cGMP-independent signaling.

    PubMed

    Liu, Ming; Zollbrecht, Christa; Peleli, Maria; Lundberg, Jon O; Weitzberg, Eddie; Carlström, Mattias

    2015-07-01

    The kidney is vulnerable to hypoxia, and substantial efforts have been made to ameliorate renal ischemic injury secondary to pathological conditions. Stimulation of the nitrate-nitrite-nitric oxide pathway is associated with renal and cardiovascular protection in disease models, but less is known about the vascular effects during renal ischemia. This study was aimed at investigating the vascular effects of nitrite in the kidney during normoxic and ischemic conditions. Using a multiwire myograph system, we assessed nitrite-mediated relaxation (10(-9)-10(-4)mol/L) in isolated and preconstricted renal interlobar arteries from C57BL/6 mice under normal conditions (pO2 13kPa; pH 7.4) and with low oxygen tension and low pH to mimic ischemia (pO2 3kPa; pH 6.6). Xanthine oxidoreductase expression was analyzed by quantitative PCR, and production of reactive nitrogen species was measured by DAF-FM DA fluorescence. During normoxia significant vasodilatation (15±3%) was observed only at the highest concentration of nitrite, which was dependent on NO-sGC-cGMP signaling. The vasodilatory responses to nitrite were greatly sensitized and enhanced during hypoxia with low pH, demonstrating significant dilatation (11±1%) already in the physiological range (10(-8)mol/L), with a maximum response of 27±2% at 10(-4) mol/L. In contrast to normoxia, and to that observed with a classical NO donor (DEA NONOate), this sensitization was independent of sGC-cGMP signaling. Moreover, inhibition of various enzymatic systems reported to reduce nitrite in other vascular beds, i.e., aldehyde oxidase (raloxifene), aldehyde dehydrogenase (cyanamide), and NO synthase (L-NAME), had no effect on the nitrite response. However, inhibition of xanthine oxidoreductase (XOR; febuxostat or allopurinol) abolished the sensitized response to nitrite during hypoxia and acidosis. In conclusion, in contrast to normoxia, nitrite exerted potent vasorelaxation during ischemic conditions already at physiological

  13. Alcohol intake in high alcohol drinking (HAD) rats is suppressed by FG5865, a novel 5-HT1A agonist/5-HT2 antagonist.

    PubMed

    Long, T A; Kalmus, G W; Björk, A; Myers, R D

    1996-01-01

    Both the 5-HT2 antagonist, FG5606 (amperozide), and the mixed 5-HT1 agonist/5-HT2 antagonist, FG5893, attenuate significantly the volitional intake of alcohol in the cyanamide treated rat. The purpose of the present study was to investigate the effect on alcohol drinking in the selectively bred, high alcohol drinking (HAD) rat of a new and novel 5-HT1A agonist/5-HT2 antagonist, FG5865 (2-[4-[4,4-bis(4-fluorophenyl)butyl]-1-piperazinyl]-3-pyridinecarboxy lic acid methyl ester), which shares pharmacological properties with FG5893. Initially, a standard three bottle preference test for water vs. 3% to 30% alcohol solutions was given over 11 days to determine the maximally preferred concentration for each animal. Then water and this solution, which ranged between 9% and 20% with an overall mean absolute intake of 6.3 +/- 0.5 g/kg per day, was offered over three consecutive 4-day test sequences: (1) predrug control; (2) SC injections b.i.d. of either 1.0 mg/kg or 2.5 mg/kg FG5865 or saline control vehicle; and (3) postdrug. Whereas saline failed to alter alcohol consumption of the HAD rats, FG5865 caused a significant dose dependent reduction by as much as 75% in the intakes of alcohol during its administration in terms of both g/kg (p < 0.01) and proportion of alcohol to total fluid intake (p < 0.01). During the administration of 2.5 mg/kg FG5865, alcohol drinking declined from 6.5 +/- 0.3 g/kg to as low as 2.3 +/- 0.2 g/kg per day. Neither the body weight of the HAD animals nor their intake of food was affected by either dose of FG5865. These results uphold the concept that the 5-HT1A and 5-HT2 receptor subtypes in the brain play a part in the aberrant drinking of alcohol of the HAD rat. Because FG5865 influences the activity of serotonergic neurons in the mesolimbic system of the rat, it is envisaged that the drug suppresses alcohol drinking by way of its action on these neurons.

  14. Hydrologic monitoring of a waste-injection well near Milton, Florida, June 1975 - June 1977

    USGS Publications Warehouse

    Pascale, Charles A.; Martin, J.B.

    1978-01-01

    This report presents the hydraulic and chemical data collected from June 1, 1975, when injection began, to June 30, 1977 through a monitoring program at a deep-well waste-injection system at the American Cyanamid Company's plant near Milton, about 12 miles northwest of Pensacola. The injection system consists of a primary injection well, a standby injection well, and two deep monitor wells all completed open hole in the lower limestone of the Floridan aquifer and one shallow-monitor well completed in the upper limestone of the Floridan aquifer. Two of the monitor wells and the standby injection well are used to observe hydraulic and geochemical effects of waste injection in the injection zone at locations 8,180 feet northeast, 1,560 feet south, and 1,025 feet southwest of the primary injection well. The shallow-monitor well, used to observe any effects in the first permeable zone above the 200-foot-thick confining bed, is 28 feet north of the primary injection well. Since injection began in June 1975, 607 million gallons of treated industrial liquid waste with a pH of 4.6 to 6.3 and containing high concentrations of nitrate, organic nitrogen and carbon have been injected into a saline-water-filled limestone aquifer. Wellhead pressure at the injection well in June 1977 average 137 pounds per square inch and the hydraulic pressure gradient was 0.53 pound per square inch per foot of depth to the top of the injection zone. Water levels rose from 36 to 74 feet at the three wells used to monitor the injection zone during the 25-month period. The water level in the shallow-monitor well declined about 8 feet. No changes were detected in the chemical character of water from the shallow-monitor well and deep-monitor well-north. Increases in concentration of bicarbonate and dissolved organic carbon were detected in water from the deep-test monitor well in February 1976 and at the standby injection well in August 1976. In addition to increases in bicarbonate and dissolved

  15. Did the Pre-RNA World Rest Upon DNA Molecules?

    NASA Technical Reports Server (NTRS)

    Lazcano, Antonio; Dworkin, Jason P.; Miller, Stanley L.

    2004-01-01

    The isolation of a DNA sequence that catalyzes the ligation of oligodeoxynucleotides via the formation of 3' - 5' phosphodiester linkage significance in selection experiments has been reported. Ball recently used this to discuss the possibility that natural DNA molecules may have formed in the primitive Earth leading to the origin of life. As noted by Ferris and Usher, if metabolic pathways evolved backwards, it could be argued that the biosynthesis of 2-deoxyribose from ribose suggests that RNA came from DNA. As summarized elsewhere, there are several properties of deoxyribose which could be interpreted to support the possibility that DNA-like molecules arose prior to the RNA world. For example, 2-deoxyribose is slightly more soluble than ribose (which may have been an advantage in a drying pool scenario), may have been more reactive under possible prebiotic conditions (it forms a nucleoside approx. 150 times faster than ribose with the alternative base urazole at 25 C), while it decomposes in solution (approximately 2.6 times more slowly than ribose at 100 C). Other advantages of DNA over RNA are that it has one fewer chiral center, has a greater stability at the 8.2 pH value of the current oceans, and does not has the 2'5' and 3'5' ambiguity in polymerizations. Yet, there is strong molecular biological and biochemical evidence that RNA was featured in the biology well before the last common ancestor. The presence of sugar acids, including both ribo- and deoxysugar acids, in the 4.6 Ga old Murchison meteorite suggest that both may have been available in the primitive Earth, derived from the accretion of extraterrestrial sources and/or from endogenous processes involving formaldehyde and its derivatives. However, the abiotic synthesis of deoxyribose, ribose, and other sugars from glyceraldehyde and acetaldehyde under alkaline conditions is inefficient and unespecific. Although sugars are labile compounds, the role of cyanamide or borate minerals in the

  16. [Biological actions of acetaldehyde].

    PubMed

    Ijiri, I

    1999-11-01

    before and after drinking. The decrease in low molecular kininogen levels indicates that kallidin released from glandular kallikrein exists in the glandular tissues such as the kidneys, sweat glands, saliva glands, etc. We hypothesize that kallikrein activated by AcH in the sweat glands produces kallidin which cause vessels around the glands to dilate, and flushing of the face and the whole body occurs due to escalation of the sphere of dilatation of blood vessels. 4. A isolated 30 cm length of the canine jejunum segment with intact vascular supply was performed. After pretreatment with cyanamide (CY), a potent inhibitor of aldehyde dehydrogenase, or pyrazole (PY), a potent inhibitor of alcohol dehydrogenase, a 17% EtOH solution (0.4 g/kg) was administered into the jejunum segment, and 150 min after the administration of EtOH, the fluid from the segment was collected to determine its volume and EtOH concentration. The CY-pretreatment group, in which an extremely high AcH concentration developed, in comparison with the control and PY-pretreatment groups, showed a gradual increase of portal blood EtOH, a 25% reduction in the amount of absorbed EtOH, and an 85% smaller absorption rate constant value (Ka value). These facts indicate that the presence of a high AcH concentration in the blood results in a reduction of EtOH absorption and retardation of EtOH reaching the systemic circulation. The rapid reduction of portal blood flow and lower EtOH level in the portal vein observed in the CY group, in comparison with the other groups, also indicate that the reduction of EtOH permeability through the absorption site to the blood is an important retarding factor induced by AcH. 5. After segmenting a 20 cm length of rat intestine, cannulae for EtOH perfusion were inserted into each end of the intestine segment. Perfusion of EtOH solution (4%) was performed for 30 min at steady rate, beginning 60 min after pretreatment with CY and/or PY. The blood EtOH and AcH concentrations in the